JP2010185009A - Raw material mixture for nitride-based or oxynitride-based fluorescent material and method for producing nitride-based or oxynitride-based fluorescent material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a nitride-based or oxynitride-based fluorescent material having light-emission intensity higher than heretofore. <P>SOLUTION: The nitride-based or oxynitride-based fluorescent material having light-emission intensity higher than that of a conventional fluorescent material obtained by a conventional method is obtained by using a raw material mixture for the nitride-based or oxynitride-based fluorescent material, which contains an europium siliconitride powder including trivalent europium. A method for producing the raw material mixture for the fluorescent material includes mechanically mixing the europium-containing siliconitride powder and a host crystal raw material compound. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a raw material mixture used for the synthesis of a nitride-based or oxynitride-based phosphor containing europium as a light-emitting ion, and in particular, a nitride-based material containing europium-containing silicon nitride powder as a europium source or The present invention relates to an oxynitride-based phosphor raw material powder.

Phosphors are widely 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.
In any application, in order to make the phosphor emit light, it is necessary to supply the phosphor with energy for exciting the phosphor, and it has high energy such as vacuum ultraviolet rays, ultraviolet rays, electron beams, and blue light. The phosphor is excited by the excitation source and emits visible light.
However, as a result of exposure of the phosphor to the excitation source as described above, the brightness of the phosphor decreases or the brightness of the phosphor decreases due to an increase in the phosphor operating temperature due to an increase in the output of the excitation source. Thus, there is a demand for phosphors with less luminance reduction. Therefore, instead of conventional phosphors such as silicate phosphors, phosphate phosphors, aluminate phosphors, and sulfide phosphors, nitride-based phosphors and oxynitrides are used as phosphors with low luminance reduction. Physical phosphors have been proposed.

An example of the nitride-based or oxynitride-based phosphor is an α-sialon phosphor (see Patent Document 1 below). This sialon phosphor is manufactured by a manufacturing process generally described below. First, silicon nitride (Si ₃ N ₄ ), aluminum nitride (AlN), calcium carbonate (CaCO ₃ ), europium oxide (Eu ₂ O ₃ ) are mixed at a predetermined molar ratio, and in nitrogen at 10 atm (1 MPa) In the above, it is manufactured by holding at a temperature of 1700 ° C. for 1 hour and firing by a hot press method (see, for example, Patent Document 1). It has been reported that α sialon in which Eu ions obtained by this process are dissolved is a phosphor that emits yellow light of 550 to 600 nm when excited by blue light of 450 to 500 nm.

Patent Document 2 describes a phosphor having the same crystal structure as M ₂ Si ₅ N ₈ (M is an II-valent element or rare earth element). Patent Document 3 describes a phosphor made of MSi ₂ O ₂ N ₂ (M is a II-valent element). This phosphor emits yellow light when the element M is Ca, yellow-green light when it is Sr, and blue-green light when it is Ba.

As another nitride-based or oxynitride-based phosphor, for example, Patent Document 4 includes MSi ₃ N ₅ , M ₂ Si ₄ N ₇ , M ₄ Si ₆ N ₁₁ , M ₉ Si ₁₁ N ₂₃ , M ₁₆ Si ₁₅ O ₆ N ₃₂ , M ₁₃ Si ₁₈ Al ₁₂ O ₁₈ N ₃₆ , MSi ₅ Al ₂ ON ₉ , M ₃ Si ₅ AlON ₁₀ (where M is a II-valent element or rare earth element) as a base crystal, In this, phosphors activated with Eu or Ce are described, and among these, phosphors emitting yellow light are also described. Also, LED lighting units using these phosphors are known.

Furthermore, CaSiN ₂ (see the following Patent Document 5), CaSiAlN ₃ (see the following Non-Patent Document 1), SrSiAlN ₃ (see the following Non-Patent Document 2), Sr-α-sialon (see the following Non-Patent Document 3), β- Sialon (see Non-Patent Document 4 below) has been reported.

As a prior art of a lighting device using a phosphor, a white light emitting diode using a combination of a blue light emitting diode element and a blue absorbing yellow light emitting phosphor is known and has been put to practical use in various lighting applications. Representative examples thereof include Japanese Patent No. 2900928 “Light Emitting Diode” (Patent Document 6), Japanese Patent No. 2927279 (Patent Document 7) “Light Emitting Diode”, Japanese Patent No. 3364229 (Patent Document 8) “Wavelength Conversion Casting Material and Examples of the manufacturing method and the light-emitting element ”are given.
In these light-emitting diodes, a phosphor that is particularly often used is a cerium-activated yttrium-aluminum-garnet-based fluorescence represented by the general formula (Y, Gd) ₃ (Al, Ga) ₅ O ₁₂ : Ce ³⁺ Is the body.

  Such an illuminating device can be manufactured by the well-known method as described in patent document 9, patent document 10, etc., for example.

JP 2002-363554 A JP 2006-206729 A JP 2004-277547 A JP 2003-206481 A JP 2002-322474 A Japanese Patent No. 2900928 Japanese Patent No. 2927279 Japanese Patent No. 3364229 JP-A-5-152609 JP-A-7-99345

Physica Status Solodi, A 203 (2006) 2712 J. et al. Solid State Chemistry, Chem Proceedings of the 55th Japan Society of Applied Physics 3, 1522, 29p-ZJ-10 (2008) Appl. Phys. Lett. , (2005) 86: 2195

In a conventional manufacturing process of a nitride-based or oxynitride-based phosphor using europium as a light-emitting ion, a raw material mixture containing europium oxide or europium nitride having a valence of III has been generally used. In this case, the valence III europium is reduced to the valence II during the calcination process and taken into the host crystal. However, in recent years, it has been clarified that a considerable amount of trivalent europium remains in these phosphors. The residue of trivalent europium causes a deviation from the stoichiometric composition of the phosphor, and as a result, there is a problem that a sufficiently high emission intensity cannot be obtained.
In addition, europium nitride has poor chemical stability and is difficult to handle in the atmosphere. Therefore, it is necessary to prepare the sample in an environment that is strictly cut off from air by a well-controlled glove box or the like, and there are problems such as complicated processes and increased manufacturing costs. Furthermore, unless manufacturing equipment with a structure in which the glove box and the baking furnace are integrated is used, a large amount of impurity oxygen is mixed because the sample must be brought into contact with air in the steps of placing the sample in the baking furnace and vacuuming. However, this also caused a decrease in emission intensity.

  The present invention has been made in view of the above circumstances, and provides a raw material mixture that enables the production of a nitride-based or oxynitride-based phosphor exhibiting a higher emission intensity than conventional methods. is there.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have obtained a nitride-based or oxynitride-based phosphor raw material containing europium siliconitride powder made of europium having a valence of II. By using the mixture, it has been found that a higher emission intensity can be obtained than when a raw material containing europium oxide or europium nitride having a valence of III is used, and the present invention shown below has been completed.

(1) A nitride-based or oxynitride-based phosphor raw material mixture containing europium-containing siliconitride powder.
(2) the europium-containing珪窒compound _{powder, (Eu x, M 1-} x) SiN 2, (Eu x, M 1-x) 2 Si 5 N 8, (Eu x, M 1-x) Si 6 N ₈ (M is at least one selected from alkaline earth metal elements and II-valent lanthanide-based rare earth elements excluding Eu. 0 <x ≦ 1) (1) 4. A nitride-based or oxynitride-based phosphor raw material mixture described in 1.
(3) The nitride-based or oxynitride-based phosphor raw material mixture according to (1) or (2), wherein the average particle size is 100 μm or less.
(4) Contains the europium-containing silicon nitride powder and elements selected from Si, Al, alkaline earth metal elements, II-valent lanthanide rare earth elements excluding Eu, Sc, Y, and III-valent lanthanide rare earth elements The nitride-based or oxynitride-based phosphor raw material mixture according to any one of (1) to (3), including a base crystal raw material compound.
(5) The base crystal raw material compound is Si ₃ N ₄ , SrSi ₂ , AlN, Ca ₃ N ₂ , Si ₃ N ₄ , Sr ₃ N ₂ , CaSi ₂ , SrSi ₂ , SrO, SrCO ₃ , BaCO ₃ , SiO ₂ , the nitride-based or oxynitride-based phosphor raw material mixture according to (4), which contains any two or more of CaSiN ₂ and SrSiN ₂ .
(6) A method for producing a nitride-based or oxynitride-based phosphor, comprising using a nitride-based or oxynitride-based phosphor raw material mixture containing a europium-containing silicon nitride powder.
(7) A method for producing a nitride-based or oxynitride-based phosphor, comprising firing a nitride-based or oxynitride-based phosphor raw material mixture containing a europium-containing silicon nitride powder.
(8) the europium-containing珪窒compound _{powder, (Eu x, M 1-} x) SiN 2, (Eu x, M 1-x) 2 Si 5 N 8, (Eu x, M 1-x) Si 6 N ₈ (M is at least one selected from alkaline earth metal elements and II-valent lanthanide rare earth elements excluding Eu. 0 <x ≦ 1) (6) Or the method for producing a nitride-based or oxynitride-based phosphor according to (7).
(9) The phosphor raw material mixture according to any one of (1) to (5) is used as the phosphor raw material mixture (6) or (6) 7) A method for producing a nitride-based or oxynitride-based phosphor.
(10) The nitride material or the acid according to any one of (6) to (9), wherein the phosphor raw material mixture is fired in a state where the bulk density is maintained at a filling rate of 40% or less. A method for producing a nitride-based phosphor.
(11) The target phosphor powder is added in the range of 1 to 50 parts by mass with respect to 100 parts by mass of the phosphor raw material mixture as a seed material, and fired. The method for producing a nitride-based or oxynitride-based phosphor according to any one of the above.
(12) The phosphor raw material mixture is fired at a firing temperature of 1400 ° C. to 2200 ° C. in a nitrogen atmosphere at a pressure of 0.1 MPa to 100 MPa. A method for producing a nitride-based or oxynitride-based phosphor according to claim 1.
(13) The phosphor raw material mixture is baked in the presence of carbon or a carbon-containing compound. The nitride or oxynitride type according to any one of (6) to (12) A method for producing a phosphor.

