KR20160010311A - Phosphor and Method of Preparing Same - Google Patents

Abstract

The present invention relates to a phosphor having excellent light-emitting properties and small diameter, and comprising at least one of nitride and oxynitride containing an alkaline earth metal element, silicon, an activator element, and to a producing method thereof. The phosphor has the volume mean diameter of 50 to 400 nm or more, and internal quantum efficiency of 60% in 450 nm wavelength.

Description

FIELD OF THE INVENTION [0001] The present invention relates to a phosphor,

The present invention relates to a phosphor and a method for producing the same.

2. Description of the Related Art In recent years, in a light emitting device such as an LED illumination or a display, a phosphor responsible for light conversion has been assembled in the device. For example, there has been developed a method of coating a chip with a phosphor by dropping a phosphor dispersed in a silicone resin or the like onto an InGaN-based semiconductor chip emitting blue light or near ultraviolet light, which is considered to be promising as an excitation light source, as LED illumination have. In this case, the color / tone is adjusted by the light emitted by the light emitted from the InGaN-based semiconductor chip and the phosphor excited by the light emitted by the chip.

In such a light emitting device, the luminescent characteristics of the phosphor plays a very important role in the characteristics of the device. The improvement of the luminescence properties of the phosphor for light conversion is important and at the same time improves the characteristics of the light emitting device.

At present, as the light emitting device, Y3Al12O5: Ce which exhibits yellow light emission and CaAlSiN3: Eu visible light excitation type phosphor which mainly emits red light are mainly used. These phosphors are considered to have the best luminescence characteristics at particle diameters of several μm to several tens of μm. For this reason, phosphor particles having an average particle diameter of the above value are used. Particulate phosphors having an average particle diameter of less than 1 m have insufficient crystallinity, have many defects, and are not sufficiently dispersed in the resolved elements, resulting in a significant reduction in luminance. Generally, the use of LEDs / phosphors for light- It is inappropriate.

On the other hand, a particulate phosphor having a luminescence efficiency of less than 1 mu m is highly required for many applications. For example, in a fluorescent lamp which has been used for a long time, the particulate fluorescent material having a particle size of less than 1 μm has a better coating performance than that of the fluorescent material having a particle size of about 10 μm, and has a small amount of coating and tends to be clear. This is also true in the LED lighting package that has risen over the past several years, so that the fine particle fluorescent substance having a particle size of less than 1 μm has a great advantage that the dispersibility is better than that of the fluorescent substance having a size of about 10 μm.

A particulate phosphor having a size of less than 1 mu m that is excited by visible light is similarly required for many applications. The visible light-excited phosphor in this case needs to be a phosphor of a nitrogen anion having a sufficiently large nephelauxetic effect and a sufficiently large crystal dislocation in an activated ion such as Eu ^{2 +} or Ce ^{3 +} . Therefore, it is a problem to raise the luminous efficiency of the oxynitride fine particle phosphor of less than 1 占 퐉 or the nitride fine particle phosphor of less than 1 占 퐉 to the same level as that of the LED fluorescent material by sufficiently raising the above effect.

In order to form an alkaline earth metal element having a small particle diameter and a silicon-containing nitride phosphor or an oxynitride phosphor, the following methods have been tested.

For example, in Patent Document 1, first, a phosphor precursor powder composed of a mixture of phosphor raw material powder having an average particle size of 50 nm or less is prepared. As the phosphor raw material powder, for example, silicon nitride powder can be used. A solvent is added to the phosphor precursor powder to form a slurry. Then, an organic binder is added to this slurry. Thereafter, the slurry to which the organic binder is added is dried by a spray drying method to form granules having a particle diameter of 2 탆 or less. The granules thus formed are fired to obtain a target phosphor.

In the method disclosed in Patent Document 1, if the phosphor precursor powder formed by the spray drying method is fired with granules having a particle diameter of 2 μm or less, the precursor powder is sintered. For this reason, it is difficult to synthesize phosphor particles having small particle diameters. Further, since an organic binder is used to form granules having a particle size of 2 탆 or less, carbon which can not be completely removed by firing may hinder the emission characteristics of the phosphor. In addition, since a compound of an activated element such as Eu and a compound of an alkaline earth metal element that provides a site where the activated element is substituted are prepared separately as raw materials, Eu is sufficiently dispersed in the site of the alkaline earth metal element by firing it's difficult. As a result, the luminous efficiency of the resulting phosphor is lowered.

In Patent Document 2, a mixture of precursor particles comprising a phosphor raw material is formed. At least one of the precursor particles has an average primary particle size of less than 100 nm. As the precursor particles having an average primary particle size smaller than 100 nm, for example, silicon nitride particles can be used. Thereafter, this mixture is calcined, and a target phosphor is obtained by solid-phase reaction.

In the method disclosed in Patent Document 2, a phosphor obtained by baking 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 small particle diameters due to adhesion between primary particles or the like. In addition, since the compound of the activated element and the compound of the alkaline earth metal element are prepared separately as in the case of Patent Document 1, sufficient Eu is not dispersed until the particle reaches the sub-micron, .

(Patent Document 1) Japanese Patent Application Laid-Open No. 2007-314726

(Patent Document 2) Special Publication No. 2011-515536

As described above, the luminous efficiency of the particulate fluorescent substance of less than 1 mu m required for the phosphor used for the application of the high-performance light emitting device in which the amount of the phosphor is reduced or the like is set at a level achieving a particle diameter of several mu m to several ten mu m It is not reaching.

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems, and it is an object of the present invention to provide a method for producing a nitride phosphor which is characterized in that at least one of an alkaline earth metal element and a nitride containing silicon and an oxynitride having an average luminescent efficiency of a phosphor alone, And a method for producing the same.

The inventors of the present invention have conducted intensive studies to achieve the above object and have found that the fine particle type phosphor precursor particles obtained by finely depositing an alkaline earth metal element and an activated element by wet chemical method on the surface of silicon nitride fine particles have excellent light- It has been found that a phosphor containing at least one of these small, alkaline earth metal elements and silicon-containing nitride and oxynitride can be obtained.

The present invention has been made in accordance with this finding and has the following configuration.

(Configuration 1)

A phosphor comprising at least one of an alkaline earth metal element, silicon, and an activator element, the nitride and the oxynitride having a volume average particle diameter of 50 nm or more and 400 nm or less and an internal quantum efficiency at an excitation wavelength of 450 nm of 60% Phosphor.

(Composition 2)

The phosphor is represented by the composition formula MSi ₂ O ₂ N ₂ Lt; / RTI >

The oxynitride is SrSi ₂ O ₂ N ₂ , ≪ / RTI >

Wherein the element M is at least one kind of alkaline earth metal element selected from the group consisting of Ca, Sr, Ba, and Mg, including at least Sr, and at least one activator selected from the group consisting of Eu and Ce, , And Sr and an activator element in an amount of not less than 15 mol% and not more than 99 mol% and not less than 1 mol% and not more than 20 mol%, based on the total amount of the element M.

(Composition 3)

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

(Composition 4)

And a silicon-containing compound having a crystal structure different from that of the oxynitride,

The phosphor according to component 2 or 3, wherein the oxynitride is contained in an amount of 50 mass% or more based on the total amount of the oxynitride and the silicon-containing compound.

(Composition 5)

A method of producing a phosphor comprising at least one of an alkaline earth metal element, silicon, and a nitride and an oxynitride containing an activator element,

A precursor preparation step of preparing 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 diameter of 250 nm or less;

A firing step of firing the phosphor precursor particles

To form a phosphor.

(Composition 6)

Wherein the precursor preparation step is a step of applying a wet chemical method to a suspension containing silicon nitride particles and a substance containing an alkaline earth metal element and a substance containing an activator element to form a compound containing the alkaline earth metal element on the surface of the silicon nitride grains And a precursor forming step of forming phosphor precursor particles in which the compound containing the activating element is mixed and deposited.

(Composition 7)

Wherein the phosphor precursor particles comprise a silicon nitride particle and a compound containing at least one alkaline earth metal element selected from the group consisting of Ca, Sr, Ba and Mg deposited on the surface of the silicon nitride particle and containing at least Sr, And Ce, wherein the molar ratio of the sum of the alkaline earth metal element and the activating element to the silicon is in the range of 1: 1.4 to 1: 2.86 Including,

Wherein the phosphor precursor particles contain 15 mol% or more and 99 mol% or less of Sr and 1 mol% or more and 20 mol% or less of an activator element relative to the total amount of the alkaline earth metal element and the activator element. ≪ / RTI >

(Composition 8)

Wherein the precursor preparation step comprises a step of preparing a precursor comprising a material including at least one kind of alkaline earth metal element selected from the group consisting of silicon nitride particles and at least Sr from the group consisting of Ca, Sr, Ba and Mg and at least Eu from the group consisting of Eu and Ce A suspension forming step of forming a suspension containing at least one kind of activating element selected from the group consisting of alkaline earth metal element and activator element in a molar ratio of silicon to silicon in the range of 1: 1.4 to 1: 2.86;

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 on the surface of the silicon nitride particle, and a compound containing the alkaline earth metal element and the activator And a precursor forming step of forming phosphor precursor particles in which the element-containing compounds are mixed and deposited,

The suspension contains 15 mol% or more and 99 mol% or less of Sr and 1 mol% or more and 20 mol% or less of an activator element relative to the total amount of the alkaline earth metal element and the activator element. Way.

(Composition 9)

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

(Configuration 10)

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 each selected from the group consisting of a carbonate, a bicarbonate, a phosphate, a carbonate, a oxalate, a sulfate, an organometallic compound and a hydroxide A method for producing a phosphor according to any one of Structures 5 to 10, comprising a compound of a kind or more.

(Configuration 12)

Wherein the compound containing the alkaline earth metal element and the compound containing the activator element each contain at least one compound selected from the group consisting of a carbonate and a hydroxide.

(Composition 13)

The method for producing a phosphor according to any one of Structures 5 to 12, wherein the silicon nitride particles have a volume average particle diameter of 150 nm or less.

(Composition 14)

The method for producing a phosphor according to any one of Structures 5 to 13, wherein the silicon nitride particles are amorphous.

(Composition 15)

The method for producing a phosphor according to any one of Structures 5 to 14, wherein the firing step is performed at a temperature of from 1150 DEG C to 1650 DEG C in a mixed gas atmosphere of hydrogen and nitrogen or a mixed gas atmosphere of ammonia and nitrogen.

As described above, according to the phosphor containing at least one of the alkaline earth metal element, silicon, and the nitride and the oxynitride containing the activator element according to the present invention, the phosphor having a volume average particle diameter of 50 nm or more and 400 nm or less, Lt; RTI ID = 0.0 > 60% < / RTI >

For this reason, it is possible to obtain a phosphor containing at least one of an alkaline earth metal element having a small light-emitting property, silicon, and a nitride and an oxynitride containing an activator element.

According to the method for producing a phosphor containing at least one of an alkaline earth metal element, silicon, and an activator element and a nitride and an oxynitride element according to the present invention, it is possible to obtain a phosphor containing silicon nitride particles and an alkaline earth metal element deposited on the surface thereof A phosphor precursor particle having a volume average particle diameter of 250 nm or less including a compound and a compound containing an activator element is prepared, and the phosphor precursor particle is baked.

The phosphor precursor particles are in a state in which a compound containing an alkaline earth metal element and a compound containing an activator element are deposited on the surface of silicon nitride particles. Therefore, at the time of firing, cation exchange between the silicon ion and the alkaline earth metal ion and the ion of the activator element can be easily performed. Therefore, the synthesis reaction of the nitride or oxynitride of the target composition can be accomplished only with little grain growth. Accordingly, it is possible to produce a phosphor containing at least one of an alkaline earth metal element having a small light-emitting property, silicon, and a nitride and an oxynitride containing an activator element, which is excellent in light emission characteristics.

