JP2006008889A - Nitride phosphor, method for producing the same, white light-emitting element and pigment - Google Patents

Nitride phosphor, method for producing the same, white light-emitting element and pigment Download PDF

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JP2006008889A
JP2006008889A JP2004189714A JP2004189714A JP2006008889A JP 2006008889 A JP2006008889 A JP 2006008889A JP 2004189714 A JP2004189714 A JP 2004189714A JP 2004189714 A JP2004189714 A JP 2004189714A JP 2006008889 A JP2006008889 A JP 2006008889A
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nitride
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nitride phosphor
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JP4356539B2 (en
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Fujio Amada
富士夫 天田
Yoshikazu Touno
義和 投野
Tadashi Endo
忠 遠藤
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Shoei Chemical Inc
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Abstract

<P>PROBLEM TO BE SOLVED: To provide a nitride phosphor having a light-emitting peak wavelength at ≥650 nm, especially at 660-690 nm, having a red emitted light color and a high light-emitting intensity, a method for producing the nitride phosphor, a white light-emitting element and a pigment. <P>SOLUTION: This nitride phosphor has a chemical composition expressed by general formula (1): Mg<SB>m-x</SB>Eu<SB>x</SB>Si<SB>9</SB>Al<SB>y</SB>N<SB>(12+2/3m+y)</SB>[wherein, 0<m≤5.0, 0<x/m<0.5, 0≤y≤3.0]. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

本発明は、650nm以上の長波長域(特に660〜690nm)に発光ピークを有し、かつ発光強度の高い赤色発光窒化物蛍光体、窒化物蛍光体の製造方法、白色発光素子及び顔料に関する。   The present invention relates to a red light-emitting nitride phosphor having a light emission peak in a long wavelength region of 650 nm or more (particularly from 660 to 690 nm) and a high light emission intensity, a method for producing the nitride phosphor, a white light-emitting element, and a pigment.

現在、600nm以上の長波長域に発光ピークを有する赤色発光蛍光体として実用化されているものは、主として硫化物系や酸化物系でのものであり、酸化物系では、三波長型蛍光ランプに用いられているユーロピウム(Eu)付活酸化イットリウム蛍光体等がある。しかし、これら赤色蛍光体の発光ピーク波長は650nm以下であり、これ以上の波長で強い発光強度を示すものは殆どない。   Currently, red phosphors having an emission peak in a long wavelength region of 600 nm or more are practically used as sulfide-based or oxide-based phosphors, and oxide-based three-wavelength fluorescent lamps. There are europium (Eu) activated yttrium oxide phosphors and the like used in the above. However, the emission peak wavelength of these red phosphors is 650 nm or less, and there are few that show strong emission intensity at wavelengths longer than this.

また、窒化物系の蛍光体は、紫外線〜青色の光を吸収して、比較的長波長の黄色〜黄赤色の蛍光色を示すものが多く、白色発光素子に適した蛍光体として近年注目されている。白色発光素子は、GaN系などの青色系の半導体発光素子(青色LED)の発光の一部をフォトルミネセンス蛍光体により波長変換し、青色LEDの光と波長変換された光(主として黄色系の光)との混色により、LEDの光と異なる発光色、特に白色系の光を発する発光素子である。このような発光素子は、小型で電力効率が高いため、信号灯、車載照明や液晶のバックライト、駅の行き先案内板等の表示板等、各種の光源として利用されている。青色LEDと組み合わせて白色発光素子に用いられるフォトルミネセンス蛍光体としては、現在、セリウム(Ce)で付活されたイットリウム・アルミニウム・ガーネット系蛍光体(以下「YAG系蛍光体」と言う。)が主流であるが、黄色〜黄赤色に発光する窒化物系蛍光体は、YAG系蛍光体に代わる白色発光素子用フォトルミネセンス蛍光体として期待されている。
一方、YAG系蛍光体が放射する光は、黄緑色〜黄色であり、白色発光素子の発光色がやや青白い白色になるので、簡単な照明には良いが、高い演色性が要求される照明用途や、カラー液晶ディスプレイ(LCD)のバックライトとして使用される場合、出力光が赤色成分不足となる。このため、発光色補正用、すなわち赤色成分を補うために、YAG系蛍光体に、前記窒化物系の蛍光体を併用することも提案されている。
In addition, many nitride-based phosphors absorb ultraviolet to blue light and exhibit a relatively long-wavelength yellow to yellow-red fluorescent color, and have recently attracted attention as phosphors suitable for white light-emitting elements. ing. The white light emitting element converts a part of light emitted from a blue semiconductor light emitting element (blue LED) such as a GaN system with a photoluminescence phosphor, and converts the wavelength of the blue LED light into the wavelength converted light (mainly a yellow light emitting element). It is a light emitting element that emits a light emission color different from that of LED light, particularly white light, by mixing with light. Since such a light emitting element is small and has high power efficiency, it is used as various light sources such as a signal lamp, an in-vehicle illumination, a liquid crystal backlight, and a display board such as a station destination guide plate. As a photoluminescence phosphor used in a white light emitting element in combination with a blue LED, an yttrium / aluminum / garnet phosphor activated with cerium (Ce) (hereinafter referred to as “YAG phosphor”). However, nitride-based phosphors that emit yellow to yellow-red are expected as photoluminescent phosphors for white light-emitting elements that replace YAG-based phosphors.
On the other hand, the light emitted from the YAG phosphor is yellow-green to yellow, and the light emission color of the white light-emitting element is slightly bluish-white, which is good for simple lighting but requires high color rendering properties. In addition, when used as a backlight of a color liquid crystal display (LCD), the output light has a short red component. For this reason, it has also been proposed to use the nitride phosphor together with the YAG phosphor in order to correct the emission color, that is, to supplement the red component.

