CA2191333C - Phosphor with afterglow characteristic - Google Patents
Phosphor with afterglow characteristic Download PDFInfo
- Publication number
- CA2191333C CA2191333C CA002191333A CA2191333A CA2191333C CA 2191333 C CA2191333 C CA 2191333C CA 002191333 A CA002191333 A CA 002191333A CA 2191333 A CA2191333 A CA 2191333A CA 2191333 C CA2191333 C CA 2191333C
- Authority
- CA
- Canada
- Prior art keywords
- moles
- phosphor
- mol
- afterglow
- proportion
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7783—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals one of which being europium
- C09K11/7792—Aluminates
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
- C09K11/7734—Aluminates
Abstract
A phosphor exhibiting afterglow more intensely and persistently than (Sr, Eu, Dy)O.cndot.Al2O3 phosphors. The phoshor has a chemical composition comprising mainly an Eu2+ activated strontium aluminate phosphor substance as a matrix in which a part of the strontium (Sr) is substituted with at least one of Pb, Dy and Zn.
Description
PHOSPHOR WITH AFTERGLOW CHARACTERISTIC
Technical Field The present invention relates to a phosphor or fluorescent substance having afterglow characteristics and adapted for example for use in luminous paint and the like.
Background Art In the past, there has been the occurrence of a so-called "afterglow phenomenon" as a characteristic of a phosphor or fluorescent substance. For instance, in the case of zinc silicate (Zn~SiO,:Mn2*)-type phosphor, the occurrence of such "afterglow phenomenon" will be caused depending on the selection of its composition, firing conditions, etc. Also, "afterglow phenomenon" occurs not only in the case of zinc silicate (ZnSiO,:EuZ') type but also in the case of strontium aluminate type SAE ( 4Sr0~ 7A12 03 : EuZ * ) , etc .
However, the duration times of their afterglow are merely on the order of several seconds at the most, and also it is recognized that as regards the characteristics of the phosphor, generally the possession of afterglow characteristics is not desirable and rather tends to deteriorate the fluorescence characteristics.
Then, in addition to the above-mentioned SAE (49'0 nm), such substances as 2Sr0~3A1203 (SAL: 460 nm) are also known as the so-called strontium aluminate phosphor. It has been reported that not only these phosphors are different in the emission peaking but also they are different compounds in terms of the crystal structure (B. Smets, J. Rutten, G. Hocks and J. Verlijsdonk; J. Electrochem. Soc. 136, 2119, 1989).
However, while the investigations have been vigorously conducted on the strontium aluminates having emission wave-lengths of "blue" or "blue green" as light emitting phosphors for lamps, such investigations as aimed toward improving the afterglow phenomenon as in the case of the so-called "luminous paints" have been practically unknown.
Recently, phosphors have been proposed which have long afterglow characteristics by virtue of the addition of dysprosium (Dy) or the like (JP-A-7-11250, EP-A-0 622 440, US-A-5,424,006). Such phosphor is represented in terms of a compound MA1z04, and more particularly it is a compound in the form of a mother crystal in which M represents at least one metal element selected from the group consisting of calcium, strontium and barium and which contains europium (Eu) as an activator in an amount of not less than 0.001 o and not greater than 10 ~ in terms of mol o relative to the metal element represented by M and also, as a co-activator, at least one element selected from the group consisting of lanthanum, cerium, praseodymium, neodymium, samarium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, manganese, tin and bismuth in an amount of not less than 0.001 ~ and not greater than 10 ~ in terms of mol ~ relative to the metal element represented by M. It is to be noted that the afterglow of this proposed phosphor is the emission of light having a greenish color tone.
Disclosure of Invention The inventors have made earnest efforts in the production of a phosphor having more intense and longer afterglow characteristics by utilizing one of the previously mentioned 2 i 9 i 333 compounds MA12 O4 , more particularly a phosphor ( SrO~ A12 03 : Euz Dyz+) in which strontium and aluminate are added in the same mol with each other as a reference sample.
As a result, the inventors have succeeded in the production of phosphors having more intense and longer afterglow characteristics by utilizing as matrices the phosphor SrO~ yAl2 03 : Eu2 ' containing strontium and aluminate in varying proportions. In addition, the production of a phosphor having more intense and longer afterglow characteristics has been succeeded by adding a trace amount of a novel additive element to the previously mentioned compound MA1204.
In other words, it is the primary object of the present invention to provide a phosphor having more intense and longer afterglow characteristics, and more particularly, it is another object of the present invention to provide a phosphor in which strontium and aluminate are activated by europium and added in the same mol proportion with each other, thus ensuring more intense and longer afterglow characteristics than those of the conventional phosphor ( SrO~ A12 03 : Eu2 + Dyz + ) .
In accordance with the present invention, the above objects are achieved by any of the phosphors with afterglow characteristic which are stated in the claims.
The present invention provides a first phosphor with afterglow characteristic which comprises a matrix composed of an Euz+ activated strontium aluminate-type phosphor and has a chemical composition expressed by:
(Sr, Eu, Pb)O~y(A1, Bi)z03 where Sr + Eu + Pb = 1, A1 + Bi = 2y.
A preferred aspect of the first phosphor has a chemical composition shown as follows:
Technical Field The present invention relates to a phosphor or fluorescent substance having afterglow characteristics and adapted for example for use in luminous paint and the like.
Background Art In the past, there has been the occurrence of a so-called "afterglow phenomenon" as a characteristic of a phosphor or fluorescent substance. For instance, in the case of zinc silicate (Zn~SiO,:Mn2*)-type phosphor, the occurrence of such "afterglow phenomenon" will be caused depending on the selection of its composition, firing conditions, etc. Also, "afterglow phenomenon" occurs not only in the case of zinc silicate (ZnSiO,:EuZ') type but also in the case of strontium aluminate type SAE ( 4Sr0~ 7A12 03 : EuZ * ) , etc .
However, the duration times of their afterglow are merely on the order of several seconds at the most, and also it is recognized that as regards the characteristics of the phosphor, generally the possession of afterglow characteristics is not desirable and rather tends to deteriorate the fluorescence characteristics.
Then, in addition to the above-mentioned SAE (49'0 nm), such substances as 2Sr0~3A1203 (SAL: 460 nm) are also known as the so-called strontium aluminate phosphor. It has been reported that not only these phosphors are different in the emission peaking but also they are different compounds in terms of the crystal structure (B. Smets, J. Rutten, G. Hocks and J. Verlijsdonk; J. Electrochem. Soc. 136, 2119, 1989).
However, while the investigations have been vigorously conducted on the strontium aluminates having emission wave-lengths of "blue" or "blue green" as light emitting phosphors for lamps, such investigations as aimed toward improving the afterglow phenomenon as in the case of the so-called "luminous paints" have been practically unknown.
Recently, phosphors have been proposed which have long afterglow characteristics by virtue of the addition of dysprosium (Dy) or the like (JP-A-7-11250, EP-A-0 622 440, US-A-5,424,006). Such phosphor is represented in terms of a compound MA1z04, and more particularly it is a compound in the form of a mother crystal in which M represents at least one metal element selected from the group consisting of calcium, strontium and barium and which contains europium (Eu) as an activator in an amount of not less than 0.001 o and not greater than 10 ~ in terms of mol o relative to the metal element represented by M and also, as a co-activator, at least one element selected from the group consisting of lanthanum, cerium, praseodymium, neodymium, samarium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, manganese, tin and bismuth in an amount of not less than 0.001 ~ and not greater than 10 ~ in terms of mol ~ relative to the metal element represented by M. It is to be noted that the afterglow of this proposed phosphor is the emission of light having a greenish color tone.
Disclosure of Invention The inventors have made earnest efforts in the production of a phosphor having more intense and longer afterglow characteristics by utilizing one of the previously mentioned 2 i 9 i 333 compounds MA12 O4 , more particularly a phosphor ( SrO~ A12 03 : Euz Dyz+) in which strontium and aluminate are added in the same mol with each other as a reference sample.
As a result, the inventors have succeeded in the production of phosphors having more intense and longer afterglow characteristics by utilizing as matrices the phosphor SrO~ yAl2 03 : Eu2 ' containing strontium and aluminate in varying proportions. In addition, the production of a phosphor having more intense and longer afterglow characteristics has been succeeded by adding a trace amount of a novel additive element to the previously mentioned compound MA1204.
In other words, it is the primary object of the present invention to provide a phosphor having more intense and longer afterglow characteristics, and more particularly, it is another object of the present invention to provide a phosphor in which strontium and aluminate are activated by europium and added in the same mol proportion with each other, thus ensuring more intense and longer afterglow characteristics than those of the conventional phosphor ( SrO~ A12 03 : Eu2 + Dyz + ) .
In accordance with the present invention, the above objects are achieved by any of the phosphors with afterglow characteristic which are stated in the claims.
The present invention provides a first phosphor with afterglow characteristic which comprises a matrix composed of an Euz+ activated strontium aluminate-type phosphor and has a chemical composition expressed by:
(Sr, Eu, Pb)O~y(A1, Bi)z03 where Sr + Eu + Pb = 1, A1 + Bi = 2y.
A preferred aspect of the first phosphor has a chemical composition shown as follows:
(Sro.9ss.Euo.o3.pbo.ois)0'Alz.s9i Blo.oos ~4.s%
The present invention also provides a second phosphor with afterglow characteristic which comprises a matrix composed of an Eu2' activated strontium aluminate-type phosphor and has a chemical composition expressed by:
(Sr, Eu, Pb, Dy)O~ y(A1, Hi)20, (where Sr + Eu + Pb + Dy = 1, A1 + Hi = 2y) with the range of y being selected 0.83 ~ y ~ 1.67 and the proportions (mol) of the respective elements being selected 0.016 ,~ Eu ~ 0.033, 0.006 s_ Pb ~ 0.017, 0.050 ~ Dy ~ 0.133, 1.655 ~ A1 ~ 3.334, and 0.0030 ~ Bi ~ 0.0100.
In accordance with a preferred aspect of the second phosphor, the range of y is 1.00 ~ y ~ 1.15, and the proportions (mol) of the respective elements are 0.020 ~ Eu ~ 0.023, 0.010 ,~ Pb ~ 0.011, 0.05 ~ Dy ~ 0.133, 1.994 ~ A1 ~ 2.2964 and 0.0036 ~ Bi ~ 0.006.
The present invention also provides a third phosphor with afterglow characteristic which comprises a matrix composed of an Eu" activated strontium aluminate-type phosphor and has a chemical composition expressed by:
(Sr, Eu, Pb, Dy)O~ (A1, Bi)z03 (where Sr + Eu + Pb + Dy = 1, Al + Bi = 2 with the_proportions (mol) of the respective elements being selected 0.016 ,~ Eu ,S 0.02, 0.006 ~, Pb ~ 0.010, 0.060 ~ Dy ~
0.133, 1.994 ,~ A1 ~ 1.9964 and 0.0036 ,~ Bi ~ 0.006.
In accordance with a preferred aspect of the third phosphor, the proportions (mol) of the respective elements are selected 0.017 ~ Eu ~, 0.03, 0.008 ~, Pb ,~ 0.017, 0.08 ,~ Dy ~
0.11, 1.994 ~ A1 ~ 1.9964 and 0.0036 ~ Hi ~ 0.006.
The present invention also provides a second phosphor with afterglow characteristic which comprises a matrix composed of an Eu2' activated strontium aluminate-type phosphor and has a chemical composition expressed by:
(Sr, Eu, Pb, Dy)O~ y(A1, Hi)20, (where Sr + Eu + Pb + Dy = 1, A1 + Hi = 2y) with the range of y being selected 0.83 ~ y ~ 1.67 and the proportions (mol) of the respective elements being selected 0.016 ,~ Eu ~ 0.033, 0.006 s_ Pb ~ 0.017, 0.050 ~ Dy ~ 0.133, 1.655 ~ A1 ~ 3.334, and 0.0030 ~ Bi ~ 0.0100.
In accordance with a preferred aspect of the second phosphor, the range of y is 1.00 ~ y ~ 1.15, and the proportions (mol) of the respective elements are 0.020 ~ Eu ~ 0.023, 0.010 ,~ Pb ~ 0.011, 0.05 ~ Dy ~ 0.133, 1.994 ~ A1 ~ 2.2964 and 0.0036 ~ Bi ~ 0.006.
The present invention also provides a third phosphor with afterglow characteristic which comprises a matrix composed of an Eu" activated strontium aluminate-type phosphor and has a chemical composition expressed by:
(Sr, Eu, Pb, Dy)O~ (A1, Bi)z03 (where Sr + Eu + Pb + Dy = 1, Al + Bi = 2 with the_proportions (mol) of the respective elements being selected 0.016 ,~ Eu ,S 0.02, 0.006 ~, Pb ~ 0.010, 0.060 ~ Dy ~
0.133, 1.994 ,~ A1 ~ 1.9964 and 0.0036 ,~ Bi ~ 0.006.
In accordance with a preferred aspect of the third phosphor, the proportions (mol) of the respective elements are selected 0.017 ~ Eu ~, 0.03, 0.008 ~, Pb ,~ 0.017, 0.08 ,~ Dy ~
0.11, 1.994 ~ A1 ~ 1.9964 and 0.0036 ~ Hi ~ 0.006.
The above-mentioned first, second and third phosphors according to the present invention can each have a chemical composition in which a part of strontium (Sr) is substituted with zinc (Zn).
This substitution of zinc (Zn) is such that a good result can be obtained by substituting several mol o, preferably 1.3 to 2.6 mol o of strontium (Sr) with zinc.
The present invention also provides a fourth phosphor with afterglow characteristic which comprises a matrix composed of an Eu2+ activated strontium aluminate-type phosphor and has a chemical composition expressed by:
(Sr, Zn, Eu, Pb, Dy)O~ (A1, Bi)z03 where Sr + Zn + Eu + Pb + Dy = 1, A1 + Bi = 2, and the proportions of the respective elements in one molecule are 0.013 s Zn s 0.027, 0.017 S Eu s 0.03, 0.008 s Pb S_ 0.017, 0.05 S Dy s 0.133, 1.994 s A1 s 1.9964 and 0.0036 s Bi S 0.006.
The present invention also provides a fifth phosphor with afterglow characteristic which comprises a matrix composed of an Eu2+ activated strontium aluminate-type phosphor and has a chemical composition expressed by:
(Sr, Zn, Eu, Dy)O~ A1z 03 where Sr + Zn + Eu + Dy = 1.
In accordance with a preferred aspect of the fifth phosphor, the proportions (mol) of the respective elements are 0.005 S Zn S 0.010, Eu = 0.20 and Dy = 0.05.
