TW202113034A - Α-type sialon phosphor, light emitting member and light emitting device - Google Patents

Abstract

An [alpha]-type SiAlON phosphor of the invention contains [alpha]-type SiAlON particles, and in a volume frequency particle distribution of the [alpha]-type SiAlON particles measured by laser diffraction scattering, if the particle size at a cumulative value of 5% is deemed D5, the particle size at a cumulative value of 50% is deemed D50, and the particle size at a cumulative value of 98% is deemed D98, then the value of ((D98-D5)/D50) is at least 1.00 but not more than 10.00, and the internal quantum efficiency relative to excitation light with a wavelength of 455 nm is 75% or higher.

Description

Alpha-type silicon aluminum oxynitride phosphor, light-emitting component, and light-emitting device

The present invention relates to an α-type silicon aluminum oxynitride phosphor, a light-emitting member, and a light-emitting device.

So far, various α-type silicon aluminum oxynitride phosphors have been developed. With respect to such a technique, for example, a technique described in Patent Document 1 is known. Patent Document 1 describes a technique for adjusting the composition of an α-type silicon aluminum oxynitride phosphor (claim 1 of Patent Document 1). [Prior Technical Literature] [Patent Literature]

[Patent Document 1] JP 2003-124527 A

[The problem to be solved by the invention]

However, after the inventors of the present case studied, they found that there is still room for improvement in terms of the external quantum efficiency of the α-type silicon aluminum oxynitride phosphor described in Patent Document 1. [Means to solve the problem]

In recent years, there has been progress in the development of miniaturization of light-emitting devices using α-type silicon aluminum oxynitride phosphors. Along with this, there has also been a demand for a smaller particle size of α-type silicon aluminum oxynitride particles. However, the discussion on the particle size of α-type silicon aluminum oxynitride particles has not yet been fully described.

The inventors of this case focused on the particle size and studied, and found that by appropriately removing the fine powder contained in the α-type silicon aluminum oxynitride particles that have been appropriately reduced in particle size, the α-type silicon aluminum oxynitride can be oxidized. The external quantum efficiency of the α-type silicon aluminum oxynitride phosphor of the material particles. In addition, by using an α-type silicon aluminum oxynitride phosphor with an internal quantum efficiency of 75% or more relative to the excitation light with a wavelength of 455 nm, the external quantum efficiency can be further improved.

Based on such knowledge and insights, after further research, it is found that the particle size at which the cumulative value of the volume frequency particle size distribution of the α-type silicon aluminum oxynitride phosphor measured by the laser diffraction scattering method becomes 5% as D5, becomes When 50% of the particle size is D50 and 98% of the particle size is D98, using ((D98-D5)/D50) as an index, the properties of α-type silicon aluminum oxynitride particles after fine powder removal can be stably evaluated , By using the index ((D98-D5)/D50) to fall within an appropriate value range and the internal quantum efficiency is above the predetermined value, the α-type silicon aluminum nitride containing α-type silicon aluminum oxynitride particles can be improved The external quantum efficiency of the oxide phosphor has completed the present invention.

According to the present invention, An α-type silicon aluminum oxynitride phosphor can be provided, which contains α-type silicon aluminum oxynitride particles, In the volume frequency particle size distribution of the α-type silicon aluminum oxynitride phosphor measured by the laser diffraction scattering method, the particle size at which the cumulative value becomes 5% is regarded as D5, and the particle size at 50% is regarded as D50, which is 98 When the particle size of% is taken as D98, ((D98-D5)/D50) is 1.00 or more and 8.00 or less, D50 is less than 10μm, and The internal quantum efficiency relative to the excitation light with a wavelength of 455nm measured according to the following procedure is above 75%; program: (1) Use the α-type silicon-aluminum oxynitride phosphor as a sample, fill the sample in such a way that the surface of the concave type spectroscopy tube becomes smooth, and install the concave type spectroscopy tube in the opening of the integrating sphere After the part, the monochromatic light of predetermined wavelength emitted from the luminous light source is used as the excitation light and guided into the integrating sphere; At 25°C, irradiate the sample in the concave spectrophotometer with excitation light, and measure the spectrum of the sample with a spectrophotometer. Calculate the number of excited reflected light photons (Qref) and the number of fluorescent photons (Qem) from the obtained spectral data; (2) Instead of using a concave spectrophotometer, a standard reflector with a reflectivity of 99% is used. In addition, proceed as in (1) above. Install the standard reflector on the opening of the integrating sphere to excite The light is irradiated to the standard reflector, the spectrum of the excitation light with a wavelength of 455nm is measured, and the number of excitation light photons (Qex) is calculated from the obtained spectrum data; According to the following formula, find the above internal quantum efficiency; Internal quantum efficiency=(Qem/(Qex-Qref))×100.

In addition, according to the present invention, A light emitting component can be provided, which has: Light-emitting elements, and The wavelength converter converts the light irradiated from the light-emitting element and emits light; The wavelength conversion body has the above-mentioned α silicon aluminum oxynitride phosphor.

