WO2022044792A1 - 蛍光体粉末の製造方法、蛍光体粉末、及び発光装置 - Google Patents
蛍光体粉末の製造方法、蛍光体粉末、及び発光装置 Download PDFInfo
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Definitions
- the present invention relates to a method for producing a fluorescent substance powder, a fluorescent substance powder, and a light emitting device.
- Patent Document 1 describes that near-infrared light is emitted by activating Eu in Ba 26 Si 51 O 2 N 84 (paragraph 0001, Example 1, paragraph 0090 of Patent Document 1). ⁇ 0092 etc.).
- the orange-emitting heterogeneous phase contained in the above fluorescent powder was a fluorescent substance in which Eu was activated in Ba 2 Si 5 N 8 . It was found that this orange-emitting heterogeneous phase can be reduced by calcining after designing the composition so that Ba in the stoichiometric ratio becomes excessive.
- the above-mentioned method for reducing the different phase that emits orange light is adopted, a new different phase that emits red light is generated.
- the heterogeneous phase that emits red light is a fluorescent substance in which Eu is activated in Ba 3 Si 3 O 3 N 4 . It was found that this red emission heterogeneous phase can be reduced by washing with an acid or the like.
- the present inventor calcins the raw material mixed powder whose composition is designed to have an excess of Ba, and cleans the obtained calcined product by acid treatment and / or water treatment to obtain an orange emission different phase and a red emission outer phase. We have found that it can be reduced, and have completed the present invention.
- the present invention contains an inorganic compound in which Eu is solid-solved as an activator in an inorganic crystal having the same crystal structure as the crystal shown by Ba 26 Si 51 O 2 N 84 or the crystal shown by Ba 26 Si 51 O 2 N 84 . It is a method for producing a phosphor powder.
- a firing step of calcining the raw material mixed powder to obtain a calcined product In the mixing step of obtaining a raw material mixed powder blended so as to satisfy / 51, A firing step of calcining the raw material mixed powder to obtain a calcined product, Provided is a method for producing a fluorescent substance powder, which comprises a cleaning treatment step of treating the fired product with acid and / or water.
- It contains an inorganic compound in which Eu is solid-solved as an activator in an inorganic crystal having the same crystal structure as the crystal shown by Ba 26 Si 51 O 2 N 84 or the crystal shown by Ba 26 Si 51 O 2 N 84 .
- It ’s a phosphor powder, In the emission spectrum obtained by irradiating the phosphor powder with excitation light having a wavelength of 450 nm, the emission intensity at the peak wavelength in the range of 700 nm or more and 1500 nm or less is P0, and the emission intensity at the peak wavelength in the range of 500 nm or more and less than 700 nm is P1.
- a fluorescent powder is provided in which P0 and P1 satisfy P1 / P0 ⁇ 0.20.
- 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 the wavelength of the primary light.
- a light emitting device is provided in which the wavelength converter contains the phosphor powder.
- a method for producing a fluorescent substance powder capable of reducing different phases, a fluorescent substance powder having excellent light emitting characteristics, and a light emitting device having excellent light emitting characteristics are provided.
- the method for producing the fluorescent powder of the present embodiment will be outlined.
- Eu is added to an inorganic crystal having the same crystal structure as the crystal shown by Ba 26 Si 51 O 2 N 84 or the crystal shown by Ba 26 Si 51 O 2 N 84 .
- It is a method for producing a fluorescent substance powder containing an inorganic compound dissolved as an activator.
- the reason why the Eu-activated phosphor was by-produced in Ba 2 Si 5 N 8 was that the Ba element was insufficient due to the vaporization of the raw material.
- a raw material containing a Ba element such as Ba 2N may vaporize depending on the firing conditions and may dissipate to the outside from the reaction vessel.
- the synthesis condition is such that Ba 2 Si 5 N 8 which is a compound having a smaller Ba amount than Ba 26 Si 51 O 2 N 84 is easily produced. Therefore, it was found that the formation of an orange-emitting heterogeneous phase can be suppressed by firing after designing the composition so that Ba is excessive so as to make up for the shortage due to vaporization.
- composition ratios of Ba / Si of the three compounds of the different phase Ba 2 Si 5 N 8 , Ba 26 Si 51 O 2 N 84 , and the different phase Ba 3 Si 3 O 3 N 4 , respectively, are 0.4, respectively. Since it is 0.51 and 1.0, it is difficult to reduce both of the two different phases by controlling the composition design.
