JP6903455B2 - Fluorescent material manufacturing method, phosphor and light emitting element and light emitting device - Google Patents
Fluorescent material manufacturing method, phosphor and light emitting element and light emitting device Download PDFInfo
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims description 133
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- 238000002189 fluorescence spectrum Methods 0.000 claims description 10
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- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
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- AEBZCFFCDTZXHP-UHFFFAOYSA-N europium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Eu+3].[Eu+3] AEBZCFFCDTZXHP-UHFFFAOYSA-N 0.000 description 2
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- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
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- XPIIDKFHGDPTIY-UHFFFAOYSA-N F.F.F.P Chemical compound F.F.F.P XPIIDKFHGDPTIY-UHFFFAOYSA-N 0.000 description 1
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- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
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Description
本発明は、酸窒化物蛍光体の製造方法、酸窒化物蛍光体、及び前記酸窒化物蛍光体を含む発光素子と前記発光素子を用いた発光装置に関する。 The present invention relates to a method for producing an oxynitride phosphor, an oxynitride phosphor, and a light emitting element containing the oxynitride phosphor and a light emitting device using the light emitting element.
発光素子として、青色ＬＥＤと緑色蛍光体、赤色蛍光体などを組み合わせて白色光を得る発光素子は広く知られている（特許文献１参照）。また、前記発光素子を用いて様々な照明器具などの発光装置を作ることができる。発光素子に用いる蛍光体の製造方法としては、蛍光体の原料を混合後に焼成し、さらに焼成温度より低い温度で不活性雰囲気や還元雰囲気、真空中で、再焼成またはアニールする工程を伴う製法は一般的に知られている（特許文献２参照）。このアニール工程を実施することにより、蛍光体の蛍光特性が改善されることが知られている。またアニール工程終了後の冷却過程において、冷却速度を遅くすることで特性を改善する手法も知られている。例えばβサイアロンに代表される酸窒化物蛍光体についても、前述した通りアニール工程の冷却中に冷却速度を遅くすることで、蛍光体の結晶欠陥が除去されて特性が向上することが認められている（特許文献３参照）。但し、酸窒化物蛍光体の製造過程において、特に蛍光体が１０００℃以下の冷却過程に置かれる履歴が、蛍光体の特性に及ぼす影響の程度については十分判ってなかった。なお本発明の酸窒化物蛍光体では、その化学組成などに由来して、その蛍光スペクトルのピーク波長に差が生じるが、例えば蛍光ピーク波長が短くなるほど外部量子効率は低下する傾向があるため、蛍光ピーク波長が異なる同種蛍光体を、例えばその輝度や外部量子効率の絶対値のみで一概に優劣を比較することが難しかった。そのため本発明では、蛍光ピーク波長に差がある酸窒化物蛍光体をも包括した上で、酸窒化物蛍光体の蛍光ピーク波長から、当該蛍光体の外部量子効率の値が超えるべき値を設定して、本発明の効果を検証し、他の酸窒化物蛍光体との区別を明確にしたものである。 As a light emitting element, a light emitting element that obtains white light by combining a blue LED with a green phosphor, a red phosphor, or the like is widely known (see Patent Document 1). In addition, various light emitting devices such as lighting fixtures can be made by using the light emitting element. As a method for producing a phosphor used in a light emitting element, a production method involving a step of mixing the raw materials of the phosphor and then firing the mixture, and then re-baking or annealing in an inert atmosphere or a reducing atmosphere at a temperature lower than the firing temperature, or in a vacuum is used. It is generally known (see Patent Document 2). It is known that the fluorescence characteristics of the phosphor are improved by carrying out this annealing step. Further, a method of improving the characteristics by slowing down the cooling rate in the cooling process after the completion of the annealing process is also known. For example, it has been confirmed that the oxynitride phosphor represented by β-sialon also has improved characteristics by removing crystal defects of the phosphor by slowing the cooling rate during cooling in the annealing step as described above. (See Patent Document 3). However, in the manufacturing process of the oxynitride phosphor, the degree of influence of the history of the phosphor being placed in the cooling process of 1000 ° C. or lower on the characteristics of the phosphor has not been fully understood. In the oxynitride phosphor of the present invention, there is a difference in the peak wavelength of the fluorescence spectrum due to its chemical composition and the like. However, for example, the shorter the fluorescence peak wavelength, the lower the external quantum efficiency tends to be. It has been difficult to unequivocally compare the superiority and inferiority of homologous phosphors having different fluorescence peak wavelengths based only on their brightness and the absolute value of external quantum efficiency, for example. Therefore, in the present invention, the value of the external quantum efficiency of the phosphor is set from the fluorescence peak wavelength of the oxynitride phosphor after including the oxynitride phosphors having different fluorescence peak wavelengths. Then, the effect of the present invention was verified, and the distinction from other oxynitride phosphors was clarified.
酸窒化物蛍光体が用いられている液晶ディスプレーのバックライトや照明などの発光装置では色再現性、演色性の改善、輝度の改善が常に求められている。そのため各部材の特性向上が必要とされており、蛍光体についても輝度、色再現性、演色性の改善が求められている。本発明は、特に高い輝度を有する酸窒化物蛍光体の製造方法、酸窒化物蛍光体、及び前記酸窒化物蛍光体を含む発光素子と前記発光素子を用いた発光装置に関する。 In light emitting devices such as backlights and lighting of liquid crystal displays in which oxynitride phosphors are used, improvement in color reproducibility, color rendering property, and brightness are always required. Therefore, it is necessary to improve the characteristics of each member, and it is also required to improve the brightness, color reproducibility, and color rendering property of the phosphor. The present invention relates to a method for producing an oxynitride phosphor having particularly high brightness, an oxynitride phosphor, and a light emitting element containing the oxynitride phosphor and a light emitting device using the light emitting element.
即ち本発明は、
（１）原料を混合して原料混合物を得る混合工程と、前記原料混合物を焼成して第１の焼成物を得る高温焼成工程と、前記第１の焼成物を前記高温焼成工程の焼成温度より低い温度で焼成して第２の焼成物を得る低温焼成工程と、前記第２の焼成物を酸処理する酸処理工程を有する、（式１）で示される化学組成の酸窒化物蛍光体の製造方法であって、前記低温焼成工程の終了後から室温までの冷却過程の途中において、８００℃以上１０００℃以下の範囲内の一定温度で少なくとも３時間以上保持してから得た第２の焼成物を酸処理する酸窒化物蛍光体の製造方法である。
Ｓｉ１２−ａＡｌａＯｂＮ１６−ｂ：Ｅｕｘ （式１）
但し（式１）において、０＜ａ≦３、０＜ｂ≦３、０＜ｘ≦０．１
（２）本発明の前記（１）記載の酸窒化物蛍光体の製造方法では、前記第１の焼成物を解砕及び粉砕する解砕・粉砕工程を好ましく備えることができる。
（３）また本発明の前記（１）または（２）記載の酸窒化物蛍光体の製造方法では、前記高温焼成工程の焼成温度が１８００℃以上２５００℃以下であり、前記低温焼成工程の焼成温度が１２００℃以上１８００℃以下であることが好ましい。
（４）また本発明の前記（１）〜（３）いずれか１項記載の酸窒化物蛍光体の製造方法では、前記低温焼成工程を、不活性ガス及び還元性ガスの少なくともどちらか一方の雰囲気下で好ましく行うことが可能である。
（５）また本発明は、（式１）で示される化学組成を有する酸窒化物蛍光体であり、前記蛍光体に波長４５５ｎｍの光を照射した際に発する蛍光のスペクトルのピーク波長をＶｎｍ、そのときの外部量子効率をＷ％としたとき、前記Ｖ及びＷが（式２）で示される関係を満たす酸窒化物蛍光体である。
Ｓｉ１２−ａＡｌａＯｂＮ１６−ｂ：Ｅｕｘ （式１）
但し、式（１）において、０＜ａ≦３、０＜ｂ≦３、０＜ｘ≦０．１
Ｗ＞１．３×Ｖ−６４８．５ （式２）
（６）また、前記（５）記載の本発明の酸窒化物蛍光体は、好ましくは波長４５５ｎｍの光を照射した際に発する蛍光のスペクトルのピーク波長が、５２４ｎｍ以上５５５ｎｍ以下である酸窒化物蛍光体である。
（７）また、前記（５）または（６）記載の本発明の酸窒化物蛍光体は、波長４５５ｎｍの光に対する吸収率をＭ％、波長６００ｎｍの光に対する吸収率をＮ％としたとき、前記Ｍ及びＮが（式３）で示される関係を満たす酸窒化物蛍光体とすることができる。
Ｍ＞６Ｎ （式３）
（８）さらに、前記（７）記載の本発明の酸窒化物蛍光体においては、波長６００ｎｍの光に対する吸収率が９％以下であることが好ましい。
（９）本発明は、前記（５）〜（８）いずれか１項記載の酸窒化物蛍光体を含む発光素子である。
（１０）本発明は、前記（９）記載の発光素子を用いた発光装置である。
That is, the present invention
(1) A mixing step of mixing raw materials to obtain a raw material mixture, a high-temperature firing step of firing the raw material mixture to obtain a first fired product, and a high-temperature firing step of obtaining the first fired product from the firing temperature of the high-temperature firing step. An oxynitride phosphor having a chemical composition represented by (Formula 1), which comprises a low-temperature firing step of firing at a low temperature to obtain a second fired product and an acid treatment step of acid-treating the second fired product. A second firing method, which is obtained after holding at a constant temperature within the range of 800 ° C. or higher and 1000 ° C. or lower for at least 3 hours in the middle of the cooling process from the end of the low-temperature firing step to room temperature. This is a method for producing an oxynitride phosphor that treats an object with an acid.