Furthermore, according to the present invention, it is possible to provide a light-emitting device including the above-mentioned light-emitting member. [Effects of Invention]

According to the present invention, an α-type silicon aluminum oxynitride phosphor with excellent external quantum efficiency, a light-emitting member and a light-emitting device using the same can be provided.

Hereinafter, the embodiments of the present invention will be described using drawings. In addition, in all the drawings, the same constituent elements are given the same reference numerals, and the description is appropriately omitted. In addition, the figure is a schematic drawing, and it does not correspond to the actual size ratio.

The α-type silicon aluminum oxynitride phosphor of this embodiment will be described.

The α-type silicon aluminum oxynitride phosphor of this embodiment contains α-type silicon aluminum oxynitride particles, and the volume of the α-type silicon aluminum oxynitride phosphor is measured by the laser diffraction scattering method In the frequency particle size distribution, when the cumulative value becomes 5% as D5, 50% as D50, and 98% as D98, ((D98-D5)/D50) is 1.00 or more and 8.00 Hereinafter, D50 is 10 μm or less, and the internal quantum efficiency with respect to excitation light with a wavelength of 455 nm measured according to the following procedure is 75% or more.

(program) (1) Use the α-type silicon-aluminum oxynitride phosphor as a sample, fill the sample in such a way that the surface of the concave type spectroscopy tube becomes smooth, and install the concave type spectroscopy tube in the opening of the integrating sphere After the part, the monochromatic light of the predetermined wavelength emitted from the luminous light source is used as the excitation light and guided into the integrating sphere. At 25°C, irradiate the sample in the concave spectrophotometer with excitation light, and measure the spectrum of the sample with a spectrophotometer. Calculate the number of excited reflected light photons (Qref) and the number of fluorescent photons (Qem) from the obtained spectral data; (2) Instead of using a concave spectrophotometer, a standard reflector with a reflectivity of 99% is used. In addition, proceed as in (1) above. Install the standard reflector on the opening of the integrating sphere to excite The light is irradiated to the standard reflector, the spectrum of the excitation light with a wavelength of 455nm is measured, and the number of excitation light photons (Qex) is calculated from the obtained spectrum data. According to the following formula, find the above internal quantum efficiency; Internal quantum efficiency=(Qem/(Qex-Qref))×100.

Based on the knowledge and insights of the inventors of the present case, it was found that by appropriately removing the fine powder contained in the α-type silicon aluminum oxynitride particles that have been appropriately reduced in particle size, it is possible to make the α-type silicon aluminum oxynitride particles contained The external quantum efficiency of the α-type silicon aluminum oxynitride phosphor is better. In addition, it has been clearly known that by using ((D98-D5)/D50) as an index, the properties of α-type silicon aluminum oxynitride particles after the removal of fine powder can be stably evaluated. By using this index (( Setting D98-D5)/D50) within an appropriate value range can increase the external quantum efficiency of α-type silicon aluminum oxynitride phosphors containing α-type silicon aluminum oxynitride particles.

Although the detailed mechanism has not yet been determined, it can be inferred that the specific surface area of the fine powder produced by the micronization of the particles, etc., is relatively large, the reflection is more, and the crystal defects are relatively large. Therefore, by removing such fine powder, the inside of 455nm can be improved. Quantum efficiency and reflectivity, thereby increasing the external quantum efficiency of 455nm.

The upper limit of ((D98-D5)/D50) may be 8.00 or less, preferably 7.70 or less, more preferably 7.30 or less. Thereby, the external quantum efficiency of the α-type silicon aluminum oxynitride phosphor containing α-type silicon aluminum oxynitride particles whose fine powder has been appropriately removed can be improved.

On the other hand, the lower limit of ((D98-D5)/D50) can be, for example, 1.00 or more, preferably 3.00 or more, and more preferably 4.00 or more. Thereby, the α-type silicon-aluminum oxynitride phosphor containing α-type silicon-aluminum oxynitride particles from which the fine powder has been appropriately removed can reduce the absorption rate at 700 nm.

In addition, by setting ((D98-D5)/D50) within the above numerical range, the fluorescence intensity and light absorption rate at 455nm can be improved.

D50, for example, may be 1.0 μm to 10.0 μm, preferably 2.5 μm to 9.0 μm, more preferably 3.0 μm to 9.0 μm. By setting D50 below the above upper limit, an α-type silicon aluminum oxynitride phosphor containing appropriately small-sized α-type silicon aluminum oxynitride particles can be achieved. By setting D50 above the above lower limit, the fluorescence intensity at 455nm can be increased.

In this manual, if there are no special restrictions, "~" means that the upper limit and the lower limit are included.

In the volume frequency particle size distribution of the α-type silicon aluminum oxynitride phosphor measured by the laser diffraction scattering method, the particle size at which the cumulative value becomes 90% is taken as D90. D90, for example, may be 5.5 μm to 35.0 μm, preferably 8.5 μm to 27.0 μm, more preferably 10.0 μm to 25.0 μm. By setting D90 below the above upper limit, an α-type silicon aluminum oxynitride phosphor containing appropriately small-sized α-type silicon aluminum oxynitride particles can be achieved. By setting D90 above the above lower limit, the fluorescence intensity at 455nm can be increased.