- the color is orange by firing in a state where Ba is charged in excess of the stoichiometric composition shown in (Ba, Eu) 26 Si 51 O 2 N 84 , and then acid-treated and / or water-treated. It has been found that the heterogeneous phase that emits light and the heterogeneous phase that emits red light can be reduced.
- a phosphor powder that can be excited by visible light from ultraviolet light such as about 300 nm to 650 nm and can emit light having a peak in the near infrared region of 700 nm to 1500 nm.
- the wavelength converter containing the phosphor powder of the present embodiment is composed of a member that converts the irradiated light (excitation light) and emits light having an emission peak in a wavelength range different from that of the excitation light.
- the wavelength converter may constitute at least a part of the following light emitting device.
- the wavelength converter may emit light having an emission peak in a wavelength range of 700 nm or more and 1500 nm or less, for example.
- the wavelength converter may contain one or more phosphors other than the fluorophore powder of the present embodiment.
- the wavelength converter may be composed only of the fluorescent material powder, or may contain a base material in which the fluorescent material powder is dispersed.
- the base material known materials can be used, and examples thereof include glass, resin, and inorganic materials.
- the shape of the wavelength converter is not particularly limited, and may be configured in a plate shape, or may be configured to seal a part of a light emitting element or the entire light emitting surface, for example.
- An example of a light emitting device including the phosphor powder of the present embodiment is a light emitting element that emits primary light and the above wavelength that absorbs a part of the primary light and emits secondary light having a wavelength longer than the wavelength of the primary light. It is equipped with a transformant.
- a light emitting device it can be used for various purposes such as sensor / inspection / analysis, security, optical communication, medical use, food, etc.
- Devices, medical / healthcare devices, infrared cameras, moisture measuring devices, gas detecting devices, etc. may be mentioned.
- An example of a method for producing a phosphor is an inorganic crystal having the same crystal structure as the crystal shown by Ba 26 Si 51 O 2 N 84 or the crystal shown by Ba 26 Si 51 O 2 N 84 , in which Eu is used as an activator.
- the raw material containing the Ba element is a single substance or a mixture of two or more selected from metals, silicates, oxides, carbonates, nitrides, oxynitrides, chlorides, fluorides, and acid fluorides containing Ba. And so on.
- the raw material containing the Si element is a single substance or a mixture of two or more selected from metals, silicates, oxides, carbonates, nitrides, oxynitrides, chlorides, fluorides, and acid fluorides containing Si. And so on.
- the raw material containing the Eu element is a single substance or a mixture of two or more selected from metals, silicates, oxides, carbonates, nitrides, oxynitrides, chlorides, fluorides, and acid fluorides containing Eu. Etc. are used.
- the raw material mixed powder for example, those containing a nitride of Ba, a nitride and / or an oxide of Si, and a nitride and / or an oxide of Eu may be used. Thereby, the reaction at the time of firing can be promoted.
- Ba is excessively blended in the raw material mixed powder.
- the a, b and c further satisfy 0.51 ⁇ a / b ⁇ 1.
- the lower limit of a / b may be, for example, more than 0.51, 0.55 or more, or 0.60 or more.
- the upper limit of a / b may be, for example, less than 1.0, 0.8 or less, or 0.7 or less.
- the molar ratio of Ba in the charged composition is more than 1.0 times, preferably more than 1.0 times the stoichiometric ratio, in the composition represented by the general formula: (Ba 1-x , Eu x ) 26 Si 51 O 2 N 84 . It is 1.5 times or more, more preferably 1.8 times or more, still more preferably 2.0 times or more.
- the molar ratio of x in the above general formula, that is, Eu is not particularly limited, but may be 0.0001 or more, 0.0005 or more, 0.001 or more, and 0.5 or less, 0. It may be 0.3 or less, or 0.2 or less. By setting it within an appropriate range, the absorption rate, the internal quantum efficiency, and the external quantum efficiency can be improved.
- the method of mixing the raw materials is not particularly limited, but for example, there is a method of sufficiently mixing using a mixing device such as a mortar, a ball mill, a V-type mixer, and a planetary mill.
- a mixing device such as a mortar, a ball mill, a V-type mixer, and a planetary mill.
- the obtained raw material mixed powder is fired (firing step).