Si 12-a Al a Ob N 16-b : Eu x (Equation 1)
However, in (Equation 1), 0 <a ≦ 3, 0 <b ≦ 3, 0 <x ≦ 0.1
(2) The method for producing an oxynitride phosphor according to the above (1) of the present invention can preferably include a crushing / crushing step of crushing and crushing the first fired product.
(3) Further, in the method for producing an oxynitride phosphor according to the above (1) or (2) of the present invention, the firing temperature in the high temperature firing step is 1800 ° C. or higher and 2500 ° C. or lower, and the firing in the low temperature firing step. The temperature is preferably 1200 ° C. or higher and 1800 ° C. or lower.
(4) Further, in the method for producing an oxynitride phosphor according to any one of (1) to (3) of the present invention, the low-temperature firing step is performed on at least one of an inert gas and a reducing gas. It can be preferably performed in an atmosphere.
(5) Further, the present invention is an oxynitride phosphor having a chemical composition represented by (Formula 1), and the peak wavelength of the fluorescence spectrum emitted when the phosphor is irradiated with light having a wavelength of 455 nm is Vnm. When the external quantum efficiency at that time is W%, it is an oxynitride phosphor that satisfies the relationship represented by (Equation 2) by V and W.
Si 12-a Al a Ob N 16-b : Eu x (Equation 1)
However, in the formula (1), 0 <a ≦ 3, 0 <b ≦ 3, 0 <x ≦ 0.1
W> 1.3 × V-64.8 (Equation 2)
(6) Further, the oxynitride phosphor of the present invention according to (5) above is preferably an oxynitride having a peak wavelength of a fluorescence spectrum of 524 nm or more and 555 nm or less when irradiated with light having a wavelength of 455 nm. It is a phosphor.
(7) Further, when the oxynitride phosphor of the present invention according to the above (5) or (6) has an absorptance rate of M% for light having a wavelength of 455 nm and an absorptance rate for light having a wavelength of 600 nm as N%. The oxynitride phosphor can be an oxynitride phosphor in which M and N satisfy the relationship represented by (Equation 3).
M> 6N (Equation 3)
(8) Further, in the oxynitride phosphor of the present invention described in (7) above, the absorption rate for light having a wavelength of 600 nm is preferably 9% or less.
(9) The present invention is a light emitting device containing the oxynitride phosphor according to any one of (5) to (8) above.
(10) The present invention is a light emitting device using the light emitting element according to the above (9).
本発明の実施により、特に高い輝度を有する酸窒化物蛍光体の製造方法、酸窒化物蛍光体、及び前記酸窒化物蛍光体を含む発光素子と前記発光素子を用いた発光装置を提供することが可能となる。 By implementing the present invention, a method for producing an oxynitride phosphor having particularly high brightness, an oxynitride phosphor, and a light emitting element containing the oxynitride phosphor and a light emitting device using the light emitting element are provided. Is possible.
以下、本発明を実施するための形態について詳細を説明する。 Hereinafter, embodiments for carrying out the present invention will be described in detail.
本発明の酸窒化物蛍光体の製造方法は、原料を混合して原料混合物を得る混合工程と、前記原料混合物を焼成して第１の焼成物を得る高温焼成工程と、前記第１の焼成物を前記高温焼成工程の焼成温度より低い温度で焼成して第２の焼成物を得る低温焼成工程と、前記第２の焼成物を酸処理する酸処理工程を有する、（式１）で示される化学組成の酸窒化物蛍光体の製造方法であって、前記低温焼成工程の終了後から室温までの冷却過程の途中において、８００℃以上１０００℃以下の範囲内の一定温度で３時間以上保持してから酸処理する製造方法である。
Ｓｉ１２−ａＡｌａＯｂＮ１６−ｂ：Ｅｕｘ （式１）
但し（式１）において、０＜ａ≦３、０＜ｂ≦３、０＜ｘ≦０．１
以下、各工程について説明する。
The method for producing an oxynitride phosphor of the present invention includes a mixing step of mixing raw materials to obtain a raw material mixture, a high-temperature firing step of firing the raw material mixture to obtain a first fired product, and the first firing. It is represented by (Equation 1), which comprises a low-temperature firing step of firing a product at a temperature lower than the firing temperature of the high-temperature firing step to obtain a second fired product, and an acid treatment step of acid-treating the second fired product. A method for producing an oxynitride phosphor having a chemical composition, which is maintained at a constant temperature within the range of 800 ° C. or higher and 1000 ° C. or lower for 3 hours or more during the cooling process from the end of the low-temperature firing step to room temperature. This is a manufacturing method in which the acid treatment is performed after that.
Si 12-a Al a Ob N 16-b : Eu x (Equation 1)
However, in (Equation 1), 0 <a ≦ 3, 0 <b ≦ 3, 0 <x ≦ 0.1
Hereinafter, each step will be described.
＜混合工程＞
前記混合工程では、例えば窒化ケイ素などのケイ素化合物、例えば窒化アルミニウム、酸化アルミニウムなどのアルミニウム化合物、例えば窒化ユーロピウムや酸化ユーロピウムなどの光学活性元素を含む化合物（まとめて原料化合物という）を、それぞれ本発明の酸窒化蛍光体を構成するように秤量して混合し、原料混合物を調製する。原料化合物を混合する方法は特に限定されないが、例えば、例えばＶ型混合機等の公知の混合装置を用いて混合し、さらに乳鉢、ボールミル、遊星ミル、ジェットミルなどを用いて十分に混合する。なお空気中の水分及び酸素と激しく反応する窒化ユーロピウム等を混合する場合は、不活性雰囲気で置換されたグローブボックス内で取り扱うことが適切である。
<Mixing process>
In the mixing step, for example, a silicon compound such as silicon nitride, for example, an aluminum compound such as aluminum nitride and aluminum oxide, and a compound containing an optically active element such as europium nitride and europium oxide (collectively referred to as a raw material compound) are used in the present invention. Weigh and mix to form the oxynitride phosphor of the above to prepare a raw material mixture. The method of mixing the raw material compounds is not particularly limited, but for example, the mixture is mixed using a known mixing device such as a V-type mixer, and further sufficiently mixed using a mortar, a ball mill, a planetary mill, a jet mill, or the like. When mixing europium nitride or the like that reacts violently with moisture and oxygen in the air, it is appropriate to handle it in a glove box replaced with an inert atmosphere.
前記アルミニウム化合物としては、加熱により分解して酸化アルミニウムを産生するアルミニウム含有化合物から選ばれる１種以上のアルミニウム化合物も挙げることができる。 Examples of the aluminum compound include one or more aluminum compounds selected from aluminum-containing compounds that are decomposed by heating to produce aluminum oxide.
また前記光学活性元素を含む化合物とは、Ｍｎ、Ｃｅ、Ｐｒ、Ｎｄ、Ｓｍ、Ｅｕ、Ｔｂ、Ｄｙ、Ｈｏ、Ｅｒ、Ｔｍ、Ｙｂからなる群から選択される１種または２種以上の元素を含む化合物であり、好ましくは酸化物である。これらの元素が蛍光体の発光中心として機能して蛍光特性を発現する。本発明の酸窒化物蛍光体には、ユーロピウムを含む化合物、例えば酸化ユーロピウムが原料として好ましく用いられ、得られる蛍光体は黄色または緑色光を発光する。 The compound containing the optically active element is one or more elements selected from the group consisting of Mn, Ce, Pr, Nd, Sm, Eu, Tb, Dy, Ho, Er, Tm, and Yb. It is a compound containing, preferably an oxide. These elements function as the light emitting center of the phosphor and exhibit fluorescence characteristics. For the oxynitride phosphor of the present invention, a compound containing europium, for example, europium oxide is preferably used as a raw material, and the obtained phosphor emits yellow or green light.
