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US4353808A
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Phosphors and process for producing the same
Assignee: Hitachi Ltd
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Filing: 1980-03-27
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Granted: 1982-10-12
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Expires: 2000-03-27
Abstract
Abstract A phosphor represented by the formula: a (Sr1-x-y-zMxIIMyIIIEuz2+)3(PO4)2xb M'X2 (I) wherein MII is at least one element selected from the group consisting of Zn, Mg, Ca and Ba; MIII is at least one element selected from the group consisting of Al, Y, Gd and La; M' is at least one element selected from the group consisting of Ca, Sr and Ba; X is one or more halogens; x, y and z should satisfy the following conditions, i.e. 0</=x</=0.999, 0</=y</=0.999, 0.0015</=z</=0.20 and x+y+z</=1; and the ratio a/b is in the range of 0.3</=a/b</=3.0, provided that when y=0, the ratio a/b should be in the range of 0.3</=a/b<3.0, and when x=0, the ratio a/b should be in the range of 0.3</=a/b</=1.2, is stable against the baking in the air and has high emission efficiency and excitation purity and can be used effectively as a blue phosphor of light sources for illumination. Said phosphor can be produced by firing corresponding raw materials under a reducing atmosphere.
Inventors
- 👤 Shinkichi Tanimizu
- 👤 Masaki Nakano
- 👤 Teruki Suzuki
- 👤 Toshikatsu Manabe
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-09 07:16
CPC Classifications
C; C09; C09K; C09K11/00; C09K11/08; C09K11/77; C09K11/7783; C09K11/7795; C09K11/7796; C09K11/779; C09K11/7791
Claims Analysis
Total Claims: 46
Claim 1
Independent Claim
86 words
A phosphor represented by the formula: a(SR.sub.1-x-y-z M.sub.x.sup.II M.sub.y.sup.III Eu.sub.z.sup.2+).sub.3 (PO.sub.4).sub.2.b M'X.sub.2 (I) wherein M II is at least one element selected from the group consisting of Zn, Mg, Ca and Ba; M III is at least one element selected from the group consisting of Y, Gd and La; M' is at least one element selected from the group consisting of Ca, Sr and Ba; X is one or more halogens; 0≦x≦0.999, 0.001≦y≦0.15, 0.0015≦z≦0.20 and x+y+z≦1; and the ratio a/b is in the range of 0.3≦a/b≦1.2.
Claim 2
Dependent Claim
86 words
A phosphor represented by the formula: a(SR.sub.1-x-y-z M.sub.x.sup.II M.sub.y.sup.III Eu.sub.z.sup.2+).sub.3 (PO.sub.4).sub.2.b M'X.sub.2 (I) wherein M II is at least one element selected from the group consisting of Zn, Mg, Ca and Ba; M III is at least one element selected from the group consisting of Y, Gd and La; M' is at least one element selected from the group consisting of Ca, Sr and Ba; X is one or more halogens; 0≦x≦0.999, 0.001≦y≦0.15, 0.0015≦z≦0.20 and x+y+z≦1; and the ratio a/b is in the range of 0.3≦a/b≦1.2.
Claim 3
Dependent Claim
29 words
A phosphor according to claim 1, wherein X in the formula (I) contains 50% by mole or more of Cl or Br or a mixture of Cl and Br.
Claim 4
Dependent Claim
29 words
A phosphor according to claim 1, wherein X in the formula (I) contains 80% by mole or more of Cl or Br or a mixture of Cl and Br.
Claim 5
Dependent Claim
23 words
A phosphor according to claim 1, wherein X in the formula (I) is Cl or Br or a mixture of Cl and Br.
Claim 6
Dependent Claim
16 words
A phosphor according to claim 1, wherein the ratio a/b is in the range of 0.4≦a/b≦0.7.
Claim 7
Dependent Claim
20 words
A phosphor according to claim 1, wherein M' in the formula (I) contains 90% by mole or more of Ca.
Claim 8
Dependent Claim
19 words
A phosphor according to claim 1, wherein the value of x in the formula (I) is larger than zero.
Claim 9
Dependent Claim
21 words
A phosphor according to claim 1, 2, 3, 4, 6 or 7, wherein M III in the formula (I) is Y.
