WO2006132188A1 - Procédé de production de cristal inorganique - Google Patents

Procédé de production de cristal inorganique Download PDF

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Publication number
WO2006132188A1
WO2006132188A1 PCT/JP2006/311239 JP2006311239W WO2006132188A1 WO 2006132188 A1 WO2006132188 A1 WO 2006132188A1 JP 2006311239 W JP2006311239 W JP 2006311239W WO 2006132188 A1 WO2006132188 A1 WO 2006132188A1
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compound
precursor
particles
crystal
nitride
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PCT/JP2006/311239
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Japanese (ja)
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Naoto Hirosaki
Takayuki Suehiro
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National Institute For Materials Science
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Priority to JP2007520093A priority Critical patent/JP5212691B2/ja
Publication of WO2006132188A1 publication Critical patent/WO2006132188A1/fr

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    • 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
    • C09K11/0883—Arsenides; Nitrides; Phosphides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B21/00—Nitrogen; Compounds thereof
    • C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
    • C01B21/0602—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with two or more other elements chosen from metals, silicon or boron
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B21/00—Nitrogen; Compounds thereof
    • C01B21/082—Compounds containing nitrogen and non-metals and optionally metals
    • C01B21/0821—Oxynitrides of metals, boron or silicon
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/30—Particle morphology extending in three dimensions
    • C01P2004/32—Spheres

Definitions

  • the present invention relates to the production of nitride or oxynitride powders. More specifically, phosphor applications such as CaAISi N crystal powder or CaAlSiN crystal activated with optically active elements
  • Phosphors are used in fluorescent display tubes (VFD), field emission displays (FED), plasma display panels (PDP), cathode ray tubes (CRT), white light emitting diodes (LEDs), and the like.
  • VFD fluorescent display tubes
  • FED field emission displays
  • PDP plasma display panels
  • CRT cathode ray tubes
  • LEDs white light emitting diodes
  • the phosphor in order for the phosphor to emit light, it is necessary to supply the phosphor with energy for exciting the phosphor, and the phosphor is not suitable for vacuum ultraviolet rays, ultraviolet rays, electron beams, blue light, etc. It is excited by a high energy excitation source and emits visible light.
  • the luminance of the phosphor tends to decrease.
  • sialon phosphors have been proposed as phosphors with little reduction in luminance in place of phosphors such as conventional silicate phosphors, phosphate phosphors, aluminate phosphors, and sulfide phosphors. .
  • Patent Document 1 a phosphor based on a CaAlSiN crystal was synthesized from a nitride powder such as calcium nitride, aluminum nitride, silicon nitride, and europium nitride. .
  • a nitride powder such as calcium nitride, aluminum nitride, silicon nitride, and europium nitride.
  • calcium nitride and europium nitride are unstable in the air, and the powder mixing and preparation work must be performed in a glove box that is shut off from the air, and the production process is complicated. It was.
  • calcium nitride and europium nitride powder are difficult to obtain high-purity and high-quality raw materials, and the quality of synthetic products is reduced.
  • Patent Document 1 Japanese Unexamined Patent Publication No. 2006-8721
  • Patent Document 2 Japanese Patent Publication No. 4-60050
  • Patent Document 3 Japanese Patent Laid-Open No. 2005-306692
  • Patent Document 4 Japanese Patent Laid-Open No. 2002-97006
  • Patent Document 5 Japanese Patent Publication No. 7-91043
  • An object of the present invention is to provide a fine nitride or oxynitride powder which is suitable for phosphor use and has no coloration due to contamination with impurities.
  • the present inventors have conducted extensive research on a method of reacting a gas in a reducing nitriding atmosphere with a precursor compound containing an element constituting nitride or oxynitride. Those with a specific precursor composition are fired by the firing reaction such as CaAlSiN crystals.
