Fluorescent body powder and light-emitting device

Abstract

This fluorescent body powder comprises fluorescent body particles represented by general formula (Ca1-x-ySrxEuy)AlSiN3 in which 0≤x<1, 0<y<1, and 1-x-y>0 are satisfied. In a cumulative distribution (1) of volume-based particle sizes determined by a laser diffraction scattering method and measured after an ultrasonic homogenization treatment is performed on a dispersion of the fluorescent body powder, when the particle sizes at which the integrated value from the small particle size side reaches 50% and 97% of the total are respectively defined as Dy50 and Dy97, and, in a cumulative distribution (2) of volume-based particle sizes determined by the laser diffraction scattering method but measured without performing said ultrasonic homogenization treatment, when the particle size at which the integrated value from the small particle size side reaches 97% of the total is defined as Dx97, Dx97 / Dy97 is 5.0 or less and Dy50 is less than 1.7 µm.

Description

Phosphor powder and light-emitting device

[0001] The present disclosure relates to phosphor powders and light emitting devices.

[0002] Phosphor particles with reduced particle size are used as color conversion materials in micro LED displays that achieve high-brightness, high-resolution light emission, etc. Patent Document 1 discloses phosphor particles in which phosphor powder is pulverized and decanted under appropriate conditions to reduce the particle size while suppressing particle aggregation.

[0003] International Publication No. 2022 / 118600

[0004] If phosphor powder with a small particle size aggregates, the dispersibility of the phosphor powder decreases, which may lead to a decrease in the uniformity of the coated surface. On the other hand, if aggregation of the phosphor powder can be suppressed, the dispersibility of the phosphor powder improves, enabling highly uniform coating.

[0005] The tendency of powder particles to agglomerate, i.e., the tendency of particles to adhere to each other, is expressed by the magnitude of the relative adhesive force, calculated as the ratio of the cohesive force, such as van der Waals force, to the separating force, such as gravity (≒ van der Waals force / gravity). Here, van der Waals force is proportional to particle size, and gravity is proportional to the cube of the particle size, so the relative adhesive force is inversely proportional to the square of the particle size. Therefore, generally, the smaller the particle size, the greater the relative adhesive force, and the more likely the particles are to agglomerate. Furthermore, if the particle size is made too small, there is a concern that the amount of ultrafine powder in the powder will increase, resulting in a decrease in light absorption. The present disclosure provides a phosphor powder that can suppress particle agglomeration even with a small particle size and has high light absorption. It also provides a light-emitting device that includes a phosphor powder that can suppress particle agglomeration even with a small particle size and has high light absorption.

[0006] One aspect of the present disclosure provides the following phosphor powder:

[0007] [1] General formula (Ca １－ｘ－ｙ Sr ｘ EU ｙ ) AlSiN ３wherein 0≦x<1, 0<y<1, 1-x-y>0, and wherein in a cumulative distribution (1) of volumetric particle diameters measured by a laser diffraction / scattering method after subjecting a dispersion of the phosphor powder to ultrasonic homogenization, Dy50 and Dy97 are the particle diameters at which the integrated values ​​from small particle diameters reach 50% and 97% of the total, respectively, and in a cumulative distribution (2) of volumetric particle diameters measured by a laser diffraction / scattering method without subjecting the phosphor powder to ultrasonic homogenization, Dx97 is the particle diameter at which the integrated value from small particle diameters reaches 97% of the total, where Dx97 / Dy97 is 5.0 or less and Dy50 is less than 1.7 μm.

[0008] The phosphor powder of [1] above has a Dx97 / Dy97 ratio of 5.0 or less and a Dy50 ratio of less than 1.7 μm. Dy represents the particle diameter calculated from the cumulative particle diameter distribution (1) after ultrasonic homogenization under specified conditions, and Dx represents the particle diameter calculated from the cumulative particle diameter distribution (2) before ultrasonic homogenization. By performing ultrasonic homogenization, it is possible to measure the particle diameter after agglomeration due to physical bonding of agglomerated particles has been deaggregated. Therefore, the smaller the Dx97 / Dy97 value, the smaller the difference in particle diameter between agglomerated particles and deaggregated particles, and the phosphor powder can be said to have reduced aggregation. Therefore, the phosphor powder of [1] above has a small particle diameter while suppressing aggregation. Such phosphor powder contains little ultrafine powder, which causes aggregation. This reduces light scattering due to excessive surface area of ​​the phosphor powder. Therefore, such phosphor powder has high light absorptivity.

[0009] The phosphor powder of the above [1] may be any of the following [2] to [7].

[0010] [2] When measuring X-ray diffraction, the diffraction intensity at 2θ of 32° is I １ , the diffraction intensity at 2θ of 33° is I ２ , and the maximum peak intensity detected in the 2θ range of 32 to 33° is I ０ When I ０ / [(I １ -I２ ) / 2] is 2.0 or less.

[0011] The phosphor powder of [2] above has a sufficiently reduced amount of heterogeneous crystal phases in the phosphor. Such phosphor powder can suppress the light absorption inhibition caused by heterogeneous phases. Therefore, the phosphor powder of [2] above has a higher light absorption rate.

[0012] [3] The phosphor powder according to [1] or [2], wherein Dx90 is the particle diameter when the integrated value from small particle diameters reaches 90% of the total in the cumulative distribution (2), and Dy90 is the particle diameter when the integrated value from small particle diameters reaches 90% of the total in the cumulative distribution (1), and Dx90 / Dy90 is 2.0 or less.

[0013] The phosphor powder of the above [3] is more inhibited from agglomerating, and has a higher light absorption rate.

[0014] [4] In the cumulative distribution (1), when the particle diameter when the integrated value from small particle diameters reaches 10% of the whole is defined as Dy10, Dy10 is 0.4 μm or more. [5] The phosphor powder according to any one of [1] to [3].

[0015] The phosphor powder of [4] above has a further sufficient reduction in ultrafine particles with small particle diameters that cause aggregation. Such phosphor powder can further suppress light scattering. Therefore, such phosphor powder has a higher light absorption rate.

