JP2009287024A - (oxy)nitride phosphor material, white-colored light-emitting element containing the same and method for producing the phosphor material - Google Patents
(oxy)nitride phosphor material, white-colored light-emitting element containing the same and method for producing the phosphor material Download PDFInfo
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Abstract
Description
本発明は、（オキシ）ナイトライド蛍光体、それを含む白色発光素子及びナイトライド
蛍光体の製造方法に係り、特に優秀な赤色及び優秀な発光効率を具現する（オキシ）ナイ
トライド蛍光体、それを含む白色発光素子及びマイルドな工程条件を有する蛍光体の製造
方法に関する。
The present invention relates to a (oxy) nitride phosphor, a white light emitting device including the same, and a method for manufacturing the nitride phosphor, and in particular, an (oxy) nitride phosphor that realizes excellent red and excellent luminous efficiency, and The present invention relates to a white light-emitting element containing phosphor and a method of manufacturing a phosphor having mild process conditions.
従来の光システムとして蛍光灯及び白熱灯が広く使われる。しかし、蛍光灯で使われる
Ｈｇは、環境問題をもたらす。また、前記従来の光システムは、寿命が非常に短いだけで
なく、その効率も非常に低いため、節電の側面から望ましくない。これに対し、最近多く
の研究により白色発光素子の効率が向上している。
Fluorescent lamps and incandescent lamps are widely used as conventional light systems. However, Hg used in fluorescent lamps causes environmental problems. In addition, the conventional optical system not only has a very short lifetime, but also has a very low efficiency, which is undesirable from the viewpoint of power saving. On the other hand, the efficiency of white light emitting devices has been improved by many recent studies.
かかる白色発光素子を具現する方法は、ＵＶ発光ダイオード（Ｌｉｇｈｔ Ｅｍｉｔｔ
ｉｎｇ Ｄｉｏｄｅ：ＬＥＤ、以下、ＵＶ−ＬＥＤとも称する）を光源として利用し、光
の三原色である三原色蛍光体を励起させて白色を具現する方式、青色発光ダイオード（以
下、青色ＬＥＤとも称する）を光源として使用して赤色及び緑色蛍光体を励起させて白色
を具現する方式、または青色ＬＥＤを光源として使用して黄色蛍光体を励起させることに
よって白色を具現する方式に区分される。
A method of realizing such a white light emitting device is a UV light emitting diode (Light Emitt).
ing Diode: LED (hereinafter also referred to as UV-LED) as a light source, and a method of realizing white by exciting three primary color phosphors that are the three primary colors of light, blue light emitting diode (hereinafter also referred to as blue LED) as a light source And a method for realizing white by exciting red and green phosphors, and a method for realizing white by exciting yellow phosphors using a blue LED as a light source.
前記三つの方法のうち、青色ＬＥＤを光源として使用して黄色蛍光体を励起させること
によって白色を具現する方式は、赤色の強度が低下して色再現の側面で問題がある。
Of the three methods, the method of realizing white by exciting a yellow phosphor using a blue LED as a light source has a problem in terms of color reproduction due to a decrease in the intensity of red.
したがって、前記三つの方式のうち、残りのＵＶ及び青色ＬＥＤ及び蛍光体を使用して
光システムを開発しようとする研究が増加している。しかし、それらの方式は、色再現に
は優れているが、効率が低下するという短所がある。
Therefore, among the above three methods, research for developing a light system using the remaining UV and blue LEDs and phosphors is increasing. However, these methods are excellent in color reproduction, but have a disadvantage that efficiency is lowered.
一方、従来の公知の赤色蛍光体は、白色発光素子に適用するのに適していない。それら
は、カソードレイ、ＶＵＶ（Ｖａｃｕｕｍ Ｕｌｔｒａｖｉｏｌｅｔ）レイ及び短波長光
に対しては発光効率が優れているが、前記白色発光素子で使われるＵＶ及び青色光に対す
る発光効率に劣る。したがって、白色発光素子の技術分野で、ＵＶ及び青色光に対して高
効率を有する赤色蛍光体の開発が強く要求されている。
On the other hand, the conventional known red phosphor is not suitable for application to a white light emitting element. They are excellent in luminous efficiency for cathode ray, VUV (vacuum ultraviolet) ray and short wavelength light, but inferior in luminous efficiency for UV and blue light used in the white light emitting device. Accordingly, there is a strong demand for the development of red phosphors having high efficiency with respect to UV and blue light in the technical field of white light emitting devices.
かかる状況で、ナイトライド蛍光体の開発が進められている。 Under such circumstances, development of nitride phosphors is underway.
しかしながら、従来のナイトライド蛍光体は、ＵＶ及び青色光に対して発光するものの
、白色発光素子として商業化されるには発光強度が十分な程度ではない。また、公知のナ
イトライド蛍光体の製造方法は、高い温度、０．１ＭＰ以上の高い窒素ガス圧力の工程条
件が必要となる。したがって、かかる高温、高圧に耐えるように考案された特別な装置が
必要となり、また、出発物質として不安定な物質を使用しているため、それらの出発物質
の取扱時に要求される条件が厳しい。このように、現在までは商業化するのに適した赤色
蛍光体が開発されていないのが実情である。
However, although conventional nitride phosphors emit light with respect to UV and blue light, the light emission intensity is not sufficient to be commercialized as a white light emitting device. Moreover, the manufacturing method of a well-known nitride fluorescent substance requires the process conditions of high temperature and high nitrogen gas pressure of 0.1 MP or more. Therefore, a special apparatus designed to withstand such high temperature and high pressure is required, and since unstable materials are used as starting materials, the conditions required when handling these starting materials are severe. Thus, until now, no actual red phosphor suitable for commercialization has been developed.
本発明が解決しようとする課題は、前述した問題点を解決した赤色蛍光体として（オキ
シ）ナイトライド蛍光体を提供するところにある。
The problem to be solved by the present invention is to provide an (oxy) nitride phosphor as a red phosphor that solves the above-mentioned problems.
本発明が解決しようとする他の課題は、前記（オキシ）ナイトライド蛍光体を含む白色
発光素子を提供するところにある。
Another problem to be solved by the present invention is to provide a white light emitting device including the (oxy) nitride phosphor.
本発明が解決しようとするさらに他の課題は、安定かつマイルドな工程条件を有する蛍
光体の製造方法を提供するところにある。
Still another problem to be solved by the present invention is to provide a method for producing a phosphor having stable and mild process conditions.
前記課題を解決するために、本発明では、下記化学式１の化合物で表示される（オキシ
）ナイトライド蛍光体を提供する。
In order to solve the above-mentioned problems, the present invention provides an (oxy) nitride phosphor represented by a compound represented by the following chemical formula 1.
前記式で、Ｍは、アルカリ土類金属であり、０＜ｘ＜１、１．８＜ａ＜２．２、４．５
＜ｂ＜５．５、０≦ｃ＜８、０＜ｄ≦８及び０＜ｃ＋ｄ≦８である。
In the above formula, M is an alkaline earth metal, and 0 <x <1, 1.8 <a <2.2, 4.5
<B <5.5, 0 ≦ c <8, 0 <d ≦ 8, and 0 <c + d ≦ 8.
前記化学式１の化合物の（オキシ）ナイトライド蛍光体は、ポアを含みうる。 The (oxy) nitride phosphor of the compound of Formula 1 may include a pore.
前記他の課題を解決するために、本発明では、ＵＶ−ＬＥＤと、前記本発明による（オ
キシ）ナイトライド赤色蛍光体と、を含む白色発光素子を提供する。
In order to solve the other problems, the present invention provides a white light emitting device including a UV-LED and the (oxy) nitride red phosphor according to the present invention.
前記さらに他の課題を解決するために、本発明では、（ａ）アルカリ土類金属前駆体化
合物、Ｅｕ前駆体化合物、酸、Ｓｉ３Ｎ４粉末及びキレート化合物の混合物をゲル状態に
形成する工程と、（ｂ）前記ゲル状態の混合物を乾燥及び１次焼成する工程と、（ｃ）前
記（ｂ）工程の結果物を粉砕及び２次焼成する工程と、を含む蛍光体の製造方法を提供す
る。
In order to solve the above-described further problems, in the present invention, (a) a step of forming a mixture of an alkaline earth metal precursor compound, an Eu precursor compound, an acid, Si 3 N 4 powder and a chelate compound in a gel state And (b) a step of drying and primary firing the mixture in the gel state, and (c) a step of pulverizing and secondary firing the resultant product of the step (b). To do.
