JP2012201759A - Nitride-based phosphor, illuminating device made by using the same and method for producing nitride-based phosphor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a green color-based phosphor having a new composition.SOLUTION: This phosphor includes a composition expressed by formula [1]: (A, Eu)DENO, wherein A is an alkaline earth metal element including Ba as an essential element; D is a tetravalent metal element including Si as an essential element; E is a trivalent metal element including Al as an essential element; and (x) and (y) are each a number satisfying the formula: 1<x≤3 and 0.0001≤y≤0.15.

Description

  The present invention relates to a nitride-based phosphor, a light emitting device using the same, and a method for manufacturing a nitride-based phosphor.

The phosphor is used for a fluorescent display tube (VFD), a field emission display (FED), a plasma display panel (PDP), a cold cathode tube (CRT), a white light emitting diode (LED), and the like. In any of these applications, in order to cause the phosphor to emit light, it is necessary to supply energy for exciting the phosphor to the phosphor. The phosphor is excited by an excitation source having high energy such as vacuum ultraviolet rays, ultraviolet rays, electron beams, blue light, and emits visible light.
In recent years, improvement in color rendering properties of light emitting devices has been demanded, and development of new phosphors is desired. In addition to conventional phosphors such as silicate phosphors, phosphate phosphors, aluminate phosphors and sulfide phosphors, nitride phosphors and oxynitride phosphors are also being searched for.

_Recently, M _{y Ba} (wherein, M is one or more Eu and Ce, y satisfies 0.001 <y ≦ 0.1.) ( 1-y) Si 6 N 8 O phosphor represented by Has been reported (Patent Document 1). This phosphor is known to emit blue-green light.
Further, it has been reported that Si can be substituted with Al as represented by (Ba, Eu) Si _6-y Al _y N _{8 -y} O _{1 + y} (where y is 1 or less) (non- Patent Document 1). The phosphor in which Si is replaced with Al also emits blue-green light. Non-Patent Document 1 also reports that an impurity phase is generated when the value of y in the composition formula is larger than 1.

JP 2009-138070

Nagaveni Karkada et al, ECS Transactions, 16 (31) 41-50 (2009)

  The phosphors described in Patent Document 1 and Non-Patent Document 1 emit blue-green, but in order to obtain color rendering properties, phosphors that emit green light are required.

Result of various studies on manufacturing conditions, _{surprisingly, (A 1-y, Eu} y) D 6-x E x N 8-x O 1 + x (A is an alkaline earth metal element essentially containing Ba , D represents a tetravalent metal element in which Si is essential, and E represents a trivalent metal element in which Al is essential.) In the composition, Si can be replaced with Al. That is, it was found that x can be larger than 1. A phosphor obtained by substituting Si for Al was found to be a green-emitting phosphor, and the present invention was completed.

That is, the gist of the present invention resides in the following (1) to (4).
(1) A phosphor having a composition represented by the following formula [1].
(A _1-y , Eu _y ) D _6-x E _x N _{8 -x} O _{1 + x} [1]
(However, in the formula [1], A represents an alkaline earth metal element in which Ba is essential, D represents a tetravalent metal element in which Si is essential, and E is indispensable Al. Represents a trivalent metal element.

X and y represent numbers satisfying the following expression.
1 <x ≦ 3
0.0001 ≦ y ≦ 0.15)
(2) A phosphor material mixture comprising a step of adjusting a phosphor material mixture having a composition ratio represented by the following formula [2] and firing the phosphor material mixture at 0.2 MPa or more and 100 MPa or less. Production method.
(A _1-y , Eu _y ) D _6-x E _x N _{8 -x} O _{1 + x} [2]
(However, in the formula [1], A represents an alkaline earth metal element in which Ba is essential, D represents a tetravalent metal element in which Si is essential, and E is indispensable Al. Represents a trivalent metal element.

X and y represent numbers satisfying the following expression.
1 <x ≦ 3
0.0001 ≦ y ≦ 0.15)
(3) In the said baking process, baking temperature is the range of 1500 degreeC or more and 2000 degrees C or less, The manufacturing method of the fluorescent substance as described in (2) characterized by the above-mentioned.
(4) A light emitting device comprising the phosphor according to (1).

According to the present invention, it is possible to provide a green phosphor having a composition that could not be produced.
Moreover, if the phosphor obtained by the present invention is combined with an LED or the like, a light emitting device having excellent color rendering properties can be provided.

It is a typical perspective view which shows one Example of the semiconductor light-emitting device of this invention. FIG. 2A is a schematic cross-sectional view showing an embodiment of a bullet-type light emitting device of the present invention, and FIG. 2B is a schematic view showing an embodiment of the surface-mounted light-emitting device of the present invention. It is sectional drawing. It is typical sectional drawing which shows one Example of the illuminating device of this invention. The emission spectrum of the fluorescent substance manufactured in Examples 1-2 and Comparative Example 2 is shown. It is the X-ray pattern obtained by powder X-ray diffraction about the fluorescent substance manufactured in Examples 1-3, Reference Examples 1-2, and Comparative Examples 1-4. In Examples 1-3 and Comparative Examples 1-4, it is the graph showing the change of the lattice constant a accompanying the change of x. In Examples 1-3 and Comparative Examples 1-4, it is the graph showing the change of the lattice constant b accompanying the change of x. In Examples 1-3 and Comparative Examples 1-4, it is the graph showing the change of the lattice constant c accompanying the change of x.

Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments, and various modifications can be made within the scope of the gist of the present invention.
In the present specification, a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
Further, in the phosphor composition formula in this specification, each composition formula is delimited by a punctuation mark (,). In addition, when a plurality of elements are listed separated by commas (,), one or two or more of the listed elements may be included in any combination and composition. For example, the composition formula “(Ca, Sr, Ba) Al ₂ O ₄ : Eu” has “CaAl ₂ O ₄ : Eu”, “SrAl ₂ O ₄ : Eu”, and “BaAl ₂ O ₄ : Eu”. “Ca _1−x Sr _x Al ₂ O ₄ : Eu”, “Sr _1−x Ba _x Al ₂ O ₄ : Eu”, “Ca _1−x Ba _x Al ₂ O ₄ : Eu”, _{"Ca 1-x-y Sr x} Ba y Al 2 O 4: Eu " and all assumed to generically indicated (in the above formula, 0 <x <1,0 <y <1,0 <X + y <1).

