CN101045860B - Oxynitride fluorescent material, method for producing the same, and luminescent device using the same - Google Patents
Oxynitride fluorescent material, method for producing the same, and luminescent device using the same Download PDFInfo
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- CN101045860B CN101045860B CN2007101010937A CN200710101093A CN101045860B CN 101045860 B CN101045860 B CN 101045860B CN 2007101010937 A CN2007101010937 A CN 2007101010937A CN 200710101093 A CN200710101093 A CN 200710101093A CN 101045860 B CN101045860 B CN 101045860B
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- oxonitride phosphor
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Abstract
An oxonitride phosphor which comprises a crystal containing at least one Group II element selected from the group consisting of Be, Mg, Ca, Sr, Ba and Zn, at least one Group IV element selected from the group consisting of C, Si, Ge, Sn, Ti, Zr and Hf, and a rare earth metal as an activator R. The oxonitride phosphor is exited by an excitation light source of an ultraviolet to visible region and emits a light having a color of from a blue-green region to a yellow region.
Description
The application divides an application, the application number of its female case application: 200380101648.8, and the applying date: 2003.10.15, denomination of invention: oxonitride phosphor and manufacture method thereof and the light-emitting device that uses this oxonitride phosphor
Technical field
The present invention relates to a kind of fluor, this fluor can be by hertzian wave such as light, X ray, electron beam or hot equal excitation and luminous, relates in particular to general lighting such as luminescent lamp, vehicle-mounted illumination, the liquid crystal light-emitting device with backlight, indicating meter etc.Relate in particular to the light-emitting device that white light is and polychrome is that adopts semiconductor light-emitting elements.
Background technology
Adopt the light-emitting device of luminous element, small-sized, electrical efficiency is good, sends the light of distinct color.In addition, therefore this luminous element does not worry filament break etc. owing to be semiconductor element.In addition, it is of fine quality different that this luminous element also has initial driven nature, and the characteristics of vibration resistance and anti-switch lighting repeatedly.Owing to have the feature of excellence like this, therefore use the light-emitting device of semiconductor light-emitting elements such as LED and LD, be used as various light sources.
Developing a kind of part or all light wavelength of utilizing the light of fluor conversion luminescence element, and the light of the luminous element that is not converted of the light that this wavelength is converted and wavelength sends after mixing, thereby sends the light-emitting device of the illuminant colour of the light that is different from luminous element.
In these light-emitting devices, in illumination such as luminescent lamp, load illumination, indicating meter and liquid crystal with wide spectrums such as backlight, demand white color system light-emitting device.In addition, by combined semiconductor luminous element and fluor, the light-emitting device of all tones such as demand light color.
Use the illuminant colour of light-emitting device of the semiconductor light-emitting elements of white color system, be based on that the colour mixture principle of light obtains.The blue light that luminous element is emitted, in inciding luminescent coating after, in layer, after multiple absorption and the scattering several times, outwards emit.On the other hand, the blue light that is absorbed in the fluor sends xanchromatic fluorescence with excitation light source work.By mixing this sodium yellow and blue light, can make people's eyes regard white as.
For example, in luminous element, adopt blue based light-emitting device, and on the surface of this blueness based light-emitting device, apply very thin fluor.This luminous element is to use the blue light emitting device of InGaN based material.In addition, fluor uses with (Y, Gd)
3(Al, Ga)
5O
12: the YAG that the composition formula of Ce is represented is a fluor.
, it is electro-optical device that the white that has blue based light-emitting device and YAG and be a fluor is sent out, by the colour mixture of near blue light the 460nm and near the yellow-green light the 565nm, and the colour system light that turns white, but near the luminous intensity deficiency 500nm.
In addition, in recent years, propose to adopt the luminous element in the short wavelength side zone of visible light, it is the fluor of light and to send yellow be that the YAG of light is the white color system light-emitting device that fluor forms that blueness is sent in combination.In such cases, the YAG that sends yellow and be light is a fluor, hardly by the optical excitation in the short wavelength side zone of visible light, does not carry out luminous.Therefore, utilizing this luminous element excitated blue is fluor, makes its colour system light that turns blue.Then, utilizing this blueness is that optical excitation YAG is a fluor, makes its jaundice colour system light.Thus, be the sodium yellow of fluor by mixing blue light and the YAG that blueness is a fluor, make its colour system light that turns white.
The fluor that is used for this light-emitting device, exploitation has multiple.
For example, the oxide based fluor at luminescence center employing rare earth element is widely known by the people, and a part is practicability.But, about nitride phosphor and oxonitride phosphor, also there is not too many research, compare with oxide based fluor, have only few research report.For example, fluor (spy opens the 2001-214162 communique, hereinafter referred to as patent documentation 1) with the oxynitride glass of expressions such as Si-O-N, Mg-Si-O-N, Ca-Al-Si-O-N is arranged.The fluor (spy opens the 2002-76434 communique, hereinafter referred to as patent documentation 2) of the oxide compound nitriding glass of representing with Ca-Al-Si-O-N that in addition, has that Eu is activated.
But, fluor in the past, luminosity is low, is not enough to be used for light-emitting device.In the light-emitting device of the luminous element that adopts zones such as near ultraviolet as excitation light source, be that to utilize this luminous element excitated blue be fluor, utilizing this excitation YAG is that two sections of fluor excite, therefore rare to high efficiency white light.For this reason, the direct Wavelength-converting of light in the short wavelength side zone of demand by utilizing visible light sends the fluor of green glow to gold-tinted.
In addition, the luminous element in the short wavelength side zone of employing visible light and the white light emitting device of fluor can not be made suitable fluor, reach practical light-emitting device and also sell.For this reason, demand is at the effective luminous fluor in the short wavelength zone of visible light.
In addition, above-mentioned patent documentation 1 and 2 luminosity such as oxonitride phosphor are low, also are not enough to be used for light-emitting device.In addition, because the fluor of oxynitride glass is a vitreum, therefore general difficult processing.
Summary of the invention
, the objective of the invention is to for this reason, a kind of fluor is provided and adopts the light-emitting device of this fluor, this fluor is excited by the excitation light source from the ultraviolet to the visible region and blue-greenish colour with wavelength Conversion is tied to the illuminant colour of yellow system.In addition, the objective of the invention is to, a kind of luminous efficiency height and the good light-emitting device of reproducibility are provided.
In addition, the objective of the invention is to, a kind of fluor of easy adjustment tone and the light-emitting device of this fluor of employing are provided.
For achieving the above object, the 1st oxonitride phosphor of the present invention, it is characterized in that, by containing the II family element of from the group that forms by Be, Mg, Ca, Sr, Ba and Zn, selecting more than at least a kind, the IV family element of selecting from the group that is made up of C, Si, Ge, Sn, Ti, Zr and Hf more than at least a kind reaches the crystallization formation as the rare earth element of activator R.
The 1st oxonitride phosphor of the present invention owing to be element by certain regularly arranged crystallization, therefore has high luminosity, has excellent characteristic as fluor.In addition, the 1st kind of oxonitride phosphor of the present invention, by selecting its composition, can from bluish-green to the xanchromatic zone, realize required luminescent spectrum.
Herein, so-called oxynitride means the structure that nitrogen places oxide compound, and as its representative, in the past, known had a unformed oxynitride glass.
In the 1st oxonitride phosphor of the present invention, for realizing more high brightness, preferred described II family element be from the group that forms by Ca, Sr, Ba and Zn, select, with Ba as essential more than a kind, and described IV family element be from the group that forms by C, Si, Ge, Sn, Ti, Zr and Hf, select, with Si as essential more than a kind, and contain Eu as activator R.
The 1st oxonitride phosphor that this contains Ba, Si and Eu has and has the luminescent spectrum of glow peak from bluish-green to green district, and has high luminous efficiency and excellent temperature profile.
In addition, in such cases, the content of described activator R, for reaching more high brightness, preferably with respect to described II family element, in molar ratio, be described II family element: described R=1: 0.005～1: 0.15, even in this is formed, also can improve luminous efficiency the biglyyest.
In described the 1st oxonitride phosphor, by in composition, containing O and N, and weight ratio with this O and this N, according to respect to 1 of O, N reaches the mode of 0.2～2.1 scope and sets, and the light that can obtain origin self-excitation light source is excited by high-level efficiency and at the fluor that has illuminant colour from blue-greenish colour to yellow system zone.
The 2nd oxonitride phosphor of the present invention is characterized in that, with general formula L
XM
YO
ZN
((2/3) X+ (4/3) Y-(2/3) Z): R or L
XM
YQ
TO
ZN
((2/3) X+ (4/3) Y+T-(2/3) Z): R represents (the II family element at least a kind or more of L for selecting from the group that is made of Be, Mg, Ca, Sr, Ba and Zn.The IV family element at least a kind or more of M for from the group that forms by C, Si, Ge, Sn, Ti, Zr and Hf, selecting.The iii group element at least a kind or more of Q for from the group that forms by B, Al, Ga and In, selecting.O is an oxygen element.N is the nitrogen element.R is a rare earth element.0.5＜X＜1.5、1.5＜Y＜2.5、0＜T＜0.5、1.5＜Z＜2.5)。
Like this 2nd oxonitride phosphor of the present invention that constitutes contains element by certain regularly arranged crystallization to small part, can be from this crystallization high efficiency light-emitting, and have the excellent characteristics of luminescence.In addition, because the 2nd oxonitride phosphor, its luminescent part is not vitreum (unformed), but therefore crystallization can reproduce stable properties, and its manufacturing and handling ease.In addition, in the above-mentioned general formula,, can provide fluor than the crystallization phases that is easier to be formed into into luminescent part with good luminous efficient by described X, Y and Z are set in the described scope.
The 2nd oxonitride phosphor of the present invention by the optical excitation in the short wavelength side zone from the near ultraviolet to the visible light, and has the luminescent spectrum that has glow peak in blue-greenish colour to yellow system zone.In addition, the 2nd oxonitride phosphor is that fluor is compared with YAG, has equal above stability.
Herein, the 2nd oxonitride phosphor of the present invention also has the damaged situation of nitrogen, general formula in the case with
Or
Expression.In addition, α is approaching more zero, and then the crystallinity of crystallization phases is good more, thereby can improve luminosity.
In addition, in the 2nd oxonitride phosphor of the present invention, for reaching more high brightness, preferred described L be from the group that forms by Ca, Sr, Ba and Zn, select, be the essential II family element more than at least a kind with Ba, and M be from the group that forms by C, Si, Ge, Sn, Ti, Zr and Hf, select, be the essential IV family element more than at least a kind with Si, and contain Eu as activator R.
Like this, contain the 2nd oxonitride phosphor of Ba, Si and Eu, have the luminescent spectrum that has its glow peak to green district from bluish-green.
Preferred described X, described Y, described Z are X=1, Y=2, Z=2.When this is formed, can form more crystallization phases, its crystallinity also can be good simultaneously, can improve luminous efficiency.
Like this, the 2nd oxonitride phosphor of the present invention, at least a portion has crystallization (crystallization phases), and this crystallization preferably contains more than the 50 weight %, more preferably contains more than the 80 weight %.That is, crystallization phases is main luminous component, if luminescent part be the ratio of crystallization phases more than 50 weight %, can obtain high efficiency luminous.Like this, crystallization phases is many more, can make luminosity high more.In addition, if the ratio of crystallization phases is many, just makes and process easily.
Structural analysis according to the X-ray diffraction figure of described fluor learns that the described crystallization in the present invention the 1st and the 2nd oxynitride has rhombic unit cell, belongs to rhombic system.
For obtaining high luminous efficiency, the rare earth element of representing with described R is preferably Eu, under the situation that adopts Eu and other rare earth element, for obtaining high luminous efficiency, is Eu more than the 50 weight % among the preferred R, is Eu more than the 70 weight % more preferably.
The the of the present invention the 1st and the 2nd oxonitride phosphor, the light that is had the excitation light source of glow peak wavelength below 490nm excites, and has at the luminescent spectrum that has the glow peak wavelength than the long long wavelength side of described glow peak ripple.That is, the 1st and the 2nd oxonitride phosphor is had the light source activation of glow peak wavelength below 490nm, can obtain high efficiency luminous.Excite the of the present invention the 1st and the excitation light source of the 2nd oxonitride phosphor, preferably have the glow peak wavelength, more preferably have the glow peak wavelength at 350～410nm place at 240～470nm place.
The the described the 1st and the 2nd oxonitride phosphor can be excited expeditiously by the light at the excitation light source of locating to have the glow peak wavelength more than the 350nm and then more than 360nm.
In addition, contain under the situation of Ba, Si and Eu at the described the 1st and the 2nd oxynitride, can be excited effectively by the light that comes comfortable 360nm～480nm place to have the excitation light source of glow peak wavelength, and can launch expeditiously at the luminescent spectrum light that has the glow peak wavelength than the long long wavelength side of described glow peak ripple.
That is, contain when described oxonitride phosphor under the situation of Ba, Si and Eu,, can use the excitation light source that has the glow peak wavelength at 240～480nm place, but preferably use the excitation light source that has the glow peak wavelength at 360～480nm place as excitation light source.380～420nm that preferred especially use is used in semiconductor light-emitting elements or the excitation light source of 450～470nm.
As mentioned above, the of the present invention the 1st and the luminescent spectrum of the 2nd oxonitride phosphor, can be set in from bluish-green to the yellowish red color zone.In addition, the YAG that has the glow peak wavelength in the xanchromatic wavelength region may is in the fluor, even the exciting light in the short wavelength side zone of employing from the near ultraviolet to the visible light (for example, near the wavelength 400nm exciting light) make it luminous, also luminous hardly, but the of the present invention the 1st and the 2nd oxonitride phosphor by this regional exciting light, demonstrates high luminous efficiency.In addition, even adopt at excitation light source under the situation of the blue light that is, also demonstrate high luminous efficiency.
In this manual, blue-greenish colour is represented according to JIS Z8110 to yellowish red color system zone.Specifically be that blue-greenish colour means the scope of 485～610nm to yellowish red color system zone.
The the 1st and the 2nd oxonitride phosphor can have luminous intensity by the light of 370nm and more be higher than excitation spectrum by the luminous intensity of the light of 500nm.If set like this, by the light activated fluor of ultra-violet region, its brightness is higher than by the light activated fluor of blue region.Compare with the situation of the luminous element that adopts blue region, more can constitute the light-emitting device that can show high-luminous-efficiency when adopting the luminous element of ultra-violet region.
Contain under the situation of Ba, Si and Eu at the described the 1st and the 2nd oxonitride phosphor, can make 460nm neighbouring than having the higher excitation spectrum of intensity near the 350nm.Therefore, and compare near the 350nm, adopt near the excitation light source the 460nm, can show high luminous efficiency, can form the light-emitting device that the visible light luminous element combination with shorter wavelength forms.
The the described the 1st and the 2nd oxonitride phosphor, preferably has the II family element of from the group that constitutes by Be, Mg, Ca, Sr, Ba and Zn, selecting more than at least 2 kinds, thus, the characteristics of luminescences such as tone, luminosity and quantum yield can be changed, the desirable characteristics of luminescence can be realized.
Contain under the situation of Sr and Ca at the described the 1st and the 2nd oxonitride phosphor, the mol ratio of preferred Sr and Ca is Sr: Ca=6: 4～9: 1.In addition, contain at described oxonitride phosphor under the situation of Sr and Ba, the mol ratio of preferred Sr and Ba is Sr: Ba=6: 4～9: 1.In addition, contain under the situation of Ca and Ba at the described the 1st and the 2nd oxonitride phosphor, the mol ratio of preferred Ca and Ba is Ca: Ba=6: 4～9: 1.By selecting combination and in above-mentioned scope, selecting it to form, can make the oxonitride phosphor of all tones.In addition, by selected this scope, can improve luminous efficiency.
In the of the present invention the 1st and the 2nd oxonitride phosphor, glow peak wavelength and tone can be set according to the addition of described activator R.
That is, the of the present invention the 1st and the 2nd oxonitride phosphor by the addition of control activator R, can arrive short wavelength or long wavelength side with the glow peak wavelength-shift, and can adjust tone.
Change at addition under the situation of glow peak wavelength and tone by described activator R, because contained part II family element is replaced by described activator R in the described oxonitride phosphor, so amount of described activator R, with respect to the combined amount of described II family's element and described activator R, preferably in molar ratio in (combined amount of described II family's element and described activator R): adjust in the scope of (amount of described activator R)=1: 0.001～1: 0.8.By selected this scope, can keep high luminosity, can change tone simultaneously.In described II family element, adopt under the situation of Sr, particularly near the excitation light source that adopts the 400nm, shine under the situation of oxonitride phosphor of the present invention, the addition of activator R is preferably (combined amount of described II family's element and described activator R): (amount of described activator R)=1: 0.01～1: 0.2.In addition, near employing 460nm excitation light source, shine under the situation of oxonitride phosphor of the present invention, the addition of activator R is preferably (combined amount of described II family's element and described activator R): (amount of described activator R)=1: 0.02～1: 0.26.In described II family element, adopt under the situation of Ca, particularly near the excitation light source that adopts the 400nm, shine under the situation of oxonitride phosphor of the present invention, the addition of activator R is preferably (combined amount of described II family's element and described activator R): (amount of described activator R)=1: 0.01～1: 0.5.In addition, near employing 460nm excitation light source, shine under the situation of oxonitride phosphor of the present invention, the addition of activator R is preferably (combined amount of described II family's element and described activator R): (amount of described activator R)=1: 0.01～1: 0.7.Be because, can provide oxonitride phosphor with high-luminous-efficiency by selected this scope.In addition, in tristimulus coordinates, by increasing the content of activator R, tone x is shifted to right, the displacement of tone y downward direction.Can make tonal variation thus.
The manufacture method of oxonitride phosphor of the present invention is characterized in that, comprising: the 1st operation, mix nitride (the II element at least a kind or more of L that contains L in this operation for from the group that forms by Be, Mg, Ca, Sr, Ba and Zn, selecting.), the nitride of M (the IV family element at least a kind or more of M for from the group that forms by C, Si, Ge, Sn, Ti, Zr and Hf, selecting.), the raw material of the oxide compound (R is a rare earth element) of the oxide compound of M and R; The 2nd operation is burnt till the mixture that is obtained by the 1st operation in this operation.
According to the manufacture method of oxonitride phosphor of the present invention, can provide to be easy to the fluor making and process.In addition, can provide stability extremely good fluor.In the parent of the oxonitride phosphor that the manufacturing processed of utilizing this manufacture method or this manufacture method are made, also can contain Li, Na, K, Rb, Cs, Mn, Re, Cu, Ag, Au etc. herein.But above-mentioned Li, Na, K etc. with respect to the weight of oxonitride phosphor, are preferably below the 1000ppm.More preferably below the 100ppm.Because if in this scope, can keep high luminous efficiency.In addition, an amount of Li, Na, K etc. can increase particle diameter, or improve luminosity etc., can adjust the characteristics of luminescence, also can improve characteristic sometimes.These Li, Na, K etc. also can be contained in the raw material composition.Because the stages of burning till in oxonitride phosphor manufacturing process such as above-mentioned Li, Na, K disperse, therefore be contained in hardly in this composition.In addition, also can under the scope that does not diminish characteristic, add other element.
In this manufacture method, preferably replace the oxide compound of described R, perhaps with the oxide compound of described R together, adopt the nitride of R.Thus, can provide luminosity high oxonitride phosphor.
In described the 1st operation, preferred remix Q (the iii group element at least a kind or more of Q) for from the group that forms by B, Al, Ga and In, selecting.Thus, can increase particle diameter, improve luminosity.
In the manufacture method of oxonitride phosphor of the present invention, preferably with the nitride of the nitride of described L, described M and the oxide compound of described M, by the mol ratio adjustment of oxide compound＜3.75 of nitride＜1.75 of nitride＜1.5 of 0.5＜L, 0.25＜M, 2.25＜M.Thus, can provide and consist of L
XM
YO
ZN
((2/3) X+ (4/3) Y-(2/3) Z): R or L
XM
YQ
TO
ZN
((2/3) X+ (4/3) Y+T-(2/3) Z): the oxonitride phosphor of R.
At least a portion of the raw material that is made of described L nitride is preferably replaced by at least one side in the nitride of the oxide compound of R or R.Thus, can provide oxonitride phosphor with high-luminous-efficiency.
The 3rd oxonitride phosphor of the present invention is the oxonitride phosphor made from the manufacture method of above-mentioned oxonitride phosphor.
As mentioned above, the technical meaning that the 1st～the 3rd oxonitride phosphor of the present invention has is: can provide by the optical excitation in the short wavelength side zone from the near ultraviolet to the visible light, send the fluor of blue-greenish colour, and can provide by the fabulous light-emitting device of luminous efficiency with suitable excitation light source combination to the light in yellow system zone.
That is, at yellow cording the YAG of glow peak wavelength being arranged is in the fluor, even adopt ultraviolet or near ultraviolet exciting light to make it luminous, also luminous hardly, but oxonitride phosphor of the present invention is luminous by the exciting light in the short wavelength side zone from ultraviolet to visible light, and shows high luminous efficiency.
,, do not limit especially herein, but be meant the zone that 240～500nm is following for short wavelength side zone from ultraviolet to visible light.Particularly, the scope of preferred 290～470nm.The more preferably scope of 340～410nm.
In addition, according to the present invention, can provide to be easy to the crystalline oxonitride phosphor making and process.The oxonitride phosphor of stability and reproducibility excellence can be provided in addition.The manufacture method of novel oxonitride phosphor can be provided in addition.
And then, the oxonitride phosphor that contains Ba, Si and Eu of the present invention, can provide can be by the optical excitation in the short wavelength zone from ultraviolet to visible light, and sending blue-greenish colour to green is the fabulous fluor of luminous efficiency of area light.
In addition, the 1st light-emitting device of the present invention, be to have excitation light source, and will it is characterized in that from the light-emitting device of the fluor of the wavelength Conversion of at least a portion of the light of described excitation light source: described fluor contains in system zone from the blue-greenish colour to the yellowish red color and has the oxonitride phosphor of glow peak wavelength.According to the 1st light-emitting device, can provide luminous efficiency high light-emitting device.
In addition, the 2nd light-emitting device of the present invention, be to have the excitation light source that has emission wavelength in the zone of the short wavelength from the ultraviolet to visible light scope, with at least a portion that absorbs from the light of this excitation light source, carry out wavelength Conversion, have the light-emitting device of the fluor of the illuminant colour different with the illuminant colour of described excitation light source, it is characterized in that: the Ba that described fluor contains to have emission wavelength in system zone from the blue-greenish colour to the green is essential oxonitride phosphor.The light-emitting device of luminous efficiency height, excellent color reproducing performance can be provided thus.In addition, can provide and come comfortable short wavelength zone to have the part of light of the excitation light source of emission wavelength from ultraviolet to visible light, and come the part of the light of the comfortable oxonitride phosphor that has the glow peak wavelength from blue-greenish colour to green system zone to become mixed light, and at the light-emitting device that has illuminant colour from bluish voilet to green area.
In addition, in the of the present invention the 1st and the 2nd light-emitting device, in described oxonitride phosphor the 1st～the 3rd oxonitride phosphor preferably of the present invention any a kind.
In addition, adopt glow peak wavelength and tone to come controlled the 1st～the 3rd oxonitride phosphor, the light-emitting device of the different required tone of glow peak wavelength and tone can be provided by the addition of activator R.
In the described the 1st and the 2nd light-emitting device, the 1st～the 3rd oxonitride phosphor is excited by the excitation light source from ultraviolet or near ultraviolet to the short wavelength side zone of visible light, absorbs the part of the light of excitation light source.By absorbing the oxonitride phosphor that this light is excited, carry out wavelength Conversion (sending the wavelength light different) with the light of absorption.The light of this wavelength Conversion is being that the zone has the glow peak wavelength from blue-greenish colour to yellow.That is, described the 1st～the 3rd oxonitride phosphor, absorption comes the part of the light of self-emission device, sends the light that has have the luminescent spectrum of glow peak wavelength to yellow system zone from blue-greenish colour.In addition, the 1st～the 3rd oxonitride phosphor has high luminous efficiency, but extreme efficiency ground wavelength Conversion is come the light of self-emission device, and can emit light.And then the colour mixture of the light of light and the 1st～the 3rd oxonitride phosphor by coming self-emission device can provide the light-emitting device that has in the middle shade of the illuminant colour of the illuminant colour of luminous element and oxonitride phosphor.
Described the 1st～the 3rd oxonitride phosphor, for respect to 1 of O, N is under 0.2～2.1 the situation in the weight ratio that contains O and N and this O and this N, can be excited expeditiously by the luminous element of near ultraviolet etc.
