JP6239456B2 - Phosphor and method for producing the same - Google Patents

Description

  The present invention relates to a phosphor and a manufacturing method thereof.

In recent years, phosphors responsible for light conversion have been incorporated into light emitting devices such as LED lighting and displays.
For example, a LED in which phosphors are dispersed in silicon resin or the like is dropped onto an InGaN-based semiconductor chip that emits blue light or near-ultraviolet light, which is considered promising as an LED light source. Have been developed that are coated with a phosphor. In this case, the color is adjusted by the light emitted by the InGaN-based semiconductor chip and the light emitted by the phosphor excited by the light emitted by the chip.

In such a light emitting device, the light emission characteristics of the phosphor play a very important role in the characteristics of the device. Improvement of the light emission characteristics of the phosphor responsible for light conversion is very important for improving the characteristics of the light emitting device. At present, such a light emitting device mainly uses visible light excitation type phosphors such as Y ₃ Al ₁₂ O ₅ : Ce that emits yellow light and CaAlSiN ₃ : Eu that emits red light. These phosphors are said to have the best light emission characteristics at a particle size of several μm to several tens of μm. For this reason, phosphor particles whose average particle diameter has the above values are used. The fine particle phosphor having an average particle size of less than 1 μm has a poor crystallinity, a large number of defects, and insufficient dispersion of the activation element, so that the luminance is greatly reduced. In general, illumination using an LED / phosphor Not suitable for light-emitting devices such as displays.

On the other hand, a fine particle phosphor of less than 1 μm with high luminous efficiency is highly necessary for many applications.
For example, in fluorescent lamps that have been used for a long time, fine particle phosphors of less than 1 μm tend to have better application performance and less application amount than phosphors of about 10 μm. The same applies to LED lighting packages that have been launched in the last decades, and the fine particle phosphors of less than 1 μm are more dispersible and less loaded than phosphors of about 10 μm, and the light dispersibility is improved. Has advantages.

A fine particle phosphor of less than 1 μm excited by visible light is also highly necessary for many applications. In this case, the visible light excitation phosphor needs to be a nitrogen anion phosphor with sufficiently large crystal field splitting due to activation ions such as Eu ²⁺ and Ce ³⁺ and a sufficiently large nephelux effect. Therefore, it becomes a problem to sufficiently enhance the above-described effect and raise the luminous efficiency of the oxynitride fine particle phosphor of less than 1 μm or the nitride fine particle phosphor of less than 1 μm to the same level as the LED phosphor.

In order to form an alkaline earth metal element having a small particle size and a silicon-containing nitride phosphor or oxynitride phosphor, the following method has been attempted.
For example, in Patent Document 1, first, a phosphor precursor powder made of a mixture of phosphor raw material powders having an average particle diameter of 50 nm or less is prepared. For example, silicon nitride powder is used as the phosphor raw material powder. A solvent is added to the phosphor precursor powder to form a slurry. Thereafter, an organic binder is added to the slurry. Thereafter, the slurry to which the organic binder has been added is dried by spray drying to form granules having a particle size of 2 μm or less. The target phosphor is obtained by firing the granules thus formed. In the method disclosed in Patent Document 1, when a granule having a particle size of 2 μm or less of a phosphor precursor powder formed by spray drying is fired, the precursor powder is in a sintered state. For this reason, it is difficult to synthesize phosphor particles having a small particle size. In addition, since an organic binder is used to obtain granules having a particle size of 2 μm or less, carbon that cannot be removed even by firing may hinder the light emission characteristics of the phosphor. In addition, since a compound of an activation element such as Eu and an alkaline earth metal element compound that provides a site where the activation element is replaced are prepared as raw materials separately, Eu is converted into an alkaline earth metal element by firing. Difficult to distribute well throughout the site. As a result, the luminous efficiency of the phosphor obtained is lowered.
In Patent Document 2, a mixture of precursor particles made of a phosphor material is formed. At least one of the precursor particles has an average primary particle size of less than 100 nm. As precursor particles having an average primary particle size of less than 100 nm, for example, silicon nitride particles are used. Then, this mixture is baked and the target fluorescent substance is obtained by solid-phase reaction. In the method disclosed in Patent Document 2, the phosphor obtained by firing a mixture of precursor particles is a deposit of silicon nitride particles or silicon oxynitride particles. For this reason, it is difficult to synthesize phosphor particles having a small particle diameter due to adhesion between primary particles. Further, as in the case of Patent Document 1, since the activation element compound and the alkaline earth metal element compound are prepared separately, sufficient dispersion of Eu occurs until the particles reach submicron. Therefore, the luminous efficiency is lowered.

JP 2007-314726 A Special table 2011-515536 gazette

  As described above, the luminous efficiency of fine particle phosphors of less than 1 μm required for phosphors used for high-performance light-emitting devices with a reduced amount of phosphors is several μ to ten or more when formed by the conventional method. The level achieved with a particle size of μm has not been reached.

  For this reason, the present invention has been made in view of the above-described problems, and an alkaline earth metal element and silicon having high luminous efficiency with a phosphor alone and an average particle size of less than 1 μm. An object of the present invention is to provide a phosphor containing at least one of a nitride and an oxynitride contained therein and a method for producing the same.

  The present inventor has intensively studied to achieve the above-described object, and fine phosphor precursor particles in which an alkaline earth metal element and an activation element are finely deposited on the surface of silicon nitride fine particles by a wet chemical method. Thus, the inventors have obtained the knowledge that a phosphor containing at least one of a nitride containing an alkaline earth metal element and silicon and an oxynitride having a small particle diameter and excellent emission characteristics can be obtained.

  This invention is made | formed based on this knowledge, and has the following structures.

(Configuration 1)
A phosphor containing at least one of a nitride and an oxynitride containing an alkaline earth metal element, silicon and an activator element,
A phosphor having a volume average particle diameter of 50 nm to 400 nm and an internal quantum efficiency of 60% or more at an excitation wavelength of 450 nm.

(Configuration 2)
The phosphor is represented by a composition formula MSi ₂ O ₂ N ₂ ,
The oxynitride has the same crystal structure as SrSi ₂ O ₂ N ₂ ,
The element M is selected from one or more alkaline earth metal elements selected from the group consisting of Ca, Sr, Ba and Mg and containing at least Eu from at least one alkaline earth metal element selected from the group consisting of Eu and Ce. 2 or more types of activator elements, and 15 mol% or more and 99 mol% or less of Sr and 1 mol% or more and 20 mol% or less of activator elements with respect to the total of element M Phosphor.

(Configuration 3)
The phosphor according to Configuration 1 or 2, wherein the volume average particle size distribution index is 1.20 or more and 1.35 or less.

(Configuration 4)
A silicon-containing compound having a different crystal structure from the oxynitride,
The phosphor according to Configuration 2 or 3, wherein the oxynitride is included in an amount of 50% by mass or more based on a total of the oxynitride and the silicon-containing compound.

(Configuration 5)
A method for producing a phosphor containing at least one of a nitride and an oxynitride containing an alkaline earth metal element, silicon and an activator element,
Phosphor precursor particles comprising a silicon nitride particle, a compound containing an alkaline earth metal element deposited on the surface of the silicon nitride particle, and a compound containing an activator element, and having a volume average particle size of 250 nm or less A precursor preparation step to prepare,
And a firing step of firing the phosphor precursor particles.

(Configuration 6)
In the precursor preparation step, a wet chemical method is applied to a suspension containing silicon nitride particles, a substance containing an alkaline earth metal element, and a substance containing an activator element, and the surface of the silicon nitride particles is applied. The phosphor according to Configuration 5, further comprising a precursor forming step of forming phosphor precursor particles in which the compound containing the alkaline earth metal element and the compound containing the activator element are mixed and deposited. Manufacturing method.

(Configuration 7)
The phosphor precursor particles are one or more kinds of alkaline earths selected from silicon nitride particles and at least Sr selected from the group consisting of Ca, Sr, Ba and Mg deposited on the surface of the silicon nitride particles. A compound containing a metal element and a compound containing one or more activator elements selected from the group consisting of Eu and Ce, including at least Eu, a total of an alkaline earth metal element and an activator element and silicon In a range of 1: 1.4 to 1: 2.86,
The phosphor precursor particles have a composition having 15 mol% or more and 99 mol% or less of Sr and 1 mol% or more and 20 mol% or less of the activator element with respect to the total of the alkaline earth metal element and the activator element. 6. The method for producing a phosphor according to 5.

(Configuration 8)
The precursor preparation step includes
Selected from the group consisting of silicon nitride particles and one or more alkaline earth metal elements selected from the group consisting of Ca, Sr, Ba and Mg and including at least Eu from the group consisting of Eu and Ce A suspension containing a substance containing one or more activator elements in a molar ratio of the total of alkaline earth metal elements and activator elements to silicon in the range of 1: 1.4 to 1: 2.86. A suspension forming step to form;
A wet chemical method is applied to the suspension to precipitate a compound containing the alkaline earth metal element and a compound containing the activator element, and the alkaline earth metal is deposited on the surface of the silicon nitride particles. A precursor forming step of forming phosphor precursor particles in which a compound containing an element and a compound containing the activator element are mixed and deposited,
The suspension has a configuration 7 having 15 mol% or more and 99 mol% or less of Sr and 1 mol% or more and 20 mol% or less of the activator element with respect to the total of the alkaline earth metal element and the activator element. The manufacturing method of fluorescent substance of description.

(Configuration 9)
The method for producing a phosphor according to Configuration 6 or 8, wherein the wet chemical method is at least one of a coprecipitation method and a citrate method.

(Configuration 10)
The method for producing a phosphor according to Configuration 9, wherein the wet chemical method is a coprecipitation method.

(Configuration 11)
The compound containing the alkaline earth metal element and the compound containing the activator element are carbonate, hydrogen carbonate, phosphate, carboxylate, oxalate, sulfate, organometallic compound and water, respectively. 11. The method for producing a phosphor according to any one of constitutions 5 to 10, comprising at least one compound selected from the group consisting of oxides.

(Configuration 12)
The phosphor according to Configuration 11, wherein the compound containing the alkaline earth metal element and the compound containing the activator element each contain one or more compounds selected from the group consisting of carbonates and hydroxides. Manufacturing method.

(Configuration 13)
13. The method for manufacturing a phosphor according to any one of configurations 5 to 12, wherein the silicon nitride particles have a volume average particle size of 150 nm or less.

(Configuration 14)
14. The method for manufacturing a phosphor according to any one of configurations 5 to 13, wherein the silicon nitride particles are amorphous.

(Configuration 15)
15. The phosphor according to claim 5, wherein the firing step is performed at a temperature of 1150 ° C. or higher and 1650 ° C. or lower in a mixed gas atmosphere of hydrogen and nitrogen or a mixed gas atmosphere of ammonia and nitrogen. Production method.

  As described above, according to the phosphor containing at least one of a nitride and an oxynitride containing an alkaline earth metal element, silicon and an activator element according to the present invention, the volume average particle diameter is 50 nm or more and 400 nm or less. Yes, the internal quantum efficiency at an excitation wavelength of 450 nm is 60% or more. For this reason, a phosphor containing at least one of a nitride and an oxynitride containing an alkaline earth metal element, silicon, and an activator element having a small particle diameter and excellent emission characteristics can be obtained.

  In addition, according to the method for producing a phosphor containing at least one of a nitride and an oxynitride containing an alkaline earth metal element, silicon and an activator element according to the present invention, silicon nitride particles and deposited on the surface thereof A phosphor precursor particle having a volume average particle diameter of 250 nm or less including a compound containing an alkaline earth metal element and a compound containing an activator element is prepared, and the phosphor precursor particles are fired. The phosphor precursor particles are in a state where a compound containing an alkaline earth metal element and a compound containing an activator element are deposited on the surface of the silicon nitride particles. For this reason, cation exchange with silicon ions, alkaline earth metal ions, and ions of activator elements easily occurs during firing. Therefore, the synthesis reaction of the nitride or oxynitride having the target composition can be achieved with only a slight grain growth. Therefore, a phosphor containing at least one of a nitride and an oxynitride containing an alkaline earth metal element, silicon, and an activator element having a small particle diameter and excellent emission characteristics can be produced.