[1. Phosphor]
(Composition of phosphor) The phosphor of the present invention has a composition represented by the following formula [1]. (A _1-y , Eu _y ) D _6-x E _x N _{8 -x} O _{1 + x} [1]
(However, in the formula [1],
A represents an alkaline earth metal element essential for Ba,
D represents a tetravalent metal element in which Si is essential,
E represents a trivalent metal element in which Al is essential.
X and y represent numbers satisfying the following expression.
1 <x ≦ 3
0.0001 ≦ y ≦ 0.15)
In the above formula [1], x means the amount of substitution of Al with respect to Si. The numerical value range of x is usually larger than 1, preferably 1.2 or more, more preferably 1.4 or more, particularly preferably 1.8 or more, and usually 3 or less, preferably 2.4 or less, Particularly preferably, it is 2.2 or less.

  In the above formula [1], y means the composition ratio of Eu. Usually, it is 0.0001 or more, preferably 0.001 or more, and usually 0.2 or less, preferably 0.15 or less, particularly preferably 0.12 or less. If the value of y is too large, concentration quenching tends to occur and the brightness tends to decrease. If it is too small, the absorption efficiency tends to decrease, and the brightness tends to decrease accordingly.

  In the formula [1], “A” represents an alkaline earth metal element in which Ba is essential. The proportion of Ba to the entire A element is preferably 50 mol% or more, more preferably 70 mol% or more, and particularly preferably 90 mol% or more. In addition to Ba, elements that may be contained in the formula [1] include alkaline earth metal elements such as Sr and Ca.

In the above formula [1], “D” represents a tetravalent metal element in which Si is essential. Ge or the like may be contained within a range that does not affect the properties of the obtained phosphor. The proportion of Si with respect to the entire D element is preferably 50 mol% or more, more preferably 70 mol% or more, and particularly preferably 90 mol% or more.
In the formula [1], “E” represents a trivalent metal element in which Al is essential. B, Ga, and the like may be contained within a range that does not affect the properties of the obtained phosphor. The proportion of Al to the entire E element is preferably 50 mol% or more, more preferably 70 mol% or more, and particularly preferably 90 mol% or more.

In the formula [1], “N” is nitrogen. Nitrogen may be used as a main component, and F, Cl, and the like may be contained within a range that does not affect the characteristics of the obtained phosphor.
In the formula [1], “O” is oxygen. As long as oxygen is a main component, F, Cl, and the like may be contained within a range that does not affect the characteristics of the obtained phosphor.
In the formula [1], “Eu” is europium.

Further, in addition to the constituent elements A, Eu, D, E, N, and O described above, impurity elements that are inevitably mixed within a range that does not affect the effects of the present invention may be included. Good.
(Emission wavelength)
The phosphor of the present invention has an emission peak in a wavelength range of usually 470 nm or more, preferably 490 nm or more, more preferably 500 nm or more, and usually 550 nm or less, preferably 530 nm or less. That is, it has a green emission color.

The emission peak wavelength can be measured by the method described in the examples, and for example, it can be measured using excitation light having a peak wavelength of 365 nm.
(Excitation wavelength)
The phosphor of the present invention has an excitation peak in a wavelength range of usually 250 nm or more, preferably 280 nm or more, and usually 350 nm or less, preferably 320 nm or less. That is, it is excited by light in the ultraviolet region.

[2. Method for producing phosphor]
In the phosphor of the present invention, each phosphor material is weighed so as to have a composition represented by the following formula [2] to prepare a phosphor material mixture, and the obtained phosphor material mixture is fired (firing). Step). In the firing step, firing under pressure, specifically 0.2 MPa or more and 100 MPa or less is preferable.
(A _1-y , Eu _y ) D _6-x E _x N _{8 -x} O _{1 + x} [2]
(However, in the previous term [1],
A represents an alkaline earth metal element essential for Ba,
D represents a tetravalent metal element in which Si is essential,
E represents a trivalent metal element in which Al is essential.
X and y represent numbers satisfying the following expression.
1 <x ≦ 3
0.0001 ≦ y ≦ 0.15)
As the phosphor material, a metal compound, a metal, or the like is used. That is, it can be manufactured by weighing the metal compound so as to have a predetermined composition, mixing, and firing. For example, when producing the phosphor represented by the above formula [2], the raw material of A (hereinafter referred to as “A source” as appropriate), the raw material of D (hereinafter referred to as “D source” as appropriate), and the raw material of E (hereinafter referred to as “ E source), N raw material (hereinafter referred to as “N source” where appropriate), O raw material (hereinafter referred to as “O source” as appropriate), and Eu raw material (hereinafter referred to as “Eu source” as appropriate) It can be manufactured by firing (mixing step), firing the obtained mixture (firing step), and washing the obtained fired product as needed (cleaning step).

(Phosphor raw material)
As the phosphor raw material used in the method for producing the phosphor of the present invention, known materials can be used, for example, BaO, BaCO ₃ or the like as the element A raw material, SiC or Si ₃ N as the raw material for the D element, for example. ₄ , SiO _2, etc. As a raw material for E element, AlN, Al ₂ O ₃ , Al ₄ C ₃ etc., and further from Eu metal, oxide, carbonate, chloride, fluoride, nitride or oxynitride A selected Eu compound can be used.

In addition, O (oxygen) and N (nitrogen) in the formula [2] may be supplied from an A source (Ba source), a D source (Si source), an E source (Al source), and an Eu source. You may supply from a baking atmosphere.
Each raw material may contain inevitable impurities.
(Mixing process)
The phosphor raw materials are weighed so as to obtain the target composition, and sufficiently mixed using a ball mill or the like to obtain a phosphor raw material mixture (mixing step).

Although it does not specifically limit as said mixing method, Specifically, the method of following (A) and (B) is mentioned.
(A) Dry pulverizer such as hammer mill, roll mill, ball mill, jet mill, etc., or pulverization using mortar and pestle, and mixer such as ribbon blender, V-type blender, Henschel mixer, or mortar and pestle And a dry mixing method in which the above phosphor raw materials are pulverized and mixed.

(B) A solvent or dispersion medium such as water is added to the phosphor material described above, and mixed using, for example, a pulverizer, a mortar and a pestle, or an evaporating dish and a stirring rod, to obtain a solution or slurry. A wet mixing method in which drying is performed by spray drying, heat drying, or natural drying.
The mixing of the phosphor raw material may be either the wet mixing method or the dry mixing method, but in order to avoid contamination of the phosphor raw material with moisture, a dry mixing method or a wet mixing method using a water-insoluble solvent is more preferable. .

