CN109415628B - Phosphor and light emitting device - Google Patents
Phosphor and light emitting device Download PDFInfo
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- CN109415628B CN109415628B CN201780040405.XA CN201780040405A CN109415628B CN 109415628 B CN109415628 B CN 109415628B CN 201780040405 A CN201780040405 A CN 201780040405A CN 109415628 B CN109415628 B CN 109415628B
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 126
- 239000002245 particle Substances 0.000 claims abstract description 21
- 230000003213 activating effect Effects 0.000 claims abstract description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 230000005284 excitation Effects 0.000 claims description 4
- 230000001678 irradiating effect Effects 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 37
- 230000007774 longterm Effects 0.000 abstract description 8
- 230000004913 activation Effects 0.000 abstract description 3
- 238000004020 luminiscence type Methods 0.000 abstract 1
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- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 3
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- AEBZCFFCDTZXHP-UHFFFAOYSA-N europium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Eu+3].[Eu+3] AEBZCFFCDTZXHP-UHFFFAOYSA-N 0.000 description 3
- RSEIMSPAXMNYFJ-UHFFFAOYSA-N europium(III) oxide Inorganic materials O=[Eu]O[Eu]=O RSEIMSPAXMNYFJ-UHFFFAOYSA-N 0.000 description 3
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- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 3
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- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910052692 Dysprosium Inorganic materials 0.000 description 2
- 229910052691 Erbium Inorganic materials 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910052779 Neodymium Inorganic materials 0.000 description 2
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- 229910052771 Terbium Inorganic materials 0.000 description 2
- 229910052775 Thulium Inorganic materials 0.000 description 2
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- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 2
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
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- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 2
- 239000006200 vaporizer Substances 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910012506 LiSi Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229910007991 Si-N Inorganic materials 0.000 description 1
- 229910006294 Si—N Inorganic materials 0.000 description 1
- ZVLDJSZFKQJMKD-UHFFFAOYSA-N [Li].[Si] Chemical compound [Li].[Si] ZVLDJSZFKQJMKD-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- PSBUJOCDKOWAGJ-UHFFFAOYSA-N azanylidyneeuropium Chemical compound [Eu]#N PSBUJOCDKOWAGJ-UHFFFAOYSA-N 0.000 description 1
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- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 1
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- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
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- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 238000007561 laser diffraction method Methods 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
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- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
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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
- C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
- C09K11/77348—Silicon Aluminium Nitrides or Silicon Aluminium Oxynitrides
-
- 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
- C09K11/55—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing beryllium, magnesium, alkali metals or alkaline earth metals
-
- 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
- C09K11/64—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/50—Wavelength conversion elements
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/50—Wavelength conversion elements
- H01L33/501—Wavelength conversion elements characterised by the materials, e.g. binder
- H01L33/502—Wavelength conversion materials
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Power Engineering (AREA)
- Luminescent Compositions (AREA)
- Led Device Packages (AREA)
Abstract
Provided is a Li-alpha sialon phosphor which is reduced in the decrease in luminance with time and has excellent long-term stability. A Li-alpha sialon phosphor having a particle size of 10 particles/nm on the surface thereof2The above existing ratio is bonded with stable OH groups, and contains a light-emitting activation element. The luminescence activating element is preferably Eu, and preferably Li is contained in a proportion of 1.8 mass% or more and 3.0 mass% or less, and Eu is contained in a proportion of 0.1 mass% or more and 1.5 mass% or less.
Description
Technical Field
The present invention relates to a Li- α sialon phosphor, a light-emitting element having the phosphor and a light-emitting source, and a light-emitting device having the light-emitting element.
Background
The characteristics of light emitting elements, in particular, white light emitting diodes (white LEDs), which synthesize the following light to emit secondary mixed light are now being greatly improved: light emitted from a blue light emitting diode (blue LED) or a Laser Diode (LD) as a light emitting source; and a phosphor which absorbs a part of the light source having a high energy and a short wavelength as excitation light and converts the light into light of another color having a long wavelength. The white LED generally has a structure in which, for example, a blue LED as a light emitting source is sealed with a sealing material such as a resin containing a phosphor, and the phosphor is generally used as a yellow phosphor or as a combination of a red phosphor and a green phosphor, and is finely dispersed in the sealing resin.
As a red phosphor used for the white LED, for example, α sialon phosphor is cited. Further, as a modification thereof, there are known: an activating element for emitting light as an alpha sialon phosphorThe phosphor host crystal (referred to as an emission activating element) which is solid-dissolved to destabilize the whole body, that is, a part of voids in the α sialon phosphor crystal further contains Ca2+Thus, stabilization of the parent crystal is achieved, for example, by the general formula: caxEuySi12-(m+n)Al(m+n)OnN16-nA Ca-. alpha.sialon phosphor is shown (see patent document 1).