  According to the above configuration, a nitride-based or oxynitride-based phosphor having higher emission intensity than the conventional method can be obtained.

Hereinafter, the nitride-based or oxynitride-based phosphor raw material mixture which is an embodiment of the present invention will be described in detail.
A nitride-based or oxynitride-based phosphor raw material mixture (hereinafter referred to as a phosphor raw material mixture) according to an embodiment of the present invention is a nitride-based or oxynitride-based phosphor containing europium as a light-emitting ion. It is a raw material mixture used for synthesis. As the host crystal of the target phosphor, ASiN ₂ , A ₂ Si ₅ N ₈ , ASi ₆ N ₈ , ASi ₇ N ₁₀ , AAlSiN ₃ , A ₃ Al ₂ N ₄ , A ₃ AlN ₃ , ARSi ₄ N _{7 , ASi 3 N 5, A 2} Si 4 N 7, A 4 Si 6 N 11, A 9 Si 11 N 23, A 16 Si 15 O 6 N 32, A 13 Si 18 Al 12 O 18 N 36, ASi 5 Al ₂ ON ₉ , A ₃ Si ₅ AlON ₁₀ , ASi ₂ N ₂ O ₂ , AlN, α-sialon, β-sialon, Sr ₆ Si _30-n Al _{2 + n On} N _46-n , Ba ₃ Si ₆ O ₁₂ N _{2, AAlSi 4 N 7 (a} ; alkaline earth metal elements, one or more selected from II-valent lanthanide rare earth elements except Eu, R; Sc, Y and III valent La One or more selected from Tanido rare earth element) and the like can be exemplified.

The above phosphor raw material mixture, as Eu source is a light emitting _{ion, (Eu x, M 1-} x) SiN 2, (Eu x, M 1-x) 2 Si 5 N 8, (Eu x, M 1 _-X ) Si ₆ N ₈ (M is at least one selected from alkaline earth metal elements and II-valent lanthanide-based rare earth elements excluding Eu. One or more europium-containing silicon nitrides selected from 0 <x ≦ 1) Si, Al, alkaline earth metal elements, II-valent lanthanide rare earth elements excluding Eu, Sc, Y, for obtaining a host crystal composition of a desired powder and a desired nitride or oxynitride phosphor And a parent crystal raw material compound containing an element selected from trivalent lanthanide-based rare earth elements.

As Eu source is a light emitting _{ion, (Eu x, M 1-} x) SiN 2, (Eu x, M 1-x) 2 Si 5 N 8, (Eu x, M 1-x) Si 6 N 8 (M Is one or more selected from alkaline earth metal elements and II-valent lanthanide rare earth elements excluding Eu. By using one or more europium-containing silicon nitride powders selected from 0 <x ≦ 1), europium oxide Further, it is possible to obtain a higher emission intensity than when using europium nitride.

Moreover, you may add the powder of the target fluorescent substance beforehand synthesize | combined as a seed to the fluorescent substance raw material mixture of this invention. When seeds are added, the synthesis reaction is promoted, so that synthesis at a low temperature is possible, and a phosphor with higher crystallinity is obtained, and the emission intensity is improved. The amount of seed added is in the range of 1 to 50 parts by mass with respect to 100 parts by mass of the phosphor raw material mixture.
Furthermore, you may add a flux to the fluorescent substance raw material mixture of this invention as needed. As the flux, an alkali metal halide or an alkaline earth metal halide can be used. For example, the flux is added in the range of 0.01 to 20 parts by mass with respect to 100 parts by mass of the phosphor raw material mixture.
The phosphor raw material mixture of the present invention is preferably a powder having an average particle diameter of 100 μm or less. By setting the average particle size of the phosphor raw material mixture to 100 μm or less, a uniform phosphor raw material mixture can be obtained, and the phosphor synthesis reaction can be facilitated.

  The method for producing the phosphor raw material mixture of the present invention can be obtained by mechanically mixing the europium-containing silicon nitride powder and the base crystal raw material compound.

The matrix crystal raw material compounds include Si ₃ N ₄ , SrSi ₂ , AlN, Ca ₃ N ₂ , Si ₃ N ₄ , Sr ₃ N ₂ , CaSi ₂ , SrSi ₂ , SrO, SrCO ₃ , BaCO ₃ , SiO ₂ , CaSiN. ₂ and SrSiN ₂ can be used. These compounds may be appropriately selected in accordance with the composition of the target phosphor crystal.

  The mixing method can be performed by a dry mill that does not use a solvent, but is generally mixed with a solvent by a wet mill. When the wet mill method using a solvent is used, a microscopically uniform phosphor raw material mixture can be obtained in a short time. As the type of mill, a ball mill, a vibration mill, an attrition mill, or the like can be used, but a ball mill is suitable from the viewpoint of equipment cost.

  As the solvent used for mixing, ethanol, methanol, isopropanol, hexane, acetone, water, or the like can be used, but ethanol or hexane is preferable in consideration of safety and the prevention of oxidation of the material. The ratio of various materials constituting the phosphor raw material mixture to the mixed solvent is determined by the viscosity of the mixed slurry. The viscosity of the preferred mixed slurry is about 50 to 500 cps. If the viscosity of the mixed slurry is less than 50 cps, the amount of energy required for drying the mixed slurry increases, which is not preferable. On the other hand, when the viscosity of the mixed slurry exceeds 500 cps, it takes a long time to obtain a uniform mixed powder, which is not preferable.

  The obtained mixed slurry may be left in a dryer or the like to evaporate the solvent. However, when a spray dryer is used, the phosphor from which the solvent is removed in a short time without worrying about re-separation of the raw material powder. A raw material mixture can be obtained. Moreover, since the phosphor raw material mixture obtained by using a spray dryer has a granular form of several tens to several hundreds μm, it is excellent in fluidity and easy to handle.

In the method for producing a phosphor using the phosphor raw material mixture of the present invention, an ordinary phosphor synthesis method can be used.
The phosphor raw material mixture is preferably fired in a state where the bulk density is maintained at a filling rate of 40% or less. The bulk density is a volume filling rate of the powder, and is a value obtained by dividing the ratio of mass to volume when filling a certain container by the theoretical density of the metal compound. As the material of the container, alumina, calcia, magnesia, graphite, or boron nitride can be used. However, since the reactivity with the metal compound is low, a boron nitride sintered body is suitable.
Firing with the bulk density kept at 40% or less is when the firing is performed in a state where there is a free space around the powder particles constituting the phosphor raw material mixture, and the reaction product crystal grows in the free space. This is because the contact between crystals due to this is reduced, so that a crystal with few defects can be synthesized.

  The filling amount of the phosphor raw material mixture is preferably 20% by volume or more as a ratio of the bulk volume of the phosphor raw material mixture to the container volume to be used in a state where the filling rate is 40% or less. Baking the phosphor raw material mixture with a filling amount of 20% by volume or more of the container to be used suppresses the volatilization of volatile components contained in the phosphor raw material mixture and suppresses the compositional deviation during the baking process. Because. Furthermore, when the filling amount is 20% by volume or more, the filling amount of the phosphor raw material mixture into the container increases, which is economical.

Firing is performed in a nitrogen atmosphere at a pressure of 0.1 MPa to 100 MPa. When the nitrogen atmosphere pressure is less than 0.1 MPa, the volatilization of the phosphor raw material mixture becomes remarkable, the composition shifts, and the emission intensity decreases. On the other hand, even if the nitrogen atmosphere pressure is higher than 100 MPa, the effect of suppressing the volatilization of the phosphor raw material mixture does not change.
The firing temperature is generally in the range of 1400 ° C to 2200 ° C. If the firing temperature is lower than 1400 ° C., it takes a long time to obtain the target phosphor. If the firing temperature is higher than 2200 ° C., melting of the raw material starts, which is not preferable.

  The furnace used for firing has a high firing temperature and the firing atmosphere is an inert atmosphere containing nitrogen. Therefore, the metal resistance heating method or the graphite resistance heating method is suitable, and will be described later as a material for the high temperature portion of the furnace. For the reason as well, an electric furnace using carbon is particularly suitable. As a firing method, a method in which mechanical pressure is not applied from the outside, such as an atmospheric pressure sintering method or a gas pressure sintering method, is preferable because firing is performed while keeping the bulk density low.

In addition, when the phosphor raw material mixture is baked in the presence of carbon or a carbon-containing compound, the phosphor raw material mixture comes into contact with the reducing atmosphere, so that a high luminance is obtained particularly when a phosphor raw material mixture having a high oxygen content is used. This is preferable because a phosphor of the above is obtained.
The carbon or carbon-containing compound used here may be amorphous carbon, graphite, silicon carbide or the like, and is not particularly limited, but is preferably amorphous carbon, graphite or the like. Carbon black, graphite powder, activated carbon, silicon carbide powder, and the like, as well as these molded products, sintered bodies, and the like can be exemplified, but all can obtain the same effect.
As a coexistence mode, when powdered carbon is contained in the phosphor raw material mixture, when a container made of carbon or a carbon-containing compound is used, it is arranged inside or outside a container made of a material other than carbon or a carbon-containing compound. In some cases, it may be used as a heating element or a heat insulator made of carbon or a carbon-containing compound, but the same effect can be obtained by adopting any arrangement method.