[0016] [5] The phosphor powder according to any one of [1] to [4], which has a light absorptance of 80.5% or more at a wavelength of 455 nm.

[0017] The phosphor powder of [5] above has a sufficiently high light absorption rate, and therefore can be suitably used as a wavelength converter for light-emitting elements such as mini-LEDs and micro-LEDs.

[0018] [6] The phosphor powder according to any one of [1] to [5], wherein the oxygen content is 6.10 mass % or less.

[0019] The phosphor powder of [6] above has a sufficiently reduced oxygen content. Such phosphor powder has a sufficiently reduced amount of impurities. Therefore, it has a higher light intensity.

[0020] [7] The phosphor powder according to any one of [1] to [6], wherein A is the oxygen content of the phosphor powder, and B is the oxygen content of the phosphor powder after storing the phosphor powder for 250 hours in an environment at a temperature of 85°C and a humidity of 85%. The phosphor powder according to any one of [1] to [6], wherein B / A is 3.00 or less.

[0021] The phosphor powder of [7] above can suppress an increase in oxygen content after storage for 250 hours in an environment at a temperature of 85°C and a humidity of 85%. Such phosphor powder can suppress performance degradation even in harsh environments. Therefore, the phosphor powder of [7] above has high reliability.

[0022] One aspect of the present disclosure provides a light-emitting device according to the following [8] or [9].

[0023] [8] A light emitting device comprising a light emitting element that emits primary light, and a wavelength converter that absorbs a part of the primary light and emits secondary light having a wavelength longer than the wavelength of the primary light, wherein the wavelength converter comprises the phosphor powder according to any one of [1] to [7]. [9] The light emitting device according to [8], wherein the light emitting element comprises at least one selected from the group consisting of a mini LED and a micro LED.

[0024] The light-emitting device of [8] above contains the phosphor powder of [1] to [7] above as a wavelength converter. Therefore, it can exhibit excellent color rendering properties. Furthermore, the light-emitting device of [9] above includes at least one light-emitting element selected from the group consisting of a mini-LED and a micro-LED. Therefore, it is possible to provide a light-emitting device that can achieve high-brightness and high-resolution light emission.

[0025] According to the present disclosure, it is possible to provide a phosphor powder having high light absorptance, which can suppress particle aggregation even when the particle size is small, and it is also possible to provide a light emitting device including a phosphor powder having high light absorptance, which can suppress particle aggregation even when the particle size is small.

[0026] 1 is a diagram showing a light emitting device. FIG. 2 is a diagram showing peaks when the phosphor powders of Example 1 and Comparative Examples 5 and 6 are measured by X-ray diffraction.

[0027] Hereinafter, embodiments of the present disclosure will be described. However, the following embodiments are merely examples for explaining the present disclosure and are not intended to limit the present disclosure to the following content. The upper or lower limit of a numerical range specified in this disclosure may be replaced with any value shown in the examples. The numerical range exemplified as "a to b" is a numerical range inclusive of a and b, with a lower limit being a and an upper limit being b. Furthermore, the upper and lower limits individually stated may be arbitrarily combined. Unless otherwise specified, the materials or components exemplified in this disclosure may be used alone or in combination of two or more.

[0028] <Phosphor Powder> The phosphor powder according to one embodiment is a phosphor powder having a general formula (Ca １－ｘ－ｙ Sr ｘ EU ｙ ) AlSiN ３ The phosphor powder includes phosphor particles having a particle diameter of 0≦x<1, 0<y<1, 1-x-y>0, and the particle diameters at which the cumulative values ​​from the smallest particle diameters reach 50% and 97% of the total in a volume-based particle diameter cumulative distribution (1) measured by a laser diffraction / scattering method after ultrasonic homogenization of a phosphor powder dispersion are defined as Dy50 and Dy97, respectively. Furthermore, the particle diameters at which the cumulative values ​​from the smallest particle diameters reach 97% of the total in a volume-based particle diameter cumulative distribution (2) measured by a laser diffraction / scattering method without ultrasonic homogenization are defined as Dx97. The Dx97 / Dy97 ratio is 5.0 or less, and the Dy50 is less than 1.7 μm. This phosphor powder has a small particle diameter and suppresses aggregation. Therefore, ultrafine particles that cause aggregation are reduced. This suppresses light scattering due to excessively high surface area of ​​the phosphor powder. Therefore, this phosphor powder has a high light absorptivity.

[0029] General formula (Ca １－ｘ－ｙ Sr ｘ EU ｙ ) AlSiN ３The phosphor particles having 0≦x<1, 0<y<1, 1-x-y>0 are at least one phosphor particle selected from the group consisting of CASN and SCASN. Generally, CASN refers to a phosphor particle having a main crystalline phase of CaAlSiN ３ On the other hand, the main crystalline phase is CaAlSiN ３ The crystal structure of SCASN is the same as that of CaAlSiN. ３ Ca ２＋ A part of Eu acts as a luminescence center. ２＋ By being substituted with Ca, it functions as a red-emitting phosphor. Therefore, CASN and SCASN are used as phosphors that convert light with a low wavelength such as blue light into light with a high wavelength such as red light. The phosphor powder in the present disclosure means an aggregate containing a plurality of such phosphor particles. １－ｘ－ｙ Sr ｘ EU ｙ ) AlSiN ３ The values ​​of x and y can be determined, for example, by quantitative analysis using an ICP emission spectrometer.

[0030] Ultrasonic homogenization of a phosphor powder dispersion is a process for breaking down aggregations between particles in the phosphor powder. In this disclosure, aggregated particles are sometimes referred to as secondary particles, and unagglomerated particles are sometimes referred to as primary particles. Homogenization breaks down the physical bonds between the secondary particles of the phosphor powder, converting them into primary particles. Therefore, by comparing the particle diameters at a predetermined integrated value in the cumulative volume-based particle diameter distribution of the phosphor powder, which can be measured by laser diffraction / scattering, before and after ultrasonic homogenization, it is possible to determine whether the primary particles of the phosphor powder are agglomerated.