An image obtained by observing phosphor precursor particles with a scanning electron microscope (SEM) is shown. The excitation light emission spectrum of the fluorescent substance of Example 1 is shown. The X-ray-diffraction spectrum of the fluorescent substance of Example 1 and Example 2 is shown. The emission spectra of the phosphors of Example 2, Comparative Example 9 and Comparative Example 10 are shown. It is a graph which shows the relationship between the volume average particle diameter of fluorescent substance, and the internal quantum efficiency in excitation wavelength 450nm. It is a graph which shows the relationship between Sr content of fluorescent substance, and the internal quantum efficiency in excitation wavelength 450nm. It is a graph which shows the relationship between Eu content of fluorescent substance, and the internal quantum efficiency in excitation wavelength 450nm. It is a graph which shows the relationship between the volume average particle diameter of a silicon nitride particle, and the volume average particle diameter of fluorescent substance. It is a graph which shows the relationship between the volume average particle diameter of a silicon nitride particle, and the volume average particle size distribution parameter | index of fluorescent substance. It is a graph which shows the relationship between the volume average particle diameter of fluorescent substance precursor particle | grains, and the volume average particle diameter of fluorescent substance. It is a graph which shows the relationship between the volume average particle diameter of fluorescent substance precursor particle | grains, and the volume average particle size distribution parameter | index of fluorescent substance. It is a graph which shows the relationship between a calcination temperature and the internal quantum efficiency in the excitation wavelength of 450 nm of fluorescent substance. It is a graph which shows the relationship between a calcination temperature and the volume average particle diameter of fluorescent substance. It is a graph which shows the relationship between a calcination temperature and the volume average particle size distribution parameter | index of fluorescent substance.

  Embodiments of the present invention will be described below.

A. The phosphor obtained by the present invention includes at least a nitride and an oxynitride containing an alkaline earth metal element, silicon and an element that functions as an activator (hereinafter referred to as an activator element). Including one. The phosphor may contain only nitride or may contain only nitride. Moreover, the case where both nitride and oxynitride are included may be sufficient. In addition to nitrides and oxynitrides, impurities may be included within a range that does not adversely affect the light emission characteristics of the phosphor.

  Examples of alkaline earth metal elements that can be contained in nitrides and oxynitrides include calcium (Ca), strontium (Sr), barium (Ba), and magnesium (Mg).

  Nitride and oxynitride contain an activator element in order to improve the light emission characteristics of the phosphor. Examples of the activator element include europium (Eu), cerium (Ce), manganese (Mn), praseodymium (Pr), neodymium (Nd), samarium (Sm), terbium (Tb), dysprosium (Dy), and holmium (Ho). ), Erbium (Er), thulium (Tm) and ytterbium (Yb).

Examples of the nitride that can be contained in the phosphor of the present invention include M ₂ Si ₅ N ₈ -based nitride (M is an alkaline earth metal element, or an alkaline earth metal element and an activator element).

Examples of the oxynitride that can be contained in the phosphor of the present invention include, for example, MSi ₂ O ₂ N ₂ -based oxynitride (M is an alkaline earth metal element, or an alkaline earth metal element and an activator element), M ₂ (Si, Al) ₅ (N, O) _8- based oxynitride (M is an alkaline earth metal element, or an alkaline earth metal element and an activator element).

B. Method for manufacturing phosphor A phosphor containing at least one of a nitride containing an alkaline earth metal element and silicon, which is a phosphor to be a subject of the present invention, and an oxynitride is prepared by preparing phosphor precursor particles. It is manufactured by the precursor preparation process to perform, and the baking process which bakes fluorescent substance precursor particle | grains.

  Hereinafter, each process will be described in detail.

1. Precursor preparation step Silicon nitride particles and a substance containing an alkaline earth metal element are used as raw materials. In addition, a substance containing an activator element is used to improve the light emission characteristics of the phosphor.

  The silicon nitride particles used as a raw material are preferably amorphous. When amorphous silicon nitride particles are used as a raw material, silicon ions between a compound containing an alkaline earth metal element and a compound containing an activator element deposited on the surface of the silicon nitride particles during firing And cation exchange between alkaline earth metal ions and activator element ions.

  The silicon nitride particles used as a raw material preferably have a volume average particle size of 150 nm or less, more specifically 120 nm or less. When silicon nitride particles having a volume average particle size of 150 nm or less are used as raw materials, phosphor precursor particles having a small particle size are obtained, and as a result, phosphors having a small particle size are obtained. Further, when silicon nitride particles having a volume average particle size of 150 nm or less are used as a raw material, the particle size distribution can be controlled, and a phosphor having a uniform particle size can be obtained.

  Regarding substances containing alkaline earth metal elements used as raw materials, examples of substances containing Ca include calcium oxide, calcium hydroxide, calcium carbonate, calcium nitrate tetrahydrate, calcium sulfate dihydrate, and calcium oxalate. Examples thereof include monohydrate, calcium acetate monohydrate, calcium chloride, calcium fluoride, calcium nitride, calcium imine, and calcium amide. Of these, calcium nitrate tetrahydrate and calcium chloride are preferable. Examples of the substance containing Sr include strontium oxide, strontium hydroxide octahydrate, strontium carbonate, strontium nitrate, strontium sulfate, strontium oxalate monohydrate, strontium acetate hemihydrate, strontium chloride, fluorine. And strontium nitride, strontium nitride, strontium imine, and strontium amide. Of these, strontium nitrate and strontium chloride are preferable. Examples of the substance containing Ba include barium oxide, barium hydroxide octahydrate, barium carbonate, barium nitrate, barium sulfate, barium oxalate, barium acetate, barium chloride, barium fluoride, barium nitride, barium imine, barium Amides are mentioned. Of these, barium nitrate and barium chloride are preferable. Examples of the substance containing Mg include magnesium oxide, magnesium hydroxide, basic magnesium carbonate, magnesium nitrate hexahydrate, magnesium sulfate, magnesium oxalate dihydrate, magnesium acetate tetrahydrate, magnesium chloride, and fluoride. Magnesium chloride, magnesium nitride, magnesium imine, and magnesium amide. Of these, magnesium nitrate and magnesium chloride are preferable.

  Regarding substances containing activator elements used as raw materials, examples of substances containing Eu include europium oxide, europium sulfate, europium oxalate decahydrate, europium chloride (II), europium chloride (III), and europium fluoride. (II), europium (III) fluoride, europium nitrate hexahydrate, europium nitride, europium imine, europium amide. Among these, europium nitrate hexahydrate, europium oxide, and europium (II) chloride are preferable. As the substance containing other activation elements Ce, Mn, Pr, Nd, Sm, Tb, Dy, Ho, Er, Tm and Yb, in each compound mentioned as a specific example of the substance containing Eu, Eu is Examples of the compound include Ce, Mn, Pr, Nd, Sm, Tb, Dy, Ho, Er, Tm, and Yb, respectively.

  In the precursor preparation step, silicon nitride particles, a compound containing an alkaline earth metal element deposited on the surface of the silicon nitride particles, and a compound containing an activator element deposited on the surface of the silicon nitride particles, And phosphor precursor particles having a volume average particle size of 250 nm or less, more specifically 210 nm or less.

For example, MSi ₂ O ₂ N ₂ -based oxynitride (M is composed of one or more alkaline earth metal elements selected from the group consisting of Ca, Sr, Ba and Mg and containing at least Sr, and Eu and Ce. One or more activator elements selected from the group including at least Eu, and 15 mol% or more and 99 mol% or less, more specifically 20 mol% or more and 95 mol% with respect to the total of the elements M In the precursor preparatory step, it is intended to obtain an Sr of not more than 1% and not more than 1 mol% and not more than 20 mol%, more specifically not less than 5 mol% and not more than 15 mol%. A compound containing at least one alkaline earth metal element selected from the group consisting of silicon nitride particles and Ca, Sr, Ba and Mg deposited on the surface of the silicon nitride particles, and at least Sr and a phosphor precursor having a volume average particle diameter of 250 nm or less, more specifically 210 nm or less, and a compound containing one or more activator elements selected from the group consisting of u and Ce. Prepare body particles. The phosphor precursor particles include silicon nitride particles, a compound containing an alkaline earth metal element, and a compound containing an activator element, and a molar ratio of the total of the alkaline earth metal element and the activator element to silicon. In the range of 1: 1.4 to 1: 2.86, more specifically in the range of 1: 1.5 to 1: 2.67. Further, the phosphor precursor particles are composed of 15 mol% or more and 99 mol% or less, more specifically 20 mol% or more and 95 mol% or less of Sr with respect to the total of the alkaline earth metal element and the activator element. 1 mol% or more and 20 mol% or less, more specifically 5 mol% or more and 15 mol% or less activator element.

  The precursor preparation step includes a suspension formation step and a precursor formation step.

[Suspension formation process]
In order to obtain a nitride or oxynitride containing an alkaline earth metal element and silicon of the target composition, as raw materials, silicon nitride particles, a substance containing an alkaline earth metal element, and a substance containing an activator element Is formed at a predetermined ratio.

For example, if for the purpose of obtaining a MSi ₂ O ₂ N ₂ based oxynitride mentioned above, as a raw material, and silicon nitride particles, a substance containing an alkaline earth metal element, a substance containing activator elements A molar ratio of the total of alkaline earth metal elements and activator elements to silicon in the range of 1: 1.4 to 1: 2.86, more specifically 1: 1.5 to 1: 2.67. Form a suspension containing in range. Outside this range, the yield of the phosphor decreases, which causes an increase in cost. In addition, this suspension is 15 mol% or more and 99 mol% or less, more specifically 20 mol% or more and 95 mol% or less of Sr and 1 mol% or more and 20 mol% or less of the total of element M, More specifically, it contains 5 mol% or more and 15 mol% or less activator element.

  The suspension is formed by charging the raw material into a solvent and stirring. The solvent used to form the suspension is, for example, one or more polyvalents selected from the group consisting of water and ethylene glycol, propylene glycol, tetramethylene glycol, heptamethylene glycol, hexamethylene glycol, glycerin, and sorbitol. A mixed solvent with alcohol is mentioned. Among these, a mixed solvent of water and ethylene glycol is preferable.

[Precursor formation process]
Volume average particles obtained by applying a wet chemical method to the resulting suspension and depositing a mixture of a compound containing an alkaline earth metal element and a compound containing an activator element on the surface of the silicon nitride particles. Phosphor precursor particles having a diameter of 250 nm or less, more specifically 210 nm or less, are formed.

For example, in the case of aiming to obtain the above-described MSi ₂ O ₂ N ₂ oxynitride, a wet chemical method is applied to the obtained suspension, and a compound containing an alkaline earth metal element and an activator The compound containing the element is precipitated, and the surface of the silicon nitride particles is deposited by mixing the compound containing the alkaline earth metal element and the compound containing the activator element. More specifically, phosphor precursor particles having a size of 210 nm or less are formed. The phosphor precursor particles include silicon nitride particles, a compound containing an alkaline earth metal element, and a compound containing an activator element, and a molar ratio of the total of the alkaline earth metal element and the activator element to silicon. In the range of 1: 1.4 to 1: 2.86, more specifically in the range of 1: 1.5 to 1: 2.67. Outside this range, the yield of the phosphor decreases, which causes an increase in cost. Further, the phosphor precursor particles are 15 mol% or more and 99 mol% or less, more specifically 20 mol% or more and 95 mol% or less of Sr and 1 mol% or more and 20 mol% or less of the total of the elements M. More specifically, it has 5 to 15 mol% of activator element.

  When the volume average particle diameter of the phosphor precursor particles is 250 nm or less, a phosphor having a small particle diameter is obtained. Moreover, when the volume average particle diameter of the phosphor precursor particles is 250 nm or less, the particle size distribution can be controlled, and a phosphor having a uniform particle diameter can be obtained.

  By applying a wet chemical method to the suspension, a compound containing an alkaline earth metal element and a compound containing an activator element are deposited in a mixed state on the surface of the silicon nitride particles. For this reason, cation exchange with silicon ions and ions of alkaline earth metal ions or activator elements easily occurs during firing. Therefore, the synthesis reaction of the nitride or oxynitride having the target composition can be achieved with only a slight grain growth.

