CN100454476C - Plasma display and method for manufacturing same - Google Patents
Plasma display and method for manufacturing same Download PDFInfo
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- CN100454476C CN100454476C CNB2004800046550A CN200480004655A CN100454476C CN 100454476 C CN100454476 C CN 100454476C CN B2004800046550 A CNB2004800046550 A CN B2004800046550A CN 200480004655 A CN200480004655 A CN 200480004655A CN 100454476 C CN100454476 C CN 100454476C
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- emitting phosphor
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- luminescent coating
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Abstract
A plasma display device including a green phosphor of which brightness is hardly deteriorated and a production method therefor are disclosed. The plasma display device comprises a plasma display panel in which a plurality of discharge cells of one color or a plurality of colors are disposed, red phosphor layers (110 R), green phosphor layers (110 G), and blue phosphor layers (110 B) are arranged correspondingly to the respective discharge cells, and the red phosphor layers (110 R), the green phosphor layers (110 G), and the blue phosphor layers (110 B) are excited by ultraviolet rays to emit light. The green phosphor layers (110 G) include a green phosphor expressed by (Ma-x-yEuxTby)O.MgO.2SiO2 (here, M is at least one element selected from Ca, Sr, and Ba).
Description
Technical field
The present invention relates to be used for the plasm display device and the manufacture method thereof of image demonstrations such as TV.
Background technology
In recent years, in the colour display device that in images such as computer and TV show, uses, the plasm display device of using plasma display floater (below be called " PDP " or " panel ") display unit, because of can realizing super large, slim, light weight, as colour display device and noticeable.
Plasm display device is to carry out colour by so-called 3 primary colors (red, green, blue) addition colour mixture to show.Show for carrying out this colour, plasm display device has and sends red (R), green (G), blue (B) luminescent coating as 3 primitive color lights, constitute the fluorophor particle of luminescent coating, be excited, produce visible light of all kinds by the ultraviolet ray that takes place in the PDP discharge cell.
As the compound that fluorophor of all kinds uses, known have (Y, the Gd) BO that for example sends ruddiness
3: Eu, Y
2O
3: Eu; Send the Zn of green glow
2SiO
4: Mn; Send the BaMgAl of blue light
10O
17: Eu.Manufacture method as these every kind fluorophor, be after the raw material of regulation are mixed, to calcine, make the making example that solid phase reaction takes place in the high temperature more than 1000 ℃, oneself has done to disclose in " fluorophor handbook) " (p219,225, オ one system society periodical) waits.In addition, by the fluorophor particle that this calcining obtains, be that (average grain diameter of red, green-emitting phosphor particle: 2 μ m～5 μ m, the average grain diameter of blue emitting phophor particle: 3 μ m～10 μ m) use the back carrying out sintering by calcining, pulverized, sieve.
But, as the Zn of existing green-emitting phosphor
2SiO
4: the Mn fluorophor particle, owing to be to make by pulverizing after the solid phase reaction, applied stress on the fluorophor particle surface and produced distortion, produce defectives such as the so-called oxygen defect in many places.These defectives are at the panel production process, and the moisture in the absorption atmosphere seals and when heating up at panel, moisture and fluorophor react in panel, the brightness of fluorophor is worsened, and the ultraviolet radiation absorption defective of the wavelength 147nm that produces during discharge has hindered exciting of luminescence center.In addition, the diaphragm MgO reaction in moisture and the panel causes the address discharge error easily.In addition, Zn
2SiO
4: the Mn fluorophor intermediate ion that is subject to discharge impacts, and the result is that brightness worsens and strengthens, and can not get very high brightness.In addition, Zn
2SiO
4: Mn because fluorophor self electronegative (-) is different with the charged tendency of red-emitting phosphors and blue emitting phophor, easily causes discharge error.
Summary of the invention
Plasm display device of the present invention wherein has plasma display, and this panel has a plurality of monochromes or the polychrome discharge cell is arranged, and the luminescent coating corresponding to each discharge cell look is set simultaneously; This luminescent coating is by ultraviolet ray excited and luminous, and luminescent coating has the green-emitting phosphor layer, and simultaneously, the green-emitting phosphor layer contains useful (M
A-x-yEu
xTb
y) O
aMgO2SiO
2The green-emitting phosphor of (in the formula, M represents at least a among Ca, Sr, the Ba) expression.
According to the present invention, a kind of plasm display device is provided, wherein have the green-emitting phosphor that worsens difficulty in the manufacturing process brightness of panel, thereby can seek brightness, the life-span of plasm display device, the raising of reliability.
The simple declaration of accompanying drawing
Fig. 1 is the PDP that uses in the plasm display device of one embodiment of this invention, removes the plane graph behind the front glass substrate.
Fig. 2 is the structural perspective of the image display area of the PDP that uses in the plasm display device of one embodiment of this invention.
Fig. 3 is the calcspar of the plasm display device of one embodiment of this invention.
Fig. 4 is the structural section figure of the image display area of the PDP that uses in the plasm display device of one embodiment of this invention.
The summary construction diagram of the printing ink apparatus for coating that Fig. 5 uses when being the PDP formation luminescent coating that uses in the plasm display device of one embodiment of this invention.
Symbol description
100 plasma displays (PDP)
101 front glass substrates
103 show electrodes
104 reading scan electrodes
105,108 dielectric glassy layers
106 protective layers
107 address electrodes
108 barrier films
110R red-emitting phosphors layer
110G green-emitting phosphor layer
The 110B blue phosphor layers
122 discharge spaces
The 150PDP drive unit
160 plasm display devices
Specific embodiments
Among the present invention, with (M
A-x-yEu
xTb
y) O
aMgO2SiO
2The fluorophor of (in the formula, M represents at least a among Ca, Sr, the Ba) expression can adopt the aqueous solution synthetic method, hydrothermal synthesis method, spraying synthetic method or the hydrolysis synthetic method that slightly are spherical particle easily to make.Promptly, make phosphor matrix from phosphor raw material, adopt this phosphor matrix to heat-treat and make in addition sintering, because the parent of fluorophor slightly is spherical in 1000 ℃～1400 ℃ high temperature, particle is difficult to be integrated each other during sintering, and the original spherical fluorophor that slightly is can be maintained.Also have, the what is called here " slightly is spherical ", be the diameter of axle of nearly all fluorophor particle is for example reached 0.9～1.0 than (short shaft diameter/major axis directly), but all the fluorophor particle particle that enters this scope is defined as and slightly is spherical.
But, because that fluorophor carries out pulverization process is few, so can obtain the high fluorophor of the few brightness of defective.In addition, as existing Zn
2SiO
4: Mn is such, because fluorophor does not contain ZnO in forming, even calcine at 1000 ℃～1400 ℃ high temperature, the selectivity distillation does not take place specific raw material, and the fluorophor composition does not change yet.Therefore, can obtain the good green-emitting phosphor of life characteristic.
