CA1125494A - Phosphor - Google Patents
PhosphorInfo
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- CA1125494A CA1125494A CA320,411A CA320411A CA1125494A CA 1125494 A CA1125494 A CA 1125494A CA 320411 A CA320411 A CA 320411A CA 1125494 A CA1125494 A CA 1125494A
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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
- C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
- C09K11/7776—Vanadates; Chromates; Molybdates; Tungstates
-
- 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
- C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
- C09K11/7777—Phosphates
-
- 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
- C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
- C09K11/778—Borates
Abstract
PHOSPHOR
Abstract of the Disclosure The specification discloses a phosphor co-activated with Nd3+ and Yb3+, which is excited by infrared rays and has an emission spectrum in the infrared wavelength region. This phosphor is represented by the following general formula:
Ln1-x-yNdxYbyA5(Mo4)4, Ln1-x-yNdxYbyD3(BO3)4, Ln1-x-yNdxYbyP5O14, Ln1-x-yNdxYbyA3(PO4)2, Ln1-x-yNdxYbyNa2Mg2(VO4)3 or Ln1-x-yNdxYbyA'(MO4)2 wherein Ln stands for Bi, Ce, Ga, Gd, In, La, Lu, Sb, Sc and/or Y, A stands for K and/or Na, M stands for W and/or Mo, D stands for A? and/or Cr and A' stands for Li, Na and/or K. The phosphor can be used for optical card readers or the like and has good emission intensity.
Abstract of the Disclosure The specification discloses a phosphor co-activated with Nd3+ and Yb3+, which is excited by infrared rays and has an emission spectrum in the infrared wavelength region. This phosphor is represented by the following general formula:
Ln1-x-yNdxYbyA5(Mo4)4, Ln1-x-yNdxYbyD3(BO3)4, Ln1-x-yNdxYbyP5O14, Ln1-x-yNdxYbyA3(PO4)2, Ln1-x-yNdxYbyNa2Mg2(VO4)3 or Ln1-x-yNdxYbyA'(MO4)2 wherein Ln stands for Bi, Ce, Ga, Gd, In, La, Lu, Sb, Sc and/or Y, A stands for K and/or Na, M stands for W and/or Mo, D stands for A? and/or Cr and A' stands for Li, Na and/or K. The phosphor can be used for optical card readers or the like and has good emission intensity.
Description
llZ5494 The present invention relates to a phosphor which is excited by infrared rays and has an emission spectrum in the infrared ray region.
A phosphor activated with neodymium ions ~Nd3+), for example, LiNdP4012, is conventionally used in optical card readers. In such readers, a card on which informa-tion has been recorded by a phosphor is exposed to the rays of an excitation light source having an emission spectrum corresponding with the excitation wavelength of the phosphor, and by detecting selectively the emission from the phosphor, the information recorded in the card can be precisely read.
However, the emission intensity of the conventional neodymium-activated phosphor is not completely satis-factory for card readers.
One of the inventors of the present invention has already proposed a phosphor having a emission intensity higher than that of the conventional neodymium-activated phosphor, for example a phosphor having a composition of NaNdxYbyP40l~ tsee U.S. Patent 4,10..7,.~73 iss.ue.d August 15, 1978~.
The following references are cited to show the state ~ .
of the art:
U.S. Patent No. 3,473,027 Japanese Patent Application Laid-Open Specification No. 60888/78 It is a pri~ary object of the present invention to provide a phosphor having a high emission intensity.
In accordance with the present invention, this and other objects can be attained by a phosphor co-activated with Nd and Yb, which is represented by the following
A phosphor activated with neodymium ions ~Nd3+), for example, LiNdP4012, is conventionally used in optical card readers. In such readers, a card on which informa-tion has been recorded by a phosphor is exposed to the rays of an excitation light source having an emission spectrum corresponding with the excitation wavelength of the phosphor, and by detecting selectively the emission from the phosphor, the information recorded in the card can be precisely read.
However, the emission intensity of the conventional neodymium-activated phosphor is not completely satis-factory for card readers.
One of the inventors of the present invention has already proposed a phosphor having a emission intensity higher than that of the conventional neodymium-activated phosphor, for example a phosphor having a composition of NaNdxYbyP40l~ tsee U.S. Patent 4,10..7,.~73 iss.ue.d August 15, 1978~.
The following references are cited to show the state ~ .
of the art:
U.S. Patent No. 3,473,027 Japanese Patent Application Laid-Open Specification No. 60888/78 It is a pri~ary object of the present invention to provide a phosphor having a high emission intensity.
In accordance with the present invention, this and other objects can be attained by a phosphor co-activated with Nd and Yb, which is represented by the following
- 2 -.~
l~Z5494 general formula:
Lnl-x-yNdxybyz wherein: Ln stands for at least one element selected from the group consisting of Bi, Ce, Ga, Gd, In, La, Lu, Sb, Sc and Y; Z stands for a composition represented by A5(Mo4)4 in which A stands for at least one element selected from the group consisting of K and Na and M
stands for at least one element selected from the group consisting of W and Mo, D3(BO3)4 in which D stands for at least one element selected from the group consisting of ~ and Cr~ PsO14, A3(PO4)2 in which A is as defined above~ Na2Mg2(vo4)3 or A'(MO4)2 in which A' stands for at least one element selected from the group consisting of Li, Na and K and M is as defined above; x is a value in the range of 0.01 < x < 0.99; ar.d y is a value in the range of 0.01 ~ y ~ 0.99 with the proviso that the sum of x and y is in the range of x + y ' 1.
- Preferred forms of the invention will be described in detail in the following with reference to the accompanying drawings, in which:-Fig. 1 is a view illustrating the relative responsivity spectrum of an example of a silicon photo-detector;
~!: Figs. 2, 4, 5, 8, 9, 13, 15 and 17 are views illus-trating the relation between the composition and the relative emission intenslty in embodiments of the phosphor of the present invention; and ., .
-, Figs. 3, 6, 7, 10, 11, 12, 14, 16 and 18 are views - showing the- emission spectra of embodiments of the phosphor of the present invention.
The phosphor o~ the present invention is an oxysalt phosphor in the broad sense, which is characterized in -" ~:
that it contains ytterbium ions (Yb3+) and neodymium ions (Nd3+) as the activator. The phosphor has a high quantum efficiency of emission and has a large absorption cross section by neodymium ions in the infrared ray region. Further, in the phosphor of the present invention, energy is transferred at high efficiency from excited neodymium ions to ytterbium ions, and emission in the vicinity of 980 nm is thereby caused in the ytterbium ions. Accordingly, the phosphor of the present invention has an emission spectrum which corresponds closely with the wavelength region of the silicon photo-detector used most commonly in the near infrared wavelegth region (for example, an Si-PIN photo-detector). The relative respon-sivity spectrum of such a silicon photo-detector is shown in Fig. 1.
The conventional neodymium-activated phosphor mainly has an emission in the vicinity of 1050 nm and an emission in the vicinity of 900 nm. The emission in the vicinity of 900 nm overlaps greatly with the emission from an ,~ ~
~20 excitation light source. Accordingly, only the emission in the vicinity of 1050 nm is detected by using an ~:
u~ appropriate filter in the conventional neodymium-activated phosphor.
The phosphor of the present invention has an emission in the vicinity of 980 nm, as pointed out hereinbefore, if the ytterbium ion concentration, namely the value of y in ~; the above general formula, is in the range of from 0.01 to 0.99. Even if the value of y is as small as 0.01, the emission intensity is drastically increased over the emission intensity of the ytterbium-free phosphor.
Further, even if an ion capable of being trivalent and ~ 5494 having no absorption in the wavelength region of 800 to 1000 nm, namely at least one ion selected from the group consisting of Bi, Ce, Ga, Gd, In, La, Lu, Sb, Sc and Y, is co-present with neodymium and ytterbium, the phosphor of the present invention has effects which are superior to those attainable from the conventional phosphor activated only with neodymium ions.
Furthermore, in the phosphor of the present invention, a high emission intensity can be obtained not only when it is excited by infrared rays but also when the energy level of the neodymium ion in the visible or ultraviolet ray region is excited by an argon laser or the like.
The present invention, and particularly preferred forms thereof, will now be described in more detail.
A first group of the phosphors of the present invention is characterized by the fact Z in the general formula stands for a composition A5(MO4)4. Thus, ; this group of phosphors can be represented by the following general formula:
Lnl-x-yNdxybyAs(Mo4~4 These phosphors can be obtained by weighing the :- .
starting materials, namely A2CO3, Ln203 (which may be CeO2 when Ln is Ce), Nd2O3, Yb2O3 and WO3 and/or MoO3, so that the intended composition will be attained, mixing them sufficiently, preferably pelletizing the mixture, and sintering the mixture at a temperature of 600 to 650C for 1 to 2 days in a platinum or quartz crucible.
Fig. 2 illustrates the relationship between the composition of the phosphor and the relative emission intensity (calculated based on the assumption that the intensity of the composition in which y is 0 ;s 1) of - . ' llZS494 I
5Ndl-yYby(wo4)4 and NasNdl_yYby(M004)4~
For excitation of the phosphors, a (Ga,~Q)As light emitting diode having a peak at 800 nm was used, and the emission intensity was measured by a photo-multiplier having a photo-cathode of the S-l type.
The phosphor of the present invention shows emission at a characteristic wavelength when the values of x and y are in the above-mentioned ranges. From Fig. 2, it can be seen that the values of x and y providing a preferred phosphor of the first group having a higher emission intensity are in the following ranges:
0.25 ' x ' 0.99 and 0.01 ' y ' 0.75.
It is most preferred that x and y be in the following ranges:
0.65 ' x ' 0.95 and 0.05 ' y ' 0.35.
