JP2019044159A - Aluminate phosphor and light emitting device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an aluminate phosphor having high emission intensity and a light emitting device. SOLUTION: The aluminate phosphor is characterized by having a composition represented by the following formula (I). X1pEutMgqMnrAlsOp + t + q + r + 1.5s (I) (In formula (I), X1 is at least one element selected from the group consisting of Ba, Sr and Ca, and p, q, r, s and t are 0.5 ≦. p≤1.0, 0≤q <0.6, 0.4 <r≤0.7, 8.5≤s≤13.0, 0 <t <0.3, 0.5 <p + t≤1. 2. A number that satisfies 0.4 <q + r ≦ 1.1.) [Selection diagram] FIG.

Description

  The present invention relates to an aluminate phosphor and a light emitting device.

  Various light emitting devices have been developed which emit white light, bulb color, orange light, etc. by combining a light emitting diode (LED) and a phosphor. In these light emitting devices, a desired light emission color can be obtained by the principle of color mixing of light. As a light emitting device, there is also known one that emits white light by combining a light emitting element emitting blue light as an excitation light source, a phosphor emitting green light and a phosphor emitting red light which is excited by light from the light source. It is done. These light emitting devices are required to be used in a wide range of fields such as general lighting, vehicle lighting, displays, backlights for liquid crystals, and the like.

For example, Patent Document 1 discloses a manganese-activated aluminate phosphor having a composition represented by (Ba, Sr) MgAl ₁₀ O ₁₇ : Mn ²⁺ as a phosphor emitting green light used in a light emitting device. ing.

Unexamined-Japanese-Patent No. 2004-155907

However, the manganese-activated aluminate phosphor disclosed in Patent Document 1 has high emission luminance by being excited by vacuum ultraviolet light, and is in the range of 430 nm to 485 nm (hereinafter, also referred to as “blue region” When combined with a light emitting element having a light emission peak wavelength within the above, the light emission luminance is not sufficient.
Then, an object of this invention is to provide the aluminate phosphor and light-emitting device which have high luminous intensity by the light excitation of a blue area | region.

The present invention includes the following aspects.
A first aspect of the present invention is an aluminate phosphor characterized by having a composition represented by the following formula (I).
X ¹ _p Eu _t Mg _q Mn _r Al _s O _{p + t + q + r + 1.5 s} (I)
(Wherein, in the formula (I), X ¹ is at least one element selected from the group consisting of Ba, Sr and Ca, and p, q, r, s and t satisfy 0.5 ≦ p ≦ 1.0) , 0 ≦ q <0.6, 0.4 <r ≦ 0.7, 8.5 ≦ s ≦ 13.0, 0 <t <0.3, 0.5 <p + t ≦ 1.2, 0.4 It is a number that satisfies <q + r ≦ 1.1.)

  A second aspect of the present invention is a light emitting device comprising a fluorescent member containing the aluminate phosphor and an excitation light source.

  According to one aspect of the present invention, it is possible to provide an aluminate phosphor having high emission intensity and a light emitting device capable of efficiently wavelength-converting light in the blue region.

FIG. 1 is a schematic cross-sectional view showing an example of a light emitting device. FIG. 2 is an emission spectrum of relative luminescence intensity (%) with respect to the wavelength of the aluminate phosphor according to Example 1 and the aluminate phosphors according to Comparative Examples 1 and 2. FIG. 3 is a reflection spectrum (%) of the reflectance (%) with respect to the wavelength of the aluminate phosphor according to Example 3 and the aluminate phosphors according to Comparative Examples 1 to 3. FIG. 4 is a SEM photograph of the aluminate phosphor according to Example 1. FIG. 5 is a SEM photograph of the aluminate phosphor according to Comparative Example 1.

  Hereinafter, the aluminate phosphor and the light emitting device according to the embodiment of the present invention will be described. However, the embodiment described below is an example for embodying the technical concept of the present invention, and the present invention is not limited to the following aluminate phosphor and a light emitting device using the same. The relationship between the color name and the chromaticity coordinates, the relationship between the wavelength range of light and the color name of monochromatic light, etc. conform to JIS Z8110.

Aluminate Phosphor The first embodiment of the present invention is an aluminate phosphor characterized by having a composition represented by the following formula (I).
X ¹ _p Eu _t Mg _q Mn _r Al _s O _{p + t + q + r + 1.5 s} (I)
(Wherein, in the formula (I), X ¹ is at least one element selected from the group consisting of Ba, Sr and Ca, and p, q, r, s and t satisfy 0.5 ≦ p ≦ 1.0) , 0 ≦ q <0.6, 0.4 <r ≦ 0.7, 8.5 ≦ s ≦ 13.0, 0 <t <0.3, 0.5 <p + t ≦ 1.2, 0.4 It is a number that satisfies <q + r ≦ 1.1.)

In the formula (I), X ¹ preferably contains Ba. In the aluminate phosphor, when X ¹ contains Ba in the formula (I), the emission intensity by light excitation in the blue region can be increased.

The variable p in the formula (I) is a molar ratio of the sum of at least one element X ¹ selected from the group consisting of Ba, Sr and Ca. The term "molar ratio" refers to the molar amount of elements in one mole of the chemical composition of the aluminate phosphor. When the variable p does not satisfy 0.5 ≦ p ≦ 1.0 in the formula (I), an aluminate phosphor having a composition represented by the formula (I) (hereinafter, “aluminate” In some cases, the crystal structure of the phosphor (I) may be unstable, and the emission intensity may be reduced. The variable p is preferably 0.60 or more, more preferably 0.80 or more. Also, the variable p may be less than or equal to 0.999.

  The variable q in the formula (I) is a molar ratio of Mg. In the formula (I), when the variable q is 0.6 or more, the molar ratio of Mg increases, and the amount of Mn or Eu serving as an activating element relatively decreases, and the aluminate phosphor (I) There is a tendency for the light emission intensity of The variable q in the formula (I) is preferably 0.05 ≦ q ≦ 0.55, more preferably 0.10 ≦, from the viewpoint of obtaining the stability of the crystal structure and high emission intensity in a desired excitation wavelength region. It is a number that satisfies q ≦ 0.55. The variable q in the above formula (I) is more preferably 0.15 or more. When the variable q in the formula (I) is a number satisfying 0 ≦ q <0.6, the aluminate phosphor (I) emits light in the range of 510 nm or more and 525 nm or less by light excitation in the blue region It has a peak wavelength and can increase the emission intensity.

  The variable r in the formula (I) is a molar ratio of Mn. Mn is an activating element of the aluminate phosphor (I). The aluminate phosphor (I) contains both Mn and Eu as an activating element. The aluminate phosphor (I) contains both Mn and Eu, and light in the blue region from the excitation light source causes Eu to absorb light and excite electrons to transfer its excitation energy from Eu to Mn. Furthermore, it is estimated that it contributes to the light emission of Mn. By including both Mn and Eu as an activating element, the aluminate phosphor (I) can increase the light emission intensity by light excitation in the blue region. In the formula (I), when the variable r exceeds 0.7, the amount of activation of Mn is too large, and the aluminate phosphor (I) tends to cause concentration quenching and the emission intensity tends to be low. . In the formula (I), the variable r is preferably a number satisfying 0.45 ≦ r ≦ 0.65.