The fired mass containing the phosphor obtained by firing is pulverized by a commonly used pulverizer such as a ball mill or jet mill made of a pulverizing medium or lining material made of alumina, silicon nitride or α-sialon. Grinding is performed until the average particle size is 50 μm or less. When the average particle size exceeds 50 μm, the fluidity of the powder and the dispersibility in the resin are deteriorated, and when the light emitting device is formed in combination with the light emitting element, the light emission intensity becomes uneven depending on the part.
The lower limit of the average particle size is not particularly limited, but generally it takes a long time to grind to a particle size of 0.5 μm or less, and furthermore, the phosphor has many defects, which may lead to a decrease in emission intensity. is there.

  The reason why the grinding medium or lining material is made of alumina, silicon nitride, or α sialon is that there is little contamination with impurities during the grinding process, and the mixed impurities do not greatly reduce the emission intensity. In particular, when pulverized using a pulverizer made of a pulverizing medium or lining material containing iron or an iron group element, the phosphor is colored black, and further, an iron or iron group element is taken into the phosphor in a heat treatment step described later. This is not preferable because the emission intensity is significantly reduced.

  The phosphor powder obtained by pulverization is classified as necessary to obtain a desired particle size distribution. As classification methods, methods such as sieving, air classification, sedimentation in liquid, and soot tube classification can be used. The classification process may be performed after the surface treatment process.

  The phosphor powder after firing, the phosphor powder after pulverization, or the phosphor powder after particle size adjustment by classification is performed at 600 ° C. in one or more atmospheres selected from nitrogen, ammonia, and hydrogen as necessary. The heat treatment is performed at a temperature of 2200 ° C. or lower. When a pulverization apparatus made of a pulverization medium or lining material made of alumina, silicon nitride or α sialon is used, contamination of impurities in the pulverization process is suppressed. Moreover, defects introduced in the pulverization step are reduced by heat-treating the pulverized powder at a temperature of 600 ° C. or higher and 2200 ° C. or lower in one or more atmospheres selected from nitrogen, ammonia, and hydrogen. The emission intensity can be recovered.

  When the heat treatment temperature is lower than 600 ° C., the effect of removing the phosphor defects is small, and it takes a long time to recover the emission intensity, which is not preferable. On the other hand, when the heat treatment temperature is higher than 2200 ° C., part of the phosphor powder is melted or particles are fixed again, which is not preferable.

The heat treatment is preferably performed in one or more atmospheres selected from nitrogen, ammonia, and hydrogen. When heat treatment is performed in these atmospheres, the phosphor powder can be removed without being oxidized. Moreover, it is preferable to perform atmospheric pressure under the pressure of 0.1 Mpa or more and 100 Mpa or less similarly to baking.
When the atmospheric pressure is smaller than 0.1 MPa, part of the phosphor constituent elements is volatilized depending on the heat treatment temperature, and the emission intensity is lowered. On the other hand, even if the nitrogen atmosphere pressure is higher than 100 MPa, the effect of suppressing the decomposition of the phosphor powder does not change, so it is uneconomical and neither is preferable.

  Furthermore, by washing the product with a solvent comprising an aqueous solution of water or an acid after firing, the content of the glass phase, the second phase, or the impurity phase contained in the product can be reduced, and the luminance is improved. . In this case, the acid can be selected from a simple substance or a mixture of sulfuric acid, hydrochloric acid, nitric acid, hydrofluoric acid, organic acid, etc. Among them, the effect of removing impurities is great when a mixture of hydrofluoric acid and sulfuric acid is used.

Europium-containing珪窒hydride powder constituting the phosphor raw material mixture of the present _{invention, (Eu x, M 1-} x) SiN 2, (Eu x, M 1-x) 2 Si 5 N 8, (Eu x, M _1-x ) Si ₆ N ₈ (M is at least one selected from alkaline earth metal elements, II-valent lanthanide rare earth elements excluding Eu. 0 <x ≦ 1). . The element constituting M is selected from at least one selected from alkaline earth metal elements and II-valent lanthanide rare earth elements excluding Eu in accordance with the target phosphor. Needless to say, the phosphor raw material mixture of the present invention can be constituted even when M is not contained (x = 0).

  The particle size of the europium-containing silicon nitride powder is preferably 100 μm or less as an average particle size. When the average particle size is 100 μm or less, a uniform phosphor raw material mixture can be obtained, thereby facilitating the phosphor synthesis reaction.

  The purity of the europium-containing silicon nitride powder is desirably as high as possible. In particular, the total content of Fe, Co, and Ni is desirably 1000 ppm or less. If the total content of Fe, Co, Ni exceeds 1000 ppm, it is not preferable because a deep level is formed in the target phosphor and the emission intensity is reduced.

  The method for producing the europium-containing siliconitride powder may be performed by heating the raw material for synthesizing the nitride in a non-oxidizing atmosphere. The raw materials for synthesizing nitrides include oxides or compounds of Eu that form oxides by heating, oxides or M that forms oxides by heating (M is an alkaline earth metal element, II-valent excluding Eu) 1 or more compounds selected from lanthanide-based rare earth elements), carbon or a compound that forms carbon by heating, silicon, silicon nitride or a compound that forms silicon nitride by heating, nitride or Eu that forms nitride by heating These compounds or simple substances, nitrides, or M compounds or simple substances that form nitrides by heating can be used in appropriate combination.

The production method of the europium-containing silicon nitride powder is roughly classified as follows:
(I) an oxide or an Eu compound that forms an oxide by heating, and an oxide or an oxide that forms an oxide by heating, if necessary (where M is an alkaline earth metal element, a divalent lanthanide excluding Eu) A compound of at least one selected from rare earth elements), carbon or a compound that forms carbon by heating, and silicon, silicon nitride, or a compound that forms silicon nitride by heating, and at least nitrogen or ammonia A method of heating in a non-oxidizing atmosphere containing
(Ii) Nitride or Eu compound that forms nitride by heating, or simple substance, and M that forms nitride by heating or nitride if necessary (M is an alkaline earth metal element, excluding Eu) A compound or a simple substance selected from II-valent lanthanide-based rare earth elements) and silicon, silicon nitride, or a compound that forms silicon nitride by heating is uniformly mixed, and contains at least nitrogen or ammonia. Heating in a sex atmosphere,
(Iii) an oxide or an Eu compound that forms an oxide by heating, and an oxide or an oxide that forms an oxide by heating if necessary (M is an alkaline earth metal element, a divalent lanthanide excluding Eu) A compound of one or more selected from rare earth elements) and silicon, silicon nitride, or a compound that forms silicon nitride by heating, and heating in a reducing atmosphere containing at least nitrogen or ammonia ,
(Vi) Although there is a method in which the methods (i) to (iii) are combined, the desired europium-containing silicon nitride powder can be obtained by any method.

Among the above-described production methods, the compounds used in the methods (i) and (iii) that form oxides by heating are carbonates, hydroxides, etc., such as carbon used in the method (i) or by heating. The compound that forms carbon is amorphous carbon, graphite, resin, and the like, and carbon black, graphite powder, activated carbon powder, phenol resin, and the like.
Examples of the compound that forms silicon nitride by heating used in the methods (i) to (iii) include silicon diimide and polysilazane.
As a compound used in the method (i) that forms oxide and carbon by heating, there is a carboxylate.
Moreover, hydrogen, argon, etc. can be mentioned as non-oxidizing atmospheres other than nitrogen and ammonia used by the method (i) or (ii).
Further, the reducing atmosphere other than nitrogen and ammonia used in the method (iii) includes hydrogen, hydrogen cyanide, carburizing gas, natural gas, methane (CH ₄ ), propane (C ₃ H ₈ ), butane (C _And hydrocarbons such as ₄ H ₁₀ ) and carbon oxides such as carbon monoxide (CO).

  In the method for producing the europium-containing silicate nitride powder, the objective europium-containing silicate nitride powder synthesized in advance may be added to the raw material as a seed material. By doing so, the synthesis reaction is promoted, and a europium-containing silicon nitride having a smaller impurity phase can be obtained.

  The addition amount of the europium-containing silicon nitride powder added as a seed material is preferably in the range of 1 to 50 parts by mass with respect to 100 parts by mass of the raw material. When the addition amount of the europium-containing silicon nitride powder is less than 1 part by mass, since the addition amount is too small, the effect of promoting the synthesis reaction is hardly seen. On the contrary, when the addition amount of the europium-containing silicon nitride powder exceeds 50 parts by mass, the amount of the raw material used for the synthesis reaction decreases, and the amount of the europium-containing silicon nitride powder to be generated decreases, which is not preferable.

Moreover, in order to improve the reactivity of reactants, you may make it react by adding a flux. The flux, an alkali metal compound (LiCl, NaC1, KCl, LiF , NaF, KF , etc.) or an alkaline earth metal compound _{(CaF 2, SrF 2, BaF} 2, CaC1 2, SrCl 2, BaCl 2 , etc.) or a halide Ammonium (NH ₄ Cl, NH ₄ F, etc.), aluminum halide (AlCl ₃ , AlF ₃ etc.), etc. are appropriately selected and used. Although the addition amount of a flux is not specifically limited, Usually, it is about 0.1-5 mass% by the outer part with respect to a fluorescent substance raw material mixture.

  The raw material for synthesizing nitride in the method for producing the europium-containing siliconitride powder uses a raw material dissolved in a solvent, etc., in addition to dry and wet mixing of the powder using a ball mill, etc. It can also be used as a raw material for synthesizing silicon nitride. In this case, all the raw materials may be in the liquid phase, but some raw materials may be in the liquid phase and other raw materials may be in the solid phase.