A phosphor belonging to the second group of the ~ -present invention is one in which Z stands for a composition represented by D3(B03)4, namely a phos-phor represented by the following general formula:
Lnl_x_yNdxybyD3(Bo3)4 This phosphor can be obtained by weighing the starting materials, namely D203, D(OH)3 or D2(S04)3, Ln203 (which may be CeO2 when Ln is Ce), Nd203, Yb203 and B203, so that a stoichiometric composition correspond-ing to the intended composition is attained; however, the amount of B203 may be up to 1.5 times in excess over the stoichiometric amount. The starting materials are mixed sufficiently, pelletized and the pellets sintered at about 1100C for 3 days in a platinum or quartz crucible.
Fig. 4 illustrates the relationship between the composition of the phosphor and the relative emission llZSq~94 I
intensity (calculated based on the assumption that the intensity of the composition in which y is 0 is 1) in phosphors of A~3Ndl_yYby(BO3)4. The measurement was conducted in the same manner as described above with respect to Fig. 2. The phosphor of the present invention shows an emission of a characteristic wavelegth when the values of x and y are in the above-mentioned ranges. From Fig. 4, it can be seen that the values of x and y pro-- viding a preferred phosphor of the second group having a high emission intensity are in the following ranges:
0.10 < x _ 0.99 and 0.01 _ y _ 0.90.
It is most preferred that x and y be in the following ranges:
0.60 ' x ' 0.98 and 0.02 ' y ' 0.40.
Fig. 5 illustrates the relationship between the Cr concentrations (z) and the relative emission intensity (calculated based on the assumption that the intensity of NdAQ3(BO3)4 is 1) in phosphors of 0.9Ybo.l(AQl-zcrz)3(Bo3)4. From Fig. 5,, ~ 20 it can be seen that the higher the A concentration, the higher the emission intensity.
~; A phosphor belonging to the third group of the present invention is one in which Z stands for a composition represented by P5014, namely a phosphor represented by the following general formula:
Lnl_x_yNdxybyp5ol4 This phosphor can be obtained by weighing the starting materials, namely Ln203 (which may be CeO2 when Ln is Ce), Nd23~ Yb23 and NH4H2PO3 so that the amount of P205 is at least 3 times in excess over the stoichiometric amount and the amounts of other components are stoichiometric amounts corresponding to the intended composition, mixing them sufficiently and sintering themixture in a lidded gold crucible at 500 to 800C. for about 1 to about 5 days.
Fig. 8 illustrates the relationship between the com-position of the phospXor and the relative emission intensity (calculated based on the assumption that the intensity of the composition in which y is 0 is 1) in phosphors of Ndl_yYbyP5014, and Fig. 9 illustrates the relationship between the composition of the phosphor and the relative emission intensity of phosphors of LnO.9-XNdXYbO.lPsO14 in which Ln is Bi, Gd or Y.
The measurement was carried out in the same manner as described above with respect to Fig. 2.
From these Figs., it can be seen that values of x and y providing a preferred phosphor of the third group having a high emission intensity are in the following ranges:
0.05 _ x _ 0.98 and 0.02 < y < 0.95.
It is most preferred that x and y be in the following ranges:
0.18 ~ x ' 0.95 and 0.05 ' y ' 0.82.
A phosphor belonging to the fourth group of the phos-phor of the present invention is one in which Z stands for a composition represented by A3(PO4)2, namely a phosphor represented by the following general formula:
~nl_x_yNdxybyA3(po4)2 This phosphor can be obtained by weighing starting materials, namely A2CO3, Ln203 ~which may be CeO2 when Ln is Ce), Nd23~ Yb203 and NH4H2PO4, so that the intended composition can be attained, mixing them sufficiently and sintering the mixture in a lidded platinum crucible at about 1200C for about 20 hours.
Fig. 13 illustrates the relationship between the 1~2Sg~94 I
composition of the phosphor and the relative emission intensity (calculated based on the assumption that the intensity of the composition in which y is O is 1) in phosphors of K3Ndl_yYby(P04)2. The measurement was carried out in the same manner as described above with respect to Fig. 2.
As can be seen from Fig. 13, values of x and y providing a preferred phosphor of this group having a high emission intensity are in the following ranges:
0.02 ' x ''0.98 and 0.02 < y c 0.98.
It is most preferred that x and y be in the following ranges:
0.09 ' x ' 0.98 and 0.02 ' y ' 0.91.
A phosphor belonging to the fifth group of the present invention is one in which Z stands for a composition represented by Na2Mg2~V04)3, namely a phosphor rep-resented by the following general formula:
-:~
~ Lnl_x yNdxybyNa2Mg2~vo4)3 ;~ This phosphor can be obtained by weighing Na2C03, MgO, Ln203 (which may be CeO2 when Ln is Ce), Nd203, Yb203 and NH4V03 so that the intended composition can be attained, mixing them sufficiently, pelletizing the mixture and sintering the pellets in a quartz, alumina or platinum crucible at about 800C for about 30 hours.
Fig. 15 illustrates the relationship between the composition of the phosphor and the relative emission intensity (calculated based on the assumption that the intensity of the composition in which y is O is 1) in phosphors of Ndl_yYbyNa2Mg2(V04)3. The measurement was carried out in the same manner as described above with respect to Fig. 2.
_ g _ . . .
l~Z5~g4 From Fig. 15, it can be seen that values of x and y providing a preferred phosphor of the fifth group having a high emission intensity are in the following ranges:
0.57 < x < 0.90 and 0.10 < y < 0.53.
A phosphor belonging to the sixth group of the phosphor of the present invention is one in which Z stands for a composition represented by A'(MO4)2, namely a phosphor represented by the following general formula:
Lnl-x-yNdxybyA (M4)2 This phosphor can be obtained by weighing A'2CO3, Ln203 (which may be CeO2 when Ln is Ce), Nd203, Yb203 and MO3 so that the intended composition can be attained, mixing them sufficiently, pelletizing the mixture and sintering the pellets in a quartz or alumina crucible at about 700C for about 3 days.
- Fig. 17 illustrates relationship between the composition of the phosphor and the relative emission intensity (calculated based on the assumption that the intensity of the composition in which y is 0 is 1) in phosphors of LiNdl_yYby(WO4)2 and LiNdl_yYby~MO04)2.
The measurement was carried out in the same manner as described above with respect to Fig. 2.
From Fig. 17, it can be seen that values of x and y providing a preferred phosphor of the sixth group having a high emission intensity are in the following ranges:
0.20 = x = 0.95 and 0.05 = y = 0.80 The phosphor of the present invention will now be described in detail by reference to the following Examples.
Example 1 A powdery starting material comprising 0.5 mole of Na2CO3, 0.-08 mole of Nd203, 0.02 mole of Yb203 and 0.8 ` -- 10 --llZ5~94 mole of WO3 was sufficiently blended and pulverized, and was then pelletized and charged to a quartz crucible. The crucible was placed in an electric furnace and the tem-perature was elevated to 650C at a rate of about 150C/hr, and the pellets were sintered at 650C for 50 hours. After completion of the sintering, the product was cooled and mechanically crushed to obtain a powdery p p or of NdO.8YbO.2Na5(WO4)4 having a particle size (as determined by a Bleine air permeability apparatus; each of the particle sizes mentioned hereinafter is one determined by this apparatus) of about 5 ~m. The emission spectrum of the so obtained phosphor is indicated by a dot line in Fig. 3. The relative emission intensity of this phosphor was 115 (calculated based on the assumption that the intensity of LiNdo gYbo lP4012 is 100; the same holds good hereinafter, unless otherwise indicated).
A phosphor of Ndo 8Ybo.2K5tWO4)4 was prepared by conducting treatments in the same manner as decribed above except that K2C~3 was used instead of Na2CO3 in the powdery starting material. The emission spectrum of this phosphor was substantially the same as the spectrum indicated by a dot line in Fig. 3.
~, A powdery starting material comprising 0.5 mole of Na2CO3, 0.09 mole of Nd203, 0.01 mole of Yb203 and 0.8 mole of MoQ3 was sufficiently blended and pulverized, and was then treated in the same manner as in Example 1 to obtain a phosphor of Ndo gYbo lNa5(MoO4)4. The emission spectrum of this phosphor is indicated by a solid line in Fig. 3. Namely, the emission spectrum of this phosphor was substantially the same as that of the phosphor of llZ5494 Example 1. The relative emission intensity of this phos-phor was 107.
A phosphor of Ndo gYbo lK5(~ioOL~)4 ~as prepared by conducting treatrnents in the same manner as described above except that K2C03 ~as used instead of Na2CO~ in the powdery starting material. The emission spectrum of -this phos~hor was substantially the same as that o~ the phosphor of Example 1.
Exam~le 3 A po~rdering starting material comprising 0.5 mole of Na2C03, 0.01 mole of Y203, 0.075 mole of Nd203, 0.015 mole of Yb203 and 0.8 mole of '.~03 was sufficiently blended and ~ pulverized, and was then treated in the same manner as ;; in Example 1 to ob-tain a phosphor ol YO lNdo 75Ybo ~W04)4 The emission spec-trum of this phosphor was substantially the same as that of the phosphor OI Example 1, and the ~' relative emission intensity was 104.
Phosphors were prepared in the same manner by using 2 3~ Ce2- Ga203~ Gd203, In203, La203~ LU23' Sb23 or 20 ~ Sc203 ( 0.02 mole in case of CeO2 ) instead of Y203.
The emission spectrum was substantiàlly the same in these phosphors.
Also in the case rhere K2CO~ was used instead of Na2C03, the emission spec-trum ~as substantially the same as above.