In addition, when measuring the particle size of powders by the laser diffraction scattering method, it is important to dissolve the agglomeration of the powders before the measurement, and to fully disperse the system in the dispersion medium. However, due to different dispersion conditions, sometimes The measured values may vary, so the measured values of D5, D50, D90, D98, Dmax, etc. obtained by the laser diffraction scattering method of the α-type silicon aluminum oxynitride phosphor of the present invention are based on JIS R1622 and R1629, put 0.5g of the phosphor to be measured into 100ml of ion-exchange aqueous solution mixed with 0.05wt% sodium hexametaphosphate, and use an ultrasonic homogenizer with transmission frequency of 19.5±1kHz, tip size of 20φ, and amplitude of 31±5μm , Place the tip in the center of the liquid and perform a 3 minute dispersion treatment to determine the measured value of the liquid. Here, 19.5±1 indicates the range of 18.5 or more and 20.5 or less, and 31±5 indicates the range of 26 or more and 36 or less.

In addition, based on the knowledge and insights of the inventors of the present case, it has been clearly known that by appropriately removing the fine powder contained in the α-type silicon aluminum oxynitride particles with a moderately small particle size, the excitation light with respect to the wavelength of 455 nm can be improved. Internal quantum efficiency.

In the α-type silicon aluminum oxynitride phosphor, the lower limit of the internal quantum efficiency relative to the excitation light with a wavelength of 455 nm is 75% or more, preferably 76% or more, and more preferably 77% or more. By setting the lower limit of the internal quantum efficiency of 455 nm to above the above lower limit, the external quantum efficiency of the α-type silicon aluminum oxynitride phosphor containing small-sized α-type silicon aluminum oxynitride particles can be improved. In addition, the upper limit of the internal quantum efficiency of 455 nm is not particularly limited. For example, it may be 100% or less, or 99% or less.

According to this embodiment, by using ((D98-D5)/D50) within a predetermined range and the internal quantum efficiency of 455nm is above the predetermined value of α-type silicon aluminum oxynitride phosphor, the external quantum efficiency can be improved, so A light-emitting device with excellent brightness can be realized. Furthermore, an α-type silicon aluminum oxynitride phosphor suitable for miniaturized light-emitting devices can be provided.

The upper limit of the light absorption rate of the α-type silicon aluminum oxynitride phosphor with respect to the excitation light with a wavelength of 700 nm, for example, is 10% or less, preferably 9% or less, more preferably 7% or less, and still more preferably 5% or less. By setting the upper limit of the light absorption rate at 700 nm below the above upper limit, a light-emitting device with excellent brightness can be achieved. In addition, the lower limit of the light absorption rate at 700 nm is not particularly limited, and it may be 0% or more.

The light absorption rate at 700nm is calculated by changing the wavelength of excitation light from 455nm to 700nm, and the number of excitation light photons (Qex) and the number of excitation reflected light photons (Qref) are calculated from the spectrum in the wavelength range of 695~710nm, except for that In addition, proceed in the same way as the above procedure, and obtain it according to the following formula, Light absorption rate=((Qex-Qref)/Qex)×100

In the α-type silicon aluminum oxynitride phosphor, the lower limit of the diffuse reflectance relative to the excitation light with a wavelength of 800 nm is, for example, 90% or more, preferably 92% or more, and more preferably 93% or more. By setting the lower limit of the diffuse reflectance of 800 nm to more than the above lower limit, a light-emitting device with excellent brightness can be achieved. In addition, the upper limit of the diffuse reflectance of 800 nm is not particularly limited, and it may be 100% or less.

The α-type silicon aluminum oxynitride phosphor of this embodiment may also include: the α-type silicon aluminum oxynitride containing Eu element represented by the following general formula (1). (M) _m(1-x)/p (Eu) _mx/2 (Si) _12-(m+n) (Al) _m+n (O) _n (N) _16-n ･･General formula (1)

In the above general formula (1), M represents one or more elements selected from the group consisting of Li, Mg, Ca, Y and lanthanides (excluding La and Ce), and p is the valence of the M element , Which means 0<x<0.5, 1.5≦m≦4.0, 0≦n≦2.0. n, for example, may be 2.0 or less, may be 1.0 or less, or may be 0.8 or less.

The solid solution composition of α-type silicon aluminum oxynitride _{is that m Si-N bonds in the unit cell of α-type silicon nitride (Si 12} N ₁₆ ) are replaced by Al-N bonds, and n Si-N bonds are replaced by Al-N bonds. It is substituted by an Al-O bond, and in order to maintain electrical neutrality, m/p cations (M, Eu) intrude into the crystal lattice and are expressed as the above-mentioned general formula. Especially for M, when Ca is used, the α-type silicon aluminum oxynitride can be stabilized in a wide range of composition. By replacing a part of it with Eu, which becomes the luminescent center, a wide range from ultraviolet to blue can be obtained. It is excited by light in the wavelength range, and shows a phosphor that emits visible light from yellow to orange.