In addition, the fluorophor that adopts this manufacture method of the present invention to form, particle diameter is little, even particle size distribution, good crystallinity, the packed density of fluorophor particle increases when forming luminescent coating.Therefore, help the light-emitting area of luminous fluorophor particle to increase in fact, the deterioration that causes because of discharge is few.Therefore, the PDP as showing high precise image also can obtain high brightness even discharge space narrows down.
Here, to 4 kinds of methods, be that example is illustrated with the green-emitting phosphor as the concrete manufacture method of fluorophor.
At first, introduce aqueous solution synthetic method.As phosphor raw material, adopt barium nitrate Ba (NO
3)
2, calcium nitrate Ca (NO
3)
2, strontium nitrate Sr (NO
3)
2, magnesium nitrate Mg (NO
3)
2, silicon oxide sio
2(silica gel) or silester Si (OC
2H
5)
4And europium nitrate Eu (NO
3)
3, terbium nitrate Tb (NO
3)
3This phosphor raw material is dissolved in aqueous medium, makes hydration mixed liquor (mixed liquor production process).Then, to the logical ultrasonic wave limit O in this hydration mixed liquor limit
2(oxygen), O
3(ozone) or O
2-N
2(oxygen-nitrogen) bubbling mixes behind the interpolation alkaline aqueous solution, is made as the hydrate (hydrate production process) of phosphor matrix.Then, the solution that contains phosphor matrix that this hydrate production process obtains is heat-treated in 700 ℃～900 ℃ temperature in air, obtain the precursor powder (heat treatment step) of fluorophor.Then, the precursor powder of fluorophor is calcined (calcination process) in 1000 ℃～1400 ℃ temperature in reduction atmosphere gas, can be made as green-emitting phosphor slightly spherical in shape.
Secondly, introduce the spraying synthetic method.Adopt the mixed liquor production process and the hydrate production process that illustrate in the aqueous solution synthetic method to carry out.Secondly,, go into to be heated to the stove interior (spraying operation) of 1000 ℃～1500 ℃ of temperature, make the phosphor matrix powder the alkaline aqueous solution drop that contains phosphor matrix that obtains by the hydrate production process.Then, this phosphor matrix powder is calcined in 1000 ℃～1400 ℃ temperature in reproducibility atmosphere gas, made the green-emitting phosphor of powder slightly spherical in shape.
Secondly, introduce hydrothermal synthesis method.Adopt the mixed liquor production process and the hydrate production process that illustrate in the aqueous solution synthetic method to carry out.Then, the alkaline aqueous solution that contains phosphor matrix that obtains by the hydrate production process, put into high-pressure bottle, in the pressure of 100 ℃～300 ℃ temperature, pressurization 0.2MPa～10MPa, carry out hydrothermal synthesis reaction (hydro-thermal synthesis procedure), make the phosphor matrix powder.Then, this phosphor matrix powder is calcined in 1000 ℃～1400 ℃ temperature in reproducibility atmosphere gas, made green-emitting phosphor powder slightly spherical in shape.
Secondly, the hydrolysis synthetic method is introduced.As phosphor raw material, adopt the organic compound (metal acetylacetonate, metal alkoxide) that contains Ca, Sr, Ba, Mg, Si, Eu, each element of Tb.This phosphor raw material and alcohol and water are mixed, adopt hydrolysis to make phosphor matrix from this mixture.Then, this phosphor matrix is heat-treated in 700 ℃～900 ℃ temperature, obtain the phosphor matrix powder.Then, this phosphor matrix powder is calcined in 1000 ℃～1400 ℃ temperature in reproducibility atmosphere gas, can be made green-emitting phosphor powder slightly spherical in shape.
Adopt above-mentioned aqueous solution synthetic method, hydrothermal synthesis method, spraying synthetic method or Hydrolyze method, it is spherical that phosphor matrix slightly is.Therefore, the green-emitting phosphor particle that obtains from its parent also slightly is spherical, and particle diameter is little of 0.05 μ m～3 μ m, and particle size distribution is better.Therefore, the packed density that forms the fluorophor particle of luminescent coating improves, and helps the light-emitting area of luminous fluorophor particle to increase in fact.Therefore, even even PDP discharge space volume be the thickness of original 1/3 and fluorophor for original 1/3, the brightness that also can improve plasm display device can suppress brightness simultaneously and worsen, and obtains the good plasm display device of light characteristic.
Particularly, by adopting with chemical formula (M
A-x-yEu
xTb
y) O
aMgO2SiO
2The fluorophor of (in the formula, M represents at least a among Ca, Sr, the Ba) expression can replace the very bad Zn of brightness
2SiO
4: the green-emitting phosphor of Mn, various defectives can be greatly improved.
Here, the fluorophor particle average grain diameter of these green-emitting phosphors preferably is in 0.1 μ m～3 mu m ranges and is.In addition, preferred maximum particle diameter 8 μ m of particle size distribution or 8 μ m are following, minimum grain size is preferably more than average grain diameter 1/4 or 1/4.The zone that the fluorophor particle middle-ultraviolet lamp arrives, shallow to about hundreds of nm from particle surface, surface light emitting only almost.Therefore, at 3 μ m or below the 3 μ m, then help the long-pending increase of luminous particle surface as the fluorophor particle average grain diameter, the luminous efficiency of fluorophor remains on higher state.In addition, when the fluorophor particle average grain diameter surpassed 3 μ m, the thickness of luminescent coating must be greater than 20 μ m, so discharge space can not guarantee fully.On the other hand, when fluorophor particle average grain diameter during less than 0.1 μ m, be easy to generate defective, brightness can not improve.
Below, describe with reference to accompanying drawing this plasma display unit one embodiment of this invention.
Fig. 1 is the schematic plan view that does not comprise front glass substrate 101 among the PDP100, and Fig. 2 is the stereogram of a part in the image display area shown in Figure 1 123 of PDP100.Also have, for simplicity's sake with regard to the radical of show electrode 103, reading scan electrode 104, address electrode 107 etc., omit a part and the diagram of carrying out among Fig. 1.The limit describes the structure of PDP100 with reference to Fig. 1, Fig. 2 limit.
As shown in Figure 1, PDP100 has: front glass substrate 101 (not shown), back side glass substrate 102, N root show electrode 103, N root reading scan electrode 104 are (when showing the n root, its digital n represents with bracket inner digital), M root address electrode 107 (when showing the m root, its digital m represents with bracket inner digital), the gas-tight seal layer 121 represented with oblique line etc.Has electrode matrix, at the intersection point formation discharge cell of show electrode 103 and reading scan electrode 104 and address electrode 107 by 3 electrode structures of each electrode 103,104,107 forms.