Described excitation light source preferably has the glow peak wavelength more than 1 at least in the short wavelength side zone from ultraviolet to visible light.Be owing to, can improve the luminous efficiency of described fluor by adopting the excitation light source of this scope.Especially, preferably adopt the excitation light source that has the glow peak wavelength at 240～470nm place, wherein, more preferably adopt the excitation light source that has the glow peak wavelength at 350～410nm place.
Described excitation light source is luminous element preferably.That is, luminous element is small-sized, electrical efficiency good, sends the light of distinct color.In addition, therefore this luminous element does not worry filament break etc. owing to be semiconductor element.And then it is characterized in that initial drive characteristic excellence, and anti-shaking and anti-switch lighting repeatedly.For this reason, in the present invention, preferably combination luminous element and oxonitride phosphor.
The luminescent layer of described luminous element preferably has the nitride-based semiconductor that contains In.Thus, luminous element is launched near the light that has the glow peak wavelength 350～410nm, and by the light from this luminous element, high-level efficiency excites described oxonitride phosphor, shows the illuminant colour of regulation.Therefore obtain high-intensity luminously owing to described oxonitride phosphor is excited by near the light 350～410nm, be fit to adopt the luminous element of this wavelength region may.In addition,, therefore can excite oxonitride phosphor efficiently, can radiate the light that does not have tonal variation in fact from light-emitting device simultaneously because this luminous element can make the narrowed width of luminescent spectrum.
The the of the present invention the 1st and the 2nd light-emitting device as described fluor, also can together contain the 2nd fluor with described oxonitride phosphor.In the present invention, the 2nd fluor preferably to carrying out wavelength Conversion from the light of described excitation light source and from least a portion of the light of described oxonitride phosphor, has the glow peak wavelength in the visible region.Thus, the colour mixture by from the light of the light of the light of excitation light source, oxonitride phosphor and the 2nd fluor can be provided at the light-emitting device that the visible region has illuminant colour.Like this light-emitting device that constitutes is as long as in the wavelength region may of the illuminant colour of illuminant colour from the illuminant colour of excitation light source to oxonitride phosphor or the 2nd fluor, just can launch desired illuminant colour.
Described the 2nd fluor for realizing desired illuminant colour (as the illuminant colour of light-emitting device), also can have the glow peak wavelength more than at least 1 from the extremely green system in blueness system zone, yellow system and red colour system zone.Especially, had the green of the oxonitride phosphor that excitation light source excited of glow peak wavelength, the blue and red three primary colours of the 2nd fluor in short wavelength side zone, can be realized all illuminant colours from ultraviolet to visible light by combination.In addition, also can be 2 kinds of light-emitting devices that color combination forms green and red and green and yellow etc.
Described the 2nd fluor preferably, from mainly by the element activated alkali earths halogen apatite fluorescent body of transition metal series such as group of the lanthanides such as Eu, Mn, alkaline-earth metal boric acid halogen fluor, alkaline-earth metal chlorate MClO 3 fluorescent substance, alkali earths silicate, alkali earths sulfide, alkali earths sulfo-gallate, alkali earths silicon nitride, germanate or mainly by lanthanon activated rare earth class aluminate such as Ce or rare earth silicate or mainly selected the organic and organic complex etc. by lanthanon activated such as Eu more than at least a kind.Thus, can provide the high light-emitting devices of luminous efficiency such as luminosity and quantum yield.In addition, can provide color developing good light-emitting device.But the 2nd fluor is not limited thereto, and can use with the luminous fluor of all tones.
Contain in the light-emitting device of described the 2nd fluor, preferably from the part of the light of described excitation light source, mix and discharge from the part of the light of described oxonitride phosphor and from the light more than at least 2 kinds in the light of described the 2nd fluor etc.Thus, the illuminant colour of light-emitting device can be adjusted, required illuminant colour can be sent.Especially, using under the situation of the luminous luminous element in ultra-violet region, people's eyes almost can not be seen the illuminant colour of ultra-violet region.Therefore, demonstration mixes the illuminant colour that forms from the light of oxonitride phosphor and the light of the 2nd fluor.For this illuminant colour, because only by fluor decision illuminant colour, the therefore as easy as rolling off a log adjustment of carrying out illuminant colour.Show that with the 2nd fluor still, the 2nd fluor is not limited to a kind, also can contain multiple fluor herein.By containing multiple fluor, can carry out more delicate chroma control.In addition, especially, under the situation of the luminous element of the short wavelength region that adopts ultraviolet ray or visible light, owing to seldom people's eyes are produced color sensation, therefore can reduce the chromaticity distortion that causes because of manufacture deviation from light that this luminous element sent.
The illuminant colour that contains the light-emitting device of described the 2nd fluor can be set in the glow peak wavelength that has from described excitation light source, the intermediary illuminant colour of the glow peak wavelength that glow peak wavelength that has to described oxonitride phosphor or the 2nd fluor have.Excitation light source has luminescent spectrum than oxonitride phosphor or the short short wavelength side of the 2nd fluor, and has high-energy.The light-emitting device that contains the 2nd fluor can be emitted from this high-energy zone to the illuminant colour of the low energy area of oxonitride phosphor and the 2nd fluor.Especially, the illuminant colour that shows the 2nd glow peak wavelength that the 1st glow peak wavelength or the 2nd fluor from the glow peak wavelength of luminous element to oxynitride have.For example, glow peak wavelength at luminous element is positioned at blue region, and the glow peak wavelength of the oxonitride phosphor that is excited is positioned at green district, and the glow peak wavelength of the 2nd fluor that is excited is positioned under the situation of red color area, by the mixing of 3 kinds of colors, can show the illuminant colour of white color system.As different examples, glow peak wavelength at luminous element is positioned at the ultraviolet region, the glow peak wavelength of the oxonitride phosphor that is excited is positioned at green district, the glow peak wavelength of the 2nd fluor that is excited is positioned under the situation of yellow and red color area, can realize the illuminant colour of flavescent white color system and polychrome system.By changing the use level of oxonitride phosphor and the 2nd fluor, can realize near the tone of the illuminant colour of oxonitride phosphor to illuminant colour near the tone of the illuminant colour of the 2nd fluor.And then, have at the 2nd fluor under the situation of the glow peak wavelength more than 2, can realize showing the light-emitting device of the illuminant colour between the glow peak wavelength more than 2 that glow peak wavelength that excitation light source has, glow peak wavelength that oxonitride phosphor has and the 2nd fluor have.The 2nd fluor not only can use a kind, use more than 2 kinds also capable of being combined.Recently, not only need to send the light-emitting device of white color system light, and need send the light-emitting device of the light of all tones such as light color.According to light-emitting device of the present invention, send oxonitride phosphor that green is a light, send the fluor of red colour system light and send the fluor that blueness is a light by combination, the light-emitting device with the tone that requires can be provided.In light-emitting device of the present invention, not only utilize the method for the kind of change fluor, also can utilize the method for the proportioning of the fluor that changes combination, or the method for change coating process of coating fluor on excitation light source, or adjust excitation light source the method etc. of fluorescent lifetime, realize all tones.
Selecting under the situation of white color system near the white the track of especially preferred blackbody radiation as the intermediary illuminant colour.The light-emitting device of such white color system can be used in various uses such as illumination is used, the backlight of liquid crystal, indicating meter.
Described light-emitting device preferably has at least the luminescent spectrum that has 1 above glow peak wavelength at 430～500nm and 500～730nm place.By combined blue light, green light and red light etc., can provide the light-emitting device that sends required tone light.Therefore, by making up several fluor, can realize the raising of color developing.Even identical white color system is luminous, the existing xanchromatic white that has also has bluish white.Therefore, has the luminescent spectrum that has the glow peak wavelength in above-mentioned scope.
As mentioned above, the technical meaning that light-emitting device of the present invention has is that employing is excited and the oxonitride phosphor of Wavelength-converting by the luminous element from ultraviolet to the visible region, and excellent light-emitting device is provided.This oxonitride phosphor is to have high luminous efficiency, and the fluor stable, that reproducibility is high.The technical meaning that has in addition is by illuminated in combination element, oxonitride phosphor and the 2nd fluor, to provide the light-emitting device with needed illuminant colour.
In addition, in this manual, the relation of light wavelength scope and monochromatic color name is according to JIS Z8110.Specifically be, 380～455nm is a bluish voilet, and 455～485nm is blue, and 485～495nm is a blue-greenish colour, and 495～548nm is green, and 548～573nm is a yellow-green colour, and 573～584nm is yellow, and 584～610nm is that yellowish red color, 610～780nm are for red.
In addition, the 2nd light-emitting device of the present invention preferably has at 360～485nm, and 485～548nm and 548～730nm place have the light-emitting device of the luminescent spectrum of at least 1 above glow peak wavelength.By three primary colours such as combined blue, green, redness, can provide the light-emitting device of the light that sends required tone.In addition, by making up several fluor, can improve color developing.Even be because identical white color system luminous, existing yellowy white also has bluish white.
Described the 2nd kind of light-emitting device preferably has at 360～485nm, and 485～548nm place has the light-emitting device of the luminescent spectrum of 1 above glow peak wavelength.For example, be fluor by combined blue based light-emitting device and YAG, can access the light-emitting device that sends white color system light, but near the light deficiency the 500nm.Therefore, can provide the light-emitting device of excellent color reproducing performance by further containing near oxonitride phosphor luminous 500nm at this light-emitting device.
Described the 2nd light-emitting device, preferably its average colour developing evaluation number (Ra) is more than 80.The light-emitting device of excellent color reproducing performance can be provided thus.Especially, the light-emitting device that can provide special color developing (R9) to improve.
As mentioned above, according to the of the present invention the 1st and the 2nd light-emitting device, can realize bright-coloured illuminant colour.Especially, by the light from the luminous element with UV-light, oxonitride phosphor shows the illuminant colour from blue-greenish colour to yellow system zone.In addition, by changing the ratio of components of oxonitride phosphor, can provide the light-emitting device of excellent in luminous characteristics.The light-emitting device of luminous efficiency height, reproducibility excellence can be provided in addition.In addition, by changing the proportioning of activator R (especially Eu), can change tone.In addition, have the excellent luminosity and the oxonitride phosphor of quantum yield by changing the proportioning of Eu, can providing.Therefore, the extremely important technical meaning that the present invention had is to provide above-mentioned such light-emitting device.
In addition, according to the 2nd light-emitting device of the present invention, for example, can provide the light-emitting device that sends from the light of bright-coloured blue to green.In addition, can make combination this oxonitride phosphor, the 2nd fluor is that YAG is the light-emitting device of fluor and blue based light-emitting device.Thus, can provide light-emitting device excellent color reproducing performance, that luminous efficiency is high that sends white color system light.This color developing especially can show the improvement of red special colour developing evaluation number (R9).
Description of drawings
Fig. 1 is the figure of the bullet cut light-emitting device 1 of expression embodiments of the present invention 2.
Fig. 2 A is the orthographic plan of light-emitting device of the surface installing type of expression embodiments of the present invention 3.
Fig. 2 B is the sectional view of light-emitting device of the surface installing type of expression embodiments of the present invention 3.
Fig. 3 is the figure of the luminescent spectrum of expression when exciting the oxonitride phosphor of embodiment 1～5 with Ex=400nm.
Fig. 4 is the figure of the luminescent spectrum of expression when exciting the oxonitride phosphor of embodiment 1～5 with Ex=460nm.
Fig. 5 is the figure of excitation spectrum of the oxonitride phosphor of expression embodiment 1～5.
Fig. 6 is the figure of reflection spectrum of the oxonitride phosphor of expression embodiment 1～5.
Fig. 7 is the SEM photo of the oxonitride phosphor of embodiment 1.
Fig. 8 is the figure of the luminescent spectrum of expression when exciting the oxonitride phosphor of embodiment 6～10 with Ex=400nm.
Fig. 9 is the figure of the luminescent spectrum of expression when exciting the oxonitride phosphor of embodiment 6～10 with Ex=460nm.
Figure 10 is the figure of the luminescent spectrum of expression when exciting the oxonitride phosphor of embodiment 11～15 with Ex=400nm.
Figure 11 is the figure of the luminescent spectrum of expression when exciting the oxonitride phosphor of embodiment 11～15 with Ex=460nm.
Figure 12 is the figure of excitation spectrum of the oxonitride phosphor of expression embodiment 11～15.
Figure 13 is the figure of reflection spectrum of the oxonitride phosphor of expression embodiment 11～15.
Figure 14 is the figure of the luminescent spectrum of expression when exciting the oxonitride phosphor of embodiment 10,16～20 with Ex=400nm.
Figure 15 is the figure of the luminescent spectrum of expression when exciting the oxonitride phosphor of embodiment 10,16～20 with Ex=460nm.
Figure 16 is the figure of excitation spectrum of the oxonitride phosphor of expression embodiment 10,16～20.
Figure 17 is the figure of reflection spectrum of the oxonitride phosphor of expression embodiment 10,16～20.
Figure 18 is the figure of the luminescent spectrum of expression when exciting the oxonitride phosphor of embodiment 21～24 with Ex=400nm.
Figure 19 is the figure of the luminescent spectrum of expression when exciting the oxonitride phosphor of embodiment 21～24 with Ex=460nm.
Figure 20 is the figure of excitation spectrum of the oxonitride phosphor of expression embodiment 21～24.
Figure 21 is the figure of reflection spectrum of the oxonitride phosphor of expression embodiment 21～24.
Figure 22 is the rhombic sketch of expression.
Figure 23 is the diagram of X-ray diffractogram of the oxonitride phosphor of expression embodiment 25.
Figure 24 is the diagram of X-ray diffractogram of the oxonitride phosphor of expression embodiment 26.
Figure 25 is the diagram of X-ray diffractogram of the oxonitride phosphor of expression embodiment 27.
Figure 26 is the orthographic plan of expression luminous element of the present invention.
Figure 27 is the A-A ' sectional view of expression luminous element of the present invention.
Figure 28 is the figure of luminescent spectrum of the light-emitting device of expression embodiments of the invention 28.
Figure 29 is the figure of tristimulus coordinates of the light-emitting device of expression embodiments of the invention 28.
Figure 30 is the figure of light-emitting device of the embodiment 30 of expression lid type of the present invention.
Figure 31 is the process picture sheet of the manufacture method of expression oxonitride phosphor.
Figure 32 is the figure of the variation of the luminous efficiency of expression when changing the content of contained activator R in the composition of oxonitride phosphor.
Figure 33 is the diagram of the variation of the luminous efficiency of expression when changing the content of contained activator R in the composition of oxonitride phosphor.
Figure 34 is the XYZ chromaticity diagram of the tonal variation of expression when changing the content of contained activator R in the composition of oxonitride phosphor.
Figure 35 is the XYZ chromaticity diagram of the amplification of Figure 34.
Figure 36 is the figure of the luminescent spectrum of expression when exciting oxonitride phosphor with Ex=400nm.
Figure 37 is the figure of the luminescent spectrum of expression when exciting oxonitride phosphor with Ex=460nm.
Figure 38 is the figure of the standardized excitation spectrum of expression oxonitride phosphor.
Figure 39 is the figure of the reflection spectrum of expression oxonitride phosphor.
Figure 40 A is the SEM photo of 1000 times of amplifications of the oxonitride phosphor of embodiment 36, Figure 40 B is the SEM photo of 5000 times of amplifications of the oxonitride phosphor of embodiment 36, and Figure 40 C is the SEM photo of 10000 times of amplifications of the oxonitride phosphor of embodiment 36.
Figure 41 is the diagram that the luminous efficiency of expression when changing the content of contained activator R in the composition of oxonitride phosphor changes.
Figure 42 is the figure that the luminous efficiency of expression when changing the content of contained activator R in the composition of oxonitride phosphor changes.
Figure 43 is the XYZ chromaticity diagram of the tonal variation of expression when changing the content of contained activator R in the composition of oxonitride phosphor.
Figure 44 is the XYZ chromaticity diagram of amplifying Figure 43.
Figure 45 is the figure of the luminescent spectrum of expression when exciting oxonitride phosphor with Ex=400nm.
Figure 46 is the figure of the luminescent spectrum of expression when exciting oxonitride phosphor with Ex=460nm.
Figure 47 is the figure of the standardized excitation spectrum of expression oxonitride phosphor.
Figure 48 is the figure of the reflection spectrum of expression oxonitride phosphor.
Figure 49 is the figure of the variation of the peak intensity of expression when changing the content of contained activator R in the composition of oxonitride phosphor.
Figure 50 is the figure of the variation of the luminous efficiency of expression when changing the content of contained activator R in the composition of oxonitride phosphor.
Figure 51 is the figure of the luminescent spectrum of expression when exciting oxonitride phosphor with Ex=400nm.
Figure 52 is the figure of the luminescent spectrum of expression when exciting oxonitride phosphor with Ex=460nm.
Figure 53 is the figure of the standardized excitation spectrum of expression oxonitride phosphor.
Figure 54 is the figure of the reflection spectrum of expression oxonitride phosphor.
Figure 55 is the figure of the luminescent spectrum of expression when exciting the oxonitride phosphor of embodiment 79 with Ex=400nm.
Figure 56 is the figure of the luminescent spectrum of expression when exciting the oxonitride phosphor of embodiment 79 with Ex=460nm.
Figure 57 is the figure of standardized excitation spectrum of the oxonitride phosphor of expression embodiment 79.
Figure 58 is the figure of reflection spectrum of the oxonitride phosphor of expression embodiment 79.
Figure 59 A is the SEM photo of 1000 times of amplifications of the oxonitride phosphor of embodiment 79, and Figure 59 B is the SEM photo of 10000 times of amplifications of the oxonitride phosphor of embodiment 79.
Figure 60 is the figure of the luminescent spectrum of expression light-emitting device 1 of the present invention.
Figure 61 is the chromaticity diagram of the tristimulus coordinates of expression light-emitting device 1 of the present invention.
Figure 62 is the process picture sheet of the manufacture method of expression oxonitride phosphor.
Figure 63 is the figure of the luminescent spectrum of expression when exciting the oxonitride phosphor of embodiment 83～87 with Ex=400nm.
Figure 64 is the figure of the luminescent spectrum of expression when exciting the oxonitride phosphor of embodiment 83～87 with Ex=460nm.
Figure 65 is the figure of excitation spectrum of the oxonitride phosphor of expression embodiment 83～87.
Figure 66 is the figure of reflection spectrum of the oxonitride phosphor of expression embodiment 83～87.
Figure 67 A, 67B are the SEM photos of the oxonitride phosphor of embodiment 83.
Figure 68 is the figure of luminescent spectrum (simulation) of the light-emitting device of expression embodiment 88.
Figure 69 is the figure of luminescent spectrum (simulation) of the light-emitting device of expression embodiment 88 to 90;
Figure 70 is the figure of the luminescent spectrum (simulation) of expression embodiment 89 and 90 light-emitting device.
Figure 71 is the figure of the luminescent spectrum of expression embodiment 91 and 92 light-emitting device.
Embodiment
Below, adopt embodiment and embodiment, oxonitride phosphor and manufacture method thereof used in light-emitting device of the present invention and this light-emitting device are described.But the present invention is not limited to this embodiment and embodiment.
The oxonitride phosphor of present embodiment 1, be that activator adopts rare earth element, and contain oxonitride phosphor crystalline fluor, this oxonitride phosphor crystallization contains the II family element of selecting more than at least a kind at least from the group that is made up of Be, Mg, Ca, Sr, Ba and Zn, and the IV family element of selecting from the group that is made up of C, Si, Ge, Sn, Ti, Zr and Hf more than at least a kind.
Herein, the oxonitride phosphor crystallization for example is by at the oxonitride phosphor that orthorhombic crystallization constitutes that belongs to shown in the embodiment described later.
The combination of above-mentioned II family's element and IV family element is arbitrarily, but the preferred combination of adopting following composition.
1 oxonitride phosphor preferred embodiment is with general formula L
XM
YO
ZN
((2/3) X+ (4/3) Y- (2/3) Z: R or L
XM
YQ
TO
ZN
((2/3) X+ (4/3) Y+T-(2/3) Z): R represents.Herein, L is the II family element of selecting from the group that is made up of Be, Mg, Ca, Sr, Ba and Zn more than at least a kind.M is the IV family element of selecting from the group that is made up of C, Si, Ge, Sn, Ti, Zr and Hf more than at least a kind.Q is the iii group element of selecting from the group that is made up of B, Al, Ga and In more than at least a kind.O is an oxygen element.N is the nitrogen element.R is a rare earth element.0.5＜X＜1.5、1.5＜Y＜2.5、0＜T＜0.5、1.5＜Z＜2.5。
With the oxonitride phosphor that this general formula is represented, can contain at least a portion element by certain regularly arranged crystallization, can send the light of high brightness from this crystallization high-level efficiency.In above-mentioned general formula, by setting 0.5＜X＜1.5,1.5＜Y＜2.5,0＜T＜0.5,1.5＜Z＜2.5 for, can be easier to form luminescent part is crystallization phases, can provide luminous efficiency well to reach the fluor of high brightness.
In addition, in above-mentioned general formula, X, Y, Z, preferably X=1, Y=2, Z=2.When this is formed, can form more crystallization phasess, its crystallinity also can be good simultaneously, can improve luminous efficiency and brightness.The ratio of contained crystallization (crystallization phases) in the oxonitride phosphor of present embodiment 1 preferably more than the 50 weight %, is more preferably more than the 80 weight %.
In addition, being purpose and contained crystalline ratio is set under the situation of desired value, in above-mentioned general formula, also can utilize X, Y, the adjustment of Z value to adjust luminosity etc.
But above-mentioned scope is a preferred range, and the present invention is not limited to above-mentioned scope.
Specifically be in oxonitride phosphor of the present invention, to contain by CaSi
2O
2N
2: Eu, SrSi
2O
2N
2: Eu, BaSi
2O
2N
2: Eu, ZnSi
2O
2N
2: Eu, CaGe
2O
2N
2: Eu, SrGe
2O
2N
2: Eu, BaGe
2O
2N
2: Eu, ZnGe
2O
2N
2: Eu, Ca
0.5Sr
0.5Si
2O
2N
2: Eu, Ca
0.5Ba
0.5Si
2O
2N
2: Eu, Ca
0.5Zn
0.5Si
2O
2N
2: Eu, Ca
0.5Be
0.5Si
2O
2N
2: Eu, Sr
0.5Ba
0.5Si
2O
2N
2: Eu, Ca
0.8Mg
0.2Si
2O
2N
2: Eu, Sr
0.8Mg
0.2Si
2O
2N
2: Eu, Ca
0.5Mg
0.5Si
2O
2N
2: Eu, Sr
0.5Mg
0.5Si
2O
2N
2: Eu, CaSi
2B
0.1O
2N
2: Eu, SrSi
2B
0.1O
2N
2: Eu, BaSi
2B
0.1O
2N
2: Eu, ZnSi
2B
0.1O
2N
2: Eu, CaGe
2B
0.01O
2N
2: Eu, SrGe
2G
0.01O
2N
2: Eu, BaGe
2In
0.01O
2N
2: Eu, ZnGe
2Al
0.05O
2N
2: Eu, Ca
0.5Sr
0.5Si
2B
0.3O
2N
2: Eu, CaSi
2.5O
1.5N
3: Eu, SrSi
2.5O
1.5N
3: Eu, BaSi
2.5O
1.5N
3: Eu, Ca
0.5Ba
0.5Si
2.5O
1.5N
3: Eu, Ca
0.5Sr
0.5Si
2.5O
1.5N
3: Eu, Ca
1.5Si
2.5O
2.5N
2.7: Eu, Sr
1.5Si
2.5O
2.5N
2.7: Eu, Ba
1.5Si
2.5O
2.5N
2.7: Eu, Ca
1.0Ba
0.5Si
2.5O
1.5N
3: Eu, Ca
1.0Sr
0.5Si
2.5O
1.5N
3: Eu, Ca
0.5Si
1.5O
1.5N
1.7: Eu, Sr
0.5Si
1.5O
1.5N
1.7: Eu, Ba
0.5Si
1.5O
1.5N
1.7: Eu, Ca
0.3Ba
0.2Si
2.5O
1.5N
3: Eu, Ca
0.2Sr
0.3Si
2.5O
1.5N
3: the oxonitride phosphor of expression such as Eu.