Generally speaking, α-type silicon-aluminum oxynitride phosphors are different from the above-mentioned α-type silicon-aluminum oxynitride as the second crystalline phase and the unavoidable amorphous phase, which cannot be solidified by composition analysis. The solvent composition is strictly regulated. As far as the crystalline phase of α-type silicon aluminum oxynitride is concerned, it is preferable to be an α-type silicon aluminum oxynitride single phase. For other crystalline phases, it may also contain β-type silicon aluminum oxynitride, aluminum nitride or Its polytypoid, Ca ₂ Si ₅ N ₈ , CaAlSiN ₃ and so on.

As far as the manufacturing method of α-type silicon aluminum oxynitride phosphor is concerned, a mixed powder composed of silicon nitride, aluminum nitride and a compound of invading solid solution elements is heated in a high-temperature nitrogen environment to make it react. method. The step of producing α-type silico-alumina oxynitride particles can use a known method. For example, it can also have a calcining step of calcining the raw material mixture powder to obtain a calcined product; and the calcined product after the calcining step can be crushed and crushed. Post-treatment steps such as treatment, classification treatment, annealing treatment and acid treatment. In addition, in the post-treatment step, ball milling and/or decantation treatment may be further performed.

According to the inventor’s knowledge and insights, it is clear that by calcination at low temperature during calcination, particle growth is suppressed, and the fine powder removal treatment conditions of ball mill pulverization and decantation treatment are optimized to appropriately remove small particle diameters. Micropowder contained in α-type silicon aluminum oxynitride particles after chemical conversion.

In this embodiment, for example, it is possible to appropriately select the type or blending amount of each component contained in the α-type silicon-aluminum oxynitride phosphor, the preparation method of the α-type silicon-aluminum oxynitride phosphor, etc. Control the above ((D98-D5)/D50), D5, D50, D90, D98, 455nm internal quantum efficiency, 700nm light absorption rate, and 800nm diffuse reflectance. Among them, for example, appropriate post-treatment steps, ball milling, decantation treatment, or classification using centrifugal force can be cited as the above-mentioned ((D98-D5)/D50), D5, D50, D90, D98, 455nm The internal quantum efficiency, 700nm light absorption rate, and 800nm diffuse reflectance fall within the expected value range.

(Wavelength converter) The wavelength conversion body of this embodiment converts the light irradiated from the light-emitting element to emit light, and has the above-mentioned α-type silicon aluminum oxynitride phosphor. The wavelength conversion body may be composed of only α-type silicon aluminum oxynitride phosphor, or may include a base material dispersed with α-type silicon aluminum oxynitride phosphor. As the base material, known ones can be used, and examples thereof include glass, resin, and inorganic materials.

The shape of the above-mentioned wavelength conversion body is not particularly limited, and may be formed in a plate shape, or may be configured to seal a part of the light-emitting element or the entire light-emitting surface.

(Light-emitting device) The light-emitting device of this embodiment will be described. The light-emitting device of this embodiment includes a light-emitting member including a light-emitting light source (light-emitting element) and the above-mentioned wavelength converter. By combining the luminous light source and the wavelength converter, it can emit light with high luminous intensity.

Fig. 1 is a schematic cross-sectional view showing an example of the structure of the light-emitting device of this embodiment. The light-emitting device 100 of FIG. 1 includes, for example, a light-emitting element 120, a heat sink 130, a housing 140, a first lead frame 150, a second lead frame 160, a bonding wire 170, a bonding wire 172, and a composite body 40.

The light-emitting element 120 is a semiconductor element that emits excitation light. As for the light-emitting element 120, for example, an LED chip that emits light with a wavelength of 300 nm or more and 500 nm or less, which is equivalent to near-ultraviolet light to blue light, can be used.

As a specific example of the light-emitting element 120, a group III nitride semiconductor light-emitting element may also be used. The III-nitride semiconductor light-emitting element is composed of, for example, a III-nitride semiconductor such as AlGaN, GaN, and InAlGaN-based materials, and includes an n-layer, a light-emitting layer, and a p-layer. For III-nitride semiconductor light-emitting devices, blue LEDs that emit blue light can be used.

One of the electrodes (not shown) installed on the top surface of the light emitting element 120 is connected to the surface of the first lead frame 150 via bonding wires 170 such as gold wires. In addition, another electrode (not shown) formed on the top surface of the light emitting element 120 is connected to the surface of the second lead frame 160 via bonding wires 172 such as gold wires.

The light emitting element 120 is installed above the heat sink 130. The heat dissipation of the light emitting element 120 can be improved through the heat sink 130. It is also possible to use the package substrate without using the heat sink 130.

The housing 140 is formed with a funnel-shaped recess whose aperture gradually expands from the bottom surface upward. The light-emitting element 120 is arranged on the bottom surface of the recess. The wall surface surrounding the recess of the light-emitting element 120 plays the role of a reflector.

The composite body 40 is filled in the recessed portion where the wall surface is formed by the housing 140. As for the composite body 40, a wavelength conversion member that lengthens the wavelength of the excitation light emitted from the light-emitting element 120 is used. As a specific example of the composite body 40, a wavelength conversion body obtained by dispersing phosphor particles 1 containing α-type silicon aluminum oxynitride phosphor in a sealing material 30 such as resin can be used.