Claim 10
Dependent Claim
21 words
A phosphor according to claim 1, 2, 3, 4, 6 or 7, wherein M III in the formula (I) is Gd.
Claim 11
Dependent Claim
21 words
A phosphor according to claim 1, 2, 3, 4, 6 or 7, wherein M III in the formula (I) is La.
Claim 12
Dependent Claim
13 words
A phosphor according to claim 2, 3, 4, 6 or 7, wherein 0.4≦a/b≦0.7.
Claim 13
Dependent Claim
13 words
A phosphor according to claim 1, wherein the value of x+y+z is x+y+z<1.
Claim 14
Dependent Claim
17 words
A phosphor according to claim 1 or 12, wherein M II in the formula (I) is Zn.
Claim 15
Dependent Claim
137 words
A process for producing a phosphor represented by the formula: a(Sr.sub.1-x-y-z M.sub.x.sup.II M.sub.y.sup.III Eu.sub.z.sup.2+).sub.3 (PO.sub.4).sub.2.b M'X.sub.2 (I) wherein M II is at least one element selected from the group consisting of Zn, Mg, Ca and Ba; M III is at least one element selected from the group consisting of Y, Gd and La; M' is at least one element selected from the group consisting of Ca, Sr, and Ba; X is one or more halogens; 0≦x≦0.999, 0.001≦y≦0.15, 0.0015≦z≦0.20 and x+y+z≦1: and the ratio a/b is in the range of 0.3≦a/b≦1.2, which comprises mixing constituent elements or raw materials containing the constituent elements of the phosphor of the formula (I) mentioned above in amounts necessary for producing the phosphor of the formula (I) and firing them at a temperature of 900° to 1300° C. under a reducing atmosphere.
Claim 16
Dependent Claim
137 words
A process for producing a phosphor represented by the formula: a(Sr.sub.1-x-y-z M.sub.x.sup.II M.sub.y.sup.III Eu.sub.z.sup.2+).sub.3 (PO.sub.4).sub.2.b M'X.sub.2 (I) wherein M II is at least one element selected from the group consisting of Zn, Mg, Ca and Ba; M III is at least one element selected from the group consisting of Y, Gd and La; M' is at least one element selected from the group consisting of Ca, Sr, and Ba; X is one or more halogens; 0≦x≦0.999, 0.001≦y≦0.15, 0.0015≦z≦0.20 and x+y+z≦1: and the ratio a/b is in the range of 0.3≦a/b≦1.2, which comprises mixing constituent elements or raw materials containing the constituent elements of the phosphor of the formula (I) mentioned above in amounts necessary for producing the phosphor of the formula (I) and firing them at a temperature of 900° to 1300° C. under a reducing atmosphere.
Claim 17
Dependent Claim
38 words
A process according to claim 14, wherein one or more halogen compounds are mixed so that the amount of halogens in the composition of raw materials is at least 1.25 times as much as the stoichiometric amount thereof.
Claim 18
Dependent Claim
42 words
A process according to claim 14, wherein one or more halogen compounds are mixed so that the amount of halogens in the composition of raw materials is in the range of 1.25 to 3.5 times as much as the stoichiometric amount thereof.
Claim 19
Dependent Claim
60 words
A process according to claim 15 or 16, wherein the halogen compound is at least one member selected from the group consisting of SrX 2 , M II X 2 , M III X 3 and NH 4 X, wherein X is halogen; and M II is Zn, Mg, Ca or Ba; and M III is Y, Gd or La.
Claim 20
Dependent Claim
14 words
A process according to claim 17, wherein the halogen compound is NH 4 X.
Claim 21
Dependent Claim
17 words
A process according to claim 14, 15, or 16, wherein X in the formula (I) is chlorine.
Claim 22
Dependent Claim
8 words
A process according to claim 14, wherein 0.4≦a/b≦0.7.