このような窒化物系赤色発光蛍光体としては、カルシウム(Ca)−α−サイアロン系の蛍光体(特許文献1参照)や、Euで付活したニトリドシリケート、例えば、Ca2Si58、Sr2Si58、Ba2Si58、Ba2Si710、Ba2-xEuxSi58のタイプの蛍光体(特許文献2、3参照)が挙げられる。
特開2002−363554号公報 特表2003−515655号公報 特表2003−515665号公報
Examples of such nitride-based red light-emitting phosphors include calcium (Ca) -α-sialon-based phosphors (see Patent Document 1), and nitridosilicates activated with Eu, such as Ca 2 Si 5 N 8. Sr 2 Si 5 N 8 , Ba 2 Si 5 N 8 , Ba 2 Si 7 N 10 , Ba 2−x Eu x Si 5 N 8 type phosphors (see Patent Documents 2 and 3).
JP 2002-363554 A Special table 2003-515655 gazette Special table 2003-515665 gazette

しかしながら、上記特許文献1に記載のCa−α−サイアロン系の蛍光体は、発光ピーク波長は殆どが500〜600nmであり、特許文献2、3に記載のニトリドシリケートにおいても、発光ピーク波長が650nmより長波長である実用的な蛍光体は殆どない。
本発明は、上記事情に鑑みてなされたもので、650nm以上、特に660〜690nmに発光ピーク波長を有し、発光色が赤色である、発光強度の高い窒化物蛍光体、窒化物蛍光体の製造方法、白色発光素子及び顔料を提供することを目的としている。
However, the Ca-α-sialon-based phosphor described in Patent Document 1 has an emission peak wavelength of 500 to 600 nm, and even in the nitridosilicates described in Patent Documents 2 and 3, the emission peak wavelength is high. Few practical phosphors have wavelengths longer than 650 nm.
The present invention has been made in view of the above circumstances, and has a peak emission wavelength at 650 nm or more, particularly 660 to 690 nm, and the emission color is red. It aims at providing a manufacturing method, a white light emitting element, and a pigment.

上記課題を解決するため、請求項1に記載の発明の窒化物蛍光体は、下記一般式(1)で表される化学組成を有することを特徴とする。
Mgm-xEuxSi9Aly(12+2/3m+y)…(1)
(ただし、上記一般式(1)中、0<m≦5.0、0<x/m<0.5、0≦y≦3.0である。)
In order to solve the above problems, the nitride phosphor of the invention described in claim 1 has a chemical composition represented by the following general formula (1).
Mg mx Eu x Si 9 Al y N (12 + 2 / 3m + y) ... (1)
(However, in the general formula (1), 0 <m ≦ 5.0, 0 <x / m <0.5, and 0 ≦ y ≦ 3.0.)

請求項2に記載の発明は、請求項1に記載の窒化物蛍光体を製造する方法であって、
窒化物を構成する珪素以外の金属元素の化合物と、窒化珪素とを、溶融した尿素及び/又は溶融した尿素誘導体に溶解又は分散させて窒化物前駆体を形成し、該窒化物前駆体を、不活性又は還元性の雰囲気中で加熱することにより窒化物蛍光体を生成することを特徴とする。
The invention according to claim 2 is a method for producing the nitride phosphor according to claim 1,
A compound of a metal element other than silicon constituting the nitride and silicon nitride are dissolved or dispersed in molten urea and / or a molten urea derivative to form a nitride precursor, and the nitride precursor is A nitride phosphor is produced by heating in an inert or reducing atmosphere.

請求項3に記載の発明の白色発光素子は、青色光を放射する半導体発光素子と、前記半導体発光素子からの光の一部を吸収して緑色〜黄色の波長領域の蛍光を発光する蛍光体と、請求項1に記載の窒化物蛍光体とを備えていることを特徴とする。   The white light-emitting device according to claim 3 is a semiconductor light-emitting device that emits blue light, and a phosphor that emits fluorescence in the green to yellow wavelength region by absorbing part of the light from the semiconductor light-emitting device. And the nitride phosphor according to claim 1.

請求項4に記載の発明の白色発光素子は、紫外線〜青紫色の領域の光を放射する半導体発光素子と、前記半導体発光素子からの光を吸収して青色の蛍光を発光する蛍光体、もしくは緑色の蛍光を発光する蛍光体の少なくとも一方と、請求項1に記載の窒化物蛍光体とを備えていることを特徴とする。   The white light-emitting device according to claim 4 is a semiconductor light-emitting device that emits light in the ultraviolet to blue-violet region, and a phosphor that absorbs light from the semiconductor light-emitting device and emits blue fluorescence, or It is characterized by comprising at least one of phosphors emitting green fluorescence and the nitride phosphor according to claim 1.