The light-emitting device 100 emits light emitted from the phosphor particles 1 that are excited by absorbing the light emitted by the light-emitting element 120, or emits mixed light with the light emitted from the light-emitting element 120. The light emitting device 100 can also use the color mixing of the light of the light emitting element 120 and the light emitted from the phosphor particles 1 to emit white light.

In addition, FIG. 1 is an example of a surface-mounted light-emitting device. However, the light-emitting device is not limited to the surface mount type. The light-emitting device can also be a cannonball type or a COB (chip directly packaged) type.

Above, the embodiments of the present invention have been described, but these are only examples of the present invention, and various configurations other than the above may be adopted. In addition, the present invention is not limited to the above-mentioned embodiments, and changes, improvements, etc., are also included in the present invention within the scope of achieving the purpose of the present invention. [Example]

Hereinafter, the present invention will be described in detail with reference to embodiments, but the present invention is not limited in the description of these embodiments.

＜Production of α silicon aluminum oxynitride type phosphor＞ (Comparative example 1) ･The mixing step is to maintain the moisture content below 1 mass ppm and the oxygen content below 1 mass ppm in a glove box in a nitrogen environment. Silicon powder (Si ₃ N ₄ , grade SN-E10, manufactured by Ube Industries Co., Ltd.) 62.8 g, calcium nitride powder (Ca ₃ N ₂ , manufactured by Materion Co., Ltd.) 13.4 g, aluminum nitride powder (AlN , E grade, manufactured by Tokuyama Co., _{Ltd.), and 1.1 g of europium oxide powder (Eu 2} O ₃ , grade RU, manufactured by Shin-Etsu Chemical Co., Ltd.) were mixed to obtain a raw material mixed powder. 100 g of the raw material mixed powder was filled into a cylindrical boron nitride container (manufactured by Denka Co., Ltd., grade N-1) with a lid with an internal volume of 0.4 liters.

･Calcination step Place the raw material mixed powder and the entire container in an electric furnace with a carbon heater in an atmospheric nitrogen atmosphere, and heat treatment at 1800°C for 16 hours. In addition, since the calcium nitride contained in the raw material mixed powder is easily hydrolyzed in the air, the boron nitride container filled with the raw material mixed powder is taken out of the glove box and quickly placed in the electric furnace and immediately vacuum exhausted. Prevent the reaction of calcium nitride. The orange lumps recovered from the container were gently broken with a mortar, and all of them were passed through a sieve with a mesh of 150 μm to obtain a powder. After that, a silicon nitride ball with a spherical diameter of φ5 was used in water to disintegrate for 4 hours, then filtered, dried at 120°C for 5 hours, and passed through a 150 μm sieve to obtain phosphor powder. The obtained phosphor powder was used as an α-silicon aluminum oxynitride type phosphor A.

(Comparative Example 2) In a glove box that maintains a nitrogen atmosphere with a moisture content of 1 mass ppm or less and an oxygen content of 1 mass ppm or less, α-type silicon nitride powder (Si ₃ N ₄ , SN-E10 grade, Ube Industries Co., Ltd.) 56.56 g, calcium nitride powder (Ca ₃ N ₂ , manufactured by Materion Co., Ltd.) 12.02 g, aluminum nitride powder (AlN, grade E, manufactured by Tokuyama Co., Ltd.) 20.41 g, europium oxide powder (Eu ₂ O ₃ , RU grade, manufactured by Shin-Etsu Chemical Co., Ltd.) 1.00 g and 10.00 g of the phosphor powder of Comparative Example 1 were mixed to obtain a raw material mixed powder. The same procedure was performed as in Comparative Example 1. The phosphor powder is obtained. The obtained phosphor powder was used as α silicon aluminum oxynitride type phosphor B.

(Example 1) The phosphor powder obtained in Comparative Example 1 was subjected to ball milling and decantation in order under the following conditions to obtain phosphor powder. The obtained phosphor powder was used as α silicon aluminum oxynitride type phosphor C. ·ball milling 0.8 L of ion-exchange water and 50 g of the phosphor powder (sample) obtained in Comparative Example 1 were put into an alumina kettle with a kettle capacity of 2 L. For the alumina kettle containing this sample, ball milling was carried out for 8 hours under the conditions of a silicon nitride ball φ5mm, a ball weight of 1000g, and a rotation speed of about 150rpm. After that, it was filtered, dried at 120°C for 5 hours, and stored. ·Decantation Disperse the ball-milled sample in a 0.05wt% Na hexametaphosphate aqueous solution and let it stand for 2 hours to remove the fine powder by removing the supernatant from the water surface to a depth of 4 cm. After the removal, it was filtered, dried at 120°C for 5 hours, and passed through a 150 μm sieve to obtain phosphor powder.