1 shows an image obtained by observing a phosphor precursor particle by a scanning electron microscope (SEM).
Fig. 2 shows the excitation emission spectrum of the phosphor of Example 1. Fig.
Fig. 3 shows an X-ray diffraction spectrum of the phosphor of Example 1 and Example 2. Fig.
Fig. 4 shows emission spectra of the phosphors of Example 2, Comparative Example 9 and Comparative Example 10. Fig.
5 is a graph showing the relationship between the volume average particle diameter of the phosphor and the internal quantum efficiency at an excitation wavelength of 450 nm.
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.
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.
8 is a graph showing the relationship between the volume average particle diameter of the silicon nitride particles and the volume average particle diameter of the phosphor.
9 is a graph showing the relationship between the volume average particle size of the silicon nitride particles and the volume average particle size distribution index of the phosphors.
10 is a graph showing the relationship between the volume average particle diameter of the phosphor precursor particles and the volume average particle diameter of the phosphor.
11 is a graph showing the relationship between the volume average particle size of the phosphor precursor particles and the volume average particle size distribution index of the phosphor.
12 is a graph showing the relationship between the baking temperature and the internal quantum efficiency at the excitation wavelength of 450 nm of the phosphor.
13 is a graph showing the relationship between the firing temperature and the volume average particle diameter of the phosphor.
14 is a graph showing the relationship between the firing temperature and the volume average particle size distribution index of the phosphor.

Hereinafter, embodiments of the present invention will be described.

A. The phosphor of the present invention

The phosphor obtained by the present invention comprises at least one of an alkaline earth metal element, silicon, and a nitride and an oxynitride containing an element functioning as an activator (hereinafter referred to as an activator element).

The phosphor may include only nitride or only an oxynitride. It may also include both a nitride and an oxynitride. Further, in addition to the nitride and the oxynitride, impurities may be contained within a range not adversely affecting the luminescent characteristics of the phosphor.

Examples of the alkaline earth metal element that can be contained in the nitride or the oxynitride include calcium (Ca), strontium (Sr), barium (Ba), and magnesium (Mg).

The nitride or oxynitride contains an activator element to improve the luminescent properties of the phosphor. As the activating element, for example, Eu, Ce, Mn, Pr, Ne, Sm, Tb, Dysprosium, Dy), holmium (Ho), erbium (Er), thulium (Tm) and ytterbium (Yb).

As the nitride to be obtained in the phosphor of the present invention, for example, an M ₂ Si ₅ N ₈ nitride (M is an alkaline earth metal element or an alkaline earth metal element and an activator element) can be mentioned.

As the oxynitride obtained in the phosphor of the present invention, 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. Manufacturing Method of Phosphor

The phosphor containing at least one of an alkaline earth metal element, a nitride containing silicon and an oxynitride, which is a phosphor to be the object of the present invention described above, can be obtained by a precursor preparation step of preparing phosphor precursor particles, a firing step of firing the phosphor precursor particles .

Hereinafter, each step will be described in detail.

1. Precursor preparation process

As the raw material, a material containing silicon nitride particles and an alkaline earth metal element is used. Further, in order to improve the luminescent property of the phosphor, a substance containing an activator element is used.

The silicon nitride particles used as the raw material are preferably amorphous. When amorphous silicon nitride particles are used as a raw material, it is preferable to use a mixture of a silicon ion and an alkaline earth metal ion or an ion of an activator element between a compound containing an alkaline earth metal element deposited on the surface of the silicon nitride particles upon firing and a compound containing an activator element Cation exchange is likely to occur.

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

With respect to a substance containing an alkaline earth metal element used as a raw material, examples of the substance containing Ca include calcium oxide, calcium hydroxide, calcium carbonate, calcium nitrate tetrahydrate, calcium sulfate dihydrate, calcium oxalate monohydrate, calcium acetate Monohydrate, calcium chloride, calcium fluoride, calcium nitride, calcium imine and calcium amide. Among them, calcium nitrate tetrahydrate and calcium chloride are preferable.

Examples of the material containing Sr include strontium oxide, strontium hydroxide octahydrate, strontium carbonate, strontium nitrate, strontium sulfate, strontium oxalate monohydrate, strontium acetate tetrahydrate, strontium chloride, strontium chloride, strontium nitrate, strontium imine, 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, . Of these, barium nitrate and barium chloride are preferable.

As the substance containing Mg, for example, magnesium oxide, magnesium hydroxide, basic magnesium carbonate, magnesium nitrate hexahydrate, magnesium sulfate, magnesium oxalate dihydrate, magnesium acetate tetrahydrate, magnesium chloride, magnesium fluoride, magnesium nitrate, , And magnesium amide. Of these, magnesium nitrate and magnesium chloride are preferable.

Examples of substances containing Eu include europium oxide, europium sulfate, europium oxalate, europium (II) chloride and europium (III) chloride as a substance containing an activator element used as a raw material. ), Europium fluoride (II), europium fluoride (III), europium nitrate hexahydrate, europium nitrate, europium imine and europium amide. Among them, europium nitrate hexahydrate, europium oxide and europium (II) chloride are preferable.

As the material containing other activated elements Ce, Mn, Pr, Nd, Sm, Tb, Dy, Ho, Er, Tm and Yb, Ce, Mn, Pr, Nd, Sm, Tb, Dy, Ho, Er, Tm and Yb.

In the precursor preparation step, 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 deposited on the surface of the silicon nitride particle, More specifically, phosphor precursor particles having a size of 210 nm or less are prepared.

For example, MSi ₂ O ₂ N ₂ based oxynitride (M is at least one alkaline earth metal element selected from the group consisting of Ca, Sr, Ba and Mg including at least Sr, and at least one element selected from the group consisting of Eu and Ce At least one activator selected from the group consisting of Eu and at least 15 mol% of Sr and not more than 99 mol% of Sr, more specifically not less than 20 mol% and not more than 95 mol% % Or more and 20 mol% or less, more specifically 5 mol% or more and 15 mol% or less) of the activator element in the precursor preparation step, the silicon nitride particles and the silicon nitride particles are deposited A compound containing at least one alkaline earth metal element selected from the group consisting of Ca, Sr, Ba and Mg and containing at least Sr, and a compound containing at least Eu selected from the group consisting of Eu and Ce Phosphor particles having a volume average particle size of 250 nm or less, more specifically 210 nm or less are prepared.

The phosphor precursor particles are obtained by mixing silicon nitride particles, a compound containing an alkaline earth metal element and a compound containing an activator element in such a ratio that the molar ratio of the sum of the elements of the alkaline earth metal element and the activator to the silicon is 1: 1.4 to 1: Range, more specifically in the range of 1: 1.5 to 1: 2.67.

The phosphor precursor particles are contained in an amount of 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 amount of the alkaline earth metal element and the activator element. Mol% or less, more specifically 5 mol% or more and 15 mol% or less of the activator element.

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

[Suspension Formation Step]

A suspension containing silicon nitride particles, a substance containing an alkaline earth metal element, and a substance containing an activator element in a predetermined ratio as a raw material in order to obtain a nitride or an oxynitride containing an alkaline earth metal element of a target composition and silicon, .

For example, in order to obtain the above-mentioned MSi ₂ O ₂ N ₂ -based oxynitride, it is possible to use a material containing silicon nitride particles, an alkaline earth metal element, and an activator element as a raw material in an alkali earth metal Element and the activator element and the molar ratio of 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 of this range, the yield of the phosphor decreases, which causes a rise in cost.

The suspension is contained in an amount of not less than 15 mol% and not more than 99 mol%, more specifically not less than 20 mol% and not more than 95 mol%, of Sr and not less than 1 mol% and not more than 20 mol% Contains not less than 5 mol% and not more than 15 mol% of an activator element.

The suspension is formed by charging a raw material into a solvent and stirring.

As a solvent used for forming the suspension, for example, water and one or more polyhydric alcohols selected from the group consisting of ethylene glycol, propylene glycol, tetramethylene glycol, heptamethylene glycol, hexamethylene glycol, glycerin and sorbitol Mixed solvents. Among them, a mixed solvent of water and ethylene glycol is preferable.

[Precursor Formation Process]

A wet chemical method is applied to the obtained suspension to deposit on the surface of the silicon nitride particles a compound containing an alkaline earth metal element and a compound containing an activator element mixed and deposited and having a volume average particle diameter of 250 nm or less, Or less of phosphor precursor particles.

For example, in order to obtain the aforementioned MSi ₂ O ₂ N ₂ -based oxynitride, wet chemical method is applied to the obtained suspension to precipitate a compound containing an alkaline earth metal element and a compound containing an activator element And a phosphor precursor particle having a volume average particle diameter of 250 nm or less, more specifically 210 nm or less, in which a compound containing an alkaline earth metal element and a compound containing an activator element are mixed and deposited on the surface of silicon nitride particles is formed.

The phosphor precursor particles are obtained by mixing silicon nitride particles, a compound containing an alkaline earth metal element and a compound containing an activator element in such a ratio that the molar ratio of the sum of the elements of the alkaline earth metal element and the activator to the silicon is 1: 1.4 to 1: Range, more specifically in the range of 1: 1.5 to 1: 2.67. Outside of this range, the yield of the phosphor decreases, which causes a rise in cost.

The phosphor precursor particles are contained in an amount of 15 mol% or more and 99 mol% or less, more specifically 20 mol% or more and 95 mol% or less, and 1 mol% or more and 20 mol% or less of the total amount of the element M, Contains not less than 5 mol% and not more than 15 mol% of an 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 can be obtained. When the volume average particle diameter of the phosphor precursor particles is 250 nm or less, a phosphor having a uniform particle diameter capable of controlling the particle size distribution can be obtained.

By applying the wet chemical method to the suspension, 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 in a mixed state with each other. Therefore, at the time of firing, the cation exchange with the silicon ion, the alkaline earth metal ion or the ion of the activating element easily occurs. Thus, the synthesis reaction of nitrides or oxynitrides of the desired composition can be accomplished with only a small amount of grain growth.

The wet chemical method may be any method as far as it can deposit on the surface of the silicon nitride particles in a state in which a compound containing an alkaline earth metal element and a compound containing an activator element are mixed with each other. Preferably, it is at least one of a co-precipitation method and a citrate method. Only the co-precipitation method may be used as the wet chemical method, or only the citrate method may be used. Alternatively, both the coprecipitation method and the citrate method may be used.

When a coprecipitation method or a citrate method is used as the wet chemical method, a compound containing an alkaline earth metal element or a compound containing an activator element can be easily precipitated on the surface of the silicon nitride particles, and the silicon nitride particles can easily be entrapped and contacted . Therefore, at the time of firing, the cation exchange with the silicon ion, the alkaline earth metal ion or the ion of the activating element easily occurs. Thus, the synthesis reaction of nitrides or oxynitrides of the desired composition can be accomplished with only a small amount of grain growth.

The coprecipitation is carried out by adding a co-agent to the suspension. Examples of the co-agent added to the suspension include aqueous ammonia hydrogencarbonate solution, ammonium carbonate aqueous solution, urea aqueous solution, acetamide aqueous solution, thiourea aqueous solution and thioacetamide aqueous solution. Among these, an aqueous solution of hydrogen carbonate and an aqueous solution of ammonium carbonate are preferable.

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

A compound containing an alkaline earth metal element deposited on the surface of silicon nitride particles and a compound containing an activator element are each selected from the group consisting of carbonates, bicarbonates, phosphates, carboxylates, oxalates, sulfates, organometallic compounds and hydroxides May be any compound as long as it is one or more kinds of compounds selected from the group consisting of Preferably, it is at least one compound selected from the group consisting of carbonates and hydroxides. Carbonates or hydroxides can be easily precipitated by coprecipitation or citrate method.

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

2. Firing process

The obtained phosphor precursor particles are baked. The firing is carried out under firing conditions in which a phosphor containing an alkaline earth metal element of the target composition, silicon, and a nitride or an oxynitride containing an activator element is obtained as a phosphor having a small particle diameter and excellent in light emission characteristics.

For example, when it is intended to obtain the above-mentioned MSi ₂ O ₂ N ₂ -based oxynitride, the obtained phosphor precursor particles are heated at a temperature of not lower than 1150 ° C. in a mixed gas atmosphere of hydrogen and nitrogen or a mixed gas of ammonia and nitrogen , And is baked at a temperature of not more than 1650 ° C, more specifically not less than 1200 ° C and not more than 1600 ° C.