Claim 23
Dependent Claim
148 words
A process for producing a phosphor represented by the formula: a(Sr.sub.1-x-y-z M.sub.x.sup.II M.sub.y.sup.III Eu.sub.z.sup.2+).sub.3 (PO.sub.4).sub.2.b M'X.sub.2 (I) wherein M II is at least one element selected from the group consisting of Zn, Mg, Ca and Ba; M III is at least one element selected from the group consisting of Y, Gd and La; M' is at least one element selected from the group consisting of Ca, Sr and Ba; X is one or more halogens; 0<x≦0.999, 0.001≦y≦0.15, 0.0015≦z≦0.20 and x+y+z≦1: and the ratio a/b is in the range of 1.2<a/b≦3.0, whereby said phosphor is not deteriorated by baking in air, which comprises mixing constituent elements or raw materials containing the constituent elements of the phosphor of the formula (I) mentioned above in amounts necessary for producing the phosphor of the formula (I) and firing them at a temperature of 900° C. to 1300° C. under a reducing atmosphere.
Claim 24
Dependent Claim
148 words
A process for producing a phosphor represented by the formula: a(Sr.sub.1-x-y-z M.sub.x.sup.II M.sub.y.sup.III Eu.sub.z.sup.2+).sub.3 (PO.sub.4).sub.2.b M'X.sub.2 (I) wherein M II is at least one element selected from the group consisting of Zn, Mg, Ca and Ba; M III is at least one element selected from the group consisting of Y, Gd and La; M' is at least one element selected from the group consisting of Ca, Sr and Ba; X is one or more halogens; 0<x≦0.999, 0.001≦y≦0.15, 0.0015≦z≦0.20 and x+y+z≦1: and the ratio a/b is in the range of 1.2<a/b≦3.0, whereby said phosphor is not deteriorated by baking in air, which comprises mixing constituent elements or raw materials containing the constituent elements of the phosphor of the formula (I) mentioned above in amounts necessary for producing the phosphor of the formula (I) and firing them at a temperature of 900° C. to 1300° C. under a reducing atmosphere.
Claim 25
Dependent Claim
44 words
A process according to claim 2, wherein one or more halogen compounds are mixed so that the amount of halogen atom in the composition of raw materials is in the range of from 1.25 to 3.5 times as much as the stoichiometric amount thereof.
Claim 26
Dependent Claim
44 words
A process according to claim 21, wherein one or more halogen compounds are mixed so that the amount of halogen atom in the composition of raw materials is in the range of from 1.5 to 3.5 times as much as the stoichiometric amount thereof.
Claim 27
Dependent Claim
37 words
A process according to claim 21, 22 or 23, wherein the halogen atom in the formula (I) is obtained from raw materials in which at least one portion thereof is in the form of an ammonium halide.
Claim 28
Dependent Claim
47 words
A process according to claim 21, 22 or 23, wherein the halogen atom in the formula (I) is obtained from one or more raw materials selected from the group consisting of SrX 2 , M II X 2 , M III X 3 and NH 4 X.
Claim 29
Dependent Claim
27 words
A process according to claim 14 or 21, wherein said reducing atmosphere is a mixture of an inert gas and hydrogen in a volume ratio of 20:1-5.
Claim 30
Dependent Claim
12 words
A process according to claim 26, wherein said inert gas is nitrogen.
Claim 31
Dependent Claim
18 words
A process according to claim 21, wherein said phosphor has a host crystal structure of the mineral apatite.
Claim 32
Dependent Claim
97 words
A phosphor represented by the formula: a(Sr.sub.1-x-y-z M.sub.x.sup.II M.sub.y.sup.III Eu.sub.z.sup.2+).sub.3 (PO.sub.4).sub.2.b M'X.sub.2 (I) wherein M II is at least one element selected from the group consisting of Zn, Mg, Ca and Ba; M III is at least one element selected from the group consisting of A, Y, Gd and La; M' is at least one element selected from the group consisting of Ca, Sr and Ba; X is one or more halogens; 0<x≦0.999, 0.001≦y≦0.15, 0.0015≦z≦0.20 and x+y+z≦1; and the ratio a/b is in the range of 1.2<a/b≦3.0, whereby said phosphor is not deteriorated by baking in air.