  • At least an element of M, Si, Al, or O (where M is one or more elements selected from Mg, Ca, Sr, and Ba), and if necessary, R Element (where R is Mn, Ce, Pr, Nd, Eu, Tb, Dy, Er, Tm, Yb or more)
  • M is one or more elements selected from Mg, Ca, Sr, and Ba
  • R Element where R is Mn, Ce, Pr, Nd, Eu, Tb, Dy, Er, Tm, Yb or more
  • the precursor compound is synthesized by heat treatment in a reducing nitriding atmosphere to reduce the oxygen content in the precursor and increase the nitrogen content.
  • An inorganic crystal mainly composed of the nitride or oxynitride is CaAlSiN or SrAl
  • An inorganic crystal mainly composed of the nitride or oxynitride is CaAlSiN, SrAlSiN,
  • a compound in which the precursor compound becomes silicon dioxide, silicon oxynitride or silicon nitride by heating SiH compound SiX
  • M oxide, oxynitride or nitride by heating A compound (compound MX) which becomes aluminum oxide, aluminum oxynitride or aluminum nitride by heating (Ich compound A1X), and, if necessary, an R oxide, oxynitride or nitride by heating.
  • Compound SiX is silicon dioxide (SiO 2), silicon oxynitride (Si N O), silicon nitride (Si N
  • Force is one or a mixture of two or more selected, compound MX, M oxide, water
  • Compound A1X Strength Aluminum oxides, hydroxides, alkoxides, carbonates One or a mixture of two or more selected from salts, nitrates, and chlorides.
  • the method for producing an inorganic crystal according to (8) above which is one or a mixture of two or more selected from oxides, hydroxides, alkoxides, carbonates, nitrates, and chlorides of R.
  • the precursor compound is obtained by dispersing SiX particles in a solution in which MX, A1X, and RX as required are dissolved in a solvent, and then drying and removing the solvent. M on the particle surface,
  • the precursor compound is dissolved in an aqueous solution in which MX, A1X, and RX as necessary are dissolved.
  • the precursor compound is dissolved in an aqueous solution in which MX, A1X, and RX as necessary are dissolved.
  • the compound of (8) to (13) above which is a compound obtained by carrying out a caloric heat treatment on a complex citrate by decomposing and removing the citrate by adding citrate after dispersing X, drying and dehydrating.
  • M is an element of R relative to an inorganic compound containing one or more elements selected from Mg, Ca, Sr, and Ba (where R is Mn, Ce, Pr, After adding a compound containing one or more elements selected from Nd, Eu, Tb, Dy, Er, Tm, and Yb, firing is performed at a temperature of 1200 ° C to 2000 ° C in a nitrogen-containing atmosphere.
  • R is Mn, Ce, Pr
  • a method for producing an inorganic crystal characterized in that a phosphor having R activated in 3 is obtained.
  • the inorganic crystalline phosphor obtained by the production method of the present invention is finer and higher in purity than the conventional inorganic crystalline powder, and is suitable as a phosphor.
  • Such fine phosphor powder is suitable for VFD, FED, PDP, CRT, white LED, etc., and it is highly significant to provide novel and useful materials in material design in this kind of field. It is expected to greatly contribute to the development of
  • FIG. 1 is an SEM photograph of the precursor of Example 1.
  • FIG. 2 is an X-ray diffraction pattern of the composite of Example 1.
  • FIG. 3 is an X-ray diffraction pattern of the composite of Example 2.
  • FIG. 4 is a flowchart showing the procedure of Example 1.
  • FIG. 5 is an excitation emission spectrum of the synthesized product of Example 7.
  • the precursor compound contains at least an element of M, Si, Al, O (wherein M is one or more elements selected from Mg, Ca, Sr, Ba), As needed Element (where R is Mn, Ce, Pr, Nd, Eu, Tb, Dy, Er, Tm, Yb, or one element selected from two or more elements), and optionally N element Use things. Since oxides, hydroxides, or a mixture thereof can provide high-purity raw materials, when these are used as precursors, high-purity inorganic crystals suitable for optical applications can be obtained.
  • the elements M, Si, and Al are metal elements that constitute an inorganic crystal for optical use.
  • an inorganic crystal an inorganic crystal having the same crystal structure as CaAlSiN or SrAlSiN is synthesized.
  • nitride or oxynitride suitable for the phosphor or the host crystal for the phosphor can be obtained.