Firing under a mixed gas atmosphere of hydrogen and nitrogen or a mixed gas atmosphere of ammonia and nitrogen to obtain a phosphor containing MSi ₂ O ₂ N ₂ based oxynitride of the target composition as a main component. By including MSi ₂ O ₂ N ₂ based oxynitride of the target composition as a main component, a phosphor excellent in light emission characteristics can be obtained.

In addition, the calcination of the MSi ₂ O ₂ N ₂ -based oxynitride of the target composition can be prevented by firing at a temperature of 1150 ° C or higher, and the generation of impurities other than the target composition of the MSi ₂ O ₂ N ₂ -based oxynitride Can be prevented. It is possible to prevent insufficient firing and generation of impurities, so that a phosphor excellent in light emission characteristics can be obtained.

In addition, by firing at a temperature of 1650 ° C or lower, it is possible to prevent the grain growth from progressing excessively and to prevent the melting of the MSi ₂ O ₂ N ₂ -based oxynitride of the target composition.

It is possible to prevent the particle growth from progressing excessively, so that a phosphor having a small particle diameter can be obtained. In addition, since melting of the MSi ₂ O ₂ N ₂ -based oxynitride of the target composition can be prevented, it is easy to produce a phosphor containing an MSi ₂ O ₂ N ₂ -based oxynitride of the target composition.

The firing is performed, for example, in the following order.

First, the obtained phosphor precursor particles are charged into a heat-resistant container made of a material having a low reactivity. Examples of the heat-resistant container include a crucible and a tray. Examples of the material of the heat-resistant container include ceramics such as alumina, boron nitride, silicon nitride, silicon carbide, magnesium and mullite, metals such as platinum, molybdenum, tungsten, tantalum, niobium, iridium and rhodium, Alloy, and carbon (graphite). Preferably, heat-resistant containers made of boron nitride, alumina, silicon nitride, silicon carbide, platinum, molybdenum, tungsten, and tantalum can be used.

Thereafter, the heat-resistant container filled with the phosphor precursor particles is placed in a firing apparatus. Examples of the firing apparatus include a metal furnace and a carbon furnace.

Thereafter, the inside of the firing apparatus into which the heat-resistant container is put is put into a reduced pressure state such as a vacuum. Thereafter, the temperature in the firing apparatus is raised to the firing / calcination temperature. Then, a predetermined gas is introduced into the firing apparatus so that the phosphor containing the alkaline earth metal element of the target composition, silicon, and the nitride containing phosphorus element and the oxynitride is obtained as a phosphor having a small luminescence characteristic and a small particle diameter , And the pressure in the firing apparatus is returned to about atmospheric pressure. For example, in order to obtain the aforementioned 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, in order to obtain a phosphor containing an alkaline earth metal element of the target composition, silicon, and a nitride or an oxynitride containing an activator element as a phosphor having a small luminescent property and a small particle diameter, The temperature rises and is held for a predetermined time. For example, in order to obtain the above-described MSi ₂ O ₂ N ₂ based oxynitride, the temperature is raised to a sintering 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 the alkaline earth metal element, silicon, and the nitride containing an activator element and the oxynitride obtained by the above-described production method 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 the internal quantum efficiency at the excitation wavelength of 450 nm is not less than 60%, more specifically not less than 70%. Due to this, this phosphor has excellent luminescence characteristics and small particle diameter.

For example, a phosphor containing an alkaline earth metal element, an activator element and an oxynitride containing silicon, obtained by the above-described production method for the purpose of obtaining the above-described MSi ₂ O ₂ N ₂ system oxynitride, MSi ₂ O ₂ N ₂ wherein M is at least one element selected from the group consisting of Ca, Sr, Ba and Mg, including at least Sr, and at least Eu from the group consisting of Eu and Ce At least one kind of activating element, and contains at least 15 mol% and at most 99 mol%, more particularly at least 20 mol% and at most 95 mol% of Sr, and at least 1 mol% and not more than 20 mol% , More specifically 5 mol% or more and 15 mol% or less of an activator element), and the oxynitride has a crystal structure such as SrSi ₂ O ₂ N ₂ .

The phosphor preferably 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 has an internal quantum efficiency of 60% or more, more specifically 70% or more at 450 nm. Due to this, the phosphor has excellent luminescence characteristics and small particle diameter.

Further, since this phosphor contains at least 15 mol% of Sr relative to the total of the element M, it is possible to prevent the melting point of the MSi ₂ O ₂ N ₂ -based oxynitride of the target composition from lowering. For this reason, it is easy to produce a phosphor containing an MSi ₂ O ₂ N ₂ based oxynitride of the target composition.

Further, since this phosphor contains 99 mol% or less of Sr relative to the total of the element M, it is possible to prevent the content of the activator element from lowering. Therefore, a phosphor excellent in light emission characteristics can be obtained.

In addition, since this phosphor contains at least 1 mol% of the activator element relative to the total of the element M, the content of the activator element can be secured. Therefore, a phosphor excellent in light emission characteristics can be obtained.

Further, since this phosphor contains not more than 20 mol% of the activator element relative to the total of the element M, it is possible to prevent the occurrence of the concentration quenching. Therefore, a phosphor excellent in light emission characteristics can be obtained.

The phosphor obtained by the above-described production method 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 particle diameter.

When the phosphor obtained by the above-described production method contains an oxynitride of the target composition and a silicon-containing compound having a different crystal structure, the oxynitride of the target composition is added to the sum of the oxynitride and the silicon- By mass, more preferably not less than 50% by mass, more specifically not less than 70% by mass. By containing at least 50% by mass of the oxynitride of the target composition, the MSi ₂ O ₂ N ₂ -based oxynitride of the target composition becomes the main component. Therefore, a phosphor excellent in light emission characteristics can be obtained.

D. Uses of Phosphor

The phosphor obtained by the present invention can be used in a light conversion device such as an LED illumination or a display. In addition, since the particle diameter is as small as 400 nm or less, it can be used as a substitute for conventional pigments.

(Example)

Hereinafter, the present invention will be described in detail with reference to Examples.

Various measurements and analyzes in the examples and comparative examples were carried out as follows.

≪ Measurement of particle size distribution &

In Examples and Comparative Examples, particle size distribution of particles was measured using ELS-Z1000ZS (manufactured by Otsuka Electronics Co., Ltd.). For the measurement, a sample for measurement 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 contained in the divided particle size range was accumulated from the smaller particle diameter, and the particle diameter of 16% cumulative is D16V, the particle diameter of 50% cumulative is D50V, And a particle size of 84% cumulative is defined as D84V. At this time, D50V is defined as a volume average particle diameter, and D84V / D16V is defined as a volume average particle size distribution index PSDV.

On the basis of the particle size distribution of the particles measured, the number of particles contained in the divided particle size range is defined as the number average particle diameter in which the number of particles accumulated from the smaller particle diameter is 50%.

<Measurement of excitation spectrum>

In the examples and comparative examples, the excitation light emission spectrum was measured using a fluorescence spectrophotometer F-7000 (manufactured by Hitachi High-Technologies Coroporation).

<Internal Quantum Efficiency Measurement>

In the examples, the internal quantum efficiency was measured using an absolute PL quantum yield measuring apparatus (manufactured by Hamamatsu Photonics K.K.).

For the measurement, 0.1 g of the sample was used. The measurement was carried out at an excitation wavelength of 450 nm.

<Observation by scanning electron microscope>

In the examples, particles were observed using a scanning electron microscope (SEM) SU8020 (manufactured by Hitachi High-Technologies Coroporation).

&Lt; Metal element analysis >

In the examples and comparative examples, metal element analysis was performed using ICP-MS (manufactured by Agilent Technologies Japan, Ltd.) and ICP-AES (manufactured by Shimadzu Corporation).

For the analysis of metallic elements, a sample for measurement was used in which alkali was melted using a flux (borax: sodium carbonate = 1: 1), and then hydrochloric acid was added thereto to make a constant capacity.

The analysis of the europium was carried out by ICP-MS (manufactured by Agilent Technologies Japan, Ltd.), and the analysis of the other metallic elements was performed by ICP-AES (manufactured by Shimadzu Corporation).

&Lt; Powder X-ray diffraction &

In Examples and Comparative Examples, powder X-ray diffraction was performed using an X-ray diffraction device Smart Laboratory (manufactured by Rigaku Corporation).

In powder X-ray diffraction, CuK alpha was used as a source.

The X-ray diffraction spectrum obtained by powder X-ray diffraction analysis was used to perform qualitative analysis and quantitative analysis of the inorganic compound formed in the sample.

Table 1 shows various production conditions in the precursor preparation step and the firing step of the following examples and comparative examples. Table 2 shows the properties of the obtained precursor and fired product.

Purpose composition Precursor Formation Process Firing process Si ₃ N ₄ Sr (NO _{3) 2} Ca (NO _{3) 2}
ㆍ 4H ₂ O Eu (NO _{3) 3}
ㆍ 6H ₂ O atmosphere Temperature D50v
(nm) mass% mass% mass% mass% Kinds Furtherance
(volume) ℃ Example 1 Eu _{0 . 1} Sr _{0 . 9} Si ₂ O ₂ N ₂ 50 28.461 57.964 - 13.575 H ₂ / N ₂ 4% / 96% 1450 Example 2 Eu _0.1 Sr _0.45 Ca _0.45 Si ₂ O ₂ N ₂ 50 27.537 28.040 31.289 13.134 H ₂ / N ₂ 4% / 96% 1450 Example 3 Eu _{0 . 1} Sr _{0 . 9} Si ₂ O ₂ N ₂ 50 28.461 57.964 - 13.575 NH ₃ / N ₂ 4% / 96% 1450 Example 4 Eu _{0 . 1} Sr _{0 . 9} Si ₂ O ₂ N ₂ 50 28.461 57.964 - 13.575 H ₂ / N ₂ 4% / 96% 1250 Example 5 Eu _{0 . 1} Sr _{0 . 9} Si ₂ O ₂ N ₂ 50 28.461 57.964 - 13.575 H ₂ / N ₂ 4% / 96% 1550 Example 6 Eu _0.1 Sr _0.7 Ca _0.2 Si ₂ O ₂ N ₂ 50 28.043 44.420 14.162 13.575 H ₂ / N ₂ 4% / 96% 1450 Example 7 Eu _0.1 Sr _0.2 Ca _0.7 Si ₂ O ₂ N ₂ 50 27.048 12.241 47.809 12.901 H ₂ / N ₂ 4% / 96% 1450 Example 8 Eu _{0 . 15} Sr _{0 . 85} Si ₂ O ₂ N ₂ 50 27.481 52.858 - 19.661 H ₂ / N ₂ 4% / 96% 1450 Example 9 Eu _{0 . 05} Sr _{0 . 95} Si ₂ O ₂ N ₂ 50 29.514 63.447 - 7.039 H ₂ / N ₂ 4% / 96% 1450 Example 10 Eu _{0 . 1} Sr _{0 . 9} Si ₂ O ₂ N ₂ 110 28.461 57.964 - 13.575 H ₂ / N ₂ 4% / 96% 1450 Example 11 Eu _{0 . 1} Sr _{0 . 9} Si ₂ O ₂ N ₂ 25 28.461 57.964 - 13.575 H ₂ / N ₂ 4% / 96% 1450 Comparative Example 1 Eu _{0 . 1} Sr _{0 . 9} Si ₂ O ₂ N ₂ 195 28.461 57.964 - 13.575 H ₂ / N ₂ 4% / 96% 1450 Comparative Example 2 Eu _{0 . 1} Sr _{0 . 9} Si ₂ O ₂ N ₂ 50 28.461 57.964 - 13.575 N ₂ 100% 1450 Comparative Example 3 Eu _{0 . 1} Sr _{0 . 9} Si ₂ O ₂ N ₂ 50 28.461 57.964 - 13.575 H ₂ / N ₂ 4% / 96% 1100 Comparative Example 4 Eu _{0 . 1} Sr _{0 . 9} Si ₂ O ₂ N ₂ 50 28.461 57.964 - 13.575 H ₂ / N ₂ 4% / 96% 1700 Comparative Example 5 Eu _{0 . 1} Sr _{0 . 457} Ca _{0 .45}
Si ₂ O ₂ N ₂ 50 27.537 28.040 31.289 13.134 H ₂ / N ₂ 4% / 96% 1700 Comparative Example 6 Eu _0.1 Sr _0.1 Ca _0.8 Si ₂ O ₂ N ₂ 50 26.858 6.078 54.254 12.810 H ₂ / N ₂ 4% / 96% 1450 Comparative Example 7 Eu _0.005 Sr _0.995 Si ₂ O ₂ N ₂ 50 30.530 68.741 - 0.728 H ₂ / N ₂ 4% / 96% 1450 Comparative Example 8 Eu _{0 . 25} Sr _{0 . 75} Si ₂ O ₂
N ₂ 50 25.710 43.634 - 30.657 H ₂ / N ₂ 4% / 96% 1450 Comparative Example 9 A commercially available MSi ₂ O ₂ N ₂ -based phosphor Comparative Example 10 A commercially available MSi ₂ O ₂ N ₂ -based phosphor was milled with a bead mill