The raw material for synthesizing silicon nitride is preferably fired with a porosity of 80% or less. When fired in a state where the porosity is 80% or more, since there is little contact between the raw materials for synthesizing silicon nitride, it takes a long time to synthesize the desired europium-containing silicon nitride powder, Since oxygen and residual carbon increase, it is not preferable.
Examples of the material of the container containing the raw material for synthesizing silicon nitride can include alumina, calcia, magnesia, graphite, boron nitride, etc., and among these, since the reactivity with the metal compound is low, graphite or A boron nitride sintered body is preferred.
In addition, the raw material for synthesizing silicon nitride may be filled in the above-mentioned container, but if a molded body that has been previously pressurized with a mold or the like to have a desired porosity is used, the synthesis reaction is promoted or residual oxygen, Not only is this effective in reducing residual carbon, but it is also economical because the amount of europium-containing siliconitride powder that can be synthesized by a single firing increases.

In the method for producing the europium-containing silicate nitride powder, the preferable calcination temperature is 1400 to 2200 ° C., and the more preferable calcination temperature is that the intended europium-containing silicate nitride powder is (Eu _x , M _1-x ) SiN ₂ , In the case of (Eu _x , M _1-x ) ₂ Si ₅ N ₈ , the temperature is 1400 to 1800 ° C., and in the case where the target europium-containing siliconitride powder is (Eu _x , M _1-x ) Si ₆ N ₈ It is 1500-2200 degreeC. M is one or more selected from alkaline earth metal elements and II-valent lanthanide rare earth elements excluding Eu, and x is in the range of 0 <x ≦ 1.

  In the firing step, secondary firing may be performed after performing primary firing and then mixing again. Furthermore, the firing step may be repeated and performed in a plurality of times. By doing so, the reactivity can be further improved, and impurities such as residual oxygen and residual carbon can be further reduced.

  As described above, when performing firing a plurality of times, the atmosphere gas to be used can be appropriately selected in each firing step. For example, when the firing order and firing temperature are low, an atmosphere gas having a large reduction effect (for example, a mixed gas of nitrogen and hydrogen, ammonia gas, etc.) is used, and the firing order and firing temperature after the secondary firing are high. If nitrogen gas is used, the present invention can be implemented without using expensive baking equipment, and the manufacturing cost can be reduced.

  In addition, in a low firing temperature range of 1200 ° C. or lower or in the temperature rising process, if the inside of the firing furnace is in a reduced pressure state, the decomposition gas containing oxygen can be exhausted outside the furnace, which is effective in reducing the amount of residual oxygen. . In particular, when a carboxylate containing Eu or M (M is at least one selected from alkaline earth metal elements and II-valent lanthanide rare earth elements excluding Eu) is included in the raw material mixture, Since a large amount of cracked gas containing oxygen is released, it is effective in reducing the amount of oxygen in the finally synthesized nitride.

  At the start of firing, it is necessary to once reduce the pressure or vacuum and exhaust the residual air in the furnace to the outside of the furnace or purge the air remaining in the furnace with the atmospheric gas used. In this case, since it takes a long time to remove residual air, it is preferable to reduce the pressure or vacuum.

  The preferable pressure of the atmospheric gas varies depending on the firing temperature, but in order to suppress the decomposition of nitride at a high temperature, 1500 to 1800 ° C. is 5 atm, and preferably 1800 ° C. or more and 9 atm or more.

  The rate of temperature increase in the method for producing europium-containing silicon nitride is preferably 20 ° C./min or less. As described above, in the method for producing the europium-containing siliconitride constituting the phosphor raw material mixture of the present invention, the raw materials for synthesizing silicon nitride are sufficiently brought into contact with each other to promote the nitride synthesis reaction. In addition, the porosity is set to 80% or less. In such a situation, if the rate of temperature rise exceeds 20 ° C./min, decomposition gas containing oxygen is generated abruptly, and the sample protrudes from the crucible and scatters into the furnace, which is not preferable. In particular, the raw material for synthesizing nitrides contains Eu or M (M is at least one selected from alkaline earth metal elements and II-valent lanthanide rare earth elements excluding Eu). In this case, since the amount of cracked gas containing oxygen is large, the rate of temperature rise is preferably 20 ° C./min or less.

  When the nitride obtained by firing is firmly fixed as a powder aggregate, it may be pulverized by a commonly used pulverizer such as a ball mill or a jet mill to form a powder. Furthermore, the particle size may be adjusted by sieving, water tank classification, soot tube classification, and the like.

  With respect to the europium-containing silicon nitride obtained by firing, the europium-containing silicon nitride powder after the grinding treatment or the europium-containing silicon nitride powder after adjusting the particle size, further at a temperature of 1000 ° C. or more Heat treatment may be performed. By performing this heat treatment, it is possible to reduce various defects present in the nitride, such as defects introduced during grinding, and improve the chemical stability and other characteristics of the europium-containing siliconitride powder. Can be made.

  Furthermore, you may wash | clean the europium containing silicon nitride powder obtained by baking with the solvent which consists of water or an acid aqueous solution. By performing this washing step, the content of the glass phase, the second phase, or the impurity phase contained in the europium-containing silicate nitride powder can be reduced, and the purity of the europium-containing silicate nitride powder can be improved. it can. As the acid used in the acid aqueous solution, sulfuric acid, hydrochloric acid, nitric acid, hydrofluoric acid, an organic acid alone or a mixture thereof can be used. In particular, it is preferable to use a mixture of hydrofluoric acid and sulfuric acid as the acid used in the acid aqueous solution. This is because the effect of removing impurities can be increased.

  Hereinafter, the present invention will be specifically described based on examples. However, the present invention is not limited only to these examples.

<Examples 1-9>
Silicon nitride powder (Si ₃ N ₄ ) having an average particle size of 0.5 μm, an oxygen content of 0.93% by mass and an α-type content of 92% as a raw material for synthesizing silicon nitride, and europium oxide having a purity of 99.9% Powder (Eu ₂ O ₃ ) and carbon powder (C) having a purity of 99.9999% were used.

Silicon nitride powder (Si ₃ N ₄ ), europium oxide powder (Eu ₂ O ₃ ) and carbon powder (C) were weighed in the proportions shown in Table 1, and uniformly mixed by a wet ball mill using ethanol. Next, the obtained slurry was evaporated to dryness, placed in a container made of hBN, and loaded into a firing furnace.
The firing atmosphere was a reduced pressure from room temperature to 1000 ° C., and a nitrogen atmosphere of 1 MPa was used at 1000 ° C. or higher. The temperature was raised at a rate of 5 ° C./min, held at the temperature shown in Table 1 for 2 hours, and then cooled to room temperature.
The obtained product (europium-containing siliconitride powder) is subjected to chemical analysis of Eu and Si using an inductively coupled plasma emission spectroscopic analyzer and combined with chemical analysis of nitrogen using an oxygen / nitrogen analyzer. went. Table 1 shows the chemical composition of the product, which was clarified from the chemical analysis results.

<Examples 10 to 12>
Silicon nitride powder (Si ₃ N ₄ ) having an average particle size of 0.5 μm, an oxygen content of 0.93% by mass and an α-type content of 92%, and europium acetate having a purity of 99.9% (Eu (CH ₃ COO) ₃ .3H ₂ O) was used.
Silicon nitride powder (Si ₃ N ₄ ) and europium acetate (Eu-Ace) were weighed in the proportions shown in Table 2, and mixed uniformly by a wet ball mill using ethanol.
Next, the obtained slurry was evaporated to dryness, placed in a container made of hBN, and loaded into a firing furnace.
After vacuum deaeration at room temperature, the inside of the furnace was placed in an ammonia atmosphere, heated to the temperature shown in Table 1 at a rate of 5 ° C./min, held for 2 hours, and then cooled to room temperature.
The obtained product (europium-containing siliconitride powder) is subjected to chemical analysis of Eu and Si using an inductively coupled plasma emission spectroscopic analyzer and combined with chemical analysis of nitrogen using an oxygen / nitrogen analyzer. went. Table 2 shows the chemical composition of the product as revealed from the chemical analysis results.

<Example 13>
As a phosphor raw material mixture, silicon nitride powder (Si ₃ N ₄ ) having an average particle size of 0.5 μm, an oxygen content of 0.93% by mass and an α-type content of 92%, and strontium silicide (SrSi ₂ ) having a purity of 99% And a mixture of Eu ₂ Si ₅ N ₈ (europium-containing silicon nitride powder) synthesized in Example 6 was used to synthesize a Sr ₂ Si ₅ N ₈ : Eu phosphor as follows.
First, 1.36 g of silicon nitride powder (Si ₃ N ₄ ), 8.38 g of strontium silicide (SrSi ₂ ), and 0.25 g of Eu ₂ Si ₅ N ₈ powder were weighed and mixed by a dry ball mill. Next, the obtained mixed powder was filled into a container made of hBN and loaded into a firing furnace.
The firing atmosphere was a reduced pressure from room temperature to 1000 ° C., and a nitrogen atmosphere of 1 MPa was used at 1000 ° C. or higher. The temperature increase rate was 5 ° C./min, and after holding at 1800 ° C. for 2 hours, the furnace was cooled to room temperature.
As a result of powder X-ray diffraction measurement using CuKα rays for the obtained product, it was confirmed that Sr ₂ Si ₅ N ₈ was produced.
As a result of irradiating the powder with light having a wavelength of 365 nm with an ultraviolet lamp, it was confirmed that the powder emitted reddish orange. Moreover, as a result of measuring the emission spectrum of this powder in the blue light excitation of 450 nm using the fluorescence spectrophotometer, the peak height of the emission spectrum was 100 counts. Since the count value varies depending on the measuring device and conditions, the unit is an arbitrary unit.

