Phosphor, production method for same, light-emitting device, image display device, pigment, and ultraviolet absorber
09828547 · 2017-11-28
Assignee
Inventors
- Naoto Hirosaki (Ibaraki, JP)
- Takashi Takeda (Ibaraki, JP)
- Shiro Funahashi (Ibaraki, JP)
- Eiichirou Narimatsu (Ibaraki, JP)
Cpc classification
H01L2224/8592
ELECTRICITY
H01L33/504
ELECTRICITY
H01L2924/00012
ELECTRICITY
H01L2924/00014
ELECTRICITY
C09K11/77348
CHEMISTRY; METALLURGY
H01L2924/00014
ELECTRICITY
H01L2924/00012
ELECTRICITY
C09K11/77928
CHEMISTRY; METALLURGY
International classification
Abstract
A phosphor having different light emission characteristics from the conventional phosphor, having high emission intensity and chemical and thermal stability, combined with LED of less than 450 nm. This phosphor includes an inorganic compound comprising: a crystal represented by Ba.sub.1Si.sub.4Al.sub.3N.sub.9, an inorganic crystal having the same crystal structure as Ba.sub.1Si.sub.4Al.sub.3N.sub.9 crystal, or a solid solution crystal thereof, comprising A element, D element, E element, and X element (A is one or more elements selected from Li, Mg, Ca, Sr, Ba, and La; D is one or more elements selected from Si, Ge, Sn, Ti, Zr, and Hf; E is one or more elements selected from B, Al, Ga, In, Sc, and Y; X is one or more elements selected from O, N, and F), into which M element is solid-solved (M is one or more elements selected from Mn, Ce, Pr, Nd, Sm, Eu, Tb, Dy, and Yb).
Claims
1. A phosphor comprising: an inorganic compound comprising: a crystal represented by BaSi.sub.4Al.sub.3N.sub.9, an inorganic crystal having a same crystal structure as the crystal represented by BaSi.sub.4Al.sub.3N.sub.9, or a solid solution crystal thereof, which comprises at least an A element, a D element, an E element, and an X element (wherein A is one or more kinds of elements selected from a group consisting of Li, Mg, Ca, Sr, Ba, and La; D is one or more kinds of elements selected from a group consisting of Si, Ge, Sn, Ti, Zr, and Hf; E is one or more kinds of elements selected from a group consisting of B, Al, Ga, In, Sc, and Y; X is one or more kinds of elements selected from a group consisting of O, N, and F), into which an M element is solid-solved (wherein M is one or more kinds of elements selected from a group consisting of Mn, Ce, Pr, Nd, Sm, Eu, Tb, Dy, and Yb) wherein the inorganic crystal having the same crystal structure as the crystal represented by BaSi.sub.4Al.sub.3N.sub.9 comprises a crystal represented by A(D, E).sub.7X.sub.9.
2. The phosphor according to claim 1, wherein: the D element includes Si; the E element includes Al; and the X element includes N and, if necessary, the X element further includes O.
3. The phosphor according to claim 1, wherein the inorganic crystal having the same crystal structure as the crystal represented by BaSi.sub.4Al.sub.3N.sub.9 comprises BaSi.sub.4Al.sub.3N.sub.9, MgSi.sub.4Al.sub.3N.sub.9, CaSi.sub.4Al.sub.3N.sub.9, SrSi.sub.4Al.sub.3N.sub.9, LaSi.sub.4Al.sub.3N.sub.9, LiSi.sub.4Al.sub.3N.sub.9, (Ba,Mg)Si.sub.4Al.sub.3N.sub.9, (Ba,Ca)Si.sub.4Al.sub.3N.sub.9, (Ba,Sr)Si.sub.4Al.sub.3N.sub.9, (Ba,La)Si.sub.4Al.sub.3N.sub.9, or (Ba,Li)Si.sub.4Al.sub.3N.sub.9.
4. The phosphor according to claim 1, wherein the inorganic crystal having the same crystal structure as the crystal represented by BaSi.sub.4Al.sub.3N.sub.9 is represented by a composition formula of: BaSi.sub.4−pAl.sub.3+pO.sub.pN.sub.9−p, MgSi.sub.4−pAl.sub.3+pO.sub.pN.sub.9−p, CaSi.sub.4−pAl.sub.3+pO.sub.pN.sub.9−p, SrSi.sub.4−pAl.sub.3+pO.sub.pN.sub.9−p, LaSi.sub.4−pAl.sub.3+pO.sub.pN.sub.9−p, LiSi.sub.4−pAl.sub.3+pO.sub.pN.sub.9−p, (Ba,Mg)Si.sub.4−pAl.sub.3+pO.sub.pN.sub.9−p, (Ba,Ca)Si.sub.4−pAl.sub.3+pO.sub.pN.sub.9−p, (Ba,Sr)Si.sub.4−pAl.sub.3+pO.sub.pN.sub.9−p, (Ba,La)Si.sub.4−pAl.sub.3+pO.sub.pN.sub.9−p, or (Ba,Li)Si.sub.4−pAl.sub.3+pO.sub.pN.sub.9−p (here 0≦p<4).
5. The phosphor according to claim 1, wherein the M element comprises Eu.
6. The phosphor according to claim 1, wherein the inorganic crystal having the same crystal structure as the crystal represented by BaSi.sub.4Al.sub.3N.sub.9 comprises a crystal of the monoclinic crystal system.
7. The phosphor according to claim 1, wherein the inorganic crystal having the same crystal structure as the crystal represented by BaSi.sub.4Al.sub.3N.sub.9 comprises a crystal of the monoclinic crystal system having a symmetry of space group P2(1)/c and lattice constants a, b, and c having values in following ranges: a=0.58465±0.05 nm, b=2.67255±0.05 nm, and c=0.58386±0.05 nm.
8. The phosphor according to claim 1, wherein the inorganic compound is represented by a composition formula of M.sub.dA.sub.eD.sub.fE.sub.gX.sub.h (wherein, in the formula, d+e+f+g+h=1; M is one or more kinds of elements selected from a group consisting of Mn, Ce, Pr, Nd, Sm, Eu, Tb, Dy, and Yb; A is one or more kinds of elements selected from a group consisting of Li, Mg, Ca, Sr, Ba, and La; D is one or more kinds of elements selected from a group consisting of Si, Ge, Sn, Ti, Zr, and Hf; E is one or more kinds of elements selected from a group consisting of B, Al, Ga, In, Sc, and Y; and X is one or more kinds of elements selected from a group consisting of O, N, and F) and the inorganic compound is expressed by a composition in a range where parameters d, e, f, g, and h satisfy all conditions of: 0.00001≦d≦0.05, 0.01≦e≦0.07, 0.10≦f≦0.30, 0.10≦g≦0.30, and 0.45≦h≦0.65.
9. The phosphor according to claim 8, wherein the parameters d, e, f, g, and h have values in a range satisfying all conditions of: d+e=(1/17)±0.05, f+g=(7/17)±0.05, and h=(9/17)±0.05.
10. The phosphor according to claim 8, wherein the parameters f and g satisfy a condition of: 0<f/(f+g)≦1.
11. The phosphor according to claim 8, wherein: the X element includes O and N and the inorganic compound is represented by a composition formula of M.sub.dA.sub.eD.sub.fE.sub.gO.sub.h1N.sub.h2 (wherein, in the formula, d+e+f+g+h1+h2=1 and h1+h2=h), and a condition of 0<h1/(h1+h2)≦6/9 is satisfied.
12. The phosphor according to claim 8, wherein at least Eu is included as the M element.
13. The phosphor according to claim 8, wherein: at least Ba is included as the A element; at least Al is included as the E element; and at least N is included as the X element.
14. The phosphor according to claim 1, wherein the inorganic compound is represented by a composition formula of
Eu.sub.qBa.sub.1−qSi.sub.4−pAl.sub.3+pN.sub.9−pO.sub.p using parameters p and q wherein: 0≧≦p<4 and 0.0001≦q<1.
15. The phosphor according to claim 1, wherein the phosphor emits fluorescence having a peak in a wavelength range that is at least 450 nm and not exceeding 530 nm upon irradiation by an excitation source.
16. A method of manufacturing a phosphor as recited in claim 1 comprises the step of: firing a raw material mixture, which comprises a mixture of metal compounds and could constitute an inorganic compound as recited in claim 1 by firing, in an inert atmosphere including nitrogen at a temperature range of at least 1200° C. and not exceeding 2200° C.
17. A light-emitting device comprising at least a light-emitting body or an emission source and a phosphor wherein the phosphor comprises at least a phosphor as recited in claim 1.
18. An image display device comprising at least an excitation source and a phosphor wherein the phosphor comprises at least a phosphor as recited in claim 1.
19. A pigment comprising an inorganic compound as recited in claim 1.
20. An ultraviolet absorber comprising an inorganic compound as recited in claim 1.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
(1)
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EMBODIMENT FOR CARRYING OUT THE INVENTION
(9) Hereafter, a phosphor according to the present invention is described in detail with reference to the drawings.