本発明の（オキシ）ナイトライド蛍光体は、ＵＶ−ＬＥＤ及び青色ＬＥＤ型白色発光素
子に使用するのに優れた赤色を具現し、優秀な効率を具現する。また、本発明による蛍光
体の製造方法は、安定した物質を出発物質として使用し、工程条件がマイルドかつ環境親
和的であるので、商業的に活用するのに有効である。
The (oxy) nitride phosphor of the present invention realizes a red color that is excellent for use in UV-LED and blue LED type white light emitting devices, and realizes excellent efficiency. In addition, the method for producing a phosphor according to the present invention uses a stable substance as a starting material, and the process conditions are mild and environmentally friendly. Therefore, it is effective for commercial use.
以下、本発明をさらに詳細に説明する。 Hereinafter, the present invention will be described in more detail.
本発明は、下記化学式１の（オキシ）ナイトライド系蛍光体を提供する。 The present invention provides an (oxy) nitride phosphor of the following chemical formula 1.
前記式で、Ｍは、アルカリ土類金属であり、０＜ｘ＜１、１．８＜ａ＜２．２、４．５
＜ｂ＜５．５、０≦ｃ＜８、０＜ｄ≦８及び０＜ｃ＋ｄ≦８である。
In the above formula, M is an alkaline earth metal, and 0 <x <1, 1.8 <a <2.2, 4.5
<B <5.5, 0 ≦ c <8, 0 <d ≦ 8, and 0 <c + d ≦ 8.
前記化学式１の化合物の例として下記の化学式が挙げられる。 Examples of the compound represented by Formula 1 include the following chemical formula.
前記式で、Ｍは、アルカリ土類金属であり、０＜ｘ＜１、１．８＜ａ＜２．２、４．５
＜ｂ＜５．５、０＜ｃ＜８、０＜ｄ≦８及び０＜ｃ＋ｄ≦８である。
In the above formula, M is an alkaline earth metal, and 0 <x <1, 1.8 <a <2.2, 4.5
<B <5.5, 0 <c <8, 0 <d ≦ 8, and 0 <c + d ≦ 8.
前記（オキシ）ナイトライド蛍光体は、ポアを含みうる。 The (oxy) nitride phosphor may include a pore.
前記化学式１の（オキシ）ナイトライド蛍光体は、赤色蛍光体であって、ＵＶ及び青色
光に対して励起され、赤色発光時に高効率を表す物質である。したがって、前記化学式１
の（オキシ）ナイトライド蛍光体を含む白色発光素子は、ＵＶ−ＬＥＤ及び青色−ＬＥＤ
を励起光源として使用できる。
The (oxy) nitride phosphor of Formula 1 is a red phosphor, which is excited by UV and blue light and exhibits high efficiency when emitting red light. Therefore, the chemical formula 1
White light-emitting elements containing (oxy) nitride phosphors of the present invention are UV-LED and blue-LED
Can be used as an excitation light source.
本発明による化学式１の（オキシ）ナイトライド蛍光体は、従来の赤色蛍光体が有する
色々な短所を効果的に改善する。例えば、発光元素が窒素と結合することによって、消光
と関連した熱活性化エネルギーが非常に大きくなる。このため、赤色発光の熱損失を減ら
すことができ、赤色発光の高い効率が得られる。また、既存の赤色蛍光体には、空気中の
水分に敏感である、バインダと予期せぬ反応を起こす、熱に対する耐久性が弱いといった
問題点があった。オキシナイトライド蛍光体は、従来の赤色蛍光体が有するかような問題
を解決しうる物質であるため、白色発光素子用の赤色蛍光体として非常に有効である。
The (oxy) nitride phosphor of Formula 1 according to the present invention effectively improves various disadvantages of the conventional red phosphor. For example, when the luminescent element is combined with nitrogen, the thermal activation energy associated with quenching becomes very large. For this reason, heat loss of red light emission can be reduced, and high efficiency of red light emission can be obtained. In addition, the existing red phosphor has a problem that it is sensitive to moisture in the air, causes an unexpected reaction with the binder, and has low durability against heat. Since the oxynitride phosphor is a substance that can solve the problems of conventional red phosphors, it is very effective as a red phosphor for white light emitting devices.
したがって、本発明による（オキシ）ナイトライド赤色蛍光体は、ＵＶ−ＬＥＤを光源
として利用し、赤色、緑色、青色を有する３個の蛍光体を組み合わせて白色を具現する方
式、及び青色ＬＥＤを光源として使用して赤色及び緑色蛍光体を励起させることによって
白色を具現する方式の白色発光素子の類型に非常に適している。かかる白色発光素子は、
良好な白色発光を実現し、かつ高い効率を具現できる。
Therefore, the (oxy) nitride red phosphor according to the present invention uses a UV-LED as a light source, combines three phosphors having red, green, and blue to realize white, and a blue LED as a light source. It is very suitable for the type of white light-emitting element that realizes white by exciting red and green phosphors. Such a white light emitting element is
Realizing good white light emission and realizing high efficiency.
一方、前記本発明による（オキシ）ナイトライド蛍光体は、人の目に対する敏感度が高
い赤色を再現できる。
On the other hand, the (oxy) nitride phosphor according to the present invention can reproduce red having high sensitivity to human eyes.
また、本発明は、ポアを含む（オキシ）ナイトライド蛍光体を提供する。ポアを有する
オキシナイトライド蛍光体の製造過程で、活性窒素（Ｎ＊）がポア内に浸透して窒化を起
こす。オキシナイトライド蛍光体がポアを有すると、ポアを通じて円滑なガスの出入が行
われる。したがって窒化の観点から見るとき、ポアが蛍光体の合成過程上、肯定的な役割
を行う側面があると見られる。
The present invention also provides (oxy) nitride phosphors containing pores. In the process of manufacturing the oxynitride phosphor having pores, active nitrogen (N * ) permeates into the pores to cause nitriding. When the oxynitride phosphor has pores, smooth gas flow in and out through the pores. Therefore, when viewed from the viewpoint of nitriding, it seems that the pore plays a positive role in the phosphor synthesis process.
本発明による（オキシ）ナイトライド蛍光体がポアを含む場合、前記ポアは、平均直径
が０．６μｍ以下であり、望ましくは、約０．２μｍないし０．６μｍである。ポアの平
均直径が０．２μｍ未満の場合、Ｎの含量が少なくなる可能性がある。これは、蛍光体の
製造過程で前述したように活性窒素（Ｎ＊）がポア内に浸透して窒化を起こすが、ポアが
小さくなれば、かかる作用が不十分になるためである。また、ポアの平均直径が０．６μ
ｍを超える場合、蛍光体の密度が減少して発光強度が低下するという問題点がありうる。
なお、ポアが概略円形以外の場合、平均直径を算出する際の直径とは、楕円形の場合、長
径を指し、多角形の場合、各頂点を結んだ長さのうち最大径を指す。
When the (oxy) nitride phosphor according to the present invention includes pores, the pores have an average diameter of 0.6 μm or less, preferably about 0.2 μm to 0.6 μm. When the average diameter of the pores is less than 0.2 μm, the N content may be reduced. This is because active nitrogen (N * ) permeates into the pore and causes nitridation as described above in the process of manufacturing the phosphor, but this effect becomes insufficient when the pore is reduced. Also, the average pore diameter is 0.6μ
When it exceeds m, there may be a problem that the density of the phosphor decreases and the emission intensity decreases.
When the pore is other than a substantially circular shape, the diameter when calculating the average diameter indicates the major axis in the case of an ellipse, and indicates the maximum diameter among the lengths connecting the vertices in the case of a polygon.