[0031] Ultrasonic homogenization can be performed, for example, by the following method. A dispersion of 30 mg of phosphor powder dispersed in 100 mL of a 0.2% by mass aqueous solution of sodium hexametaphosphate is placed in a cylindrical container with a bottom inner diameter of 5.5 cm. Next, the transducer (a cylindrical tip with an outer diameter of 20 mm) of an ultrasonic homogenizer is inserted from above the dispersion, and with the transducer immersed to a depth of 1.0 cm, ultrasonic waves are irradiated onto the dispersion at a frequency of 19.5 kHz and an output of 150 W for 3 minutes. Ultrasonic homogenization of phosphor powder can be performed using the method described above.

[0032] The laser diffraction / scattering method can be measured in accordance with the method described in JIS Z 8825:2013 "Particle size analysis - Laser diffraction / scattering method." A laser diffraction / scattering particle size distribution analyzer (manufactured by Beckman Coulter, Inc., product name: LS-13 320) or the like can be used for the measurement. In the present disclosure, the cumulative distribution of volume-based particle sizes measured by the laser diffraction / scattering method after subjecting a dispersion of phosphor powder to ultrasonic homogenization is referred to as cumulative distribution (1). Furthermore, the cumulative distribution of volume-based particle sizes measured by the laser diffraction / scattering method before subjecting the dispersion to ultrasonic homogenization is referred to as cumulative distribution (2).

[0033] The Dx97 / Dy97 ratio of the phosphor powder is 5.0 or less. Such phosphor powder has a low content of ultrafine powder and suppressed aggregation, resulting in high light absorption. Dx97 / Dy97 may be 4.0 or less, 3.0 or less, 2.0 or less, or 1.5 or less. Phosphor powder with a Dx97 / Dy97 ratio in this range has further suppressed aggregation, sufficiently reduced ultrafine powder, and thus has even higher light absorption. Dx97 / Dy97 may be 1.0 or more. The Dx97 / Dy97 range may be, for example, 1.0 to 5.0, 1.0 to 4.0, 1.0 to 3.0, 1.0 to 2.0, or 1.0 to 1.5.

[0034] Dx97 may be 20.0 μm or less, 10.0 μm or less, or 5.0 μm or less. Having Dx97 in this range suppresses aggregation of the phosphor powder, allowing for even smaller particle diameters. Dx97 may be 2.5 μm or more, or 3.0 μm or more. Having Dx97 in this range reduces ultrafine particles in the phosphor powder, suppresses light scattering, and further increases light absorptance. The range of Dx97 may be, for example, 2.5 to 20.0 μm, 2.5 to 10.0 μm, 2.5 to 5.0 μm, 3.0 to 20.0 μm, 3.0 to 10.0 μm, or 3.0 to 5.0 μm.

[0035] Dy97 may be 10.0 μm or less, 5.0 μm or less, 4.0 μm or less, or 3.0 μm or less. By having Dy97 in this range, the particle size of the phosphor can be further reduced. Dy97 may be 1.5 μm or more, or 2.0 μm or more. By having Dy97 in this range, the amount of ultrafine powder in the phosphor powder can be reduced, light scattering can be suppressed, and light absorption can be further increased. The range of Dy97 may be, for example, 1.5 to 10.0 μm, 1.5 to 5.0 μm, 1.5 to 4.0 μm, 1.5 to 3.0 μm, 2.0 to 10.0 μm, 2.0 to 5.0 μm, 2.0 to 4.0 μm, or 2.0 to 3.0 μm.

[0036] In the cumulative distribution (2), the particle diameter when the integrated value from the small particle diameter reaches 90% of the total is defined as Dx90, and in the cumulative distribution (1), the particle diameter when the integrated value from the small particle diameter reaches 90% of the total is defined as Dy90. Dx90 / Dy90 may be 2.0 or less, 1.5 or less, 1.2 or less, or 1.1 or less. Such phosphor powders have higher light absorption rates because aggregation is further suppressed. Dx90 / Dy90 may be 1.0 or more. The range of Dx90 / Dy90 may be, for example, 1.0 to 2.0, 1.0 to 1.5, 1.0 to 1.2, or 1.0 to 1.1.

[0037] Dx90 may be 10.0 μm or less, 5.0 μm or less, 3.0 μm or less, or 2.5 μm or less. Having Dx90 in this range reduces secondary particles formed by aggregation of the phosphor powder, thereby further reducing the particle size. Dx90 may be 1.0 μm or more, or 1.5 μm or more. Having Dx90 in this range reduces ultrafine particles of the phosphor powder, suppresses light scattering, and further increases the light absorption rate. The Dx90 range may be, for example, 1.0 to 10.0 μm, 1.0 to 5.0 μm, 1.0 to 3.0 μm, 1.0 to 2.5 μm, 1.5 to 10.0 μm, 1.5 to 5.0 μm, 1.5 to 3.0 μm, or 1.5 to 2.5 μm.

[0038] Dy90 may be 3.5 μm or less, 3.0 μm or less, 2.5 μm or less, or 2.0 μm or less. By having Dy90 in this range, the particle size of the phosphor can be further reduced. Dy90 may be 1.0 μm or more, or 1.5 μm or more. By having Dy90 in this range, the amount of ultrafine powder in the phosphor powder can be reduced, light scattering can be suppressed, and light absorption can be further increased. The range of Dy90 may be, for example, 1.0 to 3.5 μm, 1.0 to 3.0 μm, 1.0 to 2.5 μm, 1.0 to 2.0 μm, 1.5 to 3.5 μm, 1.5 to 3.0 μm, 1.5 to 2.5 μm, or 1.5 to 2.0 μm.

[0039] The Dy50 of the phosphor powder is less than 1.7 μm, and may be 1.6 μm or less, 1.3 μm or less, or 1.0 μm or less. Because such phosphor powders can have a sufficiently small particle size, they are suitable for use as wavelength converters in small-sized light-emitting devices such as mini-LEDs and micro-LEDs. The Dy50 may be 0.6 μm or more. The Dy50 range may be, for example, 0.6 μm or more but less than 1.7 μm, 0.6 to 1.6 μm, 0.6 to 1.3 μm, or 0.6 to 1.0 μm.