(Example 2) In a glove box that maintains a nitrogen atmosphere with a moisture content of 1 mass ppm or less and an oxygen content of 1 mass ppm or less, α-type silicon nitride powder (Si ₃ N ₄ , SN-E10 grade, Ube Industries Co., Ltd.) 56.56 g, calcium nitride powder (Ca ₃ N ₂ , manufactured by Materion Co., Ltd.) 12.02 g, aluminum nitride powder (AlN, grade E, manufactured by Tokuyama Co., Ltd.) 20.41 g, europium oxide powder (Eu ₂ O ₃ , RU grade, manufactured by Shin-Etsu Chemical Co., Ltd.) 1.00 g and 10.00 g of the phosphor powder of Comparative Example 1 were mixed to obtain a raw material mixed powder, except that the same procedure was performed as in Example 1. The phosphor powder is obtained. The obtained phosphor powder was used as an α-silicon aluminum oxynitride type phosphor D.

(Example 3) Except that the calcination temperature was changed to 1900°C, the same procedure as in Example 1 was performed to obtain phosphor powder. The obtained phosphor powder was used as an α-silicon aluminum oxynitride type phosphor E.

For the phosphor powders obtained in Examples 1 to 3 and Comparative Examples 1 and 2, the crystalline phases were investigated by powder X-ray diffraction measurement (XRD measurement) using CuKα rays, and it was confirmed that the crystalline phases were all containing Eu and Ca. α-type silicon aluminum oxynitride. In addition, the alpha silicon aluminum oxynitride type phosphors A to E all conform to the above-mentioned general formula (1).

[Table 1] Example 2 Example 3 Example 1 Comparative example 1 Comparative example 2 α-type silicon aluminum oxynitride phosphor D E C A B Volume frequency particle size distribution D5 1.10 1.33 0.93 0.56 0.78 D50 4.00 7.70 3.50 1.60 3.58 D90 12.20 23.70 12.40 6.50 12.91 D98 24.00 47.98 26.20 16.80 31.14 Dmax 43.70 87.50 51.40 36.40 86.90 D98-D5/D50 5.73 6.06 7.22 10.15 8.48 455nm Internal quantum efficiency 82 78 78 77 77 External quantum efficiency 53 55 48 41 45 Fluorescence intensity 144 145 131 121 125 Light absorption rate 64 71 62 54 59 700nm Light absorption rate 3 3 5 4 6 800nm Diffuse reflectance 96.1 96.8 94.0 96.8 96.1 Chromaticity x 0.548 0.551 0.546 0.545 0.548 Chromaticity y 0.447 0.445 0.448 0.448 0.447 Peak wavelength 593.5 593.5 593.5 594.5 592.3 Half width 84.5 84.0 84.0 84.3 84.3

For the obtained α silicon aluminum oxynitride type phosphors A to E, the following evaluation items were evaluated. The evaluation results are shown in Table 1.

(Particle size distribution) The particle size distribution of α silicon aluminum oxynitride phosphors is measured by Microtrac MT3300EXII (Microtrac MT3300EXII (Microtrac Bayer Co., Ltd.), which is a particle size measuring device that is a laser diffraction scattering method. For the measurement procedure, 0.5g of the phosphor to be measured is put into 100ml of an aqueous solution of ion-exchange water mixed with 0.05wt% of sodium hexametaphosphate, and an ultrasonic homogenizer, namely Ultrasonic Homogenizer US-150E (Nippon Seiki Manufacturing Co., Ltd. Co., Ltd., Amplitude100%, oscillation frequency 19.5±1kHz, tip size 20φ, the tip is placed in the center of the liquid and dispersed at an amplitude of about 31μm for 3 minutes, and then the particle size measurement is performed using the aforementioned MT3300EXII. The measurement results are shown in Table 1. . In Table 1, in the volume frequency particle size distribution of α-type silicon aluminum oxynitride phosphors measured by the laser diffraction scattering method, the particle size (μm) whose cumulative value becomes 5% is regarded as D5, which becomes 50% of the particles The diameter (μm) is defined as D50, the particle diameter (μm) which becomes 90% is defined as D90, and the particle diameter (μm) which becomes 98% is defined as D98.