(10) A phosphor according to the present invention may be a phosphor comprising, as a main component, an inorganic compound comprising: a crystal represented by BaSi.sub.4Al.sub.3N.sub.9, an inorganic crystal having the same (or identical) crystal structure as the crystal represented by BaSi.sub.4Al.sub.3N.sub.9, or a solid solution crystal of these, which comprises at least an A element, a D element, an E element, and an X element (here, A is one or two or more kinds of elements selected from the group consisting of Li, Mg, Ca, Sr, Ba, and La; D is one or two or more kinds of elements selected from the group consisting of Si, Ge, Sn, Ti, Zr, and Hf; E is one or two or more kinds of elements selected from the group consisting of B, Al, Ga, In, Sc, and Y; X is one or two or more kinds of elements selected from the group consisting of O, N, and F), where an M element is solid-solved into the crystal (here, M is one or two or more kinds of elements selected from the group consisting of Mn, Ce, Pr, Nd, Sm, Eu, Tb, Dy, and Yb), thereby allowing the phosphor to function as an excellent phosphor. Here, in the present specification, the crystal represented by BaSi.sub.4Al.sub.3N.sub.9, the inorganic crystal having the same crystal structure as the crystal represented by BaSi.sub.4Al.sub.3N.sub.9, or a solid solution crystal of these crystals may also be collectively referred to as “BaSi.sub.4Al.sub.3N.sub.9 system crystal” for the sake of simplicity.
(11) The crystal represented by BaSi.sub.4Al.sub.3N.sub.9, which was newly synthesized and confirmed to be a new crystal through the crystal structure analysis by the present inventors, is a crystal which has not been reported prior to the present invention.
(12)
(13) According to the single crystal structure analysis performed with respect to the BaSi.sub.4Al.sub.3N.sub.9:Eu.sup.2+ crystal synthesized by the present inventors, the BaSi.sub.4Al.sub.3N.sub.9:Eu.sup.2+ crystal belongs to the monoclinic system and the P2(1)/c space group (space group No. 14 in the International Tables for Crystallography), and has crystal parameters and occupancy of the atomic coordinate positions as shown in Table 1.
(14) In Table 1, lattice constants a, b, and c signify respective lengths of the axes of the unit cell, and α, β, and γ signify respective angles between axes of the unit cell. The atomic coordinates indicate a position of each atom in the unit cell in terms of a value from 0 to 1 using the unit cell as a unit. According to the analysis results thus obtained, there were atoms of Ba, Si, Al, N, and Eu, respectively, and Ba and Eu interexchangeably existed in one kind of site: (Ba, Eu(1)). And the analysis results showed that Si and Al also interexchangeably existed in ten (10) kinds of sites from (Si, Al(2)) to (Si, Al(5)), (Si, Al(6A)) and (Si, Al(6B)), (Si, Al(7A)) and (Si, Al(7B)), (Si, Al(8A)) and (Si,Al(8B)). Further, the analysis results showed that N existed in eleven (11) kinds of sites from N(1) to N(7), N(8A) and N(8B), and N(9A) and N(9B).
(15) TABLE-US-00001 TABLE 1 Crystal structure data of BaSi.sub.4Al.sub.3N.sub.9: Eu.sup.2+ crystal Crystal composition BaSi.sub.4Al.sub.3N.sub.9: Eu.sup.2+ Formula weight (Z) 1 Crystal system Monoclinic Space group P2(1)/c Space group number 7 Lattice constants a 5.8465 Å b 26.7255 Å c 5.8386 Å α 90 degree β 118.897 degree γ 90 degree Atomic coordinate Atom x y z Site occupancy rate Ba,Eu(1) 1.1274 0.1343 0.8732 1 Si,Al(2) 0.4477 0.1328 0.5539 1 Si,Al(3) 0.8037 0.1371 1.1931 1 Si,Al(4) 0.6291 0.2305 0.8674 1 Si,Al(5) 1.1318 0.2716 0.872 1 Si,Al(6A) 0.6509 0.0595 1.3483 0.706 Si,Al(6B) 0.6007 0.0589 1.3989 0.294 Si,Al(7A) 0.6604 0.0338 0.8365 0.5 Si,Al(7B) 0.5905 0.0327 0.9109 0.5 Si,Al(8A) 0.1631 0.0338 0.3403 0.5 Si,Al(8B) 1.0892 0.033 1.4096 0.5 N(1) 0.6277 0.1627 0.8587 1 N(2) 1.1386 0.3384 0.8766 1 N(3) 0.3879 0.0697 0.6143 1 N(4) 0.6214 0.1247 1.3755 1 N(5) 0.8486 0.0675 1.1504 1 N(6) 0.7996 0.2464 1.2054 1 N(7) 1.2948 0.2493 1.1993 1 N(8A) 0.5742 −0.0251 0.8956 0.5 N(8B) 0.6564 −0.0279 0.8317 0.5 N(9A) 1.105 −0.0256 1.4265 0.5 N(9B) 0.1696 −0.0278 0.3417 0.5
(16) As a result of analysis using data in Table 1, the BaSi.sub.4Al.sub.3N.sub.9:Eu.sup.2+ crystal was found to have the structure as shown in
(17) As the crystal having the same crystal structure as the BaSi.sub.4Al.sub.3N.sub.9 crystal that was synthesized and analyzed with respect to the structure, there are A(D, E).sub.7X.sub.9 crystal, specifically, A(Si, Al).sub.7 (O, N).sub.9 crystal, and, more specifically, ASi.sub.4Al.sub.3N.sub.9 crystal. The A element is typically Ba. With respect to A(D, E).sub.7X.sub.9 crystal, A can occupy sites which Ba is supposed to occupy, D and E can interexchangeably occupy sites which Si and Al are supposed to occupy, and X can occupy sites which N is supposed to occupy, in the BaSi.sub.4Al.sub.3N.sub.9 crystal. Thus, a relative ratio of numbers of atoms can be adjusted to be 1 for the A element, 7 for the sum of D and E, and 9 for the sum of X, while the crystal structure remains the same. However, it is desirable to have a ratio of cation such as A, D, and E to anion such as X satisfying an electrical neutrality condition in the crystal. With respect to A.sub.1(Si, Al).sub.7 (O, N).sub.9 crystal, Si and Al can occupy sites which Si and Al are supposed to occupy without any distinction with each other, and O and N can occupy sites which N is supposed to occupy, in BaSi.sub.4Al.sub.3N.sub.9 crystal. Thus, a relative ratio of numbers of atoms can be adjusted to be 1 for the A element, 7 for the sum of Si and Ai, and 9 for the sum of O and N, while the crystal structure remains the same. However, it is desirable to have such a ratio of Si/Al and a ratio of O/N as to satisfy the condition of the electrical neutrality in the crystal.
(18) The BaSi.sub.4Al.sub.3N.sub.9 system crystal of the present invention can be identified by means of the X-ray diffraction or the neutron diffraction. A substance exhibiting the identical diffraction to that of the BaSi.sub.4Al.sub.3N.sub.9 system crystal as a result of the X-ray diffraction in the present invention includes a crystal designated by A(D, E).sub.7X.sub.9. Further, the substance includes a crystal in which lattice constants or atomic positions are changed by substituting other elements for constituent elements in the BaSi.sub.4Al.sub.3N.sub.9 crystal. Here, specific examples of materials in which the constituent elements are substituted with other elements include a material in which Ba in the BaSi.sub.4Al.sub.3N.sub.9 crystal is partially or completely substituted with the A element other than Ba (here, A is one or two or more kinds of elements selected from Li, Mg, Ca, Sr, and La) and/or the M element (here, M is one or two or more kinds of elements selected from Mn, Ce, Pr, Nd, Sm, Eu, Tb, Dy, and Yb). Further, the specific examples include a material in which Si in the crystal is partially or completely substituted with the D element other than Si (here, D is one or two or more kinds of elements selected from Ge, Sn, Ti, Zr, and Hf). Further, the specific examples include a material in which Al in the crystal is partially or completely substituted with the E element other than Al (here, E is one or two or more kinds of elements selected from B, Ga, In, Sc, and Y). Further, the specific examples include a material in which N in the crystal is partially or completely substituted with oxygen and/or fluorine. These substitutions are performed such that the neutrality of charges in the whole crystal is maintained. The material in which a crystal structure thereof is not changed as a result of such element substitutions is included in the BaSi.sub.4Al.sub.3N.sub.9 system crystal. Since emission characteristics, chemical stability, and thermal stability of the phosphor are changed by the substitution of elements, the substitution of elements may be selectively utilized at an appropriate time for each application thereof as far as the crystal structure remains the same.