[0040] In the cumulative distribution (2), when the particle diameter when the integrated value from the small particle diameter reaches 10% of the total is defined as Dy10, Dy10 may be 0.4 μm or more, or may be 0.5 μm or more. Phosphor powders with Dy10 in this range have a sufficiently reduced amount of ultrafine powder. Because the amount of ultrafine powder is sufficiently reduced, light scattering caused by an excessively high surface area of ​​the phosphor powder can be suppressed. Therefore, such phosphor powders have a higher light absorption rate. Dy10 may be 1.0 μm or less. An example of the range of Dy10 may be 0.4 to 1.0 μm, or 0.5 to 1.0 μm.

[0041] When measuring the phosphor powder by X-ray diffraction, the diffraction intensity at 2θ of 32° is I １ , the diffraction intensity at 2θ of 33° is I ２ , and the maximum peak intensity detected in the 2θ range of 32 to 33° is I ０ When I ０ / [(I １ -I ２ ) / 2] may be 2.0 or less, or may be 1.5 or less. In such a phosphor powder, the amount of heterophases in the crystal is sufficiently reduced, and the inhibition of light absorption by the heterophases can be suppressed. Therefore, the phosphor powder has a higher light absorption rate. ０ / [(I １ -I ２ ) / 2] may be 0.1 or more, 0.5 or more, or 1.0 or more. ０ / [(I １ -I ２ ) / 2] may be, for example, 0.1 to 2.0, 0.1 to 1.5, 0.5 to 2.0, 0.5 to 1.5, 1.0 to 2.0, or 1.0 to 1.5.

[0042] X-ray diffraction measurement can be performed using, for example, an X-ray diffractometer (UItimal V, manufactured by Rigaku Corporation) with a Cu-Ka ray as the X-ray source, a diffraction angle of 10°<2θ<75°, a voltage of 40 kV, and a current of 40 mA. The peak intensity value represents the height of the peak relative to the baseline.

[0043] The oxygen content A of the phosphor powder may be 6.10% by mass or less, or 6.05% by mass or less. The oxygen content in this disclosure refers to the oxygen content as a total amount of oxygen. The oxygen content can be measured using a commercially available oxygen / nitrogen analyzer. When the oxygen content A is within this range, the oxygen content in the phosphor powder is sufficiently reduced. Such phosphor powders have a sufficiently reduced amount of impurities. Therefore, they have a higher light intensity. The oxygen content A may be 3.00% by mass or more, or 3.20% by mass or more. The range of the oxygen content A may be, for example, 3.00 to 6.10% by mass, 3.00 to 6.05% by mass, 3.20 to 6.10% by mass, or 3.20 to 6.05% by mass.

[0044] The oxygen content B after storing the phosphor powder for 250 hours in an environment at a temperature of 85°C and humidity of 85% may be 10.0% by mass or less, or may be 9.0% by mass or less. By keeping the oxygen content within this range, the oxygen content does not increase even when stored in a harsh environment, and a decrease in light absorption can be suppressed. The oxygen content B may be 5.00% by mass or more. An example of the range of the oxygen content B may be 5.00 to 10.0% by mass, or 5.00 to 9.0% by mass.

[0045] The ratio B / A may be 3.00 or less, or 2.00 or less. Such phosphor powders do not increase in oxygen content even when stored in harsh environments, and reduction in light absorption can be suppressed. Therefore, they have high reliability. The ratio B / A may be 1.00 or more. The range of the ratio B / A may be, for example, 1.00 to 3.00, or 1.00 to 2.00.

[0046] The light absorptance C of the phosphor powder at a wavelength of 455 nm may be 80.5% or more, or may be 81.0% or more. When the light absorptance C at a wavelength of 455 nm is in this range, blue light is not unnecessarily transmitted and the light absorptance is sufficiently high, making it suitable for use as a wavelength converter in light-emitting elements such as mini-LEDs and micro-LEDs. The light absorptance at a wavelength of 455 nm can be measured, for example, using an MCPD-7000 manufactured by Otsuka Electronics Co., Ltd.

[0047] When the light absorptance of the phosphor powder at a wavelength of 455 nm is C and the light absorptance of the phosphor powder at a wavelength of 455 nm after storing the phosphor powder for 250 hours in an environment at a temperature of 85°C and a humidity of 85% is D, D / C may be 0.95 to 1.00, or may be 0.98 to 1.00. By keeping D / C within this range, it is possible to suppress a decrease in light absorptance and maintain performance even when stored in a harsh environment. Therefore, such phosphor powder has high reliability.

[0048] A method for producing a phosphor powder according to the present disclosure is described below. The method for producing a phosphor powder includes a mixing step in which raw material powders are mixed to obtain a mixed powder, a firing step in which the mixed powder is fired to obtain a fired product, and an acid treatment step in which the fired product is heat-treated in an acid solution having an acid concentration of less than 0.500 mol / L. By using an acid solution having an acid concentration of less than 0.500 mol / L in the acid treatment step, it is possible to form an oxide film on the particle surface while suppressing hydrolysis of the phosphor crystals. This makes it possible to obtain a phosphor powder that suppresses aggregation and sufficiently suppresses the generation of ultrafine powder. The phosphor powder obtained by the above manufacturing method has high light absorption.

[0049] In the mixing step, raw material powders are mixed to form a mixed powder. Examples of raw material powders include europium compounds, strontium compounds such as strontium nitride, calcium compounds such as calcium nitride, silicon nitrides such as α-type silicon nitride, and aluminum nitride. Each of the raw material powders is preferably in the form of a powder.

[0050] Examples of europium compounds include oxides containing europium, hydroxides containing europium, nitrides containing europium, oxynitrides containing europium, and halides containing europium. These can be used alone or in combination of two or more. Among these, it is preferable to use europium oxide, europium nitride, and europium fluoride alone, and it is more preferable to use europium oxide alone.

[0051] In the firing step described below, europium is divided into those that form a solid solution with the CASN or SCASN crystal, those that volatilize, and those that remain as heterophase components. The heterophase components must be removed in the acid treatment step described below to reduce the light absorption rate.