<Example 14>
As a phosphor raw material mixture, silicon nitride powder (Si ₃ N ₄ ) having an average particle size of 0.5 μm, an oxygen content of 0.93% by mass and an α-type content of 92%, and an aluminum nitride powder having a purity of 99.9% ( AlN), calcium nitride powder (Ca ₃ N ₂ ), and EuSi ₆ N ₈ (europium-containing siliconitride powder) synthesized in Example 9 were used as follows, and CaAlSiN ₃ : Eu A phosphor was synthesized.
First, 3.18 g of silicon nitride powder (Si ₃ N ₄ ), aluminum nitride powder (AlN 2.97 g, calcium nitride powder (Ca ₃ N ₂ ) 3.54 g, and EuSi ₆ N ₈ powder 0.31 g were weighed. After mixing with a dry ball mill filled with nitrogen gas, the obtained mixed powder was filled into a container made of hBN and loaded into a firing furnace.
The firing atmosphere was a reduced pressure from room temperature to 1000 ° C., and a nitrogen atmosphere of 1 MPa was used at 1000 ° C. or higher. The temperature increase rate was 5 ° C./min, and after holding at 1850 ° C. for 2 hours, the furnace was cooled to room temperature.
As a result of powder X-ray diffraction measurement using CuKα rays for the obtained product, it was confirmed that CaAlSiN ₃ was produced.
As a result of irradiating the powder with light having a wavelength of 365 nm with an ultraviolet lamp, it was confirmed that the powder emitted red light. Moreover, as a result of measuring the emission spectrum of this powder in 450 nm blue light excitation using the fluorescence spectrophotometer, the peak height of the emission spectrum was 125 counts. Since the count value varies depending on the measuring device and conditions, the unit is an arbitrary unit.

<Example 15>
As a phosphor raw material mixture, silicon nitride powder (Si ₃ N ₄ ) having an average particle size of 0.5 μm, an oxygen content of 0.93% by mass and an α-type content of 92%, and an aluminum nitride powder having a purity of 99.9% ( Using a mixture of AlN), strontium nitride powder (Sr ₃ N ₂ ), and EuSi ₆ N ₈ (europium-containing silicon nitride powder) synthesized in Example 9, SrAlSiN ₃ : Eu A phosphor was synthesized.
First, 2.37 g of silicon nitride powder (Si ₃ N ₄ ), 2.21 g of aluminum nitride powder (AlN), 5.18 g of strontium nitride powder (Sr ₃ N ₂ ), and 0.23 g of EuSi ₆ N ₈ powder were weighed. And mixed by a dry ball mill filled with nitrogen gas. Next, the obtained mixed powder was filled into a container made of hBN and loaded into a firing furnace.
The firing atmosphere was a reduced pressure from room temperature to 1000 ° C., and a nitrogen atmosphere of 1 MPa was used at 1000 ° C. or higher. The temperature increase rate was 5 ° C./min, and after holding at 1850 ° C. for 2 hours, the furnace was cooled to room temperature.
As a result of powder X-ray diffraction measurement using CuKα rays for the obtained product, it was confirmed that SrAlSiN ₃ was produced.
As a result of irradiating the powder with light having a wavelength of 365 nm with an ultraviolet lamp, it was confirmed that the powder emitted reddish orange. Moreover, as a result of measuring the emission spectrum of this powder in 450 nm blue light excitation using the fluorescence spectrophotometer, the peak height of the emission spectrum was 132 counts. Since the count value varies depending on the measuring device and conditions, the unit is an arbitrary unit.

<Example 16>
As a phosphor raw material mixture, silicon nitride powder (Si ₃ N ₄ ) having an average particle size of 0.5 μm, an oxygen content of 0.93% by mass and an α-type content of 92%, and an aluminum nitride powder having a purity of 99.9% ( and AlN), with a purity of 99% calcium silicide powder (CaSi _2), a mixture of EuSi ₆ N ₈ synthesized in example 9 (europium-containing珪窒compound powder), as follows, Ca- α-SiAlON: Eu phosphor was synthesized.
First, 8.72 g of silicon nitride powder (Si ₃ N ₄ ), 0.55 g of aluminum nitride powder (AlN), 0.62 g of calcium silicide powder (CaSi ₂ ), and 0.12 g of EuSi ₆ N ₈ powder were weighed. Mixed by a dry ball mill. Next, the obtained mixed powder was filled into a container made of hBN and loaded into a firing furnace.
The firing atmosphere was a reduced pressure from room temperature to 1000 ° C., and a nitrogen atmosphere of 1 MPa was used at 1000 ° C. or higher. The temperature increase rate was 5 ° C./min, and the temperature was kept at 1900 ° C. for 2 hours, and then cooled to room temperature.
As a result of performing powder X-ray diffraction measurement using CuKα rays for the obtained product, it was confirmed that Ca-α-SiAlON was produced.
As a result of irradiating the powder with light having a wavelength of 365 nm with an ultraviolet lamp, it was confirmed that the powder emitted orange light. Moreover, as a result of measuring the emission spectrum of this powder in 450 nm blue light excitation using the fluorescence spectrophotometer, the peak height of the emission spectrum was 116 counts. Since the count value varies depending on the measuring device and conditions, the unit is an arbitrary unit.

<Example 17>
As a phosphor raw material mixture, silicon nitride powder (Si ₃ N ₄ ) having an average particle size of 0.5 μm, an oxygen content of 0.93% by mass and an α-type content of 92%, and an aluminum nitride powder having a purity of 99.9% ( AlN), a 99% pure strontium silicide powder (SrSi ₂ ), and a mixture of EuSi ₆ N ₈ (europium-containing silicon nitride powder) synthesized in Example 9 was used as follows. α-SiAlON: Eu phosphor was synthesized.
First, 8.46 g of silicon nitride powder (Si ₃ N ₄ ), 0.53 g of aluminum nitride powder (AlN), 0.90 g of strontium silicide powder (SrSi ₂ ), and 0.11 g of EuSi ₆ N ₈ powder are weighed. Mixed by a dry ball mill. Next, the obtained mixed powder was filled into a container made of hBN and loaded into a firing furnace.
The firing atmosphere was a reduced pressure from room temperature to 1000 ° C., and a nitrogen atmosphere of 1 MPa was used at 1000 ° C. or higher. The temperature increase rate was 5 ° C./min, and the temperature was kept at 1900 ° C. for 2 hours, and then cooled to room temperature.
As a result of performing powder X-ray diffraction measurement using CuKα rays for the obtained product, it was confirmed that Sr-α-SiAlON was produced.
As a result of irradiating the powder with light having a wavelength of 365 nm with an ultraviolet lamp, it was confirmed that the powder emitted orange light. Moreover, as a result of measuring the emission spectrum of this powder in 450 nm blue light excitation using the fluorescence spectrophotometer, the peak height of the emission spectrum was 116 counts. Since the count value varies depending on the measuring device and conditions, the unit is an arbitrary unit.

<Example 18>
As a phosphor raw material mixture, silicon nitride powder (Si ₃ N ₄ ) having an average particle size of 0.5 μm, an oxygen content of 0.93% by mass and an α-type content of 92%, and an aluminum nitride powder having a purity of 99.9% ( AlN), a strontium oxide powder (SrO) having a purity of 98%, and EuSi ₆ N ₈ (europium-containing silicon nitride powder) synthesized in Example 9 were used as follows, and Sr ₆ Si was used as follows. _A 24Al ₈ O ₆ N ₄₀ : Eu phosphor was synthesized.
First, 4.98 g of silicon nitride powder (Si ₃ N ₄ ), 1.57 g of aluminum nitride powder (AlN), 2.83 g of strontium oxide powder (SrO) and 0.62 g of EuSi ₆ N ₈ powder are weighed and dried. Mix by ball mill. Next, the obtained mixed powder was filled into a container made of hBN and loaded into a firing furnace.
The firing atmosphere was a reduced pressure from room temperature to 1000 ° C., and a nitrogen atmosphere of 1 MPa was used at 1000 ° C. or higher. The temperature increase rate was 5 ° C./min, and the temperature was kept at 1900 ° C. for 2 hours, and then cooled to room temperature.
The obtained product was subjected to chemical analysis using an inductively coupled plasma emission spectrometer and an oxygen / nitrogen analyzer. As a result, Sr _5.7 Eu _0.3 Si ₂₄ Al ₈ O ₆ N ₄₀ was produced. It was confirmed that
As a result of irradiating the powder with light having a wavelength of 365 nm with an ultraviolet lamp, it was confirmed that the powder emitted greenish blue light. Moreover, as a result of measuring the emission spectrum of this powder in the blue light excitation of 450 nm using the fluorescence spectrophotometer, the peak height of the emission spectrum was 188 counts. Since the count value varies depending on the measuring device and conditions, the unit is an arbitrary unit.

<Example 19>
As a phosphor raw material mixture, silicon nitride powder (Si ₃ N ₄ ) having an average particle size of 0.5 μm, an oxygen content of 0.93% by mass and an α-type content of 92%, and an aluminum nitride powder having a purity of 99.9% ( AlN), 99% pure strontium silicide powder (SrSi ₂ ), 99.9% pure strontium carbonate powder (SrCO ₃ ), and EuSi ₆ N ₈ synthesized in Example 9 (europium-containing silicon nitride powder) Was used to synthesize Sr ₃ Si ₁₃ Al ₃ O ₂ N ₂₁ : Eu phosphor as follows.
First, 4.45 g of silicon nitride powder (Si ₃ N ₄ ), 1.13 g of aluminum nitride powder (AlN), 1.12 g of strontium silicide powder (SrSi ₂ ), 2.70 g of strontium carbonate powder (SrCO ₃ ) and EuSi ₆ was weighed N ₈ powder 0.59 g, it was mixed with a dry ball mill. Next, the obtained mixed powder was filled into a container made of hBN and loaded into a firing furnace.
The firing atmosphere was a reduced pressure from room temperature to 1000 ° C., and a nitrogen atmosphere of 1 MPa was used at 1000 ° C. or higher. The temperature increase rate was 5 ° C./min, and the temperature was kept at 1900 ° C. for 2 hours, and then cooled to room temperature.
The obtained product was subjected to chemical analysis using an inductively coupled plasma emission spectrometer and an oxygen / nitrogen analyzer. As a result, Sr _0.85 Eu _0.15 Si ₁₃ Al ₃ O ₂ N ₂₁ was produced. It was confirmed that
As a result of irradiating the powder with light having a wavelength of 365 nm with an ultraviolet lamp, it was confirmed that the powder emitted blue-green light. Moreover, as a result of measuring the emission spectrum of this powder in the blue light excitation of 450 nm using the fluorescence spectrophotometer, the peak height of the emission spectrum was 181 counts. Since the count value varies depending on the measuring device and conditions, the unit is an arbitrary unit.