In addition, as shown here, the oxonitride phosphor of present embodiment 1 can change the ratio of O and N, by changing this ratio, can regulate tone or brightness.In addition, also can change, also can accurately adjust luminescent spectrum or intensity thus by positively charged ion shown in (L+M)/(O+N) and anionic mol ratio.This can be by for example implementing processing such as vacuum, take off N or take off O and wait and carry out, but the present invention is not limited to this method.In the composition of oxonitride phosphor, also can contain among Li, Na, K, Rb, Cs, Mn, Re, Cu, Ag and the Au more than at least a kind, by adding these compositions, can adjust luminous efficiencies such as brightness, quantum yield.In addition, in the scope that does not diminish characteristic, also can add other element.
The part of the contained II family element agent R that can be activated replaces in the oxonitride phosphor.With respect to the combined amount of II family element and described activator R, the amount of described activator R is preferably (combined amount of described II family's element and described activator R): the mol ratio of the mol ratio of (amount of described activator R)=1: 0.001 to 1: 0.8.
In addition, L is the II family element of selecting from the group that is made up of Be, Mg, Ca, Sr, Ba and Zn more than at least a kind.In the present invention, L also can be monomers such as Ca and Sr, but also can form the multielement combination of Ca and Sr, Ca and Ba, Sr and Ba and Ca and Mg etc.In addition, when L is the multielement combination, also can change its ratio of components.For example, the mixture of Sr and Ca can change proportioning by institute's requirement.
Especially, preferred L is to be the essential II family element more than at least a kind with any a kind among the Ca, the Sr that select from the group that is made up of Mg, Ca, Sr, Ba and Zn or the Ba.
M is the IV family element of selecting from the group that is made up of C, Si, Ge, Sn, Ti, Zr and Hf more than at least a kind.M also can be monomers such as Si, Ge, also can be combined by Si and Ge and multielements such as Si and C.In the present invention, can adopt above-mentioned IV family element, but preferably adopt Si and Ge.By adopting Si, Ge, can provide fluor cheap, that have well-crystallized.
Especially, preferred M be from the group that forms by C, Si, Ge, Sn, Ti, Hf, select, be the essential IV family element more than at least a kind with Si.
R is a rare earth element.Particularly, R is the element of selecting from La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu more than a kind or 2 kinds.In the present invention, the preferred Eu that adopts in these rare earth elements.In addition, the element more than at least a kind that also can contain Eu and from rare earth element, select.In such cases, preferably contain Eu more than the 50 weight % as R, more preferably contain the above Eu of 70 weight %.That is, activator R, preferably from the group that forms by La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu, select, be the essential rare earth element more than at least a kind with Eu.Element beyond the Eu is in order to play a role with coactivator.
In present embodiment 1, use rare earth elements europium Eu at luminescence center.Europium mainly has divalent and 3 valence levels.The fluor of present embodiment 1 is a silicon nitride for the alkaline-earth metal of parent, adopts Eu
2+As activator.Eu
2+Oxidized easily, common Eu with 3 valencys
2O
3Composition sell.
In addition, in this manual, the situation when adopting typical example Eu as luminescence center describes sometimes, but the present invention is not limited thereto.
As fertile material, principal constituent L, M also can adopt compound separately.The L of these principal constituents, M can adopt metal, oxide compound, imide, acid amides, nitride and various salt.In addition, also can be pre-mixed the L of principal constituent and the element of M, re-use.
Q is the iii group element of selecting from the group that is made up of B, Al, Ga and In more than at least a kind.Q also can adopt metal, oxide compound, imide, acid amides, nitride and various salt.For example, B
2O
6, H
3BO
3, Al
2O
3, Al (NO
3)
39H
2O, AlN, GaCl
3, InCl
3Deng.
As fertile material, mix nitride, the nitride of M and the oxide compound of M of L.In this fertile material, sneak into the oxide compound of Eu as activator.These materials of weighing make it reach desired fluor and form, and are mixed into evenly.Especially, the oxide compound of the nitride of the L in this fertile material, the nitride of M and M is preferably by the mixed in molar ratio of oxide compound＜3.75 of nitride＜1.75 of nitride＜1.5 of 0.5＜L, 0.25＜M, 2.25＜M.That is, to reach
Or
The mode of ratio of components, measure these fertile materials of weighing in accordance with regulations, mix.
(manufacture method of oxonitride phosphor)
The oxonitride phosphor CaSi of present embodiment 1 then, is described
2O
2N
2: the manufacture method of Eu.In addition, the present invention is not limited to following manufacture method.
At first, prepare nitride, the nitride of Si, the oxide compound of Si and the oxide compound of Eu of Ca.As these raw materials, preferably adopt purified, but also can adopt commercially available person.
1.Ca the preparation of nitride
At first, raw materials of Ca is pulverized.Raw materials of Ca is preferably used monomer, but also can use inferior amide compound, compound such as amide compound and CaO.In addition, raw materials of Ca also can contain B, Ga etc.Raw materials of Ca is pulverized in the ball case in argon gas atmosphere.The preferred median size of pulverizing the Ca of gained is approximately 0.1 μ m～15 μ m, but is not limited to this scope.The purity of Ca is preferably more than the 2N, but is not limited to this scope.
Then, will be through raw materials of Ca nitrogenize in nitrogen atmosphere of pulverizing.By making Ca through pulverizing about 5 hours of nitrogenize in nitrogen atmosphere, under 600～900 ℃ the temperature, can obtain the nitride of Ca.This reaction formula is shown in formula 1.
(formula 1)
3Ca+N
2→Ca
3N
2
The nitride of Ca, preferably highly purified certainly.As the nitride of Ca, also can adopt commercially available.
Then, pulverize the nitride of Ca.In argon gas atmosphere or in the nitrogen atmosphere, in the ball case, carry out the pulverizing of the nitride of Ca.
2.Si the preparation of nitride
At first, raw material Si is pulverized.The monomeric raw material Si of preferred use, but also can use nitride, imide compound, amide compound etc., for example Si
3N
4, Si (NH
2)
2, Mg
2Si, Ca
2Si, SiC etc.The purity of Si is preferably more than the 3N, but also can contain B, Ga etc.The pulverizing of raw material Si, same during also with raw materials of Ca, in argon gas atmosphere or in the nitrogen atmosphere, in the ball case, carry out.The median size of preferred Si compound is approximately 0.1 μ m～15 μ m.
Nitrogenization raw material Si in nitrogen atmosphere.By in nitrogen atmosphere, under 800～1200 ℃,, can obtain silicon nitride with about 5 hours of silicon (Si) nitrogenize.This reaction formula is shown in formula 2.
(formula 2)
3Si+2N
2→Si
3N
4
Used silicon nitride among the present invention, preferably highly purified certainly.In addition, as silicon nitride, also can use commercially available.
Then, pulverize the nitride of Si.
3.Si the preparation of oxide compound
The oxide compound of Si is SiO
2, use commercially available (with the pure medicine system Silicon of light Dioxide 99.9%, 190-09072).
In the mode of the molar weight that reaches regulation, the so refining or raw material (nitride of Ca, the oxide compound of the nitride of Si, the oxide compound of Si and Eu) made of weighing.
Then, the raw material that mixes weighing.
Then, in ammonia atmosphere, under about 1500 ℃, burn till the nitride of Ca, the nitride of Si, the oxide compound of Si and the hopcalite of Eu.The mixture that burns till is dropped into crucible, burn till.
By mixing and burning till, can access with CaSi
2O
2N
2: the oxonitride phosphor that Eu represents.The reaction formula of the basic comprising element that this burns till is shown in formula 3.
(formula 3)
(1/3)Ca
3N
2+(1/3)Si
3N
4+SiO
2+aEu
2O
3→CaSi
2O
2N
2:Eu
But this composition near this ratio, has enough characteristics of anti-practicality by representational composition that cooperates ratio to infer.In addition, by changing the cooperation ratio of each raw material, can change composition as the fluor of purpose.
Burn till, can use tube furnace, small-sized stove, high frequency furnace and metal furnaces etc.Firing temperature does not limit especially, but preferably burns till under 1200～1700 ℃ temperature range, more preferably burns till in 1400～1700 ℃ temperature range.The raw material of fluor, preferred use is burnt till by the crucible and the vessel of boron nitride (BN) material.Except that the crucible of boron nitride material, also can adopt aluminum oxide (Al
2O
3) crucible of material.
In addition, reducing atmosphere is inert gas atmospheres such as nitrogen atmosphere, nitrogen-nitrogen atmosphere, ammonia atmosphere, argon gas etc.
By adopting above-mentioned manufacture method, can access desired oxonitride phosphor.
In addition, to contain B's
The oxonitride phosphor of expression can be by following manufacturing.
In advance, in the oxide compound of Eu, the compound H of dry mixed B
3BO
3As the Eu compound, adopt europium sesquioxide, but also can be same with above-mentioned other formation element, use europium sesquioxide, nitrogenize europium etc.In addition, raw material Eu also can use inferior amide compound, amide compound etc.Europium sesquioxide is preferably highly purified, but also can use commercially available.Can dry mixed to the compound of B, but also can wet-mixed.
Compound H with B
3BO
3Be example, the manufacture method of oxonitride phosphor is described, but the composition beyond B constitutes in the element, and Li, K and Na etc. are arranged, and can adopt their compound, for example LiOHH
2O, Na
2CO
3, K
2CO
3, RbCl, CsCl, Mg (NO
3)
2, CaCl
26H
2O, SrCl
26H
2O, BaCl
22H
2O, TiOSO
4H
2O, ZrO (NO
3)
2, HfCl
4, MnO
2, ReCl
5, Cu (CH
3COO)
2H
2O, AgNO
3, HAuCl
44H
2O, Zn (NO
3)
26H
2O, GeO
2, Sn (CH
3COO)
2Deng.
Pulverize the mixture of Eu and B.Pulverize the median size of the mixture of back Eu and B, preferably approximately is 0.1 μ m～15 μ m.
After having carried out above-mentioned pulverizing, roughly with described CaSi
2O
2N
2: the manufacturing process of Eu is same, the oxide compound of the nitride of mixed C a, the nitride of Si, Si and contain the Eu oxide compound of B.After this mixes, burn till, can obtain the purpose oxonitride phosphor.
The oxonitride phosphor of above-mentioned embodiment 1, have with YAG be the equal above stability of fluor, and then have following feature.
(1) oxonitride phosphor of present embodiment 1, by selecting its composition and ratio of components, can in the scope of the ratio broad in blue-greenish colour zone～yellowish red color zone, set needed illuminant colour, and can make the setting range of tone, luminosity, quantum yield wide.
For example,, change its ratio, can adjust tone, luminosity and quantum yield by using the II family element more than 2 kinds.
(2) YAG is a fluor, in caused the exciting of light by ultraviolet～short wavelength's visible region, luminous hardly, but the oxonitride phosphor of present embodiment 1, exciting of the light of visibility region that can be by ultraviolet～short wavelength obtains high luminous efficiency.
That is,, can provide the fluor that is fit to the luminous element combination of ultraviolet～short wavelength's visibility region by the oxonitride phosphor of present embodiment 1.
(3) because oxonitride phosphor is crystallization, therefore make its processing and handling ease easily as powder or particle.
Fig. 1 is the sectional view that the light-emitting device of expression embodiments of the present invention 2 constitutes, and light-emitting device of the present invention has luminous element at least, at least a portion light from the light of this luminous element carried out the 1st fluor of wavelength Conversion., especially in the light-emitting device of present embodiment 2, it is characterized in that herein,, use the oxonitride phosphor of embodiment 1 as the 1st fluor.
In addition, in this manual, the relation of color designation and tristimulus coordinates is with reference to JIS Z8110.
In the light-emitting device of embodiment 2, luminous element 10 by sapphire substrate 1, be formed on the semiconductor layer 2 on the sapphire substrate 1 and the positive and negative electrode that is formed on the semiconductor layer 2 is formed.This luminous element 10 is bonded in the cup-shaped portion (cup) of lead frame 13a, and its positive and negative electrode is connected with lead frame 13a and lead frame 13b respectively by conductor wire 14.In addition, in the mode of covering luminous element 10, in the cup-shaped portion of lead frame 13a, form the application member 12 that contains fluor 11.Then, be provided with luminous element and contain the lead frame 13a of application member 12 of fluor 11 and whole mode of lead frame 13b, form moulding part 15 with covering.
In the light-emitting device of embodiment 2, the semiconductor layer 2 of luminous element 10 is by a plurality of layers of formation that comprise luminescent layer (not shown), to this luminescent layer, reaches the mode below the 500nm of blue region from ultraviolet with the glow peak wavelength, adjusts its composition.In addition, on the same planar side of this semiconductor layer 2, form positive and negative electrode 3.
The light-emitting device of present embodiment 2 is by following making.
At first, luminous element 10 is placed on the little wafer bonder (die bonder), in being provided with the lead frame 13a of cup-shaped portion, its joint that faces up.Behind the joint, lead frame 13 is moved on on the patching machine, be bonded on the lead frame 13a that is provided with cup-shaped portion, positive electrode 3 lines are bonded on another lead frame 13b with negative potential 3 lines of gold thread with luminous element.
Then, move on in the shaped device,, in the cup-shaped portion of lead frame 13, inject fluor 11 and application member 12 with the divider of shaped device.At this moment, fluor 11 and application member 12 are good in desirable ratio uniform mixing in advance.
After the coating, lead frame 13 is immersed in the mold box of injection molding parts 15 in advance after, by removing molding box and making hardening of resin, make bullet cut light-emitting device shown in Figure 1.
Below, each composed component of the light-emitting device of detailed description present embodiment 2
(fluor 11)
Fluor 11 comprises the oxonitride phosphor of embodiment 1.In addition, fluor 11 also can use the fluor of combination oxonitride phosphor and the 2nd fluor.
(luminous element 10)
In present embodiment 2, but luminous element 10 preferably has and can send the semiconductor light-emitting elements of luminescent layer of light that high-level efficiency excites the wavelength of oxonitride phosphor.As the material of such semiconductor light-emitting elements, can enumerate multiple semi-conductors such as BN, SiC, ZnSe or GaN, InGaN, InAlGaN, AlGaN, BAlGaN and BInAlGaN.In these elements,, also can contain Si or Zn etc., as luminescence center as impurity element.But launch the light of the ultraviolet region of high-level efficiency excited fluophor 11 (oxonitride phosphor) as the energy high-level efficiency, or the semiconductor material of the light of the relative short wavelength in the visible region, especially, be more suitable for enumerating nitride-based semiconductor (for example, as the nitride-based semiconductor that contains Al or Ga, contain the nitride-based semiconductor In of In or Ga
XAl
YGa
1-X-YN, 0≤X, 0≤Y, X+Y≤1).
In addition, as the structure of semiconductor light-emitting elements, preferably enumerate the homogeneous texture, heterojunction structure or the double-heterostructure that have that MIS engages, PIN engages, pn engages etc.Can select all emission wavelengths according to material or its mixed crystal ratio of semiconductor layer.In addition, constitute single quantum well structure or the multiple quantum trap structure that forms the film that produces quantum effect, also can improve output by making the semiconductor active layer.
Under the situation that luminous element 10 is made of nitride-based semiconductor, be fit to use the substrate that constitutes by materials such as sapphire, spinel, SiC, Si, ZnO, GaAs and GaN.For forming nitride-based semiconductor, preferably use sapphire substrate with well-crystallized with big mass productivity.Can on this sapphire substrate, adopt HVPE method or mocvd method etc., form nitride-based semiconductor.Specifically be, on sapphire substrate, form the buffer layer of growth formation on-monocrystalline at low temperatures such as GaN, AlN, GaAlN, form nitride-based semiconductor in the above with pn joint.
But use high-level efficiency nitride-based semiconductor, that have the pn joint to launch the luminous element of ultraviolet region light, for example, by following making.
At first, on buffer layer, with the orientation flat near normal ground strip formation SiO of sapphire substrate
2Then, in bar shaped, adopt the HVPE method, ELOG (Epitaxial Lateral Over GrowsGaN) growing GaN.Then, use mocvd method, the active coating of the multi-quantum pit structure of the barrier layer of the 1st tectum that stacks gradually the 1st contact layer that forms with n type GaN, forms with n type AlGaN, the trap layer of multilayer laminated InAlGaN and AlGaN, the 2nd tectum that forms with p type AlGaN, and the 2nd contact layer that forms with p type GaN.Like this, make nitride semiconductor luminescent element with double-heterostructure.
In addition, active coating is formed the vallum shape, clamp, the resonator end face is set simultaneously, also can form the semiconductor Laser device that can use in the present invention with guide layer.
In addition, nitride-based semiconductor shows n type electroconductibility under the state of impurity that undopes, but to improve luminous efficiency etc. is purpose, if will form the n type nitride-based semiconductor of desirable carrier concentration, as preferably suitable Si, Ge, Se, Te, the C etc. of importing of n type hotchpotch.On the other hand, under the situation that forms p type nitride-based semiconductor, preferred doped p type impurity is Zn, Mg, Be, Ca, Sr, Ba etc.In addition, because nitride-based semiconductor is only by the doped p type hotchpotch, therefore difficult p typeization preferably after importing p type hotchpotch, utilizes stove heating or plasma irradiation etc., makes its low resistanceization.Under the situation of not removing sapphire substrate, by etch into the surface of the 1st contact layer from p type side, the part of the 1st contact layer is exposed, on each contact layer, form electrode respectively.Then, by cutting into shaped like chips, make the luminous element (nitride semiconductor luminescent element that for example, has structure shown in Figure 1) that constitutes by nitride-based semiconductor from semiconductor wafer.
In the light-emitting device of present embodiment 2, when fixedly during fluor 11,, preferably using resin (transparent resin) for forming good mass productivity at luminous element 10 near surfaces.In such cases, when considering with the relation of the emission wavelength of fluor 11 and preventing the both sides of deterioration of transparent resin, luminous element 10 preferably uses ultraviolet region have luminescent spectrum, its glow peak wavelength as 360nm the luminous element below the above 420nm, or the luminous element below the above 470nm of 450nm.
Herein, used semiconductor light-emitting elements 10 in the present embodiment 2 preferably is adjusted to, according to reaching impurity concentration 10
17～10
20/ cm
3The sheet resistance Rn of the n type contact layer that forms of mode and the sheet resistance Rp of the light transmission p electrode relation that forms Rp 〉=Rn.N type contact layer is preferably formed thickness 3～10 μ m, more preferably forms thickness 4～6 μ m, and its sheet resistance Rn is estimated as 10～15 Ω/.Therefore, the mode that preferably reaches 10～15 Ω/more than the according to the sheet resistance Rp of light transmission p electrode is set thickness.Specifically be that light transmission p electrode also can be formed by the film below the thick 150 μ m.
In addition, using by a kind that from the group of gold and platinum family element, selects and at least a kind of multilayer film or alloy that other element constitutes, form under the situation of light transmission p electrode, if utilize the content of contained gold and platinum family element, adjust the sheet resistance of transparent p electrode, can improve stability and reproducibility.Gold or metallic element, because at the uptake factor height of the wavelength region may of the used semiconductor light-emitting elements of the present invention, so the amount of contained gold or platinum family element is low more in the light transmission p electrode, perviousness is just good more.The relation of the sheet resistance of semiconductor light-emitting elements in the past is Rp≤Rn, but in present embodiment 2, owing to adjust to Rp 〉=Rn, therefore light transmission p electrode is compared with product in the past, can form film, easily carry out filming by reducing the content of gold or platinum family element this moment.
As mentioned above, the semiconductor light-emitting elements 10 that the present invention is used, the sheet resistance Rn Ω/ of preferred n contact layer and the sheet resistance Rp Ω/ of light transmission p electrode, the relation of formation Rp 〉=Rn.After having made semiconductor light-emitting elements 10, be difficult to measure Rn, can't learn the relation of Rp and Rn in fact, but light intensity distributions state that can be when luminous is understood the relation which kind of forms between Rp and Rn.
When light transmission p electrode and n type contact layer have concerning of Rp 〉=Rn, if with described light transmission p electrode contiguously, be provided with and have the p side group seat electrode that extends conducting part, just can further improve external quantum efficiency.The shape and the direction of extending conducting part do not limit, and are positioned under the situation on the parallel extending conducting part, and be therefore preferred because the shading area reduces, but can form mesh shape yet.In addition, about shape, except that rectilinear form, also can be curve-like, reticulation, dendritic and hook-shaped.At this moment, because the total area of shaded effect and p side group seat electrode increases pro rata, therefore preferably be no more than the mode of luminous increase effect, the live width of design extension conductive part and length with shaded effect.
In present embodiment 2, as mentioned above,, not only can use the luminous element of ultra-violet light-emitting, and can use the luminous element that sends blue light as luminous element 10.Send the luminous element 10 of blue light, also III-th family nitride based compound luminous element preferably.Such luminous element 10 for example have on sapphire substrate 1 by the GaN buffer layer stack gradually the n type GaN layer of the Si that do not mix, the rhythmo structure of n type contact layer, the unadulterated GaN layer that constitutes by the n type GaN of doping Si, luminescent layer (quantum well structure of GaN barrier layer/InGaN trap layer), the p coating layer that constitutes by the p type GaN of doped with Mg, the p type contact layer that constitutes by the p type GaN of doped with Mg with multiple quantum trap structure.Form electrode in the following manner.But, also can use the luminous element different with this formation.
The p Ohmic electrode is formed on on the p type contact layer roughly whole, on the part on this p Ohmic electrode, forms p pad (pad) electrode.
In addition, the n electrode after removing unadulterated GaN layer by etching from p type contact layer, exposing the part of n type contact layer, is formed on this exposed portions.
In addition, in the present embodiment, used the luminescent layer with multiple quantum trap structure, but the present invention is not limited thereto, for example, the present invention also can form the single quantum well structure that has utilized InGaN, also can utilize the GaN of doping Si, Zn.
In addition, the luminescent layer of luminous element 10 by changing In content, can change the main glow peak wavelength in the scope from 420nm to 490nm.In addition, the glow peak wavelength is not limited to above-mentioned scope, also can use at 360～550nm to have the glow peak wavelength.
(application member 12)
Application member 12 (photopermeability material) mixes use with fluor 11 in the cup-shaped portion that is located at lead frame 13.As the concrete material of application member 12, can adopt as Resins, epoxy, urea resin and silicone resin equitemperature characteristic and the transparent resin that has excellent weather resistance, silica gel, glass, inorganic adhesive etc.In addition, also can together contain diffusant, barium titanate, titanium oxide, aluminum oxide etc. with fluor.In addition, also can contain Photostabilised dose, tinting material.
(lead frame 13)
Lead-in wire 13a is installed, is used to dispose luminous element 10.Cup-shaped is formed at the top that lead-in wire 13a is installed, and engages luminous element 10 in cup.To cover the mode of this luminous element 10, cover in the cup-shaped portion with described fluor 11 and described application member 12.In addition, also can in cup-shaped portion, dispose a plurality of luminous elements 10, will the common electrode of lead-in wire 13a as a plurality of luminous elements 10 be installed.In such cases, require enough electroconductibility and with the connectivity of conductor wire 14.Engage (bonding) of luminous element 10 and the cup-shaped portion that lead-in wire 13a is installed can be undertaken by heat-curing resin etc.As heat-curing resin, can enumerate Resins, epoxy, acrylic resin and imide resin etc.In addition,, be electrically connected when engaging, can adopt Ag paste, carbon paste, metal protrusion (bump) etc. with installation lead-in wire 13a in order to utilize upside-down mounting (facedown) luminous element 10 etc.In addition, also can use inorganic adhesive.
(conductor wire)
(application member 12)
It is that resin and inorganic materials are various application members (tackiness agent) adhesions such as glass that fluor 11 can adopt organic materials.Application member 12 also has as the effect that is used for fluor 11 is fixed on the tackiness agent on luminous element 10 or the window portion 107 etc.As application member (tackiness agent), use under the organic situation, as concrete material, be fit to the transparent resin that uses Resins, epoxy, acrylic resin and silicone resin etc. to have excellent weather resistance.Especially, if adopt silicone resin, the reliability excellence, and can improve the dispersiveness of fluor 11, therefore preferred.
In addition,,, can on described window portion 107, connect airtight fluor 108 well, so preferred this material if use the inorganics of the coefficient of thermal expansion of similar window portion 107 as application member (tackiness agent) 12.As concrete method, can adopt settling process or sol-gel method, gunite etc.For example, about fluor 11 and 108, by mixed silanes alcohol (Si (OEt)
3OH) and ethanol, form slurry,, 300 ℃ of heating 3 hours down, silanol is changed into SiO then from nozzle ejection slurry
2, fluor is fixed on the desirable position.
In addition, also can use inorganic adhesive as application member (tackiness agent) 12 and 109.About tackiness agent, preferred so-called low melting glass, subparticle and little to the absorption of radiation ray, very stable application member (tackiness agent) 12 and 109 from ultraviolet to the visible region.