In accordance with the present invention, a phosphor in which the proportions of Sr0 and A1203 are different from 1:1 is used as a matrix. This matrix phosphor is mixed with trace elements of various proportions so as to produce a phosphor which is excellent in afterglow characteristics.
With the phosphor according to this invention comprising as its matrix an Sr0-yA1z03:Eu2'-type phosphor in which the proportions of Sr0 and A1203 are different from 1:1, where the proportion of Sr(or Sr0) is selected to be 1 mol, if the proportion of A1, for example, is 3 mol (namely, the proportion of A1203 is 1.5 mol), it is possible to ensure more intense afterglow characteristics by substituting a part of Sr with Pb and also substituting a part of A1 with Bi even if it is set so that Dy = 0. Thus, the first phosphor according to the present invention has the chemical composition expressed by:
(Sr, Eu, Pb)O-y(A1, Bi)a0$
where Sr + Eu + Pb = 1, A1 + Hi = 2y.
The contents of Pb and Bi in the first phosphor can be very small, and where the proportion of Sr (or Sr0) is selected to be 1 mol,if the proportion of A1, for example, is 3 mol (namely, the proportion of A120g is 1.5 mol), it is preferable to select so that the proportion of Pb substituting a part of Sr is 0.015 mol and the proportion of Hi substituting a part of A1 is 0.009 mol. Also, in the case of this fluorescent substance, .the afterglow characteristics will be deteriorated extremely if any of Pb and Bi lacks. Therefore, an especially preferred chemical composition of the first phosphor is represented by:
(Sro.9ss.Euo.omPbo.ois)O~Al2.ssi Blo.oos ~e.sJ
It is to be noted that even in the preparation process of the phosphor according to the invention, it is desirable to use a trace amount of boric acid (HaH03) as a flux in the like manner as the conventional procedure. It has been confirmed that the composition of the fired phosphor will be caused to loose its uniformity and the emission characteristic will be deteriorated considerably if no boric acid is used or if it is used in an extremely small amount. Not only boric acid acts as a flux (the promotion of crystal growth) but also a very small part of it remains as boron in the phosphor. While it is presumed that this remaining boron changes the phase of beta-alumina, its reason has not been generally clarified as yet.
However, where at least two crystals or phases are present, it is considered that boron has an action of bonding the two together.
Then, while the afterglow produced by a phosphor having the composition represented by (Sr, Eu, Pb)0~y(A1, Bi)ZOs (where Sr + Eu + Pb = 1, A1 + Bi = 2y) is comparatively intense and excellent in color tone, the duration time of the afterglow is not so long as intended by the present invention although it is longer than in the case of the conventional phosphors.
In this connection, the second phosphor according to the present invention contains Dy in addition to Pb and Hi so as to ensure the afterglow of a still longer life (in the case of Pb and Hi alone, the afterglow decays rapidly although its intensity is high).
More specifically, the second phosphor has the composition expressed by (Sr, Eu, Pb, Dy)O~y(A1, Hi)Z03 (where Sr + Eu + Pb + Dy = 1_, A1 + Bi = 2y) . ' As regards the proportions of (Sr + Eu + Pb + Dy) and (A1 + Hi) relative to each other in the second phosphor (Sr, Eu, Pb, Dy)O~y(A1, Hi}ZOa (where Sr + Eu + Pb + Dy = 1, A1 + Hi = 2y), it has been confirmed that if, for example, the proportion of (A1 + Hi) is 3 mol, the proportion of (Sr + Eu + Pb + Dy) is in the range from 0.9 to 1.8 mol and an especially preferred range is from 1.3 to 1.5 mol. Also, it has been confirmed that this ratio (Sr + Eu + Pb + Dy)/(A1 + Bi) is the same in the cases where proportion of (A1 + Bi) is 4 mol and 5 mol, respectively.
Thus, in the case of the second phosphor (Sr, Eu, Pb, Dy)0 ~y(A1, Bi)203, it is possible to improve the afterglow characteristics by increasing the proportion of Dy.
AS regards the relation between (Sr + Eu + Pb + Dy) and (A1 + Bi), it has been confirmed that if the proportion of (Sr + Eu + Pb + Dy) is excessively high as compared with that of (A1 + Bi), the afterglow performance is deteriorated extremely, whereas if the proportion of (Sr + Eu + Pb + Dy) is excessively low as compared with that of (A1 + Bi), the afterglow performance is deteriorated and the duration time of the afterglow is also decreased.
It follows from this that it is most preferable to prepare the phosphor in a way that the proportions of (Sr + Eu + Pb + Dy)0 and (A1 + Bi)203 are the same with each other. In other words, it has been confirmed that it is most preferable to blend (A1 + Bi) in a way that its proportion becomes two times that of (Sr + Eu + Pb + Dy).
Thus, the third phosphor according to this invention has the chemical composition given by (Sr, Eu, Pb, Dy)O~(Al,Bi)ZOa (where Sr + Eu + Pb + Dy = 1, A1 + Bi = 2).
In this third phosphor (Sr, Eu, Pb, Dy)O~y(A1, Bi)203, the proportion of Dy has a certain range for ensuring excellent afterglow characteristics. For instance, where the proportion of Sr (or Sr0) in one unit molecule is selected to be 1.5 mol, if the proportion of A1 is 3 mol (namely, the proportion of A1z03 is 1.5 mol), the proportion of 0.09 for Dy is still insufficient although the afterglow characteristics are 21913.3 recognized. Preferably, excellent afterglow characteristics can be obtained by selecting the proportion of Dy to come within the range from 0.12 to 0.15 mol. While the afterglow intensity is still decreased slightly when the proportion of Dy is selected to come within the range of 0.18 to 0.20 mol, contrary the duration time of the afterglow is increased in proportion to an increase in the proportion of Dy.
This third phosphor corresponds to a phosphor produced by substituting a part of Sr with Pb and a part of A1 with Bi in the previously mentioned reference phosphor having the composition of (Sr, Eu, Dy)O~A1z03 (where Sr + Eu + Dy = 1).
However, while, in the case of the third phosphor of the present invention, it is certainly most preferable to blend (A1 + Bi) in a manner that its proportion becomes two times that of (Sr + Eu + Pb + Dy) as compared with the previously mentioned composition of (Sr, Eu, Dy)O~A1z03 (where Sr + Eu +
Dy = 1) which requires an exact control of the proportions, the third phosphor differs greatly from the conventional phosphor in that sufficient afterglow characteristics can be obtained without performing any exact control of the proportions.
This can be considered in this way that the inclusion of Pb in the fluorescent substance results in a crystal structure which is different from the conventional phosphor of (Sr, Eu, Dy)O~A1z03 or, while the crystal structure is the same, the presence of Pb maintains the crystal structure stable thus making it possible to withstand the further addition of Dy.
Further, in the case of this third phosphor produced by substituting a part of Sr with Pb and substituting a part of A1 with Bi in the conventional phosphor of the composition (Sr, Eu, Dy)O~A1z03 (where Sr + Eu + Dy = 1), the characteristics as the 21913.x:3 phosphor are improved over two times at the maximum.
With the above-mentioned first, second and third phosphors of (Sr, Eu, Pb, Dy)O~y(A1, Bi)z03 according to the invention, while it is not clear how the substitution of a part of Sr with Zn relates to the afterglow characteristics, it has been found that the addition of Zn remarkably improves the response of the fluorescent characteristics in addition to the improvement of the basic fluorescent characteristics. While it is difficult to give any definite expression in terms of a numerical value and generally the afterglow is hidden by the reflected light thus making its visual observation difficult in a condition where there is even a slight light, the addition of Zn improves the initial intensity thus making it possible to easily perceive the afterglow.
Particularly, the fourth phosphor having afterglow characteristics according to the invention has the composition given by (Sr, Zn, Eu, Pb, Dy)O~(A1, Bi)zOa (where Sr + Zn + Eu + Pb + Dy = 1, A1 + Bi = 2) and the proportions (mol) of the respective elements are 0.013 5_ Zn s 0.027, 0.017 s Eu s 0.03, 0.008 S_ Pb S 0.017, 0.05 S_ Dy s 0.133, 1.994 s A1 s 1.9964 and 0.0036 S_ Bi S_ 0.006).
While, in the fourth phosphor, a part of strontium (Sr) is substituted with lead (Pb), dysprosium (Dy) and zinc (Zn), the composition of this fourth phosphor has been examined as regards the afterglow characteristics of the composition without the addition of Pb. As a result, it has been confirmed that the phosphor of the composition in which a part of Sr is substituted with zinc (Zn) shows the lasting afterglow characteristics even if a part of Sr is not substituted with lead (Pb).
Therefore, the fifth phosphor according to the present invention has the composition given by (Sr, Zn, Eu, Dy)O~A1203 (where Sr + Zn + Eu + Dy = 1, and the proportions (mol) of the respective elements are 0.005 ~ Zn ~ 0.010, Eu = 0.20 and Dy =
0.05).
Brief Description of the Drawings Fig. 1 shows a graph for explaining the afterglow characteristics of a phosphor with the ordinate representing the output voltage (mV) of a luminance meter and the abscissa representing the time (min).
Fig. 2 is a graph showing the measurement results of the afterglow characteristics of sample phosphors (SG-A1-3-5 to SG-A1-3-10) obtained by fixing the proportion of A1 + Bi at 3 mol, the proportion of Eu at 0.03 mol, the proportion of Pb at 0.015 mol and the proportion of Dy at 0.09 mol and varying the proportion of Sr + Eu + Pb + Dy within the range of 0.9 to 2.0 in the case of (Sr, Eu, Pb, Dy)O~y(A1, Bi)z03 phosphor, with the ordinate representing the afterglow intensity Is (the output voltage (mV) of a luminance meter) and the abscissa reprsenting the proportion (mol) of Sr + Eu + Pb + Dy.
Fig. 3 is a graph showing the variations of the afterglow intensity relative to the proportions of Dy in the case of the sample phosphors (SG-A1-3-5, SG-A1-3-12 to SG-A1-3-1T) and the sample phosphor (SG-Dy-6), with the ordinate representing the afterglow intensity Is (the output voltage (mV) of a luminance meter) and the abscissa representing the proportion (mol) of Dy.
Best Mode for Carrying Out the Invention Preparation of phosphors:
~1 ~1 ~~~
Using the following raw materials A to H, the below-mentioned embodiments and comparative phosphors were prepared.
A) Strontium carbonate SrC03 B ) Europium oxide Euz 03 C ) Dysprosium oxide Dyz 03 D) Aluminum oxide alpha-A1203 E) Lead fluoride PbFz F) Basic bismuth carbonate b-BiC03 G) Zinc carbonate ZnC03 H) Boric acid H3 B03 Then, the ranges (mol) of addition per molecule of the respective elements were as follows.
a) Sr 0.90 s Sr s 3.00 b) Eu 0.02 s Eu S 0.05 c) Dy 0.04 s Dy s 0.24 d) A1 2.00 s A1 s 6.00 e) Pb 0.01 S Pb s 0.03 f) Bi 0.009 _S Bi S_ 0.03 g ) Zn 0 . 01 .s Zn s 0 . 04 h) B 0.005 s B s 0.035 It is to be noted that as in the case of the ordinary aluminate-type phosphors, chiefly aluminum fluoride was used in substitution for a part of aluminum oxide for use as a flux.
Also, boric acid was used singly or along with aluminum fluoride as mentioned previously. In fact, when preparing the phosphors, the raw material mixtures were fired in a weak reducing air stream for several hours thereby producing the phosphors which were extremely excellent in fluorescence and afterglow characteristics.
21913~~
Preparation of comparative phosphor (Sr, Eu, Dy)O~A1203:
(Sr, Eu, Dy)O~A1203 phosphor was prepared as the object of comparison for the phosphor having afterglow characteristics according to the present invention. This comparative phosphor comprises a phosphor containing Sr0 and A1203 with the 1:1 ratio. More specifically, 0.925 mol of Sr, 0.025 mol of Eu, 0.05 mol of Dy and 2.00 mol of A1 were mixed and then fired using 0.03 mol of H3B03 as a flux. This comparative phosphor was represented as SG-Dy-6. This comparative phosphor (SG-Dy-6) belonged to the conventional phosphors represented by the previously mentioned compound MA1204 (where M is a compound as a mother crystal comprising at least one metal element selected from a group consisting of calcium, strontium and barium, and there were contained 0.001 o to 10 0 of europium (Eu) in terms of mol o relative to M as an activator and 0.001 % to 10 % in terms of mol ~ relative to the metal element represented by M
of at least one metal element selected from a.group consisting of lanthanum, cerium, praseodymium, neodymium, samarium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, manganese, tin and bismuth as a co-activator).
Verification of afterglow characteristics:
Fig. 1 shows a graph for explaining the afterglow characteristics of the phosphor. Here, the ordinate represents the emission intensity (namely, the output voltage (mV) of a luminance meter) and the abscissa represents the time (min).
The phosphor having the afterglow characteristics means a fluorescent substance adapted to produce the emission of light that lasts even after the interruption of the excitation radiation (a so-called "afterglow"). The initial intensity of the afterglow of the Eu2' activated strontium aluminate-type phosphor is considerably high. However, the afterglow is a kind of radiation and therefore its emission energy decays with the passage of time. Thus, in the verification of the afterglow characteristics of the below-mentioned embodiments the periods of rapid decay of the emission intensity-were avoided and the measured values were recorded after the establishment of the comparatively stable conditions.
More specifically, after a holder containing a sample had been kept in a dark place for over 16 hours, the light from a 27-watt fluorescent lamp was irradiated (for 10 minutes) to the sample in the holder at a distance of 300 mm and then instantly placed in a measuring instrument (the luminance meter;
manufactured by Matsushita Denshi Kogyo R&D Center Corp., the phototube; 8847 manufactured by Hamamatsu Photonix Corp., the recorder; Phoenix PRR5000 manufactured by Toa Dempa Co.,Ltd.), thereby measuring the afterglow characteristics. As shown in Fig. 1, the time at which the digital reading of the luminance meter reached at 1,000 mV after several minutes from the start time (L) of measurement was used as the recording starting time and the decaying conditions thereafter were recorded.
It is to be noted that in the case of the respective embodiments, the readings (mV) at the expiration of 5 minutes from the time of the output voltage of the luminance meter dropping to 1,000 mV were taken as the afterglow intensities (Is) of the samples and also the readings (mV) at the expiration of 30 minutes after the start of the recording were taken as the retention amounts (Im) of the afterglow. Therefore, the afterglow characteristics discussed in connection with the 219 i 3~3 present invention are evaluated in accordance with the afterglow intensity (Is) and the retention amount (Im).
The following TABLE 1 shows the measurement results of the afterglow characteristics of the comparative phosphor (SG-Dy-6).