  The variable t in the formula (I) is a molar ratio of Eu which is an activating element of the aluminate phosphor (I). When the variable t exceeds 0.3, the emission intensity tends to decrease. When the variable t is 0, that is, when the aluminate phosphor (I) does not contain Eu, light absorption in the blue region by Eu is lost, and transmission of excitation energy from Eu to Mn is lost, so The emission intensity of the aluminate phosphor decreases. When the aluminate phosphor (I) contains Eu, the light absorption in the blue region is increased, and the light emitting device using the aluminate phosphor (I) efficiently converts the light emitted from the light emitting element can do. Therefore, in the aluminate phosphor (I) according to the embodiment of the present invention, the amount of the phosphor of the light emitting device decreases, and the light emitting device can be miniaturized. In the formula (I), the variable t is preferably 0.001 ≦ t ≦ 0.250, more preferably 0.001 ≦ t ≦ 0.225, and still more preferably 0.001 ≦ t ≦ 0.200. .

The sum of the variable p and the variable t in the formula (I) (hereinafter sometimes referred to as “variable p + t”) is at least one element X ¹ and Eu selected from the group consisting of Ba, Sr and Ca Total molar ratio. If the variable p + t is less than 0.5 or more than 1.2, the crystal structure of the aluminate phosphor (I) tends to be unstable, and the emission intensity may be reduced. The variable p + t is preferably 0.55 or more, more preferably 0.60 or more. The variable p + t is preferably 1.15 or less, more preferably 1.10 or less.

  The sum of the variable q and the variable r in the formula (I) (hereinafter sometimes referred to as “variable q + r”) is a molar ratio of the sum of Mg and Mn. When the variable q + r is 0.4 or less or more than 1.1, the crystal structure of the aluminate phosphor (I) tends to be unstable, and sufficient emission intensity may not be obtained. The variable q + r is preferably 0.4 <q + r ≦ 1.0, more preferably 0.5 or more, and more preferably 0.55 or more.

  The sum of the variable r and the variable t in the formula (I) (hereinafter sometimes referred to as “variable r + t”) is a molar ratio of the total of the activating elements Mn and Eu, and 0.4 <r + t < It is preferable that it is 0.8. When the variable r + t is 0.8 or more, for example, when excited with light in the blue region, concentration quenching occurs and the emission intensity tends to be low. In the formula (I), when the variable r + t is 0.4 or less, the activation amount is small, and the aluminate phosphor (I) absorbs less light when excited by light in the blue region. It may be difficult to increase the light emission intensity.

  The variable s in the formula (I) is a molar ratio of Al. If the variable s is less than 8.5 or exceeds 13.0, the crystal structure becomes unstable, and the aluminate phosphor (I) emits light intensity when excited by light in the near ultraviolet to blue region. Tend to decrease. In the formula (I), the variable s is preferably a number satisfying 9.0 ≦ s ≦ 13.0. In the formula (I), the variable s is more preferably 12.0 or less, further preferably 11.0 or less.

  The aluminate phosphor (I) may be manufactured using a flux such as a halide to enhance the reactivity of the raw material. In this case, when a flux containing an alkali metal is used, a trace amount of alkali metal element may be detected from the aluminate phosphor (I). Even in such a case, the alkali metal element contained in the aluminate phosphor (I) is 100 ppm or more and 1000 ppm or less, may be 200 ppm or more, may be 300 ppm or more, and 990 ppm or less It may be. Further, the aluminate phosphor (I) has a composition represented by the above formula (I) even when a trace amount of alkali metal element is detected. Moreover, when using the halide containing the element which comprises the composition represented by said Formula (I), the said halide becomes a raw material which comprises aluminate fluorescent substance (I), and acts also as a flux . In the case of using both a halide containing an element constituting the composition represented by the formula (I) and a compound containing an element constituting the composition represented by the formula (I) other than the halide, Molar ratio of elements constituting the composition represented by the formula (I) contained in the halide and molar ratio of elements constituting the composition represented by the formula (I) contained in the compound other than the halide The halide and compounds other than the halide can be used such that the total of the above satisfies the molar ratio of each element represented by the formula (I). As long as the aluminate phosphor (I) satisfies the composition represented by the above-mentioned formula (I), the element constituting the aluminate phosphor (I) may be an element derived from a flux.

Average particle size D
The aluminate phosphor (I) preferably has an average particle diameter D of 10 μm or more as measured by FSSS (Fisher Sub-Sieve Sizer) method. The average particle diameter D measured by the FSSS method of the aluminate phosphor (I) is more preferably 10.5 μm or more. Since the aluminate phosphor (I) has a large average particle diameter D of 10 μm or more, it can well absorb light from the excitation light source and can further increase the emission intensity. The FSSS method is a kind of air permeation method, and is a method of measuring the specific surface area using the flow resistance of air to determine the particle size. The average particle diameter D by the FSSS method can be measured, for example, using Fisher Sub-Sieve Sizer Model 95 (manufactured by Fisher Scientific). The average particle diameter D measured by the FSSS method of the aluminate phosphor (I) is preferably large, but is usually 50 μm or less, and preferably 30 μm or less from the viewpoint of easiness of production.

Volume average particle diameter D50
The aluminate phosphor (I) has a volume average particle diameter D50 at which the volume cumulative frequency from the small diameter side reaches 50% in the volume-based particle size distribution by laser diffraction particle size distribution measurement method, preferably 10 μm or more, more preferably Is 12 μm or more, more preferably 15 μm or more. The laser diffraction type particle size distribution measuring method is a method of measuring particle size without discriminating primary particles and secondary particles by using scattered light of laser light irradiated to particles. The volume average particle diameter D50 according to the laser diffraction / scattering particle size distribution measurement method can be measured, for example, using a laser diffraction particle size distribution measuring device (MASTER SIZER (master sizer) 3000, manufactured by MALVERN Co., Ltd.). As the average particle diameter D and the volume average particle diameter D50 are closer to each other, the aggregation of particles is less. The volume-based volume average particle diameter D50 of the aluminate phosphor (I) according to a laser diffraction / scattering particle size distribution measurement method is usually 75 μm or less, preferably 65 μm or less, more preferably 55 μm or less.

Light Emitting Device An example of a light emitting device according to a second embodiment of the present invention will be described based on the drawings. FIG. 1 is a schematic cross-sectional view showing a light emitting device 100 according to a second embodiment of the present invention. A light emitting device according to a second embodiment of the present invention includes a fluorescent member containing an aluminate phosphor (I) and an excitation light source.

  The light emitting device 100 includes the molded body 40, the light emitting element 10, and the fluorescent member 50. The molded body 40 is formed by integrally molding the first lead 20 and the second lead 30 and the resin portion 42 containing a thermoplastic resin or a thermosetting resin. The molded body 40 forms a recess having a bottom surface and a side surface, and the light emitting element 10 is mounted on the bottom surface of the recess. The light emitting element 10 has a pair of positive and negative electrodes, and the pair of positive and negative electrodes are electrically connected to the first lead 20 and the second lead 30 through the wires 60 respectively. The light emitting element 10 is covered by a fluorescent member 50. The fluorescent member 50 includes, for example, a phosphor 70 for converting the wavelength of light from the light emitting element 10 and a resin that is also used as a sealing material. The phosphor 70 further includes a first phosphor 71 and a second phosphor 72. The first phosphor 71 includes the aluminate phosphor (I) according to the first embodiment of the present invention. The first lead 20 and the second lead 30 connected to the pair of positive and negative electrodes of the light emitting element 10 are directed to the outside of the package constituting the light emitting device 100 to form the first lead 20 and the second lead 30. Some of the are exposed. Power can be supplied from the outside via the first lead 20 and the second lead 30 to cause the light emitting device 100 to emit light.