＜455nm internal quantum efficiency, external quantum efficiency, fluorescence intensity, light absorption rate＞ The 455nm internal quantum efficiency, external quantum efficiency, fluorescence intensity, and light absorption rate of α-type silicon aluminum oxynitride phosphor are calculated by the following procedure. The α-type silicon aluminum oxynitride phosphor was used as a sample, and filled in such a way that the surface of the concave spectrophotometer became smooth. Install the concave light analysis tube in the opening of the integrating sphere. The monochromatic light with a wavelength of 455nm separated from the light source (Xe lamp) is used as the excitation light of the phosphor and guided into the integrating sphere by optical fiber. The phosphor sample was irradiated with this monochromatic light, and the fluorescence spectrum of the sample was measured using a spectrophotometer (MCPD-7000 manufactured by Otsuka Electronics Co., Ltd.). Calculate the number of excited reflected light photons (Qref) and the number of fluorescent photons (Qem) from the obtained spectral data. The number of excitation reflected light photons is calculated in the same wavelength range as the number of excitation light photons, and the number of fluorescent photons is calculated in the range from 465 nm to 800 nm. In addition, using the same device, instead of using a concave spectrophotometer, a standard reflector with a reflectivity of 99% (Spectralon (registered trademark) manufactured by Labsphere Co., Ltd.) was installed in the opening of the integrating sphere, and the spectrum of excitation light with a wavelength of 455nm was measured. . At this time, calculate the number of excitation light photons (Qex) from the spectrum in the wavelength range of 450 to 465 nm. The 455nm light absorption rate and internal quantum efficiency of α-type silicon aluminum oxynitride are obtained from the calculation formula shown below. 455nm light absorption rate (%)=((Qex-Qref)/Qex)×100 Internal quantum efficiency (%)=(Qem/(Qex-Qref))×100 Furthermore, the external quantum efficiency is obtained by the calculation formula shown below, External quantum efficiency (%)=(Qem/Qex)×100 Therefore, based on the above formula, the external quantum efficiency has the relationship shown below. External quantum efficiency = 455nm light absorption rate × internal quantum efficiency In addition, when the standard sample of β-type silicon aluminum oxynitride phosphor (NIMS Standard Green lot No.NSG1301, manufactured by Sialon Co., Ltd.) was measured by the above-mentioned measurement method, the external quantum efficiency was 55.6%, and the light absorption The rate is 74.4%, and the internal quantum efficiency is 74.8%. Quantum efficiency and light absorption rate may vary due to changes in the measurement device manufacturer, manufacturing lot number, etc., so when the measurement device manufacturer, manufacturing lot number, etc. change, use the β-type silicon aluminum oxynitride phosphor The standard sample of the light body is used as the reference value and the measurement data is corrected.

＜700nm light absorption rate＞ The wavelength of the excitation light is changed from 455nm to 700nm. The number of excitation light photons (Qex) and the number of excitation reflected light photons (Qref) are calculated from the spectrum in the wavelength range of 695~710nm. In addition, the light absorption rate is less than 455nm. The measurement procedure of >Similarly calculates the 700nm light absorption rate based on the following formula. 700nm light absorption rate (%)=((Qex(700nm)-Qref(700nm))/Qex(700nm))×100

＜800nm diffuse reflectance＞ The diffuse reflectance of the α-type silicon aluminum oxynitride phosphor was measured by installing the integrating sphere device (ISV-469) on the UV-Vis spectrophotometer (V-550) manufactured by JASCO Corporation. Use a standard reflector (Spectralon (registered trademark)) for baseline calibration, and install a solid sample holder filled with α-type silicon aluminum oxynitride phosphor (phosphor powder), and measure in the wavelength range of 500~850nm Diffuse reflectance. The 800nm diffuse reflectance (%) referred to in the present invention is the value of the diffuse reflectance especially at 800nm. In addition, when the standard sample of the β-type silicon aluminum oxynitride phosphor (NIMS Standard Green lot No. NSG1301, manufactured by Sialon Co., Ltd.) was measured by the above-mentioned measurement method, the 800 nm diffuse reflectance was 95.7%. The 800nm diffuse reflectance may change the measurement value due to changes in the manufacturer and manufacturing lot number of the measuring device. Therefore, when the manufacturer and manufacturing lot number of the measuring device are changed, the β-type silicon aluminum oxynitride phosphor is used. The standard sample is used as the reference value and the measurement data is corrected.

＜Chromaticity x, y＞ The chromaticities x and y are CIE1931 values, and they are measured with a spectrophotometer (MCPD-7000 manufactured by Otsuka Electronics Co., Ltd.). In the same way as above, irradiate monochromatic light with a wavelength of 455nm, measure the excitation reflection light spectrum in the range of 465~800nm, and calculate the color intensity x and y. In addition, when the standard sample of β-type silicon aluminum oxynitride phosphor (NIMS Standard Green lot No. NSG1301, manufactured by Sialon Co., Ltd.) was measured by the above-mentioned measurement method, the chromaticity x was 0.356. Chromaticity x may change due to changes in the manufacturer and manufacturing lot number of the measuring device. Therefore, when the manufacturer and manufacturing lot number of the measuring device are changed, the β-type silicon aluminum oxynitride phosphor is used. The standard sample is used as a reference value and the measurement data is corrected.

<Peak wavelength, half-value width> The peak wavelength and half-value width were measured with a spectrophotometer (MCPD-7000 manufactured by Otsuka Electronics Co., Ltd.). In the same way as above, irradiate monochromatic light with a wavelength of 455nm, measure the excitation reflection light spectrum in the range of 465~800nm, and calculate the peak wavelength (nm) and half-value width of the fluorescence. The half-value width represents the width (nm) of the spectrum at which the intensity of the peak wavelength becomes half of the intensity. In addition, when the standard sample of β-type silicon aluminum oxynitride phosphor (NIMS Standard Green lot No.NSG1301, manufactured by Sialon Co., Ltd.) was measured according to the above-mentioned measurement method, the peak wavelength was 543.3 nm and the half-value width was 543.3 nm. It is 53.3nm. Since the peak wavelength and half-value width may change due to changes in the measurement device manufacturer, manufacturing batch number, etc., when the measurement device manufacturer, manufacturing batch number, etc. change, use β-type silicon aluminum oxynitride The standard sample of the fluorophore is used as the reference value and the measurement data is corrected.