また、ポアは、（オキシ）ナイトライド蛍光体の断面１μｍ２当たり約０．０１個以下
、望ましくは、約０．００５個ないし０．０１個を含む。前記単位面積当たりポアの個数
、すなわち（オキシ）ナイトライド蛍光体の断面１μｍ２当たりポアが０．００５個未満
の場合、Ｎの含量が少なくなる虞れがある。これも、蛍光体の製造過程で活性窒素（Ｎ＊
）がポア内に浸透して窒化を起こすが、ポアの個数が少なくなれば、かかる作用が不十分
になるためである。前記単位面積当たりポアの個数、すなわち（オキシ）ナイトライド蛍
光体の断面１μｍ２当たりポアが０．０１個を超える場合、蛍光体の密度が減少して発光
強度が低下するという問題点がありうる。
Further, the pore contains about 0.01 or less, preferably about 0.005 to 0.01 per 1 μm 2 of the cross section of the (oxy) nitride phosphor. If the number of pores per unit area, that is, less than 0.005 pores per 1 μm 2 cross section of the (oxy) nitride phosphor, the N content may be reduced. This is also the case of active nitrogen (N *) during the phosphor manufacturing process .
) Penetrates into the pores and causes nitridation. However, if the number of pores decreases, such an effect becomes insufficient. When the number of pores per unit area, that is, when the number of pores exceeds 1 per 1 μm 2 of the cross section of the (oxy) nitride phosphor, there may be a problem that the phosphor density decreases and the emission intensity decreases. .
ポア間の平均距離は、約１μｍ以上、望ましくは、約１μｍないし３μｍである。ポア
間の平均距離が１μｍ未満で形成される場合、蛍光体の密度が減少して発光強度が低下す
るという問題点がありうる。３μｍを超えて形成される場合、Ｎの含量が少なくなる可能
性がある。これも、前記蛍光体の製造過程で活性窒素（Ｎ＊）がポア内に浸透して窒化を
起こすが、ポア間の平均距離が大きくなれば、かかる作用が不十分になるためである。
The average distance between the pores is about 1 μm or more, preferably about 1 μm to 3 μm. When the average distance between the pores is less than 1 μm, there may be a problem that the density of the phosphor decreases and the emission intensity decreases. When formed to exceed 3 μm, the N content may be reduced. This is also because active nitrogen (N * ) permeates into the pores during the manufacturing process of the phosphor to cause nitriding, but this effect becomes insufficient if the average distance between the pores increases.
ポアは、色々な形態を有するところ、その断面が円形、楕円形、多角形などでありうる
。
The pore has various forms, and its cross section may be circular, elliptical, polygonal, or the like.
化学式１において、Ｍはアルカリ土類金属であり、好ましくはＢａ、ＳｒまたはＣａで
ある。ここでＭは、１種のアルカリ土類金属であっても、あるいは２種以上のアルカリ土
類金属を表すものであってもよい。
In Chemical Formula 1, M is an alkaline earth metal, preferably Ba, Sr or Ca. Here, M may be one kind of alkaline earth metal or may represent two or more kinds of alkaline earth metals.
前記化学式１の化合物の具体例としては、（Ｓｒ１−ｘＥｕｘ）ａＳｉｂＯｃＮｄ（０
＜ｘ≦０．１、１．８＜ａ＜２．２、４．５＜ｂ＜５．５、０≦ｃ＜８及び０＜ｃ＋ｄ≦
８、望ましくは、（Ｓｒ１−ｘＥｕｘ）２Ｓｉ５Ｎ８（０＜ｘ≦０．１）が挙げられる。
Specific examples of the compound represented by Formula 1 include (Sr 1-x Eu x ) a Si b O c N d (0
<X ≦ 0.1, 1.8 <a <2.2, 4.5 <b <5.5, 0 ≦ c <8 and 0 <c + d ≦
8, preferably, include (Sr 1-x Eu x) 2 Si 5 N 8 (0 <x ≦ 0.1).
前記化学式１の化合物の他の具体例としては、（Ｓｒ１−ｘＥｕｘ）２Ｓｉ５Ｎ８（０
＜ｘ＜１）、（Ｓｒ１−ｘＥｕｘ）１．９９Ｓｉ５Ｎ８（０＜ｘ＜１）、（Ｂａ１−ｘ−
ｙＳｒｘＥｕｙ）２Ｓｉ５Ｎ８（０＜ｘ＜１、０＜ｙ＜１及び０＜ｘ＋ｙ＜１）、（Ｓｒ
１−ｘ−ｙＣａｘＥｕｙ）２Ｓｉ５Ｎ８（０＜ｘ＜１、０＜ｙ＜１及び０＜ｘ＋ｙ＜１）
または（Ｂａ０．５Ｓｒ１−ｘＣａ０．５Ｅｕｘ）Ｓｉ５Ｎ８（０＜ｘ＜１）のような化
合物でありうる。
As another specific example of the compound of the chemical formula 1, (Sr 1-x Eu x ) 2 Si 5 N 8 (0
<X <1), (Sr 1-x Eu x) 1.99 Si 5 N 8 (0 <x <1), (Ba 1-x-
y Sr x Eu y ) 2 Si 5 N 8 (0 <x <1, 0 <y <1 and 0 <x + y <1), (Sr
1-xy Ca x Eu y ) 2 Si 5 N 8 (0 <x <1, 0 <y <1 and 0 <x + y <1)
Alternatively, it may be a compound such as (Ba 0.5 Sr 1-x Ca 0.5 Eu x ) Si 5 N 8 (0 <x <1).
本発明は、また、ＵＶ−ＬＥＤと、本発明による（オキシ）ナイトライド赤色蛍光体（
ポアを有する場合及びポアを有さない場合いずれも可能である）と、を含む白色発光素子
を提供する。
The invention also relates to UV-LEDs and (oxy) nitride red phosphors according to the invention (
A white light-emitting element including a pore and a case without a pore).
望ましくは、ＵＶ−ＬＥＤは、励起光源が紫外線または近紫外線領域の電磁波である。 Preferably, in the UV-LED, the excitation light source is an electromagnetic wave in the ultraviolet or near ultraviolet region.
さらに望ましくは、白色発光素子において、ＵＶ−ＬＥＤの励起光源の波長帯域が３９
０〜４６０ｎｍの範囲である。
More preferably, in the white light emitting element, the wavelength band of the excitation light source of the UV-LED is 39.
It is in the range of 0 to 460 nm.
ＵＶ−ＬＥＤと、本発明によるオキシナイトライド赤色蛍光体を含む白色発光素子は、
青色蛍光体および／または緑色蛍光体をさらに含む。
A white light-emitting element comprising a UV-LED and an oxynitride red phosphor according to the present invention,
It further includes a blue phosphor and / or a green phosphor.
前記青色蛍光体の例としては、（Ｓｒ，Ｂａ，Ｃａ）５（ＰＯ４）３Ｃｌ：Ｅｕ２＋；
ＢａＭｇ２Ａｌ１６Ｏ２７：Ｅｕ２＋；Ｓｒ４Ａｌ１４Ｏ２５：Ｅｕ２＋；ＢａＡｌ８Ｏ
１３：Ｅｕ２＋；（Ｓｒ，Ｍｇ，Ｃａ，Ｂａ）５（ＰＯ４）３Ｃｌ：Ｅｕ２＋；ＢａＭｇ
Ａｌ１０Ｏ１７：Ｅｕ２＋及びＳｒ２Ｓｉ３Ｏ８２ＳｒＣｌ２：Ｅｕ２＋などが挙げられ
る。これらは１種単独で用いてもよいし、２種以上併用してもよい。
Examples of the blue phosphor include (Sr, Ba, Ca) 5 (PO 4 ) 3 Cl: Eu 2+ ;
BaMg 2 Al 16 O 27 : Eu 2+ ; Sr 4 Al 14 O 25 : Eu 2+ ; BaAl 8 O
13 : Eu 2+ ; (Sr, Mg, Ca, Ba) 5 (PO 4 ) 3 Cl: Eu 2+ ; BaMg
Al 10 O 17 : Eu 2+ and Sr 2 Si 3 O 8 2SrCl 2 : Eu 2+ can be used. These may be used alone or in combination of two or more.
前記緑色蛍光体の例としては、（Ｂａ，Ｓｒ，Ｃａ）２ＳｉＯ４：Ｅｕ２＋；Ｂａ２Ｍ
ｇＳｉ２Ｏ７：Ｅｕ２＋；Ｂａ２ＺｎＳｉ２Ｏ７：Ｅｕ２＋；ＢａＡｌ２Ｏ４：Ｅｕ２＋
；ＳｒＡｌ２Ｏ４：Ｅｕ２＋；ＢａＭｇＡｌ１０Ｏ１７：Ｅｕ２＋，Ｍｎ２＋及びＢａＭ
ｇ２Ａｌ１６Ｏ２７：Ｅｕ２＋，Ｍｎ２＋などが挙げられる。これらは１種単独で用いて
もよいし、２種以上併用してもよい。
Examples of the green phosphor include (Ba, Sr, Ca) 2 SiO 4 : Eu 2+ ; Ba 2 M
gSi 2 O 7 : Eu 2+ ; Ba 2 ZnSi 2 O 7 : Eu 2+ ; BaAl 2 O 4 : Eu 2+
SrAl 2 O 4 : Eu 2+ ; BaMgAl 10 O 17 : Eu 2+ , Mn 2+ and BaM
g 2 Al 16 O 27 : Eu 2+ , Mn 2+ and the like. These may be used alone or in combination of two or more.