- a reaction product (calcined product) after the firing step can be obtained.
- a firing furnace such as an electric furnace may be used.
- the raw material mixed powder filled inside the firing container may be fired.
- the firing vessel is preferably made of a material that is stable under high temperature atmospheric gas and does not easily react with the mixture of raw materials and its reaction products, for example, a vessel made of boron nitride or carbon, molybdenum or tantalum. It is preferable to use a container made of a refractory metal such as molybdenum or tungsten.
- a gas containing nitrogen as an element can be preferably used.
- Specific examples include nitrogen and / or ammonia, with nitrogen being particularly preferred.
- an inert gas such as argon or helium can also be preferably used. Of these, nitrogen gas is preferable.
- the firing atmosphere gas may be composed of one type of gas or may be a mixed gas of a plurality of types of gases.
- the inside of the firing container may be filled with the above-mentioned firing atmosphere gas.
- An appropriate temperature range is selected for the firing temperature in the firing step from the viewpoint of reducing unreacted raw materials after the firing step and suppressing decomposition of the main component.
- the lower limit of the firing temperature in the firing step is preferably 1500 ° C. or higher, more preferably 1600 ° C. or higher, and even more preferably 1700 ° C. or higher.
- the upper limit of the firing temperature is preferably 2200 ° C. or lower, more preferably 2000 ° C. or lower, and even more preferably 1900 ° C. or lower.
- the pressure of the firing atmosphere gas is selected according to the firing temperature, but is usually in a pressurized state in the range of 0.1 MPa or more and 10 MPa or less. Considering industrial productivity, it is preferably 0.5 MPa or more and 1 MPa or less.
- the lower limit of the firing time is preferably 0.5 hours or more, more preferably 1 hour or more.
- the upper limit of the firing time is preferably 48 hours or less, more preferably 24 hours or less, and even more preferably 16 hours or less.
- reaction product (calcined product) after the firing step may be subjected to powder treatment in which at least one of crushing, crushing, and / or sieving is performed (powder processing step).
- the state of the calcined product obtained by the calcining step varies from powdery to lumpy depending on the raw material composition and the calcining conditions.
- the fired product can be made into a powder of a predetermined size.
- a process known in the field of phosphor may be added.
- the cleaning treatment step comprises contacting the calcined product with at least one of an acid, an acidic solution containing an acid, water, and / or a neutral aqueous solution.
- the acid treatment is preferably carried out using an acidic solution. This makes it possible to reduce the heterogeneous phase of (Ba, Eu) 3 Si 3 O 3 N 4 while retaining the main phase of (Ba, Eu) 26 Si 51 O 2 N 84 . Further, the heterogeneous phase of (Ba, Eu) SiN 2 can be reduced.
- neutral means that the pH is 7 when a measurement target having a liquid temperature of 23 ° C. ⁇ 0.5 ° C. is measured using a pH meter.
- the calcined product may be added to the acid solution and / or water, and the calcined product in the solution may be added with acid and / or water.
- the acid solution and / or water may be allowed to stand during the treatment, but may be stirred under appropriate conditions.
- decantation solid-liquid separation treatment
- Decantation may be performed once or more than once. This makes it possible to remove the acid from the fired product. After that, the fired product may be filtered, dried or the like.
- an inorganic acid for example, an inorganic acid may be used, and specific examples thereof include HNO 3 , HCl, H 2 SO 4 , and H 3 P 04 . These may be used alone or in combination of two or more.
- the inorganic acids it is preferable to contain at least one of HNO 3 and HCl, and it is preferable to contain HNO 3 .
- the acid solution may contain water or alcohol as a solvent.
- the concentration of the acid in the acid solution may be, for example, 0.1% by mass to 20% by mass, preferably 0.5% by mass to 10% by mass.
- the phosphor particles of the present embodiment can be obtained. Then, if necessary, post-treatment such as crushing / classification treatment, purification treatment, and drying treatment may be performed.
- the fluorescent powder of this embodiment will be described in detail.
- Eu is solidified as an activator in an inorganic crystal having the same crystal structure as the crystal shown by Ba 26 Si 51 O 2 N 84 or the crystal shown by Ba 26 Si 51 O 2 N 84 . Contains dissolved inorganic compounds.