(19) In the BaSi.sub.4Al.sub.3N.sub.9 system crystal, the lattice constants change as the constituent components are substituted with other elements or as an activating element such as Eu is solid-solved therein, but the atomic positions given by the crystal structure, sites to be occupied by atoms, and coordinates thereof do not significantly change to an extent in which a chemical bond between skeleton atoms is broken. In the present invention, a crystal structure is defined to be identical (or the same) to that of the BaSi.sub.4Al.sub.3N.sub.9 crystal if lengths of chemical bonds (distance of neighboring atoms) of Al—N and Si—N calculated from the lattice constants and atomic coordinates obtained by conducting the Rietveld analysis of the results from the X-ray diffraction or the neutron diffraction in the space group of P2(1)/c are compared with lengths of chemical bonds calculated from the lattice constants and atomic coordinates of BaSi.sub.4Al.sub.3N.sub.9:Eu.sup.2+ crystal as shown in Table 1 such that each difference between corresponding lengths is within ±5%, and using the definition it is determined whether the crystal having the crystal structure belongs to the BaSi.sub.4Al.sub.3N.sub.9 system crystal or not. This determination criterion is employed herein since it was confirmed that a crystal in the BaSi.sub.4Al.sub.3N.sub.9 system crystal was changed to become another crystal due to breakage of chemical bonds when lengths of the chemical bonds were changed beyond ±5% according to the prior experiments.
(20) Further, in case an amount of solid-solution is small, a simple method for determining whether it belongs to the BaSi.sub.4Al.sub.3N.sub.9 system crystal or not is described as follows. A new substance can be identified to have the same crystal structure if main peaks of the resultant X-ray diffraction pattern measured with the new substance are respectively located at diffraction peak positions, which agree with the peak positions (2θ) of the diffraction pattern calculated using the crystal structure data of Table 1 and the lattice constants calculated from the resultant X-ray diffraction pattern.
(21)
(22) It is possible to make a simple determination whether a subject substance belongs to the BaSi.sub.4Al.sub.3N.sub.9 system crystal or not by comparing
(23) A phosphor can be obtained if the BaSi.sub.4Al.sub.3N.sub.9 system crystal is activated by the M element, one or two or more kinds of which are selected from Mn, Ce, Pr, Nd, Sm, Eu, Tb, Dy, Ho, Er, Tm, and Yb. Since emission characteristics such as an excitation wavelength, an emission wavelength, and emission intensity may vary depending on the composition of the BaSi.sub.4Al.sub.3N.sub.9 system crystal, and the kind and quantity of the activating element, such conditions may be chosen in accordance with an application thereof.
(24) With respect to a crystal represented by A(D, E).sub.7X.sub.9, if the crystal has a composition in which, at least, the A element includes at least one element selected from the group consisting of Li, Mg, Ca, Sr, Ba, and La; the D element includes Si; the E element includes Al; and the X element includes N, and the X element includes O if necessary, then the crystal exhibits high emission intensity. In particular, it is the phosphor exhibiting high emission intensity that comprises the BaSi.sub.4Al.sub.3N.sub.9 system crystal as the host and has a composition in which A is a mixture of Ba and Mg or a mixture of Ba and Li; D is Si; E is Al; and X is N or a combination of O and N.
(25) The phosphor has a stable crystal and exhibits high emission intensity if the inorganic crystal thereof having the same crystal structure as the crystal represented by BaSi.sub.4Al.sub.3N.sub.9 may be BaSi.sub.4Al.sub.3N.sub.9, MgSi.sub.4Al.sub.3N.sub.9, CaSi.sub.4Al.sub.3N.sub.9, SrSi.sub.4Al.sub.3N.sub.9, LaSi.sub.4Al.sub.3N.sub.9, LiSi.sub.4Al.sub.3N.sub.9, (Ba,Mg)Si.sub.4Al.sub.3N.sub.9, (Ba,Ca)Si.sub.4Al.sub.3N.sub.9, (Ba,Sr)Si.sub.4Al.sub.3N.sub.9, (Ba,La)Si.sub.4Al.sub.3N.sub.9, or (Ba,Li)Si.sub.4Al.sub.3N.sub.9.
(26) The phosphor exhibits high emission intensity and is a phosphor in which the change of color tone can be controlled by changing the composition thereof if the inorganic crystal thereof having the same crystal structure as the crystal represented by BaSi.sub.4Al.sub.3N.sub.9 may be represented by a composition formula of: BaSi.sub.4−pAl.sub.3+pO.sub.pN.sub.9−p, MgSi.sub.4−pAl.sub.3+pO.sub.pN.sub.9−p, CaSi.sub.4−pAl.sub.3+pO.sub.pN.sub.9−p, SrSi.sub.4−pAl.sub.3+pO.sub.pN.sub.9−p, LaSi.sub.4−pAl.sub.3+pO.sub.pN.sub.9−p, LiSi.sub.4−pAl.sub.3+pO.sub.pN.sub.9−p, (Ba,Mg)Si.sub.4−pAl.sub.3+pO.sub.pN.sub.9−p, (Ba,Ca)Si.sub.4−pAl.sub.3+pO.sub.pN.sub.9−p, (Ba,Sr)Si.sub.4−pAl.sub.3+pO.sub.pN.sub.9−p, (Ba,La)Si.sub.4−pAl.sub.3+pO.sub.pN.sub.9−p, or (Ba,Li)Si.sub.4−pAl.sub.3+pO.sub.pN.sub.9−p (where 0≦p<4).
(27) It is Eu that is used as the activating element M such that a phosphor exhibiting particularly high emission intensity can be obtained.
(28) In an inorganic crystal having a crystal structure identical to that of the crystal represented by BaSi.sub.4Al.sub.3N.sub.9, the inorganic crystal is particularly stable if the inorganic crystal is a crystal that belongs to the monoclinic system, and a phosphor having such crystal as a host crystal exhibits high emission intensity.
(29) Further, if an inorganic crystal having a crystal structure identical to that of the crystal represented by BaSi.sub.4Al.sub.3N.sub.9 is a crystal that belongs to the monoclinic system and has the symmetry of space group P2(1)/c, and in which lattice constants thereof a, b, and c are in the following ranges:
(30) a=0.58465±0.05 nm,
(31) b=2.67255±0.05 nm, and
(32) c=0.58386±0.05 nm,
(33) the crystal is particularly stable such that a phosphor having the crystal as a host crystal exhibits high emission intensity. If the crystal is prepared out of the above ranges, the crystal may become unstable and the emission intensity may occasionally decrease.
(34) If the above-described inorganic compound is represented by a composition formula M.sub.dA.sub.eD.sub.fE.sub.gX.sub.h (here, in the formula, d+e+f+g+h=1, M is one or two or more kinds of elements selected from Mn, Ce, Pr, Nd, Sm, Eu, Tb, Dy, and Yb; A is one or two or more kinds of elements selected from. Li, Mg, Ca, Sr, Ba, and La; D is one or two or more kinds of elements selected from Si, Ge, Sn, Ti, Zr, and Hf; E is one or two or more kinds of elements selected from B, Al, Ga, In, Sc, and Y; X is one or two or more kinds of elements selected from O, N, and F), and parameters d, e, f, g, and h thereof satisfy all the following conditions:
(35) 0.00001≦d≦0.05;
(36) 0.01≦e≦0.07;
(37) 0.10≦f≦0.30;
(38) 0.10≦g≦0.30; and
(39) 0.45≦h≦0.65,
(40) the phosphor comprising the inorganic compound exhibits particularly high emission intensity.
(41) The parameter d represents an additive amount of the activating element, and if the amount is less than 0.00001, an amount of light-emitting ions is insufficient such that brightness thereof may be decreased. If the amount of parameter d is more than 0.05, the emission intensity may be decreased due to the concentration quenching by a mutual interaction between light-emitting ions. The parameter e is a parameter representing a constituent amount of the A element such as Ba, and if the amount is less than 0.01 or higher than 0.7, the crystal structure may become unstable so as to cause the emission intensity to decrease. The parameter f is a parameter representing a constituent amount of the D element such as Si, and if the amount is less than 0.10 or higher than 0.3, the crystal structure may become unstable so as to cause the emission intensity to decrease. The parameter g is a parameter representing a constituent amount of the E element such as Al, and if the amount is less than 0.10 or higher than 0.3, the crystal structure may become unstable so as to cause the emission intensity to decrease. The parameter h is a parameter representing a constituent amount of the X element such as O, N, and F, and if the amount is less than 0.45 or higher than 0.65, the crystal structure may become unstable so as to cause the emission intensity to decrease. The element X is an anion, and composition ratios of O, N, and F may be determined so as to maintain the charge neutrality with cations of the A, M, D and E elements.
(42) The crystal, in which values of the parameters d, e, f, g, and h satisfy all the following conditions:
(43) d+e=(1/17)±0.05,
(44) f+g=(7/17)±0.05, and
(45) h=(9/17)±0.05,
(46) is stable in the crystal structure and exhibits particularly high emission intensity. In particular, the crystal, in which the values satisfy all the following conditions:
(47) d+e=1/17;
(48) f+g=7/17; and
(49) h=9/17,
(50) that is to say, the crystal having the composition of (M,A)(D,E).sub.7X.sub.9, is especially stable in the crystal structure and exhibits particularly high emission intensity.
(51) Further, the crystal having the composition, in which the parameters f and g satisfy the condition:
(52) 0<f/(f+g)≦1,
(53) is stable in the crystal structure and exhibits high emission intensity. More preferably, the crystal having the composition, in which the parameters f and g satisfy the condition:
(54) 2/7≦f/(f+g)≦4/7,
(55) is more stable in the crystal structure and exhibits higher emission intensity.