Precursor Phosphor Powder X-ray diffraction Particle characteristics Luminescence characteristic inside
Quantum efficiency D50v
(nm) The silicon-containing compound content
(mass%) D50v
(nm) PSDv Excitation light
(nm) Emission peak (nm) % Example 1 127 SiO ₂ 15 165 1.26 200 to 500 550 73 Example 2 112 SiO ₂ 11 142 1.24 200 to 500 543 81 Example 3 127 SiO ₂ 8 153 1.27 200 to 500 550 83 Example 4 127 SiO ₂ 18 148 1.25 200 to 500 550 72 Example 5 127 SiO ₂ 12 173 1.24 200 to 500 552 80 Example 6 121 SiO ₂ 14 151 1.27 200 to 500 548 79 Example 7 114 SiO ₂ 12 146 1.23 200 to 500 541 77 Example 8 131 SiO ₂ 16 168 1.31 200 to 500 551 75 Example 9 133 SiO ₂ 15 157 1.29 200 to 500 550 74 Example
10 208 SiO ₂ 13 329 1.22 200 to 500 549 79 Example
11 53 SiO ₂ 16 113 1.30 200 to 500 550 73 Comparative Example 1 286 SiO ₂ 15 438 1.41 200 to 500 550 76 Comparative Example 2 127 Sr ₂ SiO ₄ 95 184 1.33 200 to 500 557 50 Comparative Example 3 127 Phosphor is not obtained due to lack of firing Comparative Example 4 127 SiO ₂ 7 960 1.45 200 to 500 551 81 Comparative Example 5 112 Since the Ca content is high and the melting point is lowered and dissolved upon firing, the phosphor can not be obtained Comparative Example 6 118 Since the Ca content is high and the melting point is lowered and dissolved upon firing, the phosphor can not be obtained Comparative Example 7 123 SiO ₂ 17 186 1.32 200 to 500 548 52 Comparative Example 8 132 SiO ₂ 16 172 1.31 200 to 500 545 48 Comparative Example 9 - - 0 15400 2.22 200 to 500 550 77 Comparative Example
10 - - 0 364 1.33 200 to 500 562 36

Example 1.

[Precursor preparation process]

(Suspension forming step)

Amorphous silicon nitride particles (Sigma-Aldrich Co. LLC), strontium nitrate (manufactured by KISHIDA CHEMICAL Co., Ltd.) having a volume average particle diameter D50V of 50 nm, Europium 6 hydrate (manufactured by Kishida Chemical Co., Ltd.) was used.

28.461 mass%, 57.964 mass%, and 13.575 mass% of silicon nitride particles, strontium nitrate and europium nitrate hexahydrate were respectively added to obtain an oxynitride represented by the composition formula Eu _0.1 Sr _0.9 Si ₂ O ₂ N ₂ Weighed. The suspension and the phosphor precursor particles to be described later were mixed with a mixture of Sr and Eu in a molar ratio of 1: 2, and Sr and Eu in a total amount of 90 mol% of Sr and 10 mol% of Eu . The weighed raw material was added to a mixed solvent consisting of 100 g of water and 50 g of ethylene glycol and stirred to form a suspension.

(Precursor forming step)

Ammonium hydrogencarbonate (manufactured by Kishida Chemical Co., Ltd.) was dissolved in water, and 216 ml of a 0.158 mol / L aqueous hydrogen carbonate solution was formed as a co-precipitant.

Thereafter, while stirring and mixing the suspension obtained as described above, the co-infiltrant was added dropwise over one hour. After the co-precipitant was added, stirring was continued for 2 hours. In this manner, the strontium ion and the europium ion were precipitated as carbonate and hydroxide, respectively, and the strontium carbonate and the europium hydroxide were uniformly mixed and deposited on the surface of the silicon nitride particles to form the phosphor precursor particles.

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

[Firing Step]

The obtained phosphor precursor particles were fired in the following procedure.

First, the obtained phosphor precursor particles were charged into a crucible made of boron nitride. Thereafter, the crucible filled with the phosphor precursor particles was placed in a metallocene vacuum atmosphere furnace (NEMS Co., Ltd.). After placing the crucible in the furnace, the inside of the furnace was first evacuated by a diffusion pump. Thereafter, the inside of the furnace was heated from room temperature to 1100 占 폚 at a rate of 300 占 폚 every hour. Thereafter, a mixed gas of 4% by volume of hydrogen and 96% by volume of nitrogen was introduced into the furnace while the temperature in the furnace was maintained at 1100 DEG C, and the pressure in the furnace was returned to about atmospheric pressure. Thereafter, the inside of the furnace was raised at a rate of 300 DEG C per hour to 1450 DEG C, and the temperature in the furnace was maintained at 1450 DEG C for 3 hours to burn the phosphor precursor particles to obtain a fired product.

[Characteristics of phosphor precursor particles]

The obtained phosphor precursor particles were observed using a scanning electron microscope.

1 shows an image obtained by observing a phosphor precursor particle by a scanning electron microscope (SEM). In Fig. 1, a number of particles having a particle size of about 100 nm are seen. From this, it can be confirmed that strontium carbonate and hydroxide of europium are deposited on the surface of the silicon nitride particles.

The particle size distribution of the obtained phosphor precursor particles was measured.

From the measurement results of the particle size distribution, the volume average particle diameter D50V of the phosphor precursor particles is 127 nm.

[Characteristics of phosphor]

The excited luminescence spectrum of the obtained fired product was measured.

Fig. 2 shows the excitation emission spectrum of the fired product of Example 1. Fig.

In Fig. 2, the horizontal axis is the wavelength, and the vertical axis is the intensity.

From the excitation spectrum, it can be seen that it is excited by light in a wide wavelength range from ultraviolet light of 200 nm or more to visible light of 500 nm or less, and the emission peak wavelength is 550 nm. From this, it can be confirmed that the obtained calcined product is a phosphor that is excited by visible light.

Powder X-ray diffraction of the obtained fired product was also carried out.

Fig. 3 (a) shows the X-ray diffraction spectrum of the fired product of Example 1. Fig.

The horizontal axis in Fig. 3 is an angle formed in the incident X-ray direction and the diffraction X-ray direction, and the vertical axis is the intensity.

This X-ray diffraction spectrum was analyzed by the lead-belt method, and an oxynitride containing a crystal structure such as SrSi ₂ O ₂ N ₂ and a silicon-containing compound containing a crystal structure such as SiO ₂ were produced in the resulting fired product .

It is also understood that 85% by mass of oxynitrides is produced and 15% by mass of silicon-containing compounds are produced relative to the sum of the oxynitrides and the silicon-containing compounds.

On the other hand, c in Fig. 3 represents the X-ray diffraction spectrum of the SrSi ₂ O ₂ N ₂ crystal obtained by calculation.

In addition, the obtained fired product was analyzed for metallic elements.

From the measurement results of the metal element analysis, it can be seen that Sr and Eu are contained in the obtained fired product in a molar ratio of Sr: Eu = 0.9: 0.1.

The particle size distribution of the obtained fired product was measured.

From the measurement results of the particle size distribution, the volume average particle diameter D50V of the fired product is 165 nm, and the volume average particle size distribution index PSDV is 1.26.

The internal quantum efficiency at the excitation wavelength of 450 nm of the obtained fired product was measured.

From the measurement results, the internal quantum efficiency at the excitation wavelength 450 nm of the fired product is 73%.

From the above, the phosphor obtained by Example 1 contains an oxynitride containing Sr, Eu and Si. This phosphor is represented by the composition formula Eu _0.1 Sr _0.9 Si ₂ O ₂ N ₂ . From this composition formula, this phosphor has 90 mol% of Sr and 10 mol% of Eu relative to the total of Sr and Eu. The oxynitride has a crystal structure such as SrSi ₂ O ₂ N ₂ .

The phosphor had a volume average particle diameter D50V of 165 nm and a volume average particle size distribution index PSDV of 1.26.

The phosphor had an internal quantum efficiency of 73% at an excitation wavelength of 450 nm.

Incidentally, this phosphor contains an oxynitride of 85 mass% with respect to the total of the oxynitride and the silicon-containing compound.

Example 2.

Amorphous silicon nitride particles (Sigma-Aldrich Co. LLC), strontium nitrate (manufactured by KISHIDA CHEMICALS Co., Ltd.) having a volume average particle diameter D50V of 50 nm, Calcium tetrahydrate (manufactured by Kishida Chemical Co., Ltd.) and europium nitrate hexahydrate (manufactured by Kishida Chemical Co., Ltd.) were used.

In order to obtain an oxynitride expressed by the 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 dissolved in an amount of 27.537 mass% , 28.040 mass%, 31.289 mass%, and 13.134 mass%, respectively.

The suspension and the phosphor precursor particles contained 45 mol% of Sr and 10 mol% of Sr, Ca and Eu in a total molar ratio of silicon to silicon of 1: % Eu.

Other than that, phosphor precursor particles and fired product were obtained in the same manner as in Example 1.

The particle size distribution of the obtained phosphor precursor particles was measured. As a result, the volume average particle diameter D50V of the phosphor precursor particles was 112 nm.

When the excited luminescence spectrum of the obtained fired product was measured, it was excited by light in a wavelength range of 200 nm or more and 500 nm or less, indicating that the luminescence peak wavelength was 543 nm. From this, it can be confirmed that the obtained calcined product is a phosphor that is excited by visible light.

4 (a) 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.

When the obtained fired product was subjected to powder X-ray diffraction, an oxynitride containing a crystal structure such as SrSi ₂ O ₂ N ₂ and a silicon-containing compound containing a crystal structure such as SiO ₂ were produced in the obtained fired product .

It is also found that an oxynitride is produced in an amount of 89% by mass and a silicon-containing compound is produced in an amount of 11% by mass based on the total amount of the oxynitride and the silicon-containing compound.

3 (b) shows the X-ray diffraction spectrum of the fired product of Example 2. Fig.

Elemental analysis of the obtained fired product revealed that the fired product contained Sr and Ca and Eu in a molar ratio of Sr: Ca: Eu = 0.45: 0.45: 0.1.

When the particle size distribution of the obtained fired product was measured, the volume average particle diameter D50V of the fired product was 142 nm, and the volume average particle size distribution index PSDV was 1.24.

The internal quantum efficiency at the excitation wavelength of 450 nm of the obtained fired product was measured. As a result, the internal quantum efficiency at the excitation wavelength of 450 nm of the fired product was 81%.

From the above, the phosphor obtained by Example 2 contains an oxynitride containing Sr, Ca, Eu and Si. This phosphor is represented by the 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% of Sr and 10 mol% of Eu relative to the total of Sr, Ca and Eu.

The oxynitride has the same crystal structure as SrSi 2 O 2 N 2.

The phosphor had a volume average particle diameter D50V of 142 nm and a volume average particle size distribution index PSDV of 1.24.

This phosphor has an internal quantum efficiency of 81% at an excitation wavelength of 450 nm.

Incidentally, this phosphor contains an oxynitride of 89 mass% with respect to the total of the oxynitride and the silicon-containing compound.

Example 3.

The phosphor precursor particles were obtained in the same manner as in Example 1.

The fired precursor particles were fired in the same manner as in Example 1 except that the phosphor precursor particles were fired in a mixed gas atmosphere of 4% by volume of ammonia and 96% by volume of nitrogen, to obtain fired products.