In addition, when under the situation of the fluor that adheres to big particle diameter on application member (tackiness agent) 12 and 109, even the preferred fusing point height that uses, particle also is the tackiness agent of ultramicro powder, for example the pyrophosphate salt and the orthophosphoric acid salt of silica gel, aluminum oxide or the fine-grained alkaline-earth metal that obtains with settling process.The use of can using separately or be mixed with each other of these tackiness agents.
Below, the coating method of above-mentioned tackiness agent is described.For fully improving bonding effect, tackiness agent preferably carries out case of wet attrition in vehicle, make pulp-like, uses as binder paste.Described vehicle is the high viscosity solution that obtains by dissolving a little binder in organic solvent or deionization.For example,, contain the tackiness agent Nitrocellulose of 1wt%, can obtain the organic system vehicle by with respect to the organism solvent butyl acetate.
Obtaining to such an extent that add fluor 11,108, preparation coating liquid in the binder paste like this.The addition of the slurry in the coating liquid is that with respect to the fluorescence scale of construction in the coating liquid, the total amount of the tackiness agent in the slurry can be set in the scope of 1～3wt%.For suppressing the reduction of light beam sustainment rate, the addition of preferred adhesive is few.
Described coating liquid is coated on the back side of described window portion 107.Then, be blown into warm wind or hot blast, make its drying.At last, under 400 ℃～700 ℃ temperature, toast, described vehicle is disperseed.Thus, with tackiness agent luminescent coating is sticked on the desirable position.
(moulding part)
Moulding part 15 is avoided ectocine setting for making luminous element 10, fluor 11, application member 12, lead frame 13, conductor wire 14 etc.Moulding part 15 except that above-mentioned these of protection make them avoid also having the expanded field of vision angle the purpose of ectocine, or relaxes the directivity of self-emission device 10, or brings, spreads luminous purpose together.For reaching these purposes, moulding part 15 can form desirable shape.In addition, moulding part 15 except that convex lens shape, concavees lens shape, also can be multilayer laminated structure.As the concrete material of moulding part 15, can use the material of light transmissions such as Resins, epoxy, urea resin, silicone resin, silicon sol, glass, weather resisteant, excellent in temperature characteristic.In moulding part 15, also can contain diffusant, tinting material, UV light absorber and fluor.As diffusant, preferred barium carbonate, titanium oxide, aluminum oxide etc.For reducing the repellency with the material of application member 12, and consider specific refractory power, preferably use homogeneous material.
According to the light-emitting device of the embodiment 2 that as above constitutes, can realize having the light-emitting device of various illuminant colours.
For example, in the light-emitting device of embodiment 2,, can realize the light-emitting device that illuminant colour is identical with the illuminant colour of oxonitride phosphor by the luminous element and the oxonitride phosphor of combination ultraviolet.
In addition, by combined blue luminous element and oxonitride phosphor, can realize illuminant colour light-emitting device of (centre) illuminant colour from the illuminant colour of luminous element to oxonitride phosphor.
In addition, the light-emitting device of present embodiment 2 because oxonitride phosphor of the present invention can adjusted illuminant colour, luminosity etc. in the scope widely, therefore can be realized the light-emitting device of various tones.
And then, the light-emitting device of present embodiment 2, because oxonitride phosphor of the present invention can carry out the luminous of high brightness, and the luminous efficiency height, therefore can provide brightness height and the high light-emitting device of luminous efficiency.
Embodiment 3
Fig. 2 is the orthographic plan (Fig. 2 A) and the sectional view (Fig. 2 B) of formation of the light-emitting device of expression embodiments of the present invention 3.The light-emitting device of present embodiment 3 is surface-mount type light emitting devices.In the light-emitting device of present embodiment 3, as luminous element 101, can use the nitride semiconductor luminescent element of the light that sends ultraviolet region, also can use the nitride semiconductor luminescent element of the light that sends blue region.In addition, about concrete formation, identical with the luminous element of embodiment 2.
Herein, the luminous element 101 with the light that sends ultraviolet region is the example explanation.In present embodiment 3, luminous element 101 is as luminescent layer, has the semi-conductive nitride semiconductor luminescent element of InGaN that the glow peak wavelength is approximately 370nm.As the component structure of LED more specifically, have on sapphire substrate stacked comprise unadulterated nitride-based semiconductor be n type GaN layer, formed the n type electrode of doping Si and become the GaN layer of n type contact layer, the doped nitride semi-conductor is not that n type GaN layer, nitride-based semiconductor are the structure of luminescent layer of the single quantum well structure of n type AlGaN layer, InGaN trap layer.On this luminescent layer, more successively lamination as the AlGaN layer of the p type coating layer of doped with Mg and as the GaN layer of the p type contact layer of doped with Mg.In addition, on sapphire substrate, form the buffer layer that makes the GaN layer growth at low temperatures.In addition, for the p N-type semiconductorN, after film forming, in annealing more than 400 ℃.In such rhythmo structure, utilize etching, on the nitride-based semiconductor on the sapphire substrate, on same one side side, the surface of exposing each contact layer of pn.On the n type contact layer that exposes, form the n electrode with band shape, on roughly whole of remaining p type contact layer, form the light transmission p electrode that constitutes by metallic film.In addition, on light transmission p electrode, adopt sputtering method, form base electrode abreast with the n electrode.
In embodiment 3, adopt packaged piece 105 by Kovar alloy system, have recess at packaged piece 105 central parts, and in the both sides of described recess, airtight insulation ground inserts fixing lead-in wire electrode 102 by Kovar alloy system.The surface of described packaged piece 105 and lead-in wire electrode 102 is provided with the Ni/Ag layer.In the recess of packaged piece 105, use the Ag-Sn alloy, engage above-mentioned luminous element 101.By such formation, the component parts of light-emitting device all can be defined as inorganics, even can access the luminous also very high light-emitting device of short wavelength's zone reliability that sends from luminous element 101 at ultraviolet region or visible light.
Then, respectively with Ag silk 104 make joint luminous element 101 each electrode and be electrically connected by the electrode 102 that respectively goes between that expose encapsulation recess bottom surface.After fully getting rid of the moisture in the encapsulation recess, be used in lid 106 sealings that Kovar alloy that central part has glass port portion 107 is made, stitch weldering.In glass port portion, make to contain in the slurry that constitutes by 90wt% Nitrocellulose and 10wt% gama-alumina to comprise CaSi
2O
2N
2: Eu, (Y
0.8Gd
0.2)
3Al
5O
12: the fluor 108 of Ce etc., and mixture is coated in the back side of covering 106 transparent window portion 107, under 220 ℃, be heating and curing 30 minutes, constitute the look inverting element.If make the light-emitting device of such formation luminous, but can be made into the turn white photodiode of coloured light of high brightness.Thus, can make that chroma control is open-and-shut, the light-emitting device of mass productivity, reliability excellence.Below, describe each formation of the present invention in detail.
In addition,,, can on described window portion 107, connect airtight fluor 108 well, so preferred this material if use the inorganics of the coefficient of thermal expansion of similar window portion 107 as application member (tackiness agent) 12.As connecting airtight method, can adopt settling process or sol-gel method, gunite etc.For example, about fluor 108, by mixed silanes alcohol (Si (OEt)
3OH) and ethanol, form slurry, spray this slurry, 300 ℃ of heating 3 hours down, silanol is changed into SiO then from nozzle
2, fluor is fixed on the desirable position.
In addition, also can use inorganic adhesive as application member (tackiness agent) 109.About tackiness agent, preferred so-called low melting glass, subparticle, and little to the absorption of radiation ray from ultraviolet to the visible region, very stable in application member (tackiness agent) 109.
The light-emitting device of the embodiment 3 of Gou Chenging like this has the action effect identical with embodiment 2.
Embodiment 4
The light-emitting device of embodiment 4 is in the light-emitting device of embodiment 2 or 3, as fluor 11 and 108, with oxonitride phosphor together, contain the light-emitting device of the 2nd fluor.
As the 2nd fluor, preferably, from mainly by element activated alkali earths halogen apatite fluorescent body, alkaline-earth metal borate halogen fluor, alkaline-earth metal chlorate MClO 3 fluorescent substance, alkali earths silicate, alkali earths sulfide, alkali earths sulfo-gallate, alkaline earth silicon nitride, the germanate of transition metal series such as group of the lanthanides such as Eu, Mn, perhaps, mainly by lanthanon activated rare earth class aluminate, rare earth class silicate such as Ce, perhaps, mainly selected in the organic and organic complex etc. by lanthanon activated such as Eu more than at least a kind.As concrete example, enumerate following fluor, but be not limited thereto.
By the element activated alkali earths halogen apatite fluorescent body of transition metal series such as group of the lanthanides such as Eu, Mn, M is arranged as mainly
5(PO
4)
3X:R (M be from Sr, Ca, Ba, Mg and Zn, select more than at least a kind.X be from F, Cl, Br and I, select more than at least a kind.R is any more than a kind among Eu, Mn, Eu and the Mn) etc.
As alkaline-earth metal boric acid halogen fluor, M is arranged
2B
5O
9X:R (M be from Sr, Ca, Ba, Mg and Zn, select more than at least a kind.X be from F, Cl, Br and I, select more than at least a kind.R is any more than a kind among Eu, Mn, Eu and the Mn) etc.
As the alkaline-earth metal chlorate MClO 3 fluorescent substance, SrAl is arranged
2O
4: R, Sr
4Al
14O
25: R, CaAl
2O
4: R, BaMg
2Al
16O
27: R, BaMg
2Al
16O
12: R, BaMgAl
10O
17: R (R be among Eu, Mn, Eu and the Mn any more than a kind) etc.
As the alkali earths sulphide phosphor, La is arranged
2O
2S:Eu, Y
2O
2S:Eu, Gd
2O
2S:Eu etc.
, had by lanthanon activated rare earth class chlorate MClO 3 fluorescent substances such as Ce as mainly with composition formula Y
3Al
5O
12: Ce, (Y
0.8Gd
0.2)
3Al
5O
12: Ce, Y
3(Al
0.8Ga
0.2)
5O
12: Ce and (Y, Gd)
3(Al, Ga)
5O
12YAG Deng expression is a fluor etc.
As other fluor, ZnS:Eu, Zn are arranged
2GeO
4: Mn, MGa
2S
4: Eu (M be from Sr, Ca, Ba, Mg and Zn, select more than at least a kind.X be from F, Cl, Br and I, select more than at least a kind.) etc.In addition, also has M
2Si
5N
8: Eu, MSi
7N
10: Eu, M
1.8Si
5O
0.2N
8: Eu, M
0.9Si
7O
0.1N
10: Eu (M be from Sr, Ca, Ba, Mg and Zn, select more than at least a kind) etc.
Above-mentioned the 2nd fluor also can be as required, replaces Eu, perhaps, except that Eu, contain again from Tb, Cu, Ag, Au, Cr, Nd, Dy, Co, Ni and Ti, select more than a kind.
In addition, also can use above-mentioned fluor fluor in addition, that have identical performance and effect.
As the 2nd such fluor, remove the exciting light that can use by luminous element 10,101, have outside the fluor of luminescent spectrum at yellow, red, green and blue place, also can use, blue-greenish colour promptly yellow and zone such as orange to have the fluor of luminescent spectrum in their middle shade.By these the 2nd fluor and the 1st fluor are used in combination, can make light-emitting device with various illuminant colours.
For example, promptly send green CaSi by using to sodium yellow by the 1st fluor
2O
2N
2: Eu or SrSi
2O
2N
2: Eu and the 2nd fluor promptly send blue light (Sr, Ca)
5(PO
4)
3Cl:Eu reaches (Ca, the Sr) at burn red
2Si
5N
8: the fluor 11,108 that Eu constitutes can provide color developing the good light-emitting device that sends white light.This is owing to use three primary colours red, blue and green, so only pass through to change the proportioning of the 1st and the 2nd fluor, just can realize needed white light.
Especially, when near the light that adopts as excitation light source the 460nm, when irradiation oxonitride phosphor and the 2nd fluor, oxonitride phosphor sends near the light the 500nm.Thus, can provide white color system light-emitting device with good color developing.
Above-mentioned fluor 11 and 108 particle diameter, the scope of preferred 1 μ m～20 μ m, more preferably 2 μ m～8 μ m, most preferably 5 μ m～8 μ m.Have fluor, the tendency of easy formation condensation product is arranged less than the particle diameter of 2 μ m.On the other hand, the fluor of the particle size range of 5 μ m～8 μ m, the specific absorption of light and efficiency of conversion height.Like this, by containing the fluor of big particle diameter, can improve the mass productivity of light-emitting device with excellent optical signature.
Herein, particle diameter means the median size that obtains by the air penetrant method.Specifically be under the environment of 25 ℃ of temperature, humidity 70%, to take by weighing 1cm
3The sample of share, in being encased in special-purpose tubular vessel after, feed the dry air of certain pressure, read specific surface area from pressure reduction, be converted into the value of median size.The median size of used fluor among the present invention, the scope of preferred 2 μ m～8 μ m.In addition, preferred high frequency contains the fluor with this median size value.In addition, preferable particle size is distributed in the narrow scope, the few particle diameter of micropartical that preferred especially 2 μ m are following.So, by adopting particle diameter and the little fluor of size distribution deviation, can access the light-emitting device that the color inequality is suppressed, has good tone more.
The allocation position of the fluor 108 in the light-emitting device of Fig. 2 in the position with luminous element 101 concerns, can be configured in all places.For example, in the moulding material of covering luminous element 101, can contain fluor 108.In addition, also can dispose luminous element 101 and fluor 108 in the compartment unoccupied place, also can directly place fluor 108 on the top of luminous element 101.
The light-emitting device of the embodiment 4 of above-mentioned formation except that having the effect identical with the light-emitting device of embodiment 2, also has following effect.
Promptly, in the light-emitting device of embodiment 4, except that oxonitride phosphor, by adopting the 2nd fluor, can realize the light-emitting device of the illuminant colour that the luminous colour mixture by the luminous of oxonitride phosphor and the 2nd fluor produces or the light-emitting device of the illuminant colour that produces by the luminous colour mixture of luminous and the 2nd fluor of luminous, the oxonitride phosphor of luminous element (luminous element of visible light).
In addition, in the light-emitting device of present embodiment 4, the kind by changing the 2nd fluor and with respect to the ratio of oxonitride phosphor can be adjusted illuminant colour, luminosity etc. in broad range, can realize kind of analogy embodiment 2 and 3 more tones.
Embodiment 5
Embodiments of the present invention 5 are with SrSi
2O
2N
2: the manufacture method of the oxonitride phosphor that Eu represents, Figure 31 is the process picture sheet of manufacture method of the oxonitride phosphor of expression embodiment 5.
In this manufacture method, at first prepare the nitride of Sr, the nitride of Si, the oxide compound of Si and the oxide compound of Eu.These raw materials preferably use purified, but also can use commercially available person.Particularly, this oxonitride phosphor is according to following method preparation.
As the Sr of raw material, use nitride Sr
3N
2As raw material, also can use compounds such as imide compound, amide compound, SrO, also can use the Sr monomer.In addition, raw material Sr also can contain B, Ga etc.
Pulverize the nitride Sr of Sr
3N
2(P1).
As the nitride of raw material Si, use Sr
3N
4As raw material, also can use other nitride, imide compound, amide compound etc., also can use the monomer of Si.For example, Si (NH
2)
2, Mg
2Si, Ca
2Si, SiC etc.The purity of raw material Si is preferably more than the 3N, but also can contain B, Ga etc.
Pulverize the nitride Si of Si
3N
4(P2).
As the oxide compound of raw material Si, use SiO
2Here use commercially available product (with the pure medicine system SiliconDioxide 99.9% of light, 190-09072).
Pulverize the oxide S iO of Si
2(P3).
Use the oxide compound Eu of Eu
2O
3Make raw material.Raw material preferably uses the monomer of Eu, but also can use nitride, imide compound, amide compound etc.Especially, except that europium sesquioxide, preferably use the nitrogenize europium.This is because contain aerobic or nitrogen in the resultant.
Pulverize the oxide compound Eu of Eu
2O
3(P4).
After pulverizing each raw material, in the mode of the proportioning that reaches regulation, the Sr nitride Sr of the molar weight of the regulation of weighing
3N
2, Si nitride Si
3N
4, Si oxide S iO
2And the oxide compound Eu of Eu
2O
3, mix (P5).
Then, burn till the nitride of Sr, the nitride of Si, the oxide compound of Si and the hopcalite (P6) of Eu.This mixture is dropped into crucible, burn till.
By mixing and burning till, can access with SrSi
2O
2N
2: the oxonitride phosphor that Eu represents (P7).List in formula 4 by this reaction formula that burns till the oxonitride phosphor that carries out.
(formula 4)
((1-2a)/3)Sr
3N
2+((2+3a)/6)Si
3N
4+((2-3a)/2)SiO
2+aEu
2O
3→Sr
(1-2a)Eu
2aSi
2O
2N
2+N
2a/3
But this composition is to form according to the representativeness that cooperates ratio to infer, near this ratio, has and stands practical enough characteristics.In addition, by changing the cooperation ratio of each raw material, can change composition as the fluor of target.
Firing temperature does not limit especially, but preferably burns till in 1200～2000 ℃ scope, more preferably 1400～2000 ℃ firing temperature.The raw material of fluor 11 preferably uses crucible, the vessel of boron nitride (BN) material to burn till.Except that the crucible of boron nitride material, also can use aluminum oxide (Al
2O
3) crucible of material.
In addition, burn till preferably and in reducing atmosphere, carry out.Reducing atmosphere is inert gas atmospheres such as nitrogen atmosphere, nitrogen-nitrogen atmosphere, ammonia atmosphere and argon gas etc.
By adopting above-mentioned manufacture method, can access the oxonitride phosphor of target.
In addition, can make by the following method contain B with
The oxonitride phosphor of expression.
In advance, in the oxide compound of Eu, the compound H of dry mixed B
3BO
3As the Eu compound, adopt europium sesquioxide, but also can be same with above-mentioned other formation element, use metal europium, nitrogenize europium etc.In addition, raw material Eu also can use imide compound, amide compound.Europium sesquioxide is preferably highly purified, but also can use commercially available.Compound to B carries out dry mixed, but also can carry out wet-mixed.
Compound H with B
3BO
3Be example, the manufacture method of oxonitride phosphor is described, but the composition beyond B constitutes in the element, and Li, Na and K etc. are arranged, and can adopt their compound, for example LiOHH
2O, Na
2CO
3, K
2CO
3, RbCl, CsCl, Mg (NO
3)
2, CaCl
26H
2O, SrCl
26H
2O, BaCl
22H
2O, TiOSO
4H
2O, ZrO (NO
3)
2, HfCl
4, MnO
2, ReCl
5, Cu (CH
3COO)
2H
2O, AgNO
3, HAuCl
44H
2O, Zn (NO
3)
26H
2O, GeO
2, Sn (CH
3COO)
2Deng.
Pulverize the mixture of Eu and B.The median size of Eu after the pulverizing and the mixture of B, preferably approximately are 0.1 μ m～15 μ m.
After having carried out above-mentioned pulverizing, roughly with described SrSi
2O
2N
2: the manufacturing process of Eu is same, mix nitride, the Si of Sr nitride, Si oxide compound and contain the Eu oxide compound of B.After this mixes, burn till, can obtain the purpose oxonitride phosphor.
Embodiment 6
The fluor of embodiments of the present invention 6, it is the oxonitride phosphor that is used in combination with luminous element, especially nitride semiconductor device about being specially adapted to, this fluor is in the oxonitride phosphor of embodiment 1, with Ba, Si and Eu as essential fluor.
Promptly, the oxonitride phosphor of present embodiment 6, using with Eu as activator is the essential rare earth element more than at least a kind, and to contain what select from the group that is made up of Ca, Sr, Ba and Zn at least be the essential II family element more than at least a kind and what select from the group that is made up of C, Si, Ge, Sn, Ti, Zr and Hf is the essential IV family element more than at least a kind with Si with Ba.The combination of this element is arbitrarily, but the preferred combination of using following composition.
The oxonitride phosphor of embodiment 6 can be with general formula L
XM
YO
ZN
((2/3) X+ (4/3) Y-(2/3) Z): R or L
XM
YQ
TO
ZN
((2/3) X+ (4/3) Y+T-(2/3) Z): R represents that (wherein, L is the essential II family element more than at least a kind for what select with Ba from the group that is made of Ca, Sr, Ba and Zn.M is the essential IV family element more than at least a kind for what select from the group that is made up of C, Si, Ge, Sn, Ti, Zr and Hf with Si.The iii group element at least a kind or more of Q for from the group that forms by B, Al, Ga and In, selecting.O is an oxygen element.N is the nitrogen element.R is for being essential rare earth element more than at least a kind with Eu).In addition, the fluor of embodiment 6 and embodiment 1 are same, exhibit high brilliance in the scope of 0.5＜X＜1.5,1.5＜Y＜2.5,0＜T＜0.5,1.5＜Z＜2.5.In addition, wherein, in general formula, described X, described Y, described Z are more preferably 0.8＜X＜1.2,1.8＜Y＜2.2,0＜T＜0.5,1.7＜Z＜2.2, for showing high brightness, most preferably described X, described Y, described Z, the oxonitride phosphor of representing with X=1, Y=2, Z=2.But the present invention is not limited to above-mentioned scope.Specifically be, can enumerate BaSi as the oxonitride phosphor of embodiment 6
1.8Ge
0.2O
2N
2: Eu, BaSi
1.9Ge
0.1O
2N
2: Eu, BaSi
1.8C
0.2O
2N
2: Eu, BaSi
1.9C
0.1O
2N
2: Eu, BaSi
1.8Ti
0.2O
2N
2: Eu, BaSi
1.9Ti
0.1O
2N
2: Eu, BaSi
1.8Sn
0.2O
2N
2: Eu, BaSi
1.9Sn
0.1O
2N
2: Eu, Ba
0.9Ca
0.1Si
2O
2N
2: Eu, Ba
0.9Sr
0.1Si
2O
2N
2: Eu, Ba
0.9Zn
0.1Si
2O
2N
2: Eu, Ba
0.9Ca
0.1Si
1.8Ge
0.2O
2N
2: Eu, Ba
0.9Sr
0.1Si
1.8Ge
0.2O
2N
2: Eu etc.
In addition, this oxonitride phosphor, identical with embodiment 1, adjust hue and luminance by changing O with the ratio of N, in addition, also can accurately adjust luminescent spectrum and intensity by changing positively charged ion and anionic mol ratio with (L+M)/(O+N) expression.This can be by for example implementing processing such as vacuum, take off N or take off O and wait and carry out, but the present invention is not limited to this method.In the composition of oxonitride phosphor, also can contain among Li, Na, K, Rb, Cs, Mn, Re, Cu, Ag and the Au more than at least 0 kind.By adding these elements, can adjust luminous efficiencies such as brightness, quantum yield.In addition, in the scope that does not diminish characteristic, also can add other element.
L is that what to select from the group that is made up of Ca, Sr, Ba and Zn is the essential II family element more than at least a kind with Ba.That is, Ba can use with monomer, but can Ba and Ca, Ba and Sr, Ba and Ca and Sr etc. be changed to multiple combination.The mixture of these II family elements can change proportioning as requested.
M, be from by C, Si, Ge, Sn, Ti, and the group that forms of Hf what select is the essential IV family element more than at least a kind with Si.For M, Si also can use with monomer, also can Si and Ge, Si and C etc. be changed to multiple combination.Be because, can provide crystallinity good fluor at an easy rate by using Si.
R is to be the essential rare earth element more than at least a kind with Eu.Specifically be that rare earth element is La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu.In these rare earth elements, can use Eu with monomeric form, contain Eu and the element more than at least a kind from rare earth element, selected but also can use.Be because the element beyond the Eu plays a role as coactivator.R preferably contains the above Eu of 70 weight %.Especially, among the R, with respect to II family element, in molar ratio, II family element: R=1: 0.005～1: 0.15.
Luminescence center adopts rare earth elements europium Eu.In the present invention, only adopt Eu to describe, but also be not limited thereto, also can use coactivated element with Eu.Europium mainly has divalent and 3 valence levels.In the fluor of the present invention, be silicon nitride, adopt Eu as activator for the alkaline-earth metal of parent
2+Eu
2+Oxidation easily, common Eu with 3 valencys
2O
3Composition sell.
As fertile material, the L of principal constituent, M also can adopt compound separately.The L of these principal constituents, M can adopt metal, oxide compound, imide, acid amides, nitride and various salt.In addition, also can be pre-mixed the L of principal constituent and the element of M, re-use.