In recent years, studies have been made on further improvement in luminance of α sialon phosphors and reduction in wavelength of fluorescence spectrum, and it has been proposed to use Li+Li- α sialon phosphors as metal ions for stabilizing the structure of a phosphor matrix crystal (see patent documents 2 to 4).
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent publication No. 2002-363554
Patent document 2: international publication No. 2007/004493 pamphlet
Patent document 3: japanese laid-open patent publication No. 2010-202738
Patent document 4: international publication No. 2010/018873 pamphlet
Disclosure of Invention
Problems to be solved by the invention
The above Li- α sialon phosphor achieves an improvement in luminance and a reduction in wavelength as compared with the Ca- α sialon phosphor, but when a light-emitting element using the Li- α sialon phosphor is used for a long time, another problem not observed in the light-emitting element using the Ca- α sialon phosphor is caused, such that luminance of the light-emitting element is lowered with time, and it is required to solve the problem. The purpose of the present invention is to provide a Li-alpha sialon phosphor having excellent long-term stability with little decrease in luminance with time, a light-emitting element using the Li-alpha sialon phosphor, and a light-emitting device provided with the light-emitting element.
The present inventors have conducted investigations on the influence of the nature or the presence ratio of water molecules present in the vicinity of the surface of a Li- α sialon phosphor (in the present application, the vicinity of the surface and the surface are collectively referred to as the surface) and OH groups bonded to the surface on the change with time of the luminance of a light-emitting element using the Li- α sialon phosphor, and as a result, have found that the greater the presence ratio of OH groups (referred to as stable OH groups) stably bonded to the surface of the phosphor, the less the decrease with time of the luminance is, even in a particularly high temperature environment, and have completed the present invention.
Means for solving the problems
Namely, the invention is as follows:
(1) a Li-alpha sialon phosphor having a particle size of 10 particles/nm on the surface thereof2The above existing ratio is bonded with stable OH groups, and contains a light-emitting activation element.
(2) Preferably, the emission-activating element contained in the Li-. alpha.sialon phosphor is Eu.
(3) The Li content of the Li- α sialon phosphor is preferably 1.8 mass% or more and 3.0 mass% or less.
(4) Preferably, the Eu content of the Li-. alpha.sialon phosphor is 0.1 mass% or more and 1.5 mass% or less.
(5) The oxygen content of the Li- α sialon phosphor is preferably 0.4 mass% or more and 1.3 mass% or less.
(6) A light-emitting element comprising the Li-. alpha.sialon phosphor according to any one of (1) to (5) above and a light-emitting source for irradiating the phosphor with excitation light.
(7) Preferably, the light emitting source of the light emitting element is a light emitting diode or a laser diode.
(8) A light-emitting device comprising the light-emitting element according to the above (6) or (7).
ADVANTAGEOUS EFFECTS OF INVENTION
The present invention provides a light-emitting element including a Li- α sialon phosphor having improved long-term stability with less reduction in luminance with time, and a light-emitting device using the light-emitting element.
Detailed Description
One embodiment of the present invention is a methodLi-alpha sialon phosphor with 10 particles/nm on the surface2The above existing ratio is bonded with stable OH groups, and contains a light-emitting activation element. The Li-. alpha.sialon phosphor of the present invention is generally represented by the following formula: lixAySi12-(m+n)Alm+nOnN16-n(x + y. ltoreq.2, and m ═ x +2 y). In the above general formula, Li represents lithium, element a is a light-emitting active element, for example, one or two or more elements selected from Mn, Ce, Pr, Nd, Sm, Eu, Tb, Dy, Er, Tm, and Yb, Si represents silicon, Al represents aluminum, O represents oxygen, and N represents nitrogen. The Li-. alpha.sialon phosphor is an α -silicon nitride crystal in which a part of Si-N bonds is replaced by Al-N bonds and Al-O bonds, and Li and an element A enter into a part of voids solid-dissolved in the crystal in order to maintain electrical neutrality, and the values of m and N in the general formula correspond to the replacement ratios of the Al-N bonds and the Al-O bonds, respectively. In the case of the Li- α sialon phosphor, the range of the m value that can maintain the entire structure is 0.5 or more and 2 or less, and the range of the n value is 0 or more and 0.5 or less.
The Li- α sialon phosphor of the present invention is also included, and usually, moisture having different physical and chemical binding forces exists in the form of water molecules and OH groups or is bonded to the surface of an object. In the present invention, the moisture adsorbed or bonded to the surface of the Li — α sialon phosphor is defined as follows. That is, when the Li- α sialon phosphor is heated under atmospheric pressure, the moisture desorbed from the phosphor at a heating temperature of less than 200 ℃ is referred to as "physically adsorbed water", the moisture desorbed from the phosphor at a heating temperature of less than 400 ℃ other than the "physically adsorbed water" is referred to as "unstable OH group", and the moisture desorbed from the phosphor only when heated to 400 ℃ or higher is referred to as "stable OH group". The stable OH group is an OH group which is released from the surface of the phosphor and is measured when the temperature of the phosphor sample is set to 400 ℃ or higher in the Karl Fischer's method of moisture analysis. The Li-. alpha.sialon phosphor of the present invention may satisfy the predetermined condition concerning the existence ratio of the stable OH groups.