請求項5に記載の発明の顔料は、下記一般式(1)で表される化学組成を有することを特徴とする。
Mgm-xEuxSi9Aly(12+2/3m+y)…(1)
(ただし、上記一般式(1)中、0<m≦5.0、0<x/m<0.5、0≦y≦3.0である。)
The pigment of the invention described in claim 5 has a chemical composition represented by the following general formula (1).
Mg mx Eu x Si 9 Al y N (12 + 2 / 3m + y) ... (1)
(However, in the general formula (1), 0 <m ≦ 5.0, 0 <x / m <0.5, and 0 ≦ y ≦ 3.0.)

本発明に係る窒化物蛍光体は、650nm以上、特に従来あまり実用的なものがなかった660〜690nmの長波長域に発光ピーク波長を有し、かつ、高い発光強度を示すものである。また、紫外線域から黄緑色光域までの広い波長領域の光、及び電子線や電場によっても励起されて発光する。したがって、通常の照明、各種の表示管や、白色LED等に使用する蛍光体として有用である。また、ほとんどのものの物体色が黄赤色を呈しており、重金属を含まない顔料として様々な用途に適用可能である。
さらに、本発明に係る窒化物蛍光体の製造方法によれば、各原料を溶融した尿素及び/又は溶融した尿素誘導体に溶解又は分散させることにより、均一組成の窒化物前駆体を形成することができる。そして、このような窒化物前駆体を不活性又は還元性の雰囲気中で加熱することにより、優れた特性で、粒子径の揃った結晶性の良好な窒化物蛍光体を得ることができる。さらに、原料の窒化と結晶成長を同一反応容器中で行うことができるため、簡単なプロセスで効率良く製造することができ、しかも常圧で比較的低温で製造できる。
The nitride phosphor according to the present invention has an emission peak wavelength in the long wavelength region of 660 to 690 nm, which has not been particularly practical, and has a high emission intensity. Further, it emits light by being excited by light in a wide wavelength region from the ultraviolet region to the yellow-green light region, and also by an electron beam or an electric field. Therefore, it is useful as a phosphor used for ordinary illumination, various display tubes, white LEDs, and the like. Moreover, most of the object colors are yellowish red, and can be applied to various uses as pigments not containing heavy metals.
Furthermore, according to the method for producing a nitride phosphor according to the present invention, a nitride precursor having a uniform composition can be formed by dissolving or dispersing each raw material in molten urea and / or a molten urea derivative. it can. Then, by heating such a nitride precursor in an inert or reducing atmosphere, a nitride phosphor having excellent characteristics and crystallinity with a uniform particle diameter can be obtained. Furthermore, since nitriding of raw materials and crystal growth can be performed in the same reaction vessel, they can be efficiently manufactured by a simple process, and can be manufactured at normal pressure and at a relatively low temperature.

以下、本発明に係る窒化物蛍光体、用途としての白色発光素子や顔料、及び、窒化物蛍光体の製造方法について詳細に説明する。
(窒化物蛍光体)
本発明に係る窒化物蛍光体は、下記一般式(1)で表される化学組成を有している。
Mgm-xEuxSi9Aly(12+2/3m+y)…(1)
(ただし、上記一般式(1)中、0<m≦5.0、0<x/m<0.5、0≦y≦3.0である。)
Hereinafter, the nitride phosphor according to the present invention, a white light-emitting element or pigment as an application, and a method for producing the nitride phosphor will be described in detail.
(Nitride phosphor)
The nitride phosphor according to the present invention has a chemical composition represented by the following general formula (1).
Mg mx Eu x Si 9 Al y N (12 + 2 / 3m + y) ... (1)
(However, in the general formula (1), 0 <m ≦ 5.0, 0 <x / m <0.5, and 0 ≦ y ≦ 3.0.)

上記一般式(1)中、mの範囲は、1.0≦m≦4.0が好ましい。
本発明では、共有結合性の強い窒化マグネシウムを固溶した窒化珪素母体中に、発光中心となる付活剤Euをドープすることにより、深い赤色発光を有することが特徴的である。Euのドープ量で発光強度が変化するが、特にx/mの範囲が、0.1≦x/m≦0.4の範囲のものは発光強度が大きく、好ましい。発光強度はx/m=0.2近傍で最大となる。
In the general formula (1), the range of m is preferably 1.0 ≦ m ≦ 4.0.
The present invention is characterized by having deep red light emission by doping an activator Eu serving as a light emission center into a silicon nitride matrix in which magnesium nitride having a strong covalent bond is dissolved. The emission intensity varies depending on the amount of Eu doped. Particularly, the x / m range is preferably 0.1 ≦ x / m ≦ 0.4 because the emission intensity is large. The emission intensity becomes maximum near x / m = 0.2.