Q is the iii group element of selecting from the group that is made up of B, Al, Ga and In more than at least a kind.Q also can adopt metal, oxide compound, imide, acid amides, nitride and various salt.For example, B
2O
6, H
3BO
3, Al
2O
3, Al (NO
3)
39H
2O, AlN, GaCl
3, InCl
3Deng.
The oxonitride phosphor of embodiment 6 can be made in the following manner.
At first, mixing is as nitride, the nitride of M and the oxide compound of M of the L of fertile material.In this fertile material, mix the oxide compound of Eu as activator.Measure these materials of weighing in accordance with regulations, be mixed into evenly.Particularly, the oxide compound of the nitride of the L in this fertile material, the nitride of M and M is preferably by the mixed in molar ratio of oxide compound＜3.75 of nitride＜1.75 of nitride＜1.5 of 0.5＜L, 0.25＜M, 2.25＜M.That is, to reach
Or
The mode of ratio of components, measure these fertile materials of weighing in accordance with regulations, mix.
(example of the manufacture method more specifically of the oxonitride phosphor of embodiment 6)
The oxonitride phosphor BaSi of embodiment 6 then, is described
2O
2N
2: the manufacture method of Eu, but the present invention is not limited to following manufacture method.Figure 62 is the process picture sheet of manufacture method of the oxonitride phosphor of expression embodiment 6.
In the present invention, at first, prepare nitride, the nitride of Si, the oxide compound of Si and the oxide compound of Eu of Ba.These raw materials preferably use purified, but can use commercially available person.Specifically make oxonitride phosphor by the following method.
1.Ba nitride
As the nitride of raw material Ba, use Ba
3N
2As raw material, also can use as compounds such as imide compound, amide compound and BaO, also can use the monomer of Ba.In addition, raw material Ba also can contain B, Ga etc.
Pulverize the nitride Ba of this Ba
3N
2(P1).
2.Si nitride
As the nitride of raw material Si, use Si
3N
4As raw material, also can use nitride, imide compound, amide compound etc., but also can use the monomer of Si.For example, Si
3N
4, Si (NH
2)
2, Mg
2Si, Ca
2Si, SiC etc.The purity of raw material Si is preferably more than the 3N, but can contain B, Ga etc.
Pulverize the nitride Si of this Si
3N
4(P2).
3.Si oxide compound
As the oxide compound of raw material Si, use SiO
2Use commercially available product (with the pure medicine system Silicon of light Dioxide 99.9%, 190-09072) herein.
Pulverize the oxide S iO of this Si
2(P3).
4.Eu oxide compound
As the oxide compound of raw material Eu, use Eu
2O
3As raw material, also can use nitride, imide compound, amide compound etc., and also can use the monomer of Eu.Except that europium sesquioxide, preferably use the nitrogenize europium.This is because contain aerobic or nitrogen in resultant.
Pulverize the oxide compound Eu of this Eu
2O
3(P4).
The nitride Ba of the raw material Ba of the described pulverizing of weighing
3N
2, Si nitride Si
3N
4, Si oxide S iO
2And the oxide compound Eu of Eu
2O
3, and mix (P5).The described raw material of weighing reaches the proportioning of regulation.
Then, burn till the nitride of Ba, the nitride of Si, the oxide compound of Si and the hopcalite (P6) of Eu.This mixture is dropped into crucible, burn till.
By mixing and burning till, can obtain with BaSi
2O
2N
2: the oxonitride phosphor that Eu represents (P7).List in formula 5 by this reaction formula that burns till the basic comprising element that carries out.
(formula 5)
(1/3)Ba
3N
2+(1/3)Si
3N
4+SiO
2+aEu
2O
3→BaSi
2O
2N
2:Eu
But this composition, was had and stands practical enough characteristics near this ratio by representational composition that cooperates ratio to infer.In addition, by changing the cooperation ratio of each raw material, can change composition as the fluor of purpose.
Firing temperature does not limit especially, but preferably burns till under 1200～1700 ℃ temperature range, more preferably 1400～1700 ℃ firing temperature.The raw material of fluor 11 preferably uses the crucible and the vessel of boron nitride (BN) material to burn till.Except that the crucible of boron nitride material, also can adopt aluminum oxide (Al
2O
3) crucible of material.
In addition, preferably burn till in reducing atmosphere and carry out.Reducing atmosphere is inert gas atmospheres such as nitrogen atmosphere, nitrogen-nitrogen atmosphere, ammonia atmosphere, argon gas etc.
By adopting above-mentioned manufacture method, can access oxonitride phosphor as the embodiment 6 of purpose.
In addition, with
The oxonitride phosphor of expression can be made in the following manner.
In advance, in the oxide compound of Eu, the compound H of dry mixed B
3BO
3As the Eu compound, adopt europium sesquioxide, but also can be same with above-mentioned other formation element, use metal europium, nitrogenize europium etc.In addition, raw material Eu also can use imide compound, amide compound etc.Europium sesquioxide is preferably highly purified, but also can use commercially available.Compound for B carries out dry mixed, but also can carry out wet-mixed.
Compound H with B
3BO
3Be example, the manufacture method of oxonitride phosphor is described, but the composition beyond B constitutes in the element, and Li, Na and K etc. are arranged, and can adopt their compound, for example LiOHH
2O, Na
2CO
3, K
2CO
3, RbCl, CsCl, Mg (NO
3)
2, CaCl
26H
2O, SrCl
26H
2O, BaCl
22H
2O, TiOSO
4H
2O, ZrO (NO
3)
2, HfCl
4, MnO
2, ReCl
5, Cu (CH
3COO)
2H
2O, AgNO
3, HAuCl
44H
2O, Zn (NO
3)
26H
2O, GeO
2, Sn (CH
3COO)
2Deng.
Pulverize the mixture of Eu and B.The median size of Eu after the pulverizing and the mixture of B, preferably approximately are 0.1 μ m～15 μ m.
After having carried out above-mentioned pulverizing, roughly with described BaSi
2O
2N
2: the manufacturing process of Eu is same, mix nitride, the Si of Ba nitride, Si oxide compound and contain the Eu oxide compound of B.After this mixes, burn till, can obtain the purpose oxonitride phosphor.
By the oxonitride phosphor of the embodiment 6 of above formation, have with YAG be the equal above stability of fluor, have the action effect same with embodiment 1.
In addition, the oxonitride phosphor of present embodiment 6, can be to have the mode that has the luminescent spectrum of glow peak at blue-greenish colour zone～green area, select its composition and ratio of components, especially, in this scope, can realize high luminosity and luminous efficiency, also can in broad range, adjust tone, quantum yield etc.
Embodiment
Below, by enumerating embodiment, fluor of the present invention and light-emitting device are described, but are not limited thereto embodiment.
In addition, temperature profile is to be that 100% relative brightness is represented with the luminosity under 25 ℃.Particle diameter is represented described median size, is to utilize to be called the F.S.S.S.No. (value that Fisher Sub Sieve Sizer ' air penetrant method sNo.) obtains.
＜embodiment 1～5 〉
The characteristic of the embodiment 1～5 of table 1 expression oxonitride phosphor of the present invention
In addition, Fig. 3 is the figure of the luminescent spectrum of expression when exciting the oxonitride phosphor of embodiment 1～5 with Ex=400nm.Fig. 4 is the figure of the luminescent spectrum of expression when exciting the oxonitride phosphor of embodiment 1～5 with Ex=460nm.Fig. 5 is the figure of excitation spectrum of the oxonitride phosphor of expression embodiment 1～5.Fig. 6 is the figure of excitation spectrum of the oxonitride phosphor of expression embodiment 1～5.Fig. 7 is SEM (scanning electronic microscope) photo of the oxonitride phosphor of embodiment 1.Wherein, the relation of color name and tristimulus coordinates is with reference to JIS Z8110.
Table 1
In embodiment 1～5,, use Ca as raw material
3N
2, Si
3N
4, SiO
2And Eu
2O
3, and after these raw material powder are broken into 0.1～3.0 μ m, carry out by the following method respectively.
At first, by following amount weighing compound.
Ca
3N
2：6.01g
Si
3N
4：5.99g
SiO
2：7.36g
Eu
2O
3：0.66g
After the above-mentioned quantity of weighing, in nitrogen atmosphere, in the ball case, mixed C a
3N
2, Si
3N
4, SiO
2And Eu
2O
3 To even.In embodiment 1～5, the concentration of Eu is 0.43mol%.
Among the embodiment 1, the mixture ratio of raw material (mol ratio) is Ca
3N
2: Si
3N
4: SiO
2: Eu
2O
3=1: 0.51: 3.02: 0.046.By this mixture ratio, weighing Ca
3N
2(molecular weight 148.3) 6.01g, Si
3N
4(molecular weight 140.3) 5.99g, SiO
2(molecular weight 60.09) 7.36g and Eu
2O
3(molecular weight 352.0) 0.66g mixes then.
Mix above-claimed cpd, in ammonia atmosphere, mixture is dropped into boron nitride crucible, under about 1500 ℃, burnt till about 5 hours.
Thus, obtain oxonitride phosphor as target.The theory of the oxonitride phosphor of gained consists of CaSi
2O
2N
2: Eu.
The result of the O of the oxonitride phosphor of mensuration embodiment 1 and the weight % of N in total amount, contains 19.3 weight %O and 14.5 weight %N.The weight ratio of O and N is O: N=1: 0.75.
The oxonitride phosphor of embodiment is to use the crucible of boron nitride material, burns till at ammonia atmosphere.About crucible, the metal crucible of not too preferred use.Be because under the situation of using metal crucible, the etch crucible causes the reduction of the characteristics of luminescence.Thus, preferably use the crucible of pottery such as aluminum oxide system.
Ca
3N
2：5.44g
Mg
3N
2：0.43g
Si
3N
4：6.05g
SiO
2：7.43g
Eu
2O
3：0.67g
Then, under the condition identical, mix this raw material, burn till with embodiment 1.
Embodiment 3, are the oxonitride phosphors that the Ca of embodiment 1 is replaced to Sr.Among the embodiment 3, use strontium nitride Sr
3N
4(molecular weight 290.9), the mixture ratio (mol ratio) of pressing raw material is Sr
3N
2: Si
3N
4: SiO
2: Eu
2O
3=1: 0.51: 3.02: 0.046, the fine powder pulverized powder of the following quantity of weighing.
Sr
3N
2：9.14g
Si
3N
4：4.65g
SiO
2：5.71g
Eu
2O
3：0.51g
Among the embodiment 3, under the condition identical, mix this raw material, burn till with embodiment 1.The result of the O of the oxonitride phosphor of mensuration embodiment 3 and the weight % of N in total amount, contains 15.3 weight %O and 11.2 weight %N.The weight ratio of O and N is O: N=1: 0.73.
Embodiment 4, are the oxonitride phosphors that the Ca of embodiment 2 is replaced to Sr.Among the embodiment 4, the mixture ratio (mol ratio) of pressing raw material is Sr
3N
2: Mg
3N
2: Si
3N
4: SiO
2: Eu
2O
3=1: 0.12: 0.57: 3.37: 0.052, the fine powder pulverized powder of the following quantity of weighing.
Sr
3N
2：8.46g
Mg
3N
2：0.34g
Si
3N
4：4.80g
SiO
2：5.89g
Eu
2O
3：0.53g
Under the condition identical with embodiment 1, mix this raw material, burn till.
Embodiment 5, are the oxonitride phosphors that the Ca of embodiment 1 is replaced to Ba.Among the embodiment 5, use nitrogenize barium Ba
3N
2(molecular weight 316.6), the mixture ratio (mol ratio) of pressing raw material is Ba
3N
2: Si
3N
4: SiO
2: Eu
2O
3=1: 0.76: 0.22: 0.033, the fine powder pulverized powder of the following quantity of weighing.
Ba
3N
2：11.2g
Si
3N
4：3.77g
SiO
2：4.63g
Eu
2O
3：0.42g
Under the condition identical with embodiment 1, mix this raw material, burn till.
The product that burn till of embodiment 1～5 all are crystalline powder or particle.Particle diameter is roughly 1～5 μ m.
The oxonitride phosphor of embodiment 1～5 is carried out the measurement of excitation spectrum.Measuring result shows that the wavelength side shorter than 490nm is excited strongly.
Excite the oxonitride phosphor of embodiment 1～5 with Ex=460nm.Because Ex=460nm is a blue light emitting device wavelength region may commonly used, therefore excites in this wavelength region may.As a result, the oxonitride phosphor of embodiment 1 has illuminant colour in the yellow-green colour zone of tone x=0.437 and tone y=0.545.The oxonitride phosphor of embodiment 4 has illuminant colour in the yellow-green colour zone of tone x=0.351 and tone y=0.614.Whole in the oxonitride phosphor of embodiment 1～5 show the luminous efficiency than in the past fluorescence height.
Excite the oxonitride phosphor of embodiment 1～5 with Ex=400nm.The oxonitride phosphor of embodiment 1 has illuminant colour in the yellow-green colour zone of tone x=0.434 and tone y=0.543.The oxonitride phosphor of embodiment 3 has illuminant colour in the yellow-green colour zone of tone x=0.349 and tone y=0.608.The oxonitride phosphor of embodiment 1～5 whole show the luminous efficiency than in the past fluorescence height.
In addition, temperature profile is fabulous.Temperature profile is that 100% relative brightness is represented with the luminosity under 25 ℃.Particle diameter is a value of utilizing the air penetrant method be called F.S.S.S.No. (Fisher Sub Sieve Sizer ' s No.) to draw.The temperature profile of embodiment 1～5 is 95～100% in the time of 100 ℃.In the time of 200 ℃, be 65～90%.
Measured the result of the X-ray diffraction figure of above-mentioned oxonitride phosphor, found to show that all sharp keen diffraction peak, the fluor of gained are the crystallinity compounds with systematicness.
＜embodiment 6～15 〉
The characteristic of the embodiment 6～15 of table 2 expression oxonitride phosphor of the present invention.
In addition, Fig. 8 is the figure of the luminescent spectrum of expression when exciting the oxonitride phosphor of embodiment 6～10 with Ex=400nm.Fig. 9 is the figure of the luminescent spectrum figure of expression when exciting the oxonitride phosphor of embodiment 6～10 with Ex=460nm.Figure 10 is the figure of the luminescent spectrum figure of expression when exciting the oxonitride phosphor of embodiment 11～15 with Ex=400nm.Figure 11 is the figure of the luminescent spectrum figure of expression when exciting the oxonitride phosphor of embodiment 11～15 with Ex=460nm.Figure 12 is the figure of excitation spectrum of the oxonitride phosphor of expression embodiment 11～15.Figure 13 is the figure of reflection spectrum of the oxonitride phosphor of expression embodiment 11～15.
Table 2
Embodiment 6～10th,, with general formula Sr
xCa
(1-x)Si
2O
2N
2: the oxonitride phosphor of Eu (0≤X≤1) expression, make by the mol ratio that changes Sr and Ca.
Embodiment 6～10, with the roughly the same condition of embodiment 1 under carry out the manufacturing of oxonitride phosphor.Raw material uses Sr
3N
2, Ca
3N
2, Si
3N
4, SiO
2And Eu
2O
3Behind this raw material of quantity weighing in accordance with regulations, in nitrogen atmosphere, in the ball case, mix Sr
3N
2, Ca
3N
2, Si
3N
4, SiO
2And Eu
2O
3To even.In embodiment 6～15, Eu concentration is 0.43mol%.
Mix above-claimed cpd, in ammonia atmosphere, mixture is dropped into boron nitride crucible, under about 1450 ℃, burnt till about 5 hours.
Thus, manufacturing is as the oxonitride phosphor of target.
The luminosity of embodiment 6～10 and quantum yield are to be benchmark with embodiment 6, represent with relative value.
This result shows, with near light source activation embodiment 6～10 the 400nm o'clock, when mixing Sr and Ca, compares when only using Ca, shows high luminosity and quantum yield.On the other hand, with near light source activation embodiment 6～10 the 460nm o'clock, at Sr: Ca=7: 3 o'clock, luminous efficiency was the highest.In addition, by replacing portion C a,, can improve luminous efficiency along with increasing Sr.In addition, can recently make tonal variation by the mole that changes Sr and Ca.
Embodiment 11～15, are with Sr
xCa
(10-x)Si
2O
2N
2: the oxonitride phosphor of Eu (0≤X≤10) expression, make by the mol ratio that changes Sr and Ca.
Embodiment 11～15, with the roughly the same condition of embodiment 1 under carry out the manufacturing of oxonitride phosphor.Raw material uses Sr
3N
2, Ca
3N
2, Si
3N
4, SiO
2And Eu
2O
3Behind this raw material of quantity weighing in accordance with regulations, under nitrogen atmosphere, in the ball case, mix Sr
3N
2, Ca
3N
2, Si
3N
4, SiO
2And Eu
2O
3To even.In embodiment 6～15, Eu concentration is 0.43mol%.
Mix above-claimed cpd, in ammonia atmosphere, mixture is dropped in the boron nitride crucible, under about 1550 ℃, burnt till about 5 hours.
Thus, manufacturing is as the oxonitride phosphor of target.
The luminosity of embodiment 11～15 and quantum yield are to be benchmark with embodiment 15, represent with relative value.
This result shows, with near light source activation embodiment 11～15 the 400nm o'clock, when mixing Sr and Ca, compares with only with Sr the time, shows high luminosity and quantum yield.In addition, the mol ratio as Sr: Ca is Sr: Ca=6: 4～9: in the time of 1, can improve luminous efficiency.Especially, at Sr: Ca=7: 3～8: 2 o'clock, luminosity and quantum yield all showed high value.And then, by changing the mol ratio of Sr and Ca, can change tone.
＜embodiment 16～20 〉
The characteristic of the oxonitride phosphor of table 3 expression embodiments of the invention 10,16～20.
In addition, Figure 14 is the figure of the luminescent spectrum of expression when exciting the oxonitride phosphor of embodiment 10,16～20 with Ex=400nm.Figure 15 is the figure of the luminescent spectrum of expression when exciting the oxonitride phosphor of embodiment 10,16～20 with Ex=460nm.Figure 16 is the figure of excitation spectrum of the oxonitride phosphor of expression embodiment 10,16～20.Figure 17 is the figure of reflection spectrum of the oxonitride phosphor of expression embodiment 10,16～20.
Table 3
Mix above-claimed cpd, in ammonia atmosphere, mixture is dropped into boron nitride crucible, under about 1450 ℃, burnt till about 5 hours.
Thus, manufacturing is as the oxonitride phosphor of target.
This result shows, when with near the light source activation embodiment 400nm, the 460nm 10,16～20, and by Sr: Ba=2: 8 compare when mixing, and are pressing Sr: Ba=6: 4～8: during 2 mixing, show high luminosity and quantum yield.In addition, by replacing the part of Ba,, can improve luminous efficiency along with increasing Sr.In addition, by changing the mol ratio of Sr and Ca, can change tone.And then, the BaSi of embodiment 20
2N
2O
2: Eu, near 496nm, have the glow peak wavelength, show high luminous efficiency.By using the oxonitride phosphor of embodiment 20, can improve the color developing of white color system light-emitting device.
＜embodiment 21～24 〉
The characteristic of the embodiment 21～24 of table 4 expression oxonitride phosphor of the present invention.
In addition, Figure 18 is the figure of the luminescent spectrum of expression when exciting the oxonitride phosphor of embodiment 21～24 with Ex=400nm.Figure 19 is the figure of the luminescent spectrum of expression when exciting the oxonitride phosphor of embodiment 21～24 with Ex=460nm.Figure 20 is the figure of excitation spectrum of the oxonitride phosphor of expression embodiment 21～24.Figure 21 is the figure of reflection spectrum of the oxonitride phosphor of expression embodiment 21～24.
Table 4
Embodiment 21～24 is with Ca
xBa
(1-x)Si
2O
2N
2: Eu (0≤X≤1) expression, make by the mol ratio that changes Ca and Ba.
Embodiment 21～24, with the roughly the same condition of embodiment 1 under carry out the manufacturing of oxonitride phosphor.Raw material uses Ca
3N
2, Ba
3N
2, Si
3N
4, SiO
2And Eu
2O
3Behind this raw material of quantity weighing in accordance with regulations, in nitrogen atmosphere, in the ball case, mixed C a
3N
2, Ba
3N
2, Si
3N
4, SiO
2And Eu
2O
3To even.In embodiment 21～24, Eu concentration is 0.43mol%.
Mix above-claimed cpd, in ammonia atmosphere, mixture is dropped in the boron nitride crucible, under about 1450 ℃, burnt till about 5 hours.
Thus, manufacturing is as the oxonitride phosphor of target.
Embodiment 21～24, and its luminosity and quantum yield are benchmark with embodiment 21, represent by relative value.
This result shows, with near light source activation embodiment 21～24 the 400nm o'clock, and by Ca: Ba=4: 6 compare when mixing, and press Ca: Ba=8: high luminosity and the quantum yield of demonstration during 2 mixing.On the other hand, with near light source activation embodiment 21～24 the 460nm o'clock, and by Ca: Ba=2: 8 compare when mixing, and press Ca: Ba=8: high luminosity and the quantum yield of demonstration during 2 mixing.In addition, can change tone by the mol ratio that changes Ca and Ba.
＜embodiment 25～27 〉
Oxonitride phosphor to embodiment 25～27 has carried out structural analysis.Embodiment 25 consists of CaSi
2O
2N
2Embodiment 26 consists of SrSi
2O
2N
2Embodiment 27 consists of BaSi
2O
2N
2Figure 22 is the rhombic sketch of expression.Figure 23 is the figure of X-ray diffraction pattern of the oxonitride phosphor of expression embodiment 25.Figure 24 is the figure of X-ray diffraction pattern of the oxonitride phosphor of expression embodiment 26.Figure 25 is the figure of X-ray diffraction pattern of the oxonitride phosphor of expression embodiment 27.
This result shows that the crystalline unit cell of oxynitriding system fluor belongs to rhombic system.Rhombic system is a ≠ b ≠ c, α=β=γ=90 °, has 3 of orthogonal 2 symmetry axis, or 2 symmetrical planes that intersect with 2 symmetry axis.
＜embodiment 28: light-emitting device 〉
Adopt above-mentioned oxonitride phosphor, make the light-emitting device (Fig. 1) of embodiment 28.As excitation light source, use the luminous element of luminescent spectrum with 400nm.Use the CaSi of embodiment 1 as fluor
2O
2N
2: Eu, Ca
2Si
5N
8: Eu and (Ca
0.93, Eu
0.05, Mn
0.02)
10(PO
4)
6Cl
2Figure 26 is the orthographic plan of expression luminous element of the present invention.Figure 27 is the sectional view of the A-A ' of expression luminous element of the present invention.Figure 28 is the figure of luminescent spectrum of the light-emitting device of expression embodiments of the invention 28.Figure 29 is the figure of tristimulus coordinates of the light-emitting device of expression embodiments of the invention 28.
Below, the luminous element of detailed description embodiment 28.
(luminous element)
To be placed in the reaction vessel of MOVPE by the substrate 201 that sapphire (C face) constitutes,,, carry out the clean of substrate 201 Yi Bian the temperature of substrate 201 is elevated to about 1050 ℃ Yi Bian hydrogen is flowed.
Here, in embodiment 28,, use sapphire substrate, but, also can use nitride semiconductor base plates such as the dissimilar substrate different, AlN, AlGaN and GaN with nitride semiconductor base plate as substrate 201 as substrate 201.As dissimilar substrate, for example, can use with any one side in C face, R face and the A face as the sapphire of interarea and spinel (as MgAl
2O
4Such insulativity substrate), SiC (comprising 6H, 4H and 3C), ZnS, ZnO, GaAs, Si and can make nitride semiconductor growing with nitride-based semiconductor lattice coordinate oxide substrate etc. and different baseplate material with nitride-based semiconductor.As preferred dissimilar substrate, enumerate sapphire and spinel.In addition, dissimilar substrate also can be chamfered (off angle), and is in such cases, if adopt step-like substrate of chamfering, owing to the substrate layer 202 that is made of gan can crystallinity be grown well, therefore preferred.In addition, under the situation of using dissimilar substrate, after also can on dissimilar substrate, making the nitride semiconductor growing of the substrate layer 202 before becoming component structure and forming, methods such as utilization grinding are removed dissimilar substrate, monomer substrate as nitride-based semiconductor forms component structure, in addition, also can be the method for removing dissimilar substrate behind the component structure forming.Except that the GaN substrate, also can use the substrate of nitride-based semiconductors such as AlN.