- the phosphor powder has a peak wavelength in the range of 700 nm or more and 1500 nm or less in the emission spectrum obtained by irradiating the phosphor powder with excitation light having a wavelength of 450 nm.
- the half width of the emission spectrum having a peak wavelength in the range of 700 nm or more and 1500 nm or less is, for example, 100 nm or more and 400 nm or less, preferably 150 nm or more and 350 nm or less, and more preferably 200 nm or more and 300 nm or less. This makes it possible to increase the emission intensity.
- the emission intensity at the peak wavelength in the range of 700 nm or more and 1500 nm or less is set to P0, and the maximum emission intensity at the peak wavelength in the range of 500 nm or more and less than 700 nm is defined as P0. Let it be P1.
- the range of 700 nm or more and 1500 nm or less includes the main peak attributed to (Ba, Eu) 26 Si 51 O 2 N 84 .
- the range of 500 nm or more and less than 700 nm includes peaks attributed to different phases such as (Ba, Eu) 3 Si 3 O 3 N 4 and (Ba, Eu) Si N 2 .
- the upper limit of P1 / P0 calculated from P0 and P1 is 0.20 or less, preferably 0.15 or less, and more preferably 0.12 or less.
- a fluorescent powder having reduced heterogeneous phases such as (Ba, Eu) 3 Si 3 O 3 N 4 , (Ba, Eu) SiN 2 , and (Ba, Eu) 2 Si 5 N 8 .
- the lower limit of P1 / P0 is preferably 0, but it is permissible to include unavoidable different phases within a range where there is no practical problem, and for example, it may be 0.001 or more.
- P1 / P0 it is possible to control P1 / P0, for example, by appropriately selecting a method for preparing fluorescent powder.
- a method for preparing fluorescent powder for example, calcining the blended raw material mixed powder, acid-treating the calcined product, and the like can be mentioned as factors for setting P1 / P0 in the desired numerical range.
- the particle size having a cumulative value of 50% is D50
- the particle size having a cumulative value of 10% is D10
- the cumulative value is 90%.
- the particle size is D90.
- D50 is, for example, 1 ⁇ m or more and 50 ⁇ m or less, preferably 5 ⁇ m or more and 45 ⁇ m or less, and more preferably 10 ⁇ m or more and 40 ⁇ m or less. By setting it within the above range, it is possible to balance the light emission characteristics.
- the lower limit of ((D90-D10) / D50) is, for example, 1.00 or more, preferably 1.20 or more, and more preferably 1.30 or more.
- the upper limit of ((D90-D10) / D50) is 3.00 or less, preferably 2.50 or less, and more preferably 2.00 or less.
- Barium Nitride (Ba 2N, manufactured by Pacific Cement Co., Ltd.), Europium Oxide (Eu 2 O 3 , manufactured by Shinetsu Chemical Industry Co., Ltd.), (Si 3 N 4 , manufactured by Ube Kosan Co., Ltd.), and Oxidation Silicon (SiO 2 , manufactured by High Purity Chemical Co., Ltd.) was weighed and mixed for 10 minutes using a silicon nitride sintered dairy rod and a dairy pot in a glove box with a nitrogen atmosphere to obtain a powdery raw material mixture (a powdery raw material mixture). Mixing process).
- Table 1 the molar ratios of Ba, Si, and Eu in the raw material mixture are represented by a, b, and c, respectively.
- the raw material mixture was put into a crucible made of a boron nitride sintered body.
- the pot containing the raw material mixture is placed in a graphite resistance heating type electric furnace, and the firing atmosphere is set to a vacuum of 1 ⁇ 10 -1 Pa or less using an oil rotary pump and an oil diffusion pump to create a vacuum of 1 ⁇ 10 -1 Pa or less, from room temperature to 600 ° C per hour at 500 ° C.
- the pressure in the furnace was set to 0.8 MPa by introducing nitrogen having a purity of 99.999% by volume at 600 ° C., the temperature was raised to 1800 ° C. at 600 ° C. per hour, and firing was performed for 8 hours. Baking process).
- the obtained calcined product was crushed in an alumina mortar, sieved with a sieve having an opening of 150 ⁇ m (# 100 mesh), and the portion passing through the sieve was recovered (powder treatment step).
- the calcined product passed through the sieve was immersed in 300 ml of nitric acid (HNO 3 concentration 7.5%) and stirred at room temperature at a stirring speed of 350 rpm for 30 minutes (cleaning treatment step with acid). Then, the supernatant was reduced, washed with distilled water, suction filtered and dried to obtain a fluorescent powder.