Claim 33
Dependent Claim
97 words
A phosphor represented by the formula: a(Sr.sub.1-x-y-z M.sub.x.sup.II M.sub.y.sup.III Eu.sub.z.sup.2+).sub.3 (PO.sub.4).sub.2.b M'X.sub.2 (I) wherein M II is at least one element selected from the group consisting of Zn, Mg, Ca and Ba; M III is at least one element selected from the group consisting of A, Y, Gd and La; M' is at least one element selected from the group consisting of Ca, Sr and Ba; X is one or more halogens; 0<x≦0.999, 0.001≦y≦0.15, 0.0015≦z≦0.20 and x+y+z≦1; and the ratio a/b is in the range of 1.2<a/b≦3.0, whereby said phosphor is not deteriorated by baking in air.
Claim 34
Dependent Claim
36 words
A phosphor according to claim 29, wherein X in the formula (I) contains 50% by mole or more of Cl or Br or a mixture of Cl and Br based on the total amount of X.
Claim 35
Dependent Claim
29 words
A phosphor according to claim 29, wherein X in the formula (I) contains 80% by mole or more of Cl or Br or a mixture of Cl and Br.
Claim 36
Dependent Claim
20 words
A phosphor according to claim 29, wherein M' in the formula (I) contains 90% by mole or more of Ca.
Claim 37
Dependent Claim
19 words
A phosphor according to claim 29, 30, 31 or 32, wherein M III in the formula (I) is Y.
Claim 38
Dependent Claim
19 words
A phosphor according to claim 29, 30, 31 or 32, wherein M III in the formula (I) is Gd.
Claim 39
Dependent Claim
19 words
A phosphor according to claim 29, 30, 31 or 32, wherein M III in the formula (I) is La.
Claim 40
Dependent Claim
19 words
A phosphor according to claim 29, 30, 31 or 32, wherein M II in the formula (I) is Zn.
Claim 41
Dependent Claim
19 words
A phosphor according to claim 29, 30, 31 or 32, wherein M II in the formula (I) is Mg.
Claim 42
Dependent Claim
18 words
A phosphor according to claim 29, wherein said phosphor has a host crystal structure of the mineral apatite.
Claim 43
Dependent Claim
97 words
A phosphor represented by the formula: a(Sr.sub.1-x-y-z M.sub.x.sup.II M.sub.y.sup.III Eu.sub.z.sup.2+).sub.3 (PO.sub.4).sub.2.b M'X.sub.2 (I) wherein M II is at least one element selected from the group consisting of Zn, Mg, Ca and Ba; M II is at least one element selected from the group consisting of Al, Y, Gd and La; M' is at least one element selected from the group consisting of Ca, Sr, and Ba; x is one or more halogens; 0<x≦0.999, 0.001≦y≦0.15, 0.0015≦z≦0.20 and x+y+z≦1; and the ratio a/b is in the range of 1.2<a/b≦2.0, whereby said phosphor is not deteriorated by baking in air.
Claim 44
Dependent Claim
97 words
A phosphor represented by the formula: a(Sr.sub.1-x-y-z M.sub.x.sup.II M.sub.y.sup.III Eu.sub.z.sup.2+).sub.3 (PO.sub.4).sub.2.b M'X.sub.2 (I) wherein M II is at least one element selected from the group consisting of Zn, Mg, Ca and Ba; M II is at least one element selected from the group consisting of Al, Y, Gd and La; M' is at least one element selected from the group consisting of Ca, Sr, and Ba; x is one or more halogens; 0<x≦0.999, 0.001≦y≦0.15, 0.0015≦z≦0.20 and x+y+z≦1; and the ratio a/b is in the range of 1.2<a/b≦2.0, whereby said phosphor is not deteriorated by baking in air.
Claim 45
Dependent Claim
15 words
A phosphor according to claim 39, wherein M II in the formula (I) is Zn.
Claim 46
Dependent Claim
17 words
A phosphor according to claim 39, or 40, wherein M III in the formula (I) is Al.
References Cited (Backward Citations)
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1985-10-11 | 1986-04-12 | 1986-10-12 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1989-10-11 | 1990-04-12 | 1990-10-12 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1993-10-11 | 1994-04-12 | 1994-10-12 | $7700.00 | Window Closed / Lapsed |