(buffer layer)
Then, make the temperature of substrate 201 drop to 510 ℃, use hydrogen, use ammonia and TMG (trimethyl-gallium), on substrate 201, make the thickness growth (not shown) of the buffer layer that constitutes by GaN with about 100 dusts as unstripped gas as vector gas.
(substrate layer)
After buffer growth, only stop TMG, the temperature of substrate 201 is elevated to 1050 ℃.As reach 1050 ℃, and same, as unstripped gas, use TMG, ammonia, make of the thickness growth of unadulterated GaN layer with 2 μ m.
(n type layer)
Then, under 1050 ℃, use TMG, ammonia equally, use silane gas, make by with 4.5 * 10 as foreign gas as unstripped gas
18/ cm
3The n type layer 203 that the GaN of doping Si constitutes, press thickness 3 μ m and is grown as n type layer with the n side contact layer that forms n lateral electrode 211a.
(active coating)
Make the thickness growth with 50 dusts of barrier layer that the GaN by doping Si constitutes, then, making temperature is 800 ℃, uses TMG, TMI and ammonia, makes by unadulterated In
0.1Ga
0.7The trap layer that N constitutes is with the thickness growth of 50 dusts.Then, press barrier layer+trap layer+barrier layer+trap layer ... the order of+barrier layer, 4 layers of barrier layer of alternative stacked and 3 layers of trap layer, making by total film thickness is active coating 204 growths that the multiple quantum trap structure of 350 dusts constitutes.
(p side current carrier sealer coat)
Then, use TMG, TMA, ammonia and Cp
2Mg (cyclopentadienyl magnesium) makes by with 5 * 10
19/ cm
3The Al of doped with Mg
0.3Ga
0.7The p side current carrier sealer coat that N constitutes is with the thickness growth of 100 dusts.
(1p type layer)
Then, use TMG, ammonia and Cp
2Mg, the 1p type layer 206 that the GaN by doped p type impurity is constituted is grown with thickness 0.1 μ m.
(2p type layer)
As 2p type layer, form the p side contact layer 208 that forms p lateral electrode 210 from the teeth outwards.P side contact layer 208, on current-diffusion layer 207, by the thickness of 150 dusts, growth is with 1 * 10
20/ cm
3The p type GaN of doped with Mg.Because p side contact layer 208 is the layers that form p lateral electrode 210, therefore is preferably formed 1 * 10
17/ cm
3Above high carrier concentration.If be lower than 1 * 10
17/ cm
3, the tendency that is difficult to obtain with the good ohmic of electrode is then arranged.In addition, if the composition of contact layer is defined as GaN, just can obtain good ohmic easily with electrode materials.
After the reaction that finish to form the said elements structure, temperature is dropped to room temperature, then, in nitrogen atmosphere, wafer in reaction vessel, is annealed with 700 ℃, make p type layer low resistanceization more.From device, take out the wafer that forms component structure, implement electrode forming process by following explanation.
After annealing, from reactor, take out wafer, on the surface of the p of the superiors side contact layer 208, form the mask of regulation, install with RIE (reactive ion etching), carry out etching from p side contact layer 208 sides, expose the surface of n side contact layer, form electrode forming surface.
As p lateral electrode 210,, form the p lateral electrode 210 that constitutes by Ni/Au by with Ni, Au lamination successively.In addition, this p lateral electrode 210 becomes the Ohmic electrode of ohmic contact on 2p type layer, p side contact layer 208.At this moment, about the electrode branches 210a that forms, the width of the luminescent part 209 of strip is defined as about 5 μ m, and the width of strip electrode branches 210a is defined as about 3 μ m, alternately forms the luminescent part 209 and the electrode branches 210a of strip.In addition, on the zone that forms p side gasket electrode, only forming p lateral electrode 210 in part, and p side gasket electrode 210b is formed on the surface of p side contact layer 208 its part is being formed to cross over p lateral electrode 210 tops, formation conducts.At this moment, the surface of the p side contact layer 208 of p side gasket electrode 210b is set, not with p lateral electrode 210 and p side contact layer 208 ohmic contact, form Schottky barrier at the two, forming electric current does not directly flow to element internal from the formation portion of p side gasket electrode 210b, and, electric current is injected into the structure of element internal via the electrode branches 210a that is electrically connected.
Then, expose the exposing on the face 203a of n type layer 203, forming n lateral electrode 211a.N lateral electrode 211a forms by stacked Ti and Al.
Herein, n lateral electrode 211a becomes the Ohmic electrode that expose face 203a of ohmic contact at n type layer 203.Behind the p lateral electrode 210 that forms ohm usefulness, n lateral electrode 211a, use heat-treatment of annealing, make each electrode ohmic contact.The Ohmic electrode of the p side that obtain this moment becomes the luminous opaqueness film that does not roughly see through active coating 204.
Then, remove above-mentioned p lateral electrode 210 and n lateral electrode 211a one one or whole surface all on, promptly n type layer 203 expose face 203a and this expose the element surfaces such as side of face 203a all on, form by SiO
2The insulation film that constitutes.After forming insulating film, on the surface of p lateral electrode of exposing from insulating film 210 and n lateral electrode 211a, form the gasket electrode that engages usefulness respectively, itself and each ohm are led to electrode conductance.P side gasket electrode 210b, n side gasket electrode 211b form respectively by electrode superimposed layer Ni, Ti and Au in each ohm usefulness.
At last, by cutting substrate 201, obtain the luminous element of a length of side 300 μ m.
The luminous element that obtains, its glow peak wavelength is about 400nm.
The characteristic of the light-emitting device of embodiment 28 is listed in table 5.
Table 5
| Electric current I f (mA) | Voltage Vf (V) | Radiometric analysis Radiometric (mW) | Photometric measurement Photometric (lm) | The long Peak of spike (nm) | |
| Light-emitting |
20 | 3.4 | 6.2 | 1.84 | 464 |
| Tone x | Tone y | Colour temperature Tcp (K) | Average color developing Ra | Lamp efficient (lm/W) |
| 0.356 | 0.368 | 4690 | 82.2 | 27.1 |
Thus, the light-emitting device of embodiment 28 demonstrates illuminant colour at white portion.The light-emitting device of embodiment 28 is presented at 360～430nm, and 430～500nm and 500～730nm place have the luminescent spectrum of glow peak wavelength.More specifically, demonstrate at 390～410nm, 455～475nm and 550～600nm place have the luminescent spectrum of glow peak wavelength.The luminous element institute excited fluorescent body that is excited with 400nm, the CaSi of embodiment 1
2O
2N
2: Eu is that the zone has glow peak wavelength, Ca in green
2Si
5N
8: Eu has glow peak wavelength, (Ca from yellow to the red colour system zone
0.93, Eu
0.05, Mn
0.02)
10(PO
4)
6Cl
2Has the glow peak wavelength at blue region.The colour mixture of the light by these fluor can show illuminant colour in the white color system zone.By changing the use level of these fluor, can send the white light of multiple color tones.Therefore, under the situation of the light-emitting device of making the white light with regulation as excitation light source employing UV-light, a kind by the change fluor, proportioning etc. just can change illuminant colour.
＜embodiment 29: light-emitting device 〉
The light-emitting device of embodiment 29 is to use the white light emitting device that has the luminous element of glow peak wavelength at the 460nm place as excitation light source.The light-emitting device of embodiment 29 also has structure shown in Figure 1.
That is, the light-emitting device of embodiment 29 on sapphire substrate 1, forms the semiconductor layer 2 of the GaN layer of n type and p type, on the semiconductor layer 2 of this n type and p type electrode 3 is set, and this electrode 3 is electrically connected with lead frame 13 by conductor wire 14.The top of light-emitting device 10 is covered by fluor 11 and application member 12, covers the periphery of lead frame 13, fluor 11 and application member 12 etc. with moulding part 15.Semiconductor layer 2 is by n on sapphire substrate 1
+The order lamination of GaN:Si, n-AlGaN:Si, n-GaN, GaInNQWs, p-GaN:Mg, p-AlGaN:Mg and p-GaN:Mg forms.This n of etching
+The part of GaN:Si layer forms n type electrode.On this p-GaN:Mg layer, form P type electrode.Lead frame 13 uses ferruginous copper.On the top that lead-in wire 13a is installed, the cup-shaped portion that is provided for carrying light-emitting device 10, on the bottom surface of the substantial middle portion of this cup-shaped portion, engaging has this luminous element 10.As conductor wire 14, use gold, in the projection 4 that is used for electrode electrically connected 3 and conductor wire 14, implement plating Ni.As application member 12, use in accordance with regulations mixed Resins, epoxy and the mixture of diffusant, barium titanate, titanium oxide and described fluor 11.Moulding part 15 adopts Resins, epoxy.The light-emitting device 1 of this bullet cut, for the radius of moulding part 15 is 2～4mm, the top of highly about 7～10mm is the round tube type of dome-type.
If electric current flows in the light-emitting device of embodiment 29, it is just luminous roughly to have a blue light emitting device 10 of glow peak wavelength at 460nm.Cover the fluor 11 of semiconductor layer 2, this blue light is carried out tone reversal.The light-emitting device of the embodiment 29 that emits white light can be provided as a result.
The fluor 11 of the light-emitting device of embodiments of the invention 29 adopts and to have mixed the oxonitride phosphor of embodiment 1 and with CaSrSi
5N
8: the fluor 11 of the nitride phosphor that Eu represents.This fluor 11 together mixes with application member 12.
The light-emitting device of embodiment 29 is through a part of light of luminous element 10.In addition, the part light excited fluophor 11 of luminous element 10, this fluor 11 carries out wavelength Conversion, sends the green of oxonitride phosphor and the yellow red light to redness of nitride phosphor.The yellow red light to red light that the blue light that sends by these luminous elements 10, the green light that oxonitride phosphor sends and nitride phosphor send mixes, and the light-emitting device that emits white light can be provided.
＜embodiment 30: light-emitting device 〉
Figure 30 is the diagram of light-emitting device of the cup-shaped portion formula of expression embodiments of the invention 30.
In Figure 30 of light-emitting device of expression embodiment 30, to the identical additional prosign of parts of parts of the light-emitting device of embodiment 28, and omit its explanation.Luminous element 10 uses the luminous element that has the glow peak wavelength at the 400nm place.
The light-emitting device of embodiment 30 is by on the surface of the light-emitting device moulding part 15 of embodiment 28, covers by the cover 16 that fluor (not shown) dispersive photopermeability resin is constituted to constitute.
On the top that lead-in wire 13a is installed, be provided for the cup-shaped portion of element mounted 10, on the bottom surface of the substantial middle portion of this cup-shaped portion, engaging has this luminous element 10.In the light-emitting device of embodiment 30, the mode on the top of this cup-shaped portion with covering luminous element 10 is provided with fluor 11, but in the light-emitting device of embodiment 30, also can only contain fluor in cover 16.If fluor 11 is not set on luminous element 10, fluor just can directly not be subjected to the influence of the heat of luminous element 10 generations.
In cover 16, further fluor is dispersed in the photopermeability resin.The photopermeability resin that will contain this fluor is configured as the shape chimeric with the shape of moulding part 15.Perhaps, also can adopt after the photopermeability resin that will contain fluor injects in the molding box of regulation, this light-emitting device 1 is pressed in this molding box the manufacture method that forms.Concrete material as cover 16 photopermeability resin can adopt Resins, epoxy, urea resin and silicone resin equitemperature characteristic and the good transparent resin of weathering resistance, silicon sol, glass and inorganic adhesive etc.Except that above-mentioned resin, also can use thermosetting resins such as melamine resin, resol.In addition, also can use thermoplastic resins such as polyethylene, polypropylene, polyvinyl chloride and polystyrene, thermoplastic elastomers such as styrene-butadiene block copolymer and section polyurethane(s).In addition, also can together contain diffusant, barium titanate, titanium oxide, aluminum oxide etc. with fluor.In addition, also can contain photostabilizer and tinting material.Contained fluor in the cover 16 uses Ca
2Si
5N
8: the oxonitride phosphor of Eu and (Ca
0.95, Eu
0.05)
10(PO
4)
6Cl
2Fluor.The interior used fluor 11 of cup-shaped portion of lead-in wire 13a is installed, is used the oxonitride phosphor of embodiment 3.But, owing to use fluor in 16, therefore also can form oxonitride phosphor is contained in the cover 16 at cover, in the cup-shaped portion that lead-in wire 13a is installed, only form the structure of application member 12.
Like this in the light-emitting device of Gou Chenging, the oxonitride phosphor of the part optical excitation fluor 11 that is sent by luminous element 10 sends green light by oxonitride phosphor.In addition, the part light that is sent by luminous element 10 or by the part light that oxonitride phosphor sends excites the fluor of cover 16, sends blue and yellow to red light.Thus, the blueness of the green light of oxonitride phosphor and cover 16 fluor and yellowly mix to red light, the result from covering 16 surface, sends the light of white color system to the outside.
Following embodiment 31～79 is respectively the embodiment of relevant oxonitride phosphor of the present invention.
＜embodiment 31～56 〉
The characteristic of table 6 expression oxonitride phosphor embodiment 31～56 of the present invention.
In addition, Figure 32 is the figure of the variation of the luminous efficiency of expression when changing the content of contained activator R in the composition of oxonitride phosphor.Excitation light source is near the light the 400nm.Figure 33 is the figure that the luminous efficiency of expression when changing the content of contained activator R in the composition of oxonitride phosphor changes.Excitation light source is near the light the 460nm.Figure 34 is the XYZ chromaticity diagram of the tonal variation of expression when changing the content of contained activator R in the composition of oxonitride phosphor.Figure 35 is the XYZ chromaticity diagram of the amplification of Figure 34.Figure 36 is the figure of the luminescent spectrum of expression when exciting oxonitride phosphor with Ex=400nm.Figure 37 is the figure of the luminescent spectrum of expression when exciting oxonitride phosphor with Ex=460nm.Figure 38 is the figure of the standardized excitation spectrum of expression oxonitride phosphor.Figure 39 is the figure of the reflection spectrum of expression oxonitride phosphor.Figure 40 A is the SEM photo of 1000 times of amplifications of the oxonitride phosphor of embodiment 36, Figure 40 B is the SEM photo of 5000 times of amplifications of the oxonitride phosphor of embodiment 36, and Figure 40 C is the SEM photo of 10000 times of amplifications of the oxonitride phosphor of embodiment 36.
Table 6
Embodiment 31～56, are SrSi
2O
2N
2: Eu.During near using 400nm excitation light source irradiation embodiment 31～56, the embodiment 36 the highest with luminosity, energy efficiency and quantum yield is benchmark, represents luminosity, energy efficiency and the quantum yield of other embodiment with its relative value.During near using 460nm excitation light source irradiation embodiment 31～56, the embodiment 43 the highest with luminosity is benchmark, represents the luminosity of other embodiment with its relative value.In addition, be benchmark with energy efficiency and the highest embodiment 45 of quantum yield, represent energy efficiency and the quantum yield of other embodiment with its relative value.
At first, raw material uses Sr
3N
2, Si
3N
4, SiO
2And Eu
2O
3This raw material separated pulverizing to 0.1 is to 3.0 μ m.After the pulverizing, measure weighing among the embodiment 31～56 in accordance with regulations.Because the part of Sr is replaced by Eu, so oxonitride phosphor is with Sr
(1-x)Eu
xSi
2O
2N
2: Eu (0＜X＜1) expression.
After the above-mentioned quantity of weighing, under nitrogen atmosphere, in the ball case, the Sr of uniform mixing specified amount
3N
2, Si
3N
4, SiO
2And Eu
2O
3
In embodiment 35, the mixture ratio of raw material (mol ratio) is Sr
3N
2: Si
3N
4: SiO
2: Eu
2O
3Be Sr: Si: O: Eu=0.97: 2: 2: 0.03.To reach the mode of this mixture ratio, weighing Sr
3N
2, Si
3N
4, SiO
2And Eu
2O
3, mix.Among the embodiment 31～56,, change Sr in the mode of the mol ratio that reaches regulation
(1-x)Eu
xSi
2O
2N
2Sr concentration and the proportioning of Eu.The proportioning of Eu is represented the mol ratio of Eu in the table.
Mix above-claimed cpd, in nitrogen atmosphere, mixture is dropped in the boron nitride crucible, under about 1500 ℃, carry out burning till in 5 hours.
Thus, obtain oxonitride phosphor as target.The theory that is obtained by material fiting ratio of gained oxonitride phosphor consists of Sr
(1-x)Eu
xSi
2O
2N
2(0＜X＜1).
The result of the O of the oxonitride phosphor of measurement embodiment 35 and the weight % of N in the total amount, contains 15.3 weight %O and 10.1 weight %N.The weight ratio of O and N is O: N=1: 0.66.
For the oxonitride phosphor of embodiment 31～56, adopt boron nitride material crucible, under ammonia atmosphere, burn till.About crucible, not too preferably use metal system crucible.This is because for example, under the situation of using Mo system crucible, this crucible of etch causes the reduction of the characteristics of luminescence easily.Therefore, preferably use the crucible of pottery such as aluminum oxide system.
The product that burn till of embodiment 31～56 all are crystalline powder or particle.Particle diameter is approximately 1～5 μ m.
Measure the excitation spectrum of the oxonitride phosphor of embodiment 31～56.Measurement result shows, is excited strongly at 290nm～490nm place.
Excite the oxonitride phosphor of embodiment 31～56 with Ex=400nm.The oxonitride phosphor of embodiment 31 has illuminant colour in the yellow-green colour zone of tone x=0.333 and tone y=0.614.The oxonitride phosphor of embodiment 36 has illuminant colour in the yellow-green colour zone of tone x=0.356 and tone y=0.604.On tristimulus coordinates, if increase the proportioning of Eu, tone x will move to right-hand, and tone y will move downwards.About luminosity, if increase the proportioning of Eu, luminosity will improve gradually, and in embodiment 36, luminosity is the highest.If further increase the proportioning of Eu, luminosity will descend.On the other hand, about quantum yield, if increase the proportioning of Eu, quantum yield will improve gradually, and in embodiment 36, quantum yield is the highest.If further increase the proportioning of Eu, quantum yield will descend.Here, embodiment 31～47, can provide to keep high luminous efficiency and high quantum yield, the oxonitride phosphor that has specified hue simultaneously.
Excite the oxonitride phosphor of embodiment 31～56 with Ex=460nm.Because Ex=460nm is a blue based light-emitting device wavelength zone commonly used, therefore excites with this wavelength zone.As a result, the oxonitride phosphor of embodiment 31 has illuminant colour in the yellow-green colour zone of tone x=0.334 and tone y=0.623.In tristimulus coordinates, if increase the proportioning of Eu, tone x will move to right-hand, and tone y will move downwards.The oxonitride phosphor of embodiment 43 has illuminant colour in the yellow-green colour zone of tone x=0.400 and tone y=0.578.In addition, if increase the proportioning of Eu, luminosity will improve gradually, and in embodiment 43, luminosity is the highest.If further increase the proportioning of Eu, luminosity will descend.On the other hand, about quantum yield, if increase the proportioning of Eu, quantum yield will improve gradually, and in embodiment 45, quantum yield is the highest.If further increase the proportioning of Eu, quantum yield will descend.Here, embodiment 32～51, can provide to keep high luminosity and high quantum yield, the oxonitride phosphor that has specified hue simultaneously
In addition, the temperature profile of the oxonitride phosphor of embodiment 31～56 is fabulous.Temperature profile is to be that 100% relative brightness is represented with the luminosity under 25 ℃.Particle diameter is a value of utilizing the air penetrant method be called F.S.S.S.No. (Fisher Sub Sieve Sizer ' s No.) to obtain.The temperature profile of embodiment 31～56 is more than 85% in the time of 100 ℃.In the time of 200 ℃, be more than 55%.
Measured the X-ray diffractogram of above-mentioned these oxonitride phosphors, the result shows, all shows sharp keen diffraction peak, and the gained fluor is the crystalline compound with systematicness.This crystalline texture is iris.
＜embodiment 57～70 〉
The characteristic of the embodiment 57～70 of table 7 expression oxonitride phosphor of the present invention.
In addition, Figure 41 is the figure that the luminous efficiency of expression when changing the content of contained activator R in the composition of oxonitride phosphor changes.Excitation light source is near the light the 400nm.Figure 42 is the figure that the luminous efficiency of expression when changing the content of contained activator R in the composition of oxonitride phosphor changes.Excitation light source is near the light the 460nm.Figure 43 is the XYZ chromaticity diagram of the tonal variation of expression when changing the content of contained activator R in the composition of oxonitride phosphor.Figure 44 is the XYZ chromaticity diagram of amplifying Figure 43.Figure 45 is the figure of the luminescent spectrum of expression when exciting oxonitride phosphor with Ex=400nm.Figure 46 is the figure of the luminescent spectrum of expression when exciting oxonitride phosphor with Ex=460nm.Figure 47 is the figure of the standardized excitation spectrum of expression oxonitride phosphor.Figure 48 is the figure of the reflection spectrum of expression oxonitride phosphor.
Table 7
| Eu proportioning x | Peak intensity | Luminosity Y (%) | Energy efficiency E (%) | Quantum yield Q (%) | |
| Embodiment 57 | 0.01 | 99.3 | 99.4 | 98.7 | 98.5 |
| Embodiment 58 | 0.02 | 100.0 | 100.0 | 100.0 | 100.0 |
| Embodiment 59 | 0.03 | 94.3 | 94.1 | 94.6 | 95.0 |
| |
0.06 | 76.8 | 76.5 | 78.7 | 79.6 |
| Eu proportioning x | Peak intensity | Luminosity Y (%) | Energy efficiency E (%) | Quantum yield Q (%) | |
| Embodiment 61 | 0.09 | 70.0 | 69.5 | 72.7 | 74.1 |
| |
0.12 | 73.1 | 72.7 | 77.2 | 78.8 |
| Embodiment 63 | 0.15 | 74.0 | 72.9 | 77.2 | 79.0 |
| Embodiment 64 | 0.2 | 79.2 | 77.1 | 81.7 | 83.7 |
| Embodiment 65 | 0.3 | 80.2 | 76.6 | 82.0 | 84.3 |
| Embodiment 66 | 0.4 | 71.3 | 67.8 | 76.0 | 79.0 |
| Embodiment 67 | 0.5 | 69.4 | 65.4 | 76.2 | 79.9 |
| Embodiment 68 | 0.6 | 48.7 | 45.1 | 51.7 | 53.9 |
| |
0.7 | 49.4 | 45.8 | 51.9 | 54.1 |
| |
0.8 | 28.7 | 26.9 | 30.2 | 31.4 |
Embodiment 57～70, are to use CaSi
2O
2N
2: the oxonitride phosphor that Eu represents.In near excitation light source irradiation embodiment 57～70 o'clock of adopting the 400nm, the embodiment 58 the highest with luminosity, energy efficiency and quantum yield is benchmark, represents luminosity, energy efficiency and the quantum yield of other embodiment with its relative value.In near excitation light source irradiation embodiment 57～70 o'clock of adopting the 460nm, the embodiment 65 the highest with luminosity, energy efficiency and quantum yield is benchmark, represents luminosity, energy efficiency and the quantum yield of other embodiment with its relative value.
As raw material, use Ca
3N
2, Si
3N
4, SiO
2And Eu
2O
3Adopt these raw materials, and the identical manufacture method of utilization and embodiment 31, carry out the manufacturing of the oxonitride phosphor of embodiment 57～70.So that reaching the mode of regulation mol ratio, makes this raw material.The theory of gained oxonitride phosphor consists of Ca
(1-x)Eu
xSi
2O
2N
2(0＜X＜1).A replaces with Eu with portion C.The proportioning of Eu is represented the mol ratio of Eu in the table.
O and N weight % in the oxonitride phosphor of mensuration embodiment 58, the result contains 19.5 weight %O and 17.5 weight %N in total amount.The weight ratio of O and N is O: N=1: 0.90.
The product that burn till of embodiment 57～70 all are crystalline powder or particle.Particle diameter is approximately 1～8 μ m.
Measure the excitation spectrum of the oxonitride phosphor of embodiment 57～70.Measurement result shows, is excited strongly at 290nm～520nm place.
Excite the oxonitride phosphor of embodiment 57～70 with Ex=400nm.The oxonitride phosphor of embodiment 58 has illuminant colour in the yellow-green colour zone of tone x=0.428 and tone y=0.546.The oxonitride phosphor of embodiment 57 has illuminant colour in the yellow-green colour zone of tone x=0.422 and tone y=0.549.In tristimulus coordinates, if increase the proportioning of Eu, tone x will move to right-hand, and tone y will move downwards.Luminosity, energy efficiency, quantum yield are the highest in embodiment 58.Here, embodiment 57～67, can provide to keep high luminosity and high quantum yield, the oxonitride phosphor that has specified hue simultaneously.