- nitric acid HNO 3 concentration 7.5%
- the main phase was Ba 26 Si 51 O 2 N 84
- the by-produced heterogeneous phase was Ba 3 Si 3 O 3 N 4
- a peak attributed to Ba 2 Si 5 N 8 was observed. Therefore, it was found that it is possible to reduce the heterogeneous phase Ba 2 Si 5 N 8 by firing the raw material powder mixed at a specific compounding ratio.
- an emission peak attributed to the main phase (Ba, Eu) 26 Si 51 O 2 N 84 is present at 700 nm to 1500 nm, and an emission peak of 500 nm to 700 nm is present. It was confirmed that there is an emission peak attributed to (Ba, Eu) 3 Si 3 O 3 N 4 which is out of phase in the range. Further, the emission intensity of the peak of 500 nm to 700 nm showed a very high value in Comparative Example 1 as compared with Examples 1 to 5.
- the fluorescence peak intensity of the phosphor powder of the fired product after the acid treatment of Examples 1 to 5 was measured using a spectral fluorometer (Fluorolog-3, manufactured by Horiba, Ltd.) corrected by a substandard light source. went.
- the square cell holder attached to the photometer was used for the measurement, and the excitation light having a wavelength of 450 nm was irradiated to obtain an emission spectrum.
- FIG. 2 shows the emission spectra of the phosphor powder of the fired product after the acid treatment, which is normalized by the emission intensity at the peak wavelength in Examples 1, 2, 5, and Comparative Example 1.
- the peak position, full width at half maximum, and emission intensity (P0) for the peak wavelength in the range of 700 nm or more and 1500 nm or less, and the emission intensity (P1) at the peak wavelength in the range of 500 nm or more and less than 700 nm are obtained and shown in the table. Shown in 2.
- the peak intensity at each wavelength is a relative value when the peak intensity of Example 3 is 1.00.
- the fluorescent powders of Examples 1 to 5 have a lower emission intensity of a peak of 500 nm to 700 nm due to emission of a different phase than that of Comparative Example 1, and emit light having a peak in the near infrared region of 700 nm to 1500 nm. The strength has improved.