＜高温焼成工程＞
高温焼成工程では、混合工程で得た原料混合物を焼成容器に充填して焼成を行う。原料混合物を充填した焼成容器は、蓋付き容器であることが好ましい。前記焼成容器は、高温の雰囲気ガス下において物理的、化学的に安定であり、原料混合物及びその反応生成物である粗な酸窒化物蛍光体（即ち第１の焼成物）と反応しない材質で構成されることが好ましく、例えば窒化ホウ素製の容器を使用することが好ましい。
<High temperature firing process>
In the high-temperature firing step, the raw material mixture obtained in the mixing step is filled in a firing container and fired. The firing container filled with the raw material mixture is preferably a container with a lid. The firing vessel is made of a material that is physically and chemically stable under a high temperature atmospheric gas and does not react with the raw material mixture and the crude oxynitride phosphor (that is, the first fired product) which is a reaction product thereof. It is preferably configured, for example, a container made of boron nitride is preferably used.
高温焼成工程では、好ましくは１８００℃以上２５００℃以下、さらに好ましくは１８５０℃以上２０５０℃以下の温度範囲で焼成することができる。高温焼成の温度が１８００℃以上であれば発光中心元素であるＥｕ２＋が酸窒化物蛍光体結晶中に入り込むことができ、十分な発光強度を有する酸窒化物蛍光体が得られる。高温焼成工程の焼成温度が２５００℃以下であれば、焼成物の分解を抑制でき好ましい。なお、高温焼成工程の焼成温度が２０５０℃以下であれば、１．０ＭＰａ以下の圧力で焼成が可能で、特に高圧の雰囲気圧力を設定して蛍光体の分解を抑制する必要がなく、その為に特殊な装置を必要とすることもないので工業的生産性の面からは好ましい。 In the high-temperature firing step, firing can be performed in a temperature range of preferably 1800 ° C. or higher and 2500 ° C. or lower, and more preferably 1850 ° C. or higher and 2050 ° C. or lower. When the high-temperature firing temperature is 1800 ° C. or higher, Eu 2+, which is a luminescence center element, can enter the oxynitride phosphor crystal, and an oxynitride phosphor having sufficient emission intensity can be obtained. When the firing temperature in the high-temperature firing step is 2500 ° C. or lower, decomposition of the fired product can be suppressed, which is preferable. If the firing temperature in the high-temperature firing step is 2050 ° C. or lower, firing can be performed at a pressure of 1.0 MPa or lower, and it is not necessary to set a particularly high atmospheric pressure to suppress decomposition of the phosphor. It is preferable from the viewpoint of industrial productivity because it does not require any special equipment.
高温焼成工程では、雰囲気圧力が０．１ＭＰａ以上１０ＭＰａ以下の条件下で行うことが好ましい。より好ましくは０．１ＭＰａ以上２．０ＭＰａ以下であり、さらに好ましくは０．５ＭＰａ以上１．５ＭＰａ以下である。雰囲気圧力が高いほど、酸窒化物蛍光体の分解温度は高くなるが、工業的生産性や焼成装置の耐圧性を考慮すると０．５ＭＰａ以上１ＭＰａ以下とすることが好ましい。また雰囲気ガスの種類としては窒素が好ましい The high-temperature firing step is preferably performed under the condition that the atmospheric pressure is 0.1 MPa or more and 10 MPa or less. It is more preferably 0.1 MPa or more and 2.0 MPa or less, and further preferably 0.5 MPa or more and 1.5 MPa or less. The higher the atmospheric pressure, the higher the decomposition temperature of the oxynitride phosphor, but it is preferably 0.5 MPa or more and 1 MPa or less in consideration of industrial productivity and the pressure resistance of the firing apparatus. Nitrogen is preferable as the type of atmospheric gas.
高温焼成工程の焼成時間は、未反応物が多く存在したり、粒成長不足であったり、或いは生産性の低下という不都合が生じないことを考慮して時間範囲が選択される。本発明では、焼成時間は０．５時間以上２４時間以下であることが好ましく、１時間以上１８時間以下であることがより好ましい。 The firing time of the high-temperature firing step is selected in consideration of the presence of many unreacted substances, insufficient grain growth, and the absence of inconveniences such as a decrease in productivity. In the present invention, the firing time is preferably 0.5 hours or more and 24 hours or less, and more preferably 1 hour or more and 18 hours or less.
＜解砕・粉砕工程＞
高温焼成工程で得られる第１の焼成物は粗な酸窒化物蛍光体であり、粒状又は塊状となるので冷却した後、解砕、粉砕及び／又はさらに分級操作と組み合わせて所定サイズの粉末状にする、即ち、以下に示すような処理操作を行う解砕・粉砕工程を設けることが可能である。具体的な処理操作の例としては、第１の焼成物を解砕して粉砕し、目開き２０μｍ以上４５μｍ以下の範囲で篩分級処理し、篩を通過した粉末を得る方法、あるいは第１の焼成物をボールミルや振動ミル、ジェットミル等の一般的な粉砕機を使用して所定の粒度に粉砕する方法が挙げられる。なお、粉砕機を使用する場合は、なるべく緩和な粉砕装置や粉砕条件を採用し、第１の焼成物に機械的なダメージを与えないようにすることが好ましい。
<Crushing / crushing process>
The first calcined product obtained in the high-temperature calcining step is a crude oxynitride phosphor, which becomes granular or lumpy. Therefore, after cooling, it is crushed, pulverized, and / or further combined with a classification operation to form a powder of a predetermined size. That is, it is possible to provide a crushing / crushing step in which the following processing operations are performed. As an example of a specific treatment operation, a method of crushing and crushing the first fired product and sieving the first calcined product in a range of 20 μm or more and 45 μm or less to obtain a powder that has passed through the sieve, or the first method. Examples thereof include a method of crushing the fired product to a predetermined particle size using a general crusher such as a ball mill, a vibration mill, or a jet mill. When using a crusher, it is preferable to adopt a crushing device and crushing conditions that are as mild as possible so as not to cause mechanical damage to the first fired product.
また、前記粉砕処理の際には、不純物元素の混入を防ぐため、被粉砕物である第１の焼成物と接触する粉砕装置の部品は、窒化ケイ素、アルミナ、サイアロンといった高靭性セラミックス製であることが好ましい。解砕・粉砕工程が終了した第１の焼成物は、励起光の吸収効率が高く、また十分な発光効率を発揮するＬＥＤ用の酸窒化物蛍光体を最終的に得るという点からは、平均粒径が５０μｍ以下の粉末状となるように調整することが好ましい。 Further, in order to prevent the mixing of impurity elements during the crushing treatment, the parts of the crushing device that come into contact with the first fired product to be crushed are made of high toughness ceramics such as silicon nitride, alumina, and sialon. Is preferable. The first fired product after the crushing / crushing process has high absorption efficiency of excitation light and is average from the viewpoint of finally obtaining an oxynitride phosphor for LED exhibiting sufficient luminous efficiency. It is preferable to adjust the particle size so that it is in the form of a powder of 50 μm or less.
＜低温焼成工程＞
低温焼成工程は、例えば粉末状とした前記第１の焼成物を、円筒型窒化ホウ素製容器に再充填し、カーボンヒーターの電気炉で、例えば大気圧のアルゴンフロー雰囲気下で焼成する。低温焼成工程における焼成温度は、１２００℃以上１８００℃以下の範囲が好ましく、より好ましくは１４００℃以上１７００℃以下の範囲である。低温焼成する時間は、例えば、５時間以上１０時間以下の範囲である。なお本発明の酸窒化物蛍光体の製造方法では、所定の条件で実施した低温焼成工程が終了し、第２の焼成物を得る室温（２５℃）までの冷却過程の途中において、８００℃以上１０００℃以下の範囲内の一定温度で、好ましくは８５０℃以上９５０℃以下の範囲内の一定温度で、少なくとも３時間以上、好ましくは１０時間以上、より好ましくは１５時間以上保持する。本発明の酸窒化物蛍光体の製造方法においては、８００℃以上１０００℃以下の範囲内の一定温度で所定時間保持できれば、そのほか特に限定すべき条件はなく、８００℃以上１０００℃以下の範囲内で温度を一定に保つように設定したり、低温焼成工程の終了時の温度から室温（例えば２５℃）までの冷却過程において、８００℃以上１０００℃以下の温度範囲で少なくとも３時間以上要するように冷却速度を適宜設定することができる。この際は冷却速度を一定とすることが好ましい。なお一定温度で所定時間保持することの意味としては、なるべく一定温度を保つことが好ましいという意味であり、本発明では例えば焼成装置の不可避的な温度制御等に由来する温度変動幅は許容されるものとし、例えば保持する設定温度プラスマイナス１０℃の幅は認められるものとする。
<Low temperature firing process>
In the low-temperature firing step, for example, the powdered first fired product is refilled in a cylindrical boron nitride container and fired in an electric furnace of a carbon heater, for example, in an argon flow atmosphere at atmospheric pressure. The firing temperature in the low-temperature firing step is preferably in the range of 1200 ° C. or higher and 1800 ° C. or lower, and more preferably in the range of 1400 ° C. or higher and 1700 ° C. or lower. The time for low-temperature firing is, for example, in the range of 5 hours or more and 10 hours or less. In the method for producing an oxynitride phosphor of the present invention, the low temperature firing step carried out under predetermined conditions is completed, and 800 ° C. or higher is in the middle of the cooling process to room temperature (25 ° C.) for obtaining the second fired product. It is held at a constant temperature within the range of 1000 ° C. or lower, preferably at a constant temperature within the range of 850 ° C. or higher and 950 ° C. or lower, for at least 3 hours or longer, preferably 10 hours or longer, and more preferably 15 hours or longer. In the method for producing an oxynitride phosphor of the present invention, if the temperature can be maintained at a constant temperature within the range of 800 ° C. or higher and 1000 ° C. or lower for a predetermined time, there are no other conditions to be particularly limited, and the temperature is within the range of 800 ° C. or higher and 1000 ° C. or lower. In the cooling process from the temperature at the end of the low temperature firing process to room temperature (for example, 25 ° C), it takes at least 3 hours in the temperature range of 800 ° C or more and 1000 ° C or less. The cooling rate can be set as appropriate. In this case, it is preferable to keep the cooling rate constant. It should be noted that the meaning of holding the temperature at a constant temperature for a predetermined time means that it is preferable to keep the temperature constant as much as possible, and in the present invention, for example, the temperature fluctuation range derived from the unavoidable temperature control of the firing apparatus is allowed. For example, the range of the set temperature to be held plus or minus 10 ° C. is allowed.