  • the form of an inorganic crystal mainly composed of a nitride or oxynitride as a main component is not limited.
  • a powder form is desirable.
  • the particle size varies depending on the application.
  • nanophosphors it is recommended to use nanopowders of about 50 nm to 500 nm as starting materials.
  • a raw material powder with a particle size of 50nm to 5 ⁇ m is used, and a particle size of 1 ⁇ m to 10zm during the heat treatment. It can be made to grow. Further, the grain growth treatment may be performed by performing a heat treatment at a higher temperature after the heat treatment.
  • the precursor compound a mixture of compounds of respective elements of M, R, Si, and Al can be used, and a plurality of elements such as M—A1— ⁇ and Si—A1— ⁇ —N can be used. Inorganic compounds and mixtures thereof can be used.
  • the precursor compound when a mixture of compounds of respective elements of M, R, Si, and Al is used, the precursor compound can be prepared by the following method.
  • a compound that becomes silicon dioxide, silicon oxynitride, or silicon nitride by heating SiH compound SiX
  • SiH compound SiX silicon dioxide, silicon oxynitride, or silicon nitride by heating
  • oxide, oxynitride, or nitride of M by heating.
  • a compound (compound MX) a compound that becomes aluminum oxide, aluminum oxynitride or aluminum nitride by heating, and an R oxide, oxynitride or nitride by heating if necessary.
  • the compound that becomes silicon dioxide by heating is a compound that becomes silicon dioxide when heated in air, an atmosphere containing oxygen, or in an inert atmosphere, and is heated to oxynitride or nitride.
  • SiX Element (SiO: silica glass, silica sol, silica gel, crystalline silica, etc.), silicon oxynitride (Si
  • silicon nitride Si N: diamond crystal, / 3 crystal, amorphous, etc.
  • the compound that becomes an oxide of M by heating is a compound that becomes an oxide of M when heated in air, an atmosphere containing oxygen, or an inert atmosphere.
  • a compound that becomes a nitride is a compound that becomes an oxynitride or nitride of M when heated in an atmosphere containing a nitrogen element in a gas or an inert atmosphere that constitutes a gas such as nitrogen or ammonia.
  • MX include M oxide, hydroxide, anoloxide, carbonate, nitrate, chloride, fluoride, organic acid salt, and citrate salt.
  • the compound that becomes aluminum oxide by heating is a compound that becomes aluminum oxide when heated in air, in an atmosphere containing oxygen, or in an inert atmosphere, and is heated to aluminum oxynitride or aluminum nitride.
  • A1X include A1 oxides, hydroxides, alkoxides, carbonates, nitrates, chlorides, fluorides, organic acid salts, citrates, and the like.
  • the compound that becomes an oxide of R when heated is a compound that becomes an oxide of R when heated in air, an atmosphere containing oxygen, or in an inert atmosphere.
  • a compound that becomes a nitride is a compound that becomes an oxynitride or nitride when heated in an atmosphere containing a nitrogen element in a molecule constituting a gas such as nitrogen or ammonia or in an inert atmosphere. It is.
  • RX it is possible to list R oxides, hydroxides, alkoxides, carbonates, nitrates, chlorides, fluorides, organic acid salts, citrates, and the like.
  • the crystalline or amorphous material represented by 1) or a mixture thereof is preferable because the composition close to the target composition can be selected and the target product can be obtained in high yield.
  • the target product can be obtained in high yield.
  • the ratio of O to N in the precursor is preferably a composition in which O is larger than the proportion of the final product.
  • the ability to obtain a predetermined composition by terminating the reaction when the ⁇ / N ratio reaches a predetermined value controlled by the time of the firing reaction. S can.
  • the amount of oxygen and nitrogen contained in the inorganic crystal containing nitride or oxynitride as a main component as a main component is
  • a composition satisfying this relationship is preferable for optical applications because the luminance when the phosphor host is used is increased.
  • the average particle size of SiX is 2
  • MX and A1X react on the Si X surface during heating, and the target inorganic crystals are efficiently formed at a relatively low temperature. Nearly fine inorganic crystals can be synthesized.