(Baking process)
Subsequently, the phosphor material mixture obtained in the mixing step is fired (firing step). The above-mentioned phosphor raw material mixture is dried as necessary and then filled in a container such as a crucible and fired using a firing furnace, a pressure furnace or the like.
According to the study by the present inventors, when the phosphor of the present invention is produced, the above phosphor raw material mixture can be fired in the firing step under the condition that the pressure in the furnace is 0.2 MPa or more and 100 MPa or less. It turned out to be preferable. Preferred conditions in the firing step are described below.

Examples of the material of the firing container (such as a crucible) used in the firing process include boron nitride and carbon.
About baking temperature, although it changes also with other conditions, such as a pressure, baking can be normally performed in the temperature range of 1500 degreeC or more and 2100 degrees C or less. The maximum temperature reached in the firing step is usually 1500 ° C. or higher, preferably 1600 ° C. or higher, and is usually 2100 ° C. or lower, preferably 2000 ° C. or lower. If the calcination temperature is too high, the nitrogen will fly and tend to produce defects in the base crystal and color, while if too low, the progress of the solid phase reaction will tend to be slow.

The heating rate in the firing step is usually 2 ° C./min or more, preferably 5 ° C./min or more, more preferably 10 ° C./min or more, and usually 30 ° C./min or less, preferably 25 ° C./min or less. . If the rate of temperature rise is below this range, the firing time may be long. In addition, if the rate of temperature rise exceeds this range, the firing device, container, etc. may be damaged.
The firing atmosphere in the firing step is arbitrary as long as the phosphor of the present invention is obtained, but is preferably a nitrogen-containing atmosphere. Specific examples include a nitrogen atmosphere and a hydrogen-containing nitrogen atmosphere, and a nitrogen atmosphere is particularly preferable.

The oxygen content in the firing atmosphere is usually 10 ppm or less, preferably 5 ppm or less.
The firing time varies depending on the firing temperature, pressure, etc., but is usually 10 minutes or longer, preferably 1 hour or longer, and usually 24 hours or shorter, preferably 12 hours or shorter.
The pressure in the firing step varies depending on the firing temperature and the like, but is usually 0.1 MPa or more, preferably 0.4 MPa or more, and is usually 100 MPa or less, preferably 50 MPa or less, more preferably 20 MPa or less, particularly preferably 10 MPa. It is as follows. If the pressure is too high, by-products tend to increase.If the pressure is too low, the resulting phosphor may be decomposed or colored, so adjusting the pressure is important. is there.

In addition, you may repeat a baking process in multiple times as needed. In that case, the firing conditions may be the same or different between the first firing and the second firing.
(Post-processing process)
The obtained fired product is granular or massive. This is pulverized, pulverized and / or classified into a powder of a predetermined size. Here, it is good to process so that D50 may be about 30 micrometers or less.

  Specific examples of the treatment include a method of subjecting the synthesized product to sieve classification with an opening of about 45 μm, and passing the powder that has passed through the sieve to the next step, or the synthesized product to a general method such as a ball mill, a vibration mill, or a jet mill. The method of grind | pulverizing to a predetermined particle size using a grinder is mentioned. In the latter method, excessive pulverization not only generates fine particles that easily scatter light, but also generates crystal defects on the particle surface, which may cause a decrease in luminous efficiency.

Moreover, you may provide the process of wash | cleaning fluorescent substance (baked material) as needed. After the cleaning step, the phosphor is dried until it has no adhering moisture and is used. Further, if necessary, dispersion / classification treatment may be performed to loosen the aggregation.
[3. Use of phosphor]
The phosphor of the present invention can be used for any application using the phosphor. Moreover, although the phosphor obtained by the present invention can be used alone as the phosphor obtained by the present invention, two or more kinds of phosphors obtained by the present invention are used in combination or obtained by the present invention. It is also possible to use a phosphor mixture of any combination, such as a combination of a phosphor and another phosphor.

The phosphor of the present invention can be used as a phosphor-containing composition by mixing with a known liquid medium (for example, a silicone compound).
In addition, the phosphor obtained by the present invention can be suitably used for various light-emitting devices by combining with a light source that emits ultraviolet light, taking advantage of the property that it can be excited by ultraviolet light.

The emission color of the light-emitting device is not limited to purple or white, but by appropriately selecting the combination and content of phosphors, light emission that emits light in any color, such as light bulb color (warm white) or pastel color The device can be manufactured. The light-emitting device thus obtained can be used as a light-emitting portion (particularly a liquid crystal backlight) or an illumination device of an image display device.
[4. Phosphor-containing composition]
The phosphor of the present invention can be used by mixing with a liquid medium. In particular, when the phosphor of the present invention is used for applications such as a light emitting device, it is preferably used in a form dispersed in a liquid medium. The phosphor of the present invention dispersed in a liquid medium will be referred to as “the phosphor-containing composition of the present invention” as appropriate.

[4-1. Phosphor]
There is no restriction | limiting in the kind of fluorescent substance of this invention contained in the said fluorescent substance containing composition, It can select arbitrarily. Moreover, the fluorescent substance of this invention contained in a fluorescent substance containing composition may be only 1 type, and may use 2 or more types together by arbitrary combinations and a ratio. Furthermore, the phosphor-containing composition may contain a phosphor other than the phosphor of the present invention as long as the effects of the present invention are not significantly impaired.

[4-2. Liquid medium]
The kind of liquid medium used for the phosphor-containing composition is not particularly limited, and a curable material that can be molded over the semiconductor light emitting element can be used. The curable material is a fluid material that is cured by performing some kind of curing treatment. Here, the fluid state means, for example, a liquid state or a gel state. The curable material is not particularly limited as long as it secures the role of guiding the light emitted from the solid light emitting element to the phosphor. Moreover, only 1 type may be used for a curable material and it may use 2 or more types together by arbitrary combinations and a ratio. Therefore, as the curable material, any of inorganic materials, organic materials, and mixtures thereof can be used.

As the inorganic material, for example, a solution obtained by hydrolytic polymerization of a solution containing a metal alkoxide, a ceramic precursor polymer or a metal alkoxide by a sol-gel method, or a combination thereof is solidified (for example, a siloxane bond). Inorganic materials having
On the other hand, examples of the organic material include a thermosetting resin and a photocurable resin. Specific examples include (meth) acrylic resins such as methyl poly (meth) acrylate; styrene resins such as polystyrene and styrene-acrylonitrile copolymer; polycarbonate resins; polyester resins; phenoxy resins; butyral resins; Cellulose resins such as cellulose acetate and cellulose acetate butyrate; epoxy resins; phenol resins; silicone resins and the like.