Exam~le L~
po~ldery starting material comprising 0.5 mole of ~la2C03, 0.08 mole of Nd203, 0.02 mole of Yb203, 0 4 mole of ;l03 and 0.4 mole of MoO~ was sufficiently blended and pulverized, and was then treated in the same manner I
as in Example 1 to obtain a phosphor of Ndo ~Ybo 2Na5-(I~ioO 51:10 5OL)~. The emission spectrum of the phosphor was substantially the same as that of the phosphor of Example 1 and the relative emission intensity was 110.
Example 5 A powdery startin~ material comprising 0,5 mole of Na2C03, 0.01 mole of CeO2, 0~005 mole of Gd203, 0.075 mole of Nd203, 0.015 mole of Yb203, 0.56 mole of :J03 ~; and 0.24 mole of MoO3 was sufficiently blended and pulveri-zed, and then treated in the same manner as in Example 1 :
to obtain a phosphor of~CeO 05Gdo.05Ndo.75Ybo.15N 5( 0.7 MoO 304)4. The emission spectrum of this phosphor~was substantially the same as that of the phosphor of Example 1 and the relative emission intensity was 101. ~;
Example 6 A powdery starting material comprising 0.5 mole of K2C03, 0.01 mole of Bi203, 0.075 mole of ~d20~, 0.015 mole o~ Yb203 and 0.8 mole of MoO3 was sufficiently blended and pulverized, and was then treated in the same ma~ner~ ;
, ~ ~
as in Example 1 to obtain a phosphor of Bio lNdo 75Ybo 15 K5(I~IoO4)4. The emission spectrum o~ -this phosphor ~as substantially the same as that o~ the phosphor of Example 1 and the relative emission intensity was 97.
Examp3e 7 A powdery startin~ material comprisin~ 0.05 mole of K~C03, 0.45 mole of i~a2C03, 0.01 mole of La203, 0.08 mole of Nd203, 0,0] mole of Yb20~ and 0.8 mole of W03 was sufficiently blended and pulverized, and was then treated in the same manner as in Example 1 to obtain a phosphor O.lr~dO.8Y~o.l(Nao.~o.l)s(wol~)L~. The emission spectrum of this phosp~or was substantially the same as tnat of the phosphor of ~xample 1 and the relative emission intensity /as 103, l~;Y~am~le ~3 A powdery starting material comprising 0.3 mole of A~0~, 0,09 mole of Nd2~, 0,01 mole of Yb203 and 0,4 mole of B203 ~ras sufficiently blen~ed and pulverized, and was then pelle-tized and charged to a quartz crucible.
The crucible was placed in an elec-tric furnace and the temperature ~Jas elevated to 1100C, at a rate of about 100C,/hr. The pellets ~ere sintered at 1100C, for 80 hours. After completion of the sintering, the produc-t was cooled and mechanically crushed to obtain a po~dery !: ~
p p f i~0,9Ybo,lA~3(B03)4 having a particle size of about 5 ~m, The emission spectrum of the so obtained phosphor is sho~rn in Fig. 6. The relative emission .
intensity of t'ne phosphor was 130, Exam~le 9 A phosphor of l~do 9Ybo lCr3(B0~)4 ~;ras prepared by conducting treatments in the same manner as in ~xar~ple 8 2~0 ~except tha-t Cr203 was use~ instead of A~203. The emission spectrum of the so obtained phosphor is indicated by a s.olid line in Fig, 7. The relative emission intensity r the phosphor was 4, Exam~le 10 ;:
A powdery starting material comprising 0.27 mole of A~203, 0.03 mole of Cr20~, 0,09 mole of Nd203, 0,01 mole of Yb203 and 0.4 mole of B203 was su~ficiently blended and pulverized, and ras then treated in th~ same manner as in ~xample ~ to obtai.n a phosphor of Ndo gYbo lA~2 7CrO 3-(B03)4, The emission spectrum of this phosphor is indicatedby a dot line in Fig, 7. The relative emission intensity , .
~,; ,, , , ~
llZ5494 o~ -the phosphor ~ras 57.
l:x~ l c 1 1 ' .
A po~ldery material comprising 0.~ mole of AB203, 0.01 mole of Y203, 0.0~ mole of Nd2~, 0.01 mole of Yb203 and 0.4 mole of B203 ~ras sufficiently blcllded an~ pulverized, and was then treated in the same manner as in ~xample to obtain a phosphor of Y0 ll~bo.~ybo~lA 3( 3)4 erilission spectrurn of the phosphor ~/as substantially the same as that sho~m in Fig. 6.
: 10 Phosphors were prepared in the same manner as described above by using 0.01 mole of Bi20~, Ga203, Gd203, In203, La203, Lu203, Sb203 or Sc20~ or 0.02 rnole of CeO2 ins-tead of Y203. Tne ernission spectrum of each of these phosphors was substantially the same as that sho.m in Fig. 6.
The emission spectrum of a phosphor prepared in the same manner as describ:ed above by using 0.005 mole of ~ -.
,~
Bi203 and 0.005 mole of Ga203 instead of Y203 tJas sub-s-tantially -the same as that sho~m in Fig. 6.
E~arn~le 12 A powdery starting material comprising 0.06 mole of Nd203, 0.04 mole of Yb203 and 3.0 moles o~ NH4H2P04 was :: sufficiently blended an~ pulveriz~d, and was ~nen pelleti~ed and charged in a gold cruclble. The crucible was placed in an electric furnace and the temperature was elevated to 700C, at a rate of àbout 150C./hr. The pellets were :~. . O
sintered at 700 C. for 5 days. After completion of the sintering, the product ~tas cooled, ~ashed sufficiently with l"ater and mechanically crushed to obtain a pol;~dery P P f Ndo.6Ybo.~P5l4 havin~ a particle s.ize of about 5 ~m. Tne emiss.ion spectrum of this phosphor is sho-,m in Fig. 10. The relative emission intensity of the . - 15 -`` 1125494 pho sphor was :121.
1. rn~lc 13 A powdery startin~ material comprisin~ 0.02 rnole of Bi203, 0.06 mole of ~ld20~, 0.02 mole of Yb203 and 3.0 moles of i~THL~H2POL~ was suf`ficiently blended and pulverized, and .~a~ then treated in the same manner as in Example 12 to obtain a pho3phor of Bio.2Ndo.GYbo.2P5014.
The emission spectrum of this phosphor ~las substantially the same as tha-t of the phosphor of ~ample 12 and the relative emission intensity was 105, Each of the emission spectra of phosphors prepared in the same manner as described above by using Ga203, 2 3' 2 3- La23, Lu203~ Sb203, Sc203 or Y203 was substantially the same as the emission spectrum of the phosphor of EY~ample 12.
~:: Example 14 A powdery starting material comprising 0.04 mole of , :
CeO2, 0.05 mole of Nd203, 0.03 mole of Yb203 and 3.0 moles of NH4H2P04 was sufflciently blended and pulverized and was then treated in the same manner as in Example 12 to obtain a phosphor of CeO 2Ndo 5Ybo 3P5014, The emission spectrum of this phosphor is sho~m in Fig, 11. The relative emission intenxity of the phosphor :
: wa3 10~, Exam~le 15 A powdery starting material comprising 0.01 mole o~
Gd203, 0.02 mole of Y203, 0.05 mole of l~d20~, 0.02 mole of Yb20~ and 3,0 moles of NH4H2P04 was sufficiently blended and pulverized, and was then treated in the same manner as in Example 1~ to obtain a phosphor of Gdo lYo 2?ldo 5Ybo 2~5-, . .
The emission spectrurn of this phosphor i~ sho~ in Eig. 12. The relative ~mission intensity of the phosphor was 97.
~xam~le 16 -. . . - ~
A po.ldery starting material compri sing O . 3 mole of K2C0~, 0.0~ mole of Nd203, 0.02 mole of Yb203 and 0.4 mole of NII4H2POl~ was sufficiently blended and pulverized, and was then pelletized and charged in a platinum crucible.
The crucible was placed in an eIectric furnace and the temperature was elevated to 1200C. at a rate of about 200C./hr. The pellets were sintered at 1200C. for 20 hours. After completion of the sintering, the product - was cooled and mechanicaIly crushed to obtain a powdery P phor of Ndo.8YbO 2K3(P04)2 having a particle size of about~S ~m. The~emlsslon spectru.~ of this phosphor is sho~ in Fig. 14.~ me relative emission in-tensity of the phosphor ~las 87.
Examples 17 to 19 Pho3phors~ of ~YO lMdO~,gYbO.11~3~P0432~ CeO.05YO.05 0.8 20~ Ybo lK~3(PO~z :and~ GdO O5yo.o5Ndo.8ybo.l(Ko.gNao~l)3(po4)2 rere~prepared by suf~iclently blendin~ and pulverizing ` .:
po~,~rdery starting materials sho~n in the follo~rin~ Table ~`
anl treatin~ them in -the same manner as in Example 16.
: ''' ~ ' ' ~ 30 : :
;. -11;:54~4 Table ~xam~le 1'~ Example 1~ am~le 19 Na2C03 - - 0.03 mole K2C03 0 3 mole 0.3 mole 0.27 mole 203 0.01 mole 0.005 mole 0.005 mole CeO2 - 0.01 mole Gd203 - _ 0.005 mole Nd 03 0,08 mole 0,08 mole 0.0~ mole 2 3 0,01 mole 0.01 mole 0.01 mole 10 NH4H2P04 0.4 mole 0.4 mole 0.4 mole The emission spectra of these phosphors were substan-tially the same as that sho~m in Fig. 14. The rela-tive emission intensities of these phosphors were 85, 85 and 79, respectively.
.
Emission spectra of phosphors prepared in the same manner as described above by using Bi203, Ga203, In203, é~ La2~, Lu203~ ~Sb20~3 or Sc203 instead of Y203 in Example 17 were~substantially the same as that shown in Fig. 14.