望ましくは、前記赤色蛍光体の放出スペクトル（蛍光スペクトル）でピークの波長は、
６１０〜６５０ｎｍである。望ましくは、前記緑色蛍光体の放出スペクトルでピークの波
長は、５１０〜５６０ｎｍである。望ましくは、前記青色蛍光体の放出スペクトルでピー
クの波長は、４４０〜４６０ｎｍである。
Preferably, the peak wavelength in the emission spectrum (fluorescence spectrum) of the red phosphor is:
610 to 650 nm. Preferably, the peak wavelength in the emission spectrum of the green phosphor is 510 to 560 nm. Preferably, the peak wavelength in the emission spectrum of the blue phosphor is 440 to 460 nm.
また、本発明は、青色ＬＥＤと、本発明による（オキシ）ナイトライド赤色蛍光体と、
を含む白色発光素子を提供する。望ましくは、青色ＬＥＤは、励起光源であって、４２０
〜４８０ｎｍの波長帯域を有する。
The present invention also provides a blue LED, an (oxy) nitride red phosphor according to the present invention,
A white light emitting device including Preferably, the blue LED is an excitation light source, 420
It has a wavelength band of ˜480 nm.
青色ＬＥＤと、本発明によるオキシナイトライド赤色蛍光体を含む白色発光素子は、緑
色蛍光体をさらに含むことが好ましい。
The white light emitting device including the blue LED and the oxynitride red phosphor according to the present invention preferably further includes a green phosphor.
緑色蛍光体の例としては、（Ｂａ，Ｓｒ，Ｃａ）２ＳｉＯ４：Ｅｕ２＋；Ｂａ２ＭｇＳ
ｉ２Ｏ７：Ｅｕ２＋；Ｂａ２ＺｎＳｉ２Ｏ７：Ｅｕ２＋；ＢａＡｌ２Ｏ４：Ｅｕ２＋；Ｓ
ｒＡｌ２Ｏ４：Ｅｕ２＋；ＢａＭｇＡｌ１０Ｏ１７：Ｅｕ２＋，Ｍｎ２＋及びＢａＭｇ２
Ａｌ１６Ｏ２７：Ｅｕ２＋，Ｍｎ２＋などが挙げられる。これらは１種単独で用いてもよ
いし、２種以上併用してもよい
望ましくは、前記赤色蛍光体の放出スペクトルでピークの波長は、６１０〜６５０ｎｍ
である。望ましくは、前記緑色蛍光体の放出スペクトルでピークの波長は、５１０〜５６
０ｎｍである。
Examples of the green phosphor include (Ba, Sr, Ca) 2 SiO 4 : Eu 2+ ; Ba 2 MgS
i 2 O 7 : Eu 2+ ; Ba 2 ZnSi 2 O 7 : Eu 2+ ; BaAl 2 O 4 : Eu 2+ ; S
rAl 2 O 4 : Eu 2+ ; BaMgAl 10 O 17 : Eu 2+ , Mn 2+ and BaMg 2
Al 16 O 27 : Eu 2+ , Mn 2+ and the like can be mentioned. These may be used alone or in combination of two or more. Desirably, the peak wavelength in the emission spectrum of the red phosphor is 610 to 650 nm.
It is. Preferably, the peak wavelength in the emission spectrum of the green phosphor is 510 to 56.
0 nm.
本発明の白色発光素子は、信号灯、通信機器、ディスプレイ装置のバックライトまたは
照明用として用いることができる。
The white light emitting device of the present invention can be used for a signal lamp, a communication device, a backlight of a display device or illumination.
図１は、本発明の一実施形態によるＬＥＤの構造を示す概略図であって、高分子レンズ
タイプの表面実装型ＬＥＤを示すものである。ここで、高分子レンズの一実施例としてエ
ポキシレンズを使用する。
FIG. 1 is a schematic diagram illustrating the structure of an LED according to an embodiment of the present invention, and illustrates a surface mount LED of a polymer lens type. Here, an epoxy lens is used as an example of the polymer lens.
図１に示すように、ＵＶ ＬＥＤチップ１０は、金ワイヤー２０を通じて電気リード線
３０とダイボンディングされ、本発明による赤色蛍光体を含有する蛍光体組成物４０を含
むようにエポキシモールド層５０が形成されている。そして、図１において、成形モール
ド６０の内部は、アルミニウムまたは銀でコーティングされた反射膜からなり、これは、
ダイオードから放出された光を上方に反射させる役割及び適当量のエポキシを溜める役割
を行う。
As shown in FIG. 1, the UV LED chip 10 is die-bonded to an electrical lead wire 30 through a gold wire 20, and an epoxy mold layer 50 is formed so as to include a phosphor composition 40 containing a red phosphor according to the present invention. Has been. In FIG. 1, the inside of the mold 60 is made of a reflective film coated with aluminum or silver.
It plays a role of reflecting upward the light emitted from the diode and storing an appropriate amount of epoxy.
前記エポキシモールド層５０の上部には、エポキシドームレンズ７０が形成されており
、このエポキシドームレンズ７０は、所望の配向角によって形態が変化しうる。
An epoxy dome lens 70 is formed on the epoxy mold layer 50, and the shape of the epoxy dome lens 70 can be changed according to a desired orientation angle.
本発明のＬＥＤは、図１の構造にのみ限定されることを意味するものではなく、その他
の構造、例えばＬＥＤに蛍光体が実装されるタイプ、砲弾型、ＰＣＢタイプの表面実装型
の構造を有するＬＥＤでありうる。
The LED of the present invention is not limited to the structure shown in FIG. 1, and other structures such as a type in which a phosphor is mounted on the LED, a shell type, and a PCB type surface mount type structure are used. It can be LED which has.
一方、本発明の化学式１で表示されるオキシナイトライド蛍光体は、前述したＬＥＤ以
外に水銀ランプ、キセノンランプのようなランプまたは自発光液晶表示素子（ＬＣＤ）に
も適用可能である。
On the other hand, the oxynitride phosphor represented by Chemical Formula 1 of the present invention can be applied to a lamp such as a mercury lamp or a xenon lamp or a self-luminous liquid crystal display element (LCD) in addition to the LED described above.
また、本発明は、（ａ）アルカリ土類金属前駆体化合物、Ｅｕ前駆体化合物、酸、Ｓｉ
３Ｎ４粉末及びキレート化合物の混合物をゲル状態に形成する工程と、（ｂ）前記（ａ）
工程で得られる混合物を乾燥及び１次焼成する工程と、（ｃ）前記（ｂ）工程の結果物を
粉砕及び２次焼成する工程と、を含む蛍光体の製造方法を提供する。
The present invention also includes (a) an alkaline earth metal precursor compound, an Eu precursor compound, an acid, Si
Forming a mixture of 3 N 4 powder and a chelate compound into a gel state, and (b) said (a)
There is provided a method for producing a phosphor comprising: a step of drying and primary firing the mixture obtained in the step; and a step of (c) pulverizing and secondary firing the resultant product of the step (b).
上記方法を本発明の一具現例によってさらに具体的に説明すれば、次の通りである。 The above method will be described in more detail with reference to an embodiment of the present invention as follows.