(56) With respect to the above-described composition formula, if the X element includes N and O, and if the inorganic compound is represented by the composition formula of M.sub.dA.sub.eD.sub.fE.sub.gO.sub.h1N.sub.h2 (where d+e+f+g+h1+h2=1 and h1+h2=h) and the composition satisfies the condition of
(57) 0<h1/(h1+h2)≦6/9,
(58) the inorganic compound is stable in the crystal structure and exhibits high emission intensity. More preferably, the composition, in which the parameters h1 and h2 satisfy the condition of
(59) 0<h1/(h1+h2)≦2/9,
(60) may be expected to have more stable crystal structure and exhibit higher emission intensity.
(61) With respect to the above-described composition formula, a phosphor including at least Eu as the M element being the activating element is a phosphor exhibiting high emission intensity among the phosphors of the present invention, and a blue-to-green phosphor may be obtained with a specific composition.
(62) With respect to the above-described composition formula, a phosphor having a composition, in which at least Ba is included as the A element; at least Si is included as the D element; at least Al is included as the E element; and at least N is included as the X element, has a stable crystal structure and emission intensity thereof is high.
(63) Further, the phosphor may also include boron as the E element, and, in this case, the content amount of boron is at least 0.001 mass % and not exceeding 1 mass %. In this way, the emission intensity could become high.
(64) The phosphor represented by the composition formula of, using the parameters p and q,
Eu.sub.qBa.sub.1−qSi.sub.4−pAl.sub.3+pN.sub.9−pO.sub.p
where
0≦p<4 and
0.0001≦q<1,
may keep a stable crystal structure while the ratios of Eu/Ba; Si/Al; and N/O can be changed in the composition range in which the parameters p and q are changed. Thus, it is a phosphor that is easy to make a material design since an excitation wavelength thereof or an emission wavelength thereof can be continuously changed by utilizing this feature.
(65) A phosphor including an inorganic compound which comprises single crystal particles or an agglomeration of the single crystals particles having a mean particle diameter of at least 0.1 μm and not exceeding 20 μm has high emission efficiency and a good handling property when it is implemented into an LED such that it is good to control the particle diameter thereof in this range.
(66) Impurity elements of Fe, Co, and Ni included in the inorganic compound may cause the emission intensity to decrease. If the sum of these impurity elements in the phosphor is controlled to be 500 ppm or less, an influence of these elements on the emission intensity is decreased.
(67) As one of the embodiments of the present invention, there is provided a phosphor of the present invention comprising an inorganic compound including the BaSi.sub.4Al.sub.3N.sub.9 system crystal, as the host, into which the activating ion M is solid-solved, and further including an amorphous phase or another crystal phase other than the inorganic compound such that the content amount of the inorganic compound is at least 20 mass %. In the case where target characteristics cannot be obtained with a single phosphor of the BaSi.sub.4Al.sub.3N.sub.9 system crystal by itself, or in the case where an additional function such as conductivity is added, the phosphor of the present embodiment may be utilized. The content amount of the BaSi.sub.4Al.sub.3N.sub.9 system crystal may be adjusted in accordance with the target characteristics, but the emission intensity of the phosphor may be lowered if the content amount is equal to or less than 20 mass %. From this perspective, it is preferable to have 20 mass % or more of the main component of the above-described inorganic compound in the phosphor of the present invention.
(68) In the case where the phosphor is supposed to need electrical conductivity in an application in which electron beam excitation or the like is employed, an inorganic substance having electrical conductivity may be added thereto as another crystal phase or an amorphous phase.
(69) As the inorganic substance having the electrical conductivity, oxide, oxynitride, nitride, or a combination thereof of one or more kinds of elements selected from Zn, Al, Ga, In, and Sn may be named. For example, zinc oxide, aluminum nitride, indium nitride, tin oxide, and so on may be named.
(70) In the case where a target emission spectrum cannot be achieved with a single phosphor of the BaSi.sub.4Al.sub.3N.sub.9 system crystal, a second phosphor other than the phosphor of the BaSi.sub.4Al.sub.3N.sub.9 system crystal may be added. As an example of the other phosphor, an inorganic phosphor such as a BAM phosphor, a β-sialon phosphor, an α-sialon phosphor, a (Sr,Ba).sub.2Si.sub.5N.sub.8 phosphor, a CaAlSiN.sub.3 phosphor, and a (Ca,Sr)AlSiN.sub.3 phosphor may be named. The other crystal phase or the amorphous phase may be the above-described inorganic phosphor.
(71) As one of the embodiments of the present invention, there is a phosphor having a peak at a wavelength in the range of at least 450 nm and not exceeding 530 nm by irradiation of an excitation source. For example, a phosphor of the BaSi.sub.4Al.sub.3N.sub.9 system crystal in which Eu is activated has an emission peak in this range by adjusting the composition.
(72) As one of the embodiments of the present invention, there is a phosphor emitting light with vacuum ultraviolet light, ultraviolet light, or visible light having a wavelength of at least 100 nm and less than 450 nm, or electron beam or X-ray as an excitation source. The phosphor can be made to emit light efficiently by using such excitation sources.
(73) As one of the embodiments of the present invention, there is a phosphor comprising an inorganic crystal, into which Eu is solid-solved, wherein the inorganic crystal has the same crystal structure as the crystal represented by BaSi.sub.4Al.sub.3N.sub.9. Since the phosphor emits blue-to-green fluorescence of at least 450 nm and not exceeding 530 nm by adjusting the composition upon irradiation of light from 280 nm to 405 nm, the phosphor is desirable for use in blue-to-green emission application such as white color LED.
(74) As one of the embodiments of the present invention, there is a phosphor, upon irradiation of the excitation source, to emit light of a specific color which satisfies, in terms of values of (x, y) of CIE 1931 chromaticity coordinates, the following conditions:
(75) 0≦x≦0.4; and
(76) 0≦y≦0.9.
(77) For example, a phosphor to emit light of the color in the range of the chromaticity coordinates can be obtained by adjusting the composition of
Eu.sub.qBa.sub.1−qSi.sub.4−pAl.sub.3+pN.sub.9−pO.sub.p,
wherein
0≦p<4 and
0.0001≦q<1.
The phosphor is desirable for use in blue-to-green emission application such as white color LED.
(78) As mentioned above, the phosphor of the present invention is characterized in that a wide range of excitation source such as electron beam, X-ray, and light from an ultraviolet ray to visible light are applicable; that blue-to-green color light of at least 450 nm and not exceeding 530 nm is emitted with a specific composition thereof; and that the emission wavelength and the emission peak width may be adjustable. Thus, the phosphor of the present invention is suitable for an illuminating device and an image display device because of such emission characteristics. The phosphor of the present invention has also advantages of excellent heat resistance since it does not degrade even if it is exposed to high temperature, and excellent long-term stability under an oxidizing atmosphere and a moisture environment, and thus a product having excellent durability can be provided by utilizing the phosphor.
(79) The method of manufacturing such a phosphor of the present invention is not particularly limited thereto, but, for example, such a phosphor can be obtained by firing a mixture of metal compounds of a raw material mixture in a nitrogen-containing inert atmosphere in the temperature range of at least 1,200° C. and not exceeding 2,200° C. wherein the raw material mixture could constitute an inorganic compound having the BaSi.sub.4Al.sub.3N.sub.9 system crystal as the host crystal, into which the activating ion M is solid-solved. While the main crystal of the present invention belongs to the monoclinic system and the space group P2(1)/c, another crystal that belongs to another crystal system and another space group other than the above may be occasionally mixed therein depending on synthesis conditions such as firing temperature. However, even in such a case, a change of the emission characteristics is slight and therefore the thus-obtained product can be used as a phosphor of high brightness.
(80) As a starting material, for example, a mixture of metal compounds, which comprises a compound including M, a compound including A, a compound including D, a compound including E, and a compound including X (where M is one or two or more kinds of elements selected from Mn, Ce, Pr, Nd, Sm, Eu, Tb, Dy, and Yb; A is one or two or more kinds of elements selected from Li, Mg, Ca, Sr, Ba, and La; D is one or two or more kinds of elements selected from Si, Ge, Sn, Ti, Zr, and Hf; E is one or two or more kinds of elements selected from B, Al, Ga, In, Sc, and Y; and X is one or two or more kinds of elements selected from O, N, and F), may be satisfactorily used.
(81) As the starting material, the compound including M that is a single kind of substance or a mixture of at least two kinds of substances selected from the group consisting of metal, silicide, oxide, carbonate, nitride, oxynitride, chloride, fluoride and oxyfluoride, each of which includes M; the compound including A that is a single kind of substance or a mixture of at least two kinds of substances selected from the group consisting of metal, silicide, oxide, carbonate, nitride, oxynitride, chloride, fluoride, and oxyfluoride, each of which includes A; the compound including D that is a single kind of substance or a mixture of at least two kinds of substances selected from the group consisting of metal, silicide, oxide, carbonate, nitride, oxynitride, chloride, fluoride, and oxyfluoride, each of which includes D; and the compound including E that is a single kind of substance or a mixture of at least two kinds of substances selected from the group consisting of metal, silicide, oxide, carbonate, nitride, oxynitride, chloride, fluoride, and oxyfluoride, each of which includes E are desirable because they are easily available and have excellent stability. The compound including X that is a single substance or a mixture of at least two kinds of substances selected from the group consisting of oxide, nitride, oxynitride, fluoride, and oxyfluoride is desirable because the raw material is easily available and has excellent stability.