It can be seen that the α-type silicon aluminum oxynitride phosphors of Examples 1 to 3, compared with Comparative Examples 1 and 2, have excellent external quantum efficiency, fluorescence intensity, and light absorption rate at 455 nm. Therefore, by using the α-type silicon aluminum oxynitride phosphors of Examples 1 to 3, a light-emitting device with excellent brightness can be achieved.

This application claims priority based on the Japanese application Japanese Patent Application No. 2019-097116 filed on May 23, 2019, and the entire content is incorporated into the present invention.

1: Phosphor particles 30: Sealing material 40: Complex 100: Light-emitting device 120: light-emitting element 130: heat sink 140: shell 150: 1st lead frame 160: 2nd lead frame 170: joint line 172: Joint line

[Fig. 1] A schematic diagram showing an example of the structure of the light-emitting device of this embodiment.

1: Phosphor particles

30: Sealing material

40: Complex

100: Light-emitting device

120: light-emitting element

130: heat sink

140: shell

150: 1st lead frame

160: 2nd lead frame

170: joint line

172: Joint line

Claims (8)

An α-type silicon aluminum oxynitride phosphor containing α-type silicon aluminum oxynitride particles, In the volume frequency particle size distribution of the α-type silicon aluminum oxynitride phosphor measured by the laser diffraction scattering method, the particle size at which the cumulative value becomes 5% is regarded as D5, and the particle size at 50% is regarded as D50, which is 98 When the particle size of% is taken as D98, ((D98-D5)/D50) is 1.00 or more and 8.00 or less, D50 is 10μm or less, and The internal quantum efficiency relative to the excitation light with a wavelength of 455nm measured according to the following procedure is above 75%; program: (1) Use the α-type silicon-aluminum oxynitride phosphor as a sample, fill the sample in such a way that the surface of the concave type spectroscopy tube becomes smooth, and install the concave type spectroscopy tube in the opening of the integrating sphere After the part, the monochromatic light of predetermined wavelength emitted from the luminous light source is used as the excitation light and guided into the integrating sphere; At 25°C, irradiate the sample in the concave spectrophotometer with excitation light, measure the spectrum of the sample with a spectrophotometer, and calculate the number of excited reflected light photons (Qref) and the number of fluorescent photons (Qem) from the obtained spectrum data; (2) Instead of using a concave spectrophotometer, a standard reflector with a reflectivity of 99% is used, except that the standard reflector is installed in the opening of the integrating sphere in the same way as in (1) above. The excitation light is irradiated to the standard reflector, the spectrum of the excitation light with a wavelength of 455nm is measured, and the number of excitation light photons (Qex) is calculated from the obtained spectrum data; According to the following formula, find the above internal quantum efficiency; Internal quantum efficiency (%)=(Qem/(Qex-Qref))×100. Such as the α-type silicon aluminum oxynitride phosphor of claim 1, in which, The wavelength of the excitation light is changed from 455nm to 700nm, and the number of excitation light photons (Qex) and the number of excitation reflected light photons (Qref) are calculated from the spectrum in the wavelength range of 695~710nm, except that the procedure is the same as above To proceed, the light absorption rate with respect to the excitation light with a wavelength of 700nm calculated according to the following formula is 10% or less; Light absorption rate=(%)((Qex-Qref)/Qex)×100. Such as the α-type silicon aluminum oxynitride phosphor of claim 1 or 2, in which, The diffuse reflectance of excitation light with a wavelength of 800 nm is more than 90%. For example, the α-type silicon aluminum oxynitride phosphor of claim 1 or 2, wherein the α-type silicon aluminum oxynitride particles are α-type silicon aluminum nitride containing Eu elements represented by the following general formula (1) Oxide composition; (M) _m(1-x)/p (Eu) _mx/2 (Si) _12-(m+n) (Al) _m+n (O) _n (N) _16-n ･･通Formula (1) In the above general formula (1), M represents one or more elements selected from the group consisting of Li, Mg, Ca, Y and lanthanides excluding La and Ce, and p is M The valence of the element means 0<x<0.5, 1.5≦m≦4.0, 0≦n≦2.0. Such as the α-type silicon aluminum oxynitride phosphor of claim 1 or 2, in which, In the volume frequency particle size distribution of the α-type silicon aluminum oxynitride phosphor measured by the laser diffraction scattering method, when the particle size at which the cumulative value becomes 90% is taken as D90, D90 is 5.5 μm or more and 35.0 μm or less. Such as the α-type silicon aluminum oxynitride phosphor of claim 1 or 2, in which, D50 is 1.0 μm or more and 10.0 μm or less. A light emitting component, including: Light-emitting element, and The wavelength converter converts the light irradiated from the light-emitting element and emits light; The wavelength conversion body has the α silicon aluminum oxynitride phosphor according to any one of claims 1 to 6. A light-emitting device is provided with the light-emitting member as claimed in claim 7.

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