  Among these curable materials, it is preferable to use a silicon-containing compound that is less deteriorated with respect to light emitted from the semiconductor light-emitting element and is excellent in alkali resistance, acid resistance, and heat resistance. A silicon-containing compound is a compound having a silicon atom in the molecule, organic materials such as polyorganosiloxane (silicone compounds), inorganic materials such as silicon oxide, silicon nitride, and silicon oxynitride, and borosilicates and phosphosilicates. Examples thereof include glass materials such as salts and alkali silicates. Among these, silicone materials are preferable from the viewpoints of transparency, adhesion, ease of handling, and excellent mechanical and thermal stress relaxation characteristics.

The silicone-based material usually refers to an organic polymer having a siloxane bond as a main chain, and for example, condensation-type, addition-type, improved sol-gel type, photo-curing type silicone-based materials can be used.
As the condensed silicone material, for example, semiconductor light-emitting device members described in JP-A-2007-112973 to 112975, JP-A-2007-19459, JP-A-2008-34833, and the like can be used. Condensation-type silicone materials have excellent adhesion to components such as packages, electrodes, and light-emitting elements used in semiconductor light-emitting devices, so the addition of adhesion-improving components can be minimized, and crosslinking is mainly due to siloxane bonds. There is an advantage of excellent heat resistance and light resistance.

  Examples of the addition-type silicone material include potting silicone materials described in JP-A-2004-186168, JP-A-2004-221308, JP-A-2005-327777, JP-A-2003-183881, Organically modified silicone materials for potting described in JP-A-2006-206919, silicone materials for injection molding described in JP-A-2006-324596, silicone materials for transfer molding described in JP-A-2007-231173, etc. Can be suitably used. The addition-type silicone material has advantages such as a high degree of freedom in selection such as a curing speed and a hardness of a cured product, a component that does not desorb during curing, hardly shrinking due to curing, and excellent deep part curability.

Moreover, as an improved sol-gel type silicone material that is one of the condensation types, for example, the silicone materials described in JP-A-2006-077234, JP-A-2006-291018, JP-A-2007-119569 and the like can be used. It can be used suitably. The improved sol-gel type silicone material has an advantage that it has a high degree of crosslinking, heat resistance, light resistance and durability, and is excellent in the protective function of a phosphor having low gas permeability and low moisture resistance.

As the photocurable silicone material, for example, silicone materials described in JP 2007-131812 A, JP 2007-214543 A, and the like can be suitably used. The ultraviolet curable silicone material has advantages such as excellent productivity because it cures in a short time, and it is not necessary to apply a high temperature for curing, so that the light emitting element is hardly deteriorated.
These silicone materials may be used alone, or a mixture of a plurality of silicone materials may be used if curing inhibition does not occur when mixed.

[4-3. Content ratio of liquid medium and phosphor]
The content of the liquid medium is arbitrary as long as the effect of the present invention is not significantly impaired, but is usually 25% by weight or more, preferably 40% by weight or more, based on the entire phosphor-containing composition of the present invention. The amount is usually 99% by weight or less, preferably 95% by weight or less, more preferably 80% by weight or less. When the amount of the liquid medium is large, no particular problem occurs. However, in order to obtain a desired chromaticity coordinate, color rendering index, luminous efficiency, etc. in the case of a semiconductor light emitting device, it is usually at a blending ratio as described above. It is desirable to use a liquid medium. On the other hand, when there is too little liquid medium, fluidity | liquidity may fall and it may become difficult to handle.

  The liquid medium mainly serves as a binder in the phosphor-containing composition of the present invention. The liquid medium may be used alone or in combination of two or more in any combination and ratio. For example, when using a silicon-containing compound for the purpose of improving heat resistance, light resistance, etc., other thermosetting resins such as an epoxy resin are contained so as not to impair the durability of the silicon-containing compound. Also good. In this case, the content of the other thermosetting resin is usually 25% by weight or less, preferably 10% by weight or less based on the total amount of the liquid medium as the binder.

  The phosphor content in the phosphor-containing composition is arbitrary as long as the effect of the present invention is not significantly impaired, but is usually 1% by weight or more, preferably 5% with respect to the entire phosphor-containing composition of the present invention. % By weight or more, more preferably 20% by weight or more, and usually 75% by weight or less, preferably 60% by weight or less. The proportion of the phosphor of the present invention in the phosphor in the phosphor-containing composition is also arbitrary, but is usually 30% by weight or more, preferably 50% by weight or more, and usually 100% by weight or less. If the phosphor content in the phosphor-containing composition is too high, the flowability of the phosphor-containing composition may be inferior and difficult to handle, and if the phosphor content is too low, the light emission efficiency of the light-emitting device decreases. There is a tendency.

[4-4. Other ingredients]
In the phosphor-containing composition, unless the effect of the present invention is significantly impaired, in addition to the phosphor and the liquid medium, other components such as metal oxide for adjusting the refractive index, diffusing agent, filler, viscosity adjustment You may contain additives, such as an agent and a ultraviolet absorber. Only 1 type may be used for another component and it may use 2 or more types together by arbitrary combinations and a ratio.

[5. Light emitting device]
The light-emitting device of the present invention (hereinafter, appropriately referred to as “light-emitting device”) can emit visible light by converting light from the first light-emitting body (excitation light source) and the first light-emitting body into visible light. A light emitting device having a second light emitter, wherein the second light emitter is the above-described [1. It contains a first phosphor containing one or more of the phosphors of the present invention described in the section [Phosphor].

Preferable specific examples of the phosphor of the present invention used in the light emitting device of the present invention include [1. Examples thereof include the phosphor of the present invention described in the “Phosphor” column and the phosphors used in the respective Examples in the “Example” column described later. In addition, any one of the phosphors of the present invention may be used alone, or two or more may be used in any combination and ratio.
The light-emitting device of the present invention has a first light emitter (excitation light source), and at least the phosphor of the present invention is used as the second light emitter. It is possible to arbitrarily adopt the apparatus configuration. A specific example of the device configuration will be described later.