Various measurements and analyzes were performed in the same manner as in Example 1, and it was found that the obtained fired product was excited by light in a wavelength range of 200 nm or more and 500 nm or less, and the luminescence peak wavelength was 550 nm. From this, it can be confirmed that the obtained calcined product is a phosphor that is excited by visible light.

It can also be seen that an oxynitride containing a crystal structure such as SrSi ₂ O ₂ N ₂ and a silicon-containing compound containing a crystal structure such as SiO ₂ are produced in the resulting fired product.

It is also found that 92% by mass of oxynitrides is produced and 8% by mass of silicon-containing compounds is produced relative to the sum of the oxynitrides and the silicon oil compounds.

It can be seen that Sr and Eu are contained in the obtained fired product in a molar ratio of Sr: Eu = 0.9: 0.1.

The volume average particle diameter D50V of the obtained fired product was 153 nm, and the volume average particle size distribution index PSDV was 1.27.

The internal quantum efficiency at the excitation wavelength of 450 nm of the obtained fired product is 83%.

From the above, the phosphor obtained in Example 3 contains an oxynitride containing Sr, Eu and Si. This phosphor is represented by the composition formula Eu _0.1 Sr _0.9 Si ₂ O ₂ N ₂ . From this composition formula, this phosphor has 90 mol% of Sr and 10 mol% of Eu relative to the total of Sr and Eu.

The oxynitride has a crystal structure such as SrSi ₂ O ₂ N ₂ .

The phosphor had a volume average particle diameter D50V of 153 nm and a volume average particle size distribution index PSDV of 1.27.

The phosphor has an internal quantum efficiency of 83% at an excitation wavelength of 450 nm.

In addition, this phosphor contains an oxynitride of 92 mass% with respect to the total of the oxynitride and the silicon-containing compound.

Example 4.

The phosphor precursor particles were obtained in the same manner as in Example 1.

In addition, firing was performed in the same manner as in Example 1 except that the phosphor precursor particles were fired at 1250 캜 to obtain a fired product.

When the same measurement and analysis as those in Example 1 were carried out, it was found that the obtained fired product was excited by light in a wavelength range of 200 nm or more and 500 nm or less, and the emission peak wavelength was 550 nm. From this, it can be confirmed that the obtained calcined product is a phosphor that is excited by visible light. It can also be seen that oxynitride containing a crystal structure such as SrSi ₂ O ₂ N ₂ and silicon-containing compound containing a crystal structure such as SiO ₂ are generated in the resulting fired product.

It is also found that an oxynitride is produced in an amount of 82% by mass and a silicon-containing compound is produced in an amount of 18% by mass based on the total amount of the oxynitride and the silicon-containing compound.

It can be seen that Sr and Eu are contained in the obtained fired product in a molar ratio of Sr: Eu = 0.9: 0.1.

The volume average particle diameter D50V of the obtained fired product was 148 nm, and the volume average particle size distribution index PSDV was 1.25.

The internal quantum efficiency at the excitation wavelength of 450 nm of the obtained fired product is 72%.

From the above, the phosphor obtained in Example 4 contains an oxynitride containing Sr, Eu and Si. This phosphor is represented by the composition formula Eu _0.1 Sr _0.9 Si ₂ O ₂ N ₂ . From this composition formula, this phosphor has 90 mol% of Sr and 10 mol% of Eu relative to the total of Sr and Eu.

The oxynitride has a crystal structure such as SrSi ₂ O ₂ N ₂ .

The phosphor had a volume average particle diameter D50V of 148 nm and a volume average particle size distribution index PSDV of 1.25.

This phosphor has an internal quantum efficiency of 72% at an excitation wavelength of 450 nm.

In addition, this phosphor contains an oxynitride of 82 mass% with respect to the total of the oxynitride and the silicon-containing compound.

Example 5.

The phosphor precursor particles were obtained in the same manner as in Example 1.

Further, firing was carried out in the same manner as in Example 1 except that the phosphor precursor particles were fired at 1550 占 폚 to obtain a fired product.

When the same measurement and analysis as those in Example 1 were carried out, it was found that the obtained fired product was excited by light in a wavelength range of 200 nm or more and 500 nm or less, and the luminescence peak wavelength was 552 nm. From this, it can be confirmed that the obtained calcined product is a phosphor that is excited by visible light.

It can also be seen that oxynitride containing a crystal structure such as SrSi ₂ O ₂ N ₂ and silicon containing compound including a crystal structure such as SiO ₂ are generated in the resulting fired product.

It is also found that an oxynitride is produced in an amount of 88 mass% and a silicon-containing compound is produced in an amount of 12 mass% with respect to the total amount of the oxynitride and the silicon-containing compound.

It can be seen that Sr and Eu are contained in the obtained fired product in a molar ratio of Sr: Eu = 0.9: 0.1.

The volume average particle diameter D50V of the obtained fired product was 173 nm, and the volume average particle size distribution index PSDV was 1.24.

The internal quantum efficiency at the excitation wavelength of 450 nm of the obtained fired product is 80%.

From the above, the phosphor obtained by Example 5 contains an oxynitride containing Sr, Eu and Si. This phosphor is represented by the composition formula Eu _0.1 Sr _0.9 Si ₂ O ₂ N ₂ . From this composition formula, it can be seen that this phosphor has 90 mol% of Sr and 10 mol% of Eu relative to the sum of Sr and Eu.

The oxynitride has the same crystal structure as SrSi ₂ O ₂ N ₂ .

The phosphor had a volume average particle diameter D50V of 173 nm and a volume average particle size distribution index PSDV of 1.24.

The phosphor has an internal quantum efficiency of 80% at an excitation wavelength of 450 nm.

Incidentally, this phosphor contains an oxynitride of 88 mass% 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 were added to 28.043 mass %, 44.420 mass%, 14.162 mass%, and 13.375 mass%, respectively, to obtain phosphor precursor particles and calcined products.

The same measurement and analysis as in Example 1 were carried out, and the volume average particle diameter D50V of the obtained phosphor precursor particles was 121 nm.

The obtained fired product is excited by light in a wavelength range of 200 nm or more and 500 nm or less, indicating that the emission peak wavelength is 548 nm. From this, it can be confirmed that the obtained calcined product is a phosphor that is excited by visible light.

It can also be seen that oxynitride containing a crystal structure such as SrSi ₂ O ₂ N ₂ and silicon containing compound including a crystal structure such as SiO ₂ are generated in the resulting fired product.

It is also found that an oxynitride of 86 mass% is produced and a silicon-containing compound is produced of 14 mass% with respect to the total amount of the oxynitride and the silicon-containing compound.

It can also be seen that Sr, Ca and Eu are contained in the obtained fired product in a molar ratio of Sr: Ca: Eu = 0.7: 0.2: 0.1.

The volume average particle diameter D50V of the obtained fired product was 151 nm, and the volume average particle size distribution index PSDV was 1.27.

The internal quantum efficiency at the excitation wavelength of 450 nm of the obtained fired product is 79%.

From the above, the phosphor obtained by Example 6 contains Sr, Ca, oxynitrides containing Eu and Si.

This phosphor is represented by the composition formula Eu _0.1 Sr _0.7 Ca _0.2 Si ₂ O ₂ N ₂ . From this composition formula, it can be seen that this phosphor has 70 mol% of Sr and 10 mol% of Eu relative to the total of Sr, Ca and Eu.

The oxynitride has a crystal structure such as SrSi ₂ O ₂ N ₂ .

The phosphor had a volume average particle diameter D50V of 151 nm and a volume average particle size distribution index PSDV of 1.27.

This phosphor has an internal quantum efficiency of 79% at an excitation wavelength of 450 nm.

Incidentally, this phosphor contains an oxynitride of 86 mass% 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 were dissolved in 27.048 mass %, 12.241 mass%, 47.809 mass%, and 12.901 mass%, respectively, in the same manner as in Example 2, except that the phosphor precursor particles and the calcined product were obtained.

The same measurement and analysis as in Example 1 were carried out, and the volume average particle diameter D50V of the obtained phosphor precursor particles was 114 nm.

The obtained fired product is excited by light in a wavelength range of 200 nm or more and 500 nm or less, indicating that the emission peak wavelength is 541 nm. From this point of view, it can be confirmed that the obtained calcined product is a phosphor that is excited by visible light.

It can also be seen that oxides including a crystal structure such as SrSi ₂ O ₂ N ₂ and silicon-containing compounds having a crystal structure such as SiO ₂ are produced in the resulting fired product.

It is also found that an oxynitride is produced in an amount of 88 mass% and a silicon-containing compound is produced in an amount of 12 mass% with respect to the total amount of the oxynitride and the silicon-containing compound.

It can be seen that Sr, Ca and Eu are contained in the obtained fired product in a molar ratio of Sr: Ca: Eu = 0.2: 0.7: 0.1.

The volume average particle diameter D50V of the obtained fired product was 146 nm, and the volume average particle size distribution index PSDV was 1.23.

The internal quantum efficiency at the excitation wavelength of 450 nm of the obtained fired product is 77%.

From the above, the phosphor obtained by Example 7 contains an oxynitride containing Sr, Ca, Eu and Si.

This phosphor is represented by the composition formula Eu _0.1 Sr _0.2 Ca _0.7 Si ₂ O ₂ N ₂ . From this composition formula, it can be seen that this phosphor has 20 mol% of Sr and 10 mol% of Eu relative to the total of Sr, Ca and Eu.

The oxynitride has a crystal structure such as SrSi ₂ O ₂ N ₂ .

The phosphor had a volume average particle diameter D50V of 146 nm and a volume average particle size distribution index PSDV of 1.23.

The phosphor has an internal quantum efficiency of 77% at an excitation wavelength of 450 nm.

Incidentally, this phosphor contains an oxynitride of 88 mass% with respect to the total of the oxynitride and the silicon-containing compound.

Example 8.

In order to obtain an oxynitride represented by the composition formula Eu _0.15 Sr _0.85 Si ₂ O ₂ N ₂ , 27.481 mass%, 52.858 mass%, and 19.661 mass% of silicon nitride particles, strontium nitrate and europium nitrate hexahydrate, , The phosphor precursor particles and the fired product were obtained in the same manner as in Example 1. The results are shown in Table 1. &lt; tb &gt;&lt; TABLE &gt;

The same measurement and analysis as in Example 1 were carried out, and the volume average particle diameter D50V of the obtained phosphor precursor particles was 131 nm.

The obtained fired product is excited by light in a wavelength range of 200 nm or more and 500 nm or less, and it can be seen that the luminescence peak wavelength is 551 nm. From this, it can be confirmed that the obtained calcined product is a phosphor that is excited by visible light.

It can also be seen that oxynitride containing a crystal structure such as SrSi ₂ O ₂ N ₂ and silicon containing compound including a crystal structure such as SiO ₂ are generated in the resulting fired product.

It can also be seen that 84% by mass of oxynitrides is produced and 16% by mass of silicon-containing compounds are produced relative to the total amount of the oxynitride and the silicon-containing compound.

It can also be seen that Sr and Eu are contained in the obtained fired product in a molar ratio of Sr: Eu = 0.85: 0.15.

The volume average particle diameter D50V of the obtained fired product was 168 nm, and the volume average particle size distribution index PSDV was 1.31.

The internal quantum efficiency at the excitation wavelength of 450 nm of the obtained fired product is 75%.

From the above, the phosphor obtained in Example 8 contains an oxynitride containing Sr, Eu and Si.

Further, this phosphor is represented by the composition formula Eu _0.15 Sr _0.85 Si ₂ O ₂ N ₂ .

From this composition formula, it can be seen that this phosphor has 85 mol% of Sr and 15 mol% of Eu relative to the total of Sr and Eu.

The oxynitride has a crystal structure such as SrSi ₂ O ₂ N ₂ .

The phosphor had a volume average particle diameter D50V of 168 nm and a volume average particle size distribution index PSDV of 1.31.

This phosphor has an internal quantum efficiency of 75% at an excitation wavelength of 450 nm.

Incidentally, this phosphor contains an oxynitride of 84 mass% with respect to the total of the oxynitride and the silicon-containing compound.

Example 9.