(82) In the case where a phosphor of the BaSi.sub.4Al.sub.3N.sub.9 crystal system activated by Eu is manufactured, it is preferable to use a starting material comprising, at least, nitride or oxide of europium; nitride, oxide, or carbonate of barium; silicon oxide or silicon nitride; and aluminum oxide or aluminum nitride since the reaction tends to easily proceed during the firing.
(83) Since the firing temperature is high and the firing atmosphere is an inert atmosphere containing nitrogen, an electric furnace of a metal resistance heating type or a graphite resistance heating type, in which a high temperature member of the furnace made of carbon is used, is suitable as a furnace for firing.
(84) The pressure range of the nitrogen-containing inert atmosphere is preferably in the range of at least 0.1 MPa and not exceeding 100 MPa because thermal decomposition of nitride or oxynitride of the starting material or the product thereof is suppressed. The nitrogen-containing inert atmosphere is preferably a nitrogen gas atmosphere. It is preferable that the oxygen partial pressure is 0.0001% or less in the firing atmosphere in order to suppress the oxidation reaction of nitride or oxynitride of the starting material or the product thereof.
(85) Here, the firing time is, although it differs depending on the firing temperature, usually 1 to 10 hours or so.
(86) In order to manufacture the phosphor in the form of powder or agglomeration, it would be preferable to utilize a method of firing raw materials after the raw materials are filled in a container with a filling rate kept at the bulk density of 40% or lower. It is possible to prevent particles from adhering with each other by maintaining the bulk density of 40% or lower in the filling rate. Here, the term relative bulk density means the ratio of a value (bulk density) given by dividing the mass of powder material filled in the container by the capacity of the container to the real density of the substance of the powder material. Unless otherwise noted, the relative bulk density is referred to as simply the bulk density.
(87) Various kinds of heat-resistant materials can be used for the container containing the mixture in firing the mixture of metal compounds. However, in view of a low adverse effect of material deterioration on the metal nitride used in the present invention, a container made of boron nitride material such as sintered boron nitride body or a boron nitride coated container, which is exemplified by a boron nitride coated graphite crucible used for synthesis of an α-sialon as described in a scientific journal of “Journal of the American Ceramic Society” Vol. 85, No. 5, pages 1229 to 1234 in 2002. When the firing is performed under such conditions, boron or boron nitride component is mixed into the product from the container, but, if the amount thereof is small, an effect of mixing is slight since the emission characteristics are not deteriorated. Further, durability of the product may be occasionally improved by the addition of a small amount of boron nitride thereto, and such addition may be preferable in some cases.
(88) In order to manufacture the phosphor in the form of powder or agglomeration, the mixture of metal compounds is in a powder form or an agglomeration form and it is preferable to make the mean particle diameter of these equal to or less than 500 μm since the mixture has excellent reactivity and handling characteristics.
(89) As a method of adjusting a particle size of the particle or agglomeration to be 500 μm or less, it is preferable to employ a spray dryer, sieving, or pneumatic classification since such a method has excellent operating efficiency and handling characteristics.
(90) In order to manufacture a phosphor in a powder form or an agglomeration form, it is preferable to employ a method of firing in which no external mechanical pressing is applied such as a pressureless sintering method and a gas pressure sintering method, but not a hot-pressing method.
(91) A mean particle diameter of phosphor powder is preferably 50 nm or more and 200 μm or less in terms of a volume-based median diameter (d50) because the emission intensity is high. The volume-based mean particle diameter can be measured, for example, by a Microtrac or a laser light scattering method. A mean particle diameter of phosphor powder synthesized by firing may be satisfactorily adjusted to be at least 50 nm and not exceeding 200 μm by applying at least one technique selected from pulverization, classification, and acid treatment.
(92) A defect included in powder and a damage caused by pulverization may be occasionally cured by heat-treating a phosphor powder after firing, a phosphor powder after pulverizing treatment, or a phosphor powder after adjusting a particle size at a temperature of at least 1,000° C. and not exceeding the firing temperature. The defect or damage may occasionally cause a decrease in the emission intensity, but the emission intensity recovers by the heat treatment.
(93) In the case of firing for synthesis of the phosphor, an inorganic compound to form a liquid phase at a temperature of a firing temperature or lower may be added and the firing is conducted. The inorganic compound to form the liquid phase may serve as a flux to promote the reaction and particle growth such that a stable crystal may be obtained and that the emission intensity may be occasionally improved.
(94) The inorganic compound to form the liquid phase at the temperature of the firing temperature or lower may include a single kind of or a mixture of two or more kinds of fluoride, chloride, iodide, bromide, or phosphate of one or two or more kinds of elements selected from Li, Na, K, Mg, Ca, Sr, and Ba. The inorganic compounds have different melting points, respectively, and therefore may be satisfactorily used properly depending on a synthesizing temperature.
(95) Further, the content amount of the inorganic compound forming the liquid phase at the temperature of the firing temperature or lower is decreased by washing the phosphor with a solvent after the firing. Thus, the emission intensity of the phosphor may occasionally become high.
(96) When the phosphor of the present invention is used in an application of a light-emitting device or the like, it is preferable to use the phosphor dispersed in a liquid medium. Further, the phosphor can also be used in the form of a phosphor mixture containing the phosphor of the present invention. A composition prepared by dispersing the phosphor of the present invention in the liquid medium is referred to as a phosphor-containing composition.
(97) As the liquid medium that can be used for the phosphor-containing composition of the present invention, any liquid medium can be selected depending on a purpose or the like, if the liquid medium shows liquid properties under desired use conditions to suitably disperse the phosphor of the present invention, and simultaneously does not cause an undesirable reaction or the like. As examples of the liquid medium, an addition reaction type silicone resin and a condensation reaction type silicone resin before curing, a modified silicone resin, an epoxy resin, a polyvinyl resin, a polyethylene resin, a polypropylene resin, a polyester resin, and so on are named. With respect to the liquid media, a single kind of liquid medium may be used by itself, or any combination of two or more kinds of liquid media with any combination ratio thereof may be used.
(98) An amount of used liquid medium or media may be appropriately adjusted depending on an application or the like. In general, the amount is in the range of generally 3 wt % or more and preferably 5 wt % or more, to generally 30 wt % or less and preferably 15 wt % or less in terms of the weight ratio of the liquid medium to the phosphor of the present invention.
(99) Further, the phosphor-containing composition of the present invention may contain, in addition to the phosphor and the liquid medium, any other component depending on an application or the like. As examples of the other component, a dispersing agent, a thickening agent, an extending agent, a buffering agent, and so on are named. Specifically, silica fine powder such as Aerosil, alumina, and so on may be named.
(100) The light-emitting device of the present invention comprises at least a light-emitting body or an emission source, and the phosphor wherein the phosphor includes at least the above-described phosphor of the present invention.
(101) As the light-emitting body or the emission source, there are an light-emitting diode (LED) light-emitting instrument, a laser diode (LD) light-emitting instrument, a semiconductor laser, an organic EL light-emitting body (OLED), a fluorescent lamp, and so on. The LED light-emitting device can be manufactured using the phosphor of the present invention and by a publicly known method which is described in Japanese Patent Application Publication No. H05(1993)-152609, Japanese Patent Application Publication No. H07(1995)-99345, Japanese Patent No. 2927279, or the like. In this case, the light-emitting body or the emission source is preferably what emits light of a wavelength from 280 nm to 450 nm. In particular, an LED light-emitting element emitting an ultraviolet (or violet) ray of a wavelength from 280 nm to 405 nm, or an LED light-emitting element emitting blue light in a wavelength from 405 nm to 450 nm is preferable. Such LED light-emitting elements include a nitride semiconductor such as GaN or InGaN, which can be an emission source of a predetermined wavelength by adjusting the composition.
(102) As a light-emitting device of the present invention, there are a white light-emitting diode, an illuminating device including a plurality of white light-emitting diodes, a backlight for a liquid crystal panel, and the like, which include the phosphor of the present invention, respectively.
(103) In such light-emitting devices, in addition to the phosphor of the present invention, the device may further include one or two or more kinds of phosphors selected from β-sialon phosphor activated with Eu, α-sialon yellow phosphor activated with Eu, Sr.sub.2Si.sub.5N.sub.8 orange phosphor activated with Eu, (Ca,Sr)AlSiN.sub.3 orange phosphor activated with Eu, and CaAlSiN.sub.3 red phosphor activated with Eu. As the yellow phosphor other than the above, for example, YAG:Ce, (Ca,Sr,Ba)Si.sub.2O.sub.2N.sub.2:Eu, and the like may be used.