  The wet chemical method may be any method as long as it can be deposited in a state where a compound containing an alkaline earth metal element and a compound containing an activator element are mixed on the surface of the silicon nitride particles. Good. Preferably, it is at least one of a coprecipitation method and a citrate method. As the wet chemical method, only the coprecipitation method may be used, or only the citrate method may be included. Further, both the coprecipitation method and the citrate method may be used. When a coprecipitation method or a citrate method is used as a wet chemical method, a compound containing an alkaline earth metal element or a compound containing an activator element is easily deposited on the surface of the silicon nitride particles, and the silicon nitride particles Can be easily included and contacted. For this reason, cation exchange with silicon ions and ions of alkaline earth metal ions or activator elements easily occurs during firing. Therefore, the synthesis reaction of the nitride or oxynitride having the target composition can be achieved with only a slight grain growth.

  The coprecipitation method is performed by adding a coprecipitation agent to the suspension. Examples of the coprecipitate added to the suspension include an aqueous ammonium hydrogen carbonate solution, an aqueous ammonium carbonate solution, an aqueous urea solution, an aqueous acetamide solution, an aqueous thiourea solution, and an aqueous thioacetamide solution. Of these, an aqueous ammonium hydrogen carbonate solution and an aqueous ammonium carbonate solution are preferred.

  The citrate method is performed by adding citric acid to the suspension.

  Compounds containing alkaline earth metal elements and compounds containing activator elements deposited on the surface of silicon nitride particles are carbonate, bicarbonate, phosphate, carboxylate, oxalate, and sulfuric acid, respectively. Any compound may be used as long as it is at least one compound selected from the group consisting of a salt, an organometallic compound and a hydroxide. Preferably, it is one or more compounds selected from the group consisting of carbonates and hydroxides. Carbonates and hydroxides can be easily precipitated by a coprecipitation method or a citrate method.

  The phosphor precursor particles contained in the suspension are recovered using, for example, centrifugation.

2. Firing step The obtained phosphor precursor particles are fired. Firing is performed under firing conditions in which a phosphor containing a nitride or oxynitride containing an alkaline earth metal element, silicon and an activator element of the desired composition is obtained as a phosphor having a small particle size with excellent emission characteristics. .

For example, if for the purpose of obtaining a MSi ₂ O ₂ N ₂ based oxynitride mentioned above, the obtained phosphor precursor particles, a mixed gas atmosphere of a mixed gas atmosphere or ammonia and nitrogen and hydrogen and nitrogen Under the temperature, firing is performed at a temperature of 1150 ° C. to 1650 ° C., more specifically 1200 ° C. to 1600 ° C. By calcination in a mixed gas atmosphere of hydrogen and nitrogen or a mixed gas atmosphere of ammonia and nitrogen, a phosphor containing an MSi ₂ O ₂ N ₂ oxynitride having a target composition as a main component can be obtained. By including an MSi ₂ O ₂ N ₂ oxynitride having a target composition as a main component, a phosphor having excellent emission characteristics can be obtained. Further, by firing at a temperature of 1150 ° C. or higher, insufficient firing of the target composition MSi ₂ O ₂ N ₂ oxynitride can be prevented, and further, the target composition MSi ₂ O ₂ N ₂ oxynitride can be prevented. Generation of impurities other than the above can be prevented. Insufficient firing and generation of impurities can be prevented, so that a phosphor having excellent light emission characteristics can be obtained. Further, by firing at a temperature of 1650 ° C. or lower, it is possible to prevent the progress of grain growth, and it is possible to prevent the melting of the MSi ₂ O ₂ N ₂ oxynitride having the target composition. Since progress of grain growth can be prevented, a phosphor having a small particle diameter can be obtained. Furthermore, since melting of the MSi ₂ O ₂ N ₂ oxynitride having the target composition can be prevented, a phosphor containing the MSi ₂ O ₂ N ₂ oxynitride having the target composition is easily manufactured.

  Firing is performed by the following procedure, for example. First, the obtained phosphor precursor particles are filled into a heat-resistant container made of a material having low reactivity. Examples of the heat-resistant container include a crucible and a tray. As the material of the heat-resistant container, for example, ceramics such as alumina, boron nitride, silicon nitride, silicon carbide, magnesium, mullite, metals such as platinum, molybdenum, tungsten, tantalum, niobium, iridium, rhodium, or alloys containing them as a main component And carbon (graphite). Preferably, a heat-resistant container made of boron nitride, alumina, silicon nitride, silicon carbide, platinum, molybdenum, tungsten, or tantalum is used.

  Thereafter, the heat-resistant container filled with the phosphor precursor particles is placed in a baking apparatus. As a baking apparatus, a metal furnace and a carbon furnace are mentioned, for example.

Then, the inside of the baking apparatus in which the heat-resistant container was put is made into reduced pressure states, such as a vacuum. Thereafter, the temperature in the baking apparatus is raised to the calcining temperature. Thereafter, a phosphor containing a nitride or oxynitride containing an alkaline earth metal element, silicon and an activator element having a target composition is obtained as a phosphor having a small particle diameter and excellent emission characteristics. Gas is introduced into the firing apparatus, and the pressure in the firing apparatus is returned to about atmospheric pressure. For example, in the case of obtaining the above-described MSi ₂ O ₂ N ₂ -based oxynitride, a mixed gas of hydrogen and nitrogen or a mixed gas of ammonia and nitrogen is introduced into the firing apparatus. Thereafter, a firing apparatus is used so that a phosphor containing a nitride or oxynitride containing an alkaline earth metal element, silicon and an activator element having a target composition can be obtained as a phosphor having a small particle diameter and excellent emission characteristics. The inside is heated to a predetermined firing temperature and held for a predetermined time. For example, when the objective is to obtain the above-described MSi ₂ O ₂ N ₂ oxynitride, the temperature is raised to a firing temperature of 150 ° C. or higher and 1650 ° C. or lower, more specifically 1200 ° C. or higher and 1600 ° C. or lower.

C. Phosphor The phosphor containing at least one of a nitride and an oxynitride containing an alkaline earth metal element, silicon and an activator element, obtained by the above-described production method, has a volume average particle diameter of 50 nm or more and 400 nm or less. Specifically, it is 100 nm or more and 350 nm or less, and the internal quantum efficiency at an excitation wavelength of 450 nm is 60% or more, more specifically 70% or more. For this reason, this phosphor has excellent emission characteristics and a small particle size.

For example, a phosphor containing an oxynitride containing an alkaline earth metal element, an activator element, and silicon, obtained by the above-described manufacturing method for the purpose of obtaining the above-described MSi ₂ O ₂ N ₂ oxynitride Is a composition formula MSi ₂ O ₂ N ₂ (M is a group consisting of one or more alkaline earth metal elements selected from the group consisting of Ca, Sr, Ba and Mg and containing at least Sr, and Eu and Ce. One or more activator elements selected including at least Eu, and 15 mol% or more and 99 mol% or less, more specifically 20 mol% or more and 95 mol% or less with respect to the total of the elements M Sr of 1 mol% to 20 mol%, more specifically 5 mol% to 15 mol% of an activator element), and the oxynitride is SrSi ₂ O ₂ N ₂ Have the same crystal structure The This phosphor has a volume average particle diameter of 50 nm or more and 400 nm or less, more specifically 100 nm or more and 350 nm or less, and an internal quantum efficiency at an excitation wavelength of 450 nm of 60% or more, more specifically 70% or more. For this reason, this phosphor has excellent emission characteristics and a small particle size. In addition, since this phosphor has 15 mol% or more of Sr with respect to the total of the elements M, it is possible to prevent the melting point of the MSi ₂ O ₂ N ₂ oxynitride having the target composition from being lowered. it can. For this reason, it is easy to manufacture a phosphor containing an MSi ₂ O ₂ N ₂ oxynitride having a target composition. Moreover, since this phosphor has 99 mol% or less of Sr with respect to the total of the elements M, it is possible to prevent a decrease in the content of the activator element. For this reason, the fluorescent substance excellent in the light emission characteristic is obtained. Moreover, since this fluorescent substance has 1 mol% or more of activator elements with respect to the total of the elements M, the content of the activator elements can be ensured. For this reason, the fluorescent substance excellent in the light emission characteristic is obtained. Moreover, since this phosphor has an activator element of 20 mol% or less with respect to the total of the elements M, the occurrence of concentration quenching can be prevented. For this reason, the fluorescent substance excellent in the light emission characteristic is obtained.

  In addition, the phosphor obtained by the manufacturing method described above preferably has a volume average particle size distribution index of 1.20 or more and 1.35 or less, more specifically 1.21 or more and 1.32 or less. When the volume average particle size distribution index is 1.20 or more and 1.35 or less, the obtained phosphor has a uniform particle size.

In addition, when the phosphor obtained by the manufacturing method described above contains a silicon-containing compound having a crystal structure different from that of the oxynitride having the target composition, the oxynitride having the target composition is converted into It is preferable to contain 50% by mass or more, more specifically 70% by mass or more with respect to the total. By including 50% by mass or more of the oxynitride having the target composition, the main component is the MSi ₂ O ₂ N ₂ oxynitride having the target composition. For this reason, the fluorescent substance excellent in the light emission characteristic is obtained.

D. Use of fluorescent substance The fluorescent substance obtained by this invention can be used for light conversion apparatuses, such as LED illumination and a display. Moreover, since the particle diameter is as fine as 400 nm or less, it can be used as an alternative to conventional pigments.

  Hereinafter, based on an Example, this invention is demonstrated more concretely.

  Various measurements and analyzes in Examples and Comparative Examples were performed as follows.

<Particle size distribution measurement>
In Examples and Comparative Examples, the particle size distribution of particles was measured using ELS-Z1000ZS (manufactured by Otsuka Electronics). For the measurement, a measurement sample was used in which the sample was dispersed in ethanol or water and dispersed by ultrasonic waves for 30 seconds or more. Based on the particle size distribution of the measured particles, the volume occupied by the particles included in the divided particle size range is accumulated from the small diameter side, and the particle size that becomes 16% is D16 _V and the particle that becomes 50% cumulative The diameter was defined as D50 _V , and the particle diameter at 84% cumulative was defined as D84 _V. At this time, D50 _V is defined as the volume average particle size, and D84 _V / D16 _V is defined as the volume average particle size distribution index PSD _V.
Also, based on the measured particle size distribution of the particles, the number of particles included in the divided particle size range is accumulated from the smaller diameter side, and the particle size at which 50% is accumulated is defined as the number average particle size.

<Excitation emission spectrum measurement>
In Examples and Comparative Examples, excitation emission spectra were measured using a fluorescence spectrophotometer F-7000 (manufactured by Hitachi High-Technologies).

<Internal quantum efficiency measurement>
In Examples, the internal quantum efficiency was measured using an absolute PL quantum yield measuring apparatus (manufactured by Hamamatsu Photonics). A 0.1 g sample was used for the measurement. The measurement was performed at an excitation wavelength of 450 nm.

<Scanning electron microscope observation>
In Examples, particles were observed using a scanning electron microscope (SEM) SU8020 (manufactured by Hitachi High-Technologies).

<Metal element analysis>
In Examples and Comparative Examples, metal element analysis was performed using ICP-MS (manufactured by Agilent Technologies) and ICP-AES (manufactured by Shimadzu Corporation). For metal elemental analysis, a sample for measurement was used in which the sample was alkali-fused with a flux (borax: sodium carbonate = 1: 1) and then added with hydrochloric acid and the volume was adjusted. Europium was analyzed by ICP-MS (manufactured by Agilent Technologies), and other metal elements were analyzed by ICP-AES (manufactured by Shimadzu Corporation).

<Powder X-ray diffraction>
In Examples and Comparative Examples, powder X-ray diffraction was performed using an X-ray diffractometer Smart Lab (manufactured by Rigaku). In powder X-ray diffraction, CuKα was used as a radiation source. By analyzing the X-ray diffraction spectrum obtained by powder X-ray diffraction, qualitative analysis and quantitative analysis of the inorganic compound formed in the sample were performed.

  Table 1 shows various production conditions in the precursor preparation step and the firing step of Examples and Comparative Examples shown below. Table 2 shows the characteristics of the obtained precursor and fired product.

Example 1.
[Precursor preparation process]
(Suspension formation process)
As raw materials, amorphous silicon nitride particles (manufactured by Sigma-Aldrich) having a volume average particle diameter D50 _V of 50 nm, strontium nitrate (manufactured by Kishida Chemical), and europium nitrate hexahydrate (manufactured by Kishida Chemical) were used. .