  Among the light emitting devices of the present invention, in particular, as a white light emitting device, specifically, an excitation light source as described later is used as the first light emitter, and in addition to the phosphor of the present invention, blue fluorescence as described later is emitted. Phosphor that emits light (hereinafter referred to as “blue phosphor” as appropriate), phosphor that emits green fluorescence (hereinafter referred to as “green phosphor” as appropriate), phosphor that emits red fluorescence (hereinafter referred to as “red phosphor” as appropriate) And a known phosphor such as a phosphor that emits yellow fluorescence (hereinafter referred to as “yellow phosphor” as appropriate) is used in any combination, and a known apparatus configuration is obtained.

Here, the white color of the white light emitting device means all of (yellowish) white, (greenish) white, (blueish) white, (purple) white and white defined by JIS Z 8701 Of these, white is preferred.
[5-1. Configuration of light emitting device]
<5-1-1. First luminous body>
The 1st light-emitting body in the light-emitting device of this invention light-emits the light which excites the 2nd light-emitting body mentioned later.

The emission peak wavelength of the first illuminant is not particularly limited as long as it overlaps with the absorption wavelength of the second illuminant described later, and an illuminant having a wide emission wavelength region can be used. Usually, a light emitter having an emission wavelength from the ultraviolet region to the blue region is used.
The specific value of the emission peak wavelength of the first illuminant is usually 300 nm or more, preferably 330 nm or more, more preferably 360 nm or more, and usually 420 nm or less, preferably 410 nm or less, more preferably 400 nm or less. It is desirable to use a light emitter having a wavelength.

  As the first light emitter, a semiconductor light emitting element is generally used, and specifically, a light emitting diode (LED), a laser diode (LD), or the like can be used. In addition, as a light-emitting body which can be used as a 1st light-emitting body, an organic electroluminescent light emitting element, an inorganic electroluminescent light emitting element, etc. are mentioned, for example. However, what can be used as a 1st light-emitting body is not restricted to what is illustrated by this specification.

  Among these, as the first light emitter, a GaN LED or LD using a GaN compound semiconductor is preferable. This is because GaN-based LEDs and LDs have significantly higher emission output and external quantum efficiency than SiC-based LEDs that emit light in this region, and emit very bright light with low power when combined with the phosphor. It is because it is obtained. For example, for a current load of 20 mA, GaN-based LEDs and LDs usually have a light emission intensity 100 times or more that of SiC-based. As the GaN-based LED and LD, those having an AlXGaYN light emitting layer, a GaN light emitting layer, or an InXGaYN light emitting layer are preferable. Among them, since the emission intensity is very high, as the GaN-based LED, those having an InXGaYN light emitting layer are particularly preferable, and those having a multiple quantum well structure of an InXGaYN layer and a GaN layer are more preferable.

In the above, the value of X + Y is usually a value in the range of 0.8 to 1.2. In the GaN-based LED, those in which the light emitting layer is doped with Zn or Si or those without a dopant are preferable for adjusting the light emission characteristics.
A GaN-based LED has these light-emitting layers, p-layers, n-layers, electrodes, and substrates as basic components. The light-emitting layers are sandwiched between n-type and p-type AlXGaYN layers, GaN layers, or InXGaYN layers. Those having a heterostructure are preferable because of high light emission efficiency, and those having a heterostructure in a quantum well structure are more preferable because of higher light emission efficiency.

Note that only one first light emitter may be used, or two or more first light emitters may be used in any combination and ratio.
<5-1-2. Second luminous body>
The second light emitter in the light emitting device of the present invention is a light emitter that emits visible light when irradiated with light from the first light emitter described above, and one or more phosphors of the present invention are used as the first phosphor. A second phosphor (a blue phosphor, a green phosphor, a yellow phosphor, an orange phosphor, a red phosphor, etc.), which will be described later, is contained as appropriate depending on the application. Further, for example, the second light emitter is configured by dispersing the first and second phosphors in a sealing material.

The composition of the phosphor other than the phosphor of the present invention (that is, the second phosphor) used in the second light emitter is not particularly limited, but Y ₂ O ₃ , YVO to be a host crystal. ₄ , metal oxides typified by Zn ₂ SiO ₄ , Y ₃ A ₁₅ O ₁₂ , Sr ₂ SiO _4, etc., Sr ₂ Si ₅ N _8, etc., Ca ₅ (PO ₄ ) ₃ Cl Ce, Pr, Nd, Pm such as phosphates typified by ZnS, SrS, CaS, etc., oxysulfides typified by Y ₂ O ₂ S, La ₂ O ₂ S, etc. , Ions of rare earth metals such as Sm, Eu, Tb, Dy, Ho, Er, Tm, Yb and ions of metals such as Ag, Cu, Au, Al, Mn, Sb, etc. are combined as an activator element or a coactivator element. Can be mentioned.

  Specific examples of preferred crystal matrixes are shown in the following table.

However, the matrix crystal and the activator element or coactivator element are not particularly limited in element composition, and can be partially replaced with elements of the same family, and the obtained phosphor is light in the near ultraviolet to visible region. Any material that absorbs and emits visible light can be used.
Specifically, the following phosphors can be used, but these are merely examples, and phosphors that can be used in the present invention are not limited to these. In the following examples, as described above, phosphors that differ only in part of the structure are omitted as appropriate.

<5-1-2-1. First phosphor>
The 2nd light-emitting body in the light-emitting device of this invention contains the 1st fluorescent substance containing the fluorescent substance of the above-mentioned this invention at least. Any one of the phosphors of the present invention may be used alone, or two or more of them may be used in any combination and ratio, and the phosphor of the present invention may have a desired emission color. What is necessary is just to adjust a composition suitably.

<5-1-2-2. Second phosphor>
The second light emitter in the light emitting device of the present invention may contain a phosphor (that is, a second phosphor) in addition to the first phosphor described above, depending on the application. Usually, since these second phosphors are used to adjust the color tone of light emitted from the second light emitter, the second phosphor emits fluorescence having a color different from that of the first phosphor. Often phosphors are used. For example, when a green phosphor is used as the first phosphor, a phosphor other than a green phosphor such as a blue phosphor, a red phosphor, or a yellow phosphor may be used as the second phosphor. However, a phosphor having the same color as the first phosphor can be used as the second phosphor.

  The weight median diameter D50 of the second phosphor used in the light emitting device of the present invention is preferably in the range of usually 2 μm or more, especially 5 μm or more, and usually 30 μm or less, especially 20 μm or less. When the weight median diameter D50 is too small, the luminance is lowered and the phosphor particles tend to aggregate. On the other hand, if the weight median diameter is too large, there is a tendency for coating unevenness and blockage of the dispenser to occur.