Table 1 Elapsed time (min) Sample No. Dy (mol) 5 10 15 20 25 30 SG-Dy-6 0.05 290 170 115 085 065 050 (unit; mV) As shown in Table 1, the afterglow intensity (the intensity at the expiration of 5 minutes after the start of the afterglow) and the retention amount (the intensity at the expiration of 30 minutes after the start of the afterglow) of the comparative phosphor (SG-Dy-6) were respectively 290 mV and 50mV. It is to be noted that the commercially available (Sr, Eu, Dy)O~A1203 phosphor (the trade name; G-550, manufactured by Nemoto & Co.,Ltd.) showed the afterglow intensity of 220 mV and the retention amount of 42 mV and therefore it was confirmed that the comparative phosphor (SG-Dy-6) was one having the equivalent afterglow characteristics as the commercially available phosphors. Thus, this comparative phosphor (SG-Dy-6) was employed as the reference object of comparison in the case of the following embodiments.
It is to be noted that with the comparative phosphor (SG-Dy-6), the substitution amount of Dy was varied to prepare a plurality of samples and their afterglow characteristics were measured, showing that the afterglow characteristics were 219 ~ 333 gradually improved in accordance with the substitution amounts of Dy. However, it was confirmed that not only the afterglow but also the emission of fluorescence were lost in the case of the samples in which the substitution amounts of Dy were over 0.10 mol.
From this point, it follows that while the afterglow characteristics are improved in accordance with the substitution amount of Dy, there is an upper limit to the substitution amount of Dy and thus it is presumed that the crystal structure of Sr0~A1203;Eu2' itself is disintegrated if the substitution amount of Dy exceeds 0.10 mol.
In addition, this disintegration of the crystal structure inevitably gives rise to a problem that the proportions of Sr0 and A1z03 constituting the matrix must be controlled exactly.
For instant, if the relative ratio of Sr0 and A1203 deviates greatly from 1:1, that is, where the proportion of Sr (or Sr0) is 1 mol, if the proportion of A1 is 3 mol (namely, the proportion of A1z03 is 1.5 mol), no afterglow characteristics are obtained even if a part of Sr is substituted with Dy.
Embodiment 1. (Pb, Bi-substitution phosphor) In the case of the phosphor (Sr0~A120a :Euz' ) in which the ratio between the proportions of Sr0 and A1z03 is not 1:1, if, for example, the proportion of A1 is made over 3 mol, it is no longer possible to obtain a strong afterglow due to the presence of Dy alone. Thus, in accordance with this embodiment the addition of Pb and Bi resulted in an excellent phosphor.
In other words, with the SrO~ 1 . 5A12 Oa : Euz + phosphor, the afterglow, though weak, was recognized when a part of Sr was substituted with Pb (0.01 mol in terms of the proportion) in its composition. Also, when a part of A1 was substituted with Bi (0.01 mol in terms of the proportion) in this composition, no afterglow was recognized. Further, when a part of Sr was substituted with Pb (0.01 mol in terms of the proportion) and also a part of A1 was substituted with Bi (0.01 mol in terms of the proportion), the afterglow appeared intense.
In_this way, the conditions for the coexistence-of Pb and Bi were searched and the following a) to c) were confirmed.
a) In order to obtain excellent afterglow characteristics, the proportions of Pb and Bi were respectively limited to Pb: 0.015mo1 and Bi: 0.009 mol in the above-mentioned chemical compositions.
b) The afterglow became weak when the proportion of either Pb or Bi was greater than that in the above a).
c) In the above-mentioned composition, the amount of A1 for satisfying the a) had to be between 2.8 mol and 3.2 mol.
Taking the thus obtained conditions into consideration, the proportion of Eu was selected 0.03 mol thereby obtaining a Pb, Bi-substitution phosphor having the composition expressed by:
(Sro.sss. Euo.o3. Pbo.ois) O~A12.9s1 Blo.oos O~.s %
The afterglow characteristics of the phosphor having this composition were as shown by the following tables under the previously mentioned measurement conditions as compared with the ordinary luminous paint (ZnS:CuZ').
Initial 5 min.
afterglow later ZnS:Cu 900 mV ?0 mV
Pb,Hi-substitution phosphor 2,500 mV 50 mV
1 'T
As regards the afterglow retention performance of Pb, Bi-substitution phosphor, it cannot be said to be so excellent as will be seen from the examination of the values at the expiration of 5 minutes. Then, in order to obtain excellent afterglow characteristics, a sample was prepared by substituting a part of Sr with Dy as in the case of the comparative phosphor.
In other words, by utilizing the matrix of the composition Sr0~1.5A1z03:Eu2', sample phosphors having the proportions of Dy set to 0.06 mol were prepared as shown in Table 2 and their initial afterglow and afterglow intensities were measured. The results obtained are shown in Table 3.
Table 2 Sample No. Sr Eu Pb Dy x A1 Bi 2y SG-A1-3-1 0.895 0.030 0.015 0.060 1.0 2.991 0.009 3.0 SG-A1-3-2 0.910 0.030 - 0.060 1.0 3.000 - 3.0 (unit: mol) Table 3 Sample Dy Initial Afterglow No. (mol) Pb, Bi afterglow intensity SG-A1-3-1 0.06 Present 3,700 mV 189 mV
SG-A1-3-2 0.06 None 3,500 mV 180 mV
It was confirmed that as shown in Table 3, when the proportion of A1 was 3 mol, the phosphor in which Pb and Bi co-existed Was excellent in both initial afterglow and afterglow intensity as compared with the phosphor containing Dy singly as an auxiliary agent.
Embodiment 2. (Dy, Pb, Bi-substitution phosphor) With the phosphor having the composition of (Sr, Eu, Pb, Dy)O~y(A1, Bi)z03, the afterglow characteristics were verified in greater detail. As shown in the following Table 4, five kinds of sample phosphors (sample Nos. SG-A1-3-5, SG-A1-3-6, SG-A1-3-7, SG-A1-3-8, SG-A1-3-10) were prepared by fixing the proportions of the respective elements such that A1 + Bi = 3 mol, Eu = 0.03 mol, Pb = 0.015 mol and Dy = 0.09 mol and by varying the proportion of Sr + Eu + Pb + Dy within the range of 0.9 to 2Ø It is to be noted that 0.03 mol of boric acid (boron) was used as a flux in the preparation of these sample phosphors.
Table 4 Sample No. Sr Eu Pb Dy x A1 Bi 2y SG-A1-3-5 1.365 0.03 0.015 0.09 1.5 2.991 0.009 3.0 (0.910)(0.020)(0.O10)(0.06) (1.994)(0.006) SG-A1-3-6 1.165 0.03 0.015 0.09 1.3 2.991 0.009 3.0 (0.896)(0.023)(0.011)(0.069) (1.994)(0.006) SG-A1-3-7 0.865 0.03 0.015 0.09 1.0 2.991 0.009 3.0 (0.865)(0.030)(0.015)(0.09) (1.994)(0.006) SG-A1-3-8 0.765 0.03 0.015 0.09 0.9 2.991 0.009 3.0 (0.850)(0.033)(0.017)(0.10) (1.994)(0.006) SG-A1-3-10 1.665 0.03 0.015 0.09 1.8 2.991 0.009 3.0 (0.925)(0.017)(0.008)(0.05) (1.994)(0.006) * In the Table, the values in the parentheses indicate the mol ratios when (Sr+Eu+Pb+Dy) is 1 mol or (A1+Bi) is 2 mol.
With the resulting samples, the afterglow characteristics were verified according to the previously mentioned measuring method. The results are shown in the following Table 5. Note that Fig. 2 is a graph showing the results of Table 5 with the ordinate representing the afterglow intensity Is (the output ~t 9~ ~~~
voltage (mV) of a luminance meter) and the abscissa representing the proportion (mol) of Sr + Eu + Pb + Dy (= x).
Table 5 Sample Sr+Eu+Pb+Dy 5min lOmin l5min 20min 25min 30min No. (mol) (mV) SG-A1-3-5 1.5 270 165 115 075 065 055 -3-6 1.3 259 145 103 080 065 057 -3-7 1.0 250 145 100 075 060 050 -3-8 0.9 180 120 083 060 055 045 -3-10 1.8 170 110 077 055 045 035 As shown in Table 5 and Fig. 2, it was confirmed that as regards the mol ratio of (Sr + Eu + Pb + Dy) / (A1 + Bi), when, for example, the proportion of (A1 + Bi) was selected 3 mol, the proportion of (Sr + Eu + Pb + Dy) was in the range between 0.9 and 1.8 mol, preferably in the range of 1.3 to 1.5 mol. As a result, when each of the samples was given by (Sr, Eu, Pb, Dy) O~y(A1, Bi)203, the value of y was in the range between 0.83 and 1.67 and the preferred value of y was in the range from 1 to 1.15.
Also, the proportions (mol) of Sr, Eu, Pb and Dy were respectively 0.016 s Eu s 0.033, 0.006 S_ Pb s 0.017 and 0.05 S_~Dy S 0.133 and it was confirmed that the preferred proportions were respectively 0.020 s Eu s 0.023, 0.010 s Pb s 0.011 and 0.060 ~ Dy S_ 0.069.
Embodiment 3. (Dy, Pb, Bi-substitution phosphor) With the phosphors having the chemical composition of (Sr, Eu, Pb, Dy)O~y(A1, Bi)203, the afterglow characteristics were further verified in detail. As shown in Table 6, six kinds of sample phosphors (SG-A1-3-12 to SG-A1-3-17) were prepared, in addition to the sample No. SG-A1-3-5, by fixing the proportions of the respective elements in such a manner that (A1 + Bi) - 3 mol and (Sr + Eu + Pb + Dy) - 1.5 mol and by changing the proportions of Dy and Sr variously. Note that 0.03 mol of boric acid (boron) was used as aflux in the preparation of these sample phosphors, Table 6 Sample No. Sr Eu Pb Dy x A1 Bi 2y SG-A1-3-5 1.365 0.03 0.015 0.09 1.5 2.991 0.009 3.0 (0.910)(0.02)(0.010)(0.06) (1.994)(0.006) SG-A1-3-12 1.335 0.03 0.015 0.12 1.5 2.991 0.009 3.0 (0.890)(0.02)(0.010)(0.08) (1.994)(0.006) SG-A1-3-13 1.320 0.03 0.015 0.135 1.5 2.991 0.009 3.0 (0.880)(0.02)(0.010)(0.09) (1.994)(0.006) SG-A1-3-14 1.305 0.03 0.015 0.150 1.5 2.991 0.009 3.0 (0.870)(0.02)(0.010)(0.10) (1.994)(0.006) SG-A1-3-15 1.290 0.03 0.015 0.165 1.5 2.991 0.009 3.0 (0.860)(0.02)(0.010)(0.11) (1.994)(0.006) SG-A1-3-16 1.275 0.03 0.015 0.180 1.5 2.991 0.009 3.0 (0.850)(0.02)(0.010)(0.12) (1.994)(0.006) SG-A1-3-17 1.255 0.03 0.015 0.200 1.5 2.991 0.009 3.0 (0.837)(0.02)(0.010)(0.133) (1.994)(0.006) * In the Table, the parentheses indicate the values of the mol ratios when it is selected in a manner so that (Sr + Eu + Pb + Dy) - 1 mol or (A1 + Hi) - 2 mol.
With the thus obtained samples, the afterglow characteristics were verified in accordance with the previously mentioned measuring method. The results are shown in the following Table 7.
Table 7 Sample Dy mol 5min lOmin l5min 20min z5min 30min No. (mol ratio) (mV) SG-A1-3-5 0.09 270 165 115 075 065 055 (0.06) SG-A1-3-12 0.12 420 247 176 137 113 097 (0.08) SG-A1-3-13 0.135 420 243 172 133 111 099 (0.09) SG-A1-3-14 0.150 420 241 173 129 109 095 (0.10) SG-A1-3-15 0.165 416 222 165 136 114 104 (0.11) SG-A1-3-16 0.180 360 240 165 135 115 100 (0.12) SG-A1-3-17 0.200 360 230 170 138 115 100 (0.133) The sample phosphors shown in this Table 7 were such that the proportion of (A1 + Bi)(= 3 mol) was adjusted so as to be two times that of (Sr + Eu + Pb + Dy)(= 1.5 mol). This corresponded to that a part of Sr was substituted with Pb and a part of A1 was substituted with Bi in the comparative phosphor having the composition of (Sr, Eu, Dy)O~A1203 (where S r + Eu + Dy = 1 ) .
Then, the sample phosphors (SG-Al-3-5, SG-A1-3-12 to SG-A1-3-17) shown in Tables 6 and 7 were compared in afterglow intensity with the comparative sample phosphor (SG-Dy-6) shown in Table 1. Fig. 3 is a graph showing the variations of the afterglow characteristics with the proportion of Dy. In the Figure, the ordinate indicates the afterglow intensity Is (mV) and the abscissa indicates the proportion (mol) of Dy. It is to be noted that the proportions of Dy are shown in terms of mol ratio with the proportions of (Sr + Eu + Pb + Dy) and (Sr + Eu + Dy) being selected 1 mol. In the Figure, the black spots indicate the afterglow characteristics of the sample phosphors (SG-A1-3-5, SG-A1-3-12 to SG-A1-3-17) shown in Tables 6 and 7 and the white spot indicates the afterglow characteristics of the comparative sample phosphor (SG-Dy-6) shown in TABLE 1.
As mentioned previously, while, in the case of the comparative sample phosphor (SG-Dy-6) containing no Pb and Bi, not only the afterglow characteristics but also the fluorescent characteristics are lost when the proportion of Dy exceeds 0.10 mol, in the case of the sample phosphors (SG-A1-3-5, SG-A1-3-12 to SG-A1-3-17) containing Pb and Bi, as shown in Fig. 3, selecting the proportion of (Sr + Eu + Pb + Dy) to be 1 mol has the effect of ensuring an excellent afterglow intensity when the proportion of Dy is selected in the range from 0.08 to 0.11 mol and slightly decreasing the intensity with the greater proportions of Dy, whereas the retention amount (at the expiration of 30 minutes) is increased in proportion to the proportion of Dy (see Table 7).
Further, while, in the case of the comparative phosphor, the range of the composition showing the afterglow characteristics is limited thus tending to make the preparation of the phosphor difficult, the coexistence of Pb and Bi with Dy has the effect of increasing the range of variations in the substitution amount of Dy tending to make possible the maintenance of stronger afterglow characteristics of two times or over. Particularly, where there is the coexistence of Pb, Bi and Dy, the initial intensity of the afterglow has an extremely high value of about 4,500 mV.