As shown in Figure 2, the structure of PDP100 is: in front on 1 interarea of glass substrate 101, be provided with have show electrode 103, the front panel of reading scan electrode 104, dielectric glassy layer 105, protective layer 106; Overleaf on 1 interarea of glass substrate 102, be provided with have address electrode 107, the back panel of dielectric glassy layer 108, next door 109 and red-emitting phosphors layer 110R, green-emitting phosphor layer 110G, blue phosphor layers 110B, form the structure that two panels is fitted.In the discharge space 122 that forms between panel and the back panel in front, enclose the discharge gas that for example constitutes by neon (Ne) and helium (Xe) etc.
Fig. 3 is the frame diagram of the plasm display device of one embodiment of this invention.As shown in Figure 3, the structure of plasm display device 160 is that PDP drive unit 150 is connected on the PDP100.The structure of PDP drive unit 150 is to be made of the display driver circuit 153 that drives show electrode 103, the reading scan drive circuit 154 that drives reading scan electrode 104, the controller 152 that drives the address driving circuit 155 of address electrode 107 and control these circuit.When plasm display device 160 drives, control according to controller 152, in as the discharge cell that starts, reading scan electrode 104 and address electrode 107 are applied pulse voltage, after carrying out the address discharge whereby betwixt, between show electrode 103 and reading scan electrode 104, apply pulse voltage, keep discharge.Keep discharge by this ultraviolet ray takes place in discharge cell, luminous by ultraviolet ray excited luminescent coating, start discharge cell.Whereby, the bright lamp of the discharge cell by forming luminescent coating of all kinds, the combination of non-bright lamp can display images.
Secondly, to above-mentioned PDP100, its manufacture method is described with reference to Fig. 1 and Fig. 2.
Front panel; in front on the glass substrate 101; after each N root show electrode 103 and reading scan electrode 104 (only representing 2 for every kind among Fig. 2) are crossed one another and forming striated abreast; form dielectric glassy layer 105 to cover show electrode 103 and reading scan electrode 104, on dielectric glassy layer 105 surfaces, form protective layer 106 again and make front panel.
Show electrode 103 and reading scan electrode 104 are by the transparency electrode that comprises ITO (indium tin oxide) and comprise the electrode that the slot type electrode of metal material such as silver is constituted.For example, adopt sputtering method in front roughly whole of glass substrate 101 go up form the ITO film after, make wiring pattern by etching, form and have the transparency electrode of predetermined pattern (striated), after then the slot type electrode being coated with silk screen printing with silver paste, form by calcining.
Dielectric glassy layer 105 is the cream of leaded class glass material, with after the silk screen printing coating, forms the thick layer (about 20 μ m) etc. of regulation by calcining in set point of temperature, stipulated time (for example, 560 ℃, 20 minutes) and forms.As the cream of leaded class glass material, for example, can use PbO (70wt%), B
2O
3(15wt%), SiO
2(10wt%) and Al
2O
3(5wt%) and the mixture of organic bond etc.Wherein, so-called organic bond is the product that resin is dissolved in organic solvent, for example, and the product of dissolving 10% ethyl cellulose in α-terpineol.Except that ethyl cellulose, can also use acrylic resin, as butyl carbitol of organic solvent etc. as resin.In addition, in this organic bond, can also sneak into for example glycerol trioleate as dispersant etc.
Back panel, the silver paste that screen printing electrode is used on the glass substrate 102 then, forms M root address electrode 107 by calcining at first overleaf.The cream that is coated with leaded class glass material by silk screen printing makes and covers this address electrode 107, forms dielectric glassy layer 108, similarly the cream of leaded class glass material by silk screen printing, calcine formation next door 109 after being coated with repeatedly with the spacing of stipulating.By this next door 109, discharge space 122 with the parallel direction of show electrode 103 and reading scan electrode 104, on each discharge cell (unit emission regions), carry out the zone and draw and divide.
Fig. 4 is the partial cross section figure of PDP100.As shown in Figure 4, for the HD-TV of the size of space W that makes next door 109 and 32 inches～50 inches coincide, and be defined in about 130 μ m～240 μ m.And coating is by the various fluorophor particles of red (R), green (G) and blue (B) and the paste fluorophor printing ink that organic bond constitutes in the groove between next door 109 and the next door 109.Its temperature at 400 ℃～590 ℃ is calcined, organic bond is burnt, form the red-emitting phosphors layer 110R, green-emitting phosphor layer 110G, the blue phosphor layers 110B that constitute by each fluorophor particle.
The thickness L of this red-emitting phosphors layer 110R, green-emitting phosphor layer 110G, the stacked direction of blue phosphor layers 110B on address electrode 107 is preferably about about 8 times～25 times of the average grain diameter of fluorophor particle of all kinds.That is, the brightness (luminous efficiency) in order to ensure to the certain ultraviolet ray of luminescent coating irradiation the time does not see through the ultraviolet ray that takes place for making in the discharge space, wishes that fluorophor particle keeps minimum 8 layers, preferred about 20 layers stacked thickness.On the other hand, if fluorophor particle surpasses 25 layers thickness, then the luminous efficiency of luminescent coating almost reaches capacity, and can not fully guarantee the size of discharge space 122 simultaneously.
In addition, the fluorophor particle that adopts phosphor matrix to make by aqueous solution synthetic method, hydrothermal synthesis method, spraying synthetic method, hydrolysis synthetic method etc., its particle diameter is little, and slightly be spherical, with use the particle slightly be not spherical and compare, even the stacked number of plies is identical, the compactedness height of fluorophor particle.Therefore, because the increase of the total surface area of fluorophor particle, so, to the surface area increase of the actual luminous useful fluorophor particle in the luminescent coating, so luminous efficiency improves more.
Front panel of making like this and back panel, in the panel sealing operation, the show electrode 103 of front panel and reading scan electrode 104, intersecting vertically with the address electrode 107 of back panel is overlapped.At this moment, insert glass for sealing around the panel, calcining is 10 minutes～20 minutes in about 450 ℃, forms gas-tight seal layer 121 (Fig. 1) and is sealed.Then, being pumped into high vacuum (for example, 1.1 * 10 in the discharge space 122
-4Pa) after, enclose discharge gas (for example, Ne-Xe system, He-Xe are inert gas), make PDP100 with the pressure of regulation.
Fig. 5 is the simple composition diagram of printing ink apparatus for coating used when being used to form red-emitting phosphors layer 110R, green-emitting phosphor layer 110G, blue phosphor layers 110B.
As shown in Figure 5, printing ink apparatus for coating 200 has pallet 210, force (forcing) pump 220, header box 230 etc., and the fluorophor printing ink of supplying with from the pallet 210 of depositing fluorophor printing ink is by force (forcing) pump 220 forced feed header boxs 230.230a of ink chamber and nozzle 240 are set on header box 230,, spray continuously from nozzle 240 by the fluorophor printing ink of the 230a of forced feed ink chamber.For the bore D that prevents this nozzle 240 of nozzle hole plug at 30 μ m or more than the 30 μ m, and ooze out from barrier film when preventing to be coated with, below the interval W between the next door 109 preferred (about 130 μ m～240 μ m), be set at 30 μ m～130 μ m usually.