Excite the oxonitride phosphor of embodiment 57～70 with Ex=460nm.Because Ex=460nm is a blue based light-emitting device wavelength zone commonly used, therefore excites with this wavelength zone.As a result, the oxonitride phosphor of embodiment 65 has illuminant colour in the yellow area of tone x=0.464 and tone y=0.524.In tristimulus coordinates, if increase the proportioning of Eu, tone x will move to right-hand, and tone y will move downwards.In addition, if increase the proportioning of Eu, luminosity, energy efficiency, quantum yield will improve gradually, and luminosity is the highest in embodiment 65.If further increase the proportioning of Eu, luminosity will descend.Here, embodiment 57～69 can provide and keep high luminosity and high quantum yield, the oxonitride phosphor that has specified hue simultaneously
Measured the X-ray diffractogram of above-mentioned these oxonitride phosphors, the result shows, all shows sharp keen diffraction peak, and the gained fluor is the crystalline compound with systematicness.This crystalline texture is iris.
＜embodiment 71～78 〉
The characteristic of the embodiment 71～78 of table 8 expression oxonitride phosphor of the present invention.
In addition, Figure 49 is the figure of the variation of the peak intensity of expression when changing the content of contained activator R in the composition of oxonitride phosphor.Excitation light source is near the light 400nm and the 460nm.Figure 50 is the figure of the variation of the luminous efficiency of expression when changing the content of contained activator R in the composition of oxonitride phosphor.Excitation light source is the light of Ex400nm.Figure 51 is the figure of the luminescent spectrum of expression when exciting oxonitride phosphor with Ex=400nm.Figure 52 is the figure of the luminescent spectrum of expression when exciting oxonitride phosphor with Ex=460nm.Figure 53 is the figure of the standardized excitation spectrum of expression oxonitride phosphor.Figure 54 is the figure of the reflection spectrum of expression oxonitride phosphor.
Table 8
| The proportioning of Eu | Luminosity y (%) | Energy efficiency E (%) | Quantum yield Q (%) | |
| Embodiment 71 | 0.01 | 90.8 | 96.6 | 96.0 |
| Embodiment 72 | 0.02 | 100.0 | 100.0 | 100.0 |
| Embodiment 73 | 0.03 | 102.3 | 96.0 | 96.5 |
| The proportioning of Eu | Luminosity y (%) | Energy efficiency E (%) | Quantum yield Q (%) | |
| Embodiment 74 | 0.04 | 95.7 | 92.1 | 92.6 |
| Embodiment 75 | 0.05 | 102.9 | 92.9 | 94.1 |
| Embodiment 76 | 0.1 | 54.4 | 42.3 | 45.0 |
| Embodiment 77 | 0.15 | 40.3 | 23.7 | 25.5 |
| Embodiment 78 | 0.2 | 27.7 | 14.2 | 15.3 |
Embodiment 71～78th, BaSi
2O
2N
2: Eu.During near using 400nm excitation light source irradiation embodiment 71～78, be benchmark, represent peak intensity, luminosity, energy efficiency and the quantum yield of other embodiment with its relative value with embodiment 72.During near using 460nm excitation light source irradiation embodiment 71～78, be benchmark, represent the peak intensity of other embodiment with its relative value with embodiment 72.
As raw material, use Ba
3N
2, Si
3N
4, SiO
2And Eu
2O
3Adopt these raw materials, and the identical manufacture method of utilization and embodiment 31, carry out the manufacturing of the oxonitride phosphor of embodiment 71～78.So that reaching the mode of regulation mol ratio, makes this raw material.The theory of gained oxonitride phosphor consists of Ba
(1-x)Eu
xSi
2O
2N
2(0＜X＜1).Part Ba replaces with Eu.The proportioning of Eu is represented the mol ratio of Eu in the table.
O and N weight % in the oxonitride phosphor of mensuration embodiment 72, the result contains 11.3 weight %O and 10.6 weight %N in total amount.The weight ratio of O and N is O: N=1: 0.94.
The product that burn till of embodiment 71～78 all are crystalline powder or particle.Particle diameter is approximately 1～8 μ m.
Measure the excitation spectrum of the oxonitride phosphor of embodiment 71～78.Measurement result shows, is being excited strongly to the wavelength region may longer than 480nm from 290nm.
Excite the oxonitride phosphor of embodiment 71～78 with Ex=400nm.The oxonitride phosphor of embodiment 72 has illuminant colour at the green area of tone x=0.101 and tone y=0.485.The oxonitride phosphor of embodiment 75 has illuminant colour at the green area of tone x=0.132 and tone y=0.521.In tristimulus coordinates, if increase the proportioning of Eu, tone x will move to right-hand, and tone y will be moved upward.About luminosity, the highest among the embodiment 75.About energy efficiency, quantum yield, the highest among the embodiment 72.Here, embodiment 71～75, can provide to keep high luminosity and high quantum yield, the oxonitride phosphor that has specified hue simultaneously.
Excite the oxonitride phosphor of embodiment 71～78 with Ex=460nm.Because Ex=460nm is a blue based light-emitting device wavelength zone commonly used, therefore excites with this wavelength zone.As a result, the oxonitride phosphor of embodiment 72 has the highest peak intensity.
In addition, the temperature profile of the oxonitride phosphor of embodiment 71～78 is fabulous.The temperature profile of embodiment 71～78 is more than 90% in the time of 100 ℃.In the time of 200 ℃, be more than 65%.
Measured the X-ray diffractogram of above-mentioned these oxonitride phosphors, the result shows, all shows sharp keen diffraction peak, and the gained fluor is the crystalline compound with systematicness.This crystalline texture is iris.
＜embodiment 79 〉
Figure 55 is the figure of the luminescent spectrum of expression when exciting the oxonitride phosphor of embodiment 79 with Ex=400nm.Figure 56 is the figure of the luminescent spectrum of expression when exciting the oxonitride phosphor of embodiment 79 with Ex=460nm.Figure 57 is the figure of standardized excitation spectrum of the oxonitride phosphor of expression embodiment 79.Figure 58 is the figure of reflection spectrum of the oxonitride phosphor of expression embodiment 79.Figure 59 A is the SEM photo of 1000 times of amplifications of the oxonitride phosphor of embodiment 79, and Figure 59 B is the SEM photo of 10000 times of amplifications of the oxonitride phosphor of embodiment 79.
Embodiment 79, are CaSi
2O
2N
2: Eu.
At first, as raw material, use Ca
3N
2, Si
3N
4, SiO
2And Eu
2O
3With this raw material separated pulverizing to 0.1～3.0 μ m.After the pulverizing, embodiment 79 uses the raw material of following quantity.
Ca
3N
2：6.01g
Si
3N
4：5.99g
SiO
2：7.36g
Eu
2O
3：0.66g
After the above-mentioned quantity of weighing, utilize the manufacture method identical with embodiment 31～56, make.The Eu proportioning of embodiment 79 is 0.43mol%.
In embodiment 79, the ratio of mixture of raw material (mol ratio) is Ca
3N
2: Si
3N
4: SiO
2: Eu
2O
3=1: 1.05: 3.02: 0.046.
Thus, manufacturing is as the oxonitride phosphor of target.The theory of gained oxonitride phosphor is formed, and is CaSi
2O
2N
2: Eu.
Measure the O and the N weight % of the oxonitride phosphor of embodiment 79, the result contains 18.8 weight %O and 17.1 weight %N in total amount.The weight ratio of O and N is O: N=1: 0.94.
Excite the oxonitride phosphor of embodiment 79 with Ex=400nm.The oxonitride phosphor of embodiment 79 has illuminant colour in the yellow-green colour zone of tone x=0.434 and tone y=0.543.In addition, temperature profile is fabulous.
Measured the X-ray diffractogram of above-mentioned these oxonitride phosphors, the result shows sharp keen diffraction peak as can be known, and the gained fluor is the crystallinity compound with systematicness.This crystalline texture is iris.
＜embodiment 80: light-emitting device 〉
Use above-mentioned oxonitride phosphor, make the light-emitting device of embodiment 80.As excitation light source, use the luminous element of luminescent spectrum with 400nm.As fluor, use the CaSi of embodiment 79
2O
2N
2: Eu and Ca
2Si
5N
8: Eu and (Ca
0.93, Eu
0.05, Mn
0.02)
10(PO
4)
6Cl
2The light-emitting device of embodiment 80 is a structure shown in Figure 1.Figure 26 is the orthographic plan of expression luminous element of the present invention.Figure 27 is the sectional view of the A-A ' of expression luminous element of the present invention.Figure 60 is the figure of the luminescent spectrum of expression light-emitting device 1.Figure 61 is the chromaticity diagram (JIS Z8110) of the tristimulus coordinates of expression light-emitting device 1 of the present invention.
In the light-emitting device of embodiment 80, use the luminous element identical luminous element used with the light-emitting device of embodiment 28.
The characteristic of the light-emitting device 1 of embodiment 80 is listed in table 9.
Table 9
| Electric current I f (mA) | Voltage Vf (V) | Radiometric analysis Radiometric (mW) | Photometry Photometric (lm) | The long Peak of spike (nm) | |
| Light-emitting |
20 | 3.4 | 6.2 | 1.84 | 464 |
| Tone x | Tone y | Colour temperature Tcp (K) | Average color developing Ra | Lamp efficient (lm/W) |
| 0.356 | 0.368 | 4690 | 82.2 | 27.1 |
The light-emitting device of the embodiment 80 of Gou Chenging as mentioned above, the illuminant colour in display white district.The light-emitting device of embodiment 80 is presented at the luminescent spectrum that 360～430nm, 430～500nm and 500～730nm place have the glow peak wavelength.More specifically be to be presented at the luminescent spectrum that 390～410nm, 455～475nm and 550～600nm place have the glow peak wavelength.For the luminous element institute excited fluorescent body that is excited with 400nm, the CaSi of embodiment 79
2O
2N
2: Eu is that the zone has glow peak wavelength, Ca in green
2Si
5N
8: Eu has the glow peak wavelength, is reaching (Ca to the red colour system zone from yellow
0.093, Eu
0.05, Mn
0.02)
10(PO
4)
6Cl
2Has the glow peak wavelength in blueness system and yellowish red color zone.Colour mixture by the light that produced by these fluor shows illuminant colour in the white color system zone.By changing the use level of these fluor, send white light with various tones.Therefore, when manufacturing had the light-emitting device of the white light of regulation as excitation light source employing UV-light, a kind by the variation fluor, proportioning etc. just can change illuminant colour.
＜embodiment 81: light-emitting device 〉
The light-emitting device of embodiment 81, be about use the white color system light-emitting device of the luminous element of glow peak wavelength 460nm as excitation light source, in the light-emitting device (structure of Fig. 1) of embodiment 29, remove and adopt the oxonitride phosphor that has mixed embodiment 31 to reach with CaSrSi
5N
8: beyond the fluor 11 of the nitride phosphor that Eu represents, constitute in the same manner with embodiment 29.
If electric current flows in the light-emitting device of this embodiment 81, the blue based light-emitting device 10 that roughly has the glow peak wavelength at the 460nm place is luminous.11 pairs of these blue lights of fluor that cover semiconductor layer 2 carry out tone reversal.The light-emitting device of the embodiment 81 of the coloured light that turns white can be provided as a result.
That is, in the light-emitting device of embodiment 81, a part of light transmission of luminous element 10.In addition, a part of optical excitation fluor 11 of luminous element 10, this fluor 11 carries out wavelength Conversion, sends the green of oxonitride phosphor and the yellow of nitride phosphor and arrives red light.By from the blue light of these luminous elements 10, from the green light of oxonitride phosphor with from the yellow red mixing of nitride phosphor, can provide the light-emitting device that emits white light to red light.
＜embodiment 82: light-emitting device 〉
The light-emitting device of embodiment 82 removes in the light-emitting device of embodiment 30, by beyond the following change fluor, constitutes similarly to Example 30.
That is, in the light-emitting device of embodiment 82,, recommend Ca as cover 16
2Si
5N
8: the nitride phosphor of Eu and (Ca
0.95, Eu
0.05)
10(PO
4)
6Cl
2Fluor, as the fluor 11 in the cup-shaped portion that lead-in wire 13a is installed, use the oxonitride phosphor of embodiment 33.In addition, in cover 16, also can contain all fluor similarly to Example 30.
Like this in the light-emitting device of the embodiment 82 of Gou Chenging, the oxonitride phosphor of a part of excited fluophor 11 of the light that sends from luminous element 10 sends green light.In addition, the part of the light that luminous element 10 sends, or the part of the light that sends from oxonitride phosphor excite the fluor of cover 16, send from blue and yellow to red light.Thus, the blueness of the green light of oxonitride phosphor and cover 16 fluor and yellowly mix to red light, its result sends the light of white color system from covering 16 surface to the outside.
Below, embodiment 83～87th, about the embodiment of embodiments of the present invention 6.
＜embodiment 83～87 〉
Figure 63 is the figure of the luminescent spectrum of expression when exciting the oxonitride phosphor of embodiment 83～87 with Ex=400nm.Figure 64 is the figure of the luminescent spectrum of expression when exciting the oxonitride phosphor of embodiment 83～87 with Ex=460nm.Figure 65 is the figure of excitation spectrum of the oxonitride phosphor of expression embodiment 83～87.Figure 66 is the figure of reflection spectrum of the oxonitride phosphor of expression embodiment 83～87.Figure 67 is the SEM photo of the oxonitride phosphor of embodiment 83.Figure 67 A is 1000 times a photo.Figure 67 B is 5000 times a photo.
Among the embodiment 83～87, replace part Ba, change the concentration of this Eu with Eu.Embodiment 83, are Ba
0.97Eu
0.03Si
2O
2N
2Embodiment 84, are Ba
0.95Eu
0.05Si
2O
2N
2Embodiment 85, are Ba
0.90Eu
0.10Si
2O
2N
2Embodiment 86, are Ba
0.85Eu
0.15Si
2O
2N
2Embodiment 87, are Ba
0.80Eu
0.20Si
2O
2N
2
At first, as raw material, use Ba
3N
2, Si
3N
4, SiO
2And Eu
2O
3With this raw material separated pulverizing to 0.1～3.0 μ m.After the pulverizing, among the embodiment 83, by above-mentioned composition, use the raw material of following quantity, wherein, Eu is Ba: Eu=0.97: 0.03 to the mol ratio of Ba.
Ba
3N
2：5.60g
Si
3N
4：1.88g
SiO
2：2.31g
Eu
2O
3：0.21g
After the above-mentioned quantity of weighing, mix Ba equably
3N
2, Si
3N
4, SiO
2And Eu
2O
3
After mixing above-claimed cpd, in ammonia atmosphere, mixture is dropped in the boron nitride crucible, under about 1500 ℃, carry out burning till in about 5 hours.
Thus, obtain oxonitride phosphor as target.The theory of gained oxonitride phosphor consists of BaSi
2O
2N
2: Eu.
Measure the O and the N weight % of the oxonitride phosphor of embodiment 83, the result contains 12.1 weight %O and 8.9 weight %N in total amount.The weight ratio of O and N is O: N=1: 0.74.
The oxonitride phosphor of embodiment is to use the crucible of boron nitride material, burns till and gets at ammonia atmosphere.About crucible, the metal crucible of not too preferred use.Be because under the situation of using metal crucible, the etch crucible causes the reduction of the characteristics of luminescence.Thus, preferably use the crucible of pottery such as aluminum oxide system.
Embodiment 84, are the embodiment that has changed the proportioning of Eu.It is the oxonitride phosphor that replaces part Ba with Eu.The following quantity of weighing be ground into fine powder.Wherein, Eu is Ba: Eu=0.95: 0.05 to the mol ratio of Ba.
Ba
3N
2：5.48g
Si
3N
4：1.91g
SiO
2：2.28g
Eu
2O
3：0.35g
Under the condition identical with embodiment 83, mix this raw material, burn till.
Embodiment 85, are the embodiment that has changed the proportioning of Eu.It is the oxonitride phosphor that replaces part Ba with Eu.The following quantity of weighing be ground into fine powder.Wherein, Eu is Ba: Eu=0.90: 0.10 to the mol ratio of Ba.
Ba
3N
2：5.18g
Si
3N
4：1.97g
SiO
2：2.18g
Eu
2O
3：0.69g
Under the condition identical with embodiment 85, mix this raw material, burn till.
Embodiment 86, are the embodiment that has changed the proportioning of Eu.It is the oxonitride phosphor that replaces part Ba with Eu.The following quantity of weighing be ground into fine powder.Wherein, Eu is Ba: Eu=0.85: 0.15 to the mol ratio of Ba.
Ba
3N
2：4.87g
Si
3N
4：2.03g
SiO
2：2.09g
Eu
2O
3：1.03g
Under the condition identical with embodiment 83, mix this raw material, burn till.
Embodiment 87, are the embodiment that has changed the proportioning of Eu.It is the oxonitride phosphor that replaces part Ba with Eu.The following quantity of weighing be ground into fine powder.Wherein Eu is Ba: Eu=0.80: 0.20 to the mol ratio of Ba.
Ba
3N
2：4.57g
Si
3N
4：2.10g
SiO
2：1.99g
Eu
2O
3：1.37g
Under the condition identical with embodiment 83, mix this raw material, burn till.
The product that burn till of embodiment 83～87 all are crystalline powder or particle.Particle diameter is approximately 1～5 μ m.
Characteristics of luminescence when table 10 expression excites the oxonitride phosphor of embodiment 83～87 with Ex=400nm.
Table 10
| Eu concentration (mol) | Tone x | Tone y | Luminosity (%) | Quantum yield (%) | Glow peak wavelength (nm) | |
| Embodiment 83 | 0.03 | 0.106 | 0.471 | 100.0 | 100.0 | 496 |
| Embodiment 84 | 0.05 | 0.121 | 0.481 | 85.5 | 83.9 | 498 |
| Eu concentration (mol) | Tone x | Tone y | Luminosity (%) | Quantum yield (%) | Glow peak wavelength (nm) | |
| Embodiment 85 | 0.10 | 0.247 | 0.477 | 45.2 | 40.1 | 500 |
| Embodiment 86 | 0.15 | 0.289 | 0.556 | 33.4 | 22.8 | 504 |
| Embodiment 87 | 0.20 | 0.317 | 0.599 | 23.0 | 13.7 | 536 |
Measure the excitation spectrum of the oxonitride phosphor of embodiment 83～87.Measurement result shows, example 83 to 86 at the rate of induced polarization at 370nm to 470nm place stronger near the 350nm place.
Measure the reflection spectrum of the oxonitride phosphor of embodiment 83～87.Measurement result shows that embodiment 83～87 presents high-absorbility in 290nm～470nm scope.Therefore, but high-level efficiency absorbs the light from excitation light source from 290nm to 470nm, can carry out wavelength Conversion.
As excitation light source, to the oxonitride phosphor of embodiment 83～87, near the light the irradiation Ex=400nm excites it.The oxonitride phosphor of embodiment 83 has illuminant colour at the green area of tone x=0.106 and tone y=0.471, glow peak wavelength X p=496nm.Embodiment 84, have illuminant colour at the green area of tone x=0.121 and tone y=0.481, λ p=498nm.Embodiment 85 has illuminant colour at the green area of tone x=0.247 and tone y=0.477, λ p=500nm.The oxonitride phosphor of embodiment 83～85 all presents the higher luminous efficiency of fluor than in the past.Especially, the oxonitride phosphor of embodiment 83～86 presents the luminous efficiency higher than embodiment 87.In addition, for embodiment 84～87, be 100% with luminosity and the quantum yield of embodiment 83, represent with its relative value.
The temperature profile of the oxonitride phosphor of table 11 expression embodiment 83.Temperature profile is being that 100% o'clock relative brightness is represented with 25 ℃ luminosity.Excitation light source is near the light the Ex=400nm.
Table 11
| Temperature (℃) | Luminosity (%) | Quantum yield (%) |
| 25 | 100.0 | 100.0 |
| 50 | 97.0 | 97.4 |
| 100 | 88.8 | 90.2 |
| 150 | 79.2 | 81.7 |
| 200 | 64.7 | 68.2 |
The result shows, when oxonitride phosphor is warmed up to 100 ℃, keeps the luminosity up to 88.8%, even be warmed up to 200 ℃ again, also keeps the luminosity up to 64.7%.Thus, oxonitride phosphor presents fabulous temperature profile.
Measured the X-ray diffractogram of above-mentioned these oxonitride phosphors, found that all to show sharp keen diffraction peak, the gained fluor is the crystallinity compound with systematicness.
＜embodiment 88: light-emitting device 〉
Adopt above-mentioned oxonitride phosphor, make the light-emitting device of embodiment 88.As excitation light source, be to use the luminous element of luminescent spectrum with 400nm.Specifically be, in the light-emitting device of embodiment 28, except use the BaSi of embodiment 83 as fluor 11
2O
2N
2: Eu and (Y, Gd)
3(Al, Ga)
5O
12: Ce and SrCaSi
5N
8: Eu and (Ca
0.93, Eu
0.05, Mn
0.02)
10(PO
4)
6Cl
2In addition, constitute in the same manner with embodiment 28.
Figure 68 is the figure of luminescent spectrum (simulation) of the light-emitting device of expression embodiment 88.Figure 69 is the figure of tristimulus coordinates (simulation) of the light-emitting device of expression embodiment 88～90.The light-emitting device of this embodiment 88 is adjusted colour temperature in 4000～5000K scope.
In the light-emitting device of embodiment 88, use the BaSi of embodiment 83
2O
2N
2: Eu and (Ca
0.93, Eu
0.05, Mn
0.02)
10(PO
4)
6Cl
2, and (Y, Gd)
3(Al, Ga)
5O
12: Ce and SrCaSi
5N
8: Eu, but this proportioning of change that can be suitable.Use the excitation light source of Ex=400nm, shine these fluor.These fluor absorb the light from this excitation light source, carry out wavelength Conversion, have the emission wavelength of regulation.The BaSi of embodiment 83
2O
2N
2: Eu has the glow peak wavelength at 470nm～530nm.(Ca
0.93, Eu
0.05, Mn
0.02)
10(PO
4)
6Cl
2, have the glow peak wavelength at 440～500nm.(Y, Gd)
3(Al, Ga)
5O
12: Ce has the glow peak wavelength at 500～650nm.SrCaSi
5N
8: Eu has the glow peak wavelength at 580nm～730nm.
The characteristic and the color developing of the light-emitting device of table 12 expression embodiment 88.But the characteristic of the light-emitting device of this embodiment 88 and color developing are mimic, under the situation that reality is made, cause self-absorption, think to produce wavelength offset.1 light-emitting device as a comparative example adopts the excitation light source of Ex=400nm, uses (Ca
0.93, Eu
0.05, Mn
0.02)
10(PO
4)
6Cl
2, and (Y, Gd)
3(Al, Ga)
5O
12: Ce.
Table 12
For the luminous element institute excited fluorescent body that is excited with 400nm, the BaSi of embodiment 83
2O
2N
2: Eu is that the zone has glow peak wavelength, (Ca in blue-greenish colour to green
0.93, Eu
0.05, Mn
0.02)
10(PO
4)
6Cl
2In bluish voilet to blueness is that the zone has the glow peak wavelength, (Y, Gd)
3(Al, Ga)
5O
12: Ce is that the zone has glow peak wavelength, SrCaSi at green to yellowish red color
5N
8: Eu has the glow peak wavelength in yellowish red color to red colour system zone.The colour mixture of the light by these fluor shows illuminant colour at white portion.Thus, the light-emitting device of embodiment 88 shows illuminant colour in the white color system zone.In addition, owing to use near the excitation light source of the low 400nm of visibility characteristic, therefore, can change tone easily by changing the proportioning of fluor.Especially, be in the light-emitting device at the white light shown in the comparative example 1, its evaluation number (Ra) that on average develops the color is 76.0, but the white color system light-emitting device of embodiment 88, its evaluation number (Ra) that on average develops the color reaches 88.1, and is splendid.Thus, improved color developing.In addition, (R1～R15) at nearly all colour chart, color developing all improves special colour developing evaluation number.In addition, the special colour developing evaluation number (R9) of the white color system light-emitting device shown in the comparative example 1 is-1.9, and the special colour developing evaluation number (R9) of the white color system light-emitting device of embodiment 88 is 96.1, and is splendid.This special colour developing evaluation number (R9) is the colour chart of the higher redness of chroma.Visibility efficient is to be that 100% o'clock relative value is represented with the light-emitting device with comparative example 1.