<Blue phosphor>
When a blue phosphor is used in addition to the phosphor of the present invention, any blue phosphor can be used as long as the effects of the present invention are not significantly impaired. At this time, the emission peak wavelength of the blue phosphor is usually 420 nm or more, preferably 430 nm or more, more preferably 440 nm or more, and usually 490 nm or less, preferably 480 nm or less, more preferably 470 nm or less, and further preferably 460 nm or less. It is preferable to be in the wavelength range. When the emission peak wavelength of the blue phosphor used is within this range, it overlaps with the excitation band of the phosphor of the present invention, and the phosphor of the present invention can be efficiently excited by the blue light from the blue phosphor. Because. The following table shows phosphors that can be used as such blue phosphors.

Among these, as the blue phosphor, (Ca, Sr, Ba) MgAl ₁₀ O ₁₇ : Eu, (Sr, Ca, Ba, Mg) ₁₀ (PO ₄ ) ₆ (Cl, F) ₂ : Eu, (Ba , Ca, Mg, Sr) ₂ SiO ₄ : Eu, (Ba, Ca, Sr) ₃ MgSi ₂ O 8: Eu are preferred, and (Ba, Sr) MgAl ₁₀ O ₁₇ : Eu, (Ca, Sr, Ba) ₁₀ ( PO ₄ ) ₆ (Cl, F) ₂ : Eu and Ba ₃ MgSi ₂ O ₈ : Eu are more preferable, and Sr ₁₀ (PO ₄ ) ₆ Cl ₂ : Eu and BaMgAl ₁₀ O ₁₇ : Eu are particularly preferable.

<Green phosphor>
When a green phosphor is used in addition to the phosphor of the present invention, any green phosphor can be used as long as the effects of the present invention are not significantly impaired. At this time, the emission peak wavelength of the green phosphor is usually larger than 500 nm, preferably 510 nm or more, more preferably 515 nm or more, and usually 550 nm or less, especially 542 nm or less, and further preferably 535 nm or less. If this emission peak wavelength is too short, it tends to be bluish, while if it is too long, it tends to be yellowish, and the characteristics as green light may deteriorate. The phosphors that can be used as such green phosphors are shown in the table below.

Among these, as the green phosphor, Y ₃ (Al, Ga) ₅ O ₁₂ : Tb, CaSc ₂ O ₄ : Ce, Ca ₃ (Sc, Mg) ₂ Si ₃ O ₁₂ : Ce, (Sr, Ba) ₂ SiO ₄ : Eu, (Si, Al) ₆ (O, N) ₈ : Eu (β-sialon), (Ba, Sr) ₃ Si ₆ O ₁₂ : N ₂ : Eu, SrGa ₂ S ₄ : Eu, BaMgAl ₁₀ O ₁₇ : Eu, Mn is preferred.

When the obtained light-emitting device is used for a lighting device, Y ₃ (Al, Ga) ₅ O ₁₂ : Tb, CaSc ₂ O ₄ : CeCa ₃ (Sc, Mg) ₂ Si ₃ O ₁₂ : Ce, (Sr, Ba ) ₂ SiO ₄ : Eu, (Si, Al) ₆ (O, N) ₈ : Eu (β-sialon), (Ba, Sr) ₃ Si ₆ O ₁₂ N ₂ : Eu are preferable.
When the obtained light emitting device is used for an image display device, (Sr, Ba) ₂ SiO ₄ : Eu, (Si, Al) ₆ (O, N) ₈ : Eu (β-sialon), (Ba, Sr) ₃ Si ₆ O ₁₂ N ₂ : Eu, SrGa ₂ S ₄ : Eu, and BaMgAl ₁₀ O ₁₇ : Eu, Mn are preferable.

<Yellow phosphor>
When a yellow phosphor is used in addition to the phosphor of the present invention, any yellow phosphor can be used as long as the effects of the present invention are not significantly impaired. At this time, the emission peak wavelength of the yellow phosphor is usually in the wavelength range of 530 nm or more, preferably 540 nm or more, more preferably 550 nm or more, and usually 620 nm or less, preferably 600 nm or less, more preferably 580 nm or less. Is preferred. The phosphors that can be used as such yellow phosphors are shown in the table below.

More in even, as the yellow _{phosphor, Y 3 Al 5 O 12:} Ce, (Y, Gd) 3 A l5 O 12: Ce, (Sr, Ca, Ba, Mg) 2 SiO 4: Eu, (Ca, Sr) Si ₂ N ₂ O ₂ : Eu is preferred.
<Orange to red phosphor>
When an orange or red phosphor is used in addition to the phosphor of the present invention, any orange or red phosphor can be used as long as the effects of the present invention are not significantly impaired. At this time, the emission peak wavelength of the orange to red phosphor is usually in the wavelength range of 570 nm or more, preferably 580 nm or more, more preferably 585 nm or more, and usually 780 nm or less, preferably 700 nm or less, more preferably 680 nm or less. Is preferred. The phosphors that can be used as such orange or red phosphors are shown in the following table.

Among these, as red phosphors, (Ca, Sr, Ba) ₂ Si ₅ (N, O) ₈ : Eu, (Ca, Sr, Ba) Si (N, O) ₂ : Eu, (Ca, Sr , Ba) AlSi (N, O) ₃ : Eu, (Sr, Ba) ₃ SiO ₅ : Eu, (Ca, Sr) S: Eu, (La, Y) ₂ O ₂ S: Eu, Eu (dibenzoylmethane) ) Β-diketone Eu complex such as 3,1,10-phenanthroline complex, carboxylic acid Eu complex, K ₂ SiF ₆ : Mn is preferred, (Ca, Sr, Ba) ₂ Si ₅ (N, O) ₈ : Eu, (Sr, Ca) AlSi (N, O): Eu, (La, Y) ₂ O ₂ S: Eu, and K ₂ SiF ₆ : Mn are more preferable.

Further, as the orange phosphor, (Sr, Ba) ₃ SiO ₅ : Eu, (Sr, Ba) ₂ Si
O ₄ : Eu, (Ca, Sr, Ba) ₂ Si ₅ (N, O) ₈ : Eu, (Ca, Sr, Ba) AlSi (N, O) ₃ : Ce are preferable.
[6. Embodiment of Light Emitting Device]
[6-1. Embodiment of Light Emitting Device]
Hereinafter, the light-emitting device of the present invention will be described in more detail with reference to specific embodiments. However, the present invention is not limited to the following embodiments, and does not depart from the gist of the present invention. It can be implemented with arbitrary modifications.