<Example 20>
As a phosphor raw material mixture, silicon nitride powder (Si ₃ N ₄ ) having an average particle size of 0.5 μm, an oxygen content of 0.93% by mass and an α-type content of 92%, and a barium carbonate powder having a purity of 99.9% ( BaCO ₃ ), a 99.9% pure silicon oxide powder (SiO ₂ ), and EuSiN ₂ (europium-containing silicon nitride powder) synthesized in Example 3 were used as follows. _{A 3} Si ₆ O ₁₂ N ₂ : Eu phosphor was synthesized.
First, 0.62 g of silicon nitride powder (Si ₃ N ₄ ), 6.00 g of barium carbonate powder (BaCO ₃ ), 2.97 g of silicon oxide powder (SiO ₂ ) and 0.40 g of EuSiN ₂ powder are weighed and dried. Mix by ball mill. Next, the obtained mixed powder was filled into a container made of hBN and loaded into a firing furnace.
The firing atmosphere was a reduced pressure from room temperature to 1000 ° C., and a nitrogen atmosphere of 1 MPa was used at 1000 ° C. or higher. The temperature increase rate was 5 ° C./min, and the temperature was kept at 1600 ° C. for 2 hours.
As a result of chemical analysis of the obtained product using an inductively coupled plasma emission spectrometer and an oxygen / nitrogen analyzer, Ba _2.82 Eu _0.18 Si ₆ O ₁₂ N ₂ is generated. Was confirmed.
As a result of irradiating the powder with light having a wavelength of 365 nm with an ultraviolet lamp, it was confirmed that the powder emitted green light. Moreover, as a result of measuring the emission spectrum of this powder in the blue light excitation of 450 nm using the fluorescence spectrophotometer, the peak height of the emission spectrum was 157 counts. Since the count value varies depending on the measuring device and conditions, the unit is an arbitrary unit.

<Example 21>
As a phosphor raw material mixture, silicon nitride powder (Si ₃ N ₄ ) having an average particle size of 0.5 μm, an oxygen content of 0.93% by mass and an α-type content of 92%, and an aluminum nitride powder having a purity of 99.9% ( Using a mixture of AlN), 99% pure strontium silicide powder (SrSi ₂ ), and EuSiN ₂ (europium-containing silicon nitride powder) synthesized in Example 3, SrSi ₄ AlN ₇ was used as follows. : A Eu phosphor was synthesized.
First, 3.37 g of silicon nitride powder (Si ₃ N ₄ ), 1.46 g of aluminum nitride powder (AlN), 5.02 g of strontium silicide powder (SrSi ₂ ) and 0.15 g of EuSiN ₂ powder were weighed, and a dry ball mill Mixed. Next, the obtained mixed powder was filled into a container made of hBN and loaded into a firing furnace.
The firing atmosphere was a reduced pressure from room temperature to 1000 ° C., and a nitrogen atmosphere of 1 MPa was used at 1000 ° C. or higher. The temperature increase rate was 5 ° C./min, and after holding at 1800 ° C. for 2 hours, the furnace was cooled to room temperature.
As a result of chemical analysis using the inductively coupled plasma emission spectrometer and the oxygen / nitrogen analyzer, it was confirmed that Sr _0.98 Eu _0.02 Si ₄ AlN ₇ was produced. It was done.
As a result of irradiating the powder with light having a wavelength of 365 nm with an ultraviolet lamp, it was confirmed that the powder emitted reddish orange. Moreover, as a result of measuring the emission spectrum of this powder in 450 nm blue light excitation using the fluorescence spectrophotometer, the peak height of the emission spectrum was 102 counts. Since the count value varies depending on the measuring device and conditions, the unit is an arbitrary unit.

<Example 22>
As a phosphor raw material mixture, silicon nitride powder (Si ₃ N ₄ ) having an average particle size of 0.5 μm, an oxygen content of 0.93% by mass and an α-type content of 92%, and a strontium carbonate powder having a purity of 99.9% ( SrCO ₃ ), a 99.9% pure silicon oxide powder (SiO ₂ ), and a mixture of Eu ₂ Si ₅ N ₈ (europium-containing silicon nitride powder) synthesized in Example 6 were used as follows. Thus, a SrSi ₂ Al ₂ O ₂ N ₂ : Eu phosphor was synthesized.
First, 2.62 g of silicon nitride powder (Si ₃ N ₄ ), 5.76 g of strontium carbonate powder (SrCO ₃ ), 1.27 g of silicon oxide powder (SiO ₂ ) and 0.35 g of Eu ₂ Si ₅ N ₈ powder are weighed. And mixed uniformly by a wet ball mill using ethanol.
Next, the obtained slurry was evaporated to dryness, placed in a container made of hBN, and loaded into a firing furnace.
The firing atmosphere was a reduced pressure from room temperature to 1000 ° C., and a nitrogen atmosphere of 1 MPa was used at 1000 ° C. or higher. The temperature rising rate was 5 ° C./min, and after holding at 1550 ° C. for 2 hours, the furnace was cooled to room temperature.
As a result of performing powder X-ray diffraction measurement using CuKα rays for the obtained product, it was confirmed that SrSi ₂ Al ₂ O ₂ N ₂ was produced.
As a result of irradiating the powder with light having a wavelength of 365 nm with an ultraviolet lamp, it was confirmed that the powder emitted yellowish green. Moreover, as a result of measuring the emission spectrum of this powder in 450 nm blue light excitation using the fluorescence spectrophotometer, the peak height of the emission spectrum was 132 counts. Since the count value varies depending on the measuring device and conditions, the unit is an arbitrary unit.

<Example 23>
As a phosphor raw material mixture, silicon nitride powder (Si ₃ N ₄ ) having an average particle size of 0.5 μm, an oxygen content of 0.93% by mass and an α-type content of 92%, and a barium carbonate powder having a purity of 99.9% ( Using a mixture of BaCO ₃ ), silicon oxide powder (SiO ₂ ) having a purity of 99.9%, and Eu ₂ Si ₅ N ₈ (europium-containing silicon nitride powder) synthesized in Example 6, the following was used: Thus, a BaSi ₂ Al ₂ O ₂ N ₂ : Eu phosphor was synthesized.
First, 2.20 g of silicon nitride powder (Si ₃ N ₄ ), 6.45 g of barium carbonate powder (BaCO ₃ ), 1.06 g of silicon oxide powder (SiO ₂ ), and 0.29 g of Eu ₂ Si ₅ N ₈ powder were weighed. And mixed uniformly by a wet ball mill using ethanol.
Next, the obtained slurry was evaporated to dryness, placed in a container made of hBN, and loaded into a firing furnace.
The firing atmosphere was a reduced pressure from room temperature to 1000 ° C., and a nitrogen atmosphere of 1 MPa was used at 1000 ° C. or higher. The temperature rising rate was 5 ° C./min, and after holding at 1550 ° C. for 2 hours, the furnace was cooled to room temperature.
As a result of performing powder X-ray diffraction measurement using CuKα rays for the obtained product, it was confirmed that BaSi ₂ Al ₂ O ₂ N ₂ was produced.
As a result of irradiating the powder with light having a wavelength of 365 nm with an ultraviolet lamp, it was confirmed that the powder emitted greenish blue light. Moreover, as a result of measuring the emission spectrum of this powder in 450 nm blue light excitation using the fluorescence spectrophotometer, the peak height of the emission spectrum was 172 counts. Since the count value varies depending on the measuring device and conditions, the unit is an arbitrary unit.

<Example 24>
As a phosphor raw material mixture, silicon nitride powder (Si ₃ N ₄ ) having an average particle size of 0.5 μm, an oxygen content of 0.93% by mass and an α-type content of 92%, and an aluminum nitride powder having a purity of 99.9% ( AlN), a 99.9% pure silicon oxide powder (SiO ₂ ), and a mixture of EuSi ₆ N ₈ (europium-containing silicon nitride powder) synthesized in Example 9 were used as follows. A β-SiAlON: Eu phosphor was synthesized.
First, 9.04 g of silicon nitride powder (Si ₃ N ₄ ), 0.27 g of aluminum nitride powder (AlN), 0.06 g of silicon oxide powder (SiO ₂ ), and 0.63 g of EuSi ₆ N ₈ powder were weighed, It mixed uniformly with the wet ball mill using ethanol.
Next, the obtained slurry was evaporated to dryness, placed in a container made of hBN, and loaded into a firing furnace.
The firing atmosphere was a reduced pressure from room temperature to 1000 ° C., and a nitrogen atmosphere of 1 MPa was used at 1000 ° C. or higher. The temperature increase rate was 5 ° C./min, and after holding at 2000 ° C. for 2 hours, the furnace was cooled to room temperature.
The obtained product was subjected to powder X-ray diffraction measurement using CuKα rays. As a result, it was confirmed that β-SiAlON was produced.
As a result of irradiating the powder with light having a wavelength of 365 nm with an ultraviolet lamp, it was confirmed that the powder emitted green light. Moreover, as a result of measuring the emission spectrum of this powder in 450 nm blue light excitation using the fluorescence spectrophotometer, the peak height of the emission spectrum was 91 counts. Since the count value varies depending on the measuring device and conditions, the unit is an arbitrary unit.