低温焼成工程における雰囲気ガスは、ヘリウム、ネオン、アルゴン、クリプトン、キセノンまたはラドンから選ばれる１種の希ガスまたは２種以上の混合希ガスを用いることができる。好ましくはアルゴンガスである。 As the atmospheric gas in the low-temperature firing step, one kind of rare gas selected from helium, neon, argon, krypton, xenon or radon or two or more kinds of mixed rare gases can be used. Argon gas is preferable.
＜酸処理工程＞
酸処理工程は、低温焼成工程によって得られた第２の焼成物中に、なお残留する化学的に不安定な低結晶性部分や目的とする酸窒化物蛍光体と異なる相を酸で処理して除去する工程である。酸処理には特に決められた操作手順はないが、例えば塩酸、蟻酸、酢酸、硫酸、硝酸、フッ化水素酸から選ばれる１種以上の酸水溶液に、第２の焼成物を加えて分散液とし、これを必要に応じて５０℃以上、必要ならば沸騰状態になる温度になるまで加熱して、数分から数時間撹拌して処理することができる。酸処理の終了後は水洗して酸を除去し、乾燥して酸窒化物蛍光体を得ることができる。酸処理の実施によって、不純物元素、焼成工程で生じた異相を溶解除去することができる。また、蛍光体の粒子表面に蛍光体に含まれる元素と酸素との複合物からなると推定される表面層が形成されることもあり、酸窒化物蛍光体の安定性がさらに高まることもある。蛍光特性を損なうような微粉が含まれる場合には、乾燥前に湿式沈降法等により微粉を除去してもよい。
<Acid treatment process>
In the acid treatment step, a chemically unstable low crystalline portion still remaining in the second fired product obtained by the low temperature firing step and a phase different from the target oxynitride phosphor are treated with an acid. It is a process of removing. There is no specific operating procedure for acid treatment, but for example, a second calcined product is added to one or more aqueous acid solutions selected from hydrochloric acid, formic acid, acetic acid, sulfuric acid, nitric acid, and hydrofluoric acid to make a dispersion. If necessary, this can be heated to 50 ° C. or higher, and if necessary, to a temperature at which it reaches a boiling state, and the mixture can be treated by stirring for several minutes to several hours. After completion of the acid treatment, the acid can be removed by washing with water and dried to obtain an oxynitride phosphor. By carrying out the acid treatment, the impurity element and the heterogeneous phase generated in the firing step can be dissolved and removed. Further, a surface layer presumed to be composed of a composite of an element contained in the phosphor and oxygen may be formed on the particle surface of the phosphor, and the stability of the oxynitride phosphor may be further enhanced. If fine powder that impairs the fluorescence characteristics is contained, the fine powder may be removed by a wet precipitation method or the like before drying.
＜酸窒化物蛍光体の組成＞
本発明に係る酸窒化物蛍光体は、（式１）で示される化学組成を有する酸窒化物蛍光体である。
Ｓｉ１２−ａＡｌａＯｂＮ１６−ｂ：Ｅｕｘ （式１）
但し（式１）において、０＜ａ≦３、０＜ｂ≦３、０＜ｘ≦０．１
ここで（式１）に関する酸窒化物蛍光体の組成について、ａ、ｂ、ｘの値は原料化合物中に含まれるシリコン、アルミニウム、ユーロピウムについて、それぞれ合計した原子数の比から求めることができる。
<Composition of oxynitride phosphor>
The oxynitride phosphor according to the present invention is an oxynitride phosphor having a chemical composition represented by (Formula 1).
Si 12-a Al a Ob N 16-b : Eu x (Equation 1)
However, in (Equation 1), 0 <a ≦ 3, 0 <b ≦ 3, 0 <x ≦ 0.1
Here, regarding the composition of the oxynitride phosphor according to (Formula 1), the values of a, b, and x can be obtained from the ratio of the total number of atoms of silicon, aluminum, and europium contained in the raw material compound.
本発明の酸窒化物蛍光体は、波長４５５ｎｍの光を照射した際に発する蛍光のスペクトルのピーク波長をＶｎｍ、及びそのときの外部量子効率Ｗ％において、ＶとＷとが、（式２）の関係を満たしている酸窒化物蛍光体である。
Ｗ＞１．３×Ｖ−６４８．５ （式２）
In the oxynitride phosphor of the present invention, V and W are (Equation 2) when the peak wavelength of the fluorescence spectrum emitted when irradiated with light having a wavelength of 455 nm is V nm and the external quantum efficiency W% at that time. It is an oxynitride phosphor that satisfies the above relationship.
W> 1.3 × V-64.8 (Equation 2)
（蛍光スペクトルのピーク波長の測定方法）
ここで、前記波長４５５ｎｍの光を照射した際に発する蛍光のスペクトルのピーク波長は、ローダミンＢ法及び標準光源により校正した分光蛍光光度計（日立ハイテクノロジーズ社製、Ｆ−７０００）にて、専用の固体試料ホルダーに蛍光体粉末を充填して、波長４５５ｎｍに分光した励起光を照射した時の蛍光スペクトルを測定して求めた値である。なお本発明の酸窒化物蛍光体では、波長４５５ｎｍの光を照射した際に発する蛍光のスペクトルのピーク波長が、５２４ｎｍ以上５５５ｎｍ以下であることが好ましい。
(Measurement method of peak wavelength of fluorescence spectrum)
Here, the peak wavelength of the fluorescence spectrum emitted when the light having the wavelength of 455 nm is irradiated is dedicated by a spectrofluorescence photometer (manufactured by Hitachi High-Technologies Co., Ltd., F-7000) calibrated by the Rhodamine B method and a standard light source. It is a value obtained by measuring the fluorescence spectrum when the solid sample holder of No. 1 is filled with a phosphor powder and irradiated with excitation light dispersed at a wavelength of 455 nm. In the oxynitride phosphor of the present invention, the peak wavelength of the fluorescence spectrum emitted when irradiated with light having a wavelength of 455 nm is preferably 524 nm or more and 555 nm or less.