In addition, the term "at 10 atoms/nm" as used in the present invention2The phrase "stable OH groups are bonded to each other at the above ratio" means that the calculated value of the stable OH groups obtained by, for example, water content analysis by Karl Fischer's method is 1nm on average2The number of the unit areas of (2) is 10 or more. If the stable OH groups are present in a proportion of less than 10 groups/nm2The adhesion between the phosphor in the light-emitting element and the sealing material is insufficient, and the luminance is liable to decrease with time. In order to solve the problem of the present invention, the stable OH groups are present in a proportion of at least 10 groups/nm2Above, preferably 25/nm2More preferably 30/nm or more2More than, and even more preferably 35/nm2The above.
The Li- α sialon phosphor of the present invention can be produced through the following steps: a raw material mixing step of mixing various phosphor raw materials to prepare a mixed raw material; a baking step of baking the mixed raw materials to obtain mainly a Li-alpha sialon phosphor; a crushing step of crushing or pulverizing the fired body obtained in the firing step, if necessary; an acid treatment step of removing impurities and the like by immersing the substrate in an acidic liquid as required; a classification step of making the sizes uniform as required; and a heating step of reheating the Li-. alpha.sialon phosphor under atmospheric pressure and at a temperature not higher than the temperature in the baking step to adjust the proportion of stable OH groups present. The proportion of stable OH groups in the Li-. alpha.sialon phosphor of the present invention can be increased by the heat treatment step.
In the Li- α sialon phosphor of the present invention, if the Li content ratio is too small in the firing step, the progress of crystal grain growth in the step of firing the phosphor crystal tends to be very slow, and it is difficult to obtain large particles having high emission luminance. In addition, if the Li content is excessive, LiSi may be formed during firing2N3And the like (referred to as impurities and the like). Therefore, the mass ratio of Li based on the Li — α sialon phosphor containing various impurities and the like immediately after the firing step is preferably 1.8 mass% or more and 3.0 mass% or less. The Li content can be adjusted by the phosphorBatch compounding. Specifically, the amount can be adjusted by increasing or decreasing the mixing ratio of lithium nitride and lithium oxide as the Li-containing raw material.
In the Li- α sialon phosphor of the present invention, for the purpose of fine adjustment of the fluorescence characteristics, a part of Li of the general formula may be substituted with 1 or more kinds of substitution elements selected from the group consisting of Mg, Ca, Y and lanthanoid (except La, Ce, Eu) while maintaining the electroneutrality. Accordingly, in one embodiment of the Li- α sialon phosphor of the present invention, Li is partially substituted with 1 or more of such substitution elements.
The general formula of the Li-alpha sialon phosphor of the present invention is: lixAySi12-(m+n)Alm+nOnN16-nThe element a in (x + y ≦ 2, and m ═ x +2y) is an element that plays a role of light emission of the above phosphor (referred to as a light-emission active element). As the element a, one or two or more elements selected from Mn, Ce, Pr, Nd, Sm, Eu, Tb, Dy, Er, Tm, and Yb can be selected, and among them, Eu is preferably used.
If the amount of the element a as the light-emission-activating element is too small, the contribution to light emission is small, and the fluorescence intensity tends to be low, whereas if the amount is increased to a certain concentration or more, the emission luminance tends to be small due to a phenomenon that is considered to be concentration quenching due to energy transfer between the elements a, and therefore, for example, when Eu is selected as the element a, the amount is preferably 0.1 mass% or more and 1.5 mass% or less. The Eu content can be adjusted by mixing the raw materials of the phosphor. Specifically, the ratio of europium oxide to europium nitride in the Eu-containing raw material can be adjusted by increasing or decreasing the ratio.
The content of oxygen in the Li- α sialon phosphor of the present invention is preferably 0.4 mass% or more and 1.3 mass% or less, depending on the luminance. If the oxygen content in the phosphor raw material is too small and less than 0.4 mass%, the growth of crystal grains in the firing step tends to be small, and it tends to be difficult to obtain a phosphor with high luminance, whereas if the oxygen content exceeds 1.3 mass%, the fluorescence spectrum tends to be broad, and sufficient luminance tends not to be obtained.