219 ~ 333 Embodiment 4. (Dy, Pb, Bi-substitution phosphor) While, in the case of the Embodiment 3, A1 + Bi and (Sr +
Eu + Pb + Dy) were respectively fixed at 3 mol and 1.5 mol and the proportions of Dy and Sr were changed variously in the phosphor of the composition (Sr, Eu, Pb, Dy)O~y(A1, Bi)203, in the case of the Embodiment 4, as shown in Table 8, three different sample phosphors were prepared in which A1 + Bi was fixed at 3 mol and the proportions of Sr, Eu, Pb and Dy were varied in such a manner that the proportion of (Sr + Eu + Pb +
Dy) became 1.8, 1.3 or 1.6 while maintaining unchanged the ratios of Sr . Eu . Pb Dy. Note that 0.03 mol of boric acid (boron) was used as a flux in the preparation of these sample phosphors.
Table 8 Sample No. Sr Eu Pb Dy x A1 Bi 2y Sg-A1-3-10-2 1.605 0.03 0.015 0.15 1.8 2.961 0.009 3 (0.892)(0.017)(0.008)(0.083)) (1.994)(0.006) SG-A1-3-6-2 1.155 0.03 0.015 0.10 1.3 2.961 0.009 3 (0.888)(0.023)(0.012)(0.077) (1.994)(0.006) SG-A1-3-18 1.416 0.03 0.015 0.139 1.6 2.961 0.009 3 (0.885)(0.019)(0.009)(0.087) (1.994)(0.006) * In the Table, the parentheses indicate the values of the mol ratios when (Sr + Eu + Pb + Dy) was selected 1 mol or (A1 +
Bi) was selected 2 mol.
The afterglow characteristics of the sample phosphors shown in Table 8 were verified according to the previously mentioned measuring method. The results are shown in the following Table 9.
Table 9 Dy 5min lOmin l5min 20min 25min 30min Sample No. (mol) (mV) SG-A1-3-10-2 0.15 210 130 90 80 75 65 -3- 6-2 0.10 390 220 130 130 110 90 -3-18 0.139 326 214 150 120 100 88 While, as shown in TABLES 8 and 9, a comparison with the sample phosphors (SG-A1-3-5, SG-A1-3-6, SG-A1-3-7) of Table 4 and 5 shows that the afterglow characteristics can be improved by increasing the proportion of Dy, both the afterglow intensity and the retention amount are decreased in the sample (SG-A1-3-10-2) in which the ratio between the proportions of (Sr + Eu + Pb + Dy) and (A1 + Bi) is far from 1:2.
This may be conceivable to be due to the fact that particulates of good quality cannot be obtained due to not only a problem from the composition point of view but also a problem of the sintering characteristics caused by the ratio of Sr/A1 as well as the factors from the manufacturing point of view.
Embodiment 5. (Dy,Pb,Bi-substitution phosphor) While, in connection with the Embodiment 3, the verification was made of the (Sr, Eu, Pb, Dy)O~(A1, Hi)ZOa phosphor in which the ratio between the proportions of (Sr +
Eu + Pb + Dy) and (A1 + Bi) was selected 1:2, in the case of the Embodiment 5 a verification was made as to whether the same afterglow characteristics could be obtained when the proportion of (Sr + Eu + Pb + Dy) was 2 mol or over. Here, as shown in Table 10, sample phosphors were prepared in which the proportion of (Sr + Eu + Pb + Dy) was 2 mol and the proportion of (A1 + Hi) was 4 mol. Note that 0.03 mol of boric. acid (boron) was used as a flux in the preparation of these sample phosphors.
Table 10 Sample No. Sr Eu Pb Dy x A1 Bi 2y SG-A1-4-1 1.765 0.04 0.015 0.180 2 3.991 0.009 4 (0.8825)(0.02)(0.0075)(0.090) (1.9955)(0.0045) SG-A1-4-2 1.735 0.04 0.015 0.210 2 3.991 0.009 4 (0.8675)(0.02)(0.0075)(0.105) (1.9955)(0.0045) * In the Table, the parentheses indicate the values of the mol ratios when selecting (Sr + Eu + Pb + Dy) to be 1 mol or (A1 + Hi) to be 2 mol.
The afterglow characteristics of the resulting phosphors were verified in accordance with the previously mentioned measuring method. The results are shown in Table 11. As shown in Table 11, while the proportions of Pb and Bi were relatively decreased thus slightly deteriorating the afterglow characteristics, substantially the equivalent satisfactory afterglow characteristics were still obtained.
Table 11 Sample Dy 5min lOmin l5min 20min 25min 30min No. mol (mV) SG-A1-4-1 0.18 380 250 185 150 125 100 -4-2 0.21 350 230 170 138 115 097 Embodiment 6. (Dy, Pb, Hi-substitution phosphor) As shown in Table 12, two different sample phosphors were prepared in which the proportion of (Sr + Eu + Pb + Dy) was 2 mol or over and also the proportion of (A1 + Bi) was 5 mol.
The afterglow characteristics of these samples are shown in Table 13. It is to be noted that 0.03 mol of boric acid (boron) was used in the preparation of these sample phosphors.
Table 12 Sample No. Sr Eu Pb Dy x A1 Bi 2y SG-A1-5-1 1.765 0.04 0.015 0.180 2.0 4.991 0.009 5 (0.8825)(0.02) (0.0075)(0.090) (1.9964)(0.0036) SG-A1-5-2 1.725 0.04 0.015 0.220 2.0 4.991 0.009 5 (0.8625)(0.02) (0.0075)(0.110) (1.9964)(0.0036) SG-A1-5-3 2.220 0.04 0.015 0.225 2.5 4.991 0.009 5 (0.888) (0.016)(0.006) (0.090) (1.9964)(0.0036) * In the Table, the parentheses indicate the values of the mol ratios when selecting (Sr + Eu + Pb + Dy) to be 1 mol or (A1 + Bi) to be 2 mol.
Table 13 Sample Dy 5min lOmin l5min 20min 25min 30min No. mol (mV) SG-A1-5-1 0.018 360 220 165 130 110 095 SG-A1-5-2 0.022 380 230 165 145 120 099 SG-A1-5-3 0.0225 350 215 160 135 105 097 Embodiment 7. (Dy, Pb, Zn, Bi-substitution phosphor) Two different sample phosphors were prepared by substituting a part of Sr with Zn in (Sr, Eu, Pb, Dy)O~y(A1, Bi)z03 phosphor and their afterglow characteristics were verified. The compositions of the prepared samples are shown in the following Table 14. And, Table 15 shows the measured afterglow characteristics of the sample phosphors shown in Table 14.
Table 14 Sample No. Sr Zn Eu Pb Dy x A1 Bi 2y SG-A1-3-3 1.345 0.02 0.03 0.015 0.09 1.5 2.991 0.009 3 (0.900)(0.013)(0.02)(0.010)(0.06) (1.994)(0.006) SG-A1-3-4 1.325 0.04 0.03 0.015 0.09 1.5 2.991 0.009 3 (0.883)(0.026)(0.02)(0.010)(0.06) (1.994)(0.006) * In the Table, the parentheses indicate the values of the mol ratios when selecting (Sr + Eu + Pb + Dy) to be 1 mol or (A1 + Bi) to be 2 mol.
Table 15 Dy 5min l0min l5min 20min 25min 30min Sample No. mol (mV) Mol SG-A1-3-3 0.09 280 170 125 84 75 65 Zn 0.02 -3-4 0.09 255 145 120 77 65 55 Zn 0.04 As a result of a comparison between the measurement results of the sample phosphor (SG-A1-3-3) of Table 15 and the sample phosphor (SG-A1-3-5) of Table 5, it was confirmed that the response characteristics were improved remarkably in addition to the improvement of the fluorescent characteristics by substituting a part of Sr with a metal element such as Zn.
In other words, although it is difficult to express definitely in terms of numerical values and usually the afterglow is hidden by the reflected light in a condition involving even a slight light thus making its visual inspection difficult, the addition of Zn improves the initial intensity thus making it possible to easily recognize the afterglow. It is to be noted that even in this case, it is preferable to select so that Sr + Zn + Eu + Pb + Dy = 1 mol. The concentration of Zn can be on the order of several mol o of the proportion of Sr. Also in this case, it is necessary that the proportion of the activator Eu is on the order of 2 mol ~ of Sr and the proportion of Dy is two times or more of the amount of Eu.
Embodiment 8. (Zn-substitution phosphor) With the embodiment 7, the improvement in the response of the afterglow characteristics was confirmed on the sample phosphors employing as the matrix the phosphor containing Pb, Bi and Dy and substituting a part of its Sr with Zn. Then, two different sample phosphors (SAD 7-2, SAD 7-3) containing no Pb and Hi and substituting a part of Sr with Zn and a comparative sample (SAD 7-1) containing no zinc were further prepared and their afterglow characteristics were verified. The compositions of the prepared samples are shown in the following Table 16.
Table 16 shows the proportions (mol) of the respective elements per molecular weight. Note that symbol H indicates the mol of boric acid added as a flux.
Table 16 Sample No. Sr Zn Eu Dy x A1 B
SAD 7-1 0.930 - 0.020 0.050 1.0 2.000 0.033 SAD 7-2 0.925 0.005 0.020 0.050 1.0 2.000 0.033 SAD 7-3 0.920 0.010 0.020 0.050 1.0 2.000 0.033 SG-Dy-6 0.925 - 0.025 0.050 1.0 2.000 0.03 -ZnS:Cu G-550 (TM) The measurement of the afterglow characteristics was effected in the following way. The powder of each of the sample phosphors shown in Table 16 was put to fill a holder (the powder filling cavity was 33 mm in inner diameter and 5 mm in depth) and kept in storage in the dark place for more than 16 hours. Then, the light from a 27-watt fluorescent lamp was irradiated on the holder for 10 minutes at the distance of about 150 mm and variations in the intensity of the afterglow immediately thereafter were measured with a measuring instrument (a luminance meter: Type-5712 made by Matsushita Denshi Kogyo R & D Center Corp., a phototube: 8847 made by Hamamats Photonix Corp., a recorder: PRR5000T'" by Toa Denpa Co., Ltd.).
In addition, the afterglow characteristics were measured under the same conditions on the comparative phosphor (SG-Dy-6), the conventional luminous paint (ZnS:Cu) and the commercially available (Sr, Eu, Dy)O~A1203 phosphor (trade name; G-550, manufactured by Nemoto & Co., Ltd.). The results are shown in the following Table 17.
Table 17 1,000 mV- 5min lOmin l5min20min 25min 30min Sample No. time (sec) (mV) SAD 7-1 126 320 185' 128 95 75 61 SG-Dy-6 129 279 158 108 80 62 51 ZnS:Cu 6 15 6 3 2 1 1>
G-550 (TM) 84 235 126 82 59 45 36 * In the Table, 1,000 mV-time indicates the time (seconds) required for the indication value of the luminance meter to reach 1,000 mV after the irradiation of the fluorescent lamp.
As shown in Table 17, even with the sample phosphors containing no lead, the addition of zinc (Zn) resulted in the phosphors having higher afterglow characteristics than the comparative samples (SG-Dy-6, SAD 7-1) containing no lead and zinc.
Also, it was confirmed that the phosphors in which a part of its Sr was substituted with Zn were high in afterglow characteristics as compared with the conventional luminous paint (ZnS:Cu) and the commercially available phosphor (Sr, Eu, Dy)O~ A12 03 .
This substitution of zinc (Zn) is such that a good result can be obtained by substituting several mol o, preferably 1.3 to 2.6 mol o of strontium (Sr) with zinc.
The present invention also provides a fourth phosphor with afterglow characteristic which comprises a matrix composed of an Eu2+ activated strontium aluminate-type phosphor and has a chemical composition expressed by:
(Sr, Zn, Eu, Pb, Dy)O~ (A1, Bi)z03 where Sr + Zn + Eu + Pb + Dy = 1, A1 + Bi = 2, and the proportions of the respective elements in one molecule are 0.013 s Zn s 0.027, 0.017 S Eu s 0.03, 0.008 s Pb S_ 0.017, 0.05 S Dy s 0.133, 1.994 s A1 s 1.9964 and 0.0036 s Bi S 0.006.
The present invention also provides a fifth phosphor with afterglow characteristic which comprises a matrix composed of an Eu2+ activated strontium aluminate-type phosphor and has a chemical composition expressed by:
(Sr, Zn, Eu, Dy)O~ A1z 03 where Sr + Zn + Eu + Dy = 1.
In accordance with a preferred aspect of the fifth phosphor, the proportions (mol) of the respective elements are 0.005 S Zn S 0.010, Eu = 0.20 and Dy = 0.05.
In accordance with the present invention, a phosphor in which the proportions of Sr0 and A1203 are different from 1:1 is used as a matrix. This matrix phosphor is mixed with trace elements of various proportions so as to produce a phosphor which is excellent in afterglow characteristics.
With the phosphor according to this invention comprising as its matrix an Sr0-yA1z03:Eu2'-type phosphor in which the proportions of Sr0 and A1203 are different from 1:1, where the proportion of Sr(or Sr0) is selected to be 1 mol, if the proportion of A1, for example, is 3 mol (namely, the proportion of A1203 is 1.5 mol), it is possible to ensure more intense afterglow characteristics by substituting a part of Sr with Pb and also substituting a part of A1 with Bi even if it is set so that Dy = 0. Thus, the first phosphor according to the present invention has the chemical composition expressed by:
(Sr, Eu, Pb)O-y(A1, Bi)a0$
where Sr + Eu + Pb = 1, A1 + Hi = 2y.
The contents of Pb and Bi in the first phosphor can be very small, and where the proportion of Sr (or Sr0) is selected to be 1 mol,if the proportion of A1, for example, is 3 mol (namely, the proportion of A120g is 1.5 mol), it is preferable to select so that the proportion of Pb substituting a part of Sr is 0.015 mol and the proportion of Hi substituting a part of A1 is 0.009 mol. Also, in the case of this fluorescent substance, .the afterglow characteristics will be deteriorated extremely if any of Pb and Bi lacks. Therefore, an especially preferred chemical composition of the first phosphor is represented by:
(Sro.9ss.Euo.omPbo.ois)O~Al2.ssi Blo.oos ~e.sJ
It is to be noted that even in the preparation process of the phosphor according to the invention, it is desirable to use a trace amount of boric acid (HaH03) as a flux in the like manner as the conventional procedure. It has been confirmed that the composition of the fired phosphor will be caused to loose its uniformity and the emission characteristic will be deteriorated considerably if no boric acid is used or if it is used in an extremely small amount. Not only boric acid acts as a flux (the promotion of crystal growth) but also a very small part of it remains as boron in the phosphor. While it is presumed that this remaining boron changes the phase of beta-alumina, its reason has not been generally clarified as yet.
However, where at least two crystals or phases are present, it is considered that boron has an action of bonding the two together.