（外部量子効率の測定方法）
また、前記波長４５５ｎｍの光を照射した際の外部量子効率は、一般的に知られている分光光度計に積分球を搭載した測定システムを用いて求めた値である。即ち、反射率９９％の標準反射板（スペクトラロン、Ｌａｂｓｐｈｅｒｅ社製）が、その側面開口部（φ１０ｍｍ）にセットしてある積分球（φ６０ｍｍ）内に、発光光源であるＸｅランプから、４５５ｎｍの波長に分光した単色光を光ファイバーにより導入し、前記標準反射板からの反射光のスペクトルを、分光光度計（ＭＣＰＤ−７０００、大塚電子社製）により測定した。なお本測定に際し、測定時の環境温度は２５±２℃とし、４５０ｎｍ以上４６５ｎｍ以下の波長範囲のスペクトルから励起光フォトン数（Ｑｅｘとする）を得た。次に、表面が平滑になるように蛍光体サンプルを充填した凹型セルを積分球の開口部にセットし、波長４５５ｎｍの単色光を照射して、励起の反射光及び蛍光のスペクトルを分光光度計により測定した。得られたスペクトルデータから励起反射光フォトン数（Ｑｒｅｆとする）及び蛍光フォトン数（Ｑｅｍとする）を得た。なお、励起反射光フォトン数は、励起光フォトン数と同じ波長範囲で、蛍光フォトン数は、４６５ｎｍ以上８００ｎｍ以下の波長範囲で求めた値である。得られた三種類のフォトン数から、外部量子効率Ｗ（％）＝Ｑｅｍ／Ｑｅｘ×１００の値を算出した。なお、本発明でいう外部量子効率Ｗ（％）の数値部Ｗは、前記外部量子効率（％）の数値そのものを指している。
(Measurement method of external quantum efficiency)
The external quantum efficiency when irradiated with light having a wavelength of 455 nm is a value obtained by using a measurement system in which an integrating sphere is mounted on a generally known spectrophotometer. That is, a standard reflector (Spectralon, manufactured by Labsphere) having a reflectance of 99% is placed in an integrating sphere (φ60 mm) set in the side opening (φ10 mm) of the Xe lamp, which is a light emitting light source, at 455 nm. Monochromatic light dispersed in wavelength was introduced by an optical fiber, and the spectrum of the reflected light from the standard reflector was measured by a spectrophotometer (MCPD-7000, manufactured by Otsuka Electronics Co., Ltd.). In this measurement, the ambient temperature at the time of measurement was 25 ± 2 ° C., and the number of excited photons (referred to as Qex) was obtained from the spectrum in the wavelength range of 450 nm or more and 465 nm or less. Next, a concave cell filled with a phosphor sample so that the surface becomes smooth is set in the opening of the integrating sphere, monochromatic light having a wavelength of 455 nm is irradiated, and the spectra of the reflected light and fluorescence of the excitation are measured by a spectrophotometer. Measured by. From the obtained spectral data, the number of excited reflected light photons (referred to as Qref) and the number of fluorescent photons (referred to as Qem) were obtained. The number of excited reflected light photons is in the same wavelength range as the number of excited light photons, and the number of fluorescent photons is a value obtained in a wavelength range of 465 nm or more and 800 nm or less. From the obtained three types of photon numbers, the value of external quantum efficiency W (%) = Qem / Qex × 100 was calculated. The numerical value portion W of the external quantum efficiency W (%) in the present invention refers to the numerical value itself of the external quantum efficiency (%).
（光の吸収率の測定方法）
本発明の酸窒化物蛍光体は、波長４５５ｎｍの光に対する吸収率をＭ％、波長６００ｎｍの光に対する吸収率をＮ％としたとき、前記Ｍ及びＮが（式３）で示される関係を満たすことが好ましい。
Ｍ＞６Ｎ （式３）
(Measurement method of light absorption rate)
The oxynitride phosphor of the present invention satisfies the relationship represented by (Equation 3) when the absorption rate for light having a wavelength of 455 nm is M% and the absorption rate for light having a wavelength of 600 nm is N%. Is preferable.
M> 6N (Equation 3)
波長４５５ｎｍの光に対する吸収率Ｍ％、及び波長６００ｎｍの光に対する吸収率Ｎ％は、外部量子効率と同じ装置を用い、各波長の光に対する吸収率（＝（（Ｑｅｘ−Ｑｒｅｆ）／（Ｑｅｘ））×１００）を求めた値である。但し、波長６００ｎｍの光に対する吸収率を測定する際は、積分球に導入する光の波長は６００ｎｍとする必要がある。また、波長６００ｎｍの光に対する吸収率を測定する際のＱｅｘ、Ｑｒｅｆ（フォトン数）は、２２０ｎｍ以上、８００ｎｍ以下の波長範囲で求めた値である。なお、本発明の酸窒化物蛍光体では、波長６００ｎｍの光に対する吸収率は９％以下であることが好ましい。 The absorption rate M% for light having a wavelength of 455 nm and the absorption rate N% for light having a wavelength of 600 nm are the absorption rates for light of each wavelength (= ((Qex-Qref) / (Qex)) using the same device as the external quantum efficiency. ) × 100) is the calculated value. However, when measuring the absorption rate for light having a wavelength of 600 nm, the wavelength of the light introduced into the integrating sphere needs to be 600 nm. Further, Qex and Qref (number of photons) when measuring the absorption rate for light having a wavelength of 600 nm are values obtained in a wavelength range of 220 nm or more and 800 nm or less. In the oxynitride phosphor of the present invention, the absorption rate for light having a wavelength of 600 nm is preferably 9% or less.
また、本発明は、本発明の酸窒化物蛍光体を含む発光素子である。なお本発光素子では、本発明の酸窒化物蛍光体に加えて、他の蛍光体を併用してもよい。本発明の蛍光体と併用できる他の蛍光体に特に限定はなく、発光素子に要求される輝度、色や演色性等に応じて適宜選択可能である。特に白色の発光素子とする場合には、本発明の酸窒化物蛍光体の他に赤色蛍光体も含ませることができる。赤色蛍光体としては、ＫＳＦを含むフッ化物蛍光体、Ｍｎ４＋を発光源とした赤色蛍光体、一般式：Ｃａ２（Ｓｉ、Ａｌ）５Ｎ８で表される組成に希土類元素が賦活されたＣＡＳＮ、一般式：ＳｒＣａ２（Ｓｉ、Ａｌ）５Ｎ８で表される組成に希土類元素が賦活されたＳＣＡＳＮを含む窒化物蛍光体、赤色の量子ドット蛍光体の中から選定される蛍光体を挙げることができる。また前記赤色蛍光体の代わりに、赤色ＬＥＤまたは赤色ＬＤまたは赤色の有機ＥＬを組み合わせることも可能である。またシリコーン樹脂は、公知の熱硬化性シリコーン樹脂を好ましく用いることができる。発光素子の特性は、例えば実際に青色ＬＥＤのチップ上に、本発明の酸窒化物蛍光体を含む熱硬化性シリコーン樹脂組成物をポッティングした発光素子を作製し、前記発光素子が発する全光束値を測定することにより評価することができる。さらに本発明は、前記本発明の酸窒化物蛍光体を含む発光素子を用いた、液晶ディスプレー、液晶パネルのバックライト、照明装置、信号装置、画像表示装置、プロジェクター用途照明器具や発光パネルなどの発光装置である。 Further, the present invention is a light emitting device containing the oxynitride phosphor of the present invention. In the present light emitting device, in addition to the oxynitride phosphor of the present invention, another phosphor may be used in combination. The other phosphors that can be used in combination with the phosphor of the present invention are not particularly limited, and can be appropriately selected depending on the brightness, color, color rendering property, etc. required for the light emitting element. In particular, when a white light emitting device is used, a red phosphor can be included in addition to the oxynitride phosphor of the present invention. As the red phosphor, a fluoride phosphor containing KSF, a red phosphor using Mn 4+ as a light emitting source, and a rare earth element were activated in the composition represented by the general formula: Ca 2 (Si, Al) 5 N 8. CASN, general formula: SrCa 2 (Si, Al) 5 A phosphor selected from a nitride phosphor containing SCANS in which a rare earth element is activated in a composition represented by 5 N 8 and a red quantum dot phosphor. Can be mentioned. It is also possible to combine a red LED or a red LD or a red organic EL instead of the red phosphor. Further, as the silicone resin, a known thermosetting silicone resin can be preferably used. As for the characteristics of the light emitting element, for example, a light emitting element in which a thermosetting silicone resin composition containing the oxynitride phosphor of the present invention is actually potted on a blue LED chip is produced, and the total luminous flux value emitted by the light emitting element is obtained. Can be evaluated by measuring. Further, the present invention relates to a liquid crystal display, a backlight of a liquid crystal panel, a lighting device, a signal device, an image display device, a lighting fixture for a projector, a light emitting panel, etc. using the light emitting element containing the oxynitride phosphor of the present invention. It is a light emitting device.
本発明に係る実施例、比較例を以下に示し、本発明をさらに具体的に説明する。 Examples and comparative examples according to the present invention are shown below, and the present invention will be described in more detail.
（実施例１）
＜混合工程＞
配合組成としてＳｉ：Ａｌ：Ｏ：Ｅｕ＝１１．９５０：０．０５０：０．０５０：０．０１０、即ち（式１）のａが０．０５０、ｂが０．０５０、ｘが０．０１０、となるように、α型窒化ケイ素粉末（ＳＮ−Ｅ１０グレード、宇部興産社製）、窒化アルミニウム粉末（Ｅグレード、トクヤマ社製）、酸化アルミニウム粉末（ＴＭ−ＤＡＲグレード、大明化学社製）、酸化ユウロピウム（ＲＵグレード、信越化学工業社製）の原料化合物を配合し、これらを小型ミルミキサーで混合し、その後、目開き１５０μｍの篩を全通させて凝集物を取り除き、原料混合物を得た。
(Example 1)
<Mixing process>
As a compounding composition, Si: Al: O: Eu = 11.950: 0.050: 0.050: 0.010, that is, a in (Equation 1) is 0.050, b is 0.050, and x is 0.010. Α-type silicon nitride powder (SN-E10 grade, manufactured by Ube Kosan Co., Ltd.), aluminum nitride powder (E grade, manufactured by Tokuyama Co., Ltd.), aluminum oxide powder (TM-DAR grade, manufactured by Daimei Kagaku Co., Ltd.), A raw material compound of uropium oxide (RU grade, manufactured by Shin-Etsu Chemical Industry Co., Ltd.) was blended, and these were mixed with a small mill mixer. Then, a sieve having a mesh size of 150 μm was passed through to remove agglomerates to obtain a raw material mixture. ..