本発明の窒化物蛍光体においては、アルミニウム(Al)を含むことは必須ではないが、Alを含むことによって、構造が安定化すると考えられる。しかし、Alの添加量が多くなると逆に発光強度が低下してくるため、yは3.0以下とする必要がある。yの値は、好ましくは0<y≦2.0、であり、特に0.1≦y≦1.5の範囲のものが好ましい。
なお、本発明の窒化物蛍光体は、制御された量の酸素を含有する酸窒化物ではないが、不可避的に入ってしまう少量の酸素を含む窒化物を排除するものではない。
In the nitride phosphor of the present invention, it is not essential to contain aluminum (Al), but it is considered that the structure is stabilized by containing Al. However, since the emission intensity decreases conversely as the Al content increases, y needs to be 3.0 or less. The value of y is preferably 0 <y ≦ 2.0, and particularly preferably in the range of 0.1 ≦ y ≦ 1.5.
The nitride phosphor of the present invention is not an oxynitride containing a controlled amount of oxygen, but does not exclude a nitride containing a small amount of oxygen that inevitably enters.

本発明の窒化物蛍光体には、発光強度や残光性、その他の蛍光特性を調整するために、希土類金属元素等の共付活剤として作用する元素、例えばセリウム(Ce)、テルビウム(Tb)、ジスプロジウム(Dy)、サマリウム(Sm)、プラセオジウム(Pr)、ネオジム(Nd)、エルビウム(Er)、ホルミウム(Ho)、ツリウム(Tm)、マンガン(Mn)などを適宜ドープしても良い。   The nitride phosphor of the present invention includes an element that acts as a coactivator such as a rare earth metal element, such as cerium (Ce), terbium (Tb), in order to adjust emission intensity, afterglow, and other fluorescence characteristics. ), Dysprodium (Dy), samarium (Sm), praseodymium (Pr), neodymium (Nd), erbium (Er), holmium (Ho), thulium (Tm), manganese (Mn), etc. may be appropriately doped. .

本発明に係る窒化物蛍光体は、紫外線〜黄緑色光領域の光、電子線、電場による励起により650nm以上、特に従来殆どなかった660nm〜690nmの範囲に発光ピーク波長を有する蛍光を発光する新規な長波長赤色発光蛍光体である。
このような窒化物蛍光体の用途としては、従来あまり実用的なものがなかった長波長赤色蛍光体として、ランプ等の照明用蛍光体として使用したり、冷陰極管、CRT、PDP、FED、無機EL等の表示管用赤色蛍光体として使用することができる。
The nitride phosphor according to the present invention emits fluorescence having an emission peak wavelength in the range of 650 nm or more, particularly 660 nm to 690 nm, which has not been conventionally present, when excited by light, electron beam, or electric field in the ultraviolet to yellow-green light region. Long-wavelength red light emitting phosphor.
Such nitride phosphors can be used as long-wavelength red phosphors, which have not been so practical in the past, as illumination phosphors such as lamps, cold cathode tubes, CRTs, PDPs, FEDs, It can be used as a red phosphor for display tubes such as inorganic EL.

また、紫外線、及び紫色〜黄緑色の波長領域の可視光で励起され、これらの光をより長波長の光に変換することが可能なため、白色発光素子の作成に非常に有効である。
具体的には、青色LEDに、このLEDからの青色光の一部を吸収し、波長変換して緑色〜黄色に発光する第1の蛍光体と、第2の蛍光体として本発明の窒化物蛍光体とを組み合わせることにより、色バランスの優れた白色発光素子を得ることができる。
例えば、発光ピーク波長が400nm〜460nmであるGaN系やInGaN系などの青色LEDと、青色光により励起されて黄緑〜黄色に発光するYAG系蛍光体とを備えた白色発光素子に、発光色の赤色成分補色用として、本発明の窒化物蛍光体を添加することにより、演色性、色感度を向上させることができる。
また、青色LEDと、その青色光により緑色に発光する第1の蛍光体と、本発明の赤色発光窒化物蛍光体とを組み合わせることにより、青、緑、赤の光の三原色の混色による白色発光素子を得ることもできる。
また、青色LEDの代わりに、例えばピーク波長が360nm〜400nmの紫外〜青紫色の領域の光を発光する半導体素子(紫外線LED)を用い、その発光を吸収して赤、緑、又は青の蛍光を発するフォトルミネセンス蛍光体を組み合わせて、これら三原色の混色により白色系の光を発する発光素子も知られているが、本発明の窒化物蛍光体はこのような白色発光素子の赤色成分として用いることもできる。
さらに、紫外線LEDや青色LED、又は青緑〜緑色に発光するLEDに組み合わせる蛍光体として、本発明の窒化物蛍光体を単独で用い、白色光や、紫、赤紫、ピンク、赤など様々な色の光を発する発光素子を得ることもできる。
Further, it is excited by ultraviolet light and visible light in a purple to yellow-green wavelength region, and these light can be converted into light having a longer wavelength, so that it is very effective for producing a white light emitting element.
Specifically, the blue LED absorbs part of the blue light from the LED, converts the wavelength and emits green to yellow light, and the nitride of the present invention as the second phosphor. By combining with a phosphor, a white light emitting device with excellent color balance can be obtained.
For example, a white light emitting device including a GaN-based or InGaN-based blue LED having a light emission peak wavelength of 400 nm to 460 nm and a YAG phosphor that emits yellow-green to yellow light when excited by blue light is used. The color rendering property and color sensitivity can be improved by adding the nitride phosphor of the present invention for the red component complementary color.
In addition, by combining the blue LED, the first phosphor that emits green light with the blue light, and the red light emitting nitride phosphor of the present invention, white light emission by mixing three primary colors of blue, green, and red light. An element can also be obtained.
Moreover, instead of blue LED, for example, a semiconductor element (ultraviolet LED) that emits light in an ultraviolet to blue-violet region having a peak wavelength of 360 to 400 nm is used, and the emitted light is absorbed to emit red, green, or blue fluorescence. A light emitting device that emits white light by mixing these three primary colors in combination with a photoluminescent phosphor that emits light is also known, but the nitride phosphor of the present invention is used as a red component of such a white light emitting device. You can also.
Furthermore, as a phosphor combined with an ultraviolet LED, a blue LED, or an LED emitting blue-green to green, the nitride phosphor of the present invention is used alone, and various light sources such as white light, purple, magenta, pink, and red are used. A light-emitting element that emits colored light can also be obtained.