In order to obtain an oxynitride represented by a composition formula Eu _0.1 Sr _0.9 Si ₂ O ₂ N ₂ , silicon nitride particles, strontium nitrate, and europium nitrate hexahydrate were respectively mixed in 28.461 mass% and 57 It weighed so that it might become 964 mass% and 13.575 mass%. When weighed in this manner, the suspension and phosphor precursor particles described later contain a molar ratio of the sum of Sr and Eu to silicon of 1: 2, and with respect to the sum of Sr and Eu, 90 mol% Sr and 10 mol% Eu are included. The weighed raw material was put into a mixed solvent composed of 100 g of water and 50 g of ethylene glycol, and stirred to form a suspension.

(Precursor formation step)
Ammonium hydrogen carbonate (manufactured by Kishida Chemical) was dissolved in water, and 216 ml of an aqueous ammonium hydrogen carbonate solution having a concentration of 0.158 mol / L was formed as a coprecipitation agent.

  Next, the coprecipitate was added dropwise over 1 hour while stirring and mixing the suspension obtained as described above. After dropwise addition of the coprecipitate, stirring and mixing were continued for 2 hours. In this way, strontium ions and europium ions are precipitated as carbonates and hydroxides, respectively, and the strontium carbonate and europium hydroxide are uniformly mixed and deposited on the surface of the silicon nitride particles. Body precursor particles were formed.

  Thereafter, the suspension containing the phosphor precursor particles was subjected to solvent substitution from a mixed solvent composed of water and ethylene glycol to water by centrifugation. The suspension after solvent replacement was placed in a drier set at 100 ° C., and water was evaporated to collect phosphor precursor particles.

[Baking process]
The obtained phosphor precursor particles were fired by the following procedure. First, the obtained phosphor precursor particles were filled in a boron nitride crucible. Thereafter, the crucible filled with the phosphor precursor particles was placed in a vacuum atmosphere furnace (manufactured by Nemus) which is a metal furnace. After putting the crucible into the furnace, first, the inside of the furnace was evacuated by a diffusion pump. Thereafter, the temperature in the furnace was increased from room temperature to 1100 ° C. at a rate of 300 ° C. per hour. Thereafter, while maintaining the furnace temperature at 1100 ° C., a mixed gas of 4 volume% hydrogen and 96 volume% nitrogen was introduced into the furnace to return the furnace pressure to about atmospheric pressure. Thereafter, the temperature in the furnace was increased to 1450 ° C. at a rate of 300 ° C. per hour, the furnace temperature was maintained at 1450 ° C. for 3 hours, and the phosphor precursor particles were fired to obtain a fired product.

[Characteristics of phosphor precursor particles]
The obtained phosphor precursor particles were observed using a scanning electron microscope. FIG. 1 shows an image obtained by observing phosphor precursor particles with a scanning electron microscope (SEM). In FIG. 1, many particles having a particle size of about 100 nm are seen. From this, it was confirmed that strontium carbonate and europium hydroxide were deposited on the surface of the silicon nitride particles.

Further, the particle size distribution of the obtained phosphor precursor particles was measured. From the measurement result of the particle size distribution, the volume average particle diameter D50 _V of the phosphor precursor particles was 127 nm.

[Characteristics of phosphor]
The excited emission spectrum of the obtained fired product was measured. FIG. 2 shows the excitation emission spectrum of the fired product of Example 1. The horizontal axis in FIG. 2 is the wavelength, and the vertical axis is the intensity. From the excitation emission spectrum, it was found to be yellow-green light having an emission peak wavelength of 550 nm excited by light in a wide wavelength range from ultraviolet light of 200 nm or more to visible light of 500 nm or less. From this, it was confirmed that the obtained fired product was a phosphor excited by visible light.

Moreover, the powder X-ray diffraction of the obtained baked product was performed. 3 shows the X-ray diffraction spectrum of the fired product of Example 1. The horizontal axis in FIG. 3 is the angle formed by the incident X-ray direction and the diffracted X-ray direction, and the vertical axis is the intensity. When the X-ray diffraction spectrum was analyzed by the Rietveld method, the obtained fired product was obtained by using an oxynitride having the same crystal structure as SrSi ₂ O ₂ N ₂ and a silicon-containing compound having the same crystal structure as SiO _2. Was found to be generated. Moreover, it turned out that 85 mass% of oxynitrides are produced | generated and 15 mass% of silicon containing compounds are produced | generated with respect to the sum total of an oxynitride and a silicon containing compound. Incidentally, c in Figure 3 shows the X-ray diffraction spectrum of SrSi ₂ O ₂ N ₂ crystal obtained by calculation.

  Moreover, the metal element analysis of the obtained baked product was performed. From the measurement results of the metal element analysis, it was found that the obtained fired product contained Sr and Eu in a molar ratio of Sr: Eu = 0.9: 0.1.

Moreover, the particle size distribution of the obtained baked product was measured. From the measurement result of the particle size distribution, the volume average particle size D50 _V of the fired product was 165 nm, and the volume average particle size distribution index PSD _V was 1.26.

  Moreover, the internal quantum efficiency in the excitation wavelength of 450 nm of the obtained baked product was measured. From the measurement results, the internal quantum efficiency of the fired product at an excitation wavelength of 450 nm was 73%.

From the above, the phosphor obtained in Example 1 includes an oxynitride containing Sr, Eu, and Si. Further, this phosphor is represented by a composition formula Eu _0.1 Sr _0.9 Si ₂ O ₂ N ₂ . From this composition formula, this phosphor has 90 mol% Sr and 10 mol% Eu with respect to the total of Sr and Eu. This oxynitride has the same crystal structure as SrSi ₂ O ₂ N ₂ . Further, this phosphor has a volume average particle size D50 _V of 165 nm and a volume average particle size distribution index PSD _V of 1.26. Further, this phosphor has an internal quantum efficiency of 73% at an excitation wavelength of 450 nm. Further, this phosphor contains 85 mass% oxynitride with respect to the total of the oxynitride and the silicon-containing compound.

Example 2
As raw materials, amorphous silicon nitride particles having a volume average particle diameter D50 _V of 50 nm (manufactured by Sigma-Aldrich), strontium nitrate (manufactured by Kishida Chemical), calcium nitrate tetrahydrate (manufactured by Kishida Chemical), and europium nitrate Hexahydrate (manufactured by Kishida Chemical) was used. In order to obtain an oxynitride represented by a composition formula Eu _0.1 Sr _0.45 Ca _0.45 Si ₂ O ₂ N ₂ , silicon nitride particles, strontium nitrate, calcium nitrate tetrahydrate, and europium nitrate hexahydrate Were weighed to be 27.537 mass%, 28.040 mass%, 31.289 mass%, and 13.134 mass%, respectively. When weighed in this way, the suspension and phosphor precursor particles contain a molar ratio of the sum of Sr, Ca and Eu to silicon of 1: 2, and relative to the sum of Sr, Ca and Eu. 45 mol% Sr and 10 mol% Eu.

  Otherwise, phosphor precursor particles and a fired product were obtained in the same manner as in Example 1.

When the particle size distribution of the obtained phosphor precursor particles was measured, the volume average particle diameter D50 _V of the phosphor precursor particles was 112 nm.

  Moreover, when the excitation light emission spectrum of the obtained baked product was measured, it was found that the light emission peak wavelength was 543 nm by being excited by light in a wavelength range of 200 nm to 500 nm. From this, it was confirmed that the obtained fired product was a phosphor excited by visible light. 4 shows the emission spectrum of the fired product of Example 2. FIG. The horizontal axis in FIG. 4 is the wavelength, and the vertical axis is the intensity.

Moreover, when the powder X-ray diffraction of the obtained baked product was performed, the obtained baked product contained oxynitride having the same crystal structure as SrSi ₂ O ₂ N ₂ and silicon having the same crystal structure as SiO _2. It was found that the contained compound was produced. Moreover, it turned out that 89 mass% of oxynitrides are produced | generated and 11 mass% of silicon containing compounds are produced | generated with respect to the sum total of an oxynitride and a silicon containing compound. B in FIG. 3 shows the X-ray diffraction spectrum of the fired product of Example 2.

  Further, when elemental analysis of the obtained fired product was performed, the obtained fired product had a molar ratio of Sr: Ca: Eu = 0.45: 0.45: 0.1 in Sr: Ca: Eu. It was found that it was included.

Moreover, when the particle size distribution of the obtained baked product was measured, the volume average particle size D50 _V of the baked product was 142 nm, and the volume average particle size distribution index PSD _V was 1.24.

  Moreover, when the internal quantum efficiency in the excitation wavelength of 450 nm of the obtained baked product was measured, the internal quantum efficiency in the excitation wavelength of 450 nm of the baked product was 81%.

From the above, the phosphor obtained in Example 2 includes an oxynitride containing Sr, Ca, Eu, and Si. Further, this phosphor is represented by a composition formula Eu _0.1 Sr _0.45 Ca _0.45 Si ₂ O ₂ N ₂ . From this composition formula, this phosphor has 45 mol% Sr and 10 mol% Eu with respect to the total of Sr, Ca and Eu. This oxynitride has the same crystal structure as SrSi ₂ O ₂ N ₂ . Further, this phosphor has a volume average particle size D50 _V of 142 nm and a volume average particle size distribution index PSD _V of 1.24. Further, this phosphor has an internal quantum efficiency of 81% at an excitation wavelength of 450 nm. The phosphor contains 89% by mass of oxynitride with respect to the total of the oxynitride and the silicon-containing compound.

Example 3 FIG.
In the same manner as in Example 1, phosphor precursor particles were obtained. Moreover, the phosphor precursor particles were baked in the same manner as in Example 1 except that the phosphor precursor particles were baked in a mixed gas atmosphere of 4 volume% ammonia and 96 volume% nitrogen to obtain a baked product.

When various measurements and analyzes were performed in the same manner as in Example 1, it was found that the obtained fired product was excited by light having a wavelength range of 200 nm to 500 nm and had an emission peak wavelength of 550 nm. From this, it was confirmed that the obtained fired product was a phosphor excited by visible light. Further, it was found that the obtained fired product produced an oxynitride having the same crystal structure as SrSi ₂ O ₂ N ₂ and a silicon-containing compound having the same crystal structure as SiO ₂ . Moreover, it turned out that 92 mass% of oxynitrides are produced | generated and 8 mass% of silicon containing compounds are produced | generated with respect to the sum total of an oxynitride and a silicon containing compound. Further, it was found that the obtained fired product contained Sr and Eu in a molar ratio of Sr: Eu = 0.9: 0.1. The obtained fired article had a volume average particle diameter D50 _V of 153 nm and a volume average particle size distribution index PSD _V of 1.27. The obtained fired article had an internal quantum efficiency of 83% at an excitation wavelength of 450 nm.

From the above, the phosphor obtained in Example 3 includes an oxynitride containing Sr, Eu, and Si. Further, this phosphor is represented by a composition formula Eu _0.1 Sr _0.9 Si ₂ O ₂ N ₂ . From this composition formula, this phosphor has 90 mol% Sr and 10 mol% Eu with respect to the total of Sr and Eu. This oxynitride has the same crystal structure as SrSi ₂ O ₂ N ₂ . Further, this phosphor has a volume average particle diameter D50 _V of 153 nm and a volume average particle size distribution index PSD _V of 1.27. Further, this phosphor has an internal quantum efficiency of 83% at an excitation wavelength of 450 nm. Further, this phosphor contains 92% by mass of oxynitride with respect to the total of the oxynitride and the silicon-containing compound.

Example 4
In the same manner as in Example 1, phosphor precursor particles were obtained. Moreover, the phosphor precursor particles were baked by the same method as in Example 1 except that the baked product was obtained at 1250 ° C.

When various measurements and analyzes were performed in the same manner as in Example 1, it was found that the obtained fired product was excited by light having a wavelength range of 200 nm to 500 nm and had an emission peak wavelength of 550 nm. From this, it was confirmed that the obtained fired product was a phosphor excited by visible light. Further, it was found that the obtained fired product produced an oxynitride having the same crystal structure as SrSi ₂ O ₂ N ₂ and a silicon-containing compound having the same crystal structure as SiO ₂ . Moreover, it turned out that 82 mass% of oxynitrides are produced | generated and 18 mass% of silicon containing compounds are produced | generated with respect to the sum total of an oxynitride and a silicon containing compound. Further, it was found that the obtained fired product contained Sr and Eu in a molar ratio of Sr: Eu = 0.9: 0.1. The obtained fired article had a volume average particle diameter D50 _V of 148 nm and a volume average particle size distribution index PSD _V of 1.25. The obtained fired article had an internal quantum efficiency of 72% at an excitation wavelength of 450 nm.