The Li- α sialon phosphor of the present invention is a phosphor based on α sialon as a host crystal thereof and further containing elements such as Li and Eu in the α sialon, and may contain crystal phases such as silicon nitride, aluminum nitride, lithium silicon nitride, and solid solutions thereof, which are generated as by-products, as long as the influence on the fluorescence characteristics is small. The purity of the Li- α sialon phosphor is preferably 95% by mass or more, more preferably 97% by mass or more, and still more preferably 98% by mass or more as the purity is higher. The upper limit value is not particularly limited, and may be, for example, substantially 99 mass% or less. The purity of the Li- α sialon phosphor can be determined from the ratio of the crystal phase identified by powder X-ray diffraction (also referred to as XRD) using CuK α line using an X-ray diffraction device (for example, UltimaIV manufactured by Rigaku Corporation).
The compound as a raw material of the Li- α sialon phosphor of the present invention is a compound containing a Si source, an Al source, a Eu source, and a Li source. Specific examples thereof include silicon nitride powder, aluminum nitride powder, europium oxide powder, and lithium nitride powder. It is preferable to prepare each raw material in a powder state in advance.
In the raw material mixing step, first, raw materials of a phosphor other than the lithium nitride powder, such as silicon nitride powder, aluminum nitride powder, and europium oxide powder, are mixed at a desired ratio. In view of industrial productivity, the mixing is preferably performed by wet mixing. As the solvent used for the wet mixing, for example, ethanol can be used. After wet mixing, the solvent is removed, dried and crushed to obtain a premixed powder. This premixed powder is further mixed with a lithium nitride powder in a desired ratio to obtain a raw material mixed powder. The mixing of the premixed powder and the lithium nitride powder is preferably performed in an inert gas atmosphere such as nitrogen gas in order to avoid hydrolysis.
The raw material mixed powder is calcined to obtain, for example, a Li- α sialon phosphor activated with Eu. The crucible used for the firing is preferably made of a material physically and chemically stable in a high-temperature atmosphere, and is preferably made of a high-melting-point metal such as boron nitride, carbon, molybdenum, tantalum, or the like. The firing atmosphere is not particularly limited, and is usually carried out in an inert gas atmosphere or a reducing gas atmosphere. The inert gas or the reducing gas may be used alone in 1 kind, or may be used in combination of any 2 or more kinds at any combination ratio. Examples of the inert gas and the reducing gas include hydrogen, nitrogen, argon, and ammonia, and nitrogen is preferably used. The pressure of the firing atmosphere is selected according to the firing temperature. The higher the atmospheric pressure is, the higher the decomposition temperature of the phosphor is, and in view of industrial productivity, it is preferable to perform the decomposition under a pressure of about 0.02 to 1.0MPa gauge pressure. It is not preferable that the firing temperature is less than 1650 ℃ because crystal defects and unreacted residual amount of the matrix crystal increase, and more than 1900 ℃ because the matrix crystal is decomposed. Therefore, the firing temperature is preferably 1650 to 1900 ℃. If the firing time is short, crystal defects and the amount of unreacted residual material in the mother crystal become large, and if the firing time is long, it is not preferable in view of industrial productivity. Therefore, it is preferably set to 2 to 24 hours. The Li- α sialon phosphor obtained in the firing step may be crushed and classified to have a desired particle size as required in the subsequent operations.
Since the crystal ratio of the Li- α sialon phosphor obtained immediately after the firing step is generally not sufficiently high, and it is difficult to express desired fluorescence characteristics as it is, the crystal ratio of the Li- α sialon phosphor can be increased by acid treatment with a mixed solution of hydrofluoric acid and nitric acid, for example.
The Li- α sialon phosphor of the present invention is generally used as fine particles because it is finely dispersed in a sealing resin of a light emitting element, and the Li- α sialon phosphor of the present invention tends to have low fluorescence intensity when its particle diameter is too small, and tends to have uneven chromaticity of a light emitting color or uneven color of a light emitting color when it is too large in an LED sealed with a resin or the like containing a phosphor, and therefore the average primary particle diameter represented by a volume-based median diameter (D50) by a laser diffraction/scattering method of the Li- α sialon phosphor of the present invention is preferably 7 μm or more and 35 μm or less. Therefore, in order to obtain a phosphor having high luminance and not causing color unevenness, it is preferable to subject the Li- α sialon phosphor of the present invention, which has been appropriately crushed, to acid treatment, and then to provide a classification step to remove fine particles. The classification step may be carried out by any of wet and dry methods, and is preferably carried out by, for example, an elutriation classification in which an acid-treated Li- α sialon phosphor is dispersed in a mixed solvent of ion-exchanged water and sodium hexametaphosphate as a dispersant, or in a mixed alkaline solvent of ion-exchanged water and ammonia water, and the difference in settling rate after standing due to the difference in particle size, or a dry classification using a sieve.