まず、アルカリ土類金属前駆体化合物及びＥｕ前駆体化合物の混合物を準備する。アル
カリ土類金属前駆体化合物は、望ましくは、Ｂａ前駆体化合物、Ｓｒ前駆体化合物、Ｃａ
前駆体化合物などを使用できる。Ｂａ前駆体化合物の例として、ＢａＣＯ３，Ｂａ（ＮＯ
３）２，ＢａＣｌ２，ＢａＯなどがある。Ｓｒ前駆体化合物の例として、ＳｒＣＯ３，Ｓ
ｒ（ＮＯ３）２，ＳｒＣｌ２，ＳｒＯなどがある。Ｃａ前駆体化合物の例として、ＣａＣ
Ｏ３，Ｃａ（ＮＯ３）２，ＣａＣｌ２，ＣａＯなどがある。また、前記Ｅｕ前駆体化合物
として、Ｅｕ２Ｏ３，Ｅｕ（ＮＯ３）３，ＥｕＣｌ３などを使用できる。前記各前駆体化
合物は、それぞれ１種単独で用いてもよいし、２種以上併用してもよい。
First, a mixture of an alkaline earth metal precursor compound and an Eu precursor compound is prepared. The alkaline earth metal precursor compound is preferably a Ba precursor compound, an Sr precursor compound, Ca
A precursor compound or the like can be used. Examples of Ba precursor compounds include BaCO 3 , Ba (NO
3 ) 2 , BaCl 2 , BaO and the like. Examples of Sr precursor compounds include SrCO 3 , S
Examples include r (NO 3 ) 2 , SrCl 2 , SrO. Examples of Ca precursor compounds include CaC
Examples include O 3 , Ca (NO 3 ) 2 , CaCl 2 , and CaO. Further, Eu 2 O 3 , Eu (NO 3 ) 3 , EuCl 3 and the like can be used as the Eu precursor compound. Each said precursor compound may be used individually by 1 type, respectively, and may be used together 2 or more types.
次いで、前記アルカリ土類金属前駆体化合物及びＥｕ前駆体化合物の混合物を酸に溶解
させる。このとき、使用可能な酸は、無機酸または有機酸などが広く使われ、その例とし
ては、ＨＮＯ３、ＨＣｌ、Ｈ２ＳＯ４、酢酸、酪酸、パルミチン酸、シュウ酸、酒石酸な
どがある。これらは１種単独で用いてもよいし、２種以上併用してもよい。望ましくは、
前記酸は、０．１ないし１０ｍｏｌ／ｌの濃度である。
Next, the mixture of the alkaline earth metal precursor compound and the Eu precursor compound is dissolved in an acid. At this time, as the usable acid, inorganic acid or organic acid is widely used, and examples thereof include HNO 3 , HCl, H 2 SO 4 , acetic acid, butyric acid, palmitic acid, oxalic acid, tartaric acid and the like. These may be used alone or in combination of two or more. Preferably
The acid has a concentration of 0.1 to 10 mol / l.
次いで、前記アルカリ土類金属前駆体化合物及びＥｕ前駆体化合物の混合物が溶解され
た酸にＳｉ３Ｎ４粉末を添加する。
Next, Si 3 N 4 powder is added to the acid in which the mixture of the alkaline earth metal precursor compound and the Eu precursor compound is dissolved.
次いで、前記アルカリ土類金属前駆体化合物、Ｅｕ前駆体化合物の混合物が溶解された
酸及びＳｉ３Ｎ４粉末の混合物にキレート化合物を添加してゲル状態に形成する。前記キ
レート化合物の例は、クエン酸、グリシン、尿素、エチレンジアミン四酢酸（ＥＤＴＡ）
などでありうる。キレート剤の添加量は、混合物全体に対して２５〜３０質量％であるこ
とが好ましい。前記キレート化合物は、それぞれ１種単独で用いてもよいし、２種以上併
用してもよい。
Next, a chelate compound is added to the mixture of the acid in which the mixture of the alkaline earth metal precursor compound and the Eu precursor compound is dissolved and the Si 3 N 4 powder to form a gel state. Examples of the chelate compound include citric acid, glycine, urea, ethylenediaminetetraacetic acid (EDTA).
And so on. It is preferable that the addition amount of a chelating agent is 25-30 mass% with respect to the whole mixture. Each of the chelate compounds may be used alone or in combination of two or more.
前記キレート化合物を混合すれば、下記反応式によって反応してＳｒ２＋キレート化合
物、Ｅｕ３＋キレート化合物が形成される。
When the chelate compound is mixed, it reacts according to the following reaction formula to form Sr 2+ chelate compound and Eu 3+ chelate compound.
前記Ｓｒ２＋キレート化合物、Ｅｕ３＋キレート化合物の反応経路を、アルカリ土類金
属前駆体化合物としてＳｒＣＯ３を、Ｅｕ前駆体化合物としてＥｕ２Ｏ３を使用し、酸と
して硝酸を、キレート化合物としてクエン酸を使用した場合を例として説明すれば、次の
通りである。この場合、下記反応式１のような反応が起こる。
The reaction path of the Sr 2+ chelate compound and Eu 3+ chelate compound is as follows: SrCO 3 is used as the alkaline earth metal precursor compound, Eu 2 O 3 is used as the Eu precursor compound, nitric acid is used as the acid, and citric acid is used as the chelate compound. As an example, the case of using is as follows. In this case, the reaction shown in the following reaction formula 1 occurs.
さらに詳しくは、前記Ｓｒ２＋キレート化合物は、まず、ＳｒＣＯ３が硝酸と反応して
Ｓｒ２＋を形成し、次いで、クエン酸と反応して形成される。
More specifically, the Sr 2+ chelate compound is formed by first reacting SrCO 3 with nitric acid to form Sr 2+ and then reacting with citric acid.
このように形成されたＳｒ２＋キレート化合物は、図５で示した通りである。 The Sr 2+ chelate compound thus formed is as shown in FIG.
また、前記Ｅｕ３＋キレート化合物も、まず、Ｅｕ２Ｏ３が硝酸と反応してＥｕ３＋を
形成し、次いで、クエン酸と反応して形成される。
The Eu 3+ chelate compound is also formed by first reacting Eu 2 O 3 with nitric acid to form Eu 3+ and then reacting with citric acid.
図６は、前記のような過程で形成されたゲル状態の混合物を図式化したものである。図
６において、Ｓｉ３Ｎ４間に介在されたキレート化合物は、Ｓｒ２＋キレート化合物及び
Ｅｕ３＋キレート化合物がランダムに分布したことを意味する。
FIG. 6 is a schematic diagram of a gel-like mixture formed in the above process. In FIG. 6, the chelate compound interposed between Si 3 N 4 means that the Sr 2+ chelate compound and the Eu 3+ chelate compound are randomly distributed.
次いで、前記ゲル状態の結果物を乾燥した後、１次焼成する。望ましくは、前記焼成は
、３００ないし７００℃の空気雰囲気下で行う。焼成時間は特に限定されるものではない
が、好ましくは０．５〜５時間、より好ましくは１〜５時間である。かかる１次焼成によ
りアルカリ土類金属キレート化合物及びＥｕ３＋キレート化合物が酸化されて、アルカリ
土類金属酸化物及びＥｕ２Ｏ３が合成される。このように生成されたアルカリ土類金属酸
化物は、前記酸化時に共に発生するＣＯ２及びＨ２Ｏガスにより生成された複数のポアを
有する。
Next, the gel-like resultant is dried and then subjected to primary firing. Preferably, the baking is performed in an air atmosphere of 300 to 700 ° C. Although baking time is not specifically limited, Preferably it is 0.5 to 5 hours, More preferably, it is 1 to 5 hours. By such primary firing, the alkaline earth metal chelate compound and Eu 3+ chelate compound are oxidized, and the alkaline earth metal oxide and Eu 2 O 3 are synthesized. The alkaline earth metal oxide generated in this way has a plurality of pores generated by CO 2 and H 2 O gas generated together during the oxidation.
図７は、前記反応式１の例で１次焼成過程を通じた変化を概略的に示す図面である。 FIG. 7 is a view schematically showing changes through the primary firing process in the example of the reaction formula 1.
次いで、前記のように１次焼成を行って得た結果物を粉砕し、２次焼成を行う。このと
き、焼成は、１３００〜１７００℃で行うことが好ましい。また焼成時間は、１０〜１０
０時間で行うことが好ましい。さらに焼成雰囲気は、ＮＨ３及び／またはＨ２／Ｎ２混合
ガス雰囲気下で行うことが好ましい。Ｈ２／Ｎ２混合ガスの混合割合は、好ましくはＨ２
：Ｎ２＝０．０５：１〜０．２：１である。なお、工程中の一部に前記好適な条件を具備
する焼結工程が少なくとも含まれて入ればよい。かような２次焼成を行うことによって、
ナイトライド化合物が得られる。
Subsequently, the resultant obtained by performing the primary firing as described above is pulverized and subjected to secondary firing. At this time, the firing is preferably performed at 1300 to 1700 ° C. The firing time is 10 to 10
It is preferable to carry out in 0 hours. Further, the firing atmosphere is preferably performed in an NH 3 and / or H 2 / N 2 mixed gas atmosphere. The mixing ratio of the H 2 / N 2 gas mixture is preferably H 2
: N 2 = 0.05: 1 to 0.2: 1. In addition, it is sufficient that at least a sintering process having the above-described preferable conditions is included in a part of the process. By performing such secondary firing,
A nitride compound is obtained.