From the above, the phosphor obtained in Example 4 includes an oxynitride containing Sr, Eu, and Si. Further, this phosphor is represented by a composition formula Eu _0.1 Sr _0.9 Si ₂ O ₂ N ₂ . From this composition formula, this phosphor has 90 mol% Sr and 10 mol% Eu with respect to the total of Sr and Eu. This oxynitride has the same crystal structure as SrSi ₂ O ₂ N ₂ . Further, this phosphor has a volume average particle diameter D50 _V of 148 nm and a volume average particle size distribution index PSD _V of 1.25. This phosphor has an internal quantum efficiency of 72% at an excitation wavelength of 450 nm. The phosphor includes 82% by mass of oxynitride with respect to the total of the oxynitride and the silicon-containing compound.

Example 5 FIG.
In the same manner as in Example 1, phosphor precursor particles were obtained. Moreover, the phosphor precursor particles were baked by the same method as in Example 1 except that the baked product was obtained at 1550 ° C.

When various measurements and analyzes were performed in the same manner as in Example 1, it was found that the obtained fired product was excited by light having a wavelength range of 200 nm to 500 nm and had an emission peak wavelength of 552 nm. From this, it was confirmed that the obtained fired product was a phosphor excited by visible light. Further, it was found that the obtained fired product produced an oxynitride having the same crystal structure as SrSi ₂ O ₂ N ₂ and a silicon-containing compound having the same crystal structure as SiO ₂ . Moreover, it turned out that 88 mass% of oxynitrides are produced | generated and 12 mass% of silicon containing compounds are produced | generated with respect to the sum total of an oxynitride and a silicon containing compound. Further, it was found that the obtained fired product contained Sr and Eu in a molar ratio of Sr: Eu = 0.9: 0.1. The obtained fired article had a volume average particle diameter D50 _V of 173 nm and a volume average particle size distribution index PSD _V of 1.24. Moreover, the internal quantum efficiency in the excitation wavelength of 450 nm of the obtained baked product was 80%.

From the above, the phosphor obtained in Example 5 includes an oxynitride containing Sr, Eu, and Si. Further, this phosphor is represented by a composition formula Eu _0.1 Sr _0.9 Si ₂ O ₂ N ₂ . From this composition formula, this phosphor has 90 mol% Sr and 10 mol% Eu with respect to the total of Sr and Eu. This oxynitride has the same crystal structure as SrSi ₂ O ₂ N ₂ . Further, this phosphor has a volume average particle diameter D50 _V of 173 nm and a volume average particle size distribution index PSD _V of 1.24. Further, this phosphor has an internal quantum efficiency of 80% at an excitation wavelength of 450 nm. Further, this phosphor contains 88% by mass of oxynitride with respect to the total of the oxynitride and the silicon-containing compound.

Example 6
In order to obtain an oxynitride represented by the composition formula Eu _0.1 Sr _0.7 Ca _0.2 Si ₂ O ₂ N ₂ , silicon nitride particles, strontium nitrate, calcium nitrate tetrahydrate, and europium nitrate hexahydrate In the same manner as in Example 2 except that 28.043% by mass, 44.420% by mass, 14.162% by mass, and 13.375% by mass were respectively measured. And a fired product was obtained.

When various measurements and analyzes were performed in the same manner as in Example 1, the volume average particle diameter D50 _V of the obtained phosphor precursor particles was 121 nm. Moreover, it was found that the obtained fired product was excited by light having a wavelength range of 200 nm or more and 500 nm or less, and the emission peak wavelength was 548 nm. From this, it was confirmed that the obtained fired product was a phosphor excited by visible light. Further, it was found that the obtained fired product produced an oxynitride having the same crystal structure as SrSi ₂ O ₂ N ₂ and a silicon-containing compound having the same crystal structure as SiO ₂ . Moreover, it turned out that 86 mass% of oxynitrides are produced | generated and 14 mass% of silicon containing compounds are produced | generated with respect to the sum total of an oxynitride and a silicon containing compound. Moreover, it was found that the obtained fired product contained Sr, Ca, and Eu in a molar ratio of Sr: Ca: Eu = 0.7: 0.2: 0.1. The obtained fired article had a volume average particle diameter D50 _V of 151 nm and a volume average particle size distribution index PSD _V of 1.27. Moreover, the internal quantum efficiency in the excitation wavelength of 450 nm of the obtained baked product was 79%.

From the above, the phosphor obtained in Example 6 includes an oxynitride containing Sr, Ca, Eu, and Si. Moreover, this fluorescent substance is represented by a composition formula Eu _0.1 Sr _0.7 Ca _0.2 Si ₂ O ₂ N ₂ . From this composition formula, this phosphor has 70 mol% Sr and 10 mol% Eu with respect to the total of Sr, Ca and Eu. This oxynitride has the same crystal structure as SrSi ₂ O ₂ N ₂ . Further, this phosphor has a volume average particle diameter D50 _V of 151 nm and a volume average particle size distribution index PSD _V of 1.27. This phosphor has an internal quantum efficiency of 79% at an excitation wavelength of 450 nm. The phosphor includes 86% by mass of oxynitride with respect to the total of the oxynitride and the silicon-containing compound.

Example 7
In order to obtain an oxynitride represented by the composition formula Eu _0.1 Sr _0.2 Ca _0.7 Si ₂ O ₂ N ₂ , silicon nitride particles, strontium nitrate, calcium nitrate tetrahydrate, and europium nitrate hexahydrate In the same manner as in Example 2 except that 27.048% by mass, 12.241% by mass, 47.809% by mass, and 12.901% by mass were respectively measured. And a fired product was obtained.

When various measurements and analyzes were performed in the same manner as in Example 1, the volume average particle diameter D50 _V of the obtained phosphor precursor particles was 114 nm. Moreover, it was found that the obtained fired product was excited by light having a wavelength range of 200 nm or more and 500 nm or less, and the emission peak wavelength was 541 nm. From this, it was confirmed that the obtained fired product was a phosphor excited by visible light. Further, it was found that the obtained fired product produced an oxynitride having the same crystal structure as SrSi ₂ O ₂ N ₂ and a silicon-containing compound having the same crystal structure as SiO ₂ . Moreover, it turned out that 88 mass% of oxynitrides are produced | generated and 12 mass% of silicon containing compounds are produced | generated with respect to the sum total of an oxynitride and a silicon containing compound. Further, it was found that the obtained fired product contained Sr, Ca, and Eu in a molar ratio of Sr: Ca: Eu = 0.2: 0.7: 0.1. The obtained fired article had a volume average particle diameter D50 _V of 146 nm and a volume average particle size distribution index PSD _V of 1.23. Moreover, the internal quantum efficiency in the excitation wavelength of 450 nm of the obtained baked product was 77%.

From the above, the phosphor obtained in Example 7 contains an oxynitride containing Sr, Ca, Eu, and Si. Moreover, this fluorescent substance is represented by a composition formula Eu _0.1 Sr _0.2 Ca _0.7 Si ₂ O ₂ N ₂ . From this composition formula, this phosphor has 20 mol% Sr and 10 mol% Eu with respect to the total of Sr, Ca and Eu. This oxynitride has the same crystal structure as SrSi ₂ O ₂ N ₂ . Further, this phosphor has a volume average particle size D50 _V of 146 nm and a volume average particle size distribution index PSD _V of 1.23. This phosphor has an internal quantum efficiency of 77% at an excitation wavelength of 450 nm. Further, this phosphor contains 88% by mass of oxynitride with respect to the total of the oxynitride and the silicon-containing compound.

Example 8 FIG.
In order to obtain an oxynitride represented by a composition formula Eu _0.15 Sr _0.85 Si ₂ O ₂ N ₂ , silicon nitride particles, strontium nitrate, and europium nitrate hexahydrate were respectively contained in 27.481% by mass and 52%. Phosphor precursor particles and a fired product were obtained in the same manner as in Example 1 except that they were weighed so as to obtain 0.858% by mass and 19.661% by mass.

When various measurements and analyzes were performed in the same manner as Example 1, the volume average particle diameter D50 _V of the obtained phosphor precursor particles was 131 nm. Moreover, it was found that the obtained fired product was excited by light having a wavelength range of 200 nm or more and 500 nm or less, and the emission peak wavelength was 551 nm. From this, it was confirmed that the obtained fired product was a phosphor excited by visible light. Further, it was found that the obtained fired product produced an oxynitride having the same crystal structure as SrSi ₂ O ₂ N ₂ and a silicon-containing compound having the same crystal structure as SiO ₂ . Moreover, it turned out that 84 mass% of oxynitrides are produced | generated and 16 mass% of silicon containing compounds are produced | generated with respect to the sum total of an oxynitride and a silicon containing compound. Further, it was found that the obtained fired product contained Sr and Eu at a molar ratio of Sr: Eu = 0.85: 0.15. The obtained fired product had a volume average particle diameter D50 _V of 168 nm and a volume average particle size distribution index PSD _V of 1.31. Moreover, the internal quantum efficiency in the excitation wavelength of 450 nm of the obtained baked product was 75%.

From the above, the phosphor obtained in Example 8 includes an oxynitride containing Sr, Eu, and Si. This phosphor is represented by a composition formula Eu _0.15 Sr _0.85 Si ₂ O ₂ N ₂ . From this composition formula, this phosphor has 85 mol% Sr and 15 mol% Eu with respect to the sum of Sr and Eu. This oxynitride has the same crystal structure as SrSi ₂ O ₂ N ₂ . Further, this phosphor has a volume average particle diameter D50 _V of 168 nm and a volume average particle size distribution index PSD _V of 1.31. This phosphor has an internal quantum efficiency of 75% at an excitation wavelength of 450 nm. Further, this phosphor contains 84 mass% oxynitride with respect to the total of the oxynitride and the silicon-containing compound.

Example 9
In order to obtain an oxynitride represented by a composition formula Eu _0.05 Sr _0.95 Si ₂ O ₂ N ₂ , silicon nitride particles, strontium nitrate, and europium nitrate hexahydrate were mixed in 29.514 mass% and 63, respectively. Phosphor precursor particles and a fired product were obtained in the same manner as in Example 1 except that they were weighed to be .447 mass% and 7.039 mass%.

When various measurements and analyzes were performed in the same manner as in Example 1, the obtained phosphor precursor particles had a volume average particle diameter D50 _V of 133 nm. Moreover, it was found that the obtained fired product was excited by light having a wavelength range of 200 nm or more and 500 nm or less, and the emission peak wavelength was 550 nm. From this, it was confirmed that the obtained fired product was a phosphor excited by visible light. Further, it was found that the obtained fired product produced an oxynitride having the same crystal structure as SrSi ₂ O ₂ N ₂ and a silicon-containing compound having the same crystal structure as SiO ₂ . Moreover, it turned out that 85 mass% of oxynitrides are produced | generated and 15 mass% of silicon containing compounds are produced | generated with respect to the sum total of an oxynitride and a silicon containing compound. Further, it was found that the obtained fired product contained Sr and Eu at a molar ratio of Sr: Eu = 0.95: 0.05. The obtained fired article had a volume average particle diameter D50 _V of 157 nm and a volume average particle size distribution index PSD _V of 1.29. The obtained fired article had an internal quantum efficiency of 74% at an excitation wavelength of 450 nm.

From the above, the phosphor obtained in Example 9 includes an oxynitride containing Sr, Eu, and Si. This phosphor is represented by a composition formula Eu _0.05 Sr _0.95 Si ₂ O ₂ N ₂ . From this composition formula, this phosphor has 95 mol% Sr and 5 mol% Eu with respect to the sum of Sr and Eu. This oxynitride has the same crystal structure as SrSi ₂ O ₂ N ₂ . Further, this phosphor has a volume average particle size D50 _V of 157 nm and a volume average particle size distribution index PSD _V of 1.29. This phosphor has an internal quantum efficiency of 74% at an excitation wavelength of 450 nm. Further, this phosphor contains 85 mass% oxynitride with respect to the total of the oxynitride and the silicon-containing compound.