Also have, pallet 210 has not shown agitating device, by its stirring action, can prevent the precipitation of fluorophor particle in the fluorophor printing ink.In addition, header box 230 also comprises the part of 230a of ink chamber and nozzle 240 forming an integral body, and metal material is made by machining and edm.
In addition, the method as forming luminescent coating is not limited to said method, for example can adopt photo-engraving process, silk screen print method and the whole bag of tricks such as method of the film that has mixed fluorophor particle are set
Fluorophor printing ink is mixed fluorophor particle of all kinds, adhesive and solvent, and blending makes and reaches 1500CP～30000CP, also can add surfactant, silicon dioxide, dispersant (0.1wt%～5wt%) etc. as required.
As the red-emitting phosphors of in this fluorophor printing ink, concocting, can adopt with (Y, Gd)
1-xBO
3: Eu
xOr (Y
1-x)
2O
3: Eu
XThe compound of expression.
As blue emitting phophor, can adopt with Ba
1-XMgAl
10O
17: Eu
XOr Ba
1-X-ySr
yMgAl
10O
17: Eu
XThe compound of expression.
As green-emitting phosphor, can adopt with chemical formula (M
A-x-yEu
xTb
y) O
aMgO2SiO
2The compound of (in the formula, M represents at least a among Ca, Sr, the Ba) expression in order to obtain green emitting, constitutes M (Ca, Sr, Ba) the element part of its fertile material, available Eu, Tb displacement.
As the adhesive of concocting in fluorophor printing ink, (combined amount is the 0.1wt%～10wt%), can adopt α-terpineol, butyl carbitol etc. as solvent of fluorophor printing ink can to adopt ethyl cellulose or acrylic resin.In addition,, PMA (polymethyl acrylate) or PVA macromolecules such as (polyvinyl alcohol) can be adopted,, organic solvents such as diethylene glycol (DEG), methyl ether can also be adopted as solvent as adhesive.
In the present embodiment, fluorophor can adopt aqueous solution synthetic method, hydrothermal synthesis method, spraying synthetic method, hydrolysis synthetic method etc. to make, and the concrete manufacture method of fluorophor of all kinds is as described below.
At first, introduce green-emitting phosphor.(Ca when at first introducing M and being Ca
A-x-yEu
xTb
y) O
aMgO2SiO
2Synthetic.
This fluorophor when forming with the above-mentioned fluorophor of chemical formulation, becomes aCaOxEuOyTbOMgO2SiO
2Be illustrated during here to a=2.
At first, in the manufacturing process of mixed liquor, calcium nitrate Ca (NO as phosphor raw material
3)
2, magnesium nitrate Mg (NO
3)
2, silicon oxide sio
2(silica gel), europium nitrate Eu (NO
3)
3, terbium nitrate Tb (NO
2)
3Various materials mixed, make the mol ratio a that reaches in the above-mentioned chemical formula: 1: 2: x: y (a=2,0.02≤x≤0.2,0≤y≤0.05), it is dissolved in aqueous medium, make mixed liquor (hydration mixed liquor).As this aqueous medium, consider that from viewpoint free from foreign meter ion exchange water or pure water are preferred, wherein contain nonaqueous solvents (methyl alcohol, ethanol etc.) person and also can use.
Secondly, can in this hydration solution, add alkaline solution (for example, potassium hydroxide), make spherical hydrate (parent of fluorophor).Put it into by tool corrosion resistances such as gold or platinum, stable on heating metal container, for example carry out hydrothermal synthesis reaction with the equilateral device that adds the flanging heating of autoclave.Hydrothermal synthesis reaction, in high-pressure bottle in set point of temperature (for example, 100 ℃～300 ℃), authorized pressure (for example, 0.2MPa under～10MPa) the condition, put into aluminium powder or graphite powder is made reducing agent, carry out handling in 12 hours～20 hours, make the phosphor matrix powder that slightly is spherical.
In addition, can adopt the spraying synthetic method when not using autoclave, above-mentioned hydration mixed liquor is directly led to the ultrasonic wave limit to the stove internal spraying that is heated to 1000 ℃～1500 ℃ from pressurization nozzle limit, make the phosphor matrix powder that slightly is spherical.
Secondly, phosphor matrix powder (for example, atmosphere of hydrogeneous 5%, nitrogen 95%) under the reduction atmosphere, under the condition of set point of temperature, stipulated time (for example, 800 ℃～1400 ℃, 2 hours), calcine, then, with its classification, obtain desirable green-emitting phosphor (Ca
2-x-yEu
xTb
y) O
2MgO2SiO
2(Ca
2MgSi
2O
7: Eu, Tb).
Usefulness (Ca during here, to M=Ca, a=2
2-x-yEu
xTb
y) OMgO2SiO
2The green-emitting phosphor manufacture method of expression is illustrated, the usefulness (Ca when obtaining M=Ca, a=1
1-x-yEu
xTb
y) OMgO2SiO
2The green-emitting phosphor of expression, 0≤x≤0.1,0.01≤y≤0.2.In addition, the usefulness (Ca when obtaining M=Ca, a=3
3-x-yEu
xTb
y) O
3MgO2SiO
2The green-emitting phosphor of expression, 0≤x≤0.1,0.01≤y≤0.2.Therefore, change the blending ratio of phosphor raw material, adopt and above-mentioned same method, can obtain the different green-emitting phosphor of composition ratio of Ca.
In addition, when M=Sr, available strontium nitrate Sr (NO
3)
2Replaced C a (NO
3)
2, when M=Ba, available barium nitrate Ba (NO
3)
2Replaced C a (NO
3)
2As phosphor raw material.
In any case it is shaped as and slightly is spherical by adopting fluorophor particle that hydrothermal synthesis method or spraying synthetic method obtain, and particle diameter is little with comparing of making from original solid phase reaction.
[(Ca, Sr, Ba) when secondly, M being Ca, Sr, Ba mixing use
A-x-yEu
XTb
y] OMgO2SiO
2Synthetic method be illustrated.
When forming with the above-mentioned fluorophor of chemical formulation, this fluorophor is a (Ca, Sr, Ba) OxEuOyTbOMgO2SiO
2Here as (Ca, Sr, the Ba) O in the above-mentioned chemical formula, a part that only is Ca is by Sr or Ba displacement (ratio of Ca/Sr, Ba is 0.1～1).Hydrolysis during here, to a=2 is illustrated.