<Example 25>
Silicon nitride powder (Si ₃ N ₄ ) having an average particle size of 0.5 μm, an oxygen content of 0.93% by mass and an α-type content of 92%, and calcium acetate (Ca (CH ₃ COO) ₂ having a purity of 99.9% · _H with 2 O) and silicon nitride powder _{(Si 3} N 4) 6.14g, and weighed calcium acetate 3.86 g, they were uniformly mixed by a wet ball mill using ethanol. Next, the obtained slurry was evaporated to dryness, placed in a container made of hBN, and loaded into a firing furnace. After vacuum degassing at room temperature, the inside of the furnace was made an ammonia atmosphere, heated to 1500 ° C. at a rate of 5 ° C./min, held for 2 hours, and then cooled to room temperature. As a result of powder X-ray diffraction measurement using CuKα rays for the obtained product, it was confirmed that CaSiN ₂ was produced.
Next, as the phosphor raw material mixture, CaSiN ₂ obtained by the above method, aluminum nitride powder (AlN) having a purity of 99.9%, and EuSiN ₂ synthesized in Example 10 (europium-containing silicic nitride powder) Was used to synthesize a CaAlSiN ₃ : Eu phosphor as follows.
First, 6.89 g of CaSiN ₂ powder, 2.96 g of aluminum nitride powder (AlN), and 0.15 g of EuSiN ₂ powder were weighed and mixed uniformly by a wet ball mill using ethanol.
Next, the obtained slurry was evaporated to dryness, placed in a container made of hBN, and loaded into a firing furnace.
The firing atmosphere was a reduced pressure state from room temperature to 1000 ° C., and a nitrogen atmosphere of 1 MPa was used at 1000 ° C. or higher. The temperature increase rate was 5 ° C./min, and after holding at 1850 ° C. for 2 hours, the furnace was cooled to room temperature.
As a result of powder X-ray diffraction measurement using CuKα rays for the obtained product, it was confirmed that CaAlSiN ₃ was produced.
As a result of irradiating the powder with light having a wavelength of 365 nm with an ultraviolet lamp, it was confirmed that the powder emitted red light. Moreover, as a result of measuring the emission spectrum of this powder in 450 nm blue light excitation using the fluorescence spectrophotometer, the peak height of the emission spectrum was 131 counts. Since the count value varies depending on the measuring device and conditions, the unit is an arbitrary unit.

<Example 26>
Silicon nitride powder (Si ₃ N ₄ ) having an average particle size of 0.5 μm, oxygen content of 0.93% by mass and α-type content of 92%, and strontium acetate (Sr (CH ₃ COO) _2. 0.5H ₂ O) was weighed 5.66 g of silicon nitride powder (Si ₃ N ₄ ) and 4.34 g of strontium acetate, and uniformly mixed by a wet ball mill using ethanol. Next, the obtained slurry was evaporated to dryness, placed in a container made of hBN, and loaded into a firing furnace. After vacuum degassing at room temperature, the inside of the furnace was made an ammonia atmosphere, heated to 1500 ° C. at a rate of 5 ° C./min, held for 2 hours, and then cooled to room temperature. As a result of powder X-ray diffraction measurement using CuKα rays for the obtained product, it was confirmed that SrSiN ₂ was produced.
Next, as a phosphor raw material mixture, a mixture of SrSiN ₂ obtained by the above method, aluminum nitride powder (AlN) with a purity of 99.9%, and EuSiN ₂ (europium-containing siliconitride powder) synthesized in Example 10 Was used to synthesize SrAlSiN ₃ : Eu phosphor as follows.
First, 7.68 g of CaSiN ₂ powder, 2.21 g of aluminum nitride powder (AlN), and 0.11 g of EuSiN ₂ powder were weighed and mixed uniformly by a wet ball mill using ethanol.
Next, the obtained slurry was evaporated to dryness, placed in a container made of hBN, and loaded into a firing furnace.
The firing atmosphere was a reduced pressure from room temperature to 1000 ° C., and a nitrogen atmosphere of 1 MPa was used at 1000 ° C. or higher. The temperature increase rate was 5 ° C./min, and after holding at 1850 ° C. for 2 hours, the furnace was cooled to room temperature.
As a result of powder X-ray diffraction measurement using CuKα rays for the obtained product, it was confirmed that SrAlSiN ₃ was produced.
As a result of irradiating the powder with light having a wavelength of 365 nm with an ultraviolet lamp, it was confirmed that the powder emitted reddish orange. Moreover, as a result of measuring the emission spectrum of this powder in 450 nm blue light excitation using the fluorescence spectrophotometer, the peak height of the emission spectrum was 139 counts. Since the count value varies depending on the measuring device and conditions, the unit is an arbitrary unit.

<Examples 27 to 30>
Silicon nitride powder (Si ₃ N ₄ ) having an average particle size of 0.5 μm, an oxygen content of 0.93% by mass and an α-type content of 92%, and calcium carbonate having a purity of 99.99% as raw materials for synthesizing silicon nitride Powder (CaCO ₃ ), 99.9% pure strontium carbonate powder (SrCO ₃ ), 99.9% pure europium oxide powder (Eu ₂ O ₃ ), and 99.9999% pure carbon powder (C) And were used.

Silicon nitride powder (Si ₃ N ₄ ), europium oxide powder (Eu ₂ O ₃ ), calcium carbonate powder (CaCO ₃ ), strontium carbonate powder (SrCO ₃ ) and carbon powder (C) are weighed in the proportions shown in Table 3. Then, they were mixed uniformly by a wet ball mill using ethanol. Next, the obtained slurry was evaporated to dryness, placed in a container made of hBN, and loaded into a firing furnace.
The firing atmosphere was a reduced pressure from room temperature to 1000 ° C., and a nitrogen atmosphere of 1 MPa was used at 1000 ° C. or higher. The temperature was raised at a rate of 5 ° C./min, held at the temperature shown in Table 1 for 2 hours, and then cooled to room temperature.
The obtained product (europium-containing silicon nitride powder) is subjected to chemical analysis of Eu, Ca, Sr and Si using an inductively coupled plasma emission spectroscopic analyzer, and combined with an oxygen / nitrogen analyzer. The chemical analysis was conducted. Table 3 shows the chemical composition of the product that was clarified from the chemical analysis results.

<Example 31>
As a phosphor raw material mixture, a mixture of 99.9% pure aluminum nitride powder (AlN) and Ca _0.99 Eu _0.01 SiN ₂ (europium-containing calcium silicon nitride powder) synthesized in Example 27 was used. The CaAlSiN ₃ : Eu phosphor was synthesized as follows.
First, 2.96 g of aluminum nitride powder (AlN) and 7.04 g of Ca _0.99 Eu _0.01 SiN ₂ powder were weighed and mixed uniformly by a wet ball mill using ethanol. Next, the obtained slurry was evaporated to dryness, placed in a container made of hBN, and loaded into a firing furnace.
The firing atmosphere was a reduced pressure from room temperature to 1000 ° C., and a nitrogen atmosphere of 1 MPa was used at 1000 ° C. or higher. The temperature increase rate was 5 ° C./min, and after holding at 1850 ° C. for 2 hours, the furnace was cooled to room temperature.
As a result of powder X-ray diffraction measurement using CuKα rays for the obtained product, it was confirmed that CaAlSiN ₃ was produced.
As a result of irradiating the powder with light having a wavelength of 365 nm with an ultraviolet lamp, it was confirmed that the powder emitted red light. Moreover, as a result of measuring the emission spectrum of this powder in the blue light excitation of 450 nm using the fluorescence spectrophotometer, the peak height of the emission spectrum was 131 counts. Since the count value varies depending on the measuring device and conditions, the unit is an arbitrary unit.

<Example 32>
As a phosphor raw material mixture, a mixture of 99.9% pure aluminum nitride powder (AlN) and Sr _0.99 Eu _0.01 SiN ₂ (europium-containing strontium silicon nitride powder) synthesized in Example 28 was used. The SrAlSiN ₃ : Eu phosphor was synthesized as follows.
First, 2.21 g of aluminum nitride powder (AlN) and 7.79 g of Sr _0.99 Eu _0.01 SiN ₂ powder were weighed and mixed uniformly by a wet ball mill using ethanol. Next, the obtained slurry was evaporated to dryness, placed in a container made of hBN, and loaded into a firing furnace.
The firing atmosphere was a reduced pressure from room temperature to 1000 ° C., and a nitrogen atmosphere of 1 MPa was used at 1000 ° C. or higher. The temperature increase rate was 5 ° C./min, and after holding at 1850 ° C. for 2 hours, the furnace was cooled to room temperature.
As a result of powder X-ray diffraction measurement using CuKα rays for the obtained product, it was confirmed that SrAlSiN ₃ was produced.
As a result of irradiating the powder with light having a wavelength of 365 nm with an ultraviolet lamp, it was confirmed that the powder emitted reddish orange. Moreover, as a result of measuring the emission spectrum of this powder in 450 nm blue light excitation using the fluorescence spectrophotometer, the peak height of the emission spectrum was 136 counts. Since the count value varies depending on the measuring device and conditions, the unit is an arbitrary unit.