- the particle size distribution of the phosphor powders of Examples 1 to 5 was measured by a laser diffraction / scattering method particle size distribution measuring device (manufactured by Beckman Coulter, LC13 320). Water was used as the measurement solvent. A small amount of phosphor powder was added to an aqueous solution containing 0.05% by weight of sodium hexametaphosphate as a dispersant, and dispersion treatment was performed with a horn-type ultrasonic homogenizer (output 300 W, horn diameter 26 mm) to obtain a particle size distribution. It was measured.
Abstract
Description
まず蛍光体粉末中に含まれる蛍光体粒子を解析したところ、上記の蛍光体粉末中に含まれる橙色発光する異相はBa2Si5N8にEuが賦活した蛍光体であることが判明した。この橙色発光する異相は、化学量論比においてのBaが過剰となる組成設計とした上で焼成することにより、低減可能であることが分かった。
しかしながら上記の橙色発光する異相を低減する手法を採用すると、赤色発光する異相が新たに発生することになった。解析した結果、赤色発光する異相は、Ba3Si3O3N4にEuが賦活した蛍光体であることが判明した。この赤色発光異相は、酸等を用いた洗浄により低減可能であることが分かった。
このように本発明者は、Ba過剰となる組成設計した原料混合粉末を焼成し、得られた焼成物を酸処理及び/又は水処理による洗浄をすることによって、橙色発光異相及び赤色発光異相を低減できることを見出し、本発明を完成するに至った。
Ba26Si51O2N84で示される結晶、又はBa26Si51O2N84で示される結晶と同一の結晶構造を有する無機結晶にEuが賦活剤として固溶された無機化合物を含有する蛍光体粉末の製造方法であって、
前記無機化合物を構成する各元素を含む原料を混合し、原料混合粉末中のBa、Si、Euのモル比をそれぞれ、a、b、cとしたとき、b=51、a/b>(26-c)/51を満たすように配合された原料混合粉末を得る混合工程と、
前記原料混合粉末を焼成して焼成物を得る焼成工程と、
前記焼成物を酸処理及び/又は水処理する洗浄処理工程と、を含む、蛍光体粉末の製造方法が提供される。
Ba26Si51O2N84で示される結晶、又はBa26Si51O2N84で示される結晶と同一の結晶構造を有する無機結晶にEuが賦活剤として固溶された無機化合物を含有する蛍光体粉末であって、
波長450nmの励起光を当該蛍光体粉末に照射して得られる発光スペクトルにおいて、700nm以上1500nm以下の範囲にあるピーク波長における発光強度をP0とし、500nm以上700nm未満にあるピーク波長における発光強度をP1としたとき、
P0、P1が、P1/P0≦0.20を満たす、蛍光体粉末が提供される。
一次光を発する発光素子と、前記一次光の一部を吸収して、一次光の波長よりも長い波長を有する二次光を発する波長変換体とを備える発光装置であって、
前記波長変換体は上記蛍光体粉末を含む、発光装置が提供される。
本実施形態の蛍光体粉末の製造方法は、Ba26Si51O2N84で示される結晶、又はBa26Si51O2N84で示される結晶と同一の結晶構造を有する無機結晶にEuが賦活剤として固溶された無機化合物を含有する蛍光体粉末を製造するための方法である。
蛍光体粉末の製造方法は、無機化合物を構成する各元素を含む原料を混合し、Ba、Si、Euのモル比をそれぞれ、a、b、cとしたとき、b=51、a/b>(26-c)/51を満たすように配合された原料混合粉末を得る混合工程と、原料混合粉末を焼成して焼成物を得る焼成工程と、焼成物を酸処理及び/又は水処理する洗浄処理工程と、を含む。
(Ba,Eu)26Si51O2N84組成となるように原料組成を設計し、原料混合し、原料混合粉末を焼成して、蛍光体粉末を合成すると、目的とするBa26Si51O2N84で示される結晶以外に、橙色発光する異相が多量に副生成されることが判明した。解析の結果、この橙色発光する異相はBa2Si5N8にEuが賦活した蛍光体であることが分かった。
Ba2Si5N8にEuが賦活した蛍光体が副生成した原因は、検討の結果、原料の気化により、Ba元素が不足するためであると考えられた。Ba2N等のBa元素を含む原料は、焼成条件次第で気化し、反応容器から外部に散逸してしまうことがある。原料からBa元素が減少すると、Ba26Si51O2N84よりもBa量が少ない化合物のBa2Si5N8が生成されやすい合成条件となる。