To obtain the oxynitride represented by the composition formula Eu _0.05 Sr _0.95 Si ₂ O ₂ N ₂ , 29.514 mass%, 63.447 mass%, and 7.039 mass% of silicon nitride particles, strontium nitrate and europium nitrate hexahydrate, , The phosphor precursor particles and the fired product were obtained in the same manner as in Example 1. The results are shown in Table 1 below.

The same measurement and analysis as in Example 1 were carried out, and the volume average particle diameter D50V of the obtained phosphor precursor particles was 133 nm.

The obtained fired product is excited by light in a wavelength range of 200 nm or more and 500 nm or less, indicating that the emission peak wavelength is 550 nm. From this, it can be confirmed that the obtained calcined product is a phosphor that is excited by visible light.

It can also be seen that an oxynitride containing a crystal structure such as SrSi ₂ O ₂ N ₂ and a silicon-containing compound containing a crystal structure such as SiO ₂ are produced in the resulting fired product.

It is also understood that 85% by mass of oxynitrides is produced and 15% by mass of silicon-containing compounds are produced relative to the sum of the oxynitrides and the silicon-containing compounds.

It can also be seen that Sr and Eu are contained in the obtained fired product in a molar ratio of Sr: Eu = 0.95: 0.05.

The volume average particle diameter D50V of the obtained fired product was 157 nm, and the volume average particle size distribution index PSDV was 1.29.

The internal quantum efficiency at the excitation wavelength of 450 nm of the obtained fired product is 74%.

From the above, the phosphor obtained by Example 9 contains oxynitride containing Sr, Eu and Si.

This phosphor is represented by the composition formula Eu _0.05 Sr _0.95 Si ₂ O ₂ N ₂ .

From this composition formula, it can be seen that this phosphor has 95 mol% of Sr and 5 mol% of Eu relative to the sum of Sr and Eu.

The oxynitride has a crystal structure such as SrSi ₂ O ₂ N ₂ .

The phosphor had a volume average particle diameter D50V of 157 nm and a volume average particle size distribution index PSDV of 1.29.

Further, this phosphor has an internal quantum efficiency of 74% at an excitation wavelength of 450 nm.

Incidentally, this phosphor contains an oxynitride of 85 mass% with respect to the total of the oxynitride and the silicon-containing compound.

Example 10.

(Silicon nitride particles having a volume average particle diameter D50V of 110 nm) obtained by pulverizing crystalline silicon nitride (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 Ltd.) , The phosphor precursor particles and the fired product were obtained in the same manner as in Example 1. [

The same measurement and analysis as in Example 1 were carried out, and the volume average particle diameter D50V of the obtained phosphor precursor particles was 208 nm.

The obtained fired product is excited by light in a wavelength range of 200 nm or more and 500 nm or less, indicating that the emission peak wavelength is 549 nm. From this point of view, it can be confirmed that the obtained calcined product is a phosphor that is excited by visible light.

It can also be seen that oxynitride containing a crystal structure such as SrSi ₂ O ₂ N ₂ and silicon containing compound including a crystal structure such as SiO ₂ are generated in the resulting fired product.

It can also be seen that 87% by mass of oxynitrides are produced and 13% by mass of silicon-containing compounds are produced relative to the sum of the oxynitrides and the silicon-containing compounds.

It can also be seen that Sr and Eu are contained in the obtained fired product in a molar ratio of Sr: Eu = 0.9: 0.1.

The volume average particle diameter D50V of the obtained fired product was 329 nm, and the volume average particle size distribution index PSDV was 1.22.

The internal quantum efficiency at the excitation wavelength of 450 nm of the obtained fired product is 79%.

From the above, the phosphor obtained by Example 10 contains an oxynitride containing Sr, Eu and Si. This phosphor is represented by the composition formula Eu _0.1 Sr _0.9 Si ₂ O ₂ N ₂ . From this composition formula, this phosphor has 90 mol% of Sr and 10 mol% of Eu relative to the total of Sr and Eu.

The oxynitride has a crystal structure such as SrSi ₂ O ₂ N ₂ .

The phosphor had a volume average particle diameter D50V of 329 nm and a volume average particle size distribution index PSDV of 1.22.

This phosphor has an internal quantum efficiency of 79% at an excitation wavelength of 450 nm.

Incidentally, this phosphor contains 87% by mass of oxynitride relative to the total of the oxynitride and the silicon-containing compound.

Example 11.

The phosphor precursor particles and the fired product were obtained in the same manner as in Example 1, except that amorphous silicon nitride particles (made by HEFEI KAIER KK K. KAIER NANOMETER ENERGY & TECHNOLOGY CO., LTD.) Having a volume average particle diameter D50V of 25 nm was used as a raw material.

Various measurements and analyzes were performed in the same manner as in Example 1, and the volume average particle diameter D 50V of the obtained phosphor precursor particles was 53 nm.

The obtained fired product is excited by light in a wavelength range of 200 nm or more and 500 nm or less, indicating that the emission peak wavelength is 550 nm.

From this point, it can be confirmed that the obtained fired product is a phosphor that is excited by visible light.

It can also be seen that oxynitride containing a crystal structure such as SrSi ₂ O ₂ N ₂ and silicon containing compound including a crystal structure such as SiO ₂ are generated in the resulting fired product.

It can also be seen that 84% by mass of oxynitrides are produced and 16% by mass of silicon-containing compounds are produced relative to the sum of the oxynitrides and the silicon-containing compounds.

It can also be seen that Sr and Eu are contained in the obtained fired product in a molar ratio of Sr: Eu = 0.9: 0.1.

The volume average particle diameter D50V of the obtained fired product was 113 nm, and the volume average particle size distribution index PSDV was 1.30.

The internal quantum efficiency at the excitation wavelength of 450 nm of the obtained fired product is 73%.

From the above, the phosphor obtained by Example 11 contains an oxynitride containing Sr, Eu and Si. This phosphor is represented by the composition formula Eu _0.1 Sr _0.9 Si ₂ O ₂ N ₂ . From this composition formula, it can be seen that this phosphor has 90 mol% of Sr and 10 mol% of Eu relative to the sum of Sr and Eu.

The oxynitride has a crystal structure such as SrSi ₂ O ₂ N ₂ .

The phosphor had a volume average particle diameter D50V of 113 nm and a volume average particle size distribution index PSDV of 1.30.

The phosphor had an internal quantum efficiency of 73% at an excitation wavelength of 450 nm.

Incidentally, this phosphor contains an oxynitride of 84 mass% with respect to the total of the oxynitride and the silicon-containing compound.

Comparative Example 1

As a raw material, phosphor precursor particles and fired product were obtained in the same manner as in Example 1 except that crystalline silicon nitride particles (manufactured by Ube Industries) having a volume average particle diameter D50V of 195 nm were used.

The same measurement and analysis as in Example 1 were carried out, and the volume average particle diameter D50V of the obtained phosphor precursor particles was 286 nm.

The obtained fired product is excited by light in a wavelength range of 200 nm or more and 500 nm or less, indicating that the emission peak wavelength is 550 nm. From this, it can be confirmed that the obtained calcined product is a phosphor that is excited by visible light.

It can also be seen that an oxynitride containing a crystal structure such as SrSi ₂ O ₂ N ₂ and a silicon-containing compound containing a crystal structure such as SiO ₂ are produced in the resulting fired product.

It is also understood that 85% by mass of oxynitride is produced and 15% by mass of silicon-containing compound is produced relative to the total amount of the oxynitride and the silicon-containing compound.

It can also be seen that Sr and Eu are contained in the obtained fired product in a molar ratio of Sr: Eu = 0.9: 0.1.

The volume average particle diameter D50V of the obtained fired product was 438 nm, and the volume average particle size distribution index PSDV was 1.41.

The internal quantum efficiency at the excitation wavelength of 450 nm of the obtained fired product is 76%.

From the above, the phosphor obtained in Comparative Example 1 contains an oxynitride containing Sr, Eu and Si. This phosphor is represented by the composition formula Eu _0.1 Sr _0.9 Si ₂ O ₂ N ₂ .

From this composition formula, it can be seen that this phosphor has 90 mol% of Sr and 10 mol% of Eu relative to the sum of Sr and Eu.

The oxynitride has a crystal structure such as SrSi ₂ O ₂ N ₂ .

The phosphor had a volume average particle diameter D50V of 438 nm and a volume average particle size distribution index PSDV of 1.41.

This phosphor has an internal quantum efficiency of 76% at an excitation wavelength of 450 nm.

Incidentally, this phosphor contains an oxynitride of 85 mass% with respect to the total of the oxynitride and the silicon-containing compound.

Comparative Example 2

The phosphor precursor particles were obtained in the same manner as in Example 1.

Further, the phosphor precursor particles were fired in the same manner as in Example 1 except that the phosphor precursor particles were fired under a gas atmosphere of 100 volume% nitrogen, to obtain a fired product.

Various measurements and analyzes were performed in the same manner as in Example 1, and the obtained fired product was excited by light in a wavelength range of 200 nm or more and 500 nm or less, indicating that the emission peak wavelength was 557 nm. From this point of view, it can be confirmed that the obtained calcined product is a phosphor that is excited by visible light.

It can also be seen that oxynitrides containing a crystal structure such as SrSi ₂ O ₂ N ₂ and silicon-containing compounds containing a crystal structure such as Sr ₂ SiO ₄ are produced in the resulting fired product.

It is also found that an oxynitride is produced in an amount of 5% by mass and a silicon-containing compound is produced in an amount of 95% by mass based on the total amount of the oxynitride and the silicon-containing compound.

It can also be seen that Sr and Eu are contained in the obtained fired product in a molar ratio of Sr: Eu = 0.9: 0.1.

The volume average particle diameter D50V of the obtained fired product was 184 nm, and the volume average particle size distribution index PSDV was 1.33.

The internal quantum efficiency at the excitation wavelength of 450 nm of the obtained fired product is 50%.

From the above, the phosphor obtained in Comparative Example 2 contains an oxynitride containing Sr, Eu and Si. This phosphor is represented by the composition formula Eu _0.1 Sr _0.9 Si ₂ O ₂ N ₂ . From this composition formula, this phosphor has 90 mol% of Sr and 10 mol% of Eu relative to the total of Sr and Eu.

The oxynitride has a crystal structure such as SrSi ₂ O ₂ N ₂ .

The phosphor had a volume average particle diameter D50V of 184 nm and a volume average particle size distribution index PSDV of 1.33.

The phosphor has an internal quantum efficiency of 50% at an excitation wavelength of 450 nm.

In addition, this phosphor contains an oxynitride of 5 mass% with respect to the total of the oxynitride and the silicon-containing compound.

Comparative Example 3

The phosphor precursor particles were obtained in the same manner as in Example 1.

Further, firing was performed in the same manner as in Example 1 except that the phosphor precursor particles were fired at 1100 ° C to obtain a fired product.

The excited luminescence spectrum of the resulting fired product was measured. As a result, the fired product did not emit light. This is due to lack of firing. Therefore, in Comparative Example 3, no phosphor was obtained.

Comparative Example 4

The phosphor precursor particles were obtained in the same manner as in Example 1.

In addition, firing was performed in the same manner as in Example 1 except that the phosphor precursor particles were fired at 1700 캜 to obtain a fired product.

Various measurements and analyzes were carried out in the same manner as in Example 1, and the obtained fired product was excited by light in a wavelength range of 200 nm or more and 500 nm or less, indicating that the emission peak wavelength was 551 nm. From this point of view, it can be confirmed that the obtained calcined product is a phosphor that is excited by visible light.

It can also be seen that oxynitride containing a crystal structure such as SrSi ₂ O ₂ N ₂ and silicon containing compound including a crystal structure such as SiO ₂ are generated in the resulting fired product.

It is also found that an oxynitride is produced in an amount of 93 mass% and a silicon-containing compound is produced in an amount of 7 mass% based on the total amount of the oxynitride and the silicon-containing compound.

It can also be seen that Sr and Eu are contained in the obtained fired product in a molar ratio of Sr: Eu = 0.9: 0.1.

The volume average particle diameter D50V of the obtained fired product was 960 nm, and the volume average particle size distribution index PSDV was 1.45.

The internal quantum efficiency at the excitation wavelength of 450 nm of the obtained fired product is 81%.