  FIG. 1 is a schematic perspective view showing a positional relationship between a first light emitter serving as an excitation light source and a second light emitter configured as a phosphor containing portion having a phosphor in an example of the light emitting device of the present invention. Shown in In FIG. 1, reference numeral 1 denotes a phosphor-containing portion (second light emitter), reference numeral 2 denotes a surface-emitting GaN-based LD as an excitation light source (first light emitter), and reference numeral 3 denotes a substrate. In order to create a state in which they are in contact with each other, LD2 and phosphor-containing portion 1 (second light emitter) may be prepared separately, and their surfaces may be brought into contact with each other by an adhesive or other means, The phosphor-containing part 1 (second light emitter) may be formed (molded) on the light emitting surface of the LD 2. As a result, the LD 2 and the phosphor-containing part 1 (second light emitter) can be brought into contact with each other.

When such an apparatus configuration is employed, the light loss is such that light from the excitation light source (first light emitter) is reflected by the film surface of the phosphor-containing portion (second light emitter) and oozes out. Therefore, the light emission efficiency of the entire device can be improved.
FIG. 2A is a typical example of a light emitting device of a form generally referred to as a shell type, and has a light emission having an excitation light source (first light emitter) and a phosphor-containing portion (second light emitter). It is typical sectional drawing which shows one Example of an apparatus. In the light emitting device 4, reference numeral 5 is a mount lead, reference numeral 6 is an inner lead, reference numeral 7 is an excitation light source (first light emitter), reference numeral 8 is a phosphor-containing portion, reference numeral 9 is a conductive wire, and reference numeral 10 is a mold. Each member is indicated.

  FIG. 2B is a representative example of a light-emitting device in a form called a surface-mount type, and light emission having an excitation light source (first light emitter) and a phosphor-containing portion (second light emitter). It is typical sectional drawing which shows one Example of an apparatus. In the figure, reference numeral 22 is an excitation light source (first light emitter), reference numeral 23 is a phosphor-containing portion (second light emitter), reference numeral 24 is a frame, reference numeral 25 is a conductive wire, reference numerals 26 and 27 are electrodes. Respectively.

[6-2. Application of light emitting device]
The use of the light-emitting device of the present invention is not particularly limited, and can be used in various fields in which ordinary light-emitting devices are used. However, since the color rendering property is high and the color reproduction range is wide, the illumination device is particularly preferable. And as a light source for image display devices.
<6-2-1. Lighting device>
When the light-emitting device of the present invention is applied to a lighting device, the above-described light-emitting device may be appropriately incorporated into a known lighting device. For example, a surface emitting illumination device 11 incorporating the above-described light emitting device 4 as shown in FIG. 3 can be cited.

  FIG. 3 is a cross-sectional view schematically showing one embodiment of the illumination device of the present invention. As shown in FIG. 3, the surface-emitting illumination device has a large number of light-emitting devices 13 (on the light-emitting device 4 described above) on the bottom surface of a rectangular holding case 12 whose inner surface is light-opaque such as a white smooth surface. Is provided with a power source and a circuit (not shown) for driving the light-emitting device 13 on the outside, and a milky white acrylic plate or the like is provided at a position corresponding to the lid portion of the holding case 12. The diffusion plate 14 is fixed for uniform light emission.

Then, the surface-emitting illumination device 11 is driven to emit light by applying a voltage to the excitation light source (first light emitter) of the light-emitting device 13, and a part of the light emission is converted to the phosphor-containing portion (first The phosphor in the phosphor-containing resin part as the second phosphor) absorbs and emits visible light, while light emission with high color rendering is obtained by color mixing with blue light or the like not absorbed by the phosphor. The light passes through the diffusion plate 14 and is emitted upward in the drawing, and illumination light with uniform brightness is obtained within the surface of the diffusion plate 14 of the holding case 12.

<6-2-2. Image display device>
When the light emitting device of the present invention is used as a light source of an image display device, the specific configuration of the image display device is not limited, but it is preferably used together with a color filter. For example, when the image display device is a color image display device using color liquid crystal display elements, the light emitting device is used as a backlight, a light shutter using liquid crystal, and a color filter having red, green, and blue pixels; By combining these, an image display device can be formed.

EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited to a following example, unless the summary is exceeded.
[Raw materials]
As phosphor raw materials, BaO (manufactured by High Purity Chemical), Si ₃ N ₄ (manufactured by Ube Industries, Ltd.), AlN (manufactured by Tokuyama), Al ₂ O ₃ (manufactured by High Purity Chemical), Eu ₂ O ₃ (rare metallic) was used.
[Example 1]
The above phosphor materials were weighed with an electronic balance in the amounts shown in Table 6. After weighing, all of these raw material powders were put in an alumina mortar, ground and mixed until uniform. The operations of weighing, grinding and mixing were performed in a glove box filled with N ₂ gas.

The obtained raw material mixed powder was directly filled into a boron nitride crucible (BN crucible). This BN crucible was placed in a resistance heating type vacuum heat treatment furnace (manufactured by Fuji Denpa Kogyo). Then, after reducing the pressure to 5 × 10 ⁻³ Pa or less, vacuum heating was performed from room temperature to 800 ° C. at a heating rate of 20 ° C./min. When the temperature reached 800 ° C., high-purity nitrogen gas (99.9995%) was introduced for 30 minutes until the pressure in the furnace reached 0.92 MPa. After the introduction of the high purity nitrogen gas, the temperature was further increased to 1200 ° C. at a temperature increase rate of 20 ° C./min while maintaining 0.92 MPa. While maintaining at 1200 ° C. for 5 minutes, the thermocouple was changed to a radiation thermometer and further heated to 1800 ° C. at a temperature rising rate of 20 ° C./min. When the temperature reached 1800 ° C., the temperature was maintained for 2 hours, and further heated to 1900 ° C. at 20 ° C./min, and maintained at that temperature for 2 hours. After firing, the mixture was cooled to 1200 ° C. at a temperature lowering rate of 20 ° C./min, and then allowed to cool. Then, it pulverized and the fluorescent substance of Example 1 was obtained.

[Example 2, Comparative Examples 1 to 4, and Reference Examples 1 to 3]
The phosphor was subjected to the same conditions as in Example 1 except that the raw material composition of the phosphor material was changed to that shown in Table 6 (that is, the value of x in the formula [1] was changed). Manufactured.
[Measurement and evaluation method of phosphor]
In each of the above Examples, Comparative Examples, and Reference Examples, various evaluations of the phosphor particles were performed by the following methods unless otherwise specified.