Then, while the afterglow produced by a phosphor having the composition represented by (Sr, Eu, Pb)0~y(A1, Bi)ZOs (where Sr + Eu + Pb = 1, A1 + Bi = 2y) is comparatively intense and excellent in color tone, the duration time of the afterglow is not so long as intended by the present invention although it is longer than in the case of the conventional phosphors.
In this connection, the second phosphor according to the present invention contains Dy in addition to Pb and Hi so as to ensure the afterglow of a still longer life (in the case of Pb and Hi alone, the afterglow decays rapidly although its intensity is high).
More specifically, the second phosphor has the composition expressed by (Sr, Eu, Pb, Dy)O~y(A1, Hi)Z03 (where Sr + Eu + Pb + Dy = 1_, A1 + Bi = 2y) . ' As regards the proportions of (Sr + Eu + Pb + Dy) and (A1 + Hi) relative to each other in the second phosphor (Sr, Eu, Pb, Dy)O~y(A1, Hi}ZOa (where Sr + Eu + Pb + Dy = 1, A1 + Hi = 2y), it has been confirmed that if, for example, the proportion of (A1 + Hi) is 3 mol, the proportion of (Sr + Eu + Pb + Dy) is in the range from 0.9 to 1.8 mol and an especially preferred range is from 1.3 to 1.5 mol. Also, it has been confirmed that this ratio (Sr + Eu + Pb + Dy)/(A1 + Bi) is the same in the cases where proportion of (A1 + Bi) is 4 mol and 5 mol, respectively.
Thus, in the case of the second phosphor (Sr, Eu, Pb, Dy)0 ~y(A1, Bi)203, it is possible to improve the afterglow characteristics by increasing the proportion of Dy.
AS regards the relation between (Sr + Eu + Pb + Dy) and (A1 + Bi), it has been confirmed that if the proportion of (Sr + Eu + Pb + Dy) is excessively high as compared with that of (A1 + Bi), the afterglow performance is deteriorated extremely, whereas if the proportion of (Sr + Eu + Pb + Dy) is excessively low as compared with that of (A1 + Bi), the afterglow performance is deteriorated and the duration time of the afterglow is also decreased.
It follows from this that it is most preferable to prepare the phosphor in a way that the proportions of (Sr + Eu + Pb + Dy)0 and (A1 + Bi)203 are the same with each other. In other words, it has been confirmed that it is most preferable to blend (A1 + Bi) in a way that its proportion becomes two times that of (Sr + Eu + Pb + Dy).
Thus, the third phosphor according to this invention has the chemical composition given by (Sr, Eu, Pb, Dy)O~(Al,Bi)ZOa (where Sr + Eu + Pb + Dy = 1, A1 + Bi = 2).
In this third phosphor (Sr, Eu, Pb, Dy)O~y(A1, Bi)203, the proportion of Dy has a certain range for ensuring excellent afterglow characteristics. For instance, where the proportion of Sr (or Sr0) in one unit molecule is selected to be 1.5 mol, if the proportion of A1 is 3 mol (namely, the proportion of A1z03 is 1.5 mol), the proportion of 0.09 for Dy is still insufficient although the afterglow characteristics are 21913.3 recognized. Preferably, excellent afterglow characteristics can be obtained by selecting the proportion of Dy to come within the range from 0.12 to 0.15 mol. While the afterglow intensity is still decreased slightly when the proportion of Dy is selected to come within the range of 0.18 to 0.20 mol, contrary the duration time of the afterglow is increased in proportion to an increase in the proportion of Dy.
This third phosphor corresponds to a phosphor produced by substituting a part of Sr with Pb and a part of A1 with Bi in the previously mentioned reference phosphor having the composition of (Sr, Eu, Dy)O~A1z03 (where Sr + Eu + Dy = 1).
However, while, in the case of the third phosphor of the present invention, it is certainly most preferable to blend (A1 + Bi) in a manner that its proportion becomes two times that of (Sr + Eu + Pb + Dy) as compared with the previously mentioned composition of (Sr, Eu, Dy)O~A1z03 (where Sr + Eu +
Dy = 1) which requires an exact control of the proportions, the third phosphor differs greatly from the conventional phosphor in that sufficient afterglow characteristics can be obtained without performing any exact control of the proportions.
This can be considered in this way that the inclusion of Pb in the fluorescent substance results in a crystal structure which is different from the conventional phosphor of (Sr, Eu, Dy)O~A1z03 or, while the crystal structure is the same, the presence of Pb maintains the crystal structure stable thus making it possible to withstand the further addition of Dy.
Further, in the case of this third phosphor produced by substituting a part of Sr with Pb and substituting a part of A1 with Bi in the conventional phosphor of the composition (Sr, Eu, Dy)O~A1z03 (where Sr + Eu + Dy = 1), the characteristics as the 21913.x:3 phosphor are improved over two times at the maximum.
With the above-mentioned first, second and third phosphors of (Sr, Eu, Pb, Dy)O~y(A1, Bi)z03 according to the invention, while it is not clear how the substitution of a part of Sr with Zn relates to the afterglow characteristics, it has been found that the addition of Zn remarkably improves the response of the fluorescent characteristics in addition to the improvement of the basic fluorescent characteristics. While it is difficult to give any definite expression in terms of a numerical value and generally the afterglow is hidden by the reflected light thus making its visual observation difficult in a condition where there is even a slight light, the addition of Zn improves the initial intensity thus making it possible to easily perceive the afterglow.
Particularly, the fourth phosphor having afterglow characteristics according to the invention has the composition given by (Sr, Zn, Eu, Pb, Dy)O~(A1, Bi)zOa (where Sr + Zn + Eu + Pb + Dy = 1, A1 + Bi = 2) and the proportions (mol) of the respective elements are 0.013 5_ Zn s 0.027, 0.017 s Eu s 0.03, 0.008 S_ Pb S 0.017, 0.05 S_ Dy s 0.133, 1.994 s A1 s 1.9964 and 0.0036 S_ Bi S_ 0.006).
While, in the fourth phosphor, a part of strontium (Sr) is substituted with lead (Pb), dysprosium (Dy) and zinc (Zn), the composition of this fourth phosphor has been examined as regards the afterglow characteristics of the composition without the addition of Pb. As a result, it has been confirmed that the phosphor of the composition in which a part of Sr is substituted with zinc (Zn) shows the lasting afterglow characteristics even if a part of Sr is not substituted with lead (Pb).
Therefore, the fifth phosphor according to the present invention has the composition given by (Sr, Zn, Eu, Dy)O~A1203 (where Sr + Zn + Eu + Dy = 1, and the proportions (mol) of the respective elements are 0.005 ~ Zn ~ 0.010, Eu = 0.20 and Dy =
0.05).
Brief Description of the Drawings Fig. 1 shows a graph for explaining the afterglow characteristics of a phosphor with the ordinate representing the output voltage (mV) of a luminance meter and the abscissa representing the time (min).
Fig. 2 is a graph showing the measurement results of the afterglow characteristics of sample phosphors (SG-A1-3-5 to SG-A1-3-10) obtained by fixing the proportion of A1 + Bi at 3 mol, the proportion of Eu at 0.03 mol, the proportion of Pb at 0.015 mol and the proportion of Dy at 0.09 mol and varying the proportion of Sr + Eu + Pb + Dy within the range of 0.9 to 2.0 in the case of (Sr, Eu, Pb, Dy)O~y(A1, Bi)z03 phosphor, with the ordinate representing the afterglow intensity Is (the output voltage (mV) of a luminance meter) and the abscissa reprsenting the proportion (mol) of Sr + Eu + Pb + Dy.
Fig. 3 is a graph showing the variations of the afterglow intensity relative to the proportions of Dy in the case of the sample phosphors (SG-A1-3-5, SG-A1-3-12 to SG-A1-3-1T) and the sample phosphor (SG-Dy-6), with the ordinate representing the afterglow intensity Is (the output voltage (mV) of a luminance meter) and the abscissa representing the proportion (mol) of Dy.
Best Mode for Carrying Out the Invention Preparation of phosphors:
~1 ~1 ~~~
Using the following raw materials A to H, the below-mentioned embodiments and comparative phosphors were prepared.
A) Strontium carbonate SrC03 B ) Europium oxide Euz 03 C ) Dysprosium oxide Dyz 03 D) Aluminum oxide alpha-A1203 E) Lead fluoride PbFz F) Basic bismuth carbonate b-BiC03 G) Zinc carbonate ZnC03 H) Boric acid H3 B03 Then, the ranges (mol) of addition per molecule of the respective elements were as follows.
a) Sr 0.90 s Sr s 3.00 b) Eu 0.02 s Eu S 0.05 c) Dy 0.04 s Dy s 0.24 d) A1 2.00 s A1 s 6.00 e) Pb 0.01 S Pb s 0.03 f) Bi 0.009 _S Bi S_ 0.03 g ) Zn 0 . 01 .s Zn s 0 . 04 h) B 0.005 s B s 0.035 It is to be noted that as in the case of the ordinary aluminate-type phosphors, chiefly aluminum fluoride was used in substitution for a part of aluminum oxide for use as a flux.
Also, boric acid was used singly or along with aluminum fluoride as mentioned previously. In fact, when preparing the phosphors, the raw material mixtures were fired in a weak reducing air stream for several hours thereby producing the phosphors which were extremely excellent in fluorescence and afterglow characteristics.
21913~~
Preparation of comparative phosphor (Sr, Eu, Dy)O~A1203:
(Sr, Eu, Dy)O~A1203 phosphor was prepared as the object of comparison for the phosphor having afterglow characteristics according to the present invention. This comparative phosphor comprises a phosphor containing Sr0 and A1203 with the 1:1 ratio. More specifically, 0.925 mol of Sr, 0.025 mol of Eu, 0.05 mol of Dy and 2.00 mol of A1 were mixed and then fired using 0.03 mol of H3B03 as a flux. This comparative phosphor was represented as SG-Dy-6. This comparative phosphor (SG-Dy-6) belonged to the conventional phosphors represented by the previously mentioned compound MA1204 (where M is a compound as a mother crystal comprising at least one metal element selected from a group consisting of calcium, strontium and barium, and there were contained 0.001 o to 10 0 of europium (Eu) in terms of mol o relative to M as an activator and 0.001 % to 10 % in terms of mol ~ relative to the metal element represented by M
of at least one metal element selected from a.group consisting of lanthanum, cerium, praseodymium, neodymium, samarium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, manganese, tin and bismuth as a co-activator).
Verification of afterglow characteristics:
Fig. 1 shows a graph for explaining the afterglow characteristics of the phosphor. Here, the ordinate represents the emission intensity (namely, the output voltage (mV) of a luminance meter) and the abscissa represents the time (min).
The phosphor having the afterglow characteristics means a fluorescent substance adapted to produce the emission of light that lasts even after the interruption of the excitation radiation (a so-called "afterglow"). The initial intensity of the afterglow of the Eu2' activated strontium aluminate-type phosphor is considerably high. However, the afterglow is a kind of radiation and therefore its emission energy decays with the passage of time. Thus, in the verification of the afterglow characteristics of the below-mentioned embodiments the periods of rapid decay of the emission intensity-were avoided and the measured values were recorded after the establishment of the comparatively stable conditions.
More specifically, after a holder containing a sample had been kept in a dark place for over 16 hours, the light from a 27-watt fluorescent lamp was irradiated (for 10 minutes) to the sample in the holder at a distance of 300 mm and then instantly placed in a measuring instrument (the luminance meter;
manufactured by Matsushita Denshi Kogyo R&D Center Corp., the phototube; 8847 manufactured by Hamamatsu Photonix Corp., the recorder; Phoenix PRR5000 manufactured by Toa Dempa Co.,Ltd.), thereby measuring the afterglow characteristics. As shown in Fig. 1, the time at which the digital reading of the luminance meter reached at 1,000 mV after several minutes from the start time (L) of measurement was used as the recording starting time and the decaying conditions thereafter were recorded.
It is to be noted that in the case of the respective embodiments, the readings (mV) at the expiration of 5 minutes from the time of the output voltage of the luminance meter dropping to 1,000 mV were taken as the afterglow intensities (Is) of the samples and also the readings (mV) at the expiration of 30 minutes after the start of the recording were taken as the retention amounts (Im) of the afterglow. Therefore, the afterglow characteristics discussed in connection with the 219 i 3~3 present invention are evaluated in accordance with the afterglow intensity (Is) and the retention amount (Im).
The following TABLE 1 shows the measurement results of the afterglow characteristics of the comparative phosphor (SG-Dy-6).
Table 1 Elapsed time (min) Sample No. Dy (mol) 5 10 15 20 25 30 SG-Dy-6 0.05 290 170 115 085 065 050 (unit; mV) As shown in Table 1, the afterglow intensity (the intensity at the expiration of 5 minutes after the start of the afterglow) and the retention amount (the intensity at the expiration of 30 minutes after the start of the afterglow) of the comparative phosphor (SG-Dy-6) were respectively 290 mV and 50mV. It is to be noted that the commercially available (Sr, Eu, Dy)O~A1203 phosphor (the trade name; G-550, manufactured by Nemoto & Co.,Ltd.) showed the afterglow intensity of 220 mV and the retention amount of 42 mV and therefore it was confirmed that the comparative phosphor (SG-Dy-6) was one having the equivalent afterglow characteristics as the commercially available phosphors. Thus, this comparative phosphor (SG-Dy-6) was employed as the reference object of comparison in the case of the following embodiments.
It is to be noted that with the comparative phosphor (SG-Dy-6), the substitution amount of Dy was varied to prepare a plurality of samples and their afterglow characteristics were measured, showing that the afterglow characteristics were 219 ~ 333 gradually improved in accordance with the substitution amounts of Dy. However, it was confirmed that not only the afterglow but also the emission of fluorescence were lost in the case of the samples in which the substitution amounts of Dy were over 0.10 mol.
From this point, it follows that while the afterglow characteristics are improved in accordance with the substitution amount of Dy, there is an upper limit to the substitution amount of Dy and thus it is presumed that the crystal structure of Sr0~A1203;Eu2' itself is disintegrated if the substitution amount of Dy exceeds 0.10 mol.
In addition, this disintegration of the crystal structure inevitably gives rise to a problem that the proportions of Sr0 and A1z03 constituting the matrix must be controlled exactly.
For instant, if the relative ratio of Sr0 and A1203 deviates greatly from 1:1, that is, where the proportion of Sr (or Sr0) is 1 mol, if the proportion of A1 is 3 mol (namely, the proportion of A1z03 is 1.5 mol), no afterglow characteristics are obtained even if a part of Sr is substituted with Dy.