Further,~ the emlsslon spectrum of a phosphor prepared in the same manner as described above by using Na~CO instead of 1~2C03 in Example lrl was substantlally the ~ame as that sho~rn in Fig. 14.
Exam~le 20 A powdery~starting material comprising 0.2 mole of ~,t~ ' Na2C03, 0.4 mole of MgO, 0.08~mole of Nd203, 0.02 mole of Yb20~ and 0.6 mole of N~14V03 was sufficiently blended and pulverized, and ~ras then pelletized and charg~d in a , quartz crucible. The crucible was placed in a~ electric furnace and the temperature was elevated to 800C. at a rate of about 2Q0C./hr. The pellcts were sintered at ' ' ~1~25494 ~300C. for 30 hours. ~fter completion of the sintering, the product ~ras cooled and mechanically crushed -ta obtain a po~lderY phosphor of ~do gYbo 2Na2M~2(V4)3 havin~ a '~
particle size of about 5 ~m. The emission spectrum of this phosphor is sho~n in Fig. 18. The rela-tive emission intensi-ty of the phosphor was 31.
E,~amples 21 a~d 22 Phosphors of La Nd 'Yb ~I M (VO ) d ,~ Lao.o5ceo.o5Ndo~75ybo.l5Na2Mg2(vo4)3 were pr~pared by sufficiently blending a~d pulverizing po~dery starting '~
materials shown in the following Table and treating them in -the sarne manner as in Example 20.
Table E~ram~le 21 E~am~le 22 ,~La20~ , 0.005 mole 0.005 mole 2 0.01 mole Nd203 0.075 mole 0.075 mole Yb203 0.02 mole 0.015 mole . ~, .
2 3 0.2 mole 0.2 mole ; 20 ~ MgO 0.4"mole , 0.4 mole .
'i'~N~ V03 0.6 mole 0.6 mole : ~, Emission,spectra of these phosphors were substantially the same as t~lat sho-~n ln l~ig. 16, and the relative emis-: ~ .
~ sion intensities of these phosphors ~lere 29 and 28, , ~ respectively.
'- Emission spectra of phosphors prepared in the same manner as described above by usin~ Bi203, Ga203, Gd203, 03, Lu203~ Sb20~, Sc20~ or Y203 in5tead of La203in Example 21 ~Jere substantially the same as that sho~ in Fig. 16.
.
, ` 11;25494 I
~xample 23 A powdery startin~ ma-tcrial comprising 0.1 mole of Li2C03, 0.09 mole o~ Nd203, 0.01 mole of Yb20~ and 0.4 rnole of llO3 wa~ sufficiently blended and pulverized, and ~as then pelletized and charged in a quartz crucible.
The crucible was placed in an electric furnacc and the temperature ~Jas elevated to 700C. at a rate of about 150C./hr. The pellets were sintere~ at 700C. for 3 days. After completion of the sintering, the product was cooled and mechanically crushed to obtain a phosphor of LiNdo gYbo l(W04)2 having a particle size of about 5 ~m. The emission spectrum of the so obtained phosphor is indicated by a solid line in Fig. 18. The rela-tive emission intensity of the phosphor ~ras 71.
Emission spectra of phosphors prepared in the same manner as described above by usin~ r~a2C03 or K2C03 instead of Li2C03 ~ere substantially the same as that of the ; phosphor of Example 23.
ExamPles 24 to 26 Phosphora of LiNdo gYbo l(MoOL~)2, LiNdo.gYbo.l(~l0.5 MoO 50L)2 and NaO sKo~sNdo~gYbO~ 0~9 0,1 L~ 2 pr~pared by suf~iciently blending and pulverizing powdery starting materials shown in the following Table and ~-~ treating thcm in the same manner as in Example 23.
.
,"" ~:
., ` 1125494 ~, rrable EY~ample 24Exam~le 25Example 26 Li2~-0~0.1 mol~ 0,1 mole Na2~03 _ _0.05 mole K2~03 _ _0.05 mole Nd203 0.09 mole0.09 rnole0.09 mole ; Yb20~ 0.01 mole 0.01 mole0.01 mole ~I03 ' - ~ 0.2 mole0.36 mole ioO3 0,4 mole 0.2 mole0.04 mole `' The emission spectrum of the phosphor of ~xample 24 is indicated by a dot Iine in F'i~. 18, which was substan-, :~
tially the same as~the emission spectrum of the phosphor ~ of Example 23 ~rnere 11 was used, ~rhich was indicated by a ;.7~ soli.d line in Fig. 18. The relative emission lntensity ~ "
o~ the phosphor of~Example 24 was 44.~ Emission spectra ~ -of pnosphors prep~ared~ln the same manner as in Exa~ple ,24 by~using Na2C03 or K2C03 lnstead of Li2C03 ~lere the su~stantially the~same as that of the phosphor of Example 24~shown in Fig~. 18.
'20~ Emission speotra o~ the phosphors of Examples 2~ '~
and 26 ~/~re substantlall~J the same as that shown,in Fig.
~ la, and the relative~ emisslon intensi~ies were 53 and .~'``'f "',~ 62, respectively. ~ ,:
mlssion sp~ectra of phosphors prepared in the same manner as in ~xamples 23, ~4, 25 ~nd 26 by using 0.08 -;"
mo:le of Nd203 and O.Ol mole of Ga20~ instead of 0.09 mole of Nd203~ere substantially the same as tha-t sho~
in Fig. 18.
Further, emission spectra of phosphors prepared in :, :
~ 30 the same manner as in the:foregoin~ Examples by using ' ,~;
;:
11'~5494 O. 01 mole of Bi203, GC120~;, In203 La23 ~ LU23 ~ Sb23 ' Sc203 or Y203 or 0.02 mole of CeO2 instead of 0.01 mole of Ga20~ were sub stantially the same as tha-t sho~n~ in Fi~;. 18.
. . ~ .
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. .
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.
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l~Z5494 general formula:
Lnl-x-yNdxybyz wherein: Ln stands for at least one element selected from the group consisting of Bi, Ce, Ga, Gd, In, La, Lu, Sb, Sc and Y; Z stands for a composition represented by A5(Mo4)4 in which A stands for at least one element selected from the group consisting of K and Na and M
stands for at least one element selected from the group consisting of W and Mo, D3(BO3)4 in which D stands for at least one element selected from the group consisting of ~ and Cr~ PsO14, A3(PO4)2 in which A is as defined above~ Na2Mg2(vo4)3 or A'(MO4)2 in which A' stands for at least one element selected from the group consisting of Li, Na and K and M is as defined above; x is a value in the range of 0.01 < x < 0.99; ar.d y is a value in the range of 0.01 ~ y ~ 0.99 with the proviso that the sum of x and y is in the range of x + y ' 1.
- Preferred forms of the invention will be described in detail in the following with reference to the accompanying drawings, in which:-Fig. 1 is a view illustrating the relative responsivity spectrum of an example of a silicon photo-detector;
~!: Figs. 2, 4, 5, 8, 9, 13, 15 and 17 are views illus-trating the relation between the composition and the relative emission intenslty in embodiments of the phosphor of the present invention; and ., .
-, Figs. 3, 6, 7, 10, 11, 12, 14, 16 and 18 are views - showing the- emission spectra of embodiments of the phosphor of the present invention.
The phosphor o~ the present invention is an oxysalt phosphor in the broad sense, which is characterized in -" ~:
that it contains ytterbium ions (Yb3+) and neodymium ions (Nd3+) as the activator. The phosphor has a high quantum efficiency of emission and has a large absorption cross section by neodymium ions in the infrared ray region. Further, in the phosphor of the present invention, energy is transferred at high efficiency from excited neodymium ions to ytterbium ions, and emission in the vicinity of 980 nm is thereby caused in the ytterbium ions. Accordingly, the phosphor of the present invention has an emission spectrum which corresponds closely with the wavelength region of the silicon photo-detector used most commonly in the near infrared wavelegth region (for example, an Si-PIN photo-detector). The relative respon-sivity spectrum of such a silicon photo-detector is shown in Fig. 1.
The conventional neodymium-activated phosphor mainly has an emission in the vicinity of 1050 nm and an emission in the vicinity of 900 nm. The emission in the vicinity of 900 nm overlaps greatly with the emission from an ,~ ~
~20 excitation light source. Accordingly, only the emission in the vicinity of 1050 nm is detected by using an ~:
u~ appropriate filter in the conventional neodymium-activated phosphor.
The phosphor of the present invention has an emission in the vicinity of 980 nm, as pointed out hereinbefore, if the ytterbium ion concentration, namely the value of y in ~; the above general formula, is in the range of from 0.01 to 0.99. Even if the value of y is as small as 0.01, the emission intensity is drastically increased over the emission intensity of the ytterbium-free phosphor.
Further, even if an ion capable of being trivalent and ~ 5494 having no absorption in the wavelength region of 800 to 1000 nm, namely at least one ion selected from the group consisting of Bi, Ce, Ga, Gd, In, La, Lu, Sb, Sc and Y, is co-present with neodymium and ytterbium, the phosphor of the present invention has effects which are superior to those attainable from the conventional phosphor activated only with neodymium ions.
Furthermore, in the phosphor of the present invention, a high emission intensity can be obtained not only when it is excited by infrared rays but also when the energy level of the neodymium ion in the visible or ultraviolet ray region is excited by an argon laser or the like.
The present invention, and particularly preferred forms thereof, will now be described in more detail.