  • silicon dioxide and silicon nitride are particularly excellent starting materials because SiX provides reactivity and fine powder.
  • the particle diameter is defined as the diameter of a sphere with an equivalent settling velocity in the measurement by the settling method, and as the diameter of a sphere with an equivalent scattering characteristic in the laser scattering method.
  • the particle size distribution is referred to as particle size distribution.
  • the average particle size D50 is defined as the particle size when the sum of masses larger than a certain particle size occupies 50% of the total powder.
  • the sample was dispersed in water to which sodium hexamethacrylate was added as a dispersant, and the volume-based integrated frequency distribution with respect to the particle diameter was measured using a laser scattering type measuring device.
  • the volume and weight distributions are the same.
  • the particle diameter corresponding to 50% in this cumulative (cumulative) frequency distribution was determined and used as the average particle diameter D50.
  • the average particle diameter is based on the median value (D50) of the particle size distribution measured by the particle size distribution measuring means by the laser scattering method described above.
  • D50 median value
  • Various means other than those described above have been developed to determine the average particle diameter, and there are still some differences in the measured values. The meaning and significance are clear and are not necessarily limited to the above means.
  • the method for obtaining the precursor in such a form is not particularly defined.
  • a precursor in which the adhesion form is efficiently controlled can be obtained.
  • SiX particles preferably silicon dioxide or silicon nitride particles
  • a precursor compound in the form of M, R and A1 salts attached to the surface is obtained.
  • MX, RX, and A1X in an aqueous solution SiX is uniformly dispersed, and citrate is added while stirring to add MX, RX, and A1X citrate to the surface of the SiX particles. It is possible to cite a method of baking and synthesizing a compound compound precursor compound obtained by drying and dehydrating after depositing the salt.
  • MX used here may be M nitrate or chloride
  • RX may be R nitrate or chloride
  • A1X may be aluminum nitrate or chloride.
  • MX, RX, and A1X were dissolved in water or solvent, and SiX was uniformly dispersed in this, and then MX, RX, and A1X adhered to the surface of the SiX particles obtained by spray drying.
  • a method of firing the precursor compound can be mentioned.
  • the precursor compound is subjected to a heat treatment in a reducing nitridation atmosphere to reduce the oxygen content in the precursor and increase the nitrogen content, so that the oxynitride or nitride is reduced.
  • Reduction nitriding treatment for generating inorganic crystals is performed.
  • the atmospheric gas used for the reductive nitriding treatment may be a mixed gas of a gas containing nitrogen element and a reducing gas such as hydrogen or hydrocarbon.
  • Ammonia gas or a mixed gas of ammonia gas and hydrocarbon gas is preferred.
  • it can be set as mixed gas with comparatively inert gas, such as nitrogen gas and a noble gas (for example, argon gas) as needed.
  • a noble gas for example, argon gas
  • ammonia gas it is considered that hydrogen in ammonia removes oxygen in the precursor, and nitrogen in ammonia is taken into the precursor instead.
  • a mixed gas of ammonia gas and hydrocarbon gas is used, the hydrocarbon gas and oxygen in the precursor react to be removed as H0 and CO, and nitrogen in ammonia is taken into the precursor instead.
  • the hydrocarbon gas needs to be a gas under the reaction conditions, and a short-chain hydrocarbon gas such as methane, propane or LNG is used.
  • the ratio of hydrocarbon to ammonia in the mixed gas is preferably 3% by volume or less. If it exceeds 3% by volume, carbon may precipitate during firing and remain in the powder.
  • the optimum gas flow rate which varies depending on the reaction vessel, is generally considered to be a value of 0.01 to 0.1 lm / sec.
  • the reaction temperature is 1200 ° C to 1800 ° C, preferably 1300 ° C to 1600 ° C. Within this temperature range, fine powders can be obtained when fired at low temperatures, and powders with a slightly larger particle size and good crystallinity can be obtained when fired at high temperatures.
  • reaction time varies depending on the composition and type of the raw material powder, it should end when the oxygen content reduction and nitrogen content increase due to gas reduction nitriding reach the theoretical value of the target inorganic crystals.