さらに、本発明の窒化物蛍光体のほとんどは、物体色が黄赤色であるので、ベンガラ(酸化鉄)等、鉄や銅、マンガン、クロムなどの重金属を含有する顔料の代替材料として、塗料やインク等に適用できる。また、紫外線や可視光を励起源として深い赤色を発光する黄赤色顔料として、蛍光体の調色用や化粧品用に、また、紙幣や証券類等の偽造防止用インクの顔料として使用することも可能である。
さらには、紫外線、可視光吸収材料として、幅広い用途に使用することができる。
Furthermore, since most of the nitride phosphors of the present invention have a yellowish red color, as an alternative material for pigments containing heavy metals such as iron, copper, manganese, and chromium such as bengara (iron oxide), paint and Applicable to ink and the like. It can also be used as a yellow-red pigment that emits deep red light using ultraviolet light or visible light as an excitation source, for phosphor toning and cosmetics, and as a pigment for anti-counterfeiting ink such as banknotes and securities. Is possible.
Furthermore, it can be used for a wide range of applications as an ultraviolet and visible light absorbing material.

(窒化物蛍光体の製造方法)
次に、本発明に係る窒化物蛍光体の製造方法について説明する。
本発明に係る窒化物蛍光体の製造方法は、公知の固相反応法、噴霧熱分解法、液相反応法、その他の方法を適用することができるが、以下に示す尿素−前駆体を用いた方法が、均一組成で、また、粒子径の揃った結晶性の良好な窒化物を得やすい点で、好ましい。さらに、この方法は、原料の窒化や結晶成長を同一反応容器中で行うことができ、しかも常圧で比較的低温で製造できる点で好適である。
以下、本発明で好適に用いられる尿素−前駆体を用いた方法の一例について説明する。まず、尿素及び/又は尿素誘導体(以下、「尿素等」と称すこともある)をこれらの融点以上の温度まで加熱して溶融状態にする。ただし、加熱温度が高すぎると別の生成物が生ずる場合があるので、尿素等が溶解し、かつ、後述するMg化合物やEu化合物、Al化合物、窒化珪素を加えた後も溶融状態を所定時間保持することができる程度の温度とすることが好ましい。例えば、尿素を用いる場合、その融点は132℃であるので、それより若干高めの温度まで加熱すれば十分である。
(Nitride phosphor manufacturing method)
Next, a method for producing a nitride phosphor according to the present invention will be described.
As the method for producing a nitride phosphor according to the present invention, a known solid phase reaction method, spray pyrolysis method, liquid phase reaction method, and other methods can be applied, but the urea precursor shown below is used. Is preferable because it is easy to obtain a nitride having a uniform composition and a good crystallinity with a uniform particle diameter. Furthermore, this method is preferable in that the raw material can be nitrided and grown in the same reaction vessel, and can be produced at normal pressure and at a relatively low temperature.
Hereinafter, an example of the method using the urea precursor suitably used in the present invention will be described. First, urea and / or a urea derivative (hereinafter sometimes referred to as “urea or the like”) is heated to a temperature equal to or higher than these melting points to be in a molten state. However, if the heating temperature is too high, another product may be formed. Therefore, urea or the like is dissolved, and the molten state is kept for a predetermined time after adding the Mg compound, Eu compound, Al compound, or silicon nitride described later. It is preferable that the temperature is such that it can be maintained. For example, when urea is used, its melting point is 132 ° C., so it is sufficient to heat it to a slightly higher temperature.

尿素誘導体としては、尿素中の窒素原子への各種有機基の置換体としての尿素化合物、あるいはカーバメイト化合物、尿素錯化合物、尿素付加体化合物等の各種のものを使用することができる。尿素等としては、入手のしやすさや取り扱いの容易さ等の点から尿素が好適なものとして用いられる。   As the urea derivative, various compounds such as urea compounds as carbamate compounds, urea complex compounds, and urea adduct compounds can be used as substitutes of various organic groups for nitrogen atoms in urea. As urea or the like, urea is preferably used from the viewpoints of availability, ease of handling, and the like.