(104) As one aspect of the light-emitting device of the present invention, there is a light-emitting device in which a light-emitting body or an emission source emits ultraviolet light or visible light having a peak wavelength of at least 280 nm and less than 450 nm such that the phosphor of the present invention emits light of blue-to-green color, which is mixed with light having a wavelength of at least 450 nm emitted by another phosphor of the present invention such that the light-emitting device emits light of a white color or light of another color other than the white color.
(105) As one aspect of the light-emitting device of the present invention, in addition to the phosphor of the present invention, a blue phosphor emitting light having a peak wavelength of at least 420 nm and not exceeding 500 nm by means of the light-emitting body or the emission source can further be included. As examples of such a blue phosphor, there are AlN:(Eu,Si), BaMgAl.sub.10O.sub.17:Eu, SrSi.sub.9Al.sub.19O.sub.31:Eu, LaSi.sub.9Al.sub.19N.sub.32:Eu, α-sialon:Ce, JEM:Ce, and so on.
(106) As one aspect of the light-emitting device of the present invention, in addition to the phosphor of the present invention, a green phosphor emitting light having a peak wavelength of at least 500 nm and not exceeding 550 nm by means of the light-emitting body or the emission source can further be included. As examples of such a green phosphor, there are β-sialon:Eu, (Ba,Sr,Ca,Mg).sub.2SiO.sub.4:Eu, (Ca,Sr,Ba)Si.sub.2O.sub.2N.sub.2:Eu, and so on.
(107) As one aspect of the light-emitting device of the present invention, in addition to the phosphor of the present invention, a yellow phosphor emitting light having a peak wavelength of at least 550 nm and not exceeding 600 nm by means of the light-emitting body or the emission source can further be included. As examples of such a yellow phosphor, there are YAG:Ce, α-sialon:Eu, CaAlSiN.sub.3:Ce, La.sub.3Si.sub.6N.sub.11:Ce, and so on.
(108) As one aspect of the light-emitting device of the present invention, in addition to the phosphor of the present invention, a red phosphor emitting light having a peak wavelength of at least 600 nm and not exceeding 700 nm by means of the light-emitting body or the emission source can further be included. As examples of such a red phosphor, there are CaAlSiN.sub.3:Eu, (Ca,Sr)AlSiN.sub.3:Eu, Ca.sub.2Si.sub.5N.sub.8:Eu, Sr.sub.2Si.sub.5N.sub.8:Eu, and so on.
(109) As one aspect of the light-emitting device of the present invention, a light-emitting device with high efficiency can be configured since the emission efficiency is high if an LED in which the light-emitting body or the emission source emits light having a wavelength of at least 280 nm and less than 450 nm is used.
(110) An image display device of the present invention comprises at least an excitation source and a phosphor and the phosphor comprises at least the above-described phosphor of the present invention.
(111) As the image display device, there are a fluorescent display (VFD), afield emission display (FED), a plasma display panel (PDP), a cathode-ray tube (CRT), a liquid crystal display (LCD), and so on. It has been confirmed that the phosphor of the present invention emits light by excitation of a vacuum ultraviolet ray of 100 to 190 nm, an ultraviolet ray of 190 to 380 nm, an electron beam, or the like, and the above image display devices can be configured by combining these excitation sources and the phosphor of the present invention.
(112) The phosphor of the present invention comprising, as the main component, an inorganic compound having a specific chemical composition has a white color as an object color, and thus can be used as a pigment or fluorescent pigment. That is, the object color of white is observed when the phosphor of the present invention is irradiated with sunlight or light from a fluorescent lamp or the like. In view of a good coloring and no degradation over a long period of time, the phosphor of the present invention is suitable for an inorganic pigment. Therefore, when the phosphor of the present invention is used for a paint, ink, color, glaze, colorant to be added to a plastic product or the like, a favorable coloring can be maintained at a high level for a long period of time.
(113) The phosphor of the present invention absorbs ultraviolet ray so as to be suitable also as the ultraviolet absorber. Thus, when the phosphor of the present invention is used as the paint or applied onto a surface of the plastic product or kneaded into an inside thereof, a shielding effect thereof against the ultraviolet ray is so high that the product may be effectively protected from the ultraviolet degradation.
EXAMPLE
(114) The present invention will be described in more detail with reference to the examples to be shown below, but these examples are disclosed only for the purpose of facilitating understanding of the present invention readily such that the present invention is not limited to these examples.
(115) [Raw Materials Used for Synthesis]
(116) The raw material powders used for the synthesis were: silicon nitride powder with a particle size of specific surface area of 11.2 m.sup.2/g, oxygen content of 1.29 wt %, and a type content of 95% (SN-E10 grade made by Ube Industries, Ltd.); aluminum nitride powder with a particle size of specific surface area of 3.3 m.sup.2/g and oxygen content of 0.82 wt % (E-Grade made by Tokuyama Corporation); aluminum oxide powder with a particle size of specific surface area of 13.2 m.sup.2/g (TAIMICRON made by Taimei Chemicals Co., Ltd.); lithium nitride powder (Li.sub.3N; made by Kojundo Chemical Laboratory Co., Ltd.); magnesium nitride powder (Mg.sub.3N.sub.2; made by Kojundo Chemical Laboratory Co., Ltd.); strontium nitride powder of 99.5% purity (Sr.sub.3N.sub.2; made by CERAC, Inc.); barium nitride powder of 99.7% purity (Ba.sub.3N.sub.2; made by CERAC, Inc.); europium nitride (EuN; obtained by nitriding metal through heating metal europium in an ammonia vapor flow at 800° C. for 10 hours); and lanthanum nitride (LaN; made by Kojundo Chemical Laboratory Co., Ltd.).
(117) [Synthesis and Structure Analysis of Crystal of the Present Invention]
(118) A mixture composition of silicon nitride (Si.sub.3N.sub.4), barium nitride (Ba.sub.3N.sub.2), aluminum nitride (AlN), europium nitride (EuN) in the molar ratios of 1.33:0.33:3:0.02 was designed. These raw material powders were weighed to be the above-mentioned mixture composition, and mixed for 5 minutes using a pestle and a mortar, each of them being made of sintered silicon nitride body. Next, the thus-obtained powder mixture was fed into a crucible made of sintered boron nitride body. A bulk density of the powder mixture (powder) was approximately 30%.
(119) The crucible containing the powder mixture was set into an electric furnace of a graphite resistance heating type. In the firing operation, first the firing atmosphere was made vacuum of 1×10.sup.−1 Pa or less with a diffusion pump, and heated from the room temperature to 800° C. at a rate of 500° C. per hour. Nitrogen of 99.999 vol % purity was introduced at 800° C. to raise the pressure inside the furnace to 1 MPa, and the temperature was further raised to 2000° C. at a rate of 500° C. per hour, and then the temperature was maintained for two (2) hours.
(120) A synthesized material was observed by means of an optical microscope and a crystal particle having a size of 80 μm×50 μm×3 μm was collected out of the synthesized material. The crystal particle was analyzed using a scanning electron microscope (SEM; SU1510 made by Hitachi High-Technologies Corp.) equipped with an energy dispersive elemental analyzer (EDS; QUANTAX made by Bruker AXS Inc.) so as to perform the elemental analysis for the elements included in the crystal particle. As a result, presence of Ba, Si, Al, N, and Eu elements was confirmed, and ratios of the respective number of contained atoms of Ba, Si, and Al were measured to be 1:4:3.
(121) Next, the crystal was fixed to a tip top of a glass fiber with an organic adhesive. An X-ray diffraction measurement of the crystal was performed under a condition in which an output of an X-ray source was 50 kV and 50 mA using a single crystal X-ray diffractometer with a rotating target of Mo Kα-line (SMART APEX II Ultra made by Bruker AXS Inc.). As a result, the crystal particle was confirmed to be a single crystal.
(122) Next, the crystal structure was determined using a single crystal structure analysis software (APEX2 made by Bruker AXS Inc.) from the results of X-ray diffraction measurement. The crystal structure data thus-obtained are shown in Table 1, and a diagram of the crystal structure is shown in
(123) It was found that this crystal belonged to the monoclinic system, and belonged to the space group P2(1)/C, (space group No. 14 of the International Tables for Crystallography), and the lattice constants a, b, and c were determined as follows:
(124) a=0.58465 nm;
(125) b=2.67255 nm;
(126) c=0.58386 nm;
(127) angle α=90°;
(128) β=118.897°; and
(129) γ=90°.
(130) Further, the atom positions were determined as shown in Table 1. Here, in the table, Si and Ai exist in the equivalent atom positions with a certain ratio which should be determined by the composition thereof. Also, while oxygen and nitrogen can occupy the sites which X is supposed to occupy in the sialon system crystal in general, since Ba is divalent (+2), Al is trivalent (+3), and Si is tetravalent (+4), if the atomic positions and an amount ratio of Ba, Al, and Si are given, the ratio of O and N which occupy (O, N) positions can be determined from the condition of the electrical neutrality of the crystal. This crystal obtained from the ratios of Ba:Si:Al measured by the EDS and the crystal structure data was BaSi.sub.4Al.sub.3N.sub.9:Eu.sup.2+ crystal, that is, the BaSi.sub.4Al.sub.3N.sub.9 crystal into which Eu.sup.2+ was solid-solved. Further, a difference between the starting material composition and the crystal composition might has been caused by formation of a small amount of a second phase having a composition other than BaSi.sub.4Al.sub.3N.sub.9. However, the analysis results show a structure of pure BaSi.sub.4Al.sub.3N.sub.9 because the single crystal was used in the measurement.