The crystal ratio of the Li- α sialon phosphor, which is generally effective, is increased by the acid treatment step and the classification step, and thus a phosphor having high emission efficiency can be obtained. Therefore, in the present invention, the following new findings have been found: the presence ratio of water molecules and OH groups present or bonded on the surface of the Li- α sialon phosphor has an effect on the change with time in luminance of a light-emitting element including the phosphor; further, the present ratio of stably bonded OH groups (stable OH groups) among OH groups bonded to the surface of the Li-. alpha.sialon phosphor can be adjusted, and the invention of the Li-. alpha.sialon phosphor which is less likely to cause a decrease in luminance with time has been completed. In order to obtain a Li-. alpha.sialon phosphor capable of providing a light-emitting element having little decrease in luminance with time and excellent long-term stability, the proportion of stable OH groups that are unlikely to be eliminated from the Li-. alpha.sialon phosphor even in a high-temperature environment is set to 10 groups/nm2The above steps are carried out. In order to adjust the presence ratio of stable OH groups, specifically, the Li-. alpha.sialon phosphor is preferably subjected to heat treatment. The atmosphere during the heat treatment is not particularly limited, but an atmosphere of air, nitrogen gas or hydrogen gas is preferred, and an atmosphere of air is particularly preferred. The heat treatment temperature at the time of heat treatment is preferably 1000 ℃ or less, more preferably 700 ℃ or less, and still more preferably 500 ℃ or less, at least in order to leave stable OH groups, which are released only at 400 ℃ or more, on the surface. The lower limit of the heat treatment temperature is preferably 100 ℃ or more, more preferably 200 ℃ or more, and still more preferably 400 ℃ or more. When the heat treatment temperature is 1000 ℃ or higher, the Li-. alpha.sialon phosphor itself deteriorates in characteristics, and the luminance is lowered. On the other hand, when the temperature is 100 ℃ or higher, the proportion of stable OH groups present can be adjusted by adjusting the holding time. The time for heating the Li- α sialon phosphor varies depending on the heating temperature, and is preferably 3 hours or more, and in view of mass production efficiency, less than 20 hours. However, in the present invention, the existence ratio of stable OH groups stably bonded to the surface of the Li-. alpha.sialon phosphor is set to 10 groups/nm2The heating temperature and the holding time are not particularly limited.
The second embodiment of the present invention is a light-emitting element including the Li- α sialon phosphor and a light-emitting source according to the first embodiment of the present invention. The light-emitting source is preferably an LED or LD that emits monochromatic light having a peak wavelength of 240nm or more and 480nm or less. This is because monochromatic light having a peak wavelength of 240nm or more and 480nm or less exists in the peak wavelength region of the blue LED most used, and the Li- α sialon phosphor is excited with good light efficiency at a wavelength in the above range to emit light with high luminance.
The light-emitting element including the Li- α sialon phosphor of the present invention and the light-emitting source can be manufactured, for example, as follows. First, the phosphor of the present invention is mixed with a sealing material to prepare a paste. For example, the slurry may be adjusted by mixing the components at a ratio of 30 to 50 parts by mass per 100 parts by mass of the sealing material. Examples of the sealing material include thermoplastic resins, thermosetting resins, and photocurable resins. Specific examples thereof include methacrylic resins such as polymethyl methacrylate; styrene resins such as polystyrene and styrene-acrylonitrile copolymers; a polycarbonate resin; a polyester resin; a phenoxy resin; a butyral resin; polyvinyl alcohol; cellulose resins such as ethyl cellulose, cellulose acetate, and cellulose acetate butyrate; an epoxy resin; a phenolic resin; silicone resins, and the like. In addition, an inorganic material, for example, a solution obtained by hydrolytic polymerization of a solution containing a metal alkoxide, a ceramic precursor polymer, or a metal alkoxide by a sol-gel method, or a combination thereof, and an inorganic material having a siloxane bond, for example, may be used. In the case of a sealing portion (for example, an outer cover, a dome-shaped sealing portion, or the like) which can be externally attached without being in direct contact with the LED chip, a fusion-process glass may be used. The number of the sealing materials may be 1, or 2 or more in any combination and ratio.
Among the sealing materials, a resin which is thermosetting and has fluidity at normal temperature is more preferably used for reasons of dispersibility and moldability. As the resin having thermosetting properties and fluidity at normal temperature, for example, a silicone resin is used. Examples thereof include Dow Corning Toray co., ltd. product name: JCR6175, OE6631, OE6635, OE6636, OE6650, etc.
Next, for example, 3 to 4. mu.L of the paste is injected into a top-view package on which a blue LED chip having a peak emission wavelength of 460nm is mounted. The top view package injected with the slurry is heated at a temperature of 140 to 160 ℃ for 2 to 2.5 hours to cure the slurry. Thus, a light-emitting element which absorbs light having a wavelength in the range of 420 to 480nm and emits light having a wavelength exceeding 480nm and not more than 800nm can be manufactured.