次に、最終生成物の構成成分となる、Mg化合物、Eu化合物、Al化合物を溶融した尿素等に溶解し、さらに窒化珪素を分散させて窒化物前駆体を形成する。なお、Al化合物は目的とする窒化物蛍光体の組成に応じて加えれば良く、必ずしも必須ではない。また、共付活剤をドープする場合は、共付活剤として作用する金属元素の化合物を、所定量添加し、溶解する。   Next, Mg compounds, Eu compounds, and Al compounds, which are constituents of the final product, are dissolved in molten urea or the like, and silicon nitride is dispersed to form a nitride precursor. The Al compound may be added according to the composition of the target nitride phosphor, and is not necessarily essential. When the coactivator is doped, a predetermined amount of a metal element compound acting as a coactivator is added and dissolved.

窒化物を構成する珪素以外の金属元素の化合物、すなわちMg化合物、Eu化合物、Al化合物、共付活剤元素の化合物としては、溶融尿素等に溶解されるものであれば特に限定されるものではないが、例えば塩化物、硝酸塩などが挙げられる。また、窒化珪素としては、結晶質のものでも非晶質のものでも、適宜用いることができる。例えば、反応性の点では非晶質の窒化珪素の方が好ましいと考えられるが、入手が容易であること、取り扱いがし易いこと、及び収率の点からは結晶質の窒化珪素が有利である。   Compounds of metal elements other than silicon constituting the nitride, that is, Mg compounds, Eu compounds, Al compounds, and compounds of coactivator elements are not particularly limited as long as they can be dissolved in molten urea or the like. For example, chlorides, nitrates and the like can be mentioned. As silicon nitride, either crystalline or amorphous silicon can be used as appropriate. For example, amorphous silicon nitride is considered preferable in terms of reactivity, but crystalline silicon nitride is advantageous in terms of easy availability, easy handling, and yield. is there.

このようにして得られた窒化物前駆体を、例えば放冷し乾燥させて固体状にする。この固体状のものを、必要に応じて機械的に粉砕し、加熱炉を用いて加熱し、窒化物を生成する。加熱炉としては、バッチ炉、ベルト炉、管状炉、ロータリーキルン等、公知のものを使用することができる。
ただし、加熱は不活性雰囲気又は還元性雰囲気のもとで行う必要がある。
また、不活性雰囲気あるいは還元性雰囲気中、一段の加熱(焼成)で目的の生成物を形成しても良いし、複数段に分けて加熱(焼成)することにより目的とする窒化物を得ても良い。加熱温度、加熱時間等の諸条件は目的とする生成物の種類に応じて適宜設定すれば良いが、例えば、1段加熱の場合には、1200〜1800℃の範囲内の温度で0.5〜12時間程度が好ましい。また、2段加熱の場合には、第2段目の加熱温度を第1段目の加熱温度よりも高く設定することが望ましく、例えば、第1段目の加熱を、約300〜1000℃の温度で0.5〜4時間行い、第2段目の加熱を、約1200〜1800℃の温度で約0.5〜12時間行うことが望ましい。複数段の加熱は、より均一な組成の生成物を再現性良く得ることができる点で有利である。
The nitride precursor thus obtained is allowed to cool, for example, and dried to form a solid. This solid material is mechanically pulverized as necessary, and heated using a heating furnace to produce a nitride. As a heating furnace, well-known things, such as a batch furnace, a belt furnace, a tubular furnace, a rotary kiln, can be used.
However, it is necessary to perform heating under an inert atmosphere or a reducing atmosphere.
Further, the target product may be formed by one-step heating (firing) in an inert atmosphere or a reducing atmosphere, or the target nitride is obtained by heating (firing) in multiple stages. Also good. Various conditions such as the heating temperature and the heating time may be appropriately set according to the type of the target product. For example, in the case of one-stage heating, the temperature is in the range of 1200 to 1800 ° C. and 0.5. About 12 hours are preferable. In the case of two-stage heating, it is desirable to set the second stage heating temperature higher than the first stage heating temperature. For example, the first stage heating is performed at about 300 to 1000 ° C. It is desirable that the temperature is 0.5 to 4 hours, and the second stage heating is preferably performed at a temperature of about 1200 to 1800 ° C. for about 0.5 to 12 hours. Multi-stage heating is advantageous in that a product with a more uniform composition can be obtained with good reproducibility.

また、その他の加熱手段として、前駆体粉末を機械的に粉砕し、望ましくは粒度調整した後、気相中に分散させた状態で加熱することにより、微細かつ粒子径の揃った、結晶性の高い窒化物粉末を得ることができる。   Further, as other heating means, the precursor powder is mechanically pulverized, desirably adjusted in particle size, and then heated in a dispersed state in the gas phase, thereby producing a fine and uniform particle size crystalline material. High nitride powder can be obtained.