  • the typical reaction time is preferably 0.5 to 5 hours.
  • a fluoride, chloride, sulfate, phosphate, boron of an element selected from calcium, potassium, and aluminum is used as a precursor compound in order to promote a gas reduction nitridation reaction.
  • Reduced nitriding atmosphere after adding one or more reaction accelerators Heat treatment can be performed in an atmosphere. Since these reaction accelerators generate a liquid phase at high temperatures and diffusion becomes active, the reaction proceeds efficiently. In addition, since grain growth is also promoted, it is better to add these reaction accelerators, especially when producing powders with large particle sizes.
  • the ratio should be in the range of 0.5g to 20g per 100g of precursor compound.
  • the amount is less than 5 g, the reaction promoting effect is small.
  • the amount is more than 20 g, another composition is easily formed, which is not preferable.
  • a solvent water, organic solvent, acid
  • an aqueous solution of one or more of hydrofluoric acid, sulfuric acid, hydrochloric acid, and nitric acid has a high effect of removing the reaction accelerator.
  • the kind and composition of the inorganic crystals to be synthesized are not particularly limited.
  • An inorganic crystal with the same crystal structure as CaAlSiN or SrAlSiN are not particularly limited.
  • the composition should contain at least Ca or Sr. be able to .
  • Eu is contained in R, a phosphor with high luminance can be easily obtained.
  • a powder having a composition satisfying the above relationship becomes a phosphor emitting red light.
  • the divalent Eu ion is the emission center
  • M is an element of R after synthesizing one or more elements selected from Mg, Ca, Sr, and Ba (where R is Mn, Ce, Pr, Nd, Eu, Tb, Dy, There is a method in which a compound containing one or more elements selected from Er, Tm, and Yb) is added, followed by firing at a temperature of 1200 ° C to 2000 ° C in a nitrogen-containing atmosphere. According to this method, synthesis of an MSiAIN crystal with a low carbon content and synthesis of a phosphor activated with R can be performed separately.
  • the phosphor activated with R is synthesized at a temperature of 1200 ° C or higher and 2000 ° C or lower in a nitrogen-containing atmosphere. Since the reaction does not proceed sufficiently at temperatures lower than 1200 ° C, the R element is an MSiAIN crystal.
  • the nitrogen-containing atmosphere include nitrogen gas, ammonia gas, and a mixed gas of nitrogen and hydrogen.
  • a hydrocarbon gas such as methane gas can be further mixed.
  • firing temperature is high, firing can be performed in nitrogen gas at a high pressure of about 2 to 100 atm.
  • FIG. 4 summarizes the synthesis flow of Example 1.
  • Spherical amorphous silicon dioxide powder with an average particle size of 0.3 zm obtained by sol-gel synthesis from high-purity alkoxysilane, is added to an aqueous solution containing Ca and A1, and citrate is added while stirring and mixing. Added.
  • Ca and A1 citrates were adsorbed on the silicon dioxide surface, and then heated with stirring to remove moisture and dry (drying of water). Then, the citrate was converted to oxide by heating to 700 ° C in air.
  • the obtained calcined product was loosened with an agate mortar to obtain a powdery precursor compound.
  • the composition of the precursor (unit mol%) is
  • the obtained composite retained the form of the precursor and could be easily loosened with an agate mortar.
  • Fig. 2 X-ray diffraction pattern of the obtained powder
  • a spherical amorphous silicon dioxide powder with an average particle size of 0.3 ⁇ m obtained by sol-gel synthesis from high-purity alkoxysilane was added to an aqueous solution containing Ca and A1, and stirred and mixed. The acid was added. By this operation, Ca and A1 citrates were adsorbed on the silicon dioxide surface, and then heated with stirring to remove moisture and dried. Then, the citrate was converted to oxide by heating to 700 ° C in air. The obtained calcined product was loosened with an agate mortar to obtain a powdery precursor compound.
  • the composition of the precursor (unit mol%) is
  • the obtained composite retained the form of the precursor and could be easily loosened with an agate mortar.