＜高温焼成工程＞
前記原料混合物を、蓋付き円筒型窒化ホウ素製容器（デンカ社製）に充填し、カーボンヒーター電気炉で、０．８ＭＰａの加圧窒素雰囲気下、２０１０℃で１７時間の高温焼成を行い、実施例１に関する第１の焼成物を得た。これをボールミル（アルミナボール）で粉砕した後、目開き４５μｍの篩に通して回収した。
<High temperature firing process>
The raw material mixture was filled in a cylindrical boron nitride container with a lid (manufactured by Denka Co., Ltd.) and calcined at a high temperature of 2010 ° C. for 17 hours in a carbon heater electric furnace under a pressurized nitrogen atmosphere of 0.8 MPa. The first fired product according to Example 1 was obtained. This was pulverized with a ball mill (alumina ball) and then passed through a sieve having a mesh size of 45 μm for recovery.
＜低温焼成工程＞
前記４５μｍの篩に通して回収した第１の焼成物を、再度円筒型窒化ホウ素製容器（デンカ社製）に充填し、カーボンヒーター電気炉で、大気圧のアルゴンフロー雰囲気下、１５００℃で７時間の低温焼成を行った。なお低温焼成工程終了後、即ち１５００℃から室温（２５℃）までの冷却課程の途中において、９００℃で２０時間の定温保持を行い、実施例１に関する第２の焼成物を得た。なお前記冷却課程において１５００℃から９００℃まで、９００℃から室温（２５℃）までの間の冷却速度は一定とした。この冷却速度は、各実施例、各比較例共に同じとした。
<Low temperature firing process>
The first fired product recovered through the 45 μm sieve is refilled in a cylindrical boron nitride container (manufactured by Denka Co., Ltd.), and is placed in a carbon heater electric furnace at 1500 ° C. under an atmospheric argon flow atmosphere. Low temperature firing for hours was performed. After the completion of the low-temperature firing step, that is, during the cooling process from 1500 ° C. to room temperature (25 ° C.), constant temperature was maintained at 900 ° C. for 20 hours to obtain a second fired product according to Example 1. In the cooling process, the cooling rate was constant from 1500 ° C. to 900 ° C. and from 900 ° C. to room temperature (25 ° C.). This cooling rate was the same for each Example and each Comparative Example.
＜酸処理工程＞
前記第２の焼成物を、フッ化水素酸と硝酸との混酸溶液中に６０℃以上３時間浸して酸処理した。その後、上澄みと微粉を除去するためのデカンテーション操作を、溶液が中性になるまで繰り返し、最終的に得られた沈殿物をろ過、乾燥し、更に目開き４５μｍの篩を通過させ、実施例１の酸窒化物蛍光体を得た。
<Acid treatment process>
The second fired product was immersed in a mixed acid solution of hydrofluoric acid and nitric acid at 60 ° C. or higher for 3 hours for acid treatment. Then, the decantation operation for removing the supernatant and fine powder was repeated until the solution became neutral, and the finally obtained precipitate was filtered and dried, and further passed through a sieve having an opening of 45 μm. The oxynitride phosphor of 1 was obtained.
（実施例２）
実施例２では、酸窒化物蛍光体の組成がＳｉ：Ａｌ：Ｏ：Ｅｕ＝１１．９１０：０．０９０：０．０９０：０．０１６となるように原料化合物を配合し、他の工程は実施例１と同様に処理を行い、実施例２の酸窒化物蛍光体を得た。
(Example 2)
In Example 2, the raw material compound was blended so that the composition of the oxynitride phosphor was Si: Al: O: Eu = 11.910: 0.090: 0.090: 0.016, and the other steps were performed. The same treatment as in Example 1 was carried out to obtain an oxynitride phosphor of Example 2.
（実施例３）
実施例３では、酸窒化物蛍光体の組成がＳｉ：Ａｌ：Ｏ：Ｅｕ＝１１．５６０：０．４４０：０．４４０：０．０４０となるように原料化合物を配合し、他の工程は実施例１と同様に処理を行い、実施例３の酸窒化物蛍光体を得た。
(Example 3)
In Example 3, the raw material compound was blended so that the composition of the oxynitride phosphor was Si: Al: O: Eu = 11.560: 0.440: 0.440: 0.040, and the other steps were performed. The same treatment as in Example 1 was carried out to obtain an oxynitride phosphor of Example 3.
（実施例４）
実施例４では、酸窒化物蛍光体の組成がＳｉ：Ａｌ：Ｏ：Ｅｕ＝１１．４００：０．６００：０．６００：０．０６０となるように原料化合物を配合し、他の工程は実施例１と同様に処理を行い、実施例４の酸窒化物蛍光体を得た。
(Example 4)
In Example 4, the raw material compound was blended so that the composition of the oxynitride phosphor was Si: Al: O: Eu = 11.400: 0.600: 0.600: 0.060, and the other steps were performed. The same treatment as in Example 1 was carried out to obtain an oxynitride phosphor of Example 4.
（実施例５）
実施例５では、酸窒化物蛍光体の組成がＳｉ：Ａｌ：Ｏ：Ｅｕ＝１１．５６０：０．４４０：０．４４０：０．０４０となるように原料化合物を配合し、低温焼成工程終了後の冷却過程における定温保持の条件を９００℃で８時間とし、その他の条件は実施例１と同様に処理を行い、実施例５の酸窒化物蛍光体を得た。
(Example 5)
In Example 5, the raw material compound was blended so that the composition of the oxynitride phosphor was Si: Al: O: Eu = 11.560: 0.440: 0.440: 0.040, and the low-temperature firing step was completed. The condition for maintaining a constant temperature in the subsequent cooling process was set to 900 ° C. for 8 hours, and the other conditions were treated in the same manner as in Example 1 to obtain the oxynitride phosphor of Example 5.
（実施例６）
実施例６では、低温焼成工程終了後の冷却過程における定温保持の条件を１０００℃で２０時間とし、その他の酸窒化物蛍光体の組成や、工程の条件については、実施例３と同じとし、実施例６の酸窒化物蛍光体を得た。
(Example 6)
In Example 6, the condition for maintaining a constant temperature in the cooling process after the completion of the low-temperature firing step was set to 1000 ° C. for 20 hours, and the composition of other oxynitride phosphors and the step conditions were the same as in Example 3. The oxynitride phosphor of Example 6 was obtained.
（実施例７）
実施例７では、低温焼成工程終了後の冷却過程における定温保持の条件を８００℃で２０時間とし、その他の酸窒化物蛍光体の組成や、工程の条件については、実施例３と同じとし、実施例７の酸窒化物蛍光体を得た。
(Example 7)
In Example 7, the condition for maintaining a constant temperature in the cooling process after the completion of the low-temperature firing step was set to 800 ° C. for 20 hours, and the composition of other oxynitride phosphors and the step conditions were the same as in Example 3. The oxynitride phosphor of Example 7 was obtained.
（実施例８）
実施例８では、低温焼成工程終了後の冷却過程における定温保持の条件を９００℃で３時間とし、その他の酸窒化物蛍光体の組成や、工程の条件については、実施例３と同じとし、実施例８の酸窒化物蛍光体を得た。
(Example 8)
In Example 8, the condition for maintaining a constant temperature in the cooling process after the completion of the low-temperature firing step was set to 900 ° C. for 3 hours, and the composition of other oxynitride phosphors and the step conditions were the same as in Example 3. The oxynitride phosphor of Example 8 was obtained.
（比較例１）
比較例１では、酸窒化物蛍光体の組成がＳｉ：Ａｌ：Ｏ：Ｅｕ＝１１．９５０：０．０５０：０．０５０：０．０１０となるように原料化合物を配合し、低温焼成工程終了後の冷却過程においては１０００℃から８００℃までの温度範囲での定温保持を実施せず、１５００℃から室温まで実施例１と同じ条件で連続的に一定冷却速度で冷却した。その他の工程は実施例１と同様に処理を行い、比較例１の酸窒化物蛍光体を得た。
(Comparative Example 1)
In Comparative Example 1, the raw material compound was blended so that the composition of the oxynitride phosphor was Si: Al: O: Eu = 11.950: 0.050: 0.050: 0.010, and the low-temperature firing step was completed. In the subsequent cooling process, constant temperature was not maintained in the temperature range of 1000 ° C. to 800 ° C., and the mixture was continuously cooled from 1500 ° C. to room temperature under the same conditions as in Example 1 at a constant cooling rate. The other steps were carried out in the same manner as in Example 1 to obtain the oxynitride phosphor of Comparative Example 1.