Example 10
Nitriding with a volume average particle diameter D50 _V of 110 nm obtained by pulverizing crystalline silicon nitride (manufactured by High Purity Chemical) having a number average particle diameter of 500 nm as a raw material with a fine pulverizer (LMZ015 manufactured by Ashizawa Finetech) Phosphor precursor particles and a fired product were obtained by the same method as in Example 1 except that silicon particles were used.

When various measurements and analyzes were performed in the same manner as in Example 1, the volume average particle diameter D50 _V of the obtained phosphor precursor particles was 208 nm. Moreover, it was found that the obtained fired product was excited by light having a wavelength range of 200 nm or more and 500 nm or less, and the emission peak wavelength was 549 nm. From this, it was confirmed that the obtained fired product was a phosphor excited by visible light. Further, it was found that the obtained fired product produced an oxynitride having the same crystal structure as SrSi ₂ O ₂ N ₂ and a silicon-containing compound having the same crystal structure as SiO ₂ . Moreover, it turned out that 87 mass% of oxynitrides are produced | generated and 13 mass% of silicon containing compounds are produced | generated with respect to the sum total of an oxynitride and a silicon containing compound. Further, it was found that the obtained fired product contained Sr and Eu in a molar ratio of Sr: Eu = 0.9: 0.1. The obtained fired article had a volume average particle diameter D50 _V of 329 nm and a volume average particle size distribution index PSD _V of 1.22. Moreover, the internal quantum efficiency in the excitation wavelength of 450 nm of the obtained baked product was 79%.

From the above, the phosphor obtained in Example 10 includes an oxynitride containing Sr, Eu, and Si. Further, this phosphor is represented by a composition formula Eu _0.1 Sr _0.9 Si ₂ O ₂ N ₂ . From this composition formula, this phosphor has 90 mol% Sr and 10 mol% Eu with respect to the total of Sr and Eu. This oxynitride has the same crystal structure as SrSi ₂ O ₂ N ₂ . Further, this phosphor has a volume average particle size D50 _V of 329 nm and a volume average particle size distribution index PSD _V of 1.22. This phosphor has an internal quantum efficiency of 79% at an excitation wavelength of 450 nm. Further, this phosphor contains 87 mass% oxynitride with respect to the total of the oxynitride and the silicon-containing compound.

Example 11
A phosphor precursor is produced in the same manner as in Example 1 except that amorphous silicon nitride particles having a volume average particle diameter D50 _V of 25 nm (made by HEFEI KAIER NANOMETER ENERGY & TECHNOLOGY CO., LTD) are used as raw materials. Body particles and a fired product were obtained.

When various measurements and analyzes were performed in the same manner as in Example 1, the volume average particle diameter D50 _V of the obtained phosphor precursor particles was 53 nm. Moreover, it was found that the obtained fired product was excited by light having a wavelength range of 200 nm or more and 500 nm or less, and the emission peak wavelength was 550 nm. From this, it was confirmed that the obtained fired product was a phosphor excited by visible light. Further, it was found that the obtained fired product produced an oxynitride having the same crystal structure as SrSi ₂ O ₂ N ₂ and a silicon-containing compound having the same crystal structure as SiO ₂ . Moreover, it turned out that 84 mass% of oxynitrides are produced | generated and 16 mass% of silicon containing compounds are produced | generated with respect to the sum total of an oxynitride and a silicon containing compound. Further, it was found that the obtained fired product contained Sr and Eu in a molar ratio of Sr: Eu = 0.9: 0.1. The obtained fired article had a volume average particle diameter D50 _V of 113 nm and a volume average particle size distribution index PSD _V of 1.30. Moreover, the internal quantum efficiency in the excitation wavelength of 450 nm of the obtained baked product was 73%.

From the above, the phosphor obtained in Example 11 includes an oxynitride containing Sr, Eu, and Si. Further, this phosphor is represented by a composition formula Eu _0.1 Sr _0.9 Si ₂ O ₂ N ₂ . From this composition formula, this phosphor has 90 mol% Sr and 10 mol% Eu with respect to the total of Sr and Eu. This oxynitride has the same crystal structure as SrSi ₂ O ₂ N ₂ . Further, this phosphor has a volume average particle diameter D50 _V of 113 nm and a volume average particle size distribution index PSD _V of 1.30. Further, this phosphor has an internal quantum efficiency of 73% at an excitation wavelength of 450 nm. Further, this phosphor contains 84 mass% oxynitride with respect to the total of the oxynitride and the silicon-containing compound.

Comparative Example 1
Phosphor precursor particles and fired products were obtained in the same manner as in Example 1 except that crystalline silicon nitride particles having a volume average particle diameter D50 _V of 195 nm (Ube Industries) were used as raw materials.

When various measurements and analyzes were performed in the same manner as in Example 1, the volume average particle diameter D50 _V of the obtained phosphor precursor particles was 286 nm. Moreover, it was found that the obtained fired product was excited by light having a wavelength range of 200 nm or more and 500 nm or less, and the emission peak wavelength was 550 nm. From this, it was confirmed that the obtained fired product was a phosphor excited by visible light. Further, it was found that the obtained fired product produced an oxynitride having the same crystal structure as SrSi ₂ O ₂ N ₂ and a silicon-containing compound having the same crystal structure as SiO ₂ . Moreover, it turned out that 85 mass% of oxynitrides are produced | generated and 15 mass% of silicon containing compounds are produced | generated with respect to the sum total of an oxynitride and a silicon containing compound. Further, it was found that the obtained fired product contained Sr and Eu in a molar ratio of Sr: Eu = 0.9: 0.1. The obtained fired article had a volume average particle diameter D50 _V of 438 nm and a volume average particle size distribution index PSD _V of 1.41. Moreover, the internal quantum efficiency in the excitation wavelength of 450 nm of the obtained baked product was 76%.

From the above, the phosphor obtained in Comparative Example 1 includes an oxynitride containing Sr, Eu, and Si. Further, this phosphor is represented by a composition formula Eu _0.1 Sr _0.9 Si ₂ O ₂ N ₂ . From this composition formula, this phosphor has 90 mol% Sr and 10 mol% Eu with respect to the total of Sr and Eu. This oxynitride has the same crystal structure as SrSi ₂ O ₂ N ₂ . Further, this phosphor has a volume average particle size D50 _V of 438 nm and a volume average particle size distribution index PSD _V of 1.41. Further, this phosphor has an internal quantum efficiency of 76% at an excitation wavelength of 450 nm. Further, this phosphor contains 85 mass% oxynitride with respect to the total of the oxynitride and the silicon-containing compound.

Comparative Example 2
In the same manner as in Example 1, phosphor precursor particles were obtained. Moreover, the phosphor precursor particles were baked by the same method as in Example 1 except that the phosphor precursor particles were baked under a gas atmosphere of 100% by volume of nitrogen to obtain a baked product.

When various measurements and analyzes were performed in the same manner as in Example 1, it was found that the obtained fired product was excited by light having a wavelength range of 200 nm to 500 nm and had an emission peak wavelength of 557 nm. From this, it was confirmed that the obtained fired product was a phosphor excited by visible light. In addition, it was found that the obtained fired product produced an oxynitride having the same crystal structure as SrSi ₂ O ₂ N ₂ and a silicon-containing compound having the same crystal structure as Sr ₂ SiO ₄ . Moreover, it turned out that 5 mass% of oxynitrides are produced | generated and 95 mass% of silicon containing compounds are produced | generated with respect to the sum total of an oxynitride and a silicon containing compound. Further, it was found that the obtained fired product contained Sr and Eu in a molar ratio of Sr: Eu = 0.9: 0.1. The obtained fired article had a volume average particle diameter D50 _V of 184 nm and a volume average particle size distribution index PSD _V of 1.33. Moreover, the internal quantum efficiency in the excitation wavelength of 450 nm of the obtained baked product was 50%.

From the above, the phosphor obtained in Comparative Example 2 includes an oxynitride containing Sr, Eu, and Si. Further, this phosphor is represented by a composition formula Eu _0.1 Sr _0.9 Si ₂ O ₂ N ₂ . From this composition formula, this phosphor has 90 mol% Sr and 10 mol% Eu with respect to the total of Sr and Eu. This oxynitride has the same crystal structure as SrSi ₂ O ₂ N ₂ . Further, this phosphor has a volume average particle size D50 _V of 184 nm and a volume average particle size distribution index PSD _V of 1.33. Further, this phosphor has an internal quantum efficiency of 50% at an excitation wavelength of 450 nm. In addition, the phosphor includes 5% by mass of oxynitride with respect to the total of the oxynitride and the silicon-containing compound.

Comparative Example 3
In the same manner as in Example 1, phosphor precursor particles were obtained. In addition, the phosphor precursor particles were baked by the same method as in Example 1 except that the baked product was obtained at 1100 ° C.

  When the excitation emission spectrum of the obtained fired product was measured, the fired product did not emit light. This is due to insufficient firing. Therefore, in Comparative Example 3, no phosphor was obtained.

Comparative Example 4
In the same manner as in Example 1, phosphor precursor particles were obtained. Moreover, the phosphor precursor particles were baked by the same method as in Example 1 except that the baked product was obtained at 1700 ° C.

When various measurements and analyzes were performed in the same manner as in Example 1, it was found that the obtained fired product was excited by light having a wavelength range of 200 nm or more and 500 nm or less, and the emission peak wavelength was 551 nm. From this, it was confirmed that the obtained fired product was a phosphor excited by visible light. Further, it was found that the obtained fired product produced an oxynitride having the same crystal structure as SrSi ₂ O ₂ N ₂ and a silicon-containing compound having the same crystal structure as SiO ₂ . Moreover, it turned out that 93 mass% of oxynitrides are produced | generated and 7 mass% of silicon containing compounds are produced | generated with respect to the sum total of an oxynitride and a silicon containing compound. Further, it was found that the obtained fired product contained Sr and Eu in a molar ratio of Sr: Eu = 0.9: 0.1. The obtained fired article had a volume average particle diameter D50 _V of 960 nm and a volume average particle size distribution index PSD _V of 1.45. The obtained fired article had an internal quantum efficiency of 81% at an excitation wavelength of 450 nm.

From the above, the phosphor obtained in Comparative Example 4 includes an oxynitride containing Sr, Eu, and Si. Further, this phosphor is represented by a composition formula Eu _0.1 Sr _0.9 Si ₂ O ₂ N ₂ . From this composition formula, this phosphor has 90 mol% Sr and 10 mol% Eu with respect to the total of Sr and Eu. This oxynitride has the same crystal structure as SrSi ₂ O ₂ N ₂ . Further, this phosphor has a volume average particle size D50 _V of 960 nm and a volume average particle size distribution index PSD _V of 1.45. Further, this phosphor has an internal quantum efficiency of 81% at an excitation wavelength of 450 nm. In addition, this phosphor contains 93% by mass of oxynitride with respect to the total of the oxynitride and the silicon-containing compound.

Comparative Example 5
In the same manner as in Example 2, phosphor precursor particles were obtained. Further, the phosphor precursor particles were fired by the same method as in Example 1 except that the phosphor precursor particles were fired at 1700 ° C.

  In Comparative Example 5, the phosphor was not obtained because it was melted during firing. This is because the amount of calcium contained in the phosphor precursor particles is large and the melting point of the oxynitride synthesized during firing is lowered.

Comparative Example 6
In order to obtain an oxynitride represented by the composition formula Eu _0.1 Sr _0.1 Ca _0.8 Si ₂ O ₂ N ₂ , silicon nitride particles, strontium nitrate, calcium nitrate tetrahydrate, and europium nitrate hexahydrate In the same manner as in Example 2 except that 26.858 mass%, 6.078 mass%, 54.254 mass%, and 12.810 mass% were respectively measured. Got. Further, the phosphor precursor particles were fired by the same method as in Example 1.

  In Comparative Example 6, the phosphor was not obtained because it was melted during firing. This is because the amount of calcium contained in the phosphor precursor particles is large and the melting point of the oxynitride synthesized during firing is lowered.

Comparative Example 7
In order to obtain an oxynitride represented by a composition formula Eu _0.005 Sr _0.995 Si ₂ O ₂ N ₂ , silicon nitride particles, strontium nitrate, and europium nitrate hexahydrate were respectively added at 30.530% by mass and 68%. The phosphor precursor particles and the fired product were obtained in the same manner as in Example 1, except that the weight was adjusted to 0.74% by mass and 0.728% by mass.