  The light emitting element 10 is used as an excitation light source, and preferably has an emission peak wavelength in the range of 430 nm to 485 nm. The range of the emission peak wavelength of the light emitting element 10 is more preferably 440 nm or more and 480 nm or less, still more preferably 445 nm or more and 470 nm or less. The aluminate phosphor (I) according to the first embodiment of the present invention is efficiently excited by light from an excitation light source having an emission peak wavelength in the range of 430 nm to 485 nm, and has high emission intensity. By using the fluorescent member containing the aluminate phosphor (I), the wavelength of the light from the light emitting element is efficiently converted, and the phosphor 70 containing the light from the light emitting element 10 and the aluminate phosphor (I) A light emitting device 100 can be provided that emits mixed color light with light from the light source.

Light emitting element 10, for example, it is preferable to use a semiconductor light emitting device using nitride semiconductor _{(In X Al Y Ga 1-} X-Y N, 0 ≦ X, 0 ≦ Y, X + Y ≦ 1). By using a semiconductor light emitting element as an excitation light source of the light emitting device, it is possible to obtain a stable light emitting device that is highly efficient, has high output linearity with respect to an input, and is resistant to mechanical shock. The half value width of the emission spectrum of the light emitting element 10 may be, for example, 30 nm or less, 25 nm or less, or 20 nm or less. The half width refers to the full width at half maximum (FWHM) of the maximum emission peak in the emission spectrum, and is the wavelength width of the emission peak showing 50% of the maximum value of the maximum emission peak in each emission spectrum. Say.

  The first phosphor 71 includes the aluminate phosphor (I) according to the first embodiment of the present invention, and is contained in the fluorescent member 50 covering the light emitting element 10. In the light emitting device 100 in which the light emitting element 10 is covered by the fluorescent member 50 containing the first fluorescent substance 71, a part of the light emitted from the light emitting element 10 is absorbed by the aluminate phosphor (I), Emitted as green light. By using the light emitting element 10 that emits light having a light emission peak wavelength in the range of 430 nm to 485 nm, a light emitting device having high light emission intensity can be provided.

  The fluorescent member 50 preferably includes a second phosphor 72 having a light emission peak wavelength different from that of the first phosphor 71. For example, the light emitting device 100 appropriately includes the light emitting element 10 that emits light having a light emission peak wavelength in the range of 430 nm to 485 nm, and the first phosphor 71 and the second phosphor 72 excited by this light. Thus, a wide color reproduction range and high color rendering can be obtained.

What is necessary is to absorb the light from the light emitting element 10 and perform wavelength conversion to light of a wavelength different from that of the first phosphor 71 as the second phosphor 72. For example, (Ca, Sr, Ba) ₂ SiO ₄ : Eu, (Ca, Sr, Ba) ₈ MgSi ₄ O ₁₆ (F, Cl, Br) ₂ : Eu, Si _6-z Al _z O _z N _{8-z : Eu (0 <z ≦ 4.2} ), (Sr, Ba, Ca) Ga 2 S 4: Eu, (Lu, Y, Gd, Lu) 3 (Ga, Al) 5 O 12: Ce, (La, Y, Gd) ₃ Si ₆ N ₁₁ : Ce, Ca ₃ Sc ₂ Si ₃ O ₁₂ : Ce, CaSc ₄ O ₄ : Ce, K ₂ (Si, Ge, Ti) F ₆ : Mn, (Ca, Sr, Ba) ) ₂ Si ₅ N ₈ : Eu, CaAlSiN ₃ : Eu, (Ca, Sr) AlSiN ₃ : Eu, (Sr, Ca) LiAl ₃ N ₄ : Eu, (Ca, Sr) ₂ Mg ₂ Li ₂ Si ₂ N ₆ : Eu, 3.5MgO.0.5MgF ₂ .GeO ₂ : Mn Etc.

  When the fluorescent member 50 includes the second fluorescent material 72, the second fluorescent material 72 is preferably a red fluorescent material that emits red light, and light having an emission peak wavelength in the range of 430 nm to 485 nm is used. It is preferable to absorb and emit light having an emission peak wavelength in the range of 610 nm to 780 nm. When the light emitting device contains a red phosphor, a light emitting device that emits desired light in a wide range of fields such as a lighting device and a liquid crystal display device can be provided.

As red phosphors, Mn-activated phosphors having a composition represented by K ₂ SiF ₆ : Mn or 3.5MgO · 0.5MgF ₂ .GeO ₂ : Mn, CaSiAlN ₃ : Eu, (Ca, Sr) AlSiN ₃ : Eu or SrLiAl ₃ N _4: can be mentioned Eu activated nitride phosphor having a composition represented by Eu. Among them, the red phosphor is preferably a Mn-activated fluoride phosphor having a half value width of 20 nm or less from the viewpoint of increasing the color purity and widening the color reproduction range.

  The fluorescent substance 70 containing the 1st fluorescent substance 71 and the 2nd fluorescent substance 72 comprises the fluorescence member 50 which coat | covers a light emitting element with a sealing material. As a sealing material which comprises the fluorescence member 50, thermosetting resins, such as a silicone resin and an epoxy resin, can be mentioned. The amount of the fluorescent substance 70 in the composition for a fluorescent member containing the fluorescent substance 70 and the resin for constituting the fluorescent member 50 is, for example, in the range of 10 parts by mass to 200 parts by mass with respect to 100 parts by mass of the resin. .

Method of Manufacturing Aluminate Phosphor Next, an example of a method of manufacturing the aluminate phosphor will be described. The production method of the aluminate phosphor (I) is not limited to the following production method. The aluminate phosphor (I) can be produced using a compound containing an element constituting the composition of the aluminate phosphor (I).