（比較例２）
比較例２では、酸窒化物蛍光体の組成がＳｉ：Ａｌ：Ｏ：Ｅｕ＝１１．９１０：０．０９０：０．０９０：０．０１６となるように原料化合物を配合し、他の工程は比較例１と同様に処理を行い、比較例２の酸窒化物蛍光体を得た。
(Comparative Example 2)
In Comparative Example 2, the raw material compound was blended so that the composition of the oxynitride phosphor was Si: Al: O: Eu = 11.910: 0.090: 0.090: 0.016, and the other steps were performed. The same treatment as in Comparative Example 1 was carried out to obtain an oxynitride phosphor of Comparative Example 2.
（比較例３）
比較例３では、酸窒化物蛍光体の組成がＳｉ：Ａｌ：Ｏ：Ｅｕ＝１１．５６０：０．４４０：０．４４０：０．０４０となるように原料化合物を配合し、他の工程は比較例１と同様に処理を行い、比較例３の酸窒化物蛍光体を得た。
(Comparative Example 3)
In Comparative Example 3, the raw material compound was blended so that the composition of the oxynitride phosphor was Si: Al: O: Eu = 11.560: 0.440: 0.440: 0.040, and the other steps were performed. The same treatment as in Comparative Example 1 was carried out to obtain an oxynitride phosphor of Comparative Example 3.
（比較例４）
比較例４では、酸窒化物蛍光体の組成がＳｉ：Ａｌ：Ｏ：Ｅｕ＝１１．３６０：０．６４０：０．６４０：０．０６０となるように原料化合物を配合し、他の工程は比較例１と同様に処理を行い、比較例４の酸窒化物蛍光体を得た。
(Comparative Example 4)
In Comparative Example 4, the raw material compound was blended so that the composition of the oxynitride phosphor was Si: Al: O: Eu = 11.360: 0.640: 0.640: 0.060, and the other steps were performed. The same treatment as in Comparative Example 1 was carried out to obtain an oxynitride phosphor of Comparative Example 4.
（比較例５）
比較例５では、低温焼成工程終了後の冷却過程における定温保持の条件を１０５０℃で２０時間とし、その他の酸窒化物蛍光体の組成や、工程の条件については、実施例３と同じとし、比較例５の酸窒化物蛍光体を得た。
(Comparative Example 5)
In Comparative Example 5, the condition for maintaining a constant temperature in the cooling process after the completion of the low-temperature firing step was set to 1050 ° C. for 20 hours, and the composition of other oxynitride phosphors and the step conditions were the same as in Example 3. The oxynitride phosphor of Comparative Example 5 was obtained.
（比較例６）
比較例６では、低温焼成工程終了後の冷却過程における定温保持の条件を７５０℃で２０時間とし、その他の酸窒化物蛍光体の組成や、工程の条件については、実施例３と同じとし、比較例６の酸窒化物蛍光体を得た。
(Comparative Example 6)
In Comparative Example 6, the conditions for maintaining a constant temperature in the cooling process after the completion of the low-temperature firing step were set to 750 ° C. for 20 hours, and the composition of other oxynitride phosphors and the step conditions were the same as in Example 3. The oxynitride phosphor of Comparative Example 6 was obtained.
（比較例７）
比較例７では、低温焼成工程終了後の冷却過程における定温保持の条件を９００℃で２時間とし、その他の酸窒化物蛍光体の組成や、工程の条件については、実施例３と同じとし、比較例７の酸窒化物蛍光体を得た。
(Comparative Example 7)
In Comparative Example 7, the condition for maintaining a constant temperature in the cooling process after the completion of the low-temperature firing step was set to 900 ° C. for 2 hours, and the composition of other oxynitride phosphors and the step conditions were the same as in Example 3. The oxynitride phosphor of Comparative Example 7 was obtained.
（比較例８）
比較例８では、低温焼成の温度を９００℃として、そのまま２０時間焼成を続けた後、室温まで冷却した。酸窒化物蛍光体の組成、及びその他の工程の条件については、実施例３と同じとし、比較例８の酸窒化物蛍光体を得た。
(Comparative Example 8)
In Comparative Example 8, the temperature of low-temperature firing was set to 900 ° C., firing was continued for 20 hours, and then cooled to room temperature. The composition of the oxynitride phosphor and the conditions of other steps were the same as in Example 3, and the oxynitride phosphor of Comparative Example 8 was obtained.
実施例１〜８、比較例１〜８の酸窒化物蛍光体の組成に係る、（式１）のａ、ｂ、ｘの値、高温焼成温度、高温焼成時間、低温焼成温度、低温焼成時間、低温焼成温度から室温（２５℃）まで冷却過程の途中において１０００℃から８００℃までの温度範囲内での保持温度及び保持時間を表１にまとめて示した。 Values of a, b, x of (Equation 1), high temperature firing temperature, high temperature firing time, low temperature firing temperature, low temperature firing time relating to the composition of the oxynitride phosphors of Examples 1 to 8 and Comparative Examples 1 to 8. Table 1 summarizes the holding temperature and holding time in the temperature range from 1000 ° C. to 800 ° C. during the cooling process from the low temperature firing temperature to room temperature (25 ° C.).
＜酸窒化物蛍光体のピーク波長、吸収率＞
実施例１〜８、比較例１〜８の各酸窒化物蛍光体の、波長４５５ｎｍの光を励起光として照射した際に発する蛍光のスペクトルのピーク波長、及び波長４５５ｎｍと波長６００ｎｍの光に対する吸収率は、積分球（φ６０ｍｍ）と分光光度計（ＭＣＰＤ−７０００、大塚電子社製）を用いて測定し、表２に示した。例えば実施例１の酸窒化物蛍光体を測定する場合には、粉末状の前記蛍光体を、表面が平滑になるように積分球付属の凹型セルに充填して球内部に取り付け、前記積分球内に、発光光源（Ｘｅランプ）から分光した、波長４５５ｎｍまたは波長６００ｎｍの光を、光ファイバーを通じて導入し、蛍光体が発した蛍光を分光光度計で測定して、ピーク波長、吸収率を測定することができる。実施例２〜８、比較例１〜８の酸窒化物蛍光体も同様に測定することができる。なお上記の測定法を用い、株式会社サイアロンより販売している標準試料ＮＳＧ１３０１を測定した場合、波長４５５ｎｍの光に対する蛍光のピーク波長は５４３ｎｍ、波長４５５ｎｍの光に対する吸収率は７４．４％、波長６００ｎｍの光に対する吸収率は７．６％となった。この値を基準として測定値を補正した。実施例２〜８、比較例１〜８の酸窒化物蛍光体についても同様の方法で、酸窒化物蛍光体のピーク波長、吸収率の値をそれぞれ求め、表２に併せて示した。また（式２）に蛍光ピーク波長Ｖｎｍの数値部の値を代入し、本発明の酸窒化物蛍光体が、超えるべき外部量子効率Ｗの値（％表示の数値部）を算出し、表２に併せて示した。さらに（式３）に波長６００ｎｍの光に対する吸収率Ｎ％の数値部の値を代入し、本発明の酸窒化物蛍光体が、超えると好ましい波長４５０ｎｍの光に対する吸収率Ｍの値（％表示の数値部）を算出し、表２に併せて示した。なお、４５０ｎｍの光に対する吸収率Ｍの実測値が４５０ｎｍの光に対する吸収率Ｍの目標値を超えるものを○として判定し、４５０ｎｍの光に対する吸収率Ｍの目標値を超えないものを×として判定し、表２に併せて示した。
<Peak wavelength and absorption rate of oxynitride phosphor>
Absorption of the oxynitride phosphors of Examples 1 to 8 and Comparative Examples 1 to 8 into the peak wavelength of the fluorescence spectrum emitted when light having a wavelength of 455 nm is irradiated as excitation light, and to light having a wavelength of 455 nm and a wavelength of 600 nm. The rate was measured using an integrating sphere (φ60 mm) and a spectrophotometer (MCPD-7000, manufactured by Otsuka Denshi Co., Ltd.) and is shown in Table 2. For example, when measuring the oxynitride phosphor of Example 1, the powdery phosphor is filled in a concave cell attached to an integrating sphere so that the surface becomes smooth, and attached to the inside of the sphere, and the integrating sphere is attached. Light having a wavelength of 455 nm or 600 nm, which is dispersed from a light emitting light source (Xe lamp), is introduced through an optical fiber, and the fluorescence emitted by the phosphor is measured with a spectrophotometer to measure the peak wavelength and absorption rate. be able to. The oxynitride phosphors of Examples 2 to 8 and Comparative Examples 1 to 8 can be measured in the same manner. When the standard sample NSG1301 sold by Sialon Co., Ltd. was measured using the above measurement method, the peak wavelength of fluorescence for light with a wavelength of 455 nm was 543 nm, the absorption rate for light with a wavelength of 455 nm was 74.4%, and the wavelength. The absorption rate for light at 600 nm was 7.6%. The measured value was corrected based on this value. For the oxynitride phosphors of Examples 2 to 8 and Comparative Examples 1 to 8, the peak wavelengths and absorption rates of the oxynitride phosphors were obtained by the same method, and are shown in Table 2 as well. Further, by substituting the value of the numerical value part of the fluorescence peak wavelength Vnm into (Equation 2), the value of the external quantum efficiency W (numerical part indicated by%) that the oxynitride phosphor of the present invention should exceed is calculated, and Table 2 It is also shown in. Further, by substituting the value of the numerical value part of the absorption rate N% for light having a wavelength of 600 nm into (Equation 3), the value of the absorption rate M for light having a wavelength of 450 nm (% display) is preferable when the oxynitride phosphor of the present invention exceeds. (Numerical part) was calculated and shown in Table 2. If the measured value of the absorption rate M for 450 nm light exceeds the target value of the absorption rate M for 450 nm light, it is judged as ◯, and if it does not exceed the target value of the absorption rate M for 450 nm light, it is judged as ×. However, it is also shown in Table 2.