From the above, the phosphor obtained by the comparative example 4 contains an oxynitride containing Sr, Eu and Si. This phosphor is represented by the composition formula Eu _0.1 Sr _0.9 Si ₂ O ₂ N ₂ . From this composition formula, it can be seen that this phosphor has 90 mol% of Sr and 10 mol% of Eu relative to the sum of Sr and Eu.

The oxynitride has a crystal structure such as SrSi ₂ O ₂ N ₂ .

The phosphor had a volume average particle diameter D50V of 960 nm and a volume average particle size distribution index PSDV of 1.45.

This phosphor has an internal quantum efficiency of 81% at an excitation wavelength of 450 nm.

Incidentally, this phosphor contains an oxynitride of 93 mass% with respect to the total of the oxynitride and the silicon-containing compound.

Comparative Example 5

The phosphor precursor particles were obtained in the same manner as in Example 2.

Further, the phosphor precursor particles were fired in the same manner as in Example 1, except that the phosphor precursor particles were fired at 1700 캜.

In Comparative Example 5, since the phosphor melts during baking, no phosphor was obtained. 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 were added in an amount of 26.858 mass% , 6.078 mass%, 54.254 mass%, and 12.810 mass%, respectively, to obtain phosphor precursor particles. Further, the phosphor precursor particles were fired in the same manner as in Example 1.

In Comparative Example 6, since the phosphor melts during firing, no phosphor was obtained. 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

To obtain an oxynitride represented by the composition formula Eu _0.005 Sr _0.995 Si ₂ O ₂ N ₂ , 30.530 mass%, 68.741 mass%, and 0.728 mass% of silicon nitride particles, strontium nitrate and europium nitrate hexahydrate, , The phosphor precursor particles and the fired product were obtained in the same manner as in Example 1. The results are shown in Table 1 below.

The same measurement and analysis as in Example 1 were carried out, and the volume average particle diameter D50V of the obtained phosphor precursor particles was 123 nm.

The obtained fired product is excited by light in a wavelength range of 200 nm or more and 500 nm or less, indicating that the emission peak wavelength is 548 nm. From this point of view, it can be confirmed that the obtained calcined product is a phosphor that is excited by visible light.

It can also be seen that an oxynitride containing a crystal structure such as SrSi ₂ O ₂ N ₂ and a silicon-containing compound containing a crystal structure such as SiO ₂ are produced in the resulting fired product.

It is also found that an oxynitride is produced in an amount of 83 mass% and a silicon-containing compound is produced in an amount of 17 mass% with respect to the total amount of the oxynitride and the silicon-containing compound.

It can also be seen that the obtained fired product contains Sr and Eu in a molar ratio of Sr: Eu = 0.995: 0.005.

The volume average particle diameter D50V of the obtained fired product was 186 nm, and the volume average particle size distribution index PSDV was 1.32.

The internal quantum efficiency at the excitation wavelength of 450 nm of the obtained fired product is 52%.

Thus, the phosphor obtained in Comparative Example 7 contains an oxynitride containing Sr, Eu and Si. This phosphor is represented by the composition formula Eu _0.005 Sr _0.995 Si ₂ O ₂ N ₂ .

From this composition formula, this phosphor has 99.5 mol% of Sr and 0.5 mol% of Eu relative to the sum of Sr and Eu.

The oxynitride has a crystal structure such as SrSi ₂ O ₂ N ₂ .

The phosphor had a volume average particle diameter D50V of 186 nm and a volume average particle size distribution index PSDV of 1.32.

Further, this phosphor has an internal quantum efficiency of 52% at an excitation wavelength of 450 nm.

Incidentally, this phosphor contains an oxynitride of 83 mass% with respect to the total of the oxynitride and the silicon-containing compound.

Comparative Example 8

In order to obtain an oxynitride represented by the composition formula Eu _0.25 Sr _0.75 Si ₂ O ₂ N ₂ , silicon nitride particles, strontium nitrate and europium nitrate hexahydrate were added in amounts of 25.710 mass%, 43.634 mass%, and 30.657 mass% , The phosphor precursor particles and the fired product were obtained in the same manner as in Example 1. The results are shown in Table 1 below.

Various measurements and analyzes were carried out in the same manner as in Example 1, and the volume average particle diameter D50V of the obtained phosphor precursor particles was 132 nm. The obtained fired product is excited by light in a wavelength range of 200 nm or more and 500 nm or less, indicating that the emission peak wavelength is 545 nm. From this point of view, it can be confirmed that the obtained calcined product is a phosphor that is excited by visible light.

It can also be seen that oxynitride containing a crystal structure such as SrSi ₂ O ₂ N ₂ and silicon containing compound including a crystal structure such as SiO ₂ are generated in the resulting fired product.

It can also be seen that 84% by mass of oxynitrides are produced and 16% by mass of silicon-containing compounds are produced relative to the sum of the oxynitrides and the silicon-containing compounds.

It can be seen that Sr and Eu are contained in the obtained fired product in a molar ratio of Sr: Eu = 0.75: 0.25.

The volume average particle diameter D50V of the obtained fired product was 172 nm, and the volume average particle size distribution index PSDV was 1.31.

The internal quantum efficiency at the excitation wavelength of 450 nm of the obtained fired product is 48%.

From the above, the phosphor obtained in Comparative Example 8 contains an oxynitride containing Sr, Eu and Si. This phosphor is represented by the composition formula Eu _0.25 Sr _0.75 Si ₂ O ₂ N ₂ . From this composition formula, it can be seen that this phosphor has 75 mol% of Sr and 25 mol% of Eu relative to the sum of Sr and Eu.

The oxynitride has a crystal structure such as SrSi ₂ O ₂ N ₂ .

The phosphor had a volume average particle diameter D50V of 172 nm and a volume average particle size distribution index PSDV of 1.31.

This phosphor has an internal quantum efficiency of 48% at an excitation wavelength of 450 nm.

Incidentally, this phosphor contains an oxynitride of 84 mass% 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-Yufi Science and Technology Co., Ltd.) .

Various measurements and analyzes were conducted in the same manner as in Example 1, and it was found that the commercially available oxynitride phosphors were excited by light in a wavelength range of 200 nm or more and 500 nm or less, and the emission peak wavelength was 550 nm.

4 (b) shows the emission spectrum of commercially available oxynitride phosphors.

It is also understood that commercially available oxynitride phosphors do not contain crystal components other than oxynitrides containing a crystal structure such as SrSi ₂ O ₂ N ₂ .

The volume average particle diameter D50V of the commercially available oxynitride phosphors is 15400 nm, and the volume average particle size distribution index PSDV is 2.22.

The internal quantum efficiency at the excitation wavelength of 450 nm of commercially available oxynitride phosphors is 77%.

Comparative Example 10.

A commercially available oxynitride phosphor used in Comparative Example 9 was ground with a bead mill and classified to obtain an oxynitride phosphor of submicron size.

When the same measurement and analysis as in Example 1 were carried out, it was found that the commercially available oxynitride phosphors after the pulverization were excited by light in a wavelength range of 200 nm or more and 500 nm or less, and the luminescence peak wavelength was 562 nm.

Fig. 4 (c) shows the luminescence spectrum of commercially available oxynitride phosphors after pulverization.

The commercially available oxynitride phosphors after pulverization do not contain crystal components other than oxynitrides having a crystal structure such as SrSi ₂ O ₂ N ₂ , but a part of the oxynitride crystals are amorphized by pulverization .

The volume average particle diameter D50V of the commercially available oxynitride phosphors after pulverization is 364 nm, and the volume average particle size distribution index PSDV is 1.33.

The internal quantum efficiency of the commercially available oxynitride phosphor after pulverization at an excitation wavelength of 450 nm is 36%.

Examples Comparative example  Contrast Review

5 is a graph showing the relationship between the volume average particle diameter D50V of the phosphor and the internal quantum efficiency at an excitation wavelength of 450 nm.

5, the abscissa axis represents the volume average particle diameter of the phosphor, and the ordinate axis represents the internal quantum efficiency at the excitation wavelength of 450 nm of the phosphor.

5, diamond-shaped points represent Examples 1-11, and quadrangular points a and b represent Comparative Examples 9 and 10.

5, the phosphor of Example 1-11 had a volume-average particle diameter D50V of 50 nm or more and 400 nm or less, more specifically, 100 nm or more and 350 nm or less, and the internal quantum efficiency Is at least 60%, more specifically at least 70%. For this reason, the phosphor of Example 1-11 having a small particle diameter and excellent in light emission characteristics can be obtained.

Particularly, in Examples 2, 3, and 5, it is possible to obtain a phosphor having an extremely high internal quantum efficiency of 80% or more at an excitation wavelength of 450 nm and having extremely small 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 a volume average particle diameter D50V as large as 15,400 nm.

In the phosphor of Comparative Example 10 obtained by pulverizing the phosphor of Comparative Example 9, the volume average particle diameter D50V can be reduced to 364 nm, but the internal quantum efficiency at the excitation wavelength of 450 nm is reduced to 36%.

4, the luminescence intensities at the luminescence peak wavelengths of the phosphors of Comparative Examples 9 and 10 are lower than the luminescence intensities at the luminescence peak wavelength of the phosphor of Example 2. For this reason, it is not possible to obtain a phosphor having a small particle size and excellent light emission characteristics from commercially available phosphors (Comparative Examples 9 and 10).

In the phosphor of Example 1-11, the volume average particle size distribution index PSDV is 1.20 or more and 1.35 or less, more specifically 1.21 nm or more and 1.32 or less. Hence, from Examples 1-11, it is possible to obtain a phosphor having a uniform particle size.

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 abscissa of FIG. 6 is the Sr content of the phosphor, and the ordinate is the internal quantum efficiency at the excitation wavelength of 450 nm of the phosphor.

In Fig. 6, diamond-shaped points represent Examples 1-11, and quadrangular points a and b represent Comparative Examples 6 and 7.

As shown in Fig. 6, in Comparative Example 6, the Ca content is large, and Sr is less than 15 mol% with respect to the total of the alkaline earth metal elements (Sr, Ca) and Eu. As a result, the melting point of the oxynitride synthesized during firing was lowered, and the phosphor could not be obtained.

When the firing temperature is lowered, it is considered that the synthesis reaction is difficult to proceed and the internal quantum efficiency at the excitation wavelength of 450 nm is lowered because impurities such as silicon-containing compounds are increased.

The phosphor of Comparative Example 7 had an Sr content of more than 99 mol%. Therefore, the content of Eu is decreased, and the internal quantum efficiency at the excitation wavelength of 450 nm is lowered.

Therefore, the Sr content is preferably 15 mol% or more and 99 mol% or less.

The phosphor of Example 1-11 having an internal quantum efficiency of 60% or more at an excitation wavelength of 450 nm was found to contain 20 mol% or more and 95 mol% or less of Sr with respect to the total amount of the alkaline earth metal elements (Sr, Ca) I have. Therefore, the Sr content is more preferably 20 mol% or more and 95 mol% or less.

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.

The abscissa of Fig. 7 is the Eu content of the phosphor, and the ordinate is the internal quantum efficiency at the excitation wavelength of 450 nm of the phosphor.

In Fig. 7, diamond-shaped points represent Examples 1-11, and quadrangular points a and b represent Comparative Examples 7 and 8.

As shown in Fig. 7, the phosphor of Comparative Example 7 has Eu of less than 1 mol% based on the sum of the alkaline earth metal elements (Sr, Ca) and Eu. Therefore, the content of Eu is small, and the internal quantum efficiency at the excitation wavelength of 450 nm is lowered.

In addition, the phosphor of Comparative Example 8 has an Eu content of more than 20 mol%. Therefore, the concentration quenching occurs and the internal quantum efficiency at the excitation wavelength of 450 nm is lowered.

Therefore, the Eu content is preferably 1 mol% or more and 20 mol% or less.

The phosphor of Example 1-11 having an internal quantum efficiency of 60% or more at an excitation wavelength of 450 nm was found to contain Eu in an amount of 5 mol% or more and 15 mol% or less relative to the total amount of the alkaline earth metal elements (Sr, Ca) I have. Therefore, the Eu content is more preferably 5 mol% or more and 15 mol% or less.

8 is a graph showing the relationship between the volume average particle diameter D50V of the silicon nitride particles and the volume average particle diameter D50V of the phosphors.