Raw Materials Constituting the Composition of Aluminate Phosphor (I) As the raw materials Constituting the Composition of Aluminate Phosphor (I), at least one element X ¹ selected from the group consisting of Ba, Sr and Ca Containing compounds (hereinafter, also referred to as “X ¹ compounds”), compounds containing magnesium (Mg), compounds containing manganese (Mn), compounds containing aluminum metal, aluminum alloy or aluminum (Al), and europium (Eu) And compounds containing

As the compound X ¹ compound containing the element X ^1, oxide containing an element X ^1, hydroxides, carbonates, nitrates, sulfates, carboxylates, halides, nitrides, and the like. These compounds may be in the form of hydrates. The halide containing the element X ¹ also acts as a flux. _{Specifically, BaO, Ba (OH) 2} · 8H 2 O, BaCO 3, Ba (NO 3) 2, BaSO 4, Ba (OCO) 2 · 2H 2 O, Ba (OCOCH 3) 2, BaCl 2 · 6H ₂ O, Ba ₃ N ₂ , BaNH, SrO, Sr (OH) ₂ .8H ₂ O, SrCO ₃ , Sr (NO ₃ ) ₂ .4H ₂ O, SrSO ₄ , Sr (OCO) ₂ .H ₂ O, Sr (OCOCH ₃ ) ₂ · 0.5H ₂ O, SrCl ₂ · 6H ₂ O, Sr ₃ N ₂ , SrNH, CaO, Ca (OH) ₂ , CaCO ₃ , Ca (NO ₃ ) ₂ , CaSO ₄ , Ca ( _{OCO) 2, CaCl 2, Ca} 3 N 2 , and the like. One of these compounds may be used alone, or two or more thereof may be used in combination. Among these, carbonates and oxides are preferable from the viewpoint of easy handling. Carbonate containing Element X ¹ because it has good stability in air, is easily decomposed by heating, and elements other than the target composition are unlikely to remain, and it is easy to suppress the decrease in emission intensity due to residual impurity elements. More preferable.

Mg-Containing Compounds Examples of Mg-containing compounds include Mg-containing oxides, hydroxides, carbonates, nitrates, sulfates, carboxylates, halides and nitrides. These Mg-containing compounds may be in the form of hydrates. The halide containing Mg also acts as a flux. Specifically, MgO, Mg (OH) ₂ , 3MgCO ₃ · Mg (OH) ₂ · 3H ₂ O, MgCO ₃ · Mg (OH) ₂ , Mg (NO ₃ ) ₂ · 6H ₂ O, MgSO ₄ , Mg _{(OCO) 2 · H 2 O} , Mg (OCOCH 3) 2 · 4H 2 O, MgCl 2, Mg 3 N 2 , and the like. The compounds containing Mg may be used alone or in combination of two or more. Among these, carbonates or oxides are preferable from the viewpoint of easy handling. The Mg-containing oxide (MgO) is suitable because it has good stability in air, is easily decomposed by heating, and elements other than the target composition are unlikely to remain, and it is easy to suppress the decrease in emission intensity due to residual impurity elements. And / or halides that also act as fluxes (eg, MgF ₂ ) are more preferred.

Compounds Containing Mn As compounds containing Mn, oxides, hydroxides, carbonates, nitrates, sulfates, carboxylates, halides, nitrides and the like containing Mn are mentioned. The halide containing Mn also acts as a flux. The compound containing Mn may be in the form of a hydrate. Specifically, MnO ₂ , Mn ₂ O ₂ , Mn ₃ O ₄ , MnO, Mn (OH) ₂ , MnCO ₃ , Mn (NO ₃ ) ₂ , Mn (OCOCH ₃ ) ₂ · 2H ₂ O, Mn (OCOCH ₂ ) _{3) 3 · 2H 2 O,} MnCl 2 · 4H 2 O , and the like. The compound containing Mn may be used alone or in combination of two or more. Among these, carbonates and oxides are preferable from the viewpoint of easy handling. It has good stability in air, it is easily decomposed by heating, and elements other than the target composition are difficult to remain, and it is easy to suppress the decrease in emission intensity due to residual impurity elements. And MnCO ₃ ) are more preferred.

Eu-Containing Compounds Examples of Eu-containing compounds include Eu-containing oxides, hydroxides, carbonates, nitrates, sulfates, halides, nitrides and the like. The halide containing Eu also acts as a flux. These compounds containing Eu may be in the form of hydrates. Specifically, EuO, Eu ₂ O ₃ , Eu (OH) ₃ , Eu ₂ (CO ₃ ) ₃ , Eu (NO ₃ ) ₃ , Eu ₂ (SO ₄ ) ₃ , EuCl ₂ , EuF _{3 and the} like can be mentioned. . The compounds containing Eu may be used alone or in combination of two or more. Among these, carbonates and oxides are preferable from the viewpoint of easy handling. Since it has good stability in air, it is easily decomposed by heating, and elements other than the target composition are unlikely to remain, and it is easy to suppress the decrease in emission intensity due to the residual impurity element. , Eu ₂ O ₃ ) are more preferred.

Al metal, Al alloy or compound containing Al The compound containing Al includes an oxide containing Al, a hydroxide, a nitride, an oxynitride, a fluoride, a chloride and the like. The halide containing Al also acts as a flux. These compounds may be hydrates. Aluminum metal or aluminum alloy may be used. Al metal or Al alloy may be used instead of at least a part of the compound.
Specific examples of the compound containing Al include Al ₂ O ₃ , Al (OH) ₃ , AlN, AlF ₃ , AlCl _{3 and the} like. The compound containing Al may be used alone or in combination of two or more. The compound containing Al is preferably an oxide (for example, Al ₂ O ₃ ). The oxide does not contain other elements other than the target composition of the aluminate phosphor, as compared to other materials, and it is easy to obtain a phosphor of the target composition. When a compound containing an element other than the target composition is used, a residual impurity element may be present in the obtained phosphor, and this residual impurity element serves as a killer element for light emission, and the emission intensity is There is a possibility that it will decrease significantly.

It is preferable to use a flux in order to increase the reactivity of the flux material. The flux includes halides. By the flux contained in the raw material mixture, the reaction between the raw materials is promoted, and the solid phase reaction tends to progress more uniformly. It is considered that the reaction is promoted because the temperature at which the raw material mixture is heat-treated is approximately the same as the formation temperature of the liquid phase of the halide used as a flux or higher than the generation temperature of the liquid phase. Be
The halide is selected from the group consisting of a fluoride containing at least one metal element selected from the group consisting of rare earth metals, alkaline earth metals and alkali metals, rare earth metals, alkaline earth metals and alkali metals And chlorides containing at least one metal element, fluorides of aluminum, or chlorides. When a compound containing an element constituting the composition of the aluminate phosphor (I) is used as the flux, the composition of the aluminate phosphor whose target is the element ratio of the cation contained in the flux is obtained. As a compound, a flux can be added, or a flux can be further added after preparing each raw material so as to have the composition of the target aluminate phosphor.
In the case of a flux containing an element constituting the composition of the aluminate phosphor (I), the sum of the molar ratio of the elements contained in the flux and the molar ratio of the elements contained in the compound other than the flux is the formula The flux and other compounds are mixed so as to satisfy the composition represented by (I).
In the case of a flux which does not contain an element constituting the composition of the aluminate phosphor (I), each material is prepared so as to be the composition of the target aluminate phosphor (I), and then the flux is added Do.
When a halide containing an alkali metal is used as a flux, the obtained aluminate phosphor may contain a trace amount of alkali metal element. The alkali metal element contained in the aluminate phosphor is preferably at least one element selected from the group consisting of Li, K and Na, more preferably Na.

Specific examples of the flux include BaF ₂ , MgF ₂ , CaF ₂ , LiF, NaF, KF, and AlF ₃ . The flux is preferably at least one selected from the group consisting of MgF ₂ , NaF, and AlF ₃ , and more preferably MgF ₂ and / or NaF. By using MgF ₂ and / or NaF as the flux, it is possible to stabilize the crystal structure and obtain a phosphor having a relatively large average particle size. The flux may be used alone or in combination of two or more.