(131) When a similar composition thereof was examined, the BaSi.sub.4Al.sub.3N.sub.9 crystal was found to allow Li, Mg, Ca, Sr, or La to substitute partially or entirely Ba while the crystal structure remains the same. More specifically, the crystal of ASi.sub.4Al.sub.3N.sub.9 (A is one or two kinds of elements selected from Li, Mg, Ca, Sr, Ba and La) has a crystal structure identical to the crystal structure of the BaSi.sub.4Al.sub.3N.sub.9 crystal. Further, it was confirmed that Al could substitute partially Si, Si could substitute partially Al, and oxygen could substitute partially N, and that the crystal was one of the compositions of the crystal group having the same crystal structure as BaSi.sub.4Al.sub.3N.sub.9. From the condition of the electrical neutrality, it could also be described as the compositions represented by BaSi.sub.4−pAl.sub.3+pO.sub.pN.sub.9−p, MgSi.sub.4−pAl.sub.3+pO.sub.pN.sub.9−p, CaSi.sub.4−pAl.sub.3+pO.sub.pN.sub.9−p, SrSi.sub.4−pAl.sub.3+pO.sub.pN.sub.9−p, LaSi.sub.4−pAl.sub.3+pO.sub.pN.sub.9−p, LiSi.sub.4−pAl.sub.3+pO.sub.pN.sub.9−p, (Ba,Mg)Si.sub.4−pAl.sub.3+pO.sub.pN.sub.9−p, (Ba,Ca)Si.sub.4−pAl.sub.3+pO.sub.pN.sub.9−p, (Ba,Sr)Si.sub.4−pAl.sub.3+pO.sub.pN.sub.9−p, (Ba,La)Si.sub.4−pAl.sub.3+pO.sub.pN.sub.9−p, or (Ba,Li)Si.sub.4−pAl.sub.3+pO.sub.pN.sub.9−p (where 0≦p<4).
(132) From the crystal structure data, it was confirmed that the crystal was a new substance having not been reported so far. A powder X-ray diffraction pattern was calculated from the crystal structure data. The result is shown in
(133)
(134) Hereafter, it is possible to determine the formation of the BaSi.sub.4Al.sub.3N.sub.9 system crystal as shown in
Phosphor Examples and Comparative Example; Examples 1 to 14
(135) According to the design compositions as shown in Tables 2 and 3, raw materials were weighed to be raw material mixture compositions (mass ratios) as shown in Table 4. Although there may be a case where a design composition in Tables 2 and 3 and a corresponding raw material mixture composition in Table 4 show difference in the composition depending on the kind of each raw material to be used, the raw material mixture composition was determined such that the amount of each metal ion matches therebetween in such a case. Weighed raw material powders were mixed for 5 minutes using a pestle and a mortar made of silicon nitride sintered body such that a raw mixture of a mixture of metal compounds was obtained. Then, the raw material mixture in a powder condition was fed into a crucible made of boron nitride sintered body. A bulk density of the powder body was approximately from 20% to 30%.
(136) The crucible containing the raw material mixture was set into an electric furnace of a graphite resistance heating type. In the firing operation, first the firing atmosphere was made vacuum of 1×10.sup.−1 Pa or less with a diffusion pump, and heated from the room temperature to 800° C. at a rate of 500° C. per hour. Nitrogen of 99.999 vol % purity was introduced at 800° C. to raise the pressure inside the furnace to 1 MPa, and the temperature was further raised at a rate of 500° C. per hour up to each preset temperature as shown in Table 5, and then the temperature was maintained for two (2) hours.
(137) TABLE-US-00002 TABLE 2 Design compositions (atomic ratios) in examples and comparative example D E A element element element X element Example M element Ba Li Mg Sr La Si Al O N Comparative 1 1 4 3 9 example Example 2 Eu 0.1 0.9 4 3 9 Example 3 Eu 0.1 0.9 3 4 9 Example 4 Eu 0.1 0.5 0.4 4 3 9 Example 5 Eu 0.1 0.5 0.4 4 3 9 Example 6 Eu 0.1 0.5 0.4 3.5 3.5 9 Example 7 Eu 0.05 0.95 4 3 9 Example 8 Eu 0.15 0.85 4 3 9 Example 9 Eu 0.25 0.75 4 3 9 Example 10 Eu 0.5 0.5 4 3 9 Example 11 Eu 0.75 0.25 4 3 9 Example 12 Eu 0.1 0.4 0.5 4 3 0.5 8.5 Example 13 Eu 0.1 0.9 3 4 1 8 Example 14 Eu 0.1 0.9 2 5 2 7
(138) TABLE-US-00003 TABLE 3 Design compositions (parameters) in examples and comparative example D element E element A element (e) (f) (g) X element (h) Example M element (d) Ba Li Mg Sr La Si Al O(h1) N(h2) Comparative 1 0.058824 0.235294 0.176471 0.529412 example Example 2 Eu 0.005882 0.052941 0.235294 0.176471 0.529412 Example 3 Eu 0.005882 0.052941 0.176471 0.235294 0.529412 Example 4 Eu 0.005882 0.029412 0.023529 0.235294 0.176471 0.529412 Example 5 Eu 0.005882 0.029412 0.023529 0.235294 0.176471 0.529412 Example 6 Eu 0.005882 0.029412 0.023529 0.205882 0.205882 0.529412 Example 7 Eu 0.002941 0.055882 0.235294 0.176471 0.529412 Example 8 Eu 0.008824 0.05 0.235294 0.176471 0.529412 Example 9 Eu 0.014706 0.044118 0.235294 0.176471 0.529412 Example 10 Eu 0.029412 0.029412 0.235294 0.176471 0.529412 Example 11 Eu 0.044118 0.014706 0.235294 0.176471 0.529412 Example 12 Eu 0.005882 0.023529 0.029412 0.235294 0.176471 0.029412 0.5 Example 13 Eu 0.005882 0.052941 0.176471 0.235294 0.058824 0.470588 Example 14 Eu 0.005882 0.052941 0.052941 0.117647 0.294118 0.117647 0.411765
(139) TABLE-US-00004 TABLE 4 Raw material mixture compositions (mass ratios) in examples and comparative example Raw material mixture compositions (mass ratios) Example Si3N4 AiN Al203 Li3N Mg3N2 Sr3N2 Ba3N2 LaN EuN Comparative 1 40.96 26.93 32.11 example Example 2 40.79 26.82 28.78 3.62 Example 3 30.60 35.76 30.02 3.62 Example 4 45.24 29.75 3.26 17.74 4.02 Example 5 42.63 28.03 8.84 16.71 3.78 Example 6 35.72 31.31 16.00 13.35 3.62 Example 7 40.87 26.87 30.44 1.81 Example 8 40.70 26.76 27.12 5.42 Example 9 40.53 26.65 23.83 8.99 Example 10 40.11 26.37 15.72 17.80 Example 11 39.70 26.10 7.78 26.42 Example 12 47.42 27.72 4.31 1.47 14.87 4.21 Example 13 30.53 29.74 7.40 28.72 3.61 Example 14 20.31 32.65 14.77 28.67 3.61
(140) TABLE-US-00005 TABLE 5 Firing conditions in examples and comparative example Firing conditions Temperature Ambient pressure Time Example (° C.) (Mpa) (hour) Comparative example 1 1800 1 2 Example 2 1800 1 2 Example 3 1800 1 2 Example 4 1800 1 2 Example 5 1800 1 2 Example 6 1800 1 2 Example 7 1800 1 2 Example 8 1800 1 2 Example 9 1800 1 2 Example 10 1800 1 2 Example 11 1800 1 2 Example 12 1800 1 2 Example 13 1800 1 2 Example 14 1800 1 2
(141) Next, each synthesized compound was ground using an agate mortar and the powder X-ray diffraction measurement using Cu Kα-line was carried out. Main formation phases are shown in Table 6. Further, from the EDS measurement, it was confirmed that synthesized compounds of Examples 2 to 11 included an rare earth element, an alkali earth metal, Si, Al, and N; and that synthesized compounds of Examples 12 to 14 included an rare earth element, an alkali earth metal, Si, Al, O, and N. Further, with respect to the synthesized compound of Example 12, Li was analyzed using the mass spectrometer. Specifically, the synthesized compound was irradiated with laser light of the wavelength of 213 nm with a beam diameter of 30 μm emitted by the Nd:YAG laser made by New Wave Research, Inc. and the Li element sublimated from the synthesized compound was analyzed by the ICP mass spectrometer.