When various measurements and analyzes were performed in the same manner as in Example 1, the obtained phosphor precursor particles had a volume average particle diameter D50 _V of 123 nm. Moreover, it was found that the obtained fired product was excited by light having a wavelength range of 200 nm or more and 500 nm or less, and the emission peak wavelength was 548 nm. From this, it was confirmed that the obtained fired product was a phosphor excited by visible light. Further, it was found that the obtained fired product produced an oxynitride having the same crystal structure as SrSi ₂ O ₂ N ₂ and a silicon-containing compound having the same crystal structure as SiO ₂ . Moreover, it turned out that 83 mass% of oxynitrides produced | generated and 17 mass% of silicon containing compounds were produced | generated with respect to the sum total of an oxynitride and a silicon containing compound. Further, it was found that the obtained fired product contained Sr and Eu in a molar ratio of Sr: Eu = 0.959: 0.005. The obtained fired article had a volume average particle diameter D50 _V of 186 nm and a volume average particle size distribution index PSD _V of 1.32. Moreover, the internal quantum efficiency in the excitation wavelength of 450 nm of the obtained baked product was 52%.

From the above, the phosphor obtained in Comparative Example 7 includes an oxynitride containing Sr, Eu, and Si. This phosphor is represented by a composition formula Eu _0.005 Sr _0.995 Si ₂ O ₂ N ₂ . From this composition formula, this phosphor has 99.5 mol% Sr and 0.5 mol% Eu with respect to the sum of Sr and Eu. This oxynitride has the same crystal structure as SrSi ₂ O ₂ N ₂ . Further, this phosphor has a volume average particle size D50 _V of 186 nm and a volume average particle size distribution index PSD _V of 1.32. Further, this phosphor has an internal quantum efficiency of 52% at an excitation wavelength of 450 nm. Further, this phosphor contains 83% by mass of oxynitride with respect to the total of the oxynitride and the silicon-containing compound.

Comparative Example 8.
In order to obtain an oxynitride represented by a composition formula Eu _0.25 Sr _0.75 Si ₂ O ₂ N ₂ , silicon nitride particles, strontium nitrate, and europium nitrate hexahydrate were respectively contained in 25.710 mass% and 43 The phosphor precursor particles and the fired product were obtained in the same manner as in Example 1 except that the weight was adjusted to 634% by mass and 30.657% by mass.

When various measurements and analyzes were performed in the same manner as in Example 1, the obtained phosphor precursor particles had a volume average particle diameter D50 _V of 132 nm. Moreover, it was found that the obtained fired product was excited by light having a wavelength range of 200 nm or more and 500 nm or less, and the emission peak wavelength was 545 nm. From this, it was confirmed that the obtained fired product was a phosphor excited by visible light. Further, it was found that the obtained fired product produced an oxynitride having the same crystal structure as SrSi ₂ O ₂ N ₂ and a silicon-containing compound having the same crystal structure as SiO ₂ . Moreover, it turned out that 84 mass% of oxynitrides are produced | generated and 16 mass% of silicon containing compounds are produced | generated with respect to the sum total of an oxynitride and a silicon containing compound. Further, it was found that the obtained fired product contained Sr and Eu in a molar ratio of Sr: Eu = 0.75: 0.25. The obtained fired article had a volume average particle diameter D50 _V of 172 nm and a volume average particle size distribution index PSD _V of 1.31. Moreover, the internal quantum efficiency in the excitation wavelength of 450 nm of the obtained baked product was 48%.

From the above, the phosphor obtained in Comparative Example 8 includes an oxynitride containing Sr, Eu, and Si. Further, this phosphor is represented by a composition formula Eu _0.25 Sr _0.75 Si ₂ O ₂ N ₂ . From this composition formula, this phosphor has 75 mol% Sr and 25 mol% Eu with respect to the sum of Sr and Eu. This oxynitride has the same crystal structure as SrSi ₂ O ₂ N ₂ . Further, this phosphor has a volume average particle size D50 _V of 172 nm and a volume average particle size distribution index PSD _V of 1.31. Further, this phosphor has an internal quantum efficiency of 48% at an excitation wavelength of 450 nm. Further, this phosphor contains 84 mass% oxynitride with respect to the total of the oxynitride and the silicon-containing compound.

Comparative Example 9
A commercially available oxynitride phosphor represented by the composition formula Eu _0.1 Sr _0.45 Ba _0.45 Si ₂ O ₂ N ₂ (manufactured by Beijing Nakamura U.K. Technology Co., Ltd.) was used.

When various measurements and analyzes were performed in the same manner as in Example 1, it was found that the commercially available oxynitride phosphor was excited by light in the wavelength range of 200 nm to 500 nm and the emission peak wavelength was 550 nm. B in FIG. 4 shows the emission spectrum of a commercially available oxynitride phosphor. Also, commercial oxynitride phosphor was found not to contain any crystalline components other than the oxynitride having the same crystal structure as SrSi ₂ O ₂ N _2. Further, the volume average particle diameter D50 _V of the commercially available oxynitride phosphor was 15400 nm, and the volume average particle size distribution index PSD _V was 2.22. Further, the internal quantum efficiency of the commercially available oxynitride phosphor at an excitation wavelength of 450 nm was 77%.

Comparative Example 10
The commercially available oxynitride phosphor used in Comparative Example 9 was pulverized with a bead mill and classified to obtain a submicron oxynitride phosphor.

When various measurements and analyzes were performed in the same manner as in Example 1, the commercially available oxynitride phosphor after pulverization was excited by light in the wavelength range of 200 nm to 500 nm, and the emission peak wavelength was 562 nm. I understood. C in FIG. 4 shows the emission spectrum of the commercially available oxynitride phosphor after pulverization. In addition, the commercially available oxynitride phosphor after pulverization does not contain a crystal component other than oxynitride having the same crystal structure as SrSi ₂ O ₂ N ₂ , but part of the oxynitride crystals is pulverized. It was found to be amorphous. Further, the commercially available oxynitride phosphor after pulverization had a volume average particle size D50 _V of 364 nm and a volume average particle size distribution index PSD _V of 1.33. The internal quantum efficiency of the commercially available oxynitride phosphor after pulverization at an excitation wavelength of 450 nm was 36%.

Comparison between the working example and the comparative example.
FIG. 5 is a graph showing the relationship between the volume average particle diameter D50 _V of the phosphor and the internal quantum efficiency at an excitation wavelength of 450 nm. The horizontal axis of FIG. 5 is the volume average particle diameter D50 _V of the phosphor, and the vertical axis is the internal quantum efficiency at the excitation wavelength of 450 nm of the phosphor. In FIG. 5, diamond-shaped points indicate Examples 1-11, and square-shaped points a and b indicate Comparative Examples 9 and 10, respectively.

As shown in FIG. 5, the phosphor of Example 1-11 has a volume average particle diameter D50 _V of 50 nm or more and 400 nm or less, more specifically, 100 nm or more and 350 nm or less, and an internal wavelength at an excitation wavelength of 450 nm. The quantum efficiency is 60% or more, more specifically 70% or more. For this reason, the small particle diameter fluorescent substance excellent in the light emission characteristic was able to be obtained from Example 1-11. In particular, in Examples 2, 3, and 5, it was possible to obtain a phosphor having a small particle diameter having an internal quantum efficiency of 80% or more at an excitation wavelength of 450 nm and having extremely excellent emission characteristics.

On the other hand, the phosphor of Comparative Example 9 has a high internal quantum efficiency of 77% at an excitation wavelength of 450 nm, but has a large volume average particle diameter D50 _V of 15400 nm. In the phosphor of Comparative Example 10 obtained by pulverizing the phosphor of Comparative Example 9, the volume average particle diameter D50 _V could be reduced to 364 nm, but the internal quantum efficiency at an excitation wavelength of 450 nm was reduced to 36%. Declined. Further, as shown in FIG. 4, the emission intensity at the emission peak wavelength of the phosphors of Comparative Examples 9 and 10 is lower than the emission intensity at the emission peak wavelength of the phosphor of Example 2. For this reason, it was not possible to obtain a phosphor having a small particle diameter with excellent emission characteristics from commercially available phosphors (Comparative Examples 9 and 10).

Further, the phosphor of Example 1-11 has a volume average particle size distribution index PSD _V of 1.20 or more and 1.35 or less, more specifically 1.21 nm or more and 1.32 or less. For this reason, the fluorescent substance with uniform particle diameter was able to be obtained from Example 1-11.

  FIG. 6 is a graph showing the relationship between the Sr content of the phosphor and the internal quantum efficiency at an excitation wavelength of 450 nm. The horizontal axis of FIG. 6 is the Sr content of the phosphor, and the vertical axis is the internal quantum efficiency at the excitation wavelength of 450 nm of the phosphor. In FIG. 6, diamond-shaped points indicate Examples 1-11, and square-shaped points a and b indicate Comparative Examples 6 and 7, respectively.

  As shown in FIG. 6, in Comparative Example 6, the content of Ca is large, and the content of Sr is less than 15 mol% with respect to the total of the alkaline earth metal elements (Sr, Ca) and Eu. For this reason, the melting point of the oxynitride synthesized during firing decreased, and a phosphor could not be obtained. When the firing temperature is lowered, the synthesis reaction becomes difficult to proceed, and impurities such as silicon-containing compounds increase, so that the internal quantum efficiency at an excitation wavelength of 450 nm is considered to be lowered. Further, the phosphor of Comparative Example 7 has an Sr content of more than 99 mol%. For this reason, the content of Eu decreases, and the internal quantum efficiency at an excitation wavelength of 450 nm decreases.

  Therefore, the Sr content is preferably 15 mol% or more and 99 mol% or less. Further, the phosphor of Example 1-11 having an internal quantum efficiency of 60% or more at an excitation wavelength of 450 nm is 20 mol% or more and 95 mol with respect to the total of the alkaline earth metal elements (Sr, Ca) and Eu. % Of Sr. For this reason, Sr content is more preferably 20 mol% or more and 95 mol% or less.

  FIG. 7 is a graph showing the relationship between the Eu content of the phosphor and the internal quantum efficiency at an excitation wavelength of 450 nm. In FIG. 7, the horizontal axis represents the Eu content of the phosphor, and the vertical axis represents the internal quantum efficiency at the excitation wavelength of 450 nm. In FIG. 7, diamond-shaped points indicate Example 1-11, and square-shaped points a and b indicate Comparative Examples 7 and 8, respectively.

  As shown in FIG. 7, the phosphor of Comparative Example 7 has Eu less than 1 mol% with respect to the total of the alkaline earth metal elements (Sr, Ca) and Eu. For this reason, there is little content of Eu and the internal quantum efficiency in excitation wavelength 450nm falls. Further, the phosphor of Comparative Example 8 has an Eu content of more than 20 mol%. For this reason, concentration quenching occurs, and the internal quantum efficiency at the excitation wavelength of 450 nm decreases.

  Therefore, the Eu content is preferably 1 mol% or more and 20 mol% or less. Further, the phosphor of Example 1-11 having an internal quantum efficiency of 60% or more at an excitation wavelength of 450 nm is 5 mol% or more and 15 mol with respect to the total of alkaline earth metal elements (Sr, Ca) and Eu. % Eu. For this reason, the Eu content is more preferably 5 mol% or more and 15 mol% or less.

FIG. 8 is a graph showing the relationship between the volume average particle diameter D50 _V of the silicon nitride particles and the volume average particle diameter D50 _V of the phosphor. The horizontal axis of FIG. 8 is the volume average particle diameter D50 _V of the silicon nitride particles, and the vertical axis is the volume average particle diameter D50 _V of the phosphor. FIG. 9 is a graph showing the relationship between the volume average particle diameter D50 _{V of the} silicon nitride particles and the volume average particle size distribution index PSD _V of the phosphor. The horizontal axis of FIG. 9 is the volume average particle diameter D50 _V of the silicon nitride particles, and the vertical axis is the volume average particle size distribution index PSD _V of the phosphor. 8 and 9, the diamond-shaped plot shows Example 1-11, and the square-shaped plot a shows Comparative Example 1.