8, the abscissa axis indicates the volume average particle diameter of the silicon nitride particles D50V, and the ordinate axis indicates the volume average particle diameter D50V of the phosphor.

9 is a graph showing the relationship between the volume average particle diameter D50V of the silicon nitride particles and the volume average particle size distribution index PSDV of the phosphor.

The horizontal axis in FIG. 9 is the volume average particle diameter D50V of the silicon nitride particles, and the vertical axis is the volume average particle size distribution index PSDV of the phosphors.

8 and 9, the diamond-shaped plots show Examples 1-11, and the tetrahedron plot a shows Comparative Example 1. The diamond-

As shown in Fig. 8, in Comparative Example 1, the volume average particle diameter D50V of the silicon nitride particles is larger than 150 nm. For this reason, the volume average particle diameter D50V of the phosphor precursor particles was also increased. As a result, the volume average particle diameter D50V of the phosphor becomes as large as 400 nm, and a phosphor having a desired particle diameter can not be obtained.

As shown in Fig. 9, the particle size distribution can not be controlled, and the volume average particle size distribution index PSDV of the phosphor becomes larger than 1.35, and a phosphor having a desired particle size distribution can not be obtained.

Therefore, the volume average particle diameter D50V 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 D50V of 50 nm or more and 400 nm or less and a volume average particle size distribution index PSDV of 1.20 or more and 1.35 or less is obtained, the volume average particle diameter D50V of the silicon nitride particles is 120 nm or less. For this reason, the volume average particle diameter D50V of the silicon nitride particles is more preferably 120 nm or less.

10 is a graph showing the relationship between the volume average particle diameter D50V of the phosphor precursor particles and the volume average particle diameter D50V of the phosphor.

10, the abscissa axis indicates the volume average particle diameter D50V of the phosphor precursor particles, and the ordinate axis indicates the volume average particle diameter D50V of the phosphor.

11 is a graph showing the relationship between the volume average particle diameter D50V of the phosphor precursor particles and the volume average particle size distribution index PSDV of the phosphor.

The horizontal axis in FIG. 11 is the volume average particle diameter D50V of the phosphor precursor particles, and the vertical axis is the volume average particle size distribution index PSDV of the phosphor.

In FIGS. 10 and 11, the diamond-shaped plots show Examples 1-11 and the tetrahedron plot a shows Comparative Example 1. FIG.

As shown in Fig. 10, in Comparative Example 1, the volume average particle diameter D50V of the phosphor precursor particles is larger than 250 nm. Therefore, the volume average particle diameter D50V of the phosphor becomes larger than 400 nm, and a phosphor having a desired particle diameter can not be obtained.

As shown in Fig. 11, the particle size distribution can not be controlled, and the volume average particle size distribution index PSDV of the phosphor becomes larger than 1.35, and a phosphor having a desired particle size distribution can not be obtained.

Therefore, the volume average particle diameter D50V of the phosphor precursor particles is preferably 250 nm or less. In Example 1-11 in which a phosphor having a volume average particle diameter D50V of 50 nm or more and 400 nm or less and a volume average particle size distribution index PSDV of 1.20 or more and 1.35 or less is obtained, the volume average particle diameter D50V of the phosphor precursor particles is 210 nm or less. Therefore, the volume average particle diameter D50V of the phosphor precursor particles is more preferably 210 nm or less.

12 is a graph showing the relationship between the baking temperature and the internal quantum efficiency at the excitation wavelength of 450 nm of the phosphor.

12 is the firing temperature, and the vertical axis is the internal quantum efficiency at the excitation wavelength of 450 nm of the phosphor.

In Fig. 12, diamond-shaped dots represent Example 1-11, and quadrangle dots a-c represent Comparative Examples 3-5.

13 is a graph showing the relationship between the firing temperature and the volume average particle diameter D50V of the phosphor.

13, the abscissa represents the firing temperature, and the ordinate represents the volume average particle diameter D50V of the phosphor.

14 is a graph showing the relationship between the firing temperature and the volume average particle size distribution index PSDV of the phosphor.

The horizontal axis in Fig. 14 is the firing temperature, and the vertical axis is the volume average particle size distribution index PSDV of the phosphor.

In FIGS. 13 and 14, the diamond-shaped plot shows Examples 1-11 and the tetrahedron-shaped plot b shows Comparative Example 4. FIG.

As shown in Fig. 12, in Comparative Example 3, the firing temperature is lower than 1150 占 폚. For this reason, the synthesis reaction does not proceed and the phosphor can not be obtained due to the insufficient calcination. If the firing temperature is low, it is considered that the synthesis reaction is difficult to proceed and the internal quantum efficiency at the excitation wavelength of 450 nm is lowered because impurities such as silicon-containing compounds are increased.

As shown in Fig. 12, in Comparative Example 4, the firing temperature is higher than 1650 占 폚. Therefore, as shown in Fig. 13, the particle growth proceeds excessively, and the volume average particle diameter D50V of the phosphor becomes larger than 400 nm, and a phosphor having a desired particle diameter can not be obtained.

As shown in Fig. 14, the particle size distribution can not be controlled, and the volume average particle size distribution index PSDV of the phosphor becomes larger than 1.35, and a phosphor having a desired particle size distribution can not be obtained.

As shown in Fig. 12, in Comparative Example 5, the firing temperature is higher than 1650 占 폚. As in the case of Comparative Example 5, the melting point of the oxynitride synthesized during firing is lowered depending on the content ratio of the alkaline earth metal elements (Sr, Ca) and Eu, so that if the firing temperature is high, .

Therefore, the firing temperature is preferably 1150 DEG C or more and 1650 DEG C or less.

In Example 1-11 in which a phosphor having a volume average particle diameter D50V of 50 nm or more and 400 nm or less and a volume average particle size distribution index PSDV of 1.20 or more and 1.35 or less is obtained, the baking temperature is 1200 占 폚 or more and 1,600 占 폚 or less. Therefore, 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 in a mixed gas atmosphere of hydrogen and nitrogen or a mixed gas atmosphere of ammonia and nitrogen. In this case, a phosphor containing an oxynitride as a main component is obtained.

Specifically, the phosphors of Examples 1-11 include an oxynitride of 50% by mass or more, and more specifically 70% by mass or more, based on the total amount of the oxynitride and the silicon-containing compound. By including an oxynitride as a main component, a phosphor having a high internal quantum efficiency at an excitation wavelength of 450 nm can be obtained.

On the other hand, in Comparative Example 2, the phosphor precursor particles were fired in a gas atmosphere of 100 vol% nitrogen. In this case, the synthesis reaction of the oxynitride does not proceed, and a silicon-containing compound containing a crystal structure such as Sr ₂ SiO ₄ is produced as a main component.

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

On the other hand, in the above-described embodiment, only the case of using Sr as the alkaline earth metal element but the combination of Sr and Ca is explained. However, when at least one of Ba and Mg is used instead of Ca, The present invention can be applied to at least one of Mg.

In the above-described embodiment, the case where only Eu is used as an activator element has been described, but the present invention can also be applied to the case where Ce is used together with Eu.

In the above-described embodiments, only the case of using the coprecipitation method as the wet chemical method has been described, but the present invention can also be applied to the case of using the citrate method.

In the above-described embodiment, the case where the carbonate of the alkaline earth metal element and the hydroxide of the activator element are deposited on the surface of the silicon nitride particles has been described. However, the hydrocarbons other than carbonates and hydroxides, phosphates, carboxylates, oxalates , Sulfates, or organometallic compounds are deposited on the substrate.

As described above, the present invention has been described in detail by way of embodiments and examples, but it is to be understood that the present invention is not limited thereto. It will be apparent to those skilled in the art that modifications and improvements are possible within the technical scope of the present invention. It is to be understood that both the foregoing description and the following detailed description are exemplary and explanatory and are intended to provide further explanation of the invention as claimed.

Claims (15)

1. A phosphor comprising at least one of an alkaline earth metal element, silicon, and a nitride and an oxynitride containing an activator element,
A phosphor having a volume average particle diameter of 50 nm or more and 400 nm or less and an internal quantum efficiency at an excitation wavelength of 450 nm of 60% or more. The method of claim 1,
The phosphor is represented by the composition formula MSi ₂ O ₂ N ₂ ,
The oxynitride has a crystal structure such as SrSi ₂ O ₂ N ₂ ,
Wherein the element M is at least one alkaline earth metal element selected from the group consisting of Ca, Sr, Ba, and Mg, including at least Sr, and at least one element selected from the group consisting of Eu and Ce, Including an element,
And Sr and an activator element in an amount of not less than 1 mol% and not more than 20 mol%, based on the total amount of the element M, not less than 15 mol% and not more than 99 mol%. The phosphor according to claim 1 or 2, wherein the volume average particle size distribution index is 1.20 or more and 1.35 or less. A silicon-containing compound according to claim 2 or 3, wherein the oxynitride includes a silicon-containing compound having a crystal structure different from that of the oxynitride, wherein the oxynitride is contained in an amount of 50 mass% or more relative to the total amount of the oxynitride and the silicon- Phosphor. A method of producing a phosphor comprising at least one of an alkaline earth metal element, silicon, and a nitride and an oxynitride containing an activator element,
A precursor preparation step of preparing 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 diameter of 250 nm or less, and
A firing step of firing the phosphor precursor particles
To form a phosphor. The method of claim 5,
Wherein the precursor preparation step is a step of 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, and applying the alkaline earth metal element to the surface of the silicon nitride grains And a precursor forming step of forming phosphor precursor particles in which the compound containing the activator element and the compound containing the activator element are mixed and deposited. The method of claim 5,
Wherein the phosphor precursor particles comprise silicon nitride particles, a compound containing at least one alkaline earth metal element selected from the group consisting of Ca, Sr, Ba, and Mg deposited on the surface of the silicon nitride particle, including at least Sr, Ce in a molar ratio of the sum of the elements of the alkaline earth metal element and the activator to the silicon in the range of 1: 1.4 to 1: 2.86, and the compound containing at least one activator element selected from the group consisting of Ce, and,
Wherein the phosphor precursor particles comprise 15 mol% or more and 99 mol% or less of Sr and 1 mol% or more and 20 mol% or less of an activator element relative to the total amount of the alkaline earth metal element and the activator element. 8. The method of claim 7,
The precursor preparation process includes:
Silicon nitride particles and a material containing at least one kind of alkaline earth metal element selected from the group consisting of Ca, Sr, Ba and Mg including at least Sr and at least one element selected from the group consisting of Eu and Ce, A suspension forming step of forming a suspension containing the above-mentioned activator element in a molar ratio of the sum of the alkaline earth metal element and the activator element to silicon in the range of 1: 1.4 to 1: 2.86,
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 on the surface of the silicon nitride particle, and a compound containing the alkaline earth metal element and the activator And a precursor forming step of forming phosphor precursor particles in which the element-containing compounds are mixed and deposited,
The suspension contains 15 mol% or more and 99 mol% or less of Sr and 1 mol% or more and 20 mol% or less of an activator element based on the total amount of the alkaline earth metal element and the activator element. The method as claimed in claim 6 or 8,
Wherein the wet chemical method is at least one of a co-precipitation method and a citrate method. The method for producing a phosphor according to claim 9, wherein the wet chemical method is coprecipitation. 11. The method according to any one of claims 5 to 10,
The compound containing the alkaline earth metal element and the compound containing the activator element are each selected from the group consisting of a carbonate, a bicarbonate, a phosphate, a carbonate, a oxalate, a sulfate, an organometallic compound and a hydroxide Type or more of the compound. 12. The method of claim 11,
Wherein the compound containing the alkaline earth metal element and the compound containing the activator element each contain at least one compound selected from the group consisting of carbonates and hydroxides. 13. The method according to any one of claims 5 to 12,
Wherein the silicon nitride particles have a volume average particle diameter of 150 nm or less. 14. The method for producing a phosphor according to any one of claims 5 to 13, wherein the silicon nitride particles are amorphous. 15. The method according to any one of claims 5 to 14,
Wherein the firing step is carried out at a temperature of from 1150 DEG C to 1650 DEG C in a mixed gas atmosphere of hydrogen and nitrogen or in a mixed gas atmosphere of ammonia and nitrogen.

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