  • the mixture of CaAlSiN and A1N As a result of examining the X-ray diffraction pattern (Fig. 3) of the obtained powder, the mixture of CaAlSiN and A1N
  • Table 1 The powder shown in Table 1 was obtained.
  • Table 2 summarizes the weight ratio of oxygen content to the total nitrogen content and oxygen content.
  • Example 1 About 0.5 g of the same precursor compound as in Example 1 was placed in an ananoremina boat, placed in an alumina core tube having an inner diameter of 24 mm, and set in a tubular furnace having a heating element outside the core tube. Ammonia gas was introduced from one end of the reactor core tube at a flow rate of 325 ml / min, and the temperature was raised to 700 ° C at a rate of 500 ° C / hour. From this temperature, the ammonia gas flow rate was set to 1300 ml / min.
  • methane gas was introduced into the furnace at a flow rate of 19.5 ml / min, and then the temperature was increased to 1375 ° C at a rate of 200 ° C / hr. After holding at this temperature for 4 hours, the supply of methane gas was stopped, and it was cooled to room temperature in an ammonia stream. The resulting composite retained the precursor form and could be easily loosened in an agate mortar. As a result of examining the X-ray diffraction pattern of the obtained powder, it was a mixture of CaAlSiN and A1N, and SiO, Al 2 O, Ca 0 and the like were not detected.
  • Ammonia gas was introduced from one end of the reactor core tube at a flow rate of 325 ml / min, and the temperature was raised to 700 ° C at a rate of 500 ° CZ. At this temperature, the ammonia gas flow rate is set to 1300 ml / min and methane gas is introduced into the furnace at a flow rate of 19.5 ml / min. Subsequently, the temperature was increased to 1500 ° C at a rate of 200 ° C / hour. After holding at this temperature for 15 minutes, the supply of methane gas was stopped, and it was cooled to room temperature in an ammonia stream.
  • the obtained composite maintains the precursor form, and can be easily loosened with an agate mortar.
  • the excitation spectrum and fluorescence spectrum of the resulting compound were measured using a fluorescence spectrophotometer F4500 manufactured by Hitachi High-Technologies, and as shown in Fig. 5, from 3 OOnm to 450nm ultraviolet to blue light. When excited, it was confirmed to be a red phosphor having an emission peak wavelength at 620 nm. Therefore, it can be seen that this can be applied to white LED lighting fixtures in combination with blue LEDs.
  • Example 3 1 350 2. 0 200 Ca 2 AISi30 AIN 1 7. 8 1 1.80
  • Example 4 1 375 2. 0 200 Ca 2 AISi30 AIN 1 8. 4 1 2.
  • 80 example 5 1 365 4. 0 200 CaAISiNa. AIN 30. 0 2. 02 example 6 1375 3. 0 200 CaAISiN 3l AIN 5. 01

Abstract

L’invention concerne une poudre de cristal inorganique composée principalement d’un nitrure ou oxynitrure fin exempt de coloration due à une inclusion d’impureté et adapté à une utilisation en tant que phosphores. Ladite poudre de cristal inorganique est synthétisée par traitement thermique d’un composé précurseur qui contient au moins les éléments M, Si, Al et O (M étant un ou plusieurs éléments sélectionnés parmi Mg, Ca, Sr et Ba), si nécessaire un élément R (R étant un ou plusieurs éléments sélectionnés parmi Mn, Ce, Pr, Nd, Eu, Tb, Dy, Er, Tm et Yb) et également si nécessaire un élément N, dans une atmosphère de nitruration réductrice de manière à ce que le contenu d’oxygène soit réduit et que le contenu d’azote soit augmenté dans le précurseur.
PCT/JP2006/311239 2005-06-06 2006-06-05 Procédé de production de cristal inorganique WO2006132188A1 (fr)

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JP2018509480A (ja) * 2016-01-29 2018-04-05 江蘇博睿光電有限公司Ｊｉａｎｇｓｕ Ｂｒｅｅ Ｏｐｔｒｏｎｉｃｓ Ｃｏ．，Ｌｔｄ． 窒素含有発光粒子及びその調製方法、窒素含有発光体、並びに発光デバイス

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