A first group of the phosphors of the present invention is characterized by the fact Z in the general formula stands for a composition A5(MO4)4. Thus, ; this group of phosphors can be represented by the following general formula:
Lnl-x-yNdxybyAs(Mo4~4 These phosphors can be obtained by weighing the :- .
starting materials, namely A2CO3, Ln203 (which may be CeO2 when Ln is Ce), Nd2O3, Yb2O3 and WO3 and/or MoO3, so that the intended composition will be attained, mixing them sufficiently, preferably pelletizing the mixture, and sintering the mixture at a temperature of 600 to 650C for 1 to 2 days in a platinum or quartz crucible.
Fig. 2 illustrates the relationship between the composition of the phosphor and the relative emission intensity (calculated based on the assumption that the intensity of the composition in which y is 0 ;s 1) of - . ' llZS494 I
5Ndl-yYby(wo4)4 and NasNdl_yYby(M004)4~
For excitation of the phosphors, a (Ga,~Q)As light emitting diode having a peak at 800 nm was used, and the emission intensity was measured by a photo-multiplier having a photo-cathode of the S-l type.
The phosphor of the present invention shows emission at a characteristic wavelength when the values of x and y are in the above-mentioned ranges. From Fig. 2, it can be seen that the values of x and y providing a preferred phosphor of the first group having a higher emission intensity are in the following ranges:
0.25 ' x ' 0.99 and 0.01 ' y ' 0.75.
It is most preferred that x and y be in the following ranges:
0.65 ' x ' 0.95 and 0.05 ' y ' 0.35.
A phosphor belonging to the second group of the ~ -present invention is one in which Z stands for a composition represented by D3(B03)4, namely a phos-phor represented by the following general formula:
Lnl_x_yNdxybyD3(Bo3)4 This phosphor can be obtained by weighing the starting materials, namely D203, D(OH)3 or D2(S04)3, Ln203 (which may be CeO2 when Ln is Ce), Nd203, Yb203 and B203, so that a stoichiometric composition correspond-ing to the intended composition is attained; however, the amount of B203 may be up to 1.5 times in excess over the stoichiometric amount. The starting materials are mixed sufficiently, pelletized and the pellets sintered at about 1100C for 3 days in a platinum or quartz crucible.
Fig. 4 illustrates the relationship between the composition of the phosphor and the relative emission llZSq~94 I
intensity (calculated based on the assumption that the intensity of the composition in which y is 0 is 1) in phosphors of A~3Ndl_yYby(BO3)4. The measurement was conducted in the same manner as described above with respect to Fig. 2. The phosphor of the present invention shows an emission of a characteristic wavelegth when the values of x and y are in the above-mentioned ranges. From Fig. 4, it can be seen that the values of x and y pro-- viding a preferred phosphor of the second group having a high emission intensity are in the following ranges:
0.10 < x _ 0.99 and 0.01 _ y _ 0.90.
It is most preferred that x and y be in the following ranges:
0.60 ' x ' 0.98 and 0.02 ' y ' 0.40.
Fig. 5 illustrates the relationship between the Cr concentrations (z) and the relative emission intensity (calculated based on the assumption that the intensity of NdAQ3(BO3)4 is 1) in phosphors of 0.9Ybo.l(AQl-zcrz)3(Bo3)4. From Fig. 5,, ~ 20 it can be seen that the higher the A concentration, the higher the emission intensity.
~; A phosphor belonging to the third group of the present invention is one in which Z stands for a composition represented by P5014, namely a phosphor represented by the following general formula:
Lnl_x_yNdxybyp5ol4 This phosphor can be obtained by weighing the starting materials, namely Ln203 (which may be CeO2 when Ln is Ce), Nd23~ Yb23 and NH4H2PO3 so that the amount of P205 is at least 3 times in excess over the stoichiometric amount and the amounts of other components are stoichiometric amounts corresponding to the intended composition, mixing them sufficiently and sintering themixture in a lidded gold crucible at 500 to 800C. for about 1 to about 5 days.
Fig. 8 illustrates the relationship between the com-position of the phospXor and the relative emission intensity (calculated based on the assumption that the intensity of the composition in which y is 0 is 1) in phosphors of Ndl_yYbyP5014, and Fig. 9 illustrates the relationship between the composition of the phosphor and the relative emission intensity of phosphors of LnO.9-XNdXYbO.lPsO14 in which Ln is Bi, Gd or Y.
The measurement was carried out in the same manner as described above with respect to Fig. 2.
From these Figs., it can be seen that values of x and y providing a preferred phosphor of the third group having a high emission intensity are in the following ranges:
0.05 _ x _ 0.98 and 0.02 < y < 0.95.
It is most preferred that x and y be in the following ranges:
0.18 ~ x ' 0.95 and 0.05 ' y ' 0.82.
A phosphor belonging to the fourth group of the phos-phor of the present invention is one in which Z stands for a composition represented by A3(PO4)2, namely a phosphor represented by the following general formula:
~nl_x_yNdxybyA3(po4)2 This phosphor can be obtained by weighing starting materials, namely A2CO3, Ln203 ~which may be CeO2 when Ln is Ce), Nd23~ Yb203 and NH4H2PO4, so that the intended composition can be attained, mixing them sufficiently and sintering the mixture in a lidded platinum crucible at about 1200C for about 20 hours.
Fig. 13 illustrates the relationship between the 1~2Sg~94 I
composition of the phosphor and the relative emission intensity (calculated based on the assumption that the intensity of the composition in which y is O is 1) in phosphors of K3Ndl_yYby(P04)2. The measurement was carried out in the same manner as described above with respect to Fig. 2.
As can be seen from Fig. 13, values of x and y providing a preferred phosphor of this group having a high emission intensity are in the following ranges:
0.02 ' x ''0.98 and 0.02 < y c 0.98.
It is most preferred that x and y be in the following ranges:
0.09 ' x ' 0.98 and 0.02 ' y ' 0.91.
A phosphor belonging to the fifth group of the present invention is one in which Z stands for a composition represented by Na2Mg2~V04)3, namely a phosphor rep-resented by the following general formula:
-:~
~ Lnl_x yNdxybyNa2Mg2~vo4)3 ;~ This phosphor can be obtained by weighing Na2C03, MgO, Ln203 (which may be CeO2 when Ln is Ce), Nd203, Yb203 and NH4V03 so that the intended composition can be attained, mixing them sufficiently, pelletizing the mixture and sintering the pellets in a quartz, alumina or platinum crucible at about 800C for about 30 hours.
Fig. 15 illustrates the relationship between the composition of the phosphor and the relative emission intensity (calculated based on the assumption that the intensity of the composition in which y is O is 1) in phosphors of Ndl_yYbyNa2Mg2(V04)3. The measurement was carried out in the same manner as described above with respect to Fig. 2.
_ g _ . . .
l~Z5~g4 From Fig. 15, it can be seen that values of x and y providing a preferred phosphor of the fifth group having a high emission intensity are in the following ranges:
0.57 < x < 0.90 and 0.10 < y < 0.53.
A phosphor belonging to the sixth group of the phosphor of the present invention is one in which Z stands for a composition represented by A'(MO4)2, namely a phosphor represented by the following general formula:
Lnl-x-yNdxybyA (M4)2 This phosphor can be obtained by weighing A'2CO3, Ln203 (which may be CeO2 when Ln is Ce), Nd203, Yb203 and MO3 so that the intended composition can be attained, mixing them sufficiently, pelletizing the mixture and sintering the pellets in a quartz or alumina crucible at about 700C for about 3 days.
- Fig. 17 illustrates relationship between the composition of the phosphor and the relative emission intensity (calculated based on the assumption that the intensity of the composition in which y is 0 is 1) in phosphors of LiNdl_yYby(WO4)2 and LiNdl_yYby~MO04)2.
The measurement was carried out in the same manner as described above with respect to Fig. 2.
From Fig. 17, it can be seen that values of x and y providing a preferred phosphor of the sixth group having a high emission intensity are in the following ranges:
0.20 = x = 0.95 and 0.05 = y = 0.80 The phosphor of the present invention will now be described in detail by reference to the following Examples.
Example 1 A powdery starting material comprising 0.5 mole of Na2CO3, 0.-08 mole of Nd203, 0.02 mole of Yb203 and 0.8 ` -- 10 --llZ5~94 mole of WO3 was sufficiently blended and pulverized, and was then pelletized and charged to a quartz crucible. The crucible was placed in an electric furnace and the tem-perature was elevated to 650C at a rate of about 150C/hr, and the pellets were sintered at 650C for 50 hours. After completion of the sintering, the product was cooled and mechanically crushed to obtain a powdery p p or of NdO.8YbO.2Na5(WO4)4 having a particle size (as determined by a Bleine air permeability apparatus; each of the particle sizes mentioned hereinafter is one determined by this apparatus) of about 5 ~m. The emission spectrum of the so obtained phosphor is indicated by a dot line in Fig. 3. The relative emission intensity of this phosphor was 115 (calculated based on the assumption that the intensity of LiNdo gYbo lP4012 is 100; the same holds good hereinafter, unless otherwise indicated).
A phosphor of Ndo 8Ybo.2K5tWO4)4 was prepared by conducting treatments in the same manner as decribed above except that K2C~3 was used instead of Na2CO3 in the powdery starting material. The emission spectrum of this phosphor was substantially the same as the spectrum indicated by a dot line in Fig. 3.
~, A powdery starting material comprising 0.5 mole of Na2CO3, 0.09 mole of Nd203, 0.01 mole of Yb203 and 0.8 mole of MoQ3 was sufficiently blended and pulverized, and was then treated in the same manner as in Example 1 to obtain a phosphor of Ndo gYbo lNa5(MoO4)4. The emission spectrum of this phosphor is indicated by a solid line in Fig. 3. Namely, the emission spectrum of this phosphor was substantially the same as that of the phosphor of llZ5494 Example 1. The relative emission intensity of this phos-phor was 107.