Embodiment 1. (Pb, Bi-substitution phosphor) In the case of the phosphor (Sr0~A120a :Euz' ) in which the ratio between the proportions of Sr0 and A1z03 is not 1:1, if, for example, the proportion of A1 is made over 3 mol, it is no longer possible to obtain a strong afterglow due to the presence of Dy alone. Thus, in accordance with this embodiment the addition of Pb and Bi resulted in an excellent phosphor.
In other words, with the SrO~ 1 . 5A12 Oa : Euz + phosphor, the afterglow, though weak, was recognized when a part of Sr was substituted with Pb (0.01 mol in terms of the proportion) in its composition. Also, when a part of A1 was substituted with Bi (0.01 mol in terms of the proportion) in this composition, no afterglow was recognized. Further, when a part of Sr was substituted with Pb (0.01 mol in terms of the proportion) and also a part of A1 was substituted with Bi (0.01 mol in terms of the proportion), the afterglow appeared intense.
In_this way, the conditions for the coexistence-of Pb and Bi were searched and the following a) to c) were confirmed.
a) In order to obtain excellent afterglow characteristics, the proportions of Pb and Bi were respectively limited to Pb: 0.015mo1 and Bi: 0.009 mol in the above-mentioned chemical compositions.
b) The afterglow became weak when the proportion of either Pb or Bi was greater than that in the above a).
c) In the above-mentioned composition, the amount of A1 for satisfying the a) had to be between 2.8 mol and 3.2 mol.
Taking the thus obtained conditions into consideration, the proportion of Eu was selected 0.03 mol thereby obtaining a Pb, Bi-substitution phosphor having the composition expressed by:
(Sro.sss. Euo.o3. Pbo.ois) O~A12.9s1 Blo.oos O~.s %
The afterglow characteristics of the phosphor having this composition were as shown by the following tables under the previously mentioned measurement conditions as compared with the ordinary luminous paint (ZnS:CuZ').
Initial 5 min.
afterglow later ZnS:Cu 900 mV ?0 mV
Pb,Hi-substitution phosphor 2,500 mV 50 mV
1 'T
As regards the afterglow retention performance of Pb, Bi-substitution phosphor, it cannot be said to be so excellent as will be seen from the examination of the values at the expiration of 5 minutes. Then, in order to obtain excellent afterglow characteristics, a sample was prepared by substituting a part of Sr with Dy as in the case of the comparative phosphor.
In other words, by utilizing the matrix of the composition Sr0~1.5A1z03:Eu2', sample phosphors having the proportions of Dy set to 0.06 mol were prepared as shown in Table 2 and their initial afterglow and afterglow intensities were measured. The results obtained are shown in Table 3.
Table 2 Sample No. Sr Eu Pb Dy x A1 Bi 2y SG-A1-3-1 0.895 0.030 0.015 0.060 1.0 2.991 0.009 3.0 SG-A1-3-2 0.910 0.030 - 0.060 1.0 3.000 - 3.0 (unit: mol) Table 3 Sample Dy Initial Afterglow No. (mol) Pb, Bi afterglow intensity SG-A1-3-1 0.06 Present 3,700 mV 189 mV
SG-A1-3-2 0.06 None 3,500 mV 180 mV
It was confirmed that as shown in Table 3, when the proportion of A1 was 3 mol, the phosphor in which Pb and Bi co-existed Was excellent in both initial afterglow and afterglow intensity as compared with the phosphor containing Dy singly as an auxiliary agent.
Embodiment 2. (Dy, Pb, Bi-substitution phosphor) With the phosphor having the composition of (Sr, Eu, Pb, Dy)O~y(A1, Bi)z03, the afterglow characteristics were verified in greater detail. As shown in the following Table 4, five kinds of sample phosphors (sample Nos. SG-A1-3-5, SG-A1-3-6, SG-A1-3-7, SG-A1-3-8, SG-A1-3-10) were prepared by fixing the proportions of the respective elements such that A1 + Bi = 3 mol, Eu = 0.03 mol, Pb = 0.015 mol and Dy = 0.09 mol and by varying the proportion of Sr + Eu + Pb + Dy within the range of 0.9 to 2Ø It is to be noted that 0.03 mol of boric acid (boron) was used as a flux in the preparation of these sample phosphors.
Table 4 Sample No. Sr Eu Pb Dy x A1 Bi 2y SG-A1-3-5 1.365 0.03 0.015 0.09 1.5 2.991 0.009 3.0 (0.910)(0.020)(0.O10)(0.06) (1.994)(0.006) SG-A1-3-6 1.165 0.03 0.015 0.09 1.3 2.991 0.009 3.0 (0.896)(0.023)(0.011)(0.069) (1.994)(0.006) SG-A1-3-7 0.865 0.03 0.015 0.09 1.0 2.991 0.009 3.0 (0.865)(0.030)(0.015)(0.09) (1.994)(0.006) SG-A1-3-8 0.765 0.03 0.015 0.09 0.9 2.991 0.009 3.0 (0.850)(0.033)(0.017)(0.10) (1.994)(0.006) SG-A1-3-10 1.665 0.03 0.015 0.09 1.8 2.991 0.009 3.0 (0.925)(0.017)(0.008)(0.05) (1.994)(0.006) * In the Table, the values in the parentheses indicate the mol ratios when (Sr+Eu+Pb+Dy) is 1 mol or (A1+Bi) is 2 mol.
With the resulting samples, the afterglow characteristics were verified according to the previously mentioned measuring method. The results are shown in the following Table 5. Note that Fig. 2 is a graph showing the results of Table 5 with the ordinate representing the afterglow intensity Is (the output ~t 9~ ~~~
voltage (mV) of a luminance meter) and the abscissa representing the proportion (mol) of Sr + Eu + Pb + Dy (= x).
Table 5 Sample Sr+Eu+Pb+Dy 5min lOmin l5min 20min 25min 30min No. (mol) (mV) SG-A1-3-5 1.5 270 165 115 075 065 055 -3-6 1.3 259 145 103 080 065 057 -3-7 1.0 250 145 100 075 060 050 -3-8 0.9 180 120 083 060 055 045 -3-10 1.8 170 110 077 055 045 035 As shown in Table 5 and Fig. 2, it was confirmed that as regards the mol ratio of (Sr + Eu + Pb + Dy) / (A1 + Bi), when, for example, the proportion of (A1 + Bi) was selected 3 mol, the proportion of (Sr + Eu + Pb + Dy) was in the range between 0.9 and 1.8 mol, preferably in the range of 1.3 to 1.5 mol. As a result, when each of the samples was given by (Sr, Eu, Pb, Dy) O~y(A1, Bi)203, the value of y was in the range between 0.83 and 1.67 and the preferred value of y was in the range from 1 to 1.15.
Also, the proportions (mol) of Sr, Eu, Pb and Dy were respectively 0.016 s Eu s 0.033, 0.006 S_ Pb s 0.017 and 0.05 S_~Dy S 0.133 and it was confirmed that the preferred proportions were respectively 0.020 s Eu s 0.023, 0.010 s Pb s 0.011 and 0.060 ~ Dy S_ 0.069.
Embodiment 3. (Dy, Pb, Bi-substitution phosphor) With the phosphors having the chemical composition of (Sr, Eu, Pb, Dy)O~y(A1, Bi)203, the afterglow characteristics were further verified in detail. As shown in Table 6, six kinds of sample phosphors (SG-A1-3-12 to SG-A1-3-17) were prepared, in addition to the sample No. SG-A1-3-5, by fixing the proportions of the respective elements in such a manner that (A1 + Bi) - 3 mol and (Sr + Eu + Pb + Dy) - 1.5 mol and by changing the proportions of Dy and Sr variously. Note that 0.03 mol of boric acid (boron) was used as aflux in the preparation of these sample phosphors, Table 6 Sample No. Sr Eu Pb Dy x A1 Bi 2y SG-A1-3-5 1.365 0.03 0.015 0.09 1.5 2.991 0.009 3.0 (0.910)(0.02)(0.010)(0.06) (1.994)(0.006) SG-A1-3-12 1.335 0.03 0.015 0.12 1.5 2.991 0.009 3.0 (0.890)(0.02)(0.010)(0.08) (1.994)(0.006) SG-A1-3-13 1.320 0.03 0.015 0.135 1.5 2.991 0.009 3.0 (0.880)(0.02)(0.010)(0.09) (1.994)(0.006) SG-A1-3-14 1.305 0.03 0.015 0.150 1.5 2.991 0.009 3.0 (0.870)(0.02)(0.010)(0.10) (1.994)(0.006) SG-A1-3-15 1.290 0.03 0.015 0.165 1.5 2.991 0.009 3.0 (0.860)(0.02)(0.010)(0.11) (1.994)(0.006) SG-A1-3-16 1.275 0.03 0.015 0.180 1.5 2.991 0.009 3.0 (0.850)(0.02)(0.010)(0.12) (1.994)(0.006) SG-A1-3-17 1.255 0.03 0.015 0.200 1.5 2.991 0.009 3.0 (0.837)(0.02)(0.010)(0.133) (1.994)(0.006) * In the Table, the parentheses indicate the values of the mol ratios when it is selected in a manner so that (Sr + Eu + Pb + Dy) - 1 mol or (A1 + Hi) - 2 mol.
With the thus obtained samples, the afterglow characteristics were verified in accordance with the previously mentioned measuring method. The results are shown in the following Table 7.
Table 7 Sample Dy mol 5min lOmin l5min 20min z5min 30min No. (mol ratio) (mV) SG-A1-3-5 0.09 270 165 115 075 065 055 (0.06) SG-A1-3-12 0.12 420 247 176 137 113 097 (0.08) SG-A1-3-13 0.135 420 243 172 133 111 099 (0.09) SG-A1-3-14 0.150 420 241 173 129 109 095 (0.10) SG-A1-3-15 0.165 416 222 165 136 114 104 (0.11) SG-A1-3-16 0.180 360 240 165 135 115 100 (0.12) SG-A1-3-17 0.200 360 230 170 138 115 100 (0.133) The sample phosphors shown in this Table 7 were such that the proportion of (A1 + Bi)(= 3 mol) was adjusted so as to be two times that of (Sr + Eu + Pb + Dy)(= 1.5 mol). This corresponded to that a part of Sr was substituted with Pb and a part of A1 was substituted with Bi in the comparative phosphor having the composition of (Sr, Eu, Dy)O~A1203 (where S r + Eu + Dy = 1 ) .
Then, the sample phosphors (SG-Al-3-5, SG-A1-3-12 to SG-A1-3-17) shown in Tables 6 and 7 were compared in afterglow intensity with the comparative sample phosphor (SG-Dy-6) shown in Table 1. Fig. 3 is a graph showing the variations of the afterglow characteristics with the proportion of Dy. In the Figure, the ordinate indicates the afterglow intensity Is (mV) and the abscissa indicates the proportion (mol) of Dy. It is to be noted that the proportions of Dy are shown in terms of mol ratio with the proportions of (Sr + Eu + Pb + Dy) and (Sr + Eu + Dy) being selected 1 mol. In the Figure, the black spots indicate the afterglow characteristics of the sample phosphors (SG-A1-3-5, SG-A1-3-12 to SG-A1-3-17) shown in Tables 6 and 7 and the white spot indicates the afterglow characteristics of the comparative sample phosphor (SG-Dy-6) shown in TABLE 1.
As mentioned previously, while, in the case of the comparative sample phosphor (SG-Dy-6) containing no Pb and Bi, not only the afterglow characteristics but also the fluorescent characteristics are lost when the proportion of Dy exceeds 0.10 mol, in the case of the sample phosphors (SG-A1-3-5, SG-A1-3-12 to SG-A1-3-17) containing Pb and Bi, as shown in Fig. 3, selecting the proportion of (Sr + Eu + Pb + Dy) to be 1 mol has the effect of ensuring an excellent afterglow intensity when the proportion of Dy is selected in the range from 0.08 to 0.11 mol and slightly decreasing the intensity with the greater proportions of Dy, whereas the retention amount (at the expiration of 30 minutes) is increased in proportion to the proportion of Dy (see Table 7).
Further, while, in the case of the comparative phosphor, the range of the composition showing the afterglow characteristics is limited thus tending to make the preparation of the phosphor difficult, the coexistence of Pb and Bi with Dy has the effect of increasing the range of variations in the substitution amount of Dy tending to make possible the maintenance of stronger afterglow characteristics of two times or over. Particularly, where there is the coexistence of Pb, Bi and Dy, the initial intensity of the afterglow has an extremely high value of about 4,500 mV.
219 ~ 333 Embodiment 4. (Dy, Pb, Bi-substitution phosphor) While, in the case of the Embodiment 3, A1 + Bi and (Sr +
Eu + Pb + Dy) were respectively fixed at 3 mol and 1.5 mol and the proportions of Dy and Sr were changed variously in the phosphor of the composition (Sr, Eu, Pb, Dy)O~y(A1, Bi)203, in the case of the Embodiment 4, as shown in Table 8, three different sample phosphors were prepared in which A1 + Bi was fixed at 3 mol and the proportions of Sr, Eu, Pb and Dy were varied in such a manner that the proportion of (Sr + Eu + Pb +
Dy) became 1.8, 1.3 or 1.6 while maintaining unchanged the ratios of Sr . Eu . Pb Dy. Note that 0.03 mol of boric acid (boron) was used as a flux in the preparation of these sample phosphors.
Table 8 Sample No. Sr Eu Pb Dy x A1 Bi 2y Sg-A1-3-10-2 1.605 0.03 0.015 0.15 1.8 2.961 0.009 3 (0.892)(0.017)(0.008)(0.083)) (1.994)(0.006) SG-A1-3-6-2 1.155 0.03 0.015 0.10 1.3 2.961 0.009 3 (0.888)(0.023)(0.012)(0.077) (1.994)(0.006) SG-A1-3-18 1.416 0.03 0.015 0.139 1.6 2.961 0.009 3 (0.885)(0.019)(0.009)(0.087) (1.994)(0.006) * In the Table, the parentheses indicate the values of the mol ratios when (Sr + Eu + Pb + Dy) was selected 1 mol or (A1 +
Bi) was selected 2 mol.
The afterglow characteristics of the sample phosphors shown in Table 8 were verified according to the previously mentioned measuring method. The results are shown in the following Table 9.
Table 9 Dy 5min lOmin l5min 20min 25min 30min Sample No. (mol) (mV) SG-A1-3-10-2 0.15 210 130 90 80 75 65 -3- 6-2 0.10 390 220 130 130 110 90 -3-18 0.139 326 214 150 120 100 88 While, as shown in TABLES 8 and 9, a comparison with the sample phosphors (SG-A1-3-5, SG-A1-3-6, SG-A1-3-7) of Table 4 and 5 shows that the afterglow characteristics can be improved by increasing the proportion of Dy, both the afterglow intensity and the retention amount are decreased in the sample (SG-A1-3-10-2) in which the ratio between the proportions of (Sr + Eu + Pb + Dy) and (A1 + Bi) is far from 1:2.