前記ＮＨ３及び／またはＨ２／Ｎ２混合物ガス雰囲気下での２次焼成過程をさらに詳細
に説明すれば、まず、高温でＮＨ３またはＮ２は分解されて活性窒素（Ｎ＊）を生成する
。
The secondary firing process in the NH 3 and / or H 2 / N 2 mixture gas atmosphere will be described in more detail. First, NH 3 or N 2 is decomposed at a high temperature to generate active nitrogen (N * ). To do.
Ｎ＊は、ポアを通過できる。一般的に、酸化物は、前記のようなポアを有さないため、
酸化物粒子の表面積が非常に小さい。一方、本発明の蛍光体の製造過程では、ポアが生成
されるため、表面積が非常に広くなる。窒化反応は、気体及び固体の反応であるため、活
性表面が広いほどさらに望ましい。したがって、本発明の蛍光体の製造過程では、ポアの
生成により広い活性表面を提供できるので、窒化反応に対して非常に有利である。
N * can pass through the pore. In general, an oxide does not have a pore as described above.
The surface area of the oxide particles is very small. On the other hand, in the manufacturing process of the phosphor according to the present invention, since the pores are generated, the surface area becomes very wide. Since the nitriding reaction is a gas and solid reaction, a wider active surface is more desirable. Therefore, in the production process of the phosphor of the present invention, a wide active surface can be provided by the generation of pores, which is very advantageous for nitriding reaction.
前記１次焼成後に生成されたアルカリ土類金属酸化物及びＥｕ２Ｏ３のＮ＊との窒化反
応により、アルカリ土類金属窒化物、Ｅｕ３Ｎ２（このとき、Ｅ３＋は、Ｅ２＋に還元さ
れる）が生成される。前述したように、前記アルカリ土類金属がＳｒである場合、アルカ
リ土類金属窒化物はＳｒ３Ｎ２である。このように生成されたアルカリ土類金属窒化物及
びＥｕ３Ｎ２は、空気中では不安定であるが、前記本発明の蛍光体の製造方法による環境
では安定している。次いで、さらなる反応によりナイトライド蛍光体が製造される。また
、前記アルカリ土類金属がＳｒである場合の例を挙げれば、前記生成されたナイトライド
蛍光体は（Ｓｒ１−ｘＥｕｘ）２Ｓｉ５Ｎ８（０＜ｘ＜１）でありうる。
Due to the nitriding reaction of the alkaline earth metal oxide and Eu 2 O 3 produced after the primary firing with N * , alkaline earth metal nitride, Eu 3 N 2 (where E 3+ becomes E 2+ Reduced) is produced. As described above, when the alkaline earth metal is Sr, the alkaline earth metal nitride is Sr 3 N 2 . The alkaline earth metal nitride and Eu 3 N 2 produced in this way are unstable in the air, but are stable in the environment according to the phosphor manufacturing method of the present invention. The nitride phosphor is then produced by a further reaction. In addition, in the case where the alkaline earth metal is Sr, the generated nitride phosphor may be (Sr 1-x Eu x ) 2 Si 5 N 8 (0 <x <1). .
図８は、これまで詳述した２次焼成過程を通じた蛍光体の形成過程をアルカリ土類金属
がＳｒである場合の例として挙げて概略的に示す図面である。
FIG. 8 is a drawing schematically showing the phosphor formation process through the secondary firing process described in detail so far as an example when the alkaline earth metal is Sr.
図９は、本発明の他の具現例による蛍光体の製造方法の概略的なフローチャートである
。フローチャート中、使用される化合物および記載のない製造条件としては、上述したも
のと同様のものを用いることができる。
FIG. 9 is a schematic flowchart of a method for manufacturing a phosphor according to another embodiment of the present invention. In the flowchart, the same compounds as described above can be used as the compounds used and the production conditions not described.
図１０は、アルカリ土類金属としてＳｒを使用し、酸としてクエン酸を使用した場合を
例として本発明のさらに他の具現例による蛍光体の製造方法の概略的な工程図である。
FIG. 10 is a schematic process diagram of a method for manufacturing a phosphor according to still another embodiment of the present invention, using as an example the case where Sr is used as the alkaline earth metal and citric acid is used as the acid.
選択的に、前記のように得た結果物は、粉砕及び焼成する段階を反復して優秀な結晶性
を有するナイトライド蛍光体が得られる。このとき、焼成は、望ましくは、１３００〜１
７００℃で１０〜１００時間、ＮＨ３及び／またはＨ２／Ｎ２混合ガス雰囲気下で行える
。
Alternatively, the resultant obtained as described above is repeatedly pulverized and fired to obtain a nitride phosphor having excellent crystallinity. At this time, firing is desirably 1300-1
It can be performed at 700 ° C. for 10 to 100 hours in an NH 3 and / or H 2 / N 2 mixed gas atmosphere.
次いで、前記結果物を洗浄して、最終粉末状態の蛍光体結果物が得られる。 Next, the resultant product is washed to obtain a phosphor result in a final powder state.
図１１は、本発明の一具現例による（オキシ）ナイトライド蛍光体のＳＥＭ写真を示す
。前記図１１から分かるように、前記（オキシ）ナイトライド蛍光体は、ポアを有し、前
記ポアの平均直径は、０．６μｍ以下であり、前記ポアの数は、単位面積（１μｍ２）当
たり０．０１以下であり、前記ポア間の平均距離は、１μｍ以上であり、前記ポアの断面
積は、円形、楕円形、長方形、正方形、多角形などの形態を有する。
FIG. 11 is a SEM photograph of an (oxy) nitride phosphor according to an embodiment of the present invention. As can be seen from FIG. 11, the (oxy) nitride phosphor has pores, the average diameter of the pores is 0.6 μm or less, and the number of pores per unit area (1 μm 2 ). 0.01 or less, an average distance between the pores is 1 μm or more, and a cross-sectional area of the pores has a form such as a circle, an ellipse, a rectangle, a square, and a polygon.
前記本発明による蛍光体の製造方法は、特にナイトライド蛍光体の製造に有利である。
すなわち、従来技術は、不安定な一部のナイトレートを前駆体として使用するところ、グ
ローブボックスのように特別な装置の使用が要求されることと異なり、本発明による蛍光
体の製造方法は、Ｓｒ，Ｂａ，Ｃａ，Ｅｕのそれぞれの前駆体としてＳｒＣＯ３，ＳｒＯ
，Ｓｒ（ＮＯ３）２，ＳｒＣｌ２，ＢａＣＯ３，ＢａＯ，Ｂａ（ＮＯ３）２，ＢａＣｌ２
，ＣａＣＯ３，ＣａＯ，Ｃａ（ＮＯ３）２，ＣａＣｌ２，Ｅｕ２Ｏ３，Ｅｕ（ＮＯ３）３
，ＥｕＣｌ３のようにカーボネートまたはオキサイドなどの非常に安定な粉末を使用し、
一方、Ｓｉの前駆体は、大気で安定なＳｉ３Ｎ４を使用するので、グローブボックスのよ
うな特別な装置を要求しない。
The method for producing a phosphor according to the present invention is particularly advantageous for producing a nitride phosphor.
That is, the prior art uses an unstable part of the nitrate as a precursor, and unlike the use of a special device such as a glove box, the method for producing a phosphor according to the present invention includes: SrCO 3 , SrO as precursors of Sr, Ba, Ca, Eu
, Sr (NO 3 ) 2 , SrCl 2 , BaCO 3 , BaO, Ba (NO 3 ) 2 , BaCl 2
, CaCO 3 , CaO, Ca (NO 3 ) 2 , CaCl 2 , Eu 2 O 3 , Eu (NO 3 ) 3
, Using very stable powders such as carbonate or oxide such as EuCl 3 ,
On the other hand, since the Si precursor uses Si 3 N 4 which is stable in the atmosphere, no special device such as a glove box is required.