[0052] In the mixing step, the mixed powder can be obtained, for example, by dry-mixing the raw material powders, or by wet-mixing the raw material powders in an inert solvent that does not substantially react with each raw material powder, followed by removing the solvent. Examples of mixing devices that can be used include a small mill mixer, a V-type mixer, a rocking mixer, a ball mill, and a vibration mill. After mixing using the device, agglomerates can be removed using a sieve, if necessary, to obtain the mixed powder.

[0053] In order to prevent deterioration of the raw material powder and unintended incorporation of oxygen, the mixing step is preferably carried out in a nitrogen atmosphere and in an environment with as little moisture (humidity) as possible.

[0054] In the firing step, the mixed powder obtained in the mixing step is fired to obtain a fired product. The firing temperature in the firing step is not particularly limited, but is preferably 1800°C or higher and 2100°C or lower, and more preferably 1900°C or higher and 2000°C or lower. When the firing temperature is above the lower limit, grain growth of the phosphor particles progresses more effectively. Therefore, the light absorption rate can be further improved. When the firing temperature is below the upper limit, decomposition of the phosphor particles can be further suppressed. Therefore, the light absorption rate can be further improved.

[0055] Other conditions in the firing step, such as the temperature rise time, temperature rise rate, heating retention time, and pressure, are not particularly limited and may be adjusted appropriately depending on the raw materials used. The heating retention time is preferably 3 hours or more and 30 hours or less, and the pressure is preferably 0.6 MPa or more and 10 MPa or less. From the viewpoint of controlling the oxygen concentration, the firing step is preferably carried out in a nitrogen gas atmosphere. That is, the firing step is preferably carried out in a nitrogen gas atmosphere with a pressure of 0.6 MPa or more and 10 MPa or less.

[0056] In the firing step, the mixed powder can be fired, for example, by filling the mixed powder into a container made of a material (such as tungsten) that does not react with the mixed powder during firing and heating it in a nitrogen atmosphere.

[0057] The firing step may include an annealing step in which the fired product is further heated at a temperature lower than the firing temperature. The annealing step is preferably performed in an atmosphere containing at least one gas selected from the group consisting of a rare gas and an inert gas. The rare gas may contain, for example, argon, helium, or the like, or may contain argon or consist of argon. The inert gas may contain, for example, nitrogen, or the like, or may consist of nitrogen.

[0058] The annealing step may be performed under atmospheric pressure or under pressure. When the annealing step is performed under a pressure environment, the pressure in the annealing step may be, for example, 0.10 MPa or more, or 0.12 MPa or more. The pressure in the annealing step may be, for example, 0.95 MPa or less, 0.70 MPa or less, 0.50 MPa or less, or 0.30 MPa or less. The pressure in the annealing step may be, for example, 0.10 to 0.95 MPa. Pressure in the present disclosure refers to absolute pressure.

[0059] In the annealing step, the mixture of the fired product obtained in the above step and other additives may be heat-treated. The method for preparing the mixture may be the same as that in the above mixing step.

[0060] The annealing temperature in the annealing step may be, for example, 1350° C. or higher, 1400° C. or higher, 1450° C. or higher, 1500° C. or higher, or 1550° C. or higher. The annealing temperature in the annealing step may be, for example, 1850° C. or lower, 1830° C. or lower, 1820° C. or lower, 1800° C. or lower, or lower than 1800° C. The annealing temperature in the annealing step may be, for example, 1350 to 1850° C. or 1400 to 1850° C.

[0061] The heating time in the annealing step may be, for example, 0.5 hours or more, 1.0 hour or more, 1.5 hours or more, 3.0 hours or more, or 4.0 hours or more. The heating time in the annealing step may be, for example, 30.0 hours or less, 20.0 hours or less, 10.0 hours or less, 8.0 hours or less, or 5.0 hours or less. The heating time in the annealing step may be, for example, 0.5 to 30.0 hours, 1.5 to 10.0 hours, or 4.0 to 8.0 hours.

[0062] The fired product obtained through the firing step, or the firing step and the annealing step, is a granular or lumpy fired product. The fired product may be made into a powder by using the crushing step, the pulverizing step, and the classification step, either alone or in combination, as described below.

[0063] The crushing step is a step of crushing the sintered product obtained in the firing step or the firing step and the annealing step when the sintered product is in a lumpy state. For example, a mortar or a general crusher may be used for crushing.

[0064] The pulverization process is a process in which the obtained fired product is pulverized to adjust the particle size. A general pulverizer can be used in the pulverization process. Examples of general pulverizers and disintegrators include a ball mill, a jet mill, and a Henschel mixer. From the viewpoint of suppressing the occurrence of scratches, cracks, etc. on the surface of the fired product, it is desirable to perform the pulverization under gentle conditions. From the viewpoint of pulverization under gentle conditions, for example, it is desirable to perform the pulverization process by wet ball mill pulverization in the presence of a medium such as ion-exchanged water. Furthermore, zirconia balls can be used in the ball mill. The particle size of the phosphor powder can be controlled by adjusting the pulverization time in the pulverization process.

[0065] The manufacturing method of phosphor powder may include a classification step. By including the classification step, the optical properties of the resulting phosphor powder can be further improved. The classification step may be performed, for example, by decantation. The classification step is performed by adding the material to be treated (e.g., a fired product that has been subjected to a pulverization step) to a dispersion medium, preparing and stirring a dispersion, precipitating the fired product in the dispersion, and removing the supernatant. After removing the supernatant, the precipitate is collected by filtration and dried to obtain a powdered fired product from which fine particles have been removed. In the classification step, the preparation of the dispersion and the removal of the supernatant may be repeated. Examples of dispersion media include distilled water and an aqueous solution of sodium hexametaphosphate. The particle size of the phosphor powder can be controlled by adjusting the classification point in the classification step.

[0066] In the acid treatment step, the fired product obtained through the above steps is heat-treated in an acid solution with a concentration of less than 0.50 mol / L. This allows at least some of the impurities that do not contribute to light emission to be removed. It also allows the removal of heterogeneous europium components. Furthermore, an oxide film is formed on the surface of the phosphor particles, improving the reliability of the phosphor powder.