This may be conceivable to be due to the fact that particulates of good quality cannot be obtained due to not only a problem from the composition point of view but also a problem of the sintering characteristics caused by the ratio of Sr/A1 as well as the factors from the manufacturing point of view.
Embodiment 5. (Dy,Pb,Bi-substitution phosphor) While, in connection with the Embodiment 3, the verification was made of the (Sr, Eu, Pb, Dy)O~(A1, Hi)ZOa phosphor in which the ratio between the proportions of (Sr +
Eu + Pb + Dy) and (A1 + Bi) was selected 1:2, in the case of the Embodiment 5 a verification was made as to whether the same afterglow characteristics could be obtained when the proportion of (Sr + Eu + Pb + Dy) was 2 mol or over. Here, as shown in Table 10, sample phosphors were prepared in which the proportion of (Sr + Eu + Pb + Dy) was 2 mol and the proportion of (A1 + Hi) was 4 mol. Note that 0.03 mol of boric. acid (boron) was used as a flux in the preparation of these sample phosphors.
Table 10 Sample No. Sr Eu Pb Dy x A1 Bi 2y SG-A1-4-1 1.765 0.04 0.015 0.180 2 3.991 0.009 4 (0.8825)(0.02)(0.0075)(0.090) (1.9955)(0.0045) SG-A1-4-2 1.735 0.04 0.015 0.210 2 3.991 0.009 4 (0.8675)(0.02)(0.0075)(0.105) (1.9955)(0.0045) * In the Table, the parentheses indicate the values of the mol ratios when selecting (Sr + Eu + Pb + Dy) to be 1 mol or (A1 + Hi) to be 2 mol.
The afterglow characteristics of the resulting phosphors were verified in accordance with the previously mentioned measuring method. The results are shown in Table 11. As shown in Table 11, while the proportions of Pb and Bi were relatively decreased thus slightly deteriorating the afterglow characteristics, substantially the equivalent satisfactory afterglow characteristics were still obtained.
Table 11 Sample Dy 5min lOmin l5min 20min 25min 30min No. mol (mV) SG-A1-4-1 0.18 380 250 185 150 125 100 -4-2 0.21 350 230 170 138 115 097 Embodiment 6. (Dy, Pb, Hi-substitution phosphor) As shown in Table 12, two different sample phosphors were prepared in which the proportion of (Sr + Eu + Pb + Dy) was 2 mol or over and also the proportion of (A1 + Bi) was 5 mol.
The afterglow characteristics of these samples are shown in Table 13. It is to be noted that 0.03 mol of boric acid (boron) was used in the preparation of these sample phosphors.
Table 12 Sample No. Sr Eu Pb Dy x A1 Bi 2y SG-A1-5-1 1.765 0.04 0.015 0.180 2.0 4.991 0.009 5 (0.8825)(0.02) (0.0075)(0.090) (1.9964)(0.0036) SG-A1-5-2 1.725 0.04 0.015 0.220 2.0 4.991 0.009 5 (0.8625)(0.02) (0.0075)(0.110) (1.9964)(0.0036) SG-A1-5-3 2.220 0.04 0.015 0.225 2.5 4.991 0.009 5 (0.888) (0.016)(0.006) (0.090) (1.9964)(0.0036) * In the Table, the parentheses indicate the values of the mol ratios when selecting (Sr + Eu + Pb + Dy) to be 1 mol or (A1 + Bi) to be 2 mol.
Table 13 Sample Dy 5min lOmin l5min 20min 25min 30min No. mol (mV) SG-A1-5-1 0.018 360 220 165 130 110 095 SG-A1-5-2 0.022 380 230 165 145 120 099 SG-A1-5-3 0.0225 350 215 160 135 105 097 Embodiment 7. (Dy, Pb, Zn, Bi-substitution phosphor) Two different sample phosphors were prepared by substituting a part of Sr with Zn in (Sr, Eu, Pb, Dy)O~y(A1, Bi)z03 phosphor and their afterglow characteristics were verified. The compositions of the prepared samples are shown in the following Table 14. And, Table 15 shows the measured afterglow characteristics of the sample phosphors shown in Table 14.
Table 14 Sample No. Sr Zn Eu Pb Dy x A1 Bi 2y SG-A1-3-3 1.345 0.02 0.03 0.015 0.09 1.5 2.991 0.009 3 (0.900)(0.013)(0.02)(0.010)(0.06) (1.994)(0.006) SG-A1-3-4 1.325 0.04 0.03 0.015 0.09 1.5 2.991 0.009 3 (0.883)(0.026)(0.02)(0.010)(0.06) (1.994)(0.006) * In the Table, the parentheses indicate the values of the mol ratios when selecting (Sr + Eu + Pb + Dy) to be 1 mol or (A1 + Bi) to be 2 mol.
Table 15 Dy 5min l0min l5min 20min 25min 30min Sample No. mol (mV) Mol SG-A1-3-3 0.09 280 170 125 84 75 65 Zn 0.02 -3-4 0.09 255 145 120 77 65 55 Zn 0.04 As a result of a comparison between the measurement results of the sample phosphor (SG-A1-3-3) of Table 15 and the sample phosphor (SG-A1-3-5) of Table 5, it was confirmed that the response characteristics were improved remarkably in addition to the improvement of the fluorescent characteristics by substituting a part of Sr with a metal element such as Zn.
In other words, although it is difficult to express definitely in terms of numerical values and usually the afterglow is hidden by the reflected light in a condition involving even a slight light thus making its visual inspection difficult, the addition of Zn improves the initial intensity thus making it possible to easily recognize the afterglow. It is to be noted that even in this case, it is preferable to select so that Sr + Zn + Eu + Pb + Dy = 1 mol. The concentration of Zn can be on the order of several mol o of the proportion of Sr. Also in this case, it is necessary that the proportion of the activator Eu is on the order of 2 mol ~ of Sr and the proportion of Dy is two times or more of the amount of Eu.
Embodiment 8. (Zn-substitution phosphor) With the embodiment 7, the improvement in the response of the afterglow characteristics was confirmed on the sample phosphors employing as the matrix the phosphor containing Pb, Bi and Dy and substituting a part of its Sr with Zn. Then, two different sample phosphors (SAD 7-2, SAD 7-3) containing no Pb and Hi and substituting a part of Sr with Zn and a comparative sample (SAD 7-1) containing no zinc were further prepared and their afterglow characteristics were verified. The compositions of the prepared samples are shown in the following Table 16.
Table 16 shows the proportions (mol) of the respective elements per molecular weight. Note that symbol H indicates the mol of boric acid added as a flux.
Table 16 Sample No. Sr Zn Eu Dy x A1 B
SAD 7-1 0.930 - 0.020 0.050 1.0 2.000 0.033 SAD 7-2 0.925 0.005 0.020 0.050 1.0 2.000 0.033 SAD 7-3 0.920 0.010 0.020 0.050 1.0 2.000 0.033 SG-Dy-6 0.925 - 0.025 0.050 1.0 2.000 0.03 -ZnS:Cu G-550 (TM) The measurement of the afterglow characteristics was effected in the following way. The powder of each of the sample phosphors shown in Table 16 was put to fill a holder (the powder filling cavity was 33 mm in inner diameter and 5 mm in depth) and kept in storage in the dark place for more than 16 hours. Then, the light from a 27-watt fluorescent lamp was irradiated on the holder for 10 minutes at the distance of about 150 mm and variations in the intensity of the afterglow immediately thereafter were measured with a measuring instrument (a luminance meter: Type-5712 made by Matsushita Denshi Kogyo R & D Center Corp., a phototube: 8847 made by Hamamats Photonix Corp., a recorder: PRR5000T'" by Toa Denpa Co., Ltd.).
In addition, the afterglow characteristics were measured under the same conditions on the comparative phosphor (SG-Dy-6), the conventional luminous paint (ZnS:Cu) and the commercially available (Sr, Eu, Dy)O~A1203 phosphor (trade name; G-550, manufactured by Nemoto & Co., Ltd.). The results are shown in the following Table 17.
Table 17 1,000 mV- 5min lOmin l5min20min 25min 30min Sample No. time (sec) (mV) SAD 7-1 126 320 185' 128 95 75 61 SG-Dy-6 129 279 158 108 80 62 51 ZnS:Cu 6 15 6 3 2 1 1>
G-550 (TM) 84 235 126 82 59 45 36 * In the Table, 1,000 mV-time indicates the time (seconds) required for the indication value of the luminance meter to reach 1,000 mV after the irradiation of the fluorescent lamp.
As shown in Table 17, even with the sample phosphors containing no lead, the addition of zinc (Zn) resulted in the phosphors having higher afterglow characteristics than the comparative samples (SG-Dy-6, SAD 7-1) containing no lead and zinc.
Also, it was confirmed that the phosphors in which a part of its Sr was substituted with Zn were high in afterglow characteristics as compared with the conventional luminous paint (ZnS:Cu) and the commercially available phosphor (Sr, Eu, Dy)O~ A12 03 .
Claims (12)
1. ~A phosphor having afterglow characteristics, which comprises a matrix containing an Eu2+ activated strontium aluminate phosphor substance, characterized in that said phosphor has a chemical composition expressed by:
(Sr, Eu, Pb, Dy) O - y (A1, Bi)2O3 where Sr + Eu + Pb + Dy = 1, Al + Bi = 2y, wherein in said composition, the value of y is 0.83 <= y <= 1.67, and the proportions in moles of Eu, Pb, Dy, Al and Bi are 0.016 <=
Eu <= 0.033, 0.006 <=; Pb <= 0.017, 0.05 <= Dy <= 0.133, 1.655 <=
A1 <= 3.334 and 0.0030 <= Bi <= 0.0100, and containing traces of Boron, said traces being obtainable as the result of using 0.03 mol boric acid per unit of phosphor prepared by fixing the proportions of the respective elements such that (Al + Bi) - 3 mol and (Sr + Eu + Pd + Dy) - 1.5 mol.
(Sr, Eu, Pb, Dy) O - y (A1, Bi)2O3 where Sr + Eu + Pb + Dy = 1, Al + Bi = 2y, wherein in said composition, the value of y is 0.83 <= y <= 1.67, and the proportions in moles of Eu, Pb, Dy, Al and Bi are 0.016 <=
Eu <= 0.033, 0.006 <=; Pb <= 0.017, 0.05 <= Dy <= 0.133, 1.655 <=
A1 <= 3.334 and 0.0030 <= Bi <= 0.0100, and containing traces of Boron, said traces being obtainable as the result of using 0.03 mol boric acid per unit of phosphor prepared by fixing the proportions of the respective elements such that (Al + Bi) - 3 mol and (Sr + Eu + Pd + Dy) - 1.5 mol.
2. ~The phosphor according to claim 1, characterized in that a part of said strontium (Sr) is substituted with zinc.
3. ~The phosphor according to claim 1, characterized in that the value of y is 1.00 <= y <= 1.15, and the proportions in moles of Eu, Pb, Dy, Al and Bi are 0.020 <=
Eu <= 0.023, 0.010 <= Pb <= 0.011, 0.05 <= Dy <=
0.133, 1.994 <=
Al <= 2.2964 and 0.0036 <= Bi <= 0.006.
Eu <= 0.023, 0.010 <= Pb <= 0.011, 0.05 <= Dy <=
0.133, 1.994 <=
Al <= 2.2964 and 0.0036 <= Bi <= 0.006.
4. ~The phosphor according to claim 4, characterized in that a part of said strontium (Sr) is substituted with zinc.
5. ~The phosphor according to claim 1, characterized in that said phosphor contains 0.895 moles Sr, 0.030 moles Eu, 0.015 moles Pb, 0.060 moles Dy, 2.991 moles A1, 0.009 moles Hi and 2y is 3Ø
6. The phosphor according to claim 1, characterized in that said phosphor contains 1.994 moles A1, 0.006 moles Bi and 2y is 2.0 and that Sr, Eu, Pb and Dy are in amounts selected from the group consisting of (a) 0.910 moles Sr, 0.020 moles Eu, 0.010 moles Pb and 0.06 moles Dy, (b) 0.896 moles Sr, 0.023 moles Eu, 0.011 moles Pb and 0.069 moles Dy, (c) 0.865 moles Sr, 0.030 moles Eu, 0.015 moles Pb and 0.09 moles Dy, (d) 0.850 moles Sr, 0.033 moles Eu, 0.017 moles Pb and 0.10 moles Dy, and (e) 0.925 moles Sr, 0.017 moles Eu, 0.008 moles Pb and 0.05 moles Dy.
7. The phosphor according to claim 1, characterized in that said phosphor contains 0.02 moles Eu, 0.010 moles Pb, 1.994 moles Al, 0.006 moles Bi and 2y is 2.0 and that Sr and Dy are in amounts selected from the group consisting of (a) 0.890 moles Sr and 0.08 moles Dy, (b) 0.880 moles Sr and 0.009moles Dy, (c) 0.870 moles Sr and 0.10 moles Dy, (d) 0.860 moles Sr and 0.11 moles Dy, (e) 0.850 moles Sr and 0.12 moles Dy, and (f) 0.837 moles Sr and 0.133moles Dy.
8. The phosphor according to claim 1, characterized in that said phosphor contains 1.994 moles Al, 0.006 moles Bi and 2y is 2 and that Sr, Eu, Pb and Dy are in amounts selected from the group consisting of (a) 0.892 moles Sr, 0.017 moles Eu, 0.008 moles Pb and 0.083 moles Dy, (b) 0.888 moles Sr, 0.023 moles Eu, 0.012 moles Pb and 0.077 moles Dy, and (c) 0.885 moles Sr, 0.019 moles Eu, 0.009 moles Pb and 0.087 moles Dy.
9. The phosphor according to claim 1, characterized in that said phosphor contains 0.02 moles Eu, 0.0075 moles Pb, 1.9955 moles Al, 0.0045 moles Bi and 2y is 2 and that Sr and Dy are in amounts selected from the group consisting of (a) 0.8825 moles Sr and 0.090 moles Dy, and (b) 0.8675 moles Sr and 0.105 moles Dy.
10. The phosphor according to claim 1, characterized in that said phosphor contains 1.9964 moles Al and 0.0036 moles Bi and 2y is 2 and that Sr, Eu, Pb and Dy are in amounts selected from the group consisting of (a) 0.8825 moles Sr, 0.02 moles Eu, 0.0075 moles Pb and 0.090 moles Dy, (b) 0.8625 moles Sr, 0.02 moles Eu, 0.0075 moles Pb and 0.110 moles Dy, and (c) 0.888 moles Sr, 0.016 moles Eu, 0.006 moles Pb and 0.090 moles Dy.