  When a halide containing an element other than the elements constituting the composition of the aluminate phosphor (I) is used as a flux, the content of the flux is based on a total of 100 parts by mass of each raw material before containing the flux. Preferably it is 10 mass parts or less, More preferably, it is 5 mass parts or less, More preferably, it is 2 mass parts or less, Preferably it is 0.1 mass part or more. If the content of the flux containing an element other than the elements constituting the composition of the aluminate phosphor (I) is within the above range, there will be no difficulty in forming a crystal structure due to the lack of particle growth due to the small amount of flux. Moreover, it is because there is no possibility that it will become difficult to form crystal structure, because there are too many fluxes.

Mixing of Raw Materials Each raw material is weighed so as to have a molar ratio satisfying the composition of the formula (I), and then mixed to produce a raw material mixture. A halide may be added to the raw material mixture as a raw material and / or a flux. The amount of halide in the raw material mixture is preferably 1 mole to a total of 1 mole of the element amount preferably selected from the group consisting of Ba, Ca and Sr contained in the raw material mixture and the elemental amount of Eu. The amount is preferably 0.5 mol or less, more preferably 0.2 mol or less, and preferably 0.05 mol or more. Here, when 2 or more types of halides are added as 2 or more types of flux, as for the quantity of the flux in a raw material mixture, it is preferable that the molar quantity which totaled 2 types of fluxs is the said range.

  The raw material mixture may be ground and mixed using a dry grinder such as, for example, a ball mill, vibration mill, hammer mill, roll mill or jet mill, or may be ground and mixed using a mortar and a pestle, for example, ribbon blender, It may be mixed using a mixer such as a Henschel mixer or a V-type blender, or may be ground and mixed using both a dry grinder and a mixer. Also, the mixing may be dry mixing, or may be wet mixing with the addition of a solvent or the like. The mixing is preferably dry mixing. This is because the dry process can reduce the process time more than the wet process, leading to an improvement in productivity.

Heat treatment (first heat treatment)
The raw material mixture is placed in a crucible, boat, etc. made of carbon material such as graphite, boron nitride (BN), aluminum oxide (alumina), tungsten (W), molybdenum (Mo) and heat-treated to obtain aluminate phosphor ( I) can be obtained. The step of heat treating the raw material mixture is also referred to as heat treatment or first heat treatment.

  The temperature for heat treatment (first heat treatment) is preferably 1000 ° C. or more and 1800 ° C. or less, more preferably 1100 ° C. or more and 1750 ° C. or less, still more preferably 1200 ° C. or more and 1700 ° C. or less, particularly from the viewpoint of the stability of the crystal structure. Preferably it is 1300 degreeC or more and 1650 degrees C or less.

  The heat treatment time varies depending on the temperature rising rate, heat treatment atmosphere, etc., and is preferably 1 hour or more, more preferably 2 hours or more, still more preferably 3 hours or more, preferably 20 hours or less, after reaching the heat treatment temperature. Preferably it is 18 hours or less, More preferably, it is 15 hours or less.

The heat treatment may be performed in an inert atmosphere such as argon or nitrogen, a reducing atmosphere containing hydrogen or the like, or an oxidizing atmosphere such as in the air. The raw material mixture is preferably heat-treated in a reducing nitrogen atmosphere to obtain a phosphor. The atmosphere for heat-treating the raw material mixture is more preferably a nitrogen atmosphere containing reducing hydrogen gas.
The raw material mixture is improved in the reactivity of the raw material mixture in an atmosphere with high reducing power such as a reducing atmosphere containing hydrogen and nitrogen, and is heat-treated under atmospheric pressure without pressurization to obtain an aluminate phosphor ( I) can be obtained. For the heat treatment, for example, an electric furnace, a gas furnace or the like can be used.

  The raw material may be further mixed using the obtained aluminate phosphor (I) as a seed crystal, and the second heat treatment may be performed to obtain the aluminate phosphor (I). When the second heat treatment is further performed using the obtained aluminate phosphor (I) as a seed crystal, the step of obtaining the aluminate phosphor (I) to be a seed crystal is also referred to as a first heat treatment.

Dispersion Treatment The first baked product may be subjected to dispersion treatment by a dispersion treatment step described later, after the first heat treatment and before the second heat treatment. In the dispersion treatment step performed on the first baked product, for example, the first baked product is subjected to classification treatment such as wet dispersion, wet sieving, dehydration, drying, dry sieving, etc., and a seed having an intended average particle diameter You may obtain the aluminate fluorescent substance (I) used as a crystal. As a solvent used for wet dispersion, for example, deionized water can be used. The time for wet dispersion varies depending on the solid dispersion medium and solvent used, but is preferably 30 minutes or more, more preferably 60 minutes or more, still more preferably 90 minutes or more, still more preferably 120 minutes or more, and preferably 420 It is less than a minute. Preferably, the aluminate phosphor (I) to be a seed crystal is subjected to wet dispersion in a range of 30 minutes to 420 minutes to use the obtained aluminate phosphor in a light emitting device. The dispersibility in resin which comprises a fluorescence member can be improved.

Second heat treatment With the aluminate phosphor (I) obtained by the first heat treatment as a seed crystal, the raw material is further added to the aluminate phosphor (I) to be the seed crystal to carry out the second heat treatment Do. In a second mixture containing the aluminate phosphor (I) obtained by the first heat treatment and the raw material, a compound containing at least one metal element selected from the group consisting of Ba, Sr and Ca; A compound containing at least one of a compound containing Mn and a compound containing Eu, a compound containing Al, and the first fired product having a content of 10% by mass to 90% by mass with respect to the total amount of the second mixture, and necessary And Mg containing compounds. The second mixture is subjected to a second heat treatment to obtain an aluminate phosphor (I) subjected to the second heat treatment. The second mixture preferably contains a compound containing Eu and a compound containing Mn.

  The content of the aluminate phosphor (I) to be a seed crystal contained in the second mixture is preferably 15% by mass or more and 85% by mass or less, more preferably the total amount of the second mixture. The content is 20% by mass to 80% by mass, more preferably 25% by mass to 80% by mass, and still more preferably 30% by mass to 80% by mass. When the aluminate phosphor (I) as a seed crystal is contained in the second mixture in a range of 10% by mass to 90% by mass with respect to the total amount of the second mixture, the second The crystal growth is promoted from the seed crystal aluminate phosphor (I) in the heat treatment of the above, and the average particle diameter measured by the FSSS method is larger than that of the seed crystal aluminate phosphor (I), It is possible to obtain the aluminate phosphor (I) subjected to the second heat treatment.

  When mixing the second mixture, the mixing method, mixer, etc. exemplified when obtaining the first mixture can be used. Further, the second mixture can be heat-treated by placing it in a crucible, a boat or the like made of the same material as the raw material mixture.

  The second mixture preferably contains a flux, and the second baked product can be obtained by performing the second heat treatment together with the flux contained in the second mixture.

  As the second heat treatment temperature, a temperature in the same range as the first heat treatment temperature described above can be applied. The second heat treatment temperature may be the same temperature as the first heat treatment temperature described above, or may be a different temperature. For the heat treatment, for example, an electric furnace, a gas furnace or the like can be used.