<Example 33>
As a phosphor raw material mixture, silicon nitride powder (Si ₃ N ₄ ) having an average particle size of 0.5 μm, an oxygen content of 0.93% by mass and an α-type content of 92%, and an aluminum nitride powder having a purity of 99.9% ( and AlN), with a mixture of _Sr 1.92 _Eu 0.08 _Si 5 _{N 8} synthesized in example 29 (europium-containing strontium珪窒compound powder), as follows, Sr-α-SiAlON: Eu phosphor was synthesized.
First, 8.12 g of silicon nitride powder (Si ₃ N ₄ ), 0.52 g of aluminum nitride powder (AlN) and 1.37 g of Sr _1.92 Eu _0.08 Si ₅ N ₈ powder were weighed and ethanol was used. It was mixed uniformly with a wet ball mill. Next, the obtained slurry was evaporated to dryness, placed in a container made of hBN, and loaded into a firing furnace.
The firing atmosphere was a reduced pressure from room temperature to 1000 ° C., and a nitrogen atmosphere of 1 MPa was used at 1000 ° C. or higher. The temperature increase rate was 5 ° C./min, and the temperature was kept at 1900 ° C. for 2 hours, and then cooled to room temperature.
As a result of performing powder X-ray diffraction measurement using CuKα rays for the obtained product, it was confirmed that Sr-α-SiAlON was produced.
As a result of irradiating the powder with light having a wavelength of 365 nm with an ultraviolet lamp, it was confirmed that the powder emitted orange light. Moreover, as a result of measuring the emission spectrum of this powder in 450 nm blue light excitation using the fluorescence spectrophotometer, the peak height of the emission spectrum was 122 counts. Since the count value varies depending on the measuring device and conditions, the unit is an arbitrary unit.

<Example 34>
As a phosphor raw material mixture, silicon nitride powder (Si ₃ N ₄ ) having an average particle size of 0.5 μm, an oxygen content of 0.93% by mass and an α-type content of 92%, and an aluminum nitride powder having a purity of 99.9% ( A mixture of Sr _0.96 Eu _0.04 Si ₆ N ₈ (europium-containing strontium silicate nitride powder) synthesized in Example 30 and using Sr-α-SiAlON as follows: Eu phosphor was synthesized.
First, weigh out 7,43 g of silicon nitride powder (Si ₃ N ₄ ), 0.47 g of aluminum nitride powder (AlN) and 2.10 g of Sr _0.96 Eu _0.04 Si ₆ N ₈ powder, and use ethanol. It was mixed uniformly with a wet ball mill. Next, the obtained slurry was evaporated to dryness, placed in a container made of hBN, and loaded into a firing furnace.
The firing atmosphere was a reduced pressure from room temperature to 1000 ° C., and a nitrogen atmosphere of 1 MPa was used at 1000 ° C. or higher. The temperature increase rate was 5 ° C./min, and the temperature was kept at 1900 ° C. for 2 hours, and then cooled to room temperature.
As a result of performing powder X-ray diffraction measurement using CuKα rays for the obtained product, it was confirmed that Sr-α-SiAlON was produced.
As a result of irradiating the powder with light having a wavelength of 365 nm with an ultraviolet lamp, it was confirmed that the powder emitted orange light. Moreover, as a result of measuring the emission spectrum of this powder in 450 nm blue light excitation using the fluorescence spectrophotometer, the peak height of the emission spectrum was 128 counts. Since the count value varies depending on the measuring device and conditions, the unit is an arbitrary unit.

<Comparative Example 1>
As a phosphor raw material mixture, silicon nitride powder (Si ₃ N ₄ ) having an average particle size of 0.5 μm, an oxygen content of 0.93% by mass and an α-type content of 92%, strontium silicide (SrSi ₂ ) having a purity of 99%, and Sr ₂ Si ₅ N ₈ : Eu phosphor was synthesized using europium nitride (EuN) as follows.
First, 1.49 g of silicon nitride powder (Si ₃ N ₄ ), 8.31 g of strontium silicide (SrSi ₂ ), and 0.20 g of europium nitride (EuN) powder were weighed and mixed by a dry ball mill filled with nitrogen gas. . Next, the obtained mixed powder was filled into a container made of hBN and loaded into a firing furnace.
The firing atmosphere was a reduced pressure from room temperature to 1000 ° C., and a nitrogen atmosphere of 1 MPa was used at 1000 ° C. or higher. The temperature increase rate was 5 ° C./min, and after holding at 1800 ° C. for 2 hours, the furnace was cooled to room temperature.
As a result of powder X-ray diffraction measurement using CuKα rays for the obtained product, it was confirmed that Sr ₂ Si ₅ N ₈ was produced.
As a result of irradiating the powder with light having a wavelength of 365 nm with an ultraviolet lamp, it was confirmed that the powder emitted reddish orange. Moreover, as a result of measuring the emission spectrum of this powder in 450 nm blue light excitation using the fluorescence spectrophotometer, the peak height of the emission spectrum was 76 counts. Since the count value varies depending on the measuring device and conditions, the unit is an arbitrary unit.

<Comparative example 2>
As a phosphor raw material mixture, silicon nitride powder (Si ₃ N ₄ ) having an average particle size of 0.5 μm, an oxygen content of 0.93% by mass, an α-type content of 92%, and an aluminum nitride powder (AlN) of 99.9% purity ), Calcium nitride powder (Ca ₃ N ₂ ) and europium nitride (EuN), a CaAlSiN ₃ : Eu phosphor was synthesized as follows.
First, 3.24 g of silicon nitride powder (Si ₃ N ₄ ), aluminum nitride powder (3.02 g of AlN, 3.61 g of calcium nitride powder (Ca ₃ N ₂ ), and 0.12 g of europium nitride (EuN) powder were weighed. The resulting mixed powder was filled in a container made of hBN and charged in a firing furnace.
The firing atmosphere was a reduced pressure state from room temperature to 1000 ° C., and a nitrogen atmosphere of 1 MPa was used at 1000 ° C. or higher. The temperature increase rate was 5 ° C./min, and after holding at 1850 ° C. for 2 hours, the furnace was cooled to room temperature.
As a result of powder X-ray diffraction measurement using CuKα rays for the obtained product, it was confirmed that CaAlSiN ₃ was produced.
As a result of irradiating the powder with light having a wavelength of 365 nm with an ultraviolet lamp, it was confirmed that the powder emitted red light. Moreover, as a result of measuring the emission spectrum of this powder in the blue light excitation of 450 nm using the fluorescence spectrophotometer, the peak height of the emission spectrum was 94 counts. Since the count value varies depending on the measuring device and conditions, the unit is an arbitrary unit.

  According to the present invention, it is possible to obtain a nitride-based or oxynitride-based phosphor having higher light emission intensity than conventional ones. In the future, it can be expected that the present invention will be greatly utilized and greatly contribute to industrial development.

Claims (13)

  A nitride-based or oxynitride-based phosphor raw material mixture containing a europium-containing silicon nitride powder. The europium-containing珪窒compound _{powder, (Eu x, M 1-} x) SiN 2, (Eu x, M 1-x) 2 Si 5 N 8, (Eu x, M 1-x) Si 6 N 8 ( 2. The M according to claim 1, wherein M is at least one selected from alkaline earth metal elements and II-valent lanthanide-based rare earth elements excluding Eu, and is at least one selected from 0 <x ≦ 1). Nitride-based or oxynitride-based phosphor raw material mixture.   3. The nitride-based or oxynitride-based phosphor raw material mixture according to claim 1, wherein an average particle diameter is 100 μm or less.   A matrix crystal containing the europium-containing silicon nitride powder and an element selected from Si, Al, alkaline earth metal elements, II-valent lanthanide rare earth elements excluding Eu, Sc, Y, and III-valent lanthanide rare earth elements The nitride-based or oxynitride-based phosphor raw material mixture according to any one of claims 1 to 3, further comprising a raw material compound. The base crystal raw material compound is Si ₃ N ₄ , SrSi ₂ , AlN, Ca ₃ N ₂ , Si ₃ N ₄ , Sr ₃ N ₂ , CaSi ₂ , SrSi ₂ , SrO, SrCO ₃ , BaCO ₃ , SiO ₂ , CaSiN. _2. The nitride-based or oxynitride-based phosphor raw material mixture according to claim 4, comprising at least _two of S ₂ and SrSiN ₂ .   A method for producing a nitride-based or oxynitride-based phosphor, comprising using a nitride-based or oxynitride-based phosphor raw material mixture containing europium-containing silicon nitride powder.   A method for producing a nitride-based or oxynitride-based phosphor, comprising firing a nitride-based or oxynitride-based phosphor raw material mixture containing a europium-containing silicon nitride powder. The europium-containing珪窒compound _{powder, (Eu x, M 1-} x) SiN 2, (Eu x, M 1-x) 2 Si 5 N 8, (Eu x, M 1-x) Si 6 N 8 ( 7. M is at least one selected from alkaline earth metal elements and II-valent lanthanide rare earth elements excluding Eu, and is at least one selected from 0 <x ≦ 1). 8. A method for producing a nitride-based or oxynitride-based phosphor according to 7.   The nitride material or oxynitride-based phosphor material mixture according to any one of claims 1 to 5 is used as the phosphor material mixture. A method for producing a nitride-based or oxynitride-based phosphor as described in 1. above.   The nitride system or oxynitride system according to any one of claims 6 to 9, wherein the phosphor raw material mixture is fired in a state in which the bulk density is maintained at a filling rate of 40% or less. A method for manufacturing the phosphor.   The powder of the target phosphor is added as a seed material in the range of 1 to 50 parts by mass with respect to 100 parts by mass of the phosphor raw material mixture, and fired. A method for producing a nitride-based or oxynitride-based phosphor according to claim 1.   The phosphor material mixture is fired at a firing temperature of 1400 ° C or higher and 2200 ° C or lower in a nitrogen atmosphere at a pressure of 0.1 MPa or higher and 100 MPa or lower. A method for producing a nitride-based or oxynitride-based phosphor as described in 1. above.   13. The nitride-based or oxynitride-based phosphor according to claim 6, wherein the phosphor raw material mixture is fired in the presence of carbon or a carbon-containing compound. Production method.