11. A phosphor having afterglow characteristics, which comprises a matrix containing an Eu2+ activated strontium aluminate phosphor substance, characterized in that said phosphor has a chemical composition expressed by:
(Sr, Eu, Pb, Dy) O .cndot. (Al, Bi) 2O3 where Sr + Eu + Pb + Dy = 1, Al + Bi = 2, wherein the proportions in moles of Eu, Pb, Dy, Al and Bi are 0.016 <=
Eu <= 0.02, 0.006 <= Pb <= 0.010, 0.06 <= Dy <=
0.133, 1.994 <=
A1 <= 1.9964 and 0.0036 <= Bi <= 0.006, and containing traces of Boron, said traces being obtainable as the result of using 0.03 mol boric acid per unit of phosphor prepared by fixing the proportions of the respective elements such that (Al + Bi) - 3 mol and (Sr + Eu + Pd + Dy) - 1.5 mol.
(Sr, Eu, Pb, Dy) O .cndot. (Al, Bi) 2O3 where Sr + Eu + Pb + Dy = 1, Al + Bi = 2, wherein the proportions in moles of Eu, Pb, Dy, Al and Bi are 0.016 <=
Eu <= 0.02, 0.006 <= Pb <= 0.010, 0.06 <= Dy <=
0.133, 1.994 <=
A1 <= 1.9964 and 0.0036 <= Bi <= 0.006, and containing traces of Boron, said traces being obtainable as the result of using 0.03 mol boric acid per unit of phosphor prepared by fixing the proportions of the respective elements such that (Al + Bi) - 3 mol and (Sr + Eu + Pd + Dy) - 1.5 mol.
12. The phosphor according to claim 11, characterized in that a part of said strontium (Sr) is substituted with zinc.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7-112574 | 1995-04-14 | ||
| JP11257495 | 1995-04-14 | ||
| PCT/JP1996/001014 WO1996032457A1 (en) | 1995-04-14 | 1996-04-12 | Phosphor with afterglow characteristic |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2191333A1 CA2191333A1 (en) | 1996-10-17 |
| CA2191333C true CA2191333C (en) | 2006-08-01 |
Family
ID=14590131
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002191333A Expired - Fee Related CA2191333C (en) | 1995-04-14 | 1996-04-12 | Phosphor with afterglow characteristic |
Country Status (12)
| Country | Link |
|---|---|
| US (1) | US5770111A (en) |
| EP (1) | EP0765925B1 (en) |
| JP (1) | JP3759958B2 (en) |
| KR (1) | KR100426034B1 (en) |
| CN (1) | CN1102631C (en) |
| AU (1) | AU720126B2 (en) |
| CA (1) | CA2191333C (en) |
| DE (1) | DE69617850T2 (en) |
| ES (1) | ES2169796T3 (en) |
| PT (1) | PT765925E (en) |
| TW (1) | TW374796B (en) |
| WO (1) | WO1996032457A1 (en) |
Families Citing this family (45)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998042797A1 (en) * | 1997-03-26 | 1998-10-01 | Kabushiki Kaisha Tokyo Kagaku Kenkyusho | Process for producing aluminate phosphor |
| US6267911B1 (en) | 1997-11-07 | 2001-07-31 | University Of Georgia Research Foundation, Inc. | Phosphors with long-persistent green phosphorescence |
| US6117362A (en) * | 1997-11-07 | 2000-09-12 | University Of Georgia Research Foundation, Inc. | Long-persistence blue phosphors |
| WO1999050372A1 (en) * | 1998-03-27 | 1999-10-07 | Chunxiang Fang | Photoluminescent long afterglow phosphors |
| US6284156B1 (en) * | 1998-11-19 | 2001-09-04 | Kabushiki Kaisha Ohara | Long-lasting phosphor, powdered long-lasting phosphor and method for manufacturing the powdered long-lasting phosphor |
| US6123871A (en) * | 1999-01-11 | 2000-09-26 | Carroll; Michael Lee | Photoluminescence polymers, their preparation and uses thereof |
| US6696126B1 (en) | 1999-08-12 | 2004-02-24 | The United States Of America As Represented By The Secretary Of The Navy | Visual-tactile signage |
| JP2002194346A (en) * | 2000-12-22 | 2002-07-10 | Sumitomo Chem Co Ltd | Method for producing aluminate fluorescent substance |
| DE10126159A1 (en) * | 2001-05-30 | 2002-12-05 | Philips Corp Intellectual Pty | Gas discharge lamp with down conversion phosphor |
| JP2003301171A (en) * | 2002-02-06 | 2003-10-21 | Tdk Corp | Phosphor thin film, production process therefor, and el panel |
| US6969475B2 (en) * | 2002-11-22 | 2005-11-29 | Kb Alloys | Photoluminescent alkaline earth aluminate and method for making the same |
| US6953536B2 (en) | 2003-02-25 | 2005-10-11 | University Of Georgia Research Foundation, Inc. | Long persistent phosphors and persistent energy transfer technique |
| DE602005023713D1 (en) * | 2004-03-12 | 2010-11-04 | Avery Dennison Corp | NOTINFORMATIONS LIGHTING SYSTEM |
| CN100410703C (en) * | 2004-03-12 | 2008-08-13 | 艾利丹尼森公司 | Lighting system with a passive phosphorescent light source |
| US8250794B2 (en) * | 2004-03-12 | 2012-08-28 | Avery Dennison Corporation | Emergency information sign |
| WO2005093478A1 (en) * | 2004-03-12 | 2005-10-06 | Avery Dennison Corporation | Lighting system with a passive phosphorescent light source |
| KR100655894B1 (en) * | 2004-05-06 | 2006-12-08 | 서울옵토디바이스주식회사 | Light Emitting Device |
| KR100658700B1 (en) | 2004-05-13 | 2006-12-15 | 서울옵토디바이스주식회사 | Light emitting device with RGB diodes and phosphor converter |
| KR100665299B1 (en) * | 2004-06-10 | 2007-01-04 | 서울반도체 주식회사 | Luminescent material |
| US8308980B2 (en) * | 2004-06-10 | 2012-11-13 | Seoul Semiconductor Co., Ltd. | Light emitting device |
| KR100665298B1 (en) * | 2004-06-10 | 2007-01-04 | 서울반도체 주식회사 | Light emitting device |
| SG161205A1 (en) * | 2004-12-22 | 2010-05-27 | Seoul Semiconductor Co Ltd | Light emitting device |
| CN100363459C (en) * | 2005-03-31 | 2008-01-23 | 中国科学院合肥物质科学研究院 | Red strontium aluminate long-afterglow material and preparation method thereof |
| US8896216B2 (en) | 2005-06-28 | 2014-11-25 | Seoul Viosys Co., Ltd. | Illumination system |
| WO2007001116A1 (en) | 2005-06-28 | 2007-01-04 | Seoul Opto Device Co., Ltd. | Light emitting device for ac power operation |
| CN100338174C (en) * | 2005-09-09 | 2007-09-19 | 中国铝业股份有限公司 | Aluminate base long persistence phosphor powder preparation method |
| KR101258397B1 (en) * | 2005-11-11 | 2013-04-30 | 서울반도체 주식회사 | Copper-Alkaline-Earth-Silicate mixed crystal phosphors |
| KR101055772B1 (en) | 2005-12-15 | 2011-08-11 | 서울반도체 주식회사 | Light emitting device |
| KR100875443B1 (en) | 2006-03-31 | 2008-12-23 | 서울반도체 주식회사 | Light emitting device |
| KR101258227B1 (en) | 2006-08-29 | 2013-04-25 | 서울반도체 주식회사 | Light emitting device |
| EP2060616A4 (en) * | 2006-09-15 | 2010-08-04 | Mitsubishi Chem Corp | Phosphor, method for producing the same, phosphor-containing composition, light-emitting device, image display and illuminating device |
| US7959827B2 (en) * | 2007-12-12 | 2011-06-14 | General Electric Company | Persistent phosphor |
| WO2009025469A2 (en) * | 2007-08-22 | 2009-02-26 | Seoul Semiconductor Co., Ltd. | Non stoichiometric tetragonal copper alkaline earth silicate phosphors and method of preparing the same |
| KR101055769B1 (en) | 2007-08-28 | 2011-08-11 | 서울반도체 주식회사 | Light-emitting device adopting non-stoichiometric tetra-alkaline earth silicate phosphor |
| US8545723B2 (en) * | 2007-12-12 | 2013-10-01 | General Electric Company | Persistent phosphor |
| KR100924912B1 (en) | 2008-07-29 | 2009-11-03 | 서울반도체 주식회사 | Warm white light emitting apparatus and back light module comprising the same |
| US8152586B2 (en) | 2008-08-11 | 2012-04-10 | Shat-R-Shield, Inc. | Shatterproof light tube having after-glow |
| DE102009030205A1 (en) * | 2009-06-24 | 2010-12-30 | Litec-Lp Gmbh | Luminescent substance with europium-doped silicate luminophore, useful in LED, comprises alkaline-, rare-earth metal orthosilicate, and solid solution in form of mixed phases arranged between alkaline- and rare-earth metal oxyorthosilicate |
| KR101055762B1 (en) * | 2009-09-01 | 2011-08-11 | 서울반도체 주식회사 | Light-emitting device employing a light-emitting material having an oxyosilicate light emitter |
| US8017038B2 (en) * | 2009-09-04 | 2011-09-13 | Samsung Sdi Co., Ltd. | Green phosphor and plasma display panel including the same |
| CN104300077B (en) * | 2010-11-09 | 2017-12-01 | 四川新力光源股份有限公司 | A kind of luminescent material with light-decay characteristic |
| US8506843B2 (en) | 2010-12-17 | 2013-08-13 | General Electric Company | White emitting persistent phosphor |
| US8404153B2 (en) | 2010-12-17 | 2013-03-26 | General Electric Company | White persistent phosphor blend or layered structure |
| JP6292684B1 (en) * | 2016-12-28 | 2018-03-14 | 国立研究開発法人産業技術総合研究所 | Luminescent phosphor and method for producing the same |
| CN114806575A (en) * | 2022-05-23 | 2022-07-29 | 龙岩学院 | Efficient bismuth ion activated yellow fluorescent material and preparation method thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3250121B2 (en) * | 1993-02-24 | 2002-01-28 | 株式会社東京化学研究所 | Aluminate phosphor |
| CA2156495C (en) * | 1993-03-19 | 2008-11-18 | D. Allen Allen | Methods for inhibiting hiv associated disease using monoclonal antibodies directed against anti-self cytotoxic t-cells |
| JP2543825B2 (en) * | 1993-04-28 | 1996-10-16 | 根本特殊化学株式会社 | Luminescent phosphor |
| JP3232548B2 (en) * | 1994-06-29 | 2001-11-26 | 日亜化学工業株式会社 | Afterglow phosphor |
-
1996
- 1996-04-12 EP EP96909358A patent/EP0765925B1/en not_active Expired - Lifetime
- 1996-04-12 AU AU52887/96A patent/AU720126B2/en not_active Ceased
- 1996-04-12 WO PCT/JP1996/001014 patent/WO1996032457A1/en active IP Right Grant
- 1996-04-12 KR KR1019960707058A patent/KR100426034B1/en not_active IP Right Cessation
- 1996-04-12 PT PT96909358T patent/PT765925E/en unknown
- 1996-04-12 DE DE69617850T patent/DE69617850T2/en not_active Expired - Lifetime
- 1996-04-12 ES ES96909358T patent/ES2169796T3/en not_active Expired - Lifetime
- 1996-04-12 CA CA002191333A patent/CA2191333C/en not_active Expired - Fee Related
- 1996-04-12 CN CN96190555A patent/CN1102631C/en not_active Expired - Fee Related
- 1996-04-12 JP JP53089096A patent/JP3759958B2/en not_active Expired - Lifetime
- 1996-04-12 US US08/737,906 patent/US5770111A/en not_active Expired - Lifetime
- 1996-04-16 TW TW085104537A patent/TW374796B/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| TW374796B (en) | 1999-11-21 |
| US5770111A (en) | 1998-06-23 |
| EP0765925A1 (en) | 1997-04-02 |
| WO1996032457A1 (en) | 1996-10-17 |
| AU5288796A (en) | 1996-10-30 |
| PT765925E (en) | 2002-06-28 |
| JP3759958B2 (en) | 2006-03-29 |
| DE69617850D1 (en) | 2002-01-24 |
| KR100426034B1 (en) | 2004-07-05 |
| DE69617850T2 (en) | 2002-10-10 |
| CN1154710A (en) | 1997-07-16 |
| ES2169796T3 (en) | 2002-07-16 |
| CA2191333A1 (en) | 1996-10-17 |
| EP0765925B1 (en) | 2001-12-12 |
| CN1102631C (en) | 2003-03-05 |
| AU720126B2 (en) | 2000-05-25 |
| EP0765925A4 (en) | 1997-06-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA2191333C (en) | Phosphor with afterglow characteristic | |
| US5376303A (en) | Long Decay phoaphors | |
| KR0145246B1 (en) | Photoluminescent phosphor | |
| EP0877071B1 (en) | Long-lasting phosphor | |
| KR100248067B1 (en) | Aftergrow lamp | |
| CA2161820C (en) | Phosphorescent phosphor | |
| Ronda et al. | Chemical composition of and Eu2+ luminescence in the barium hexaaluminates | |
| CN108504353B (en) | High-performance europium and dysprosium codoped strontium aluminate long afterglow fluorescent powder and preparation method thereof | |
| GB2374602A (en) | Alkali earth aluminate-silicate photoluminescent materials activated by rare earth elements | |
| US5650094A (en) | Red emitting long decay phosphors | |
| JP2979984B2 (en) | Afterglow phosphor | |
| US3450642A (en) | Strontium yttrate luminescent materials | |
| JPH11255536A (en) | Glass having afterglow | |
| US6261477B1 (en) | Long-lasting phosphor | |
| JP3268761B2 (en) | High brightness and long afterglow aluminate phosphor with excellent heat and weather resistance | |
| JP2001026777A (en) | Red color light accumulation type fluorophor | |
| JP2000345154A (en) | Red light emitting alterglow photoluminescent phosphor | |
| JPH0913028A (en) | White phosphorescent phosphor | |
| JPH10168448A (en) | Phosphorescent pigment and its production | |
| JP2863160B1 (en) | Phosphorescent phosphor | |
| CN116042215B (en) | Solid solution type near infrared long afterglow luminescent material and preparation method thereof | |
| JP5774297B2 (en) | Luminescent phosphor and method for producing the same | |
| JP3250121B2 (en) | Aluminate phosphor | |
| CA1110054A (en) | Cerium activated phosphor and method of making same | |
| JPS62187785A (en) | Highly color-rendering fluorescent lamp |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| MKLA | Lapsed |