As shown in FIG. 8, in Comparative Example 1, the volume average particle diameter D50 _{V of the} silicon nitride particles is larger than 150 nm. For this reason, the volume average particle diameter D50 _{V of} the phosphor precursor particles also increased. As a result, the phosphor had a volume average particle diameter D50 _V larger than 400 nm, and a phosphor having a desired particle diameter could not be obtained. Further, as shown in FIG. 9, the particle size distribution cannot be controlled, and the volume average particle size distribution index PSD _V of the phosphor becomes larger than 1.35, and a phosphor having a desired particle size distribution can be obtained. There wasn't.

Therefore, the volume average particle diameter D50 _V of the silicon nitride particles is preferably 150 nm or less. In Example 1-11 in which a phosphor having a volume average particle diameter D50 _V of 50 nm or more and 400 nm or less and a volume average particle size distribution index PSD _V of 1.20 or more and 1.35 or less is obtained, The volume average particle diameter D50 _V is 120 nm or less. For this reason, the volume average particle diameter D50 _V of the silicon nitride particles is more preferably 120 nm or less.

Figure 10 is a graph showing the relationship between the volume average particle diameter D50 _V the volume average particle diameter D50 _V and the phosphor of the phosphor precursor particles. The horizontal axis of FIG. 10 is the volume average particle diameter D50 _V of the phosphor precursor particles, and the vertical axis is the volume average particle diameter D50 _V of the phosphor. FIG. 11 is a graph showing the relationship between the volume average particle diameter D50 _V of the phosphor precursor particles and the volume average particle size distribution index PSD _V of the phosphor. The horizontal axis of FIG. 11 is the volume average particle diameter D50 _V of the phosphor precursor particles, and the vertical axis is the volume average particle size distribution index PSD _V of the phosphor. 10 and 11, the diamond-shaped plot indicates Example 1-11, and the square-shaped plot a indicates Comparative Example 1. FIG.

As shown in FIG. 10, in Comparative Example 1, the volume average particle diameter D50 _{V of} the phosphor precursor particles is larger than 250 nm. For this reason, the volume average particle diameter D50 _V of the phosphor is larger than 400 nm, and a phosphor having a desired particle diameter cannot be obtained. Further, as shown in FIG. 11, the particle size distribution cannot be controlled, and the phosphor volume average particle size distribution index PSD _V is larger than 1.35, and a phosphor having a desired particle size distribution can be obtained. There wasn't.

Therefore, the volume average particle diameter D50 _V of the phosphor precursor particles is preferably 250 nm or less. In Example 1-11, a phosphor precursor having a volume average particle size D50 _V of 50 nm or more and 400 nm or less and a volume average particle size distribution index PSD _V of 1.20 or more and 1.35 or less is obtained. The volume average particle diameter D50 _{V of the} particles is 210 nm or less. For this reason, the volume average particle diameter D50 _V of the phosphor precursor particles is more preferably 210 nm or less.

  FIG. 12 is a graph showing the relationship between the firing temperature and the internal quantum efficiency of the phosphor at an excitation wavelength of 450 nm. The horizontal axis in FIG. 12 is the firing temperature, and the vertical axis is the internal quantum efficiency of the phosphor at an excitation wavelength of 450 nm. In FIG. 12, diamond-shaped points indicate Example 1-11, and square-shaped points ac indicate Comparative Example 3-5.

FIG. 13 is a graph showing the relationship between the firing temperature and the volume average particle diameter D50 _V of the phosphor. The horizontal axis in FIG. 13 is the firing temperature, and the vertical axis is the volume average particle diameter D50 _V of the phosphor. FIG. 14 is a graph showing the relationship between the firing temperature and the volume average particle size distribution index PSD _V of the phosphor. The horizontal axis of FIG. 14 is the firing temperature, and the vertical axis is the volume average particle size distribution index PSD _V of the phosphor. 13 and 14, the diamond-shaped plot indicates Example 1-11, and the square-shaped plot b indicates Comparative Example 4.

As shown in FIG. 12, in Comparative Example 3, the firing temperature is lower than 1150 ° C. For this reason, the synthesis reaction did not proceed and the phosphor was not obtained due to insufficient firing. In addition, when the firing temperature is low, the synthesis reaction does not proceed easily, and impurities such as silicon-containing compounds increase, so that the internal quantum efficiency at an excitation wavelength of 450 nm is considered to decrease. Moreover, as FIG. 12 shows, in the comparative example 4, baking temperature is higher than 1650 degreeC. For this reason, as shown in FIG. 13, the grain growth progressed too much, and the volume average particle diameter D50 _V of the phosphor became larger than 400 nm, and a phosphor having a desired particle diameter could not be obtained. Further, as shown in FIG. 14, the particle size distribution cannot be controlled, and the volume average particle size distribution index PSD _V of the phosphor becomes larger than 1.35, and a phosphor having a desired particle size distribution can be obtained. There wasn't. Moreover, as FIG. 12 shows, in the comparative example 5, a calcination temperature is higher than 1650 degreeC. As in Comparative Example 5, the melting point of the oxynitride synthesized during firing decreases depending on the content ratio of alkaline earth metal elements (Sr, Ca) and Eu. It melts and phosphor cannot be obtained.

Therefore, the firing temperature is preferably 1150 ° C. or higher and 1650 ° C. or lower. In Example 1-11 in which a phosphor having a volume average particle size D50 _V of 50 nm or more and 400 nm or less and a volume average particle size distribution index PSD _V of 1.20 or more and 1.35 or less is obtained, the firing temperature is 1200. It is at least 1600 ° C. For this reason, the firing temperature is more preferably 1200 ° C. or higher and 1600 ° C. or lower.

  In Example 1-11, the phosphor precursor particles were fired under a mixed gas atmosphere of hydrogen and nitrogen or a mixed gas atmosphere of ammonia and nitrogen. In that case, a phosphor containing oxynitride as a main component was obtained. Specifically, the phosphor of Example 1-11 includes 50% by mass or more, more specifically 70% by mass or more of oxynitride with respect to the total of the oxynitride and the silicon-containing compound. It is. By containing oxynitride as a main component, a phosphor having high internal quantum efficiency at an excitation wavelength of 450 nm was obtained.

On the other hand, in Comparative Example 2, the phosphor precursor particles were fired under a gas atmosphere of 100% by volume of nitrogen. In that case, the synthesis reaction of oxynitride did not proceed, and a silicon-containing compound having the same crystal structure as Sr ₂ SiO ₄ was generated as a main component.

  Therefore, the firing is preferably performed in a mixed gas atmosphere of hydrogen and nitrogen or a mixed gas atmosphere of ammonia and nitrogen.

  In the embodiment described above, only the case of using a combination of Sr and Ca in addition to the case of using only Sr as the alkaline earth metal element has been described. However, at least one of Ba and Mg is used instead of Ca. The present invention can be applied even in the case of using at least one of Ba and Mg together with Ca.

  Moreover, although the Example mentioned above demonstrated the case where only Eu was used as an activator element, even when using Ce with Eu, this invention is applicable.

  Moreover, although the Example mentioned above demonstrated only the case where a coprecipitation method was used as a wet chemical method, this invention is applicable also when using a citrate method.

  In the above-described embodiments, the case where carbonates of alkaline earth elements and hydroxides of activator elements are deposited on the surface of silicon nitride particles has been described. However, carbonates and bicarbonates other than hydroxides are described. The present invention can be applied even when phosphate, carboxylate, oxalate, sulfate or organometallic compound is deposited.

  As mentioned above, although this invention was demonstrated in detail based on embodiment and an Example, this is for demonstrating this invention concretely, This invention is not limited to this. It is obvious that those having ordinary knowledge in the relevant field can make modifications and improvements within the technical idea of the present invention. All simple variations and modifications of the present invention belong to the scope of the present invention, and the specific protection scope of the present invention includes other embodiments.

Claims (10)

Alkaline earth metal element, a phosphor containing oxynitride you containing silicon and activator element,
The volume average particle size is at 50nm or more 400nm or less state, and are internal quantum efficiency of 60% at the excitation wavelength of 450 nm,
The phosphor is represented by a composition formula MSi ₂ O ₂ N ₂ ,
The oxynitride has the same crystal structure as SrSi ₂ O ₂ N ₂ ,
The element M is selected from one or more alkaline earth metal elements selected from the group consisting of Ca, Sr, Ba and Mg and containing at least Eu from at least one alkaline earth metal element selected from the group consisting of Eu and Ce. Having more than one kind of activator elements, and having 15 mol% or more and 99 mol% or less of Sr and 1 mol% or more and 20 mol% or less of activator elements with respect to the total of the elements M,
The volume average particle size distribution index is 1.21 or more and 1.32 or less,
A silicon-containing compound having a different crystal structure from the oxynitride,
The phosphor containing the oxynitride in an amount of 50% by mass or more based on the total of the oxynitride and the silicon-containing compound . Alkaline earth metal element, a method for producing a phosphor containing oxynitride you containing silicon and activator element,
Applying a wet chemical method to a suspension containing silicon nitride particles, a substance containing an alkaline earth metal element and a substance containing an activator element, the surface of the silicon nitride particles has the alkaline earth metal element A precursor preparation step of preparing phosphor precursor particles having a volume average particle diameter of 250 nm or less, wherein the compound containing the compound and the compound containing the activator element are mixed and deposited , and
Look including a firing step of firing the phosphor precursor particles,
The firing step is performed at a temperature of 1150 ° C. or higher and 1650 ° C. or lower in a mixed gas atmosphere of hydrogen and nitrogen or a mixed gas atmosphere of ammonia and nitrogen.
The phosphor precursor particles have 15 to 99 mol% of Sr and 1 to 20 mol% of an activator element with respect to the total of the alkaline earth metal element and the activator element. ,
The phosphor is represented by a composition formula MSi ₂ O ₂ N ₂ ,
The oxynitride has the same crystal structure as SrSi ₂ O ₂ N ₂ ,
The element M is selected from one or more alkaline earth metal elements selected from the group consisting of Ca, Sr, Ba and Mg and containing at least Eu from at least one alkaline earth metal element selected from the group consisting of Eu and Ce. The manufacturing method of the fluorescent substance which has an activator element more than a kind . The phosphor precursor particles are one or more kinds of alkaline earths selected from silicon nitride particles and at least Sr selected from the group consisting of Ca, Sr, Ba and Mg deposited on the surface of the silicon nitride particles. A compound containing a metal element and a compound containing one or more activator elements selected from the group consisting of Eu and Ce, including at least Eu, a total of an alkaline earth metal element and an activator element and silicon the molar ratio of 1: 1.4 to 1: the method for producing a phosphor according to including claim 2 in the range of 2.86. The precursor preparation step includes
Selected from the group consisting of silicon nitride particles and one or more alkaline earth metal elements selected from the group consisting of Ca, Sr, Ba and Mg and including at least Eu from the group consisting of Eu and Ce A suspension containing a substance containing one or more activator elements in a molar ratio of the total of alkaline earth metal elements and activator elements to silicon in the range of 1: 1.4 to 1: 2.86. A suspension forming step to form;
A wet chemical method is applied to the suspension to precipitate a compound containing the alkaline earth metal element and a compound containing the activator element, and the alkaline earth metal is deposited on the surface of the silicon nitride particles. A precursor forming step of forming phosphor precursor particles in which a compound containing an element and a compound containing the activator element are mixed and deposited,
The suspension, according to claim 3 in which the total of alkaline earth metal elements and activator elements, and a 15 mol% to 99 mol% of Sr and 1 mol% to 20 mol% of the activator elements A method for producing the phosphor according to 1. The method for producing a phosphor according to claim 2 or 4 , wherein the wet chemical method is at least one of a coprecipitation method and a citrate method. The method for producing a phosphor according to claim 5 , wherein the wet chemical method is a coprecipitation method. The compound containing the alkaline earth metal element and the compound containing the activator element are carbonate, hydrogen carbonate, phosphate, carboxylate, oxalate, sulfate, organometallic compound and water, respectively. the method for producing a phosphor according to any one of claims 2 to 6 comprising one or more compounds selected from the group consisting of oxides. The fluorescence according to claim 7 , wherein the compound containing the alkaline earth metal element and the compound containing the activator element each contain one or more compounds selected from the group consisting of carbonates and hydroxides. Body manufacturing method. The method for producing a phosphor according to any one of claims 2 to 8 having a volume average particle diameter wherein the silicon nitride particles is 150nm or less. The method for producing a phosphor according to any one of the silicon nitride particles from claim 2 is amorphous 9.

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