＜酸窒化物蛍光体の外部量子効率＞
実施例１〜８、比較例１〜８の各酸窒化物蛍光体の外部量子効率は、分光光度計（ＭＣＰＤ−７０００、大塚電子社製）による測定値を基に、以下の手順で算出した。即ち、はじめに反射率９９％の標準反射板（スペクトラロン、Ｌａｂｓｐｈｅｒｅ社製）が、その側面開口部（φ１０ｍｍ）にセットしてある積分球（φ６０ｍｍ）内に、発光光源であるＸｅランプから、４５５ｎｍの波長に分光した単色光を光ファイバーにより導入し、前記標準反射板からの反射光のスペクトルを、分光光度計（ＭＣＰＤ−７０００、大塚電子社製）により測定した。なお本測定に際し、測定時の環境温度は２５±２℃とし、４５０〜４６５ｎｍの波長範囲のスペクトルから励起光フォトン数（Ｑｅｘとする）を得た。次に、例えば実施例１の酸窒化物蛍光体を測定する場合は、実施例１の酸窒化物蛍光体を表面が平滑になるように充填した凹型セルを積分球の開口部にセットし、波長４５５ｎｍの単色光を照射して、励起の反射光及び蛍光のスペクトルを分光光度計により測定した。得られたスペクトルデータから励起反射光フォトン数（Ｑｒｅｆとする）及び蛍光フォトン数（Ｑｅｍとする）を得た。なお、励起反射光フォトン数は、励起光フォトン数と同じ波長範囲で、蛍光フォトン数は、４６５〜８００ｎｍの波長範囲で求めた値である。得られた三種類のフォトン数から、外部量子効率（％）＝Ｑｅｍ／Ｑｅｘ×１００の値を算出し、表２に示した。なお、本発明でいう外部量子効率（％）の数値部Ｗとは、前記外部量子効率（％）の数値そのものを指している。なお本測定で、緑色蛍光体標準試料（ＮＩＭＳ Ｓｔａｎｄａｒｄ Ｇｒｅｅｎ、ｌｏｔ ＮＳＧ１３０１、株式会社サイアロン販売）を測定した場合、外部量子効率は５５．６％であり、この値を基に値を補正した。実施例２〜８、比較例１〜８の酸窒化物蛍光体についても同様の方法で、外部量子効率の値をそれぞれ求め、表２に併せて示した。なお、外部量子効率の実測値が外部量子効率の目標値を超えるものを○として判定し、外部量子効率の目標値を超えないものを×として判定し、表２に併せて示した。
<External quantum efficiency of oxynitride phosphor>
The external quantum efficiencies of the oxynitride phosphors of Examples 1 to 8 and Comparative Examples 1 to 8 were calculated by the following procedure based on the measured values by a spectrophotometer (MCPD-7000, manufactured by Otsuka Electronics Co., Ltd.). .. That is, first, a standard reflector (Spectralon, manufactured by Labsphere) having a reflectance of 99% is placed in an integrating sphere (φ60 mm) set in the side opening (φ10 mm) of the standard reflector (Spectralon, manufactured by Labsphere) at 455 nm from the Xe lamp which is a light emitting light source. Monochromatic light dispersed in the above wavelengths was introduced by an optical fiber, and the spectrum of the reflected light from the standard reflector was measured by a spectrophotometer (MCPD-7000, manufactured by Otsuka Electronics Co., Ltd.). In this measurement, the environmental temperature at the time of measurement was 25 ± 2 ° C., and the number of excitation photons (referred to as Qex) was obtained from the spectrum in the wavelength range of 450 to 465 nm. Next, for example, when measuring the oxynitride phosphor of Example 1, a concave cell filled with the oxynitride phosphor of Example 1 so as to have a smooth surface is set in the opening of the integrating sphere. The spectra of the reflected light and fluorescence of the excitation were measured by a spectrophotometer by irradiating with monochromatic light having a wavelength of 455 nm. From the obtained spectral data, the number of excited reflected light photons (referred to as Qref) and the number of fluorescent photons (referred to as Qem) were obtained. The number of excited reflected light photons is in the same wavelength range as the number of excited light photons, and the number of fluorescent photons is a value obtained in the wavelength range of 465 to 800 nm. From the obtained three types of photon numbers, the value of external quantum efficiency (%) = Qem / Qex × 100 was calculated and shown in Table 2. The numerical value portion W of the external quantum efficiency (%) in the present invention refers to the numerical value itself of the external quantum efficiency (%). In this measurement, when a green phosphor standard sample (NIMS Standard Green, lot NSG1301, sold by Sialon Co., Ltd.) was measured, the external quantum efficiency was 55.6%, and the value was corrected based on this value. For the oxynitride phosphors of Examples 2 to 8 and Comparative Examples 1 to 8, the values of the external quantum efficiencies were obtained by the same method, and are also shown in Table 2. Those in which the measured value of the external quantum efficiency exceeds the target value of the external quantum efficiency are judged as ◯, and those in which the measured value of the external quantum efficiency does not exceed the target value of the external quantum efficiency are judged as ×, which are also shown in Table 2.
表２に示された実施例及び比較例の比較結果から、本発明の酸窒化物蛍光体の製造方法により、蛍光ピーク波長に即して外部量子効率が高く好ましい特性を有する酸窒化物蛍光体が得られることが示された。 From the comparison results of Examples and Comparative Examples shown in Table 2, the oxynitride phosphor having high external quantum efficiency and preferable characteristics in accordance with the fluorescence peak wavelength by the method for producing the oxynitride phosphor of the present invention. Was shown to be obtained.
Claims (10)
Ｓｉ１２−ａＡｌａＯｂＮ１６−ｂ：Ｅｕｘ （式１）
但し、式（１）において、０＜ａ≦３、０＜ｂ≦３、０＜ｘ≦０．１
Ｗ＞１．３×Ｖ−６４８．５ （式２） It is an oxynitride phosphor having a chemical composition represented by (Equation 1), and the peak wavelength of the fluorescence spectrum emitted when the phosphor is irradiated with light having a wavelength of 455 nm is V nm, and the external quantum efficiency at that time is W. A oxynitride phosphor in which the V and W satisfy the relationship represented by (Equation 2).
Si 12-a Al a Ob N 16-b : Eu x (Equation 1)
However, in the formula (1), 0 <a ≦ 3, 0 <b ≦ 3, 0 <x ≦ 0.1
W> 1.3 × V-64.8 (Equation 2)
Ｍ＞６Ｎ （式３） The oxynitride according to claim 1 or 2 , wherein when the absorption rate for light having a wavelength of 455 nm is M% and the absorption rate for light having a wavelength of 600 nm is N%, the M and N satisfy the relationship represented by (Equation 3). Object phosphor.
M> 6N (Equation 3)
Ｓｉ１２−ａＡｌａＯｂＮ１６−ｂ：Ｅｕｘ （式１）
但し（式１）において、０＜ａ≦３、０＜ｂ≦３、０＜ｘ≦０．１ A mixing step of mixing raw materials to obtain a raw material mixture, a high-temperature firing step of firing the raw material mixture to obtain a first fired product, and a high-temperature firing step of calcining the first fired product at a temperature lower than the firing temperature of the high-temperature firing step. A method for producing an oxynitride phosphor having a chemical composition represented by (Formula 1), which comprises a low-temperature firing step of firing to obtain a second fired product and an acid treatment step of acid-treating the second fired product. Therefore, in the middle of the cooling process from the end of the low-temperature firing step to room temperature, the second fired product obtained after holding at a constant temperature within the range of 800 ° C. or higher and 1000 ° C. or lower for at least 3 hours or more is acidified. The method for producing an oxynitride phosphor according to any one of claims 1 to 4, which is processed.
Si 12-a Al a Ob N 16-b : Eu x (Equation 1)
However, in (Equation 1), 0 <a ≦ 3, 0 <b ≦ 3, 0 <x ≦ 0.1
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