  As the atmosphere for the second heat treatment, an atmosphere similar to the above-described first heat treatment atmosphere can be applied. The second heat treatment atmosphere may be the same as or different from the first heat treatment atmosphere described above.

  As the second heat treatment time, the same range of time as the first heat treatment time described above can be applied. The second heat treatment time may be the same as or different from the first heat treatment time described above.

Post-treatment The obtained phosphors may be wet-dispersed and post-treated such as wet sieving, dehydration, drying, dry sieving, etc., and these post-treatments yield phosphors having a desired average particle diameter. . For example, the phosphor after heat treatment is dispersed in a solvent, the dispersed phosphor is placed on a sieve, a solvent flow is made to flow through the sieve, and the calcined material is passed through a mesh Wet sieving, followed by dewatering, drying and dry sieving can be performed to obtain a phosphor having a desired average particle size.
By dispersing the heat-treated phosphor in a medium, it is possible to remove impurities such as a baking residue of the flux and unreacted components of the raw material. For wet dispersion, a dispersion medium such as alumina balls or zirconia balls may be used.

  EXAMPLES Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to these examples.

Example 1
As a phosphor having a composition represented by Ba _0.999 Eu _0.001 Mg _0.5 Mn _0.5 Al ₁₀ O ₁₇ , BaCO ₃ , Eu ₂ O ₃ , MgO, MnCO ₃ , Al ₂ O ₃ and flux The MgF ₂ which also acts as a raw material is used as each raw material, and the molar ratio as the preparation amount ratio is Ba: Eu: Mg: Mn: Al = 0.999: 0.001: 0.5: 0.5: 10 As a halide acting as a flux, NaF was added in addition to MgF ₂ to obtain a raw material mixture. 0.26 mass parts of NaF was added with respect to a total of 100 mass parts of each raw material before adding a flux. The raw material mixture obtained is filled in an alumina crucible, covered, and heat treated at 1500 ° C. for 5 hours in a mixed atmosphere of 3 vol% H _{2 and} 97 vol% N ₂ to obtain an aluminate A phosphor was obtained.

Example 2
As a phosphor having a composition represented by Ba _0.97 Eu _0.03 Mg _0.5 Mn _0.5 Al ₁₀ O ₁₇ , the molar ratio as the preparation amount ratio of each raw material is Ba: Eu: Mg: Mn: An aluminate phosphor was obtained in the same manner as in Example 1 except that the raw material was made Al = 0.97: 0.03: 0.5: 0.5: 10.

Example 3
As a phosphor having a composition represented by Ba _0.95 Eu _0.05 Mg _0.5 Mn _0.5 Al ₁₀ O ₁₇ , the molar ratio as the preparation amount ratio of each raw material is Ba: Eu: Mg: Mn: An aluminate phosphor was obtained in the same manner as in Example 1 except that the raw material was made Al 0.95: 0.05: 0.5: 0.5: 10.

Example 4
As a phosphor having a composition represented by Ba _0.90 Eu _0.10 Mg _0.5 Mn _0.5 Al ₁₀ O ₁₇ , the molar ratio as the preparation amount ratio of each raw material is Ba: Eu: Mg: Mn: An aluminate phosphor was obtained in the same manner as in Example 1 except that a raw material which was adjusted to Al = 0.90: 0.10: 0.5: 0.5: 10 was used.

Comparative Example 1
As a phosphor having a composition represented by Ba _1.0 Mg _0.8 Mn _0.2 Al ₁₀ O ₁₇ , the molar ratio as the feed amount ratio of each raw material is Ba: Mg: Mn: Al = 1.0: An aluminate phosphor was obtained in the same manner as in Example 1 except that the raw material was adjusted to be 0.8: 0.2: 10.

Comparative example 2
As a phosphor having a composition represented by Ba _1.0 Mg _0.5 Mn _0.5 Al ₁₀ O ₁₇ , the molar ratio of each raw material as the preparation amount ratio is Ba: Mg: Mn: Al = 1.0: An aluminate phosphor was obtained in the same manner as in Example 1 except that the raw material was made to be 0.5: 0.5: 10.

Comparative example 3
As a phosphor having a composition represented by Ba _0.70 Eu _0.30 Mg _0.5 Mn _0.5 Al ₁₀ O ₁₇ , the molar ratio as the preparation amount ratio of each raw material is Ba: Eu: Mg: Mn: An aluminate phosphor was obtained in the same manner as in Example 1 except that a raw material which was adjusted to Al = 0.70: 0.30: 0.5: 0.5: 10 was used.

Comparative example 4
As a phosphor having a composition represented by Ba _0.60 Eu _0.40 Mg _0.5 Mn _0.5 Al ₁₀ O ₁₇ , the molar ratio as the preparation amount ratio of each raw material is Ba: Eu: Mg: Mn: An aluminate phosphor was obtained in the same manner as in Example 1 except that the raw material was made to be Al = 0.60: 0.40: 0.5: 0.5: 10.

Comparative example 5
As a phosphor having a composition represented by Ba _0.60 Eu _0.40 Mg _0.7 Mn _0.3 Al ₁₀ O ₁₇ , the molar ratio as the preparation amount ratio of each raw material is Ba: Eu: Mg: Mn: An aluminate phosphor was obtained in the same manner as in Example 1 except that the raw material was made to be Al = 0.60: 0.40: 0.7: 0.3: 10.

Comparative example 6
As a phosphor having a composition represented by Ba _0.60 Eu _0.40 Mg _0.8 Mn _0.2 Al ₁₀ O ₁₇ , the molar ratio as the preparation amount ratio of each raw material is Ba: Eu: Mg: Mn: An aluminate phosphor was obtained in the same manner as in Example 1 except that the raw material was made Al = 0.60: 0.40: 0.8: 0.2: 10.

Example 5
As a phosphor having a composition represented by Ba _0.9 Eu _0.1 Mg _0.45 Mn _0.5 Al ₁₀ O _16.95 , BaCO ₃ , Eu ₂ O ₃ , MgO, MnCO ₃ , Al ₂ O ₃ and the like And MgF _2, which also acts as a flux, is used as each raw material, and the molar ratio of BaF: Eu: Mg: Mn: Al = 0.9: 0.1: 0.45: 0.5: were mixed so as to be 10, as the halide which acts as a flux, to obtain a raw material mixture was added and NaF in addition to the MgF _2. 0.26 mass parts of NaF was added with respect to a total of 100 mass parts of each raw material before adding a flux. The raw material mixture obtained is filled in an alumina crucible, covered, and subjected to first heat treatment at 1500 ° C. for 5 hours in a mixed atmosphere of 3 volume% H _{2 and} 97 volume% N _2. , Aluminate phosphor to be a seed crystal was obtained. The obtained aluminate phosphor to be a seed crystal is put in a container made of polyethylene, dispersed in deionized water, and dispersed for 240 minutes using alumina balls as a dispersion medium, followed by wet sieving, classification, dehydration, Post-treatment was performed in the order of drying and dry sieving to obtain an aluminate phosphor to be a seed crystal.
An aluminate phosphor to be a seed crystal obtained so as to be a phosphor having a composition represented by Ba _0.9 Eu _0.1 Mg _0.45 Mn _0.5 Al ₁₀ O _16.95 , and BaCO _{3, Eu 2 O 3, MgO} , using MnCO _{3, Al} 2 _O 3, and MgF ₂ that also acts as a flux as a raw material, as a halide, which acts as a flux, by adding NaF to other MgF _2, second A mixture of The second mixture was prepared to contain 30% by weight of the aluminate phosphor as seed crystals in the total amount (100% by weight) of the second mixture. The resulting second mixture is packed in an alumina crucible, covered, and subjected to a second heat treatment for 5 hours at 1500 ° C. in a mixed atmosphere of 3 vol% H _{2 and} 97 vol% N _2. Thus, a second heat-treated product was obtained. The obtained second heat-treated product is placed in a polyethylene container, dispersed in deionized water, and dispersed for 240 minutes using alumina balls as a dispersion medium, followed by wet sieving, classification, dehydration, drying, dry sieving Post-treatment was performed in the order of to obtain an aluminate phosphor.