When the long-term stability of a light-emitting device including the Li- α sialon phosphor as the first embodiment of the present invention as the second embodiment of the present invention is evaluated in use, for example, a light-emitting device sample in which a blue light-emitting diode and a phosphor are combined is actually produced, and an energization test is performed while the light-emitting device sample is left in a high-temperature and high-humidity environment, the evaluation can be made by a light flux retention (%) obtained from each total light flux measurement value immediately after the start of the energization test and after a predetermined time has elapsed. Since the luminous flux value immediately after the start of the energization test is taken as a reference, the luminous flux retention after a predetermined time is desirably close to 100%.
A third embodiment of the present invention is a light-emitting device including the light-emitting element. More specific examples of the light-emitting device according to the present invention include devices for displaying information such as traffic lights and display devices, and lighting devices such as headlights of vehicles such as automobiles, incandescent lamps, and fluorescent lamps.
Examples
The following table shows the results of comparing examples of the present invention with comparative examples.
< example 1>
A method for producing the phosphor of example 1 will be described. The phosphor is produced through a step of mixing raw materials and a step of firing.
(raw material mixing step)
The phosphor of example 1 was made of Si as a raw material3N4(E10 grade manufactured by Uyu Kyoho Co., Ltd.), AlN (F grade manufactured by Tokuyama Corporation), Eu2O3(RU grade manufactured by shin & Etsu chemical Co., Ltd.), Li3N powder (purity 99.5% by mass; manufactured by Material Co., Ltd.), -60 mesh). First, to become Si3N4：AlN：Eu2O384.5: 14.8: the powders were weighed and mixed so as to have a mol ratio of 0.64, to obtain a premixed powder.
Mixing the premixed powder with the Li3N powder in nitrogen atmosphere in the amount of moles (Si) as a premixed powder3N4AlN and Eu2O3Total number of moles): li3The mol number of N is 94.1: 5.9 to obtain a raw material mixed powder.
(baking Process)
The raw material mixed powder was charged into a boron nitride crucible in a glove box, and the mixture was calcined at 1800 ℃ for 8 hours in a pressurized nitrogen atmosphere at a gauge pressure of 0.8MPa by an electric furnace of a carbon heater to obtain a Eu-activated Li-. alpha.sialon phosphor.
(grinding step)
Since the particle shape of the Eu-activated Li- α sialon phosphor after firing is large and massive, the phosphor is pulverized by a dry pulverizer such as a roll mill or a jet mill, and the particles that pass through the sieve having a mesh size of 45 μm are selected.
(acid treatment Process)
The Eu-activated Li-. alpha.sialon phosphor after the classification is immersed in at least 300mL (80 ℃) of a mixed solution of hydrofluoric acid and nitric acid with respect to 100g of the phosphor, thereby being subjected to acid treatment.
(classifying step)
200g of the Li-. alpha.sialon phosphor after the acid treatment was allowed to stand in a sufficient amount of at least 2L of a mixed solvent of ion-exchanged water and sodium hexametaphosphate as a dispersant for 10 minutes, thereby removing fine particles having a particle size of 5 μm or less.
(Heat treatment Process)
The Li-. alpha.sialon phosphor after the classification step was filled in a magnetic crucible and heat-treated at 200 ℃ for 3 hours in an electric furnace in an atmospheric atmosphere to obtain Eu-activated Li-. alpha.sialon of the present invention shown in example 1.
< example 2>
The same production method as in example 1 was carried out except that the Eu-activated Li — α sialon of example 2 was annealed at 500 ℃ for 3 hours in the air under the conditions of the heat treatment step.
< example 3>
The same production method as in example 1 was carried out except that the Eu-activated Li — α sialon of example 3 was annealed at 700 ℃ for 3 hours in the air under the conditions of the heat treatment step.
< example 4>
The same production method as in example 1 was carried out except that the Eu-activated Li — α sialon of example 4 was annealed at 1100 ℃ for 3 hours in the air under the conditions of the air heating step.
< comparative example 1>
The Eu-activated Li — α sialon of comparative example 1 was obtained by the same production method as in example 1, except that the acid treatment step, the classification step, and the heat treatment step were omitted in the production steps of example 1.
< comparative example 2>
The Eu-activated Li — α sialon of comparative example 2 was obtained by the same production method as in example 1, except that the heat treatment step was omitted in the production step of example 1.
(Process for producing light-emitting element)
The phosphors of examples 1 to 4 and comparative examples 1 and 2 were mixed in a ratio of 30 parts by mass with respect to 100 parts by mass of a silicone resin (product name: JCR6175, manufactured by Dow Corning Toray Co., Ltd.) to prepare a paste. Then, 3 to 4 μ L of the above slurry was injected into a top view type package mounted with a blue LED chip having a peak wavelength of 460 nm. The top-view type package containing the paste was heated at 150 ℃ for 2 hours to cure the paste, thereby producing a light-emitting element of a 150mA rating as a sample.