そこで、気化による不足分を補うように、Baが過剰となる組成設計とした上で焼成することにより、橙色発光異相の生成を抑制できることが判明した。
この赤色発光する異相は、解析の結果、Ba3Si3O3N4にEuが賦活した蛍光体であることがわかった。
発光装置として、センサー・検査・分析用、セキュリティ用、光通信用、医療用、食品などの各種の用途に用いることができるが、例えば、LEDパッケージ、光源、分光光度計、食品分析計、ウェアラブルデバイス、医療用・ヘルスケア用デバイス、赤外線カメラ、水分測定装置、ガス検出装置等が挙げられる。
Si元素を含む原料としては、Siを含む、金属、ケイ化物、酸化物、炭酸塩、窒化物、酸窒化物、塩化物、フッ化物、及び酸フッ化物から選ばれる単体または2種以上の混合物等が挙げられる。
Eu元素を含む原料としては、Euを含む、金属、ケイ化物、酸化物、炭酸塩、窒化物、酸窒化物、塩化物、フッ化物、及び酸フッ化物から選ばれる単体または2種以上の混合物等が用いられる。
一方、a/bの上限は、例えば、1.0未満でもよく、0.8以下でもよく、0.7以下でもよい。このような仕込み組成の原料混合粉末を焼成することにより、(Ba,Eu)3Si3O3N4の異相を低減することが可能である。
焼成容器の内部は、上記の焼成雰囲気ガスで満たしてもよい。
焼成工程における焼成温度の下限は、1500℃以上が好ましく、1600℃以上がより好ましく、1700℃以上がさらに好ましい。一方、焼成温度の上限は、2200℃以下が好ましく、2000℃以下がより好ましく、1900℃以下がさらに好ましい。
焼成時間の下限は、0.5時間以上が好ましく、1時間以上がより好ましい。また、焼成時間の上限は、48時間以下が好ましく、24時間以下がより好ましく、16時間以下がさらに好ましい。
なお、上記の他に、蛍光体の分野で公知の工程を追加してもよい。
洗浄処理工程は、焼成物を、酸、酸を含む酸性溶液、水、及び/又は中性の水溶液の少なくとも一以上に接触させる工程を含む。好ましくは酸性溶液を用いて酸処理を行う。
これにより、(Ba,Eu)26Si51O2N84の主相を残存させつつも、(Ba,Eu)3Si3O3N4の異相を低減することが可能である。また、(Ba,Eu)SiN2の異相も低減できる。
なお、中性とは、pHメータ計を用いて、液温23℃±0.5℃の測定対象を測定したとき、pHが7であることを意味する。
また、酸処理後、必要に応じて、水やアルコールを用いてデカンテーション(固液分離処理)を施してもよい。デカンテーションは、1回又は2回以上行ってもよい。これにより、焼成物中から酸を除去できる。その後、焼成物に対して、ろ過、乾燥等を施してもよい。
その後、必要において、例えば、破砕・分級処理、精製処理、乾燥処理などの後処理を行ってもよい。
一方、P1/P0の下限は、0が好ましいが、実用上問題ない範囲で不可避の異相が含まれることを許容でき、例えば、0.001以上でもよい。
[実施例1~5、比較例1]
表1の仕込み組成に示すように、一般式:(Ba1-x,Eux)26Si51O2N84において、xを実施例1~5の順で0.002,0.005,0.008,0.01,0.02とし、実施例1~5においてはBaを化学量論比に対して1.2倍過剰、比較例1においてはBaを化学量論比に対して1倍となる目的組成を設計し、窒化バリウム(Ba2N、太平洋セメント社製)、酸化ユーロピウム(Eu2O3、信越化学工業社製)、(Si3N4、宇部興産社製)、及び酸化ケイ素(SiO2、高純度化学社製)を秤量し、窒素雰囲気のグローブボックス中で窒化ケイ素焼結体製乳棒と乳鉢とを用いて10分間混合を行い、粉末状の原料混合物を得た(混合工程)。
表1中、原料混合物中のBa、Si、Euのモル比をそれぞれ、a、b、cで表す。
その後、上澄みを低減し、蒸留水で洗浄し、吸引ろ過、乾燥し、蛍光体粉末を得た。
実施例1~5、比較例1の酸処理前後の焼成物について、粉末X線回折装置(製品名:UltimaIV、リガク社製)を用いて、下記の測定条件で回折パターンを測定した。
(測定条件)
X線源:Cu-Kα線(λ=1.54184Å)、
出力設定:40kV・40mA
測定時光学条件:発散スリット=2/3°
散乱スリット=8mm
受光スリット=開放
回折ピークの位置=2θ(回折角)
測定範囲:2θ=10°~90°
スキャン速度:2度(2θ)/sec,連続スキャン
走査軸:2θ/θ
試料調製:蛍光体粉末をサンプルホルダーに載せた。
ピーク強度はバックグラウンド補正を行って得た値とした。
一方、比較例1の酸処理前の焼成物においてはBa2Si5N8に帰属されるピークが観測された。
したがって、特定の配合比にて混合した原料粉末を焼成することにより、異相Ba2Si5N8を低減させることが可能であることが判明した。
(蛍光ピーク強度、ピーク波長、半値幅)