As phosphor raw material, can adopt the alkoxide Ca (OR) of calcium
2, strontium alkoxide Sr (OR)
2, barium alkoxide Ba (OR)
2The alkoxide Mg (OR) of [(ratio of Ca/Sr, Ba) is 0.1～1.0], magnesium
2, silicon alkoxide Si (OR)
4, europium alkoxide Eu (OR)
3, terbium alkoxide Tb (OR)
3(R is an alkyl in the formula).By mixing, make the mol ratio in the above-mentioned chemical formula reach a: 1: 2: x: y (a=2,0.02≤x≤0.2,0≤y≤0.05).Here, mol ratio a represents Ca (OR)
2And Sr (OR)
2And Ba (OR)
2The mol ratio of total amount, and following mol ratio is Mg (OR) corresponding to the record of above-mentioned phosphor raw material in proper order
2Mol ratio be 1, Si (OR)
4Mol ratio be 2, Eu (OR)
3Mol ratio be x, Tb (OR)
3Mol ratio be y.And, add water in the phosphor raw material with alkyl of above-mentioned mixing or alcohol makes hydrolysis, calcine in 900 ℃～1300 ℃ slightly being spherical parent.Then, after for example (for example, 1000 ℃～1400 ℃, 2 hours) calcines under the condition of set point of temperature, stipulated time in the atmosphere of hydrogen 5%, nitrogen 95% in the reduction atmosphere, carry out classification, obtain green-emitting phosphor with Hydrolyze method with air classifier.
Also have, a value of Ca, Sr, Ba can select 1,2,3 arbitrarily, there is no the significant change of parent crystalline texture in all cases.But, the temperature characterisitic of fluorophor, i.e. the deterioration that the fluorescence body characteristic temperature influence produces in the PDP manufacture process, a is bigger, and deterioration is littler.In addition, in above-mentioned various synthetic methods, the calcining heat of calcination process, a value big calcining heat that heals is higher.Therefore, a value can be selected arbitrarily according to fluorophor manufacture method or PDP manufacture method, condition.
In addition, Ca, Sr, Ba both can use separately, also can mix use, but when using separately, the deterioration that the fluorescence body characteristic temperature influence produces, Ba minimum, Sr take second place, Ca is the poorest.Therefore, both can select, also can select arbitrarily according to PDP manufacture method, condition to these materials.
Secondly, blue emitting phophor is introduced.To Ba as blue emitting phophor
1-XMgAl
10O
17: Eu
XOr Ba
1-X-ySr
yMgAl
10O
17: Eu
XSynthetic method introduced.
As the concrete manufacture method of blue emitting phophor, for example,, can adopt Ba (NO as phosphor raw material
3)
2, Sr (NO
3)
2, Mg (NO
3)
2, Al (NO
3)
3And Eu (NO
3)
3, same with synthesizing of green-emitting phosphor, make spherical phosphor matrix from the aqueous solution of these phosphor raw materials.Then,, under 100 ℃～300 ℃ temperature, the pressure status of 0.2MPa～10MPa, carry out hydrothermal synthesis reaction adopting its hydro-thermal synthesis procedure, then, the powder that obtains in H
2-N
2In heat-treat, carry out classification then, obtain blue emitting phophor.
Secondly, red-emitting phosphors is introduced.Introduction is as (Y, the Gd) of red-emitting phosphors
1-XBO
3: Eu
XSynthetic.
In the mixed liquor production process, yttrium hydroxide Y (OH) as phosphor raw material
3, gadolinium hydroxide Gd (OH)
3, boric acid H
3BO
3, europium hydroxide Eu (OH)
3Mixed, be dissolved in and make mixed liquor in the ion exchange water, mol ratio is reached: (Y (OH)
3+ Gd (OH)
3): H
3BO
3: Eu (OH)
3=1-x: 1: x (0.05≤x≤0.20) (ratio of Y and Gd is 65: 35).Secondly, in the hydrate production process, this mixed liquor is added alkaline aqueous solution (for example, ammonia spirit), make hydrate.
Then, at the hydro-thermal synthesis procedure, this hydrate and ion exchange water are put into by tool corrosion resistances such as gold or platinum, stable on heating metal container, for example use autoclave, in high-pressure bottle in set point of temperature (for example, 100 ℃～300 ℃), authorized pressure (for example, under the condition of 0.2MPa～10MPa), carry out hydrothermal synthesis reaction with the stipulated time (for example, 3～12 hours).By this hydro-thermal synthesis procedure, the fluorophor that obtains to be made about particle diameter 0.1 μ m～2.0 μ m, its shape forms spherical.Secondly, in air,, carry out classification then, obtain red-emitting phosphors in 800 ℃～1200 ℃ heat treatments 2 hours.
Secondly, to (the Y of red-emitting phosphors
1-X)
2O
3: Eu
XSynthetic method be illustrated.
Handle is as the yttrium nitrate Y (NO of raw material in the mixed liquor production process
3)
3With europium nitrate Eu (NO
3)
3Mixed, be dissolved in ion exchange water, made mixed liquor, mol ratio is reached: 2 (1-x): x (0.05≤x≤0.30).Then, in hydrate manufacturing process, this aqueous solution is added alkaline aqueous solution (for example, ammoniacal liquor), make the formation hydrate.
Thereafter, in the hydro-thermal synthesis procedure, hydrate and ion exchange water are put into by tool corrosion resistances such as gold or platinum, stable on heating metal container, for example use autoclave, in high-pressure bottle, under the condition of 100 ℃～300 ℃ of temperature, pressure 0.2MPa～10MPa), carried out hydrothermal synthesis reaction 3～12 hours.Then, the compound that obtains is carried out drying, obtain desirable (Y
1-X)
2O
3: Eu
X
Secondly, this fluorophor in air 800 ℃～1200 ℃ carry out 2 hours annealing in process after, carry out classification, obtain red-emitting phosphors.By the fluorophor that this hydro-thermal synthesis procedure obtains, particle diameter reaches about 0.1 μ m～2.0 μ m, and it is shaped as spherical.Its particle diameter, shape are suitable for forming the good luminescent coating of the characteristics of luminescence.
Above-mentioned each fluorophor particle, any spherical parent that synthesizes in the aqueous solution that all adopts, generate by hydrothermal synthesis method, spraying synthetic method, Hydrolyze method, therefore, can form and be shaped as particle (about average grain diameter 0.1 μ m～2.0 μ m) spherical and that particle diameter is little.
Therefore, compare with the solid reaction process of original employing solid phase reaction, the fluorophor particle that adopts spherical parent to make can suppress molten sticking caused cohesion by fluorophor particle, even particle size distribution at calcination process.Also have, adopt nitrate compound, oxyhydroxide, but other compounds, for example use the alkoxide M (OR) of metal as initiation material
2Or pentanedione M (C
5H
7O)
2(in the formula, M is a metal) also can be made.
Also have, the red-emitting phosphors layer 110R of above-mentioned PDP100, green-emitting phosphor layer 110G, blue phosphor layers 110B, what all luminescent coating adopted is the fluorophor particle that hydrothermal synthesis method is made, but both synthetic method, spraying synthetic method were made in the available water solution, and also the available water thermal synthesis method is made same luminescent coating.