The results of simple comparison and evaluation of the phosphors of examples 1 to 4 and comparative examples 1 and 2 (the above are collectively referred to as examples and the like) are shown in table 1. Table 1 shows the presence/absence of the acid treatment step and the classification step, the temperature of the heat treatment step, and the proportion of stable OH groups (unit: unit/nm) present in examples and the like2) Peak wavelength (unit: nm), median particle diameter (unit: μ m), the ratio of the α sialon crystal to the entire crystal phase (unit: %), fluorescence intensity (unit: %), light flux retention rate of LED (unit: %).
(identification of the main Crystal phase)
For each phosphor of examples and the like, a crystal phase was identified by powder X-ray diffraction (XRD) using CuK α line using an X-ray diffraction apparatus (UltimaIV manufactured by Rigaku Corporation). The X-ray diffraction patterns of the phosphors obtained in examples 1 to 4 and comparative examples 1 and 2 were observed to be the same as those of the Li-. alpha.sialon crystal, and it was confirmed that the main crystal phase was Li-. alpha.sialon.
(determination of OH number)
The stable OH groups in the present invention were quantified using the Karl Fischer method. Karl Fischer's measurement was carried out using a water vaporizer VA-122 manufactured by Mitsubishi chemical corporation and a water measuring device CA-100 manufactured by Mitsubishi chemical corporation, and AQUAMICRON AX (manufactured by Mitsubishi chemical corporation) as an anolyte of the water measuring device and AQUAMICRON CXU (manufactured by Mitsubishi chemical corporation) as a catholyte. The background value was fixed at 0.10 (. mu.g/sec) in the Karl Fischer measurement, and the measurement was continued until the detected moisture was lower than the background value. The measurement was carried out at 550 ℃. During the heat treatment, the phosphor sample was introduced into a Karl Fischer apparatus together with 300 ml/min of high-purity argon, without exposing the phosphor sample to the outside air, and the amount of water was measured. This was carried out using 4g of sample introduced into the moisture vaporizer.
< conversion of moisture content into OH number >
Since it is considered that the moisture detected in karl fischer measurement is 1 water molecule formed by condensation of 2 OH groups, the number of OH groups per unit area is calculated by the following formula:
number of OH groups per unit area (number/nm)2) 0.0668 × water content (ppm)/specific surface area (m) of phosphor sample2/g)
Note that 0.0668 as a coefficient of the above calculation formula is a coefficient for matching left and right units.
< measurement of specific surface area >
The specific SURFACE area was measured using AUTOMATIC SURFACace ANALYZER MODEL-4232-2 (Roman numerals) manufactured by Microdata.
(median particle diameter (D50))
The median particle diameter (D50) (average primary particle diameter) of each phosphor of examples and comparative examples was measured in the following manner. First, hydrofluoric acid (concentration range of 46-48 g/100ml) and nitric acid (concentration range of 60g/100ml) were mixed in a ratio of 1: 1 was diluted 4 times with distilled water to prepare a treatment solution. The treatment liquid was heated to 80 ℃ and the phosphors of examples and comparative examples were added to 100ml of the treatment liquid in an amount of 20g or less while stirring, and dispersed. The phosphor was dispersed and left to stand for 1 hour, and insoluble powder was recovered by decantation. The recovered insoluble powder was washed with water and dried. The particle size distribution of the dried insoluble powder was measured by a laser diffraction scattering particle size distribution measuring apparatus (Beckman Coulter, LS 13320, manufactured by inc.) and the particle size at 50% cumulative volume basis was defined as the median particle size (D50).
For each of the phosphors of examples and comparative examples, a fluorescence spectrum and a peak wavelength at an excitation wavelength of 455nm were measured using rhodamine B and a spectrofluorometer calibrated with an auxiliary light source (Hitachi High-Technologies Corporation, F-7000), and using a solid sample holder attached to the photometer.
(fluorescence intensity)
The fluorescence intensity is calculated from the product of the fluorescence spectral intensity and the relative visibility of the CIE standard. The unit is arbitrary because it varies depending on the measurement apparatus and conditions, and examples and comparative examples measured under the same conditions are compared with each other. The fluorescence intensity of example 1 was set as 100% as a reference. The acceptable value was indicated when the fluorescence intensity was 85% or more.