＜embodiment 89 and 90: light-emitting device 〉
(fluor in embodiment 89 and 90 the light-emitting device)
The fluor 11 that is used for the light-emitting device of embodiments of the invention 89 and 90 is oxonitride phosphors of mix embodiment 83, with (Y, Gd)
3(Al, Ga)
5O
12: the YAG fluor that Ce represents, and with CaSrSi
5N
8: the fluor of the nitride phosphor that Eu represents.This fluor 11 is mixed together with application member 12.Its proportioning can suit to change.Adopt the excitation light source of Ex=460nm to shine these fluor 11.These fluor 11 absorb the light from this excitation light source, carry out wavelength Conversion, have the emission wavelength of regulation.The BaSi of embodiment 83
2O
2N
2: Eu has the glow peak wavelength at 470nm～530nm place.(Y, Gd)
3(Al, Ga)
5O
12: Ce has the glow peak wavelength at 500～650nm place.SrCaSi
5N
8: Eu has the glow peak wavelength at 580nm～730nm place.
If electric current flows in the light-emitting device of embodiment 89 and 90, it is just luminous roughly to have a blue based light-emitting device 10 of glow peak wavelength at 460nm.In the light-emitting device of embodiment 89 and 90, a part of light transmission of luminous element 10.In addition, a part of optical excitation fluor 11 of luminous element 10 carries out wavelength Conversion, and this fluor 11 has the emission wavelength of regulation.Come the blue light of self-emission device 10 and, can provide the light-emitting device of the coloured light that turns white by these from the mixing of the light of fluor 11.
That is, cover the fluor 11 of semiconductor layer 2, the part blue light that comes self-emission device is carried out tone reversal.Its result can provide the embodiment 89 of the coloured light that turns white and 90 light-emitting device.
(characteristic of embodiment 89 and 90 light-emitting device)
Table 13 is represented the characteristic and the color developing of the light-emitting device of embodiment 89 and 90.But the characteristic and the color developing of embodiment 89 and 90 light-emitting device are mimic, make in reality under the situation of light-emitting device, think to cause self-absorption, produce wavelength offset.2 light-emitting device as a comparative example adopts the excitation light source of Ex=460nm, uses (Y, Gd)
3(Al, Ga)
5O
12: Ce.In addition, embodiment 89 and 90 is peak value luminescent spectrums when identical.
Table 13
About the luminescent spectrum of the light activated fluor of wavelength 460nm that come self-emission device, the BaSi of embodiment 83
2O
2N
2: Eu is that the zone has the glow peak wavelength in blue-greenish colour to green, (Y, Gd)
3(Al, Ga)
5O
12: Ce is that the zone has glow peak wavelength, SrCaSi at green to yellowish red color
5N
8: Eu has the glow peak wavelength in yellowish red color to red colour system zone.By the light colour mixture of these fluor, show illuminant colour in the white color system zone.Thus, embodiment 89 and 90 light-emitting device show illuminant colour at white portion as a whole.In addition, owing to adopt near the 460nm visible light as excitation light source, do not use the fluor of the coloured light that turns blue, therefore the loss along with the luminous efficiency of wavelength Conversion is few.And then, by changing the proportioning of fluor, can change tone easily.Especially, in the white color system light-emitting device shown in the comparative example 2, its evaluation number (Ra) that on average develops the color is 76.0, but the colour system light-emitting device that turns white of embodiment 89 and 90, its evaluation number (Ra) that on average develops the color is 84.5 and 83.1, and is splendid.Can improve color developing thus.In addition, (R1～R15), color developing all improves special colour developing evaluation number in nearly all colour chart.In addition, the special colour developing evaluation number (R9) of the white color system light-emitting device shown in the comparative example 2 is-1.9, and the special colour developing evaluation number (R9) of the white color system light-emitting device of embodiment 89 and 90 is 70.7 and 94.1, and is splendid.This special colour developing evaluation number (R9) is the colour chart of the higher redness of chroma.Visibility efficient is to be that 100% o'clock relative value is represented with the light-emitting device with comparative example 1.
＜embodiment 91: light-emitting device 〉
The light-emitting device of embodiment 91 is the white color system light-emitting device that adopts the luminous element of glow peak wavelength 457nm about excitation light source.Basic structure is structure shown in Figure 1.Figure 71 is the figure of the luminescent spectrum of expression embodiment 91 and 92 light-emitting device.
(luminous element)
If electric current is flowed in the light-emitting device of embodiment 91, it is just luminous roughly to have a blue based light-emitting device 10 of glow peak wavelength at 457nm.11 pairs of these blue lights of fluor that cover semiconductor layer 2 carry out tone reversal.The light-emitting device of the embodiment 91 of the coloured light that turns white can be provided as a result.
(fluor)
The fluor 11 that is used for the light-emitting device of embodiments of the invention 91 is to use the oxonitride phosphor that mixed embodiment 83, with (Y, Gd)
3(Al, Ga)
5O
12: the YAG fluor that Ce represents reaches with CaSrSi
5N
8: the fluor 11 of the nitride phosphor that Eu represents.This fluor 11 is to be mixed together with application member 12.Its proportioning can suit to change.Use the excitation light source of Ex=457nm to shine these fluor 11.These fluor 11 absorb the light from this excitation light source, carry out wavelength Conversion, have the emission wavelength of regulation.The BaSi of embodiment 83
2O
2N
2: Eu has the glow peak wavelength at 470nm～530nm place.(Y, Gd)
3(Al, Ga)
5O
12: Ce has the glow peak wavelength at 500～650nm place.SrCaSi
5N
8: Eu has the glow peak wavelength at 580nm～730nm place.
In the light-emitting device of embodiment 91, a part of light transmission of luminous element 10.In addition, the part light of luminous element 10 carries out wavelength Conversion with excited fluophor 11, and this fluor 11 has the emission wavelength of regulation.Come the blue light of self-emission device 10 and, can provide the light-emitting device of the coloured light that turns white by these from the colour mixture of the light of fluor 11.
(characteristic of the light-emitting device of embodiment 91)
The characteristic and the demonstration property of the light-emitting device of table 14 expression embodiment 91.
Table 14
For for the 457nm light institute excited fluorescent body of luminous element, the BaSi of embodiment 83
2O
2N
2: Eu is that the zone has the glow peak wavelength in blue-greenish colour to green, (Y, Gd)
3(Al, Ga)
5O
12: Ce is that the zone has glow peak wavelength, SrCaSi at green to yellowish red color
5N
8: Eu has the glow peak wavelength in yellowish red color to red colour system zone.The colour mixture of the light by these fluor shows illuminant colour in the white color system zone.Thus, the light-emitting device of embodiment 91 shows illuminant colour at white portion.In addition, owing to adopt near the 457nm visible light, and do not use the fluor of the coloured light that turns blue, therefore follow the loss of luminous efficiency of wavelength Conversion few as excitation light source.And then, by changing the proportioning of fluor, can easily change tone.The white color system light-emitting device of embodiment 91, exhibited light efficient is up to the high characteristics of luminescence of 25.01m/W.The white color system light-emitting device of embodiment 91, its evaluation number (Ra) that on average develops the color is 92.7, and is splendid.Can improve color developing thus.In addition, (R1～R15), color developing all improves in nearly all colour chart about special colour developing evaluation number.In addition, the special colour developing evaluation number (R9) of the white color system light-emitting device of embodiment 91 is 83.0, and is splendid.
Thus, the white light of embodiment 91 is a light-emitting device, and the light-emitting device with excellent color developing can be provided.
＜embodiment 92: light-emitting device 〉
The light-emitting device of embodiment 92 is about use the white color system light-emitting device of glow peak wavelength as the luminous element of 463nm as excitation light source.Basic structure is structure shown in Figure 1.Figure 71 is the figure of the luminescent spectrum of expression embodiment 91 and 92 light-emitting device.
(luminous element)
If electric current is flowed in the light-emitting device of embodiment 92, it is just luminous roughly to have a blue based light-emitting device 10 of glow peak wavelength at 463nm.The fluor 11 that covers semiconductor layer 2 carries out the tone reversal of this blue light.The light-emitting device of the embodiment 92 of the coloured light that turns white can be provided as a result.
(fluor)
As the fluor 11 of the light-emitting device that is used for embodiments of the invention 92, use mixed the oxonitride phosphor of embodiment 83, with (Y, Gd)
3(Al, Ga)
5O
12: the YAG fluor that Ce represents, and with CaSrSi
5N
8: the fluor 11 of the nitride phosphor that Eu represents.This fluor 11 is to mix with application member 12.Its proportioning can suit to change.Use the excitation light source of Ex=463nm to shine these fluor 11.The light that these fluor 11 absorb from this excitation light source carries out wavelength Conversion, has the emission wavelength of regulation.The BaSi of embodiment 83
2O
2N
2: Eu has the glow peak wavelength at 470nm～530nm place.(Y, Gd)
3(Al, Ga)
5O
12: Ce has the glow peak wavelength at 500～650nm place.SrCaSi
5N
8: Eu has the glow peak wavelength at 580nm～730nm place.
In the light-emitting device of embodiment 92, a part of light of luminous element 10 can see through.In addition, a part of optical excitation fluor 11 of luminous element 10 carries out wavelength Conversion, and this fluor 11 has the emission wavelength of regulation.By from the blue light of these luminous elements 10 with from the colour mixture of the light of fluor 11, can provide the light-emitting device of the coloured light that turns white.
(characteristic of the light-emitting device of embodiment 92)
The characteristic and the color developing of the light-emitting device of table 15 expression embodiment 92.
Table 15
About the luminous element institute excited fluorescent body that is excited with 463nm, the BaSi of embodiment 83
2O
2N
2: Eu is that the zone has the glow peak wavelength in blue-greenish colour to green, (Y, Gd)
3(Al, Ga)
5O
12: Ce is that the zone has glow peak wavelength, SrCaSi at green to yellowish red color
5N
8: Eu has the glow peak wavelength in yellowish red color to red colour system zone.The colour mixture of the light by these fluor shows illuminant colour in the white color system zone.Thus, the light-emitting device of embodiment 92 shows illuminant colour at white portion.In addition, owing to adopt near the 463nm visible light, and do not use the fluor of the coloured light that turns blue, therefore follow the loss of luminous efficiency of wavelength Conversion few as excitation light source.And then, by changing the proportioning of fluor, can easily change tone.The white color system light-emitting device of embodiment 92, exhibited light efficient is up to the high characteristics of luminescence of 21.31m/W.The white color system light-emitting device of embodiment 92, its evaluation number (Ra) that on average develops the color is 84.9, and is splendid.Can improve color developing thus.In addition, (R1～R15), color developing all improves in nearly all colour chart about special colour developing evaluation number.In addition, the special colour developing evaluation number (R9) of the white color system light-emitting device of embodiment 92 is 91.0, and is splendid.
Thus, the white luminous device of embodiment 92 can provide the light-emitting device with excellent color developing.
＜embodiment 93: light-emitting device 〉
The light-emitting device of embodiment 93 is the bell-type light-emitting device same with the light-emitting device of embodiment 30, removes in the light-emitting device of embodiment 30, by outside the following formation fluor 11, constitutes similarly to Example 30.In addition, as luminous element 10, use the luminous element that has the glow peak wavelength at the 400nm place.
In cover 16, contain BaSi
2O
2N
2: the fluor of Eu and (Y, Gd)
3(Al, Ga)
5O
12: the fluor of Ce and Ba
2Si
5N
8: the nitride phosphor of Eu.In the application member 12 in the cup-shaped portion that lead-in wire 13a is installed, contain (Ca
0.95, Eu
0.05)
10(PO
4)
6Cl
2Fluor.In addition,, therefore also can contain oxonitride phosphor, install in the cup-shaped portion of lead-in wire 13a, also can only form application member 12 at cover 16 owing to can in cover 16, contain fluor.
So in the light-emitting device that constitutes, the oxonitride phosphor that the part light that is sent by luminous element 10 can excited fluophor 11 sends green light.In addition, the part light that is sent by luminous element 10 or by the fluor of the part optical excitation cover 16 that oxonitride phosphor sent sends blue and yellow to red light.Thus, the green light of oxonitride phosphor and cover 16 fluor send bluely and yellow mix to red light, its result is from covering the light that white color system is outwards sent on 16 surface.
As above detailed description, the present invention relates to oxonitride phosphor, this oxonitride phosphor absorbs comfortable short wavelength zone from ultraviolet to visible light to have the light of the excitation light source of emission wavelength, have with from the different illuminant colour of the illuminant colour of this excitation light source, this oxonitride phosphor, be that the zone has the glow peak wavelength from blue-greenish colour to yellow, and having high luminous efficiency.In addition, the temperature profile of this oxonitride phosphor is very excellent.In addition, the present invention is a kind of manufacture method of can reproducibility making above-mentioned such oxonitride phosphor well easily.In addition, the present invention relates to have the light-emitting device of above-mentioned oxonitride phosphor and luminous element, this light-emitting device can be realized desirable illuminant colour.And then, can make and make up the light-emitting device that described oxonitride phosphor and the 2nd fluor promptly send the fluor of light such as blueness, green, redness, yellow.The light-emitting device of the excellent color reproducing performance of sending white color system light can be provided thus.And then, can make and make up this oxonitride phosphor, the 2nd fluor is the light-emitting device of YAG fluor and blue based light-emitting device.Thus, can provide light-emitting device excellent color reproducing performance, that luminous efficiency is high that sends white color system light.Therefore, the present invention has the epochmaking technical meaning that above-mentioned such light-emitting device can be provided.
Claims (22)
1. oxonitride phosphor is with general formula Sr
xCa
(1-x)Si
2O
2N
2: Eu represents, and and CaSi
2O
2N
2: it is shorter that Eu compares the glow peak wavelength, wherein, and 0.3≤X≤0.7.
2. an oxonitride phosphor is characterized in that, with general formula Ca
xBa
1-xSi
2O
2N
2: Eu represents, wherein, and 0.2≤X≤0.4.
3. an oxonitride phosphor is characterized in that, (Ca, Mg) Si that are replaced by Mg with the part of Ca
2O
2N
2: Eu represents.
4. an oxonitride phosphor is characterized in that, (Sr, Mg) Si that are replaced by Mg with the part of Sr
2O
2N
2: Eu represents.
5. oxonitride phosphor as claimed in claim 3 is characterized in that described oxonitride phosphor is with Ca
0.9Mg
0.1Si
2O
2N
2: Eu represents.
6. oxonitride phosphor as claimed in claim 4 is characterized in that described oxonitride phosphor is with Sr
0.9Mg
0.1Si
2O
2N
2: Eu represents.
7. as any described oxonitride phosphor in the claim 1～4, it is characterized in that, described oxonitride phosphor is come the following place of comfortable 490nm to have the optical excitation of the excitation light source of glow peak wavelength, and has at the luminescent spectrum that has the glow peak wavelength than the long long wavelength side of described glow peak ripple.
8. as any described oxonitride phosphor in the claim 1～4, it is characterized in that described oxonitride phosphor has the glow peak wavelength from blue-greenish colour to the yellowish red color district.
9. as any described oxonitride phosphor in the claim 1～4, it is characterized in that described oxonitride phosphor is compared with the light of 500nm, more excited by the light intensity of 370nm is strong.
10. light-emitting device has excitation light source and will it is characterized in that from the fluor of at least a portion wavelength Conversion of the light that this excitation light source sent:
Described fluor contains at the oxonitride phosphor that has the glow peak wavelength from blue-greenish colour to the yellowish red color district,
Described oxonitride phosphor is with general formula Sr
xCa
1-xSi
2O
2N
2: Eu represents, wherein, and 0.3≤X≤0.7, and and CaSi
2O
2N
2: it is shorter that Eu compares the glow peak wavelength.
11. light-emitting device, has excitation light source and will be from the fluor of at least a portion wavelength Conversion of the light that this excitation light source sent, it is characterized in that: described fluor contains and has glow peak wavelength oxonitride phosphor to the yellowish red color district from blue-greenish colour, and described oxonitride phosphor is with general formula Ca
xBa
1-xSi
2O
2N
2: Eu represents, wherein, and 0.2≤X≤0.4.
12. light-emitting device, has excitation light source and will be from the fluor of at least a portion wavelength Conversion of the light that this excitation light source sent, it is characterized in that: described fluor contains and has glow peak wavelength oxonitride phosphor to the yellowish red color district from blue-greenish colour, (Ca, Mg) Si that described oxonitride phosphor is replaced by Mg with the part of Ca
2O
2N
2: Eu represents.
13. light-emitting device, has excitation light source and will be from the fluor of at least a portion wavelength Conversion of the light that this excitation light source sent, it is characterized in that: described fluor contains at the oxonitride phosphor that has the glow peak wavelength from blue-greenish colour to the yellowish red color district, (Sr, Mg) Si that described oxonitride phosphor is replaced by Mg with the part of Sr
2O
2N
2: Eu represents.
14., it is characterized in that described excitation light source has the glow peak wavelength more than 1 at least as any described light-emitting device in the claim 10～13 in the short wavelength side zone from the ultraviolet to the visible light.
15. light-emitting device according to claim 12, described oxonitride phosphor is with Ca
0.9Mg
0.1Si
2O
2N
2: Eu represents.
16. light-emitting device according to claim 13, described oxonitride phosphor is with Sr
0.9Mg
0.1Si
2O
2N
2: Eu represents.
17., it is characterized in that described excitation light source is a luminous element as any described light-emitting device in the claim 10～13.
18., it is characterized in that as any described light-emitting device in the claim 10～13:
As described fluor, contain the 2nd fluor that together uses with described oxonitride phosphor;
The 2nd fluor will reach at least one wavelength Conversion from the light of described oxonitride phosphor, and have the luminescent spectrum that has the glow peak wavelength in the visible region from the light of described excitation light source.
19. light-emitting device as claimed in claim 18 is characterized in that, described the 2nd fluor is regional to the glow peak wavelength that has at least green system, yellow system, the red colour system zone more than 1 from blueness system.
20. as any described light-emitting device in the claim 10～13, it is characterized in that, in the described light-emitting device, from the part of the light of described excitation light source, from the light of described oxonitride phosphor, mixed from the above light of the bundle of at least 2 in the light of described the 2nd fluor, emit.
21. as any described light-emitting device in the claim 10～13, it is characterized in that, described light-emitting device has the glow peak wavelength that has from described excitation light source, the middle illuminant colour of the glow peak wavelength that is had to glow peak wavelength that described oxonitride phosphor had or the 2nd fluor.
22. light-emitting device as claimed in claim 21 is characterized in that, described intermediary illuminant colour is the white color system illuminant colour.
23. as any described light-emitting device in the claim 10～13, wherein, described light-emitting device has the luminescent spectrum that has the glow peak wavelength more than 1 in the scope of 430～500nm, 500～730nm at least.
Applications Claiming Priority (18)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002-301637 | 2002-10-16 | ||
| JP2002-301636 | 2002-10-16 | ||
| JP2002301637 | 2002-10-16 | ||
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| JP2002381025A JP2004210921A (en) | 2002-12-27 | 2002-12-27 | Oxynitride fluorophor and method for producing the same and light-emitting device using the same |
| JP2002-381025 | 2002-12-27 | ||
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| JP2003028610A JP4415547B2 (en) | 2002-10-16 | 2003-02-05 | Oxynitride phosphor and method for producing the same |
| JP200328610 | 2003-02-05 | ||
| JP2003028611A JP4415548B2 (en) | 2002-10-16 | 2003-02-05 | Light emitting device using oxynitride phosphor |
| JP2003070043A JP4442101B2 (en) | 2003-03-14 | 2003-03-14 | Oxynitride phosphor and light emitting device using the same |
| JP200370043 | 2003-03-14 | ||
| JP2003-70043 | 2003-03-14 |
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| CNB2003801016488A Division CN100334180C (en) | 2002-10-16 | 2003-10-15 | Oxonitride phosphor and method for production thereof, and luminescent device using the oxonitride phosphor |
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| CN101045860B true CN101045860B (en) | 2010-06-09 |
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| CN2007101010941A Expired - Fee Related CN101089119B (en) | 2002-10-16 | 2003-10-15 | Oxynitride fluorescent material and method for producing the same |
| CNB2003801016488A Expired - Fee Related CN100334180C (en) | 2002-10-16 | 2003-10-15 | Oxonitride phosphor and method for production thereof, and luminescent device using the oxonitride phosphor |
| CN2007101010937A Expired - Fee Related CN101045860B (en) | 2002-10-16 | 2003-10-15 | Oxynitride fluorescent material, method for producing the same, and luminescent device using the same |
| CN2007101010744A Expired - Fee Related CN101045862B (en) | 2002-10-16 | 2003-10-15 | Oxynitride fluorescent material, method for producing the same, and luminescent device using the same |
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| CN2007101010941A Expired - Fee Related CN101089119B (en) | 2002-10-16 | 2003-10-15 | Oxynitride fluorescent material and method for producing the same |
| CNB2003801016488A Expired - Fee Related CN100334180C (en) | 2002-10-16 | 2003-10-15 | Oxonitride phosphor and method for production thereof, and luminescent device using the oxonitride phosphor |
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Families Citing this family (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101077973B (en) | 2006-05-26 | 2010-09-29 | 大连路明发光科技股份有限公司 | Silicate luminescent material, preparation method thereof and luminescent device using the same |
| CN101467271B (en) * | 2006-06-12 | 2012-04-25 | 3M创新有限公司 | Led device with re-emitting semiconductor construction and converging optical element |
| US7902542B2 (en) | 2006-06-14 | 2011-03-08 | 3M Innovative Properties Company | Adapted LED device with re-emitting semiconductor construction |
| KR101439567B1 (en) | 2006-08-15 | 2014-09-11 | 다리엔 루밍라이트 컴퍼니 리미티드 | Silicate base luminescent materials having multiple emission peaks, processes for preparing the same and light emitting devices using the same |
| DE102006051757A1 (en) * | 2006-11-02 | 2008-05-08 | MAX-PLANCK-Gesellschaft zur Förderung der Wissenschaften e.V. | phosphors |
| CN101157854B (en) * | 2007-07-02 | 2010-10-13 | 北京宇极科技发展有限公司 | Oxynitrides luminescent material, preparation method and uses thereof |
| CN101671562B (en) * | 2007-07-02 | 2013-08-14 | 北京宇极科技发展有限公司 | Nitrogen oxides luminescent material and preparation method and application thereof |
| JP5183128B2 (en) * | 2007-08-30 | 2013-04-17 | 凸版印刷株式会社 | Liquid crystal display |
| DE102008058295A1 (en) * | 2008-11-20 | 2010-05-27 | Osram Gesellschaft mit beschränkter Haftung | Red-emitting phosphor from the class of nitridosilicates and light source with such a phosphor and method for producing the phosphor |
| DE102011115879A1 (en) * | 2011-10-12 | 2013-04-18 | Osram Opto Semiconductors Gmbh | Optoelectronic component and phosphors |
| JPWO2013136732A1 (en) * | 2012-03-12 | 2015-08-03 | パナソニックＩｐマネジメント株式会社 | Phosphor and light emitting device using the same |
| US20150357527A1 (en) * | 2013-01-31 | 2015-12-10 | Sharp Kabushiki Kaisha | Method for manufacturing light-emitting device, and light-emitting device |
| KR20170054801A (en) * | 2015-11-10 | 2017-05-18 | 엘지전자 주식회사 | Phosphor emitting yellow light and light emitting device using the same |
| CN105838371A (en) * | 2016-04-27 | 2016-08-10 | 山东盈光新材料有限公司 | Nitric oxide fluorescent powder for LED and preparation method |
| CN108410452B (en) * | 2017-02-09 | 2021-03-19 | 有研稀土新材料股份有限公司 | Light-emitting material composition and light-emitting device |
| WO2018145288A1 (en) * | 2017-02-09 | 2018-08-16 | 有研稀土新材料股份有限公司 | Luminescent material composition and light emitting device |
| JP6720944B2 (en) * | 2017-08-31 | 2020-07-08 | 日亜化学工業株式会社 | Nitride phosphor manufacturing method, nitride phosphor and light emitting device |
| CN110630976A (en) * | 2018-06-22 | 2019-12-31 | 株式会社小糸制作所 | Light emitting module |
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- 2003-10-15 CN CN2007101010937A patent/CN101045860B/en not_active Expired - Fee Related
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Also Published As
| Publication number | Publication date |
|---|---|
| CN1705732A (en) | 2005-12-07 |
| CN100334180C (en) | 2007-08-29 |
| CN101045862A (en) | 2007-10-03 |
| CN101045862B (en) | 2012-05-09 |
| CN101089119B (en) | 2011-01-26 |
| CN101045860A (en) | 2007-10-03 |
| CN101089119A (en) | 2007-12-19 |
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