[0067] The acid solution may be an aqueous solution containing at least one acid selected from hydrofluoric acid, sulfuric acid, phosphoric acid, hydrochloric acid, and nitric acid, with hydrochloric acid being particularly preferred.

[0068] The acid concentration of the acid solution is less than 0.500 mol / L, and may be 0.400 mol / L or less, or 0.300 mol / L or less. By ensuring that the acid concentration of the acid solution is within this range, an oxide film can be formed on the surface of the phosphor particles while preventing the generation of ultrafine powder due to hydrolysis caused by excess acid. The phosphor powder obtained by such an acid treatment process has high light absorption. Furthermore, the acid concentration of the acid solution may be 0.0100 mol / L or more. For example, the acid concentration of the acid solution may be 0.0100 mol / L or more and less than 0.500 mol / L.

[0069] The acid treatment can be carried out by dispersing the fired product in the acid solution. The stirring time is, for example, 5 minutes to 6 hours, preferably 30 minutes to 3 hours. The stirring temperature can be, for example, 25°C to 90°C, 40°C to 90°C, preferably 50°C to 70°C.

[0070] After the acid treatment step, substances other than the phosphor particles may be separated by filtration, and substances adhering to the phosphor particles may be washed with water. Also, a crushing step and a classification step may be performed before or after the acid treatment step to adjust the particle size of the phosphor powder.

[0071] The phosphor powder of this embodiment can be manufactured through the above process. However, the above manufacturing method is only an example and is not limited thereto. The phosphor powder of this embodiment can suppress particle aggregation even with a small particle diameter and has high light absorption. Such phosphor powder can be suitably used in light-emitting devices including mini-LEDs, micro-LEDs, etc.

[0072] <Light-emitting device> Fig. 1 is a diagram showing a light-emitting device 10. The light-emitting device 10 includes a light-emitting element 20 that emits primary light, and a wavelength converter 30 that absorbs part of the primary light and emits secondary light having a wavelength longer than that of the primary light. The wavelength converter 30 contains the above-mentioned phosphor powder. The wavelength converter 30 may be provided in contact with an upper portion of the light-emitting element 20.

[0073] The light emitting element 20 emits excitation light and may be a blue LED. A terminal 40 is provided on the bottom of the light emitting element 20. When the terminal 40 is connected to a power source, the light emitting element 20 can emit light.

[0074] The excitation light emitted from the light-emitting element 20 may be wavelength-converted by the wavelength converter 30. When the excitation light is blue light, the blue light is wavelength-converted to red light by the wavelength converter 30 including CASN and / or SCASN.

[0075] The wavelength converter 30 may be composed of the above-mentioned phosphor particles and a sealing material that seals the phosphor particles. Various curable resins can be used as the sealing material. Any curable resin can be used as long as it is sufficiently transparent and can obtain the optical characteristics required for the display. An example of the sealing material is a silicone resin. Silicone resin is preferably used from the viewpoints of transparency and heat resistance.

[0076] The light-emitting element 20 includes at least one element selected from the group consisting of a mini LED and a micro LED. The size of the mini LED may be 100 to 2000 μm, 200 to 1000 μm, or 300 to 800 μm. On the other hand, the size of the micro LED may be 1 μm or more and less than 100 μm, 10 to 80 μm, or 30 to 60 μm. By ensuring that the size of the mini LED or micro LED is within this range, high-brightness, high-precision light emission can be achieved in displays and the like equipped with the light-emitting device 10.

[0077] Although several embodiments of the present disclosure have been described above, the present disclosure is not limited to the above-described embodiments.

[0078] The present disclosure will be described in more detail below with reference to examples and comparative examples, but the present disclosure is not limited to the following examples.

[0079] Example 1 The following raw material powders were prepared in a glove box maintained in a nitrogen atmosphere with a moisture content of 1 mass ppm or less and an oxygen content of 1 mass ppm or less.

[0080] α-type silicon nitride powder (Si ３ N ４ , SN-E10 grade, manufactured by UBE Corporation) Calcium nitride powder (Ca ３ N ２ , manufactured by Taiheiyo Cement Corporation) Aluminum nitride powder (AlN, E grade, manufactured by Tokuyama Corporation) Strontium nitride powder (Sr ２ N, manufactured by Materion) Europium oxide powder (Eu ２ O ３ , manufactured by Nippon Yttrium Co., Ltd.)

[0081] Si ３ N ４ 25.65% by mass, Ca ３ N ２ 2.98 mass%, AlN 22.49 mass%, Sr ２ 43.09% by mass of N and Eu ２ O ３ The raw material powders were mixed using a small mill mixer so that the content of ZnO was 5.79% by mass, and after mixing, the mixture was passed through a sieve with a mesh size of 150 μm to remove aggregates, thereby obtaining a mixed powder. The mixed powder was then filled into a tungsten container with a lid.

[0082] The container filled with the mixed powder was removed from the glove box and quickly placed in an electric furnace equipped with a carbon heater. The furnace was thoroughly evacuated to 0.1 Pa or less. Heating was initiated while continuing the evacuation. After reaching 850 °C, nitrogen gas was introduced into the furnace, and the atmospheric pressure in the furnace was kept constant at 0.8 MPaG. Even after the introduction of nitrogen gas began, the temperature continued to rise to 1950 °C. The mixture was fired at this firing temperature (1950 °C) for 4 hours, after which heating was terminated and the mixture was cooled. After cooling to room temperature, the red lumps recovered from the container were crushed in a mortar (crushing process) and passed through a sieve with 250 μm openings to obtain a powder (fired product). The resulting powder was then placed in a ball mill and subjected to wet grinding to prepare a pulverized product (grinding process). The pulverized product was removed and precipitated in distilled water. Further distilled water was then added and stirred. After stirring, the pulverized product was allowed to settle, and the supernatant and fine powder were removed. This process of adding distilled water, stirring, and removing the supernatant and fine powder was repeated until the supernatant became transparent (classification step). The resulting precipitate was filtered and then dried in the air. During the classification step, the pH of the distilled water added to the pulverized material was maintained at 8 or less.