In R, G, B 3 looks, particularly original Zn
2SiO
4: the green-emitting phosphor of Mn structure, to compare with other fluorophor, brightness is low, and also big by discharge brightness deterioration, so when 3 looks simultaneously luminous, the color temperature of white had the tendency of decline.Therefore, in plasm display device, consider,, improve the color temperature that white shows with this by reducing the discharge cell brightness that green fluorophor (red, indigo plant) in addition forms from circuit.But, as adopting the usefulness (M that makes according to manufacture method of the present invention (in the aqueous solution, making the method for phosphor matrix)
A-x-yEu
xTb
y) O
aMgO2SiO
2The green-emitting phosphor of (in the formula, M represents at least a among Ca, Sr, the Ba) expression, the brightness of green discharge cell raises, and need not painstakingly to reduce the brightness of red discharge cell and blue discharge unit.Therefore, owing to can use the discharge cell brightness of whole colors to greatest extent, thus keep the white high state of color temperature that shows on one side, Yi Bian improve the brightness of plasm display device.
Below, in order to estimate the performance of plasm display device of the present invention, make sample according to above-mentioned embodiment, this sample is carried out the performance evaluation experiment.
Make various plasm display devices; size is 42 inches (styles of the HD-TV of the gap size W=150 μ m in next door 109); dielectric glassy layer 105 thickness 20 μ m; the thickness of protective layer 106 is 0.5 μ m, paired show electrode 103 and the 80 μ m of the distance between the reading scan electrode 104.In addition, the discharge gas of enclosing discharge space is to mix the gas of 10% helium (Xe) gas in the gas of neon (Ne), to enclose with the discharge air pressure of 73kPa.
The fluorophor of all kinds that uses in the plasm display device as embodiment, the spherical parent that employing is made by aqueous solution synthetic method, hydrothermal synthesis method, spraying synthetic method or Hydrolyze method is made.As green-emitting phosphor, can adopt (Ca
A-x-yEu
xTb
y) O
aMgO2SiO
2(in the formula, M represents at least a among Ca, Sr, the Ba, and a is 1,2 or 3),, can adopt Ba as blue emitting phophor
1-XMgAl
10O
17: Eu
XOr Ba
1-X-ySr
yMgAl
10O
17: Eu
X,, can adopt (Y, Gd) as red-emitting phosphors
1-xBO
3: Eu
xOr (Y
1-x)
2O
3: Eu
XThe fluorophor printing ink that uses when adopting this fluorophor of all kinds to form luminescent coating is the mixing ratio that adopts in the present embodiment, fluorophor, resin, solvent, dispersant is mixed make.The measurement result of the viscosity of fluorophor printing ink (25 ℃) is that its viscosity all remains on the scope of 1500CP～30000CP.In addition, the result who observes formed luminescent coating is, the barrier film wall all is coated with fluorophor printing ink equably, and the thickness of luminescent coating is 20 μ m.
In addition, the fluorophor of all kinds that uses in the plasm display device as a comparative example is as (the Y of red-emitting phosphors employing hydrothermal synthesis method making
0.85)
2O
3: Eu
0.15(average grain diameter 2 μ m) are as the Ba of blue emitting phophor employing hydrothermal synthesis method making
0.8MgAl
10O
17: Eu
0.2(average grain diameter 3 μ m) are as the Zn of green-emitting phosphor employing solid reaction process making
2SiO
4: Mn (average grain diameter 3.2 μ m).And, with the condition same as the plasm display device of embodiment under, adopt fluorophor printing ink to form luminescent coating (thickness is 20 μ m).
Adopt these fluorophor to carry out following experiment.
To this embodiment and comparative example sample, in panel manufacturing process, measure the green-emitting phosphor brightness rate of change of panel sealing operation (450 ℃ of temperature).Panel luminance when having or not address error and green comprehensive bright lamp when the brightness rate of change when in addition, measuring the panel accelerated life test, address discharge.
The green-emitting phosphor brightness rate of change of panel sealing operation is measured by laxative remedy.That is, after forming luminescent coating, (for example, about 20mm * 10mm) cuts the part of the preceding back side glass substrate of panel sealing to size in accordance with regulations.Then, adopt the back side glass substrate cut after the part to carry out panel sealing, (for example, about 20mm * 10mm) cuts the part of the back side glass substrate behind the panel sealing to size in accordance with regulations.And, the back side glass substrate that cuts before and after the panel sealing is placed in the vacuum chamber, irradiation exciter lamp (vacuum ultraviolet 146nm) makes luminescent coating luminous.Measuring with luminance meter should be luminous, obtained brightness rate of change r1 from the brightness of the green composition of panel sealing front and back according to following formula:
r1＝(BG1-BG0)/BG0×100
Wherein, BG0 is the green composition brightness before the panel sealing, and BG1 is the green composition brightness behind the panel sealing.
Also have, measure about the panel luminance in the plasm display device, counter plate applies the discharge of voltage 150V, frequency 30kHz and keeps pulse, only measures under the state of the bright lamp of green discharge cell.The mensuration of the brightness rate of change when carrying out the accelerated life test of panel, article on plasma body display unit applies the discharge of voltage 200V, frequency 100kHz continuously and kept pulse 100 hours, carry out accelerated life test, before and after this accelerated life test, measure the brightness of panel, obtain brightness rate of change r2 according to following formula from the brightness of this panel:
r2＝(B1-B0)/B0×100
Wherein, B0 is the panel luminance before the accelerated life test, and B1 is the panel luminance after the accelerated life test.
Also have, because luminescent coating of all kinds carries out the equalization discharge in this test, the color temperature when adjusting white the demonstration is so needn't suppress control red, green discharge cell brightness.
In addition, the address error when discharging about the address can be judged by whether seeing image deviations, even 1 place is also referred to as " having ".
Following handle adopts (M as green-emitting phosphor
1-x-yEu
xTb
y) O
aMgO2SiO
2The composition and the synthesis condition of the fluorophor of all kinds when (in the formula, M represents at least a among Ca, Sr, the Ba) are shown in table 1, and each measuring the results are shown in table 2.In addition, adopting (M as green-emitting phosphor
2-x-yEu
xTb
y) O
2MgO2SiO
2The composition and the synthesis condition of the fluorophor of all kinds when (in the formula, M represents at least a among Ca, Sr, the Ba) are shown in table 3, and each measuring the results are shown in table 4.In addition, adopting (M as green-emitting phosphor
3-x-yEu
xTb
y) O
3MgO2SiO
2The composition and the synthesis condition of the fluorophor of all kinds when (in the formula, M represents at least a among Ca, Sr, the Ba) are shown in table 5, and each measuring the results are shown in table 6.