実施例1~5の酸処理前の焼成物の蛍光体粉末について、YAG蛍光体(P46Y3)と副標準光源により補正を行った分光蛍光光度計(日立ハイテクサイエンス社製、F-7000)を用いて、蛍光ピーク強度測定を行った。測定には、光度計に付属の角セルホルダーを使用し、波長450nmの励起光を照射し、発光スペクトルを得た。図1に、実施例1、2、5における、ピーク波長における発光強度で規格化した酸処理前の焼成物の蛍光体粉末の発光スペクトルを示す。
また、500nm~700nmのピークの発光強度は、比較例1が、実施例1~5と比べて非常に高い値を示した。
各波長におけるピーク強度は、実施例3のピーク強度を1.00としたときの相対的な値である。
実施例1~5の蛍光体粉末は、比較例1よりも、異相の発光による500nm~700nmのピークの発光強度を低減し、700nm~1500nmの近赤外領域の範囲にピークを有する光の発光強度が向上した。
実施例1~5の蛍光体粉末の粒子径分布を、レーザー回折・散乱法の粒子径分布測定装置(ベックマン・コールター社製、LC13 320)で測定した。測定溶媒には水を使用した。分散剤としてヘキサメタりん酸ナトリウムを0.05重量%加えた水溶液に少量の蛍光体粉末を投入し、ホーン式の超音波ホモジナイザー(出力300W、ホーン径26mm)で分散処理を行い、粒子径分布を測定した。得られた体積頻度粒度分布曲線から、10体積%径(D10)、50体積%径(D50)、90体積%径(D90)を求め、得られた値から粒子径分布のスパン値((D90-D10)/D50)を求めた。粒子径分布の結果を表3に示す。
Claims (11)
- Ba26Si51O2N84で示される結晶、又はBa26Si51O2N84で示される結晶と同一の結晶構造を有する無機結晶にEuが賦活剤として固溶された無機化合物を含有する蛍光体粉末の製造方法であって、
前記無機化合物を構成する各元素を含む原料を混合し、原料混合粉末中のBa、Si、Euのモル比をそれぞれ、a、b、cとしたとき、b=51、a/b>(26-c)/51を満たすように配合された原料混合粉末を得る混合工程と、
前記原料混合粉末を焼成して焼成物を得る焼成工程と、
前記焼成物を酸処理及び/又は水処理する洗浄処理工程と、を含む、蛍光体粉末の製造方法。 - 請求項1に記載の蛍光体粉末の製造方法であって、
前記混合工程は、a、bが、0.51<a/b<1を満たすように配合された前記原料混合粉末を得る、蛍光体粉末の製造方法。 - 請求項1又は2に記載の蛍光体粉末の製造方法であって、
酸処理に用いる酸が、無機酸を含む、蛍光体粉末の製造方法。 - 請求項3に記載の蛍光体粉末の製造方法であって、
前記酸が、HNO3を含む、蛍光体粉末の製造方法。 - 請求項1~4のいずれか一項に記載の蛍光体粉末の製造方法であって、
前記焼成工程で得られた前記焼成物について、前記洗浄処理工程の前に、粉砕、解砕、及び/又は篩分の少なくとも一以上を行う粉体処理工程を含む、蛍光体粉末の製造方法。 - 請求項1~5のいずれか一項に記載の蛍光体粉末の製造方法であって、
レーザー回折散乱法で測定される前記蛍光体粉末の積頻度粒度分布において、累積値が50%となる粒子径をD50としたとき、D50が1μm以上50μm以下を満たす前記蛍光体粉末を得る、蛍光体粉末の製造方法。 - Ba26Si51O2N84で示される結晶、又はBa26Si51O2N84で示される結晶と同一の結晶構造を有する無機結晶にEuが賦活剤として固溶された無機化合物を含有する蛍光体粉末であって、
波長450nmの励起光を当該蛍光体粉末に照射して得られる発光スペクトルにおいて、700nm以上1500nm以下の範囲にあるピーク波長における発光強度をP0とし、500nm以上700nm未満にあるピーク波長における発光強度をP1としたとき、
P0、P1が、P1/P0≦0.20を満たす、蛍光体粉末。 - 請求項7に記載の蛍光体粉末であって、
レーザー回折散乱法で測定される、当該蛍光体粉末の体積頻度粒度分布において、累積値が50%となる粒子径をD50としたとき、D50が、1μm以上50μm以下である、蛍光体粉末。 - 請求項7又は8に記載の蛍光体粉末であって、
レーザー回折散乱法で測定される当該蛍光体粉末の体積頻度粒度分布において、累積値が10%となる粒子径をD10、累積値が50%となる粒子径をD50、90%となる粒子径をD90としたとき、
((D90-D10)/D50)が、1.00以上3.00以下である、蛍光体粉末。 - 請求項7~9のいずれか一項に記載の蛍光体粉末であって、
前記発光スペクトルにおいて、700nm以上1500nm以下の範囲にあるピーク波長における半値幅が100nm以上400nm以下である、蛍光体粉末。 - 一次光を発する発光素子と、前記一次光の一部を吸収して、一次光の波長よりも長い波長を有する二次光を発する波長変換体とを備える発光装置であって、
前記波長変換体は請求項7~10のいずれか一項に記載の蛍光体粉末を含む、発光装置。
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