[0083] An acid treatment step was further carried out to remove impurities that may have been generated during firing. Specifically, the fired product obtained through the above classification step was immersed in hydrochloric acid with a molar concentration of 0.052 mol / L so that the powder concentration was 26.7% by mass, and then subjected to acid treatment by stirring for 1 hour while heating. The powder and hydrochloric acid solution were then separated by filtration at room temperature of approximately 25°C, and the powder was washed with pure water. The powder washed with pure water was then dried for 12 hours in a dryer at 100°C or higher and 120°C or lower. The phosphor powder of Example 1 was obtained through the above procedure.

[0084] Example 2 A phosphor powder was prepared in the same manner as in Example 1, except that hydrochloric acid with a molar concentration of 0.286 mol / L was used for the acid treatment.

[0085] Example 3 A phosphor powder was produced in the same manner as in Example 2, except that the processing conditions for crushing, pulverizing, classifying, etc. of the fired product obtained through the firing step were adjusted.

[0086] Example 4 A phosphor powder was prepared in the same manner as in Example 1, except that hydrochloric acid with a molar concentration of 0.403 mol / L was used for the acid treatment.

[0087] Comparative Example 1 A phosphor powder was prepared in the same manner as in Example 1, except that hydrochloric acid with a molar concentration of 0.520 mol / L was used for the acid treatment.

[0088] Comparative Example 2 A phosphor powder was prepared in the same manner as in Example 1, except that hydrochloric acid with a molar concentration of 0.693 mol / L was used for the acid treatment.

[0089] Comparative Example 3 A phosphor powder was prepared in the same manner as in Example 1, except that hydrochloric acid with a molar concentration of 0.867 mol / L was used for the acid treatment.

[0090] Comparative Example 4 A phosphor powder was prepared in the same manner as in Example 1, except that hydrochloric acid with a molar concentration of 1.04 mol / L was used for the acid treatment.

[0091] Comparative Example 5 A phosphor powder was prepared in the same manner as in Example 1, except that hydrochloric acid with a molar concentration of 1.56 mol / L was used for the acid treatment.

[0092] Comparative Example 6 A phosphor powder was produced in the same manner as in Example 1, except that water was used instead of hydrochloric acid. That is, the phosphor powder of Comparative Example 6 was not subjected to the acid treatment step.

[0093] <X-ray Diffraction Measurement> Using an X-ray diffractometer (manufactured by Rigaku Corporation, product name: UItimal V), powder X-ray diffraction patterns of the phosphor particles of each Example and Comparative Example were measured using Cu-Kα radiation at a diffraction angle 2θ range of 10 to 75°, a voltage of 40 kV, and a current of 40 mA. The crystal structure was confirmed from the powder X-ray diffraction patterns, and the powder X-ray diffraction patterns of the phosphor particles of each Example and Comparative Example were found to be CaAlSiN ３ The diffraction pattern of the phosphor powders of each example and each comparative example was consistent with that of the crystal. １－ｘ―ｙ Sr ｘ EU ｙ ) AlSiN ３ and it was confirmed that the composition satisfies the conditions 0≦x<1, 0<y<1, and 1−x−y>0.

[0094] The results of X-ray diffraction measurements of Example 1, Comparative Example 5, and Comparative Example 6 are shown in Figure 2. As shown in Figure 2, in Comparative Example 6, which was not subjected to acid treatment, a peak was observed in the range of 32 to 33 degrees in the area surrounded by the dotted line, but in Example 1 and Comparative Example 5, which were subjected to acid treatment, the peak disappeared. The diffraction intensity at 2θ of 32 degrees measured by X-ray diffraction was expressed as I １ , the diffraction intensity at 2θ of 33° is I ２ , and the maximum peak intensity detected in the 2θ range of 32 to 33° is I ０ As, I ０ / [(I １ -I ２ ) / 2] was calculated. As a result, in Comparative Example 6, which was not subjected to acid treatment, the peak was I ０ / [(I １ -I ２ ) / 2] was 4.80. On the other hand, Example 1, which underwent acid treatment, had a value of 1.45. The other Examples and Comparative Examples, which underwent acid treatment, also had similar values. This indicates that when acid treatment is not performed, a different phase occurs in the crystal.０ / [(I １ -I ２ The calculation results of [XRD] / 2 are shown in the "XRD" column of Table 2.

[0095] <Particle size distribution measurement> In Examples 1 to 4 and Comparative Examples 1 to 5, the particle size distribution of the phosphor particles before the following treatments was measured using a Microtrac MT3300EXII (Microtrac Bell Corporation), a particle size measurement device that uses a laser diffraction / scattering method. From the obtained particle size distribution, the particle sizes Dx90 and Dx97, which correspond to the cumulative 90% and 97% from the small particle size in the volume-based cumulative distribution (2), were calculated. The results are shown in Table 1.

[0096] (Treatment) 30 mg of phosphor powder was dispersed in 100 mL of 0.2% by mass aqueous sodium hexametaphosphate solution, and the resulting dispersion was placed in a cylindrical container with an inner diameter of 5.5 cm. Next, the transducer (a cylindrical tip with an outer diameter of 20 mm) of an ultrasonic homogenizer was inserted from above the dispersion, and with the transducer immersed to a depth of 1.0 cm, the dispersion was irradiated with ultrasonic waves at a frequency of 19.5 kHz and an output of 150 W for 3 minutes.

[0097] Next, the particle size distribution of the phosphor powder subjected to the above treatment was measured, and from the obtained particle size distribution, the particle sizes Dy10, Dy50, Dy90, and Dy97 corresponding to the cumulative 10, 50, 90, and 97% from the small particle size in the volume-based cumulative distribution (1) were determined. The ultrasonic homogenizer used was a "US-150E" (manufactured by Nippon Seiki Seisakusho Co., Ltd.). From the measurement results, Dx90 / Dy90 and Dx97 / Dy97 were calculated. The results are shown in Table 1.