Example 6
As a phosphor having a composition represented by Ba _0.875 Eu _0.125 Mg _0.45 Mn _0.5 Al ₁₀ O _16.95 , BaCO ₃ , Eu ₂ O ₃ , MgO, MnCO ₃ , Al ₂ O ₃ and the like And MgF _2, which also acts as a flux, is used as each raw material, and the molar ratio of BaF: Eu: Mg: Mn: Al = 0.875: 0.125: 0.45: 0.5: An aluminate phosphor was obtained in the same manner as Example 5, except that the mixture was mixed to be 10.

Example 7
As a phosphor having a composition represented by Ba _0.85 Eu _0.15 Mg _0.45 Mn _0.5 Al ₁₀ O _16.95 , BaCO ₃ , Eu ₂ O ₃ , MgO, MnCO ₃ , Al ₂ O ₃ and the like And MgF _2, which also acts as a flux, is used as a raw material, and the molar ratio of BaF: Eu: Mg: Mn: Al = 0.85: 0.15: 0.45: 0.5: An aluminate phosphor was obtained in the same manner as Example 5, except that the mixture was mixed to be 10.

Example 8
As a phosphor having a composition represented by Ba _0.825 Eu _0.175 Mg _0.45 Mn _0.5 Al ₁₀ O _16.95 , BaCO ₃ , Eu ₂ O ₃ , MgO, MnCO ₃ , Al ₂ O ₃ and the like And MgF _2, which also acts as a flux, is used as each raw material, and the molar ratio of BaF: Eu: Mg: Mn: Al = 0.825: 0.175: 0.45: 0.5: An aluminate phosphor was obtained in the same manner as Example 5, except that the mixture was mixed to be 10.

Example 9
As a phosphor having a composition represented by Ba _0.8 Eu _0.2 Mg _0.45 Mn _0.5 Al ₁₀ O _16.95 , BaCO ₃ , Eu ₂ O ₃ , MgO, MnCO ₃ , Al ₂ O ₃ and the like And MgF _2, which also acts as a flux, is used as each raw material, and the molar ratio of BaF: Eu: Mg: Mn: Al = 0.8: 0.2: 0.45: 0.5: An aluminate phosphor was obtained in the same manner as Example 5, except that the mixture was mixed to be 10.

Example 10
As a phosphor having a composition represented by Ba _0.775 Eu _0.225 Mg _0.45 Mn _0.5 Al ₁₀ O _16.95 , BaCO ₃ , Eu ₂ O ₃ , MgO, MnCO ₃ , Al ₂ O ₃ and the like And MgF _2, which also acts as a flux, is used as each raw material, and the molar ratio of BaF: Eu: Mg: Mn: Al = 0.775: 0.225: 0.45: 0.5: An aluminate phosphor was obtained in the same manner as Example 5, except that the mixture was mixed to be 10.

Comparative example 7
As a phosphor having a composition represented by Ba _1.0 Mg _0.45 Mn _0.5 Al ₁₀ O _16.95 , BaCO ₃ , MgO, MnCO ₃ , Al ₂ O ₃ and MgF ₂ which also acts as a flux are used. Example 5 and Example 5 were used except that the raw materials were mixed so that the molar ratio as the feed amount ratio was Ba: Mg: Mn: Al = 1.0: 0.45: 0.5: 10. In the same manner, an aluminate phosphor was obtained.

Light Emitting Device The light emitting device 100 was manufactured using the aluminate phosphors of Examples 5 to 10 and Comparative Example 7 as the first phosphor 71. The light emitting device 100 uses, as the light emitting element 10, a nitride semiconductor having an emission peak wavelength of 450 nm. A silicone resin was used as a sealing material of the fluorescent member 50. As the second phosphor, a fluoride phosphor activated with manganese which emits red light was used. A phosphor 70 including a first phosphor 71 and a second phosphor 72 whose blending amounts are adjusted so that the chromaticity coordinates of light emitted from the light emitting device are in the vicinity of x = 0.262, y = 0.223 The mixture was added to a silicone resin, mixed and dispersed, and then defoamed to obtain a composition for a fluorescent member constituting a fluorescent member. The amount (parts by mass) of the phosphor 70 with respect to 100 parts by mass of the silicone resin in each composition for a fluorescent member is shown in Table 2. The composition for a fluorescent member is injected onto the light emitting element 10 in the concave portion of the molded body 40, filled in the concave portion, and further heated at 150 ° C. for 3 hours to cure the composition for a fluorescent member. Then, a light emitting device 100 as shown in FIG. 1 was manufactured.

Average particle size D
About the aluminate phosphor according to each example and comparative example, using a Fisher Sub-Sieve Sizer Model 95 (manufactured by Fisher Scientific), under a temperature of 25 ° C. and a humidity of 70% RH, aluminium of 1 cm ³ min. After the acid salt phosphor was measured as a sample and packed in a dedicated tubular container, dry air at a constant pressure was flowed, the specific surface area was read from the differential pressure, and a value converted to the average particle diameter D by FSSS method was obtained. The results are shown in Tables 1 and 2.

Volume average particle diameter D50
The volume accumulated frequency from the small diameter side of the aluminate phosphor according to each example and comparative example was measured using a laser diffraction type particle size distribution measuring apparatus (MALVERN (Malvern), MASTER SIZER (master sizer) 3000). The volume average particle size D50 reaching 50% was measured. The results are shown in Tables 1 and 2.

Evaluation of Emission Characteristics Emission Spectrum The emission characteristics of the aluminate phosphors according to Examples and Comparative Examples were measured. Each phosphor was irradiated with light having an excitation wavelength of 450 nm using a quantum efficiency measurement apparatus (QE-2000 manufactured by Otsuka Electronics Co., Ltd.), and the emission spectrum at room temperature (25 ° C. ± 5 ° C.) was measured. FIG. 2 is an emission spectrum of relative luminescence intensity (%) with respect to the wavelength of the aluminate phosphor according to Example 1, the aluminate phosphor according to Comparative Example 1, and the aluminate phosphor according to Comparative Example 2. .

Relative luminescence intensity (%)
The relative emission intensity was calculated from the measured emission spectra of the aluminate phosphors according to the examples and the comparative examples, assuming that the emission intensity at the emission peak wavelength of the aluminate phosphor according to the comparative example 1 is 100%. The results are shown in Tables 1 and 2.