A phosphor of Ndo gYbo lK5(~ioOL~)4 ~as prepared by conducting treatrnents in the same manner as described above except that K2C03 ~as used instead of Na2CO~ in the powdery starting material. The emission spectrum of -this phos~hor was substantially the same as that o~ the phosphor of Example 1.
Exam~le 3 A po~rdering starting material comprising 0.5 mole of Na2C03, 0.01 mole of Y203, 0.075 mole of Nd203, 0.015 mole of Yb203 and 0.8 mole of '.~03 was sufficiently blended and ~ pulverized, and was then treated in the same manner as ;; in Example 1 to ob-tain a phosphor ol YO lNdo 75Ybo ~W04)4 The emission spec-trum of this phosphor was substantially the same as that of the phosphor OI Example 1, and the ~' relative emission intensity was 104.
Phosphors were prepared in the same manner by using 2 3~ Ce2- Ga203~ Gd203, In203, La203~ LU23' Sb23 or 20 ~ Sc203 ( 0.02 mole in case of CeO2 ) instead of Y203.
The emission spectrum was substantiàlly the same in these phosphors.
Also in the case rhere K2CO~ was used instead of Na2C03, the emission spec-trum ~as substantially the same as above.
Exam~le L~
po~ldery starting material comprising 0.5 mole of ~la2C03, 0.08 mole of Nd203, 0.02 mole of Yb203, 0 4 mole of ;l03 and 0.4 mole of MoO~ was sufficiently blended and pulverized, and was then treated in the same manner I
as in Example 1 to obtain a phosphor of Ndo ~Ybo 2Na5-(I~ioO 51:10 5OL)~. The emission spectrum of the phosphor was substantially the same as that of the phosphor of Example 1 and the relative emission intensity was 110.
Example 5 A powdery startin~ material comprising 0,5 mole of Na2C03, 0.01 mole of CeO2, 0~005 mole of Gd203, 0.075 mole of Nd203, 0.015 mole of Yb203, 0.56 mole of :J03 ~; and 0.24 mole of MoO3 was sufficiently blended and pulveri-zed, and then treated in the same manner as in Example 1 :
to obtain a phosphor of~CeO 05Gdo.05Ndo.75Ybo.15N 5( 0.7 MoO 304)4. The emission spectrum of this phosphor~was substantially the same as that of the phosphor of Example 1 and the relative emission intensity was 101. ~;
Example 6 A powdery starting material comprising 0.5 mole of K2C03, 0.01 mole of Bi203, 0.075 mole of ~d20~, 0.015 mole o~ Yb203 and 0.8 mole of MoO3 was sufficiently blended and pulverized, and was then treated in the same ma~ner~ ;
, ~ ~
as in Example 1 to obtain a phosphor of Bio lNdo 75Ybo 15 K5(I~IoO4)4. The emission spectrum o~ -this phosphor ~as substantially the same as that o~ the phosphor of Example 1 and the relative emission intensity was 97.
Examp3e 7 A powdery startin~ material comprisin~ 0.05 mole of K~C03, 0.45 mole of i~a2C03, 0.01 mole of La203, 0.08 mole of Nd203, 0,0] mole of Yb20~ and 0.8 mole of W03 was sufficiently blended and pulverized, and was then treated in the same manner as in Example 1 to obtain a phosphor O.lr~dO.8Y~o.l(Nao.~o.l)s(wol~)L~. The emission spectrum of this phosp~or was substantially the same as tnat of the phosphor of ~xample 1 and the relative emission intensity /as 103, l~;Y~am~le ~3 A powdery starting material comprising 0.3 mole of A~0~, 0,09 mole of Nd2~, 0,01 mole of Yb203 and 0,4 mole of B203 ~ras sufficiently blen~ed and pulverized, and was then pelle-tized and charged to a quartz crucible.
The crucible was placed in an elec-tric furnace and the temperature ~Jas elevated to 1100C, at a rate of about 100C,/hr. The pellets ~ere sintered at 1100C, for 80 hours. After completion of the sintering, the produc-t was cooled and mechanically crushed to obtain a po~dery !: ~
p p f i~0,9Ybo,lA~3(B03)4 having a particle size of about 5 ~m, The emission spectrum of the so obtained phosphor is sho~rn in Fig. 6. The relative emission .
intensity of t'ne phosphor was 130, Exam~le 9 A phosphor of l~do 9Ybo lCr3(B0~)4 ~;ras prepared by conducting treatments in the same manner as in ~xar~ple 8 2~0 ~except tha-t Cr203 was use~ instead of A~203. The emission spectrum of the so obtained phosphor is indicated by a s.olid line in Fig, 7. The relative emission intensity r the phosphor was 4, Exam~le 10 ;:
A powdery starting material comprising 0.27 mole of A~203, 0.03 mole of Cr20~, 0,09 mole of Nd203, 0,01 mole of Yb203 and 0.4 mole of B203 was su~ficiently blended and pulverized, and ras then treated in th~ same manner as in ~xample ~ to obtai.n a phosphor of Ndo gYbo lA~2 7CrO 3-(B03)4, The emission spectrum of this phosphor is indicatedby a dot line in Fig, 7. The relative emission intensity , .
~,; ,, , , ~
llZ5494 o~ -the phosphor ~ras 57.
l:x~ l c 1 1 ' .
A po~ldery material comprising 0.~ mole of AB203, 0.01 mole of Y203, 0.0~ mole of Nd2~, 0.01 mole of Yb203 and 0.4 mole of B203 ~ras sufficiently blcllded an~ pulverized, and was then treated in the same manner as in ~xample to obtain a phosphor of Y0 ll~bo.~ybo~lA 3( 3)4 erilission spectrurn of the phosphor ~/as substantially the same as that sho~m in Fig. 6.
: 10 Phosphors were prepared in the same manner as described above by using 0.01 mole of Bi20~, Ga203, Gd203, In203, La203, Lu203, Sb203 or Sc20~ or 0.02 rnole of CeO2 ins-tead of Y203. Tne ernission spectrum of each of these phosphors was substantially the same as that sho.m in Fig. 6.
The emission spectrum of a phosphor prepared in the same manner as describ:ed above by using 0.005 mole of ~ -.
,~
Bi203 and 0.005 mole of Ga203 instead of Y203 tJas sub-s-tantially -the same as that sho~m in Fig. 6.
E~arn~le 12 A powdery starting material comprising 0.06 mole of Nd203, 0.04 mole of Yb203 and 3.0 moles o~ NH4H2P04 was :: sufficiently blended an~ pulveriz~d, and was ~nen pelleti~ed and charged in a gold cruclble. The crucible was placed in an electric furnace and the temperature was elevated to 700C, at a rate of àbout 150C./hr. The pellets were :~. . O
sintered at 700 C. for 5 days. After completion of the sintering, the product ~tas cooled, ~ashed sufficiently with l"ater and mechanically crushed to obtain a pol;~dery P P f Ndo.6Ybo.~P5l4 havin~ a particle s.ize of about 5 ~m. Tne emiss.ion spectrum of this phosphor is sho-,m in Fig. 10. The relative emission intensity of the . - 15 -`` 1125494 pho sphor was :121.
1. rn~lc 13 A powdery startin~ material comprisin~ 0.02 rnole of Bi203, 0.06 mole of ~ld20~, 0.02 mole of Yb203 and 3.0 moles of i~THL~H2POL~ was suf`ficiently blended and pulverized, and .~a~ then treated in the same manner as in Example 12 to obtain a pho3phor of Bio.2Ndo.GYbo.2P5014.
The emission spectrum of this phosphor ~las substantially the same as tha-t of the phosphor of ~ample 12 and the relative emission intensity was 105, Each of the emission spectra of phosphors prepared in the same manner as described above by using Ga203, 2 3' 2 3- La23, Lu203~ Sb203, Sc203 or Y203 was substantially the same as the emission spectrum of the phosphor of EY~ample 12.
~:: Example 14 A powdery starting material comprising 0.04 mole of , :
CeO2, 0.05 mole of Nd203, 0.03 mole of Yb203 and 3.0 moles of NH4H2P04 was sufflciently blended and pulverized and was then treated in the same manner as in Example 12 to obtain a phosphor of CeO 2Ndo 5Ybo 3P5014, The emission spectrum of this phosphor is sho~m in Fig, 11. The relative emission intenxity of the phosphor :
: wa3 10~, Exam~le 15 A powdery starting material comprising 0.01 mole o~
Gd203, 0.02 mole of Y203, 0.05 mole of l~d20~, 0.02 mole of Yb20~ and 3,0 moles of NH4H2P04 was sufficiently blended and pulverized, and was then treated in the same manner as in Example 1~ to obtain a phosphor of Gdo lYo 2?ldo 5Ybo 2~5-, . .
The emission spectrurn of this phosphor i~ sho~ in Eig. 12. The relative ~mission intensity of the phosphor was 97.
~xam~le 16 -. . . - ~
A po.ldery starting material compri sing O . 3 mole of K2C0~, 0.0~ mole of Nd203, 0.02 mole of Yb203 and 0.4 mole of NII4H2POl~ was sufficiently blended and pulverized, and was then pelletized and charged in a platinum crucible.
The crucible was placed in an eIectric furnace and the temperature was elevated to 1200C. at a rate of about 200C./hr. The pellets were sintered at 1200C. for 20 hours. After completion of the sintering, the product - was cooled and mechanicaIly crushed to obtain a powdery P phor of Ndo.8YbO 2K3(P04)2 having a particle size of about~S ~m. The~emlsslon spectru.~ of this phosphor is sho~ in Fig. 14.~ me relative emission in-tensity of the phosphor ~las 87.