<Measurement method of emission spectrum>
The emission spectrum was measured using a fluorescence measuring apparatus (manufactured by JASCO Corporation) equipped with a 150 W xenon lamp as an excitation light source and a multi-channel CCD detector C7041 (manufactured by Hamamatsu Photonics) as a spectrum measuring apparatus.
Specifically, the light from the excitation light source was passed through a diffraction grating spectrometer having a focal length of 10 cm, and only the excitation light having a wavelength of 365 nm was irradiated to the phosphor through the optical fiber. The light generated from the phosphor by the irradiation of the excitation light is dispersed by a diffraction grating spectroscope having a focal length of 25 cm, the emission intensity of each wavelength is measured by a spectrum measuring device in a wavelength range of 300 nm to 800 nm, and a personal computer is used. An emission spectrum was obtained through signal processing such as sensitivity correction. During the measurement, the slit width of the light-receiving side spectroscope was set to 1 nm and the measurement was performed.

The emission peak wavelength (hereinafter sometimes referred to as “peak wavelength”) was read from the obtained emission spectrum.
The relative luminance was expressed as a relative value with the peak value at the time of excitation of wavelength 365 nm of Comparative Example 1 as the reference value 100.
<Powder X-ray diffraction measurement>
Powder X-ray diffraction was precisely measured with a powder X-ray diffractometer X'Pert manufactured by PANalytical. The measurement conditions are as follows. The measurement data was subjected to automatic background processing using data processing software X'Pert High Score (manufactured by PANalytical) with a bending filter of 5.

CuKα tube used X-ray output = 45KV, 40mA
Divergent slit = 1/4 °, X-ray mirror Detector = Semiconductor array detector X'Celerator
Using Ni filter Scanning range 2θ = 10 ° ~ 65 °
Reading width = 0.05 °
Counting time = 33 seconds <Lattice constant refinement>
For the lattice constant, a peak due to the same crystal structure as BaSi ₆ N ₈ O is selected from the powder X-ray diffraction measurement data of Examples 1-2 and Comparative Examples 1-4 obtained above, and data processing software It calculated | required by implementing refinement | purification using X'Pert Plus (made by PANalytical).
[Evaluation Results of Phosphor] The emission spectra of the phosphors produced in Examples 1-2 and Comparative Example 2 are shown in FIG.

FIG. 5 shows X-ray patterns obtained by powder X-ray diffraction for the phosphors produced in Examples 1 to 3, Reference Examples 1 to 2 and Comparative Examples 1 to 4. As a result of this X-ray diffraction measurement, the X-ray diffraction patterns exhibited by the phosphors produced in Examples 1 to 3 and Comparative Examples 1 to 4 were the same as those of BaSi ₆ N ₈ O. Therefore, it was suggested that the phosphor sample having x up to 3 in the formula [1] has a BaSi ₆ N ₈ O structure, and Al is partially dissolved.
Table 7 shows the results of measuring the emission peak wavelength (nm), the relative luminance (%), and the lattice constant (Å) for the phosphors obtained in Examples 1-2, Comparative Examples 1-4, and Reference Examples 1-2. Shown in

From Table 7, it can be seen that the phosphor sample of x ≦ 3 in the formula [1] has a BaSi ₆ N ₈ O structure. It can also be seen that the emission peak wavelength is shifted to the longer wavelength side due to partial dissolution of Al, that is, green light emission is obtained compared to the phosphor described in the prior art document.
Moreover, in Examples 1-3 and Comparative Examples 1-4, the graph showing each change of the lattice constants a, b, and c accompanying the change of x is shown to FIGS. From these graphs, it can be seen that the lattice constant is proportionally changed by the dissolution of Al.

In the prior art documents, firing is performed under atmospheric pressure, and a certain amount or more of Al cannot be partially dissolved in BaSi ₆ N ₈ O. On the other hand, in the examples of the present specification, higher solid phase reactivity is realized as compared with the prior art documents, and more Al can be partially dissolved in BaSi ₆ N ₈ O. However, this is because the decomposition reaction of Si ₃ N ₄ could be suppressed by increasing the pressure during firing, and the solid phase reaction could be promoted by raising the temperature during firing. It is thought that it is made.

  The phosphor manufactured by the manufacturing method of the present invention can be used in any field where light is used. For example, in addition to indoor and outdoor lighting, mobile phones, household appliances, outdoor installation displays, etc. It can be suitably used for image display devices of various electronic devices.

1 Phosphor-containing part (second light emitter)
2 Excitation light source (first light emitter) (LD)
3 Substrate 4 Light-emitting device 5 Mount lead 6 Inner lead 7 Excitation light source (first light emitter)
DESCRIPTION OF SYMBOLS 8 Fluorescent substance containing part 9 Conductive wire 10 Mold member 11 Surface light-emitting illuminating device 12 Holding case 13 Light-emitting device 14 Diffusion plate 22 Excitation light source (1st light-emitting body)
23 Phosphor-containing part (second light emitter)
24 frame 25 conductive wire 26 electrode 27 electrode

Claims (4)

A phosphor having a composition represented by the following formula [1].
(A _1-y , Eu _y ) D _6-x E _x N _{8 -x} O _{1 + x} [1]
(However, in the formula [1],
A represents an alkaline earth metal element essential for Ba,
D represents a tetravalent metal element in which Si is essential,
E represents a trivalent metal element in which Al is essential.
X and y represent numbers satisfying the following expression.
1 <x ≦ 3
0.0001 ≦ y ≦ 0.15) A method for producing a phosphor, comprising a step of preparing a phosphor raw material mixture having a composition ratio represented by the following formula [2] and firing the phosphor raw material mixture at 0.2 MPa or more and 100 MPa or less.
(A _1-y , Eu _y ) D _6-x E _x N _{8 -x} O _{1 + x} [2]
(However, in the formula [1],
A represents an alkaline earth metal element essential for Ba,
D represents a tetravalent metal element in which Si is essential,
E represents a trivalent metal element in which Al is essential.
X and y represent numbers satisfying the following expression.
1 <x ≦ 3
0.0001 ≦ y ≦ 0.15) In the firing step,
The method for producing a phosphor according to claim 2, wherein the firing temperature is in the range of 1500 ° C or higher and 2000 ° C or lower. A light emitting device comprising the phosphor according to claim 1.

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