(142) An X-ray diffraction pattern of any one of examples matched satisfactorily the X-ray diffraction pattern of the BaSi.sub.4Al.sub.3N.sub.9:Eu.sup.2+ crystal obtained by the structure analysis as shown in
(143) TABLE-US-00006 TABLE 6 Main formation phases in examples and comparative example Main formation phases Example Main phase Comparative example 1 Crystal structure identical to that of Table 1 Example 2 Crystal structure identical to that of Table 1 Example 3 Crystal structure identical to that of Table 1 Example 4 Crystal structure identical to that of Table 1 Example 5 Crystal structure identical to that of Table 1 Example 6 Crystal structure identical to that of Table 1 Example 7 Crystal structure identical to that of Table 1 Example 8 Crystal structure identical to that of Table 1 Example 9 Crystal structure identical to that of Table 1 Example 10 Crystal structure identical to that of Table 1 Example 11 Crystal structure identical to that of Table 1 Example 12 Crystal structure identical to that of Table 1 Example 13 Crystal structure identical to that of Table 1 Example 14 Crystal structure identical to that of Table 1
(144) As shown in Table 6, it was confirmed that the synthesized compounds of the examples according to the present invention had 20 mass % or more of a phase having the identical crystal structure to that of the crystal represented by BaSi.sub.4Al.sub.3N.sub.9 as the main formation phase. In Example 4, the synthesized compound was confirmed to include Eu, Ba, Mg, Si, Al, and N from the measurement by means of EDS. In addition, the ratios of Eu:Ba:Mg:Si:Al were confirmed to be 0.1:0.5:0.4:4:3. Here, the difference between the mixed raw material composition and the chemical composition of the synthesized compound suggests that a slight amount of impurity second phase was mixed in the synthesized compound.
(145) As mentioned above, it was confirmed that the synthesized compounds of examples according to the present invention were inorganic compounds comprising the BaSi.sub.4Al.sub.3N.sub.9 system crystal into which the activating element M such as Eu was solid-solved.
(146) After firing, the thus-obtained synthesized compound (sintered body) was crushed coarsely and further ground by hand using a crucible and mortar made of silicon nitride sintered body, and then allowed to pass a 30 μm-mesh sieve. When the particle size distribution was measured, the mean particle diameter was 3 to 8 μm.
(147) As a result of irradiating light of wavelength of 365 nm emitted by the lamp onto these powder samples, it was confirmed that these powder samples emitted light of blue-to-green color. An emission spectrum and an excitation spectrum of the powder were measured using a spectrophotofluorometer. The result is shown in
(148)
(149) TABLE-US-00007 TABLE 7 Excitation emission characteristics in examples and comparative example Excitation Emission peak peak Emission wavelength wavelength intensity Example (nm) (nm) (arbitrary unit) Comparative example 1 Not emitted Example 2 296 471 0.29 Example 3 287 468 0.29 Example 4 324 477 1.17 Example 5 291 465 0.29 Example 6 296 460 0.24 Example 7 296 466 0.28 Example 8 297 466 0.24 Example 9 301 466 0.31 Example 10 307 475 0.44 Example 11 331 477 0.33 Example 12 368 473 1.86 Example 13 299 480 0.23 Example 14 368 525 0.35
(150) According to
(151) According to Table 7, it was confirmed that the synthesized compounds of the present invention could be excited by an ultraviolet ray of 250 nm to 380 nm and violet or blue light of 380 nm to 450 nm and were phosphors to emit blue-to-green light.
(152) As mentioned above, it was found that the synthesized compounds of examples according to the present invention were inorganic compounds comprising the BaSi.sub.4Al.sub.3N.sub.9 system crystal into which the activating element M such as Eu was solid-solved and that the inorganic compounds were phosphors. According to Tables 3 and 7, it should be understood that a phosphor exhibiting blue-to-green color emission can be obtained by controlling the composition to a specific composition.
(153)
(154) According to Table 4, it was confirmed that the synthesized compounds obtained in Example 4 had a white color as an object color and was excellent in the coloration. Here, the diagram is shown in black and white due to the regulation of the application documents, but the original picture is in color and the color figure is readily submitted upon request. Although not shown in the figure, synthesized compounds of other Examples also exhibited a similar object color. The inorganic compounds of the synthesized compounds according to the present invention exhibited the object color of white by irradiation of the sunlight or an illumination such as a fluorescent lamp such that it was found that they could be utilized for the pigment or the fluorescent pigment.
Examples of Light-Emitting Device and Image Display Device; Examples 15 to 18
(155) Next, a light-emitting device utilizing the phosphor of the present invention will be described.
Example 15
(156)
(157) A so-called bullet-type white light-emitting diode lamp (1) shown in
(158) In the present embodiment, a phosphor powder prepared by mixing the blue phosphor prepared for Example 4, the green phosphor prepared for Example 14, a red phosphor of CaAlSiN.sub.3:Eu was mixed into epoxy resin at the concentration of 35 wt %, and this resultant mixture was dropped in an appropriate amount with a dispenser such that the first resin (6) was formed to have blended phosphor (7) dispersed therein. The light emitted by the thus-obtained light-emitting device had an emission color of white and characterized by x=0.33 and y=0.33 in the color coordinates.
Example 16
(159)
(160) A chip-type white light-emitting diode lamp (11) for board-mounting as shown in
(161) A material prepared by mixing the first resin (16) and a phosphor (17) prepared by blending the blue phosphor prepared for Example 4 and a yellow phosphor represented by α-sialon:Eu is mounted in the vicinity of the light-emitting diode element. The first resin in which this phosphor is dispersed is transparent, and covers the entire violet light-emitting diode element (14). Also, a wall surface member (20) having a hole opened at the center portion is fixed to the ceramic board. The wall surface member (20) has the center portion formed as the hole in which the violet light-emitting diode element (14) and the resin (16) having the phosphor (17) dispersed therein are contained and the portion of the hole facing the center is made to be a slope. This slope is a reflective surface for taking out light forward, and the shape of the curved surface of the slope is determined in consideration of the direction of light reflection. Further, at least the surface which constitutes the reflective surface forms a surface having high visible light reflectance with white color or metallic luster. In the present example, the wall surface member (20) is configured with white silicone resin. The hole at the center portion of the wall surface member is formed with a recess as the final shape of the chip-type light emitting diode lamp, and is filled up with second transparent resin (18) to seal all of the violet light-emitting diode element (14) and the first resin (16) in which the phosphor (17) is dispersed. In the present example, the same epoxy resin was used for both the first resin (16) and second resin (18). The attained chromaticity and the like are approximately identical to those in Example 15.
(162) Next, an example of design of an image display device using the phosphor of the present invention will be described.
Example 17
(163)
(164) A red phosphor (CaAlSiN.sub.3:Eu) (31), a green phosphor (32) prepared for Example 14, and the blue phosphor (33) prepared for Example 4 are applied to inner surfaces of the respective cells (34, 35, 36), which are arranged via electrodes (37, 38, 39) and a dielectric layer (41) over a glass substrate (44). If electric power is supplied to the electrodes (37, 38, 39, 40), a vacuum ultraviolet ray is generated by Xe discharge in each of the cells, thereby exciting the respective phosphors so as to emit visible light of a red color, a green color, or a blue color such that the emitted light may be observed from the outside through a protective layer (43), a dielectric layer (42), and a glass substrate (45) so as to serve as an image display device.
Example 18
(165)
(166) The blue phosphor (56) prepared for Example 4 of the present invention is applied to an interior surface of an anode (53). By applying a voltage between a cathode (52) and a gate (54), electrons (57) are emitted from an emitter (55). The electrons are accelerated by the voltage between the anode (53) and cathode, and impinge on the blue phosphor (56) to excite the phosphor to emit light. The entire device is protected by a glass (51). Although the drawing shows a single light emission cell comprising one emitter and one phosphor, a display is actually configured to emit light of a variety of color by arranging many cells for a red color and a green color in addition to for a blue color. Although the phosphors to be used for cells for a green color and a red color are not particularly specified, a phosphor which exhibits high brightness under a low speed electron beam is preferable.
INDUSTRIAL APPLICABILITY
(167) The phosphor of the present invention has different emission characteristics (emission color and excitation characteristics, emission spectrum) from those of the conventional phosphor, exhibits high emission intensity in the case where it is combined with a LED of less than 450 nm, is chemically and thermally stable, and further has little degradation in the intensity of the phosphor when it is exposed to the excitation source for a long period of time such that it is a phosphor to be used suitably for the VFD, the FED, the PDP, the CRT, the white LED and LCD. It is expected that the phosphor of the present invention will be utilized in material design in various kinds of display devices so as to contribute to the development of the industry.
EXPLANATION OF NUMERALS
(168) 1 bullet-type light-emitting diode lamp. 2, 3 lead wire. 4 light-emitting diode element. 5 bonding wire. 6, 8 resin. 7 phosphor. 11 chip-type white light-emitting diode lamp for 11 board-mounting. 12, 13 lead wire. 14 light-emitting diode element. 15 bonding wire. 16, 18 resin. 17 phosphor. 19 alumina ceramic board. 20 wall surface member. 31 red phosphor. 32 green phosphor. 33 blue phosphor. 34, 35, 36 ultraviolet ray emission cell. 37, 38, 39, 40 electrode. 41, 42 dielectric layer. 43 protective layer. 44, 45 glass substrate. 51 glass. 52 cathode. 53 anode. 54 gate. 55 emitter. 56 phosphor. 57 electrons.