Examples 17 to 19 Pho3phors~ of ~YO lMdO~,gYbO.11~3~P0432~ CeO.05YO.05 0.8 20~ Ybo lK~3(PO~z :and~ GdO O5yo.o5Ndo.8ybo.l(Ko.gNao~l)3(po4)2 rere~prepared by suf~iclently blendin~ and pulverizing ` .:
po~,~rdery starting materials sho~n in the follo~rin~ Table ~`
anl treatin~ them in -the same manner as in Example 16.
: ''' ~ ' ' ~ 30 : :
;. -11;:54~4 Table ~xam~le 1'~ Example 1~ am~le 19 Na2C03 - - 0.03 mole K2C03 0 3 mole 0.3 mole 0.27 mole 203 0.01 mole 0.005 mole 0.005 mole CeO2 - 0.01 mole Gd203 - _ 0.005 mole Nd 03 0,08 mole 0,08 mole 0.0~ mole 2 3 0,01 mole 0.01 mole 0.01 mole 10 NH4H2P04 0.4 mole 0.4 mole 0.4 mole The emission spectra of these phosphors were substan-tially the same as that sho~m in Fig. 14. The rela-tive emission intensities of these phosphors were 85, 85 and 79, respectively.
.
Emission spectra of phosphors prepared in the same manner as described above by using Bi203, Ga203, In203, é~ La2~, Lu203~ ~Sb20~3 or Sc203 instead of Y203 in Example 17 were~substantially the same as that shown in Fig. 14.
Further,~ the emlsslon spectrum of a phosphor prepared in the same manner as described above by using Na~CO instead of 1~2C03 in Example lrl was substantlally the ~ame as that sho~rn in Fig. 14.
Exam~le 20 A powdery~starting material comprising 0.2 mole of ~,t~ ' Na2C03, 0.4 mole of MgO, 0.08~mole of Nd203, 0.02 mole of Yb20~ and 0.6 mole of N~14V03 was sufficiently blended and pulverized, and ~ras then pelletized and charg~d in a , quartz crucible. The crucible was placed in a~ electric furnace and the temperature was elevated to 800C. at a rate of about 2Q0C./hr. The pellcts were sintered at ' ' ~1~25494 ~300C. for 30 hours. ~fter completion of the sintering, the product ~ras cooled and mechanically crushed -ta obtain a po~lderY phosphor of ~do gYbo 2Na2M~2(V4)3 havin~ a '~
particle size of about 5 ~m. The emission spectrum of this phosphor is sho~n in Fig. 18. The rela-tive emission intensi-ty of the phosphor was 31.
E,~amples 21 a~d 22 Phosphors of La Nd 'Yb ~I M (VO ) d ,~ Lao.o5ceo.o5Ndo~75ybo.l5Na2Mg2(vo4)3 were pr~pared by sufficiently blending a~d pulverizing po~dery starting '~
materials shown in the following Table and treating them in -the sarne manner as in Example 20.
Table E~ram~le 21 E~am~le 22 ,~La20~ , 0.005 mole 0.005 mole 2 0.01 mole Nd203 0.075 mole 0.075 mole Yb203 0.02 mole 0.015 mole . ~, .
2 3 0.2 mole 0.2 mole ; 20 ~ MgO 0.4"mole , 0.4 mole .
'i'~N~ V03 0.6 mole 0.6 mole : ~, Emission,spectra of these phosphors were substantially the same as t~lat sho-~n ln l~ig. 16, and the relative emis-: ~ .
~ sion intensities of these phosphors ~lere 29 and 28, , ~ respectively.
'- Emission spectra of phosphors prepared in the same manner as described above by usin~ Bi203, Ga203, Gd203, 03, Lu203~ Sb20~, Sc20~ or Y203 in5tead of La203in Example 21 ~Jere substantially the same as that sho~ in Fig. 16.
.
, ` 11;25494 I
~xample 23 A powdery startin~ ma-tcrial comprising 0.1 mole of Li2C03, 0.09 mole o~ Nd203, 0.01 mole of Yb20~ and 0.4 rnole of llO3 wa~ sufficiently blended and pulverized, and ~as then pelletized and charged in a quartz crucible.
The crucible was placed in an electric furnacc and the temperature ~Jas elevated to 700C. at a rate of about 150C./hr. The pellets were sintere~ at 700C. for 3 days. After completion of the sintering, the product was cooled and mechanically crushed to obtain a phosphor of LiNdo gYbo l(W04)2 having a particle size of about 5 ~m. The emission spectrum of the so obtained phosphor is indicated by a solid line in Fig. 18. The rela-tive emission intensity of the phosphor ~ras 71.
Emission spectra of phosphors prepared in the same manner as described above by usin~ r~a2C03 or K2C03 instead of Li2C03 ~ere substantially the same as that of the ; phosphor of Example 23.
ExamPles 24 to 26 Phosphora of LiNdo gYbo l(MoOL~)2, LiNdo.gYbo.l(~l0.5 MoO 50L)2 and NaO sKo~sNdo~gYbO~ 0~9 0,1 L~ 2 pr~pared by suf~iciently blending and pulverizing powdery starting materials shown in the following Table and ~-~ treating thcm in the same manner as in Example 23.
.
,"" ~:
., ` 1125494 ~, rrable EY~ample 24Exam~le 25Example 26 Li2~-0~0.1 mol~ 0,1 mole Na2~03 _ _0.05 mole K2~03 _ _0.05 mole Nd203 0.09 mole0.09 rnole0.09 mole ; Yb20~ 0.01 mole 0.01 mole0.01 mole ~I03 ' - ~ 0.2 mole0.36 mole ioO3 0,4 mole 0.2 mole0.04 mole `' The emission spectrum of the phosphor of ~xample 24 is indicated by a dot Iine in F'i~. 18, which was substan-, :~
tially the same as~the emission spectrum of the phosphor ~ of Example 23 ~rnere 11 was used, ~rhich was indicated by a ;.7~ soli.d line in Fig. 18. The relative emission lntensity ~ "
o~ the phosphor of~Example 24 was 44.~ Emission spectra ~ -of pnosphors prep~ared~ln the same manner as in Exa~ple ,24 by~using Na2C03 or K2C03 lnstead of Li2C03 ~lere the su~stantially the~same as that of the phosphor of Example 24~shown in Fig~. 18.
'20~ Emission speotra o~ the phosphors of Examples 2~ '~
and 26 ~/~re substantlall~J the same as that shown,in Fig.
~ la, and the relative~ emisslon intensi~ies were 53 and .~'``'f "',~ 62, respectively. ~ ,:
mlssion sp~ectra of phosphors prepared in the same manner as in ~xamples 23, ~4, 25 ~nd 26 by using 0.08 -;"
mo:le of Nd203 and O.Ol mole of Ga20~ instead of 0.09 mole of Nd203~ere substantially the same as tha-t sho~
in Fig. 18.
Further, emission spectra of phosphors prepared in :, :
~ 30 the same manner as in the:foregoin~ Examples by using ' ,~;
;:
11'~5494 O. 01 mole of Bi203, GC120~;, In203 La23 ~ LU23 ~ Sb23 ' Sc203 or Y203 or 0.02 mole of CeO2 instead of 0.01 mole of Ga20~ were sub stantially the same as tha-t sho~n~ in Fi~;. 18.
. . ~ .
; :
. .
;
` ::
' ~ -.
.
t ~
: j: : ~ :
,',' ~ ~
:~' } :
':1 ', .'.'~: ~.
`:~
Claims (20)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A phosphor co-activated with Nd and Yb, which is represented by the following general formula:
Ln1-x-yNdxYbyZ
wherein:Ln stands for at least one element selected from the group consisting of Bi, Ce, Ga, Gd, In, La, Lu, Sb, Sc and Y; Z stands for a composition represented by A5(MO4)4 in which A stands for at least one element selected from the group consisting of K and Na,and M stands for at least one element selected from the group consisting of W and Mo, D3(BO3)4 in which D stands for at least one element selected from the group consisting of A? and Cr, P5O14, A3(PO4)2 in which A is as defined above, Na2Mg2(VO4)3 or A'(MO4)2 in which A' stands for at least one element selected from the group consisting of Li, Na and K and M is as defined above; x is a value in the range of 0.01 ? x ? 0.99;and y is a value in the range of 0.01 ? y ? 0.99 with the proviso that the sum of X and y is in the range of x + y ? 1.
Ln1-x-yNdxYbyZ
wherein:Ln stands for at least one element selected from the group consisting of Bi, Ce, Ga, Gd, In, La, Lu, Sb, Sc and Y; Z stands for a composition represented by A5(MO4)4 in which A stands for at least one element selected from the group consisting of K and Na,and M stands for at least one element selected from the group consisting of W and Mo, D3(BO3)4 in which D stands for at least one element selected from the group consisting of A? and Cr, P5O14, A3(PO4)2 in which A is as defined above, Na2Mg2(VO4)3 or A'(MO4)2 in which A' stands for at least one element selected from the group consisting of Li, Na and K and M is as defined above; x is a value in the range of 0.01 ? x ? 0.99;and y is a value in the range of 0.01 ? y ? 0.99 with the proviso that the sum of X and y is in the range of x + y ? 1.
2. A phosphor as set forth in claim 1, which is represented by the following general formula:
Ln1-x-yNdxYbyA5(MO4)4 wherein Ln, A, M, x and y arc as defined above.
Ln1-x-yNdxYbyA5(MO4)4 wherein Ln, A, M, x and y arc as defined above.
3. A phosphor as set forth in claim 2 wherein M
in the general formula is W.
in the general formula is W.
4. A phosphor as set forth in claim 2 or 3 wherein x is in the range of 0.25 ? x ? 0.99 and y is in the range of 0.01 ? y ? 0.75.
5. A phosphor as set forth in claim 2 or 3 wherein x is in the range of 0.65 ? x ? 0.95 and y is in the range of 0.05 ? y ? 0.35.