Reflectance (%)
About the aluminate phosphor according to each example and comparative example, calcium hydrogen phosphate (CaHPO) at room temperature (25 ° C. ± 5 ° C.) using a spectrofluorimeter (F-4500 manufactured by Hitachi High-Technologies Corporation) _The reflection spectrum was measured using ₄ ) as a reference sample. In the reflection spectrum, the intensity of the reflected light of the reference sample at each wavelength is 100%, and the relative intensity at each wavelength of each phosphor is expressed as reflectance (%). FIG. 3 shows the reflection spectra of the aluminate phosphors according to Example 3, Comparative Example 1, Comparative Example 2 and Comparative Example 3, respectively. For the aluminate phosphors according to each example and comparative example, the reflectance (%) of 450 nm as the excitation wavelength and the reflectance (%) of 520 nm as the emission peak wavelength of the aluminate phosphor are shown in Table 1 And in Table 2.

SEM photograph SEM photograph of the aluminate phosphor according to the example and the aluminate phosphor according to the comparative example was obtained using a scanning electron microscope (SEM). FIG. 4 is a SEM photograph of the aluminate phosphor according to Example 1, and FIG. 5 is a SEM photograph of the aluminate phosphor according to Comparative Example 1.

As shown in Table 1, in the aluminate phosphors according to Examples 1 to 4, the reflectance at 450 nm is lower than that of the aluminate phosphor of Comparative Example 1, and the absorption of excitation light in the blue region is increased. The relative light emission intensity increased. The aluminate phosphors according to Examples 1 to 4 contain both Eu and Mn, and the co-activation of Eu and Mn causes Eu to increase light absorption when excited by light in the blue region, It is presumed that the excitation energy is efficiently transferred from Eu to Mn, and the relative light emission intensity is increased.
In addition, as shown in Table 1, the aluminate phosphors according to Examples 1 to 4 have a reflectance of 92% or more in the vicinity of the emission peak wavelength of 520 nm, and have small self-absorption.

On the other hand, since the aluminate phosphor according to Comparative Example 2 does not contain Eu, the absorption of light in the blue region by Eu is not performed, and the relative emission intensity is higher as the aluminate phosphors of Examples 1 to 4 are. did not become.
Further, in the aluminate phosphors according to Comparative Examples 3 and 4, since the variable t representing the molar ratio of Eu in the formula (I) is 0.3 or more, and the reflectance at 450 nm is low, absorption in the blue region Although the amount increased, the total amount of Eu and Mn as activators was large, and the relative luminescence intensity decreased due to concentration quenching.

In addition, in the aluminate phosphor according to Comparative Example 5, the variable t representing the molar ratio of Eu in the formula (I) is greater than 0.3, the reflectance at 450 nm is relatively high, and the excitation light is It is inferred that the relative light emission intensity is reduced because the absorption at 450 nm is reduced. In the aluminate phosphor according to Comparative Example 6, the variable t representing the molar ratio of Eu in the formula (I) is greater than 0.3 and the variable r representing the molar ratio of Mn is 0.4. It is assumed that absorption of light by Eu and transfer of excitation energy from Eu to Mn are not efficiently performed, and the emission intensity is lowered.
In Comparative Examples 4 and 6, the reflectance in the vicinity of the emission peak wavelength of 520 nm is smaller than 92%, and it is estimated that the self absorption by the aluminate phosphor itself is large.

  As shown in FIG. 2, the peak wavelength of the emission spectrum of the aluminate phosphor according to Example 1 is not changed as compared to the peak wavelength of the emission spectrum of the aluminate phosphor according to Comparative Example 1 It has been confirmed that the relative luminescence intensity of the aluminate phosphor according to Example 1 is higher than that of the aluminate phosphors according to Comparative Examples 1 and 2.

As shown in FIG. 3, in the aluminate phosphor according to Example 3, in the wavelength range of 430 nm to 485 nm, the reflectance is lower than that of the aluminate phosphor according to Comparative Example 1, and light from the excitation light source Could be absorbed efficiently. Further, as shown in FIG. 3, in the aluminate phosphor according to Example 3, the reflectance at the emission peak wavelength of 520 nm is approximately the same as that of Comparative Example 2.
On the other hand, as shown in FIG. 3, the aluminate phosphor according to Comparative Example 3 has a reflectance of 520 nm in the wavelength range of 430 nm to 485 nm, although the reflectance is lower than that of the aluminate phosphor according to Comparative Example 1. The reflectance at the emission peak wavelength was lower than that of the aluminate phosphor according to Example 3.

  As shown in the SEM photographs of FIG. 4 and FIG. 5, the aluminate phosphor according to Example 1 and the aluminate phosphor according to Comparative Example 1 have a hexagonal crystal structure, and at least one side is hexagonal. The aluminate phosphor according to Example 1 and the aluminate phosphor according to Comparative Example 1 were plate-like crystals, and no significant difference in appearance was found with respect to the particle shape.

  As shown in Table 2, the aluminate phosphors according to Examples 5 to 10 had a lower reflectance at 450 nm than the aluminate phosphor of Comparative Example 7, and increased absorption of excitation light in the blue region. As shown in Table 2, in the aluminate phosphors according to Examples 5 to 10, absorption of excitation light in the blue region emitted by the light emitting element is increased, and wavelength conversion can be performed efficiently. Therefore, the amount of phosphor contained in the fluorescent member is reduced, and the light emitting device can be miniaturized.

  A light emitting device using an aluminate phosphor according to an embodiment of the present invention can be used in a wide range of fields such as general lighting, vehicle lighting, displays, backlights for liquid crystals, traffic lights, lighting switches, and the like.

10: light emitting element, 40: molded body, 50: fluorescent member, 71: first phosphor, 72: second phosphor, 100: light emitting device.

Claims (7)

An aluminate phosphor having a composition represented by the following formula (I).
X ¹ _p Eu _t Mg _q Mn _r Al _s O _{p + t + q + r + 1.5 s} (I)
(Wherein, in the formula (I), X ¹ is at least one element selected from the group consisting of Ba, Sr and Ca, and p, q, r, s and t satisfy 0.5 ≦ p ≦ 1.0) , 0 ≦ q <0.6, 0.4 <r ≦ 0.7, 8.5 ≦ s ≦ 13.0, 0 <t <0.3, 0.5 <p + t ≦ 1.2, 0.4 It is a number that satisfies <q + r ≦ 1.1.) The aluminate phosphor according to claim ¹ , wherein in the formula (I), X ¹ contains Ba.   The aluminate phosphor according to claim 1 or 2, wherein in the formula (I), r is a number satisfying 0.45 ≦ r ≦ 0.65.   The aluminate phosphor according to any one of claims 1 to 3, wherein in the formula (I), t is a number satisfying 0.001 ≦ t 50 0.250.   The average particle diameter D measured by FSSS method is 10 micrometers or more, The aluminate fluorescent substance of any one of Claim 1 to 4 characterized by the above-mentioned.   The light-emitting device containing the fluorescence member containing the aluminate fluorescence of any one of Claims 1-5, and an excitation light source. The light emitting device according to claim 6, wherein the excitation light source has an emission peak wavelength in a range of 430 nm to 485 nm.