Specimen coding 30 is above-mentioned comparative examples in table 1, table 3 and the table 5, and the specimen coding 1～4 in the table 1, the specimen coding 11～19 in the table 3, and table 5 in specimen coding 21～25 be embodiment.In addition, in table 2, table 4 and table 9, project " brightness rate of change r1 " is the brightness rate of change r1 of the green-emitting phosphor in the above-mentioned panel sealing operation, and the brightness rate of change r2 of project " brightness rate of change r2 " when carrying out above-mentioned panel accelerated life test.
Table 1
Table 2
| The test portion numbering | Brightness rate of change r1 (%) | Brightness rate of change r2 (%) | Address error | Nozzle stops up | Brightness B (cd/m 2) |
| 1 | -1.2 | -1.5 | Do not have | Do not have | 305 |
| 2 | -1.0 | -0.5 | Do not have | Do not have | 315 |
| 3 | -1.3 | -0.8 | Do not have | Do not have | 309 |
| 4 | -1.5 | -1.2 | Do not have | Do not have | 330 |
| 30 | -12.7 | -14.1 | Have | Have | 275 |
Specimen coding 30 is a comparative example
Table 3
Table 4
| Specimen coding | Brightness rate of change r1 (%) | Brightness rate of change r2 (%) | Address error | The obstruction of nozzle | Brightness B (cd/m 2) |
| 11 | -0.8 | -1.0 | Do not have | Do not have | 305 |
| 12 | -1.0 | -1.3 | Do not have | Do not have | 315 |
| 13 | -0.9 | -1.2 | Do not have | Do not have | 309 |
| 14 | -0.5 | -0.8 | Do not have | Do not have | 330 |
| 15 | -0.6 | -0.9 | Do not have | Do not have | 318 |
| 16 | -0.5 | -0.7 | Do not have | Do not have | 320 |
| 17 | -0.8 | -1.0 | Do not have | Do not have | 317 |
| 18 | -0.7 | -0.9 | Do not have | Do not have | 310 |
| 19 | -0.9 | -1.1 | Do not have | Do not have | 320 |
| 30 | -12.7 | -14.1 | Have | Have | 275 |
Specimen coding 30 is a comparative example
Table 5
Table 6
| Specimen coding | Brightness rate of change r1 (%) | Brightness rate of change r2 (%) | Address error | The obstruction of nozzle | Brightness B (cd/m 2) |
| 21 | -1.2 | -0.9 | Do not have | Do not have | 318 |
| 22 | -1.2 | -1.5 | Do not have | Do not have | 320 |
| 23 | -1.5 | -0.8 | Do not have | Do not have | 317 |
| 24 | -1.8 | -1.5 | Do not have | Do not have | 310 |
| 25 | -1.1 | -1.1 | Do not have | Do not have | 320 |
| 30 | -12.7 | -14.1 | Have | Have | 275 |
Specimen coding 30 is a comparative example
Shown in table 2, table 4 and table 6, in duplicate 10, the brightness rate of change r1 of panel sealing operation is-12.7%, and the brightness rate of change r2 during the panel accelerated life test is-14.1%.In addition, the address discharge time has address error, and the panel luminance B during green comprehensive bright lamp is 275cd/m
2In addition, be used to be coated with the printing ink apparatus for coating of fluorophor printing ink, nozzle take place when using 200 hours stop up.
On the other hand, use (M
1-x-yEu
xTb
y) OMgO2SiO
2As the specimen coding 1～4 of green-emitting phosphor, as shown in table 2, the panel luminance B during green comprehensive bright lamp shows and exceeds 300cd/m
2Value.In addition, the brightness rate of change r1 of panel sealing operation is-1.0%～-1.5%, and the brightness rate of change r2 during the panel accelerated life test is-0.5%～-1.5%.Zero-address mistake when in addition, discharge in the address.In addition, be used to be coated with the printing ink apparatus for coating of printing ink, nozzle do not take place when using 200 hours stop up.
In addition, use (M
2-x-yEu
xTb
y) O
2MgO2SiO
2As the specimen coding 11～19 of green-emitting phosphor, as shown in table 4, the panel luminance B during green comprehensive bright lamp shows and exceeds 300cd/m
2Value.In addition, the brightness rate of change r1 of panel sealing operation is-0.5%～-1.0%, and the brightness rate of change r2 during the panel accelerated life test is-0.7%～-1.3%.Zero-address mistake when in addition, discharge in the address.In addition, be used to be coated with the printing ink apparatus for coating of printing ink, nozzle do not take place when using 200 hours stop up.
In addition, use (M
3-x-yEu
xTb
y) O
3MgO2SiO
2As the specimen coding 21～25 of green-emitting phosphor, as shown in table 6, the panel luminance B during green comprehensive bright lamp shows and exceeds 300cd/m
2Value.In addition, the brightness rate of change r1 of panel sealing operation is-1.1%～-1.8%, and the brightness rate of change r2 during the panel accelerated life test is-0.8%～-1.5%.Zero-address mistake when in addition, discharge in the address.In addition, be used to be coated with the printing ink apparatus for coating of printing ink, nozzle do not take place when using 200 hours stop up.
Promptly, the embodiment sample of one embodiment of this invention (specimen coding 1～4,11～19,21～25), compare with the sample (specimen coding 30) of comparative example, the nozzle that zero-address mistake and being used to is coated with the printing ink apparatus for coating of printing ink when the brightness rate of change the when panel luminance during green comprehensive bright lamp, the brightness rate of change of panel sealing operation, panel accelerated life test, address discharge stops up and all shows excellent characteristic.
That is, green-emitting phosphor of the present invention is the (M that has that adopts aqueous solution synthetic method, hydrothermal synthesis method, spraying synthetic method or Hydrolyze method making
A-x-yEu
xTb
y) O
aMgO2SiO
2The fluorophor of (in the formula, M represents at least a among Ca, Sr, the Ba) structure since synthetic be the less spherical fluorophor particle (average grain diameter 0.1 μ m～3.0 μ m) that slightly is, so, must carry out particle hardly and pulverize.In addition, not as original Zn
2SiO
4: Mn is such, and the ZnO selectivity is dispersed (distillation) and produced oxygen defect, the thing that causes brightness to worsen.Therefore, in the green-emitting phosphor of the present embodiment, by suppressing the generation of oxygen defect, the crystallinity of oxygen defect of then resulting from descends and to be difficult to carry out, and particularly green brightness worsens and is suppressed, and the ultraviolet ray amount that absorbs in the oxygen defect reduces, then carry out exciting of luminescence center easily, therefore, with original comparing, brightness improves.
Utilize possibility on the industry
According to plasm display device of the present invention and manufacture method thereof, can be provided in the plasm display device that has the green-emitting phosphor that is difficult to Dimming in the panel manufacturing process, be conducive to improve brightness, life-span, the reliability of the plasm display device of large picture image display unit.