6. A phosphor as set forth in claim 1, which is represented by the following general formula:
Ln1-x-yNdxYbD3(BO3)4 wherein Ln, D, x and y are as defined above.
Ln1-x-yNdxYbD3(BO3)4 wherein Ln, D, x and y are as defined above.
7. A phosphor as set forth in claim 6 wherein D
is A?.
is A?.
8. A phosphor as set forth in claim 6 or 7 wherein x is in the range of 0.10 ? x ? 0.99 and y is in the range of 0.01 ? y ? 0.40.
9. A phosphor as set forth in claim 6 or 7 wherein x is in the range of 0.60 ? x ? 0.98 and y is in the range of 0.02 ? y ? 0.40.
10. A phosphor as set forth in claim 1, which is represented by the following general formula:
Ln1-x-yNdxYbyP5O14
Ln1-x-yNdxYbyP5O14
11. A phosphor as set forth in claim 10 wherein x is in the range of 0.05 ? x ? 0.98 and y is in the range of 0.02 ? y ? 0.95.
12. A phosphor as set forth in claim 10 wherein x is in the range of 0.18 ? x ? 0.95 and y is in the range of 0.05 ? y ? 0.82.
13. A phosphor as set forth in claim 1, which is represented by the following general formula:
Ln1-x-yNdxYbyA3(PO4)2 wherein Ln, A x and y are as defined above.
Ln1-x-yNdxYbyA3(PO4)2 wherein Ln, A x and y are as defined above.
14. A phosphor as set forth in claim 13 wherein x is in the range of 0,02 < x < 0.98 and y is in the range of 0.02 < y < 0.98.
15. A phosphor as set forth in claim 13 wherein x is in the range of 0.09 < x < 0.98 and y is in the range of 0.02 < y < 0.91.
16. A phosphor as set forth in claim 1, which is represented by the following general formula:
Ln1-x-yNdYbyNa2Mg2(VO4)3 wherein Ln, x and y are as defined above.
Ln1-x-yNdYbyNa2Mg2(VO4)3 wherein Ln, x and y are as defined above.
17, A phosphor as set forth in claim 16 wherein x is in the range of 0.57 < x < 0,90 and y is in the range of 0.10 < y < 0.53.
18. A phosphor as set forth in claim l, which is represented by the following general formula:
Ln1-x-yNbxYbyA'(MO4)2 wherein Ln, A', N, x and y are as defined above.
Ln1-x-yNbxYbyA'(MO4)2 wherein Ln, A', N, x and y are as defined above.
19. A phosphor as set forth in claim 18 wherein x is in the range of 0.20 < x < 0.95 and y is in the range of 0.05 < y < 0.80.
20. A phosphor as set forth in claim 2 wherein M
in the general formula is Mo.
in the general formula is Mo.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP725278A JPS54100991A (en) | 1978-01-27 | 1978-01-27 | Fluorescent substance |
| JP7252/1978 | 1978-01-27 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1125494A true CA1125494A (en) | 1982-06-15 |
Family
ID=11660827
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA320,411A Expired CA1125494A (en) | 1978-01-27 | 1979-01-29 | Phosphor |
Country Status (7)
| Country | Link |
|---|---|
| JP (1) | JPS54100991A (en) |
| CA (1) | CA1125494A (en) |
| DE (1) | DE2903073B2 (en) |
| FR (1) | FR2415657A1 (en) |
| GB (1) | GB2013233B (en) |
| NL (1) | NL179396C (en) |
| SE (1) | SE430072B (en) |
Families Citing this family (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH659145A5 (en) * | 1980-05-30 | 1986-12-31 | Gao Ges Automation Org | METHOD FOR CHECKING THE VALIDITY OF SECURITIES SECURED WITH LUMINESCENT SUBSTANCES AND DEVICE FOR IMPLEMENTING THE METHOD. |
| IT1193733B (en) * | 1980-05-30 | 1988-08-24 | Gao Ges Automation Org | VALUE CARD WITH SIGNS OF AUTHENTICITY IN THE FORM OF LUMINESCENT SUBSTANCES PROCEDURE FOR CHECKING THE VALUE CARD ITSELF AND APPARATUS FOR THE IMPLEMENTATION OF SUCH PROCEDURE |
| DE3121523A1 (en) * | 1980-05-30 | 1982-04-15 | GAO Gesellschaft für Automation und Organisation mbH, 8000 München | Securities with originality features in the form of luminescent substances, method and device for determining originality |
| ES8203280A1 (en) * | 1980-05-30 | 1982-04-01 | Gao Ges Automation Org | Paper security with authenticity mark of luminescent material and method for the authentication thereof. |
| JPS5916582U (en) * | 1982-07-26 | 1984-02-01 | 齋田 ミツ | A dried cushion that can be used as a disaster prevention tool |
| JPH0331280Y2 (en) * | 1988-12-09 | 1991-07-02 | ||
| US5611958A (en) * | 1993-05-11 | 1997-03-18 | Hitachi Maxell, Ltd. | Infrared phosphor and material having latent images and optical reading system using said phosphor |
| WO1995025148A1 (en) | 1994-03-17 | 1995-09-21 | Hitachi Maxell, Ltd. | Phosphor, phosphor composition, fluorescent mark carrier, and optical character reader |
| WO2006104081A1 (en) | 2005-03-29 | 2006-10-05 | Nemoto & Co., Ltd. | Infra-red light emitting fluorescent substance |
| WO2009064845A2 (en) * | 2007-11-16 | 2009-05-22 | Bernstein Eric F | Sterilizing compositions comprising phosphors for converting electromagnetic radiation to uvc radiation and methods for using the same |
| JP5163108B2 (en) * | 2007-12-26 | 2013-03-13 | 大日本印刷株式会社 | Writing medium and writable writing system |
| JP2011021161A (en) * | 2009-07-21 | 2011-02-03 | National Printing Bureau | Phosphor |
| CN102863961B (en) * | 2011-07-08 | 2014-07-23 | 海洋王照明科技股份有限公司 | Cerium-doped yttrium-aluminum borate luminescent material, preparation method and application thereof |
| CN102424750B (en) * | 2011-10-20 | 2013-08-21 | 北京工商大学 | Tungstate near infrared quantum cutting material and preparation method and application thereof |
| US9074137B2 (en) * | 2011-11-15 | 2015-07-07 | Honeywell International Inc. | Luminescent borates, materials and articles incorporating such borates, and methods and apparatus for their production and use in article authentication |
| US8993101B2 (en) * | 2011-11-15 | 2015-03-31 | Honeywell International Inc. | Luminescent borates, materials and articles incorporating such borates, and methods and apparatus for their production and use in article authentication |
| US9062220B2 (en) * | 2012-11-30 | 2015-06-23 | Honeywell International Inc. | Luminescent borates, luminescent materials and articles incorporating such borates |
| CN104178726A (en) * | 2013-05-23 | 2014-12-03 | 海洋王照明科技股份有限公司 | Luminescent film of antimony-terbium co-doped rare earth aluminoborate and preparation method thereof and electroluminescent device |
| CN104004519B (en) * | 2014-06-06 | 2016-02-10 | 西北大学 | A kind of near infrared down-conversion luminescent material, preparation method and application thereof |
| CN113481009B (en) * | 2021-07-02 | 2022-08-30 | 山东大学 | Cr (chromium) 3+ And Yb 3+ Codoped infrared luminescent material, and preparation method and application thereof |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3462707A (en) * | 1965-05-25 | 1969-08-19 | Bell Telephone Labor Inc | Nd and yb doped borate laser glass |
| GB1147377A (en) * | 1965-12-02 | 1969-04-02 | American Optical Corp | Method of generating laser light |
| FR1532609A (en) * | 1967-06-01 | 1968-07-12 | Infra-red radiation detector compositions and screens and corresponding preparation processes | |
| CA961147A (en) * | 1972-01-24 | 1975-01-14 | Western Electric Company, Incorporated | Laser employing a metallic pentaphosphate |
| IT1020058B (en) * | 1973-08-21 | 1977-12-20 | Max Planck Gesellschaft | PERFECTED NEODYMIUM ULTRAPHOSPHATES AND THEIR PREPARATION |
| JPS5360888A (en) * | 1976-11-12 | 1978-05-31 | Hitachi Ltd | Fluorescent substance |
| JPS53106686A (en) * | 1977-03-02 | 1978-09-16 | Hitachi Ltd | Production of fluorescent substance |
-
1978
- 1978-01-27 JP JP725278A patent/JPS54100991A/en active Granted
-
1979
- 1979-01-05 SE SE7900099A patent/SE430072B/en not_active IP Right Cessation
- 1979-01-19 FR FR7901312A patent/FR2415657A1/en active Granted
- 1979-01-26 DE DE19792903073 patent/DE2903073B2/en active Granted
- 1979-01-26 GB GB7902803A patent/GB2013233B/en not_active Expired
- 1979-01-29 NL NL7900695A patent/NL179396C/en not_active IP Right Cessation
- 1979-01-29 CA CA320,411A patent/CA1125494A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| FR2415657B1 (en) | 1983-11-10 |
| NL7900695A (en) | 1979-07-31 |
| NL179396C (en) | 1986-09-01 |
| SE7900099L (en) | 1979-07-28 |
| GB2013233B (en) | 1982-03-10 |
| DE2903073A1 (en) | 1979-08-02 |
| DE2903073B2 (en) | 1981-05-14 |
| SE430072B (en) | 1983-10-17 |
| JPS564598B2 (en) | 1981-01-30 |
| NL179396B (en) | 1986-04-01 |
| DE2903073C3 (en) | 1990-08-02 |
| FR2415657A1 (en) | 1979-08-24 |
| JPS54100991A (en) | 1979-08-09 |
| GB2013233A (en) | 1979-08-08 |
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