さらに、他の加熱手段として、噴霧熱分解法を利用しても良い。この噴霧熱分解法は、液体状の前駆体を超音波式、二流体ノズル方式等の噴霧器や他の霧化手段を用いて、微細な液滴とし、これを不活性雰囲気又は還元性雰囲気条件下で加熱し、前駆体を分解、反応させて、微細かつ粒径の揃った窒化物粉末を得ることができる。
また、上述の製造例においては、溶融状態にした尿素等に各化合物等を溶解又は分散させる方法を述べたが、予め尿素等と化合物等とを混合してから加熱して尿素等を溶融しても構わない。
Furthermore, a spray pyrolysis method may be used as another heating means. In this spray pyrolysis method, the liquid precursor is made into fine droplets using an atomizer such as an ultrasonic type or a two-fluid nozzle type or other atomizing means, and this is subjected to an inert atmosphere or a reducing atmosphere condition. Under heating, the precursor can be decomposed and reacted to obtain fine and uniform nitride powder.
In the above production example, the method of dissolving or dispersing each compound etc. in the molten urea etc. has been described, but the urea etc. and the compound etc. are mixed in advance and then heated to melt the urea etc. It doesn't matter.

以下、実施例を挙げて本発明を具体的に説明するが、本発明の実施態様はこれに限定されるものではない。
下記の方法にしたがって、試料1〜5を作製した後、各試料1〜5について以下に示す測定を行い評価した。
[試料1の作製]
尿素を134℃で溶融し、溶融尿素を得た。この溶融尿素36g中に、EuCl3・6H2O0.31g、AlCl3・6H2O0.35g及びMgCl2・6H2O2.2gを添加して溶解し、さらに、Si34粉末1.2g(宇部興産製SN−E10)を添加、攪拌し、均一に分散させた。これを攪拌しながら空冷して、元素のモル比がMg:Eu:Si:Al=3.7:0.3:9:0.5の固体の窒化物前駆体を生成した。得られた前駆体を、蓋付きカーボンボートに載置し、4%のH2を含むN2雰囲気中800℃で2時間、焼成を行った後粉砕した。これを、Mo板で挟みこみ、4%のH2を含むN2雰囲気中1600℃で2時間、加熱を行い、窒化物蛍光体を作製し、試料1とした。
EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated concretely, the embodiment of this invention is not limited to this.
Samples 1-5 were prepared according to the following method, and then the following measurements were performed for each sample 1-5 and evaluated.
[Preparation of Sample 1]
Urea was melted at 134 ° C. to obtain molten urea. In 36 g of this molten urea, 0.31 g of EuCl 3 .6H 2 O, 0.35 g of AlCl 3 .6H 2 O and 2.2 g of MgCl 2 .6H 2 O are added and dissolved, and further 1.2 g of Si 3 N 4 powder (Ube Industries SN-E10) was added, stirred, and uniformly dispersed. This was air-cooled with stirring to produce a solid nitride precursor having an element molar ratio of Mg: Eu: Si: Al = 3.7: 0.3: 9: 0.5. The obtained precursor was placed on a carbon boat with a lid, fired in an N 2 atmosphere containing 4% H 2 at 800 ° C. for 2 hours, and then pulverized. This was sandwiched between Mo plates and heated at 1600 ° C. for 2 hours in an N 2 atmosphere containing 4% of H 2 to produce a nitride phosphor.

[試料2〜5の作製]
上記試料1の作製において、原料のモル比を適宜変えて、試料1と同様の方法で表1に示す化学組成の試料2〜5を得た。なお、試料5は本発明外のものである。

Figure 2006008889
[Preparation of Samples 2 to 5]
In the preparation of Sample 1, samples 2 to 5 having chemical compositions shown in Table 1 were obtained in the same manner as Sample 1 by appropriately changing the molar ratio of the raw materials. Sample 5 is outside the present invention.
Figure 2006008889

≪外観≫
得られた試料1〜5の蛍光体粉末の外観を観察し、その物体色を表1に示した。
≪Appearance≫
The appearance of the obtained phosphor powders of Samples 1 to 5 was observed, and the object colors are shown in Table 1.

≪結晶構造≫
各試料1〜5について、(株)リガク製粉末X線回折計を用い、Cu−Kα線をX線源としてX線回折パターンを測定し、結晶構造の確認を行った。結果を表1に示す。いずれも斜方晶系のみの結晶構造を有していたことが確認される。また、図1に試料2のX線回折パターンを示す。
≪Crystal structure≫
About each sample 1-5, the X-ray-diffraction pattern was measured using Cu-K alpha ray as an X-ray source using the Rigaku Co., Ltd. powder X-ray diffractometer, and the crystal structure was confirmed. The results are shown in Table 1. It was confirmed that all had an orthorhombic crystal structure. FIG. 1 shows the X-ray diffraction pattern of Sample 2.

≪蛍光特性≫
各試料1〜5について、日本分光(株)製分光蛍光光度計(FP−6600型)を用いて460nmの単色光を励起光源とし、500nmから800nmの範囲で発光スペクトルを測定した。またそれぞれの発光ピーク波長における励起スペクトルを、250nmから640nmの範囲で測定した。各試料の発光ピーク波長と発光強度とを、表1に併せて示す。なお、発光強度は、試料2を100としたときの相対強度である。図2に試料2の蛍光スペクトル図を示す。図中、(a)は発光スペクトル、(b)は励起スペクトルである。
≪Fluorescence characteristics≫
About each sample 1-5, the emission spectrum was measured in the range of 500 nm to 800 nm using monochromatic light of 460 nm as an excitation light source using a spectrofluorometer (FP-6600 type) manufactured by JASCO Corporation. The excitation spectrum at each emission peak wavelength was measured in the range of 250 nm to 640 nm. The emission peak wavelength and emission intensity of each sample are also shown in Table 1. The emission intensity is a relative intensity when the sample 2 is 100. FIG. 2 shows a fluorescence spectrum diagram of Sample 2. In the figure, (a) is an emission spectrum, and (b) is an excitation spectrum.