このように、本発明による蛍光体の製造方法は、安定な物質を出発物質として使用し、
また、マイルドな工程条件で可能であるので、商業的に応用するのに非常に適している。
すなわち、従来の公知のナイトライド系蛍光体の製造方法は、高温、高圧の窒素雰囲気を
要求したが、前記本発明によるナイトライド蛍光体の製造方法は、それをいずれも解決し
た方法である。したがって、高温、高圧の工程条件を組成し、また、かかる高温、高圧の
工程条件に耐えるために特別に設備された装置を要求しない。
Thus, the method for producing a phosphor according to the present invention uses a stable material as a starting material,
Also, since it is possible under mild process conditions, it is very suitable for commercial application.
That is, the conventional method for producing a nitride phosphor requires a high-temperature and high-pressure nitrogen atmosphere, but the method for producing a nitride phosphor according to the present invention is a method that solves all of them. Therefore, it does not require equipment specially equipped to compose high temperature and high pressure process conditions and withstand such high temperature and high pressure process conditions.
また、本発明によるナイトライド蛍光体の製造方法は、環境問題をもたらす物質を使用
しないために環境にやさしい。
In addition, the method for manufacturing a nitride phosphor according to the present invention is environmentally friendly because it does not use substances that cause environmental problems.
本発明は、また、前記本発明による蛍光体の製造方法によって製造されたナイトライド
蛍光体を提供する。
The present invention also provides a nitride phosphor manufactured by the method for manufacturing a phosphor according to the present invention.
以下、本発明を下記実施例を挙げて詳細に説明するが、本発明が下記実施例にのみ限定
されるものではない。
Hereinafter, the present invention will be described in detail with reference to the following examples, but the present invention is not limited to the following examples.
実施例１
ＳｒＣＯ３ ５．０ｇ及びＥｕ２Ｏ３ ０．０６ｇを１０質量％硝酸水溶液１００ｃｃ
（混合物中、１．７Ｎ）に溶解した。前記混合溶液にＳｉ３Ｎ４ ４．０ｇを添加した。
クエン酸４．８ｇを前記混合溶液と混ぜて乾燥させた。前記乾燥された混合物を空気雰囲
気下で７００℃で１時間焼成した。焼成された混合物を、めのう乳鉢を利用して粉砕した
。前記粉砕して得た粉末をペレット形態に得た後、それをアルミナるつぼに入れ、それを
電気炉に入れて炭素と共にＮＨ３雰囲気で１１００℃まで加熱し（１１００℃での維持時
間；３時間）、その後５％のＨ２及び９５％のＮ２雰囲気で１６００℃まで加熱する。１
６００℃での焼成時間は、５時間行った。前記炭素は、ナイトライド出発物質の酸化を防
止するために使われる。このように得た焼結体を粉末に粉砕し、蒸溜水で洗浄した後、オ
ーブンで乾燥して蛍光体サンプル１（Ｓｒ０．９９Ｅｕ０．０１）２Ｓｉ５Ｎ８を得た。
Example 1
100 cc of 10% by mass nitric acid aqueous solution containing 5.0 g of SrCO 3 and 0.06 g of Eu 2 O 3
(1.7 N in the mixture). 4.0 g of Si 3 N 4 was added to the mixed solution.
4.8 g of citric acid was mixed with the mixed solution and dried. The dried mixture was calcined at 700 ° C. for 1 hour in an air atmosphere. The fired mixture was ground using an agate mortar. After the powder obtained by pulverization is obtained in the form of pellets, it is put in an alumina crucible, and it is put in an electric furnace and heated to 1100 ° C. in an NH 3 atmosphere together with carbon (maintenance time at 1100 ° C .; 3 hours ) And then heated to 1600 ° C. in an atmosphere of 5% H 2 and 95% N 2 . 1
The baking time at 600 ° C. was 5 hours. The carbon is used to prevent oxidation of the nitride starting material. The sintered body thus obtained was pulverized into powder, washed with distilled water, and then dried in an oven to obtain phosphor sample 1 (Sr 0.99 Eu 0.01 ) 2 Si 5 N 8 .
実施例２
出発物質としてＳｒＣＯ３ ５．０ｇ及びＥｕ２Ｏ３ ０．１２ｇを１０質量％硝酸１０
０ｃｃに溶解して使用した点を除いては、実施例１と同様に行って蛍光体サンプル２（Ｓ
ｒ０．９８Ｅｕ０．０２）２Ｓｉ５Ｎ８を得た。
Example 2
As starting materials 5.0 g SrCO 3 and 0.12 g Eu 2 O 3
Except that it was dissolved in 0 cc and used in the same manner as in Example 1, phosphor sample 2 (S
to obtain a r 0.98 Eu 0.02) 2 Si 5 N 8.
実施例３
出発物質としてＳｒＣＯ３ ５．０ｇ及びＥｕ２Ｏ３ ０．１８ｇを１０質量％硝酸１
００ｃｃに溶解した後、前記混合溶液にＳｉ３Ｎ４ ４．１ｇを添加して使用した点を除
いては、実施例１と同様に行って蛍光体サンプル３（Ｓｒ０．９７Ｅｕ０．０３）２Ｓｉ
５Ｎ８を得た。
Example 3
As starting materials 5.0 g SrCO 3 and 0.18 g Eu 2 O 3
Phosphor sample 3 (Sr 0.97 Eu 0.03 ) was prepared in the same manner as in Example 1 except that 4.1 g of Si 3 N 4 was added to the mixed solution after being dissolved in 00 cc. ) 2 Si
5 N 8 was obtained.
図２は、蛍光体サンプル１の励起スペクトルを示す。ＵＶから青色までの広い領域で光
を吸収するので、本発明の蛍光体サンプルは、ＵＶ−ＬＥＤや青色ＬＥＤにいずれも適用
可能である。
FIG. 2 shows an excitation spectrum of the phosphor sample 1. Since light is absorbed in a wide region from UV to blue, the phosphor sample of the present invention can be applied to both UV-LEDs and blue LEDs.
図３は、蛍光体サンプル１の発光スペクトルを示す。 FIG. 3 shows an emission spectrum of the phosphor sample 1.
図４は、サンプル１、２及び３に対する発光スペクトルを示す図面である。これから、
ＥｕのＳｒに対する相対的な含量が多くなるほどピーク波長が長くなることを確認した。
FIG. 4 is a diagram showing emission spectra for Samples 1, 2 and 3. from now on,
It was confirmed that the peak wavelength becomes longer as the relative content of Eu with respect to Sr increases.
本発明は、発光素子関連の技術分野に適用可能である。 The present invention is applicable to a technical field related to a light emitting element.
１０ ＬＥＤチップ
２０ 金ワイヤー
３０ 電気リード線
４０ 蛍光体組成物
５０ エポキシモールド層
６０ 成形モールド
７０ エポキシドームレンズ
10 LED chip 20 Gold wire 30 Electrical lead wire 40 Phosphor composition 50 Epoxy mold layer 60 Molding mold 70 Epoxy dome lens
Claims (30)
Ｍは、アルカリ土類金属であり、
０＜ｘ＜１、１．８＜ａ＜２．２、４．５＜ｂ＜５．５、０＜ｃ＜８、０＜ｄ≦８及び
０＜ｃ＋ｄ≦８である。 Oxynitride phosphors represented by the following chemical formula:
M is an alkaline earth metal;
0 <x <1, 1.8 <a <2.2, 4.5 <b <5.5, 0 <c <8, 0 <d ≦ 8 and 0 <c + d ≦ 8.
ある、請求項１に記載のオキシナイトライド蛍光体。 2. The oxynitride phosphor according to claim 1, wherein in the chemical formula, M is at least one selected from the group consisting of Ba, Sr, and Ca.
、１．８＜ａ＜２．２、４．５＜ｂ＜５．５、０＜ｃ＜８、０＜ｄ≦８）である、請求項
１に記載のオキシナイトライド蛍光体。 The compound of the above chemical formula is represented by {Sr (1-x) Eu x } a Si b O c N d (0 <x ≦ 0.1
The oxynitride phosphor according to claim 1, wherein 1.8 <a <2.2, 4.5 <b <5.5, 0 <c <8, 0 <d ≦ 8).