[0098] <Measurement of oxygen content A> The oxygen content A of the phosphor powder was determined as the total amount of oxygen. The oxygen content A was measured using an oxygen / nitrogen analyzer (manufactured by Horiba, Ltd., device name: EMGA-920). Specifically, the phosphor powder was heated from 20°C to 2000°C at a temperature increase rate of 8°C / sec in a helium atmosphere, and the amount of oxygen released was quantified to determine the oxygen content A (mass%) of the entire phosphor powder. The measurement results for each example and comparative example are shown in Table 2.

[0099] <Measurement of light absorptance C at 455 nm> The phosphor powder was filled into a concave cell so that the surface was smooth, and the cell was attached to the opening of an integrating sphere. Monochromatic light separated into wavelengths of 455 nm from a light source (Xe lamp) was introduced into the integrating sphere using an optical fiber as excitation light for the phosphor. This monochromatic light was irradiated onto a phosphor sample, and the fluorescence spectrum of the phosphor powder was measured using a spectrophotometer (MCPD-7000, manufactured by Otsuka Electronics Co., Ltd.).

[0100] The number of reflected excitation light photons (Qref) and the number of fluorescent photons (Qem) were calculated from the obtained spectral data. The number of reflected excitation light photons was calculated in the same wavelength range as the number of excitation light photons, and the number of fluorescent photons was calculated in the range of 465 to 800 nm.

[0101] Furthermore, using the same device, a standard reflector with a reflectance of 99% (Spectralon (registered trademark) manufactured by Labsphere) was attached to the opening of the integrating sphere to measure the spectrum of excitation light with a wavelength of 455 nm. At this time, the number of excitation light photons (Qex) was calculated from the spectrum in the wavelength range of 450 to 465 nm.

[0102] The light absorptance C at 455 nm of each phosphor powder in the Examples and Comparative Examples was calculated using the following formula. The results are shown in Table 2. Light absorptance C at 455 nm (%) = {(Qex - Qref) / Qex} x 100

[0103] <Measurement of oxygen content B after exposure test> The phosphor powder was stored for 250 hours in an environment of 85°C temperature and 85% humidity using a constant temperature and humidity dryer (IW222 (trade name), manufactured by Yamato Scientific Co., Ltd.), and the oxygen content B was measured. The measurement was performed using the same procedure as for measuring the oxygen content A. B / A was calculated from the oxygen content A and the oxygen content B. The results are shown in Table 2.

[0104] <Measurement of light absorptance D at 455 nm after exposure test> The phosphor powder was stored for 250 hours in an environment of a temperature of 85°C and a humidity of 85% using a constant temperature and humidity dryer (IW222 (trade name), manufactured by Yamato Scientific Co., Ltd.), and then the light absorptance D at 455 nm was measured. The measurement was performed using the same procedure as for measuring the light absorptance C. D / C was calculated from the light absorptance C and the light absorptance D. The results are shown in Table 2.

[0105]

[0106]

[0107] As shown in Tables 1 and 2, Examples 1 to 4, which had low acid treatment concentrations, had smaller Dx97 / Dy97 ratios and demonstrated that aggregation was suppressed compared to Comparative Examples 1 to 5, which had high acid treatment concentrations. It was also confirmed that the light absorptance at 455 nm was also higher.

[0108] According to the present disclosure, it is possible to provide a phosphor powder having high light absorptance, which can suppress particle aggregation even when the particle size is small, and it is also possible to provide a light emitting device including a phosphor powder having high light absorptance, which can suppress particle aggregation even when the particle size is small.

[0109] 10...light emitting device, 20...light emitting element, 30...wavelength converter, 40...terminal

Claims

1. A phosphor powder containing phosphor particles represented by the general formula (Ca １－ｘ－ｙ Sr ｘ Eu ｙ ).AlSiN ３ where 0 ≦ x < 1, 0 < y < 1, and 1 - x - y > 0. In the cumulative distribution (1) of the volume-based particle size measured by the laser diffraction / scattering method after subjecting the dispersion of the phosphor powder to ultrasonic homogenization treatment, the particle sizes when the integrated value from the small particle size reaches 50% and 97% of the whole are defined as Dy50 and Dy97, respectively. In the cumulative distribution (2) of the volume-based particle size measured by the laser diffraction / scattering method without performing the ultrasonic homogenization treatment, when the particle size when the integrated value from the small particle size reaches 97% of the whole is defined as Dx97, Dx97 / Dy97 is 5.0 or less, and Dy50 is less than 1.7 μm. Phosphor powder.

2. When X-ray diffraction is measured, the diffraction intensity at 2θ = 32° is I １ , the diffraction intensity at 2θ = 33° is I ２ , and the maximum value of the peak intensity detected in the range of 2θ = 32° to 33° is I ０ , when I ０ / [(I １ - I ２ ) / 2] is 2.0 or less, the phosphor powder according to claim 1.

3. In the cumulative distribution (2), when the integrated value from the small particle size reaches 90% of the whole, the particle size is defined as Dx90, and in the cumulative distribution (1), when the integrated value from the small particle size reaches 90% of the whole, the particle size is defined as Dy90. The phosphor powder according to claim 1 or 2, wherein Dx90 / Dy90 is 2.0 or less.

4. In the cumulative distribution (1), when the integrated value from the small particle size reaches 10% of the whole, the particle size is defined as Dy10. The phosphor powder according to claim 1 or 2, wherein Dy10 is 0.4 μm or more.

5. The phosphor powder according to claim 1 or 2, wherein the light absorption rate at a wavelength of 455 nm is 80.5% or more.

6. The phosphor powder according to claim 1 or 2, wherein the oxygen content rate is 6.10 mass% or less.

7. Regarding the phosphor powder, when the oxygen content rate is A, and the oxygen content rate after storing the phosphor powder in an environment of a temperature of 85°C and a humidity of 85% for 250 hours is B, the phosphor powder according to claim 1 or 2, wherein B / A is 3.00 or less.

8. A light-emitting device including a light-emitting element that emits primary light, and a wavelength converter that absorbs a part of the primary light and emits secondary light having a wavelength longer than that of the primary light, wherein the wavelength converter contains the phosphor powder according to claim 1 or 2.

9. The light-emitting device according to claim 8, wherein the light-emitting element contains at least one selected from the group consisting of a mini LED and a micro LED.

Images