試料2のX線回折パターンである。2 is an X-ray diffraction pattern of Sample 2. 試料2の蛍光スペクトルである。It is a fluorescence spectrum of sample 2.

Claims (5)

下記一般式(1)で表される化学組成を有する窒化物蛍光体。
Mgm-xEuxSi9Aly(12+2/3m+y)…(1)
(ただし、上記一般式(1)中、0<m≦5.0、0<x/m<0.5、0≦y≦3.0である。)
A nitride phosphor having a chemical composition represented by the following general formula (1).
Mg mx Eu x Si 9 Al y N (12 + 2 / 3m + y) ... (1)
(However, in the general formula (1), 0 <m ≦ 5.0, 0 <x / m <0.5, and 0 ≦ y ≦ 3.0.)
請求項1に記載の窒化物蛍光体を製造する方法であって、窒化物を構成する珪素以外の金属元素の化合物と、窒化珪素とを、溶融した尿素及び/又は溶融した尿素誘導体に溶解又は分散させて窒化物前駆体を形成し、該窒化物前駆体を、不活性又は還元性の雰囲気中で加熱することにより窒化物蛍光体を生成することを特徴とする窒化物蛍光体の製造方法。   A method for producing the nitride phosphor according to claim 1, wherein a compound of a metal element other than silicon constituting the nitride and silicon nitride are dissolved in molten urea and / or a molten urea derivative. A nitride phosphor is produced by dispersing to form a nitride precursor, and heating the nitride precursor in an inert or reducing atmosphere. . 青色光を放射する半導体発光素子と、前記半導体発光素子からの光の一部を吸収して緑色〜黄色の波長領域の蛍光を発光する蛍光体と、請求項1に記載の窒化物蛍光体とを備えていることを特徴とする白色発光素子。   A semiconductor light emitting device that emits blue light, a phosphor that absorbs part of the light from the semiconductor light emitting device and emits fluorescence in the green to yellow wavelength region, and the nitride phosphor according to claim 1. A white light emitting element comprising: 紫外線〜青紫色の領域の光を放射する半導体発光素子と、前記半導体発光素子からの光を吸収して青色の蛍光を発光する蛍光体、もしくは緑色の蛍光を発光する蛍光体の少なくとも一方と、請求項1に記載の窒化物蛍光体とを備えていることを特徴とする白色発光素子。   A semiconductor light emitting device that emits light in the ultraviolet to blue-violet region, and at least one of a phosphor that emits blue fluorescence by absorbing light from the semiconductor light emitting device, or a phosphor that emits green fluorescence, A white light emitting device comprising the nitride phosphor according to claim 1. 下記一般式(1)で表される化学組成を有する顔料。
Mgm-xEuxSi9Aly(12+2/3m+y)…(1)
(ただし、上記一般式(1)中、0<m≦5.0、0<x/m<0.5、0≦y≦3.0である。)
A pigment having a chemical composition represented by the following general formula (1).
Mg mx Eu x Si 9 Al y N (12 + 2 / 3m + y) ... (1)
(However, in the general formula (1), 0 <m ≦ 5.0, 0 <x / m <0.5, and 0 ≦ y ≦ 3.0.)
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006077740A1 (en) * 2004-12-28 2006-07-27 Nichia Corporation Nitride phosphor, method for producing same and light-emitting device using nitride phosphor
JP2008021578A (en) * 2006-07-14 2008-01-31 Koito Mfg Co Ltd Marker lamp for vehicle
KR101243773B1 (en) 2010-08-17 2013-03-14 순천대학교 산학협력단 Wavelength converting composition for light emitting device and sollar cell, light emitting device and sollar cell comprising the composition, preparing method for the composition
JP2015078317A (en) * 2013-10-17 2015-04-23 独立行政法人物質・材料研究機構 Phosphor, method for producing the same, light-emitting device, image display device, pigment, and ultraviolet absorber

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006077740A1 (en) * 2004-12-28 2006-07-27 Nichia Corporation Nitride phosphor, method for producing same and light-emitting device using nitride phosphor
US7854859B2 (en) 2004-12-28 2010-12-21 Nichia Corporation Nitride phosphor, method for producing this nitride phosphor, and light emitting device that uses this nitride phosphor
JP2008021578A (en) * 2006-07-14 2008-01-31 Koito Mfg Co Ltd Marker lamp for vehicle
KR101243773B1 (en) 2010-08-17 2013-03-14 순천대학교 산학협력단 Wavelength converting composition for light emitting device and sollar cell, light emitting device and sollar cell comprising the composition, preparing method for the composition
JP2015078317A (en) * 2013-10-17 2015-04-23 独立行政法人物質・材料研究機構 Phosphor, method for producing the same, light-emitting device, image display device, pigment, and ultraviolet absorber

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