(evaluation of Long-term stability of light-emitting element)
Next, the change rate of the total luminous flux value was measured for the light-emitting devices including the phosphor particles of examples and comparative examples, and the luminous flux retention was calculated to evaluate the long-term stability in use. For the measurement of the change in the total luminous flux, for example, a light-emitting element sample of a rated current of 150mA in which a blue light-emitting diode and a phosphor are combined is prepared according to the high-temperature high-humidity bias test and the test method 102A of the environment and durability test method (life test 1 (roman numeral)) of a semiconductor device of the electronic information technology industry association standard JEITA ED-4701/100a, and an energization test is performed for 1000 hours in a state where light is emitted under energization of 150mA at a relative humidity of 85 ℃ and 85 RH%, and the luminous flux retention (%) immediately after the elapse of 1000 hours with respect to the value after the start of the test is obtained and evaluated. The light flux retention after 1000 hours is preferably 95% or more. The luminous flux of fluorescence emitted from the light-emitting element sample was measured by using a total luminous flux measuring system (Half Moon: Otsuka electronic HH 41-0773-1).
As shown in Table 1, the Li-. alpha.sialon phosphors of examples 1 to 4 had a larger proportion of stable OH groups than those of comparative examples, and 10 groups/nm2Above, the proportion of α sialon crystals is also high. This provides a light-emitting device which has high fluorescence intensity, and which is reduced in light emission efficiency and electrical defects even when used for a long time.Since the light-emitting elements using the phosphors of examples 1 to 4 have many stable OH groups, the possibility of causing electrical failure such as short circuit is extremely low by improving the adhesion to the resin, and a long life is presumed. Since the Li- α sialon phosphors of example 4 have many stable OH groups, the Li- α sialon phosphors of examples 1 to 3 have high luminous flux maintaining rates in the same manner, but the light emission efficiency of the phosphors tends to be slightly lowered due to the high temperature in the heat treatment step.
In contrast, in comparative example 1, since stable OH groups were small and the proportion of Li-. alpha.sialon crystals was low, the fluorescence intensity was low and the luminous flux maintenance rate was also low. Comparative example 2 shows that the Li- α sialon phosphor in the range of the prior art has a high fluorescence intensity due to a high proportion of Li- α sialon crystals, but has few stable OH groups and a low light flux retention rate, and is judged to have poor long-term stability.
[ Table 1]
Claims (6)
1. A Li-alpha sialon phosphor having a ratio of 10 particles/nm on the surface thereof2The Li-alpha sialon phosphor has an oxygen content of 0.4 to 1.3 mass%, a Li content of 1.8 to 3.0 mass%, and a purity of 98 mass% or more.
2. The Li- α sialon phosphor according to claim 1, wherein the light emission activating element is Eu.
3. The Li- α sialon phosphor according to claim 1 or 2, wherein the Eu content is 0.1 mass% or more and 1.5 mass% or less.
4. A light-emitting element comprising the Li- α sialon phosphor according to any one of claims 1 to 3 and a light-emitting source for irradiating the phosphor with excitation light.
5. The light-emitting element according to claim 4, wherein the light-emitting light source is a light-emitting diode or a laser diode.
6. A light-emitting device comprising the light-emitting element according to claim 4 or 5.
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| WO2019150910A1 (en) * | 2018-02-02 | 2019-08-08 | デンカ株式会社 | β-SIALON FLUORESCENT MATERIAL, PRODUCTION METHOD THEREFOR, AND LIGHT EMITTING DEVICE |
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| JP2014221890A (en) * | 2013-05-14 | 2014-11-27 | 三菱化学株式会社 | Phosphor, phosphor-containing composition, light-emitting device, image display device, and lighting device |
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| WO2008004640A1 (en) * | 2006-07-05 | 2008-01-10 | Ube Industries, Ltd. | Sialon-base oxynitride phosphors and process for production thereof |
| JP2009132916A (en) * | 2007-11-09 | 2009-06-18 | Mitsubishi Chemicals Corp | Fluorescent substance and its preparing method |
| CN102099436A (en) * | 2008-08-13 | 2011-06-15 | 宇部兴产株式会社 | Li-containing alpha-sialon fluorescent substance and method for manufacturing same, illumination device, and image display device |
| JP2010196049A (en) * | 2009-01-30 | 2010-09-09 | Mitsubishi Chemicals Corp | Phosphor and method for producing the same, phosphor-containing composition, and light-emitting device, image display device and lighting device using the phosphor |
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| WO2013073598A1 (en) * | 2011-11-15 | 2013-05-23 | 三菱化学株式会社 | Nitride phosphor and method of producing same |
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| CN103275705A (en) * | 2013-06-21 | 2013-09-04 | 北京有色金属研究总院 | Fluorescent powder, preparation method thereof and light-emitting device comprising same |
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| TW201802229A (en) | 2018-01-16 |
| WO2018003848A1 (en) | 2018-01-04 |
| JP6987054B2 (en) | 2021-12-22 |
| CN109415628A (en) | 2019-03-01 |
| KR20190024903A (en) | 2019-03-08 |
| KR102380907B1 (en) | 2022-03-31 |
| JPWO2018003848A1 (en) | 2019-04-18 |
| TWI802542B (en) | 2023-05-21 |
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