Claims (10)
1. plasm display device, this device is the plasm display device that possesses following plasma display, described plasma display is to arrange a plurality of monochromes or polychrome discharge cell, luminescent coating corresponding to each discharge cell color is set simultaneously, this luminescent coating is by ultraviolet ray excited and luminous, it is characterized in that described luminescent coating has the green-emitting phosphor layer, described green-emitting phosphor layer contains useful chemical formula (M simultaneously
A-x-yEu
xTb
y) O
aMgO2SiO
2The green-emitting phosphor of expression, in the formula, M represents at least a among Ca, Sr, the Ba, a=1,0≤x≤0.1,0.01≤y≤0.2.
2. plasm display device, this device is the plasm display device that possesses following plasma display, described plasma display is to arrange a plurality of monochromes or polychrome discharge cell, luminescent coating corresponding to each discharge cell color is set simultaneously, this luminescent coating is by ultraviolet ray excited and luminous, it is characterized in that described luminescent coating has the green-emitting phosphor layer, described green-emitting phosphor layer contains useful chemical formula (M simultaneously
A-x-yEu
xTb
y) O
aMgO2SiO
2The green-emitting phosphor of expression, in the formula, M represents at least a among Ca, Sr, the Ba, a=2,0.02≤x≤0.2,0.01≤y≤0.05.
3. plasm display device, this device is the plasm display device that possesses following plasma display, described plasma display is to arrange a plurality of monochromes or polychrome discharge cell, luminescent coating corresponding to each discharge cell color is set simultaneously, this luminescent coating is by ultraviolet ray excited and luminous, it is characterized in that described luminescent coating has the green-emitting phosphor layer, described green-emitting phosphor layer contains useful chemical formula (M simultaneously
A-x-yEu
xTb
y) O
aMgO2SiO
2In the green-emitting phosphor formula of expression, M represents at least a among Ca, Sr, the Ba, a=3,0≤x≤0.1,0.01≤y≤0.2.
4. according to the plasm display device of any record in the claim 1～3, it is characterized in that, the average grain diameter of above-mentioned green-emitting phosphor is 0.1 μ m～3.0 μ m, and the thickness that contains the above-mentioned green-emitting phosphor layer of above-mentioned green-emitting phosphor is 3 μ m～20 μ m.
5. the manufacture method of a plasm display device, this method is to have a plurality of monochromes or polychrome discharge cell are arranged, luminescent coating corresponding to each discharge cell color is set simultaneously, this luminescent coating is by the manufacture method of the plasm display device of ultraviolet ray excited and luminous plasma display, it is characterized in that, described luminescent coating has the green-emitting phosphor layer, and the green-emitting phosphor layer contains useful (M simultaneously
A-x-yEu
xTb
y) O
aMgO2SiO
2In the green-emitting phosphor formula of expression, M represents at least a among Ca, Sr, the Ba, a=1,0≤x≤0.1,0.01≤y≤0.2, and, this green-emitting phosphor made by any synthetic method of aqueous solution synthetic method, hydrothermal synthesis method, spraying synthetic method or hydrolysis synthetic method.
6. the manufacture method of a plasm display device, this method is to have a plurality of monochromes or polychrome discharge cell are arranged, luminescent coating corresponding to each discharge cell color is set simultaneously, this luminescent coating is by the manufacture method of the plasm display device of ultraviolet ray excited and luminous plasma display, it is characterized in that, described luminescent coating has the green-emitting phosphor layer, and the green-emitting phosphor layer contains useful (M simultaneously
A-x-yEu
xTb
y) O
aMgO2SiO
2In the green-emitting phosphor formula of expression, M represents at least a among Ca, Sr, the Ba, a=2,0.02≤x≤0.2,0.01≤y≤0.05, and, this green-emitting phosphor made by any synthetic method of aqueous solution synthetic method, hydrothermal synthesis method, spraying synthetic method or hydrolysis synthetic method.
7. the manufacture method of a plasm display device, this method is to have a plurality of monochromes or polychrome discharge cell are arranged, luminescent coating corresponding to each discharge cell color is set simultaneously, this luminescent coating is by the manufacture method of the plasm display device of ultraviolet ray excited and luminous plasma display, it is characterized in that, described luminescent coating has the green-emitting phosphor layer, and the green-emitting phosphor layer contains useful (M simultaneously
A-x-yEu
xTb
y) O
aMgO2SiO
2In the green-emitting phosphor formula of expression, M represents at least a among Ca, Sr, the Ba, a=3,0≤x≤0.1,0.01≤y≤0.2, and, this green-emitting phosphor made by any synthetic method of aqueous solution synthetic method, hydrothermal synthesis method, spraying synthetic method or hydrolysis synthetic method.
8. according to the manufacture method of any plasm display device of being put down in writing in the claim 5～7, it is characterized in that, aqueous solution synthetic method as above-mentioned green-emitting phosphor synthetic method comprises: phosphor raw material and aqueous medium are mixed, form the mixed liquor production process of mixed liquor; With this mixed liquor and alkaline aqueous solution are mixed, form the hydrate production process of hydrate; The solution that contains this hydrate with handle is heat-treated under 700 ℃～900 ℃ temperature in air, makes the heat treatment step of precursor; In reducing atmosphere, in 1000 ℃～1400 ℃ operations that above-mentioned precursor is calcined.
9. according to the manufacture method of any plasm display device of being put down in writing in the claim 5～7, it is characterized in that, hydrothermal synthesis method as above-mentioned green-emitting phosphor synthetic method comprises: phosphor raw material and aqueous medium are mixed, form the mixed liquor production process of mixed liquor; With this mixed liquor and alkaline aqueous solution are mixed, form the hydrate production process of hydrate; The solution that contains this hydrate with handle carries out the hydro-thermal synthesis procedure that hydrothermal synthesis reaction is made precursor under 100 ℃～300 ℃ of temperature, pressure 0.2MPa～10MPa state; In reducing atmosphere, in 800 ℃～1400 ℃ operations that above-mentioned precursor is calcined.
10. according to the manufacture method of any plasm display device of being put down in writing in the claim 5～7, wherein, spraying synthetic method as above-mentioned green-emitting phosphor synthetic method comprises: phosphor raw material and aqueous medium are mixed, make the mixed liquor production process of mixed liquor; With, this mixed liquor and alkaline aqueous solution are mixed, make the hydrate production process of hydrate; With, the solution spray that contains this hydrate in the stove that is heated to be 1000 ℃～1500 ℃ of temperature, is made the spraying operation of precursor; In reducing atmosphere, in 800 ℃～1400 ℃ operations that above-mentioned precursor is calcined.
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|---|---|---|---|---|
| US4088599A (en) * | 1975-07-11 | 1978-05-09 | Hitachi, Ltd. | Terbium-activated alkaline-earth metal silicate phosphors |
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