Ｍは、アルカリ土類金属であり、
０＜ｘ＜１、１．８＜ａ＜２．２、４．５＜ｂ＜５．５、０≦ｃ＜８、０＜ｄ≦８及び
０＜ｃ＋ｄ≦８である。 A nitride phosphor represented by the following chemical formula and having a pore.
M is an alkaline earth metal;
0 <x <1, 1.8 <a <2.2, 4.5 <b <5.5, 0 ≦ c <8, 0 <d ≦ 8, and 0 <c + d ≦ 8.
、１．８＜ａ＜２．２、４．５＜ｂ＜５．５、０≦ｃ＜８、０＜ｄ≦８）である、請求項
４に記載のナイトライド蛍光体。 The compound of the above chemical formula is represented by {Sr (1-x) Eu x } a Si b O c N d (0 <x ≦ 0.1
The nitride phosphor according to claim 4, wherein 1.8 <a <2.2, 4.5 <b <5.5, 0 ≦ c <8, 0 <d ≦ 8).
ある、請求項４に記載のナイトライド蛍光体。 The nitride phosphor according to claim 4, wherein the compound of the chemical formula is (Sr (1-x) Eu x ) 2 Si 5 N 8 (0 <x ≦ 0.1).
−ｘＥｕｘ）１．９９Ｓｉ５Ｎ８（０＜ｘ＜１）、（Ｂａ１−ｘ−ｙＳｒｘＥｕｙ）２Ｓ
ｉ５Ｎ８（０＜ｘ＜１、０＜ｙ＜１及び０＜ｘ＋ｙ＜１）、（Ｓｒ１−ｘ−ｙＣａｘＥｕ
ｙ）２Ｓｉ５Ｎ８（０＜ｘ＜１、０＜ｙ＜１及び０＜ｘ＋ｙ＜１）または（Ｂａ０．５Ｓ
ｒ１−ｘＣａ０．５Ｅｕｘ）Ｓｉ５Ｎ８（０＜ｘ＜１）である、請求項４に記載のナイト
ライド蛍光体。 The compound of the chemical formula is (Sr 1-x Eu x ) 2 Si 5 N 8 (0 <x <1), (Sr 1
-X Eu x ) 1.99 Si 5 N 8 (0 <x <1), (Ba 1-xy Sr x Eu y ) 2 S
i 5 N 8 (0 <x <1, 0 <y <1 and 0 <x + y <1), (Sr 1-xy Ca x Eu)
y ) 2 Si 5 N 8 (0 <x <1, 0 <y <1 and 0 <x + y <1) or (Ba 0.5 S
The nitride phosphor according to claim 4, which is r 1-x Ca 0.5 Eu x ) Si 5 N 8 (0 <x <1).
載のナイトライド蛍光体。 The nitride phosphor according to claim 4, wherein the pore has an average diameter of 0.6 μm or less.
求項４ないし７のいずれか１項に記載のナイトライド蛍光体。 The nitride phosphor according to any one of claims 4 to 7, which has a pore number of 0.01 or less per 1 µm 2 in cross section of the nitride phosphor.
のナイトライド蛍光体。 The nitride phosphor according to claim 4, wherein an average distance between the pores is 1 μm or more.
記載のナイトライド蛍光体。 The nitride phosphor according to any one of claims 4 to 7, wherein a cross section of the pore is circular, elliptical, or polygonal.
請求項１ないし３のうちいずれか一項に記載のオキシナイトライド蛍光体、または請求
項４ないし１１のうちいずれか一項に記載のナイトライド蛍光体と、を含むことを特徴と
する白色発光素子。 A UV light emitting diode;
A white light emission comprising the oxynitride phosphor according to any one of claims 1 to 3 or the nitride phosphor according to any one of claims 4 to 11. element.
項１２に記載の白色発光素子。 The white light emitting element according to claim 12, wherein the UV light emitting diode has an excitation light source that is an electromagnetic wave in an ultraviolet region or a near ultraviolet region.
する、請求項１２に記載の白色発光素子。 The white light emitting device according to claim 12, wherein the excitation light source of the UV light emitting diode has a wavelength band in a range of 390 to 460nm.
白色発光素子。 The white light emitting device according to claim 12, further comprising at least one selected from a blue phosphor and a green phosphor.
Ａｌ１６Ｏ２７：Ｅｕ２＋；Ｓｒ４Ａｌ１４Ｏ２５：Ｅｕ２＋；ＢａＡｌ８Ｏ１３：Ｅｕ
２＋；（Ｓｒ，Ｍｇ，Ｃａ，Ｂａ）５（ＰＯ４）３Ｃｌ：Ｅｕ２＋；ＢａＭｇＡｌ１０Ｏ
１７：Ｅｕ２＋及びＳｒ２Ｓｉ３Ｏ８２ＳｒＣｌ２：Ｅｕ２＋からなる群から選択された
一つ以上である、請求項１５に記載の白色発光素子。 The blue phosphor is (Sr, Ba, Ca) 5 (PO 4 ) 3 Cl: Eu 2+ ; BaMg 2
Al 16 O 27 : Eu 2+ ; Sr 4 Al 14 O 25 : Eu 2+ ; BaAl 8 O 13 : Eu
2+ ; (Sr, Mg, Ca, Ba) 5 (PO 4 ) 3 Cl: Eu 2+ ; BaMgAl 10 O
The white light emitting element according to claim 15, wherein the white light emitting element is at least one selected from the group consisting of 17 : Eu 2+ and Sr 2 Si 3 O 8 2SrCl 2 : Eu 2+ .
７：Ｅｕ２＋；Ｂａ２ＺｎＳｉ２Ｏ７：Ｅｕ２＋；ＢａＡｌ２Ｏ４：Ｅｕ２＋；ＳｒＡｌ
２Ｏ４：Ｅｕ２＋；ＢａＭｇＡｌ１０Ｏ１７：Ｅｕ２＋，Ｍｎ２＋；及びＢａＭｇ２Ａｌ
１６Ｏ２７：Ｅｕ２＋，Ｍｎ２＋からなる群から選択された一つ以上である、請求項１５
に記載の白色発光素子。 The green phosphor is (Ba, Sr, Ca) 2 SiO 4 : Eu 2+ ; Ba 2 MgSi 2 O
7 : Eu 2+ ; Ba 2 ZnSi 2 O 7 : Eu 2+ ; BaAl 2 O 4 : Eu 2+ ; SrAl
2 O 4 : Eu 2+ ; BaMgAl 10 O 17 : Eu 2+ , Mn 2+ ; and BaMg 2 Al
The one or more selected from the group consisting of 16 O 27 : Eu 2+ , Mn 2+.
The white light emitting element of description.
請求項４ないし１１のうちいずれか一項に記載のナイトライド蛍光体の放出スペクトルピ
ーク波長が６１０ないし６５０ｎｍであり、前記青色蛍光体の放出スペクトルピーク波長
が４４０ないし４６０ｎｍであり、前記緑色蛍光体の放出スペクトルピーク波長が５１０
ないし５６０ｎｍであることを特徴とする請求項１５に記載の白色発光素子。 The emission spectrum peak wavelength of the oxynitride phosphor according to any one of claims 1 to 3 or the nitride phosphor according to any one of claims 4 to 11 is 610 to 650 nm. The emission spectrum peak wavelength of the blue phosphor is 440 to 460 nm, and the emission spectrum peak wavelength of the green phosphor is 510
The white light-emitting element according to claim 15, wherein the white light-emitting element has a thickness of 560 nm.
前記請求項１ないし３のうちいずれか一項に記載のオキシナイトライド蛍光体、または
請求項４ないし１１のうちいずれか一項に記載のナイトライド蛍光体と、を含む、白色発
光素子。 A blue light emitting diode,
The white light emitting element containing the oxynitride fluorescent substance as described in any one of the said Claims 1 thru | or 3, or the nitride fluorescent substance as described in any one of Claims 4 thru | or 11.
用である、請求項１２ないし２０のうちいずれか一項に記載の白色発光素子。 The white light emitting element according to any one of claims 12 to 20, wherein the white light emitting element is used for a signal lamp, a communication device, a backlight of a display device, or illumination.
レート化合物の混合物をゲル状態に形成する工程と、
（ｂ）前記（ａ）工程で得られる混合物を乾燥及び１次焼成する工程と、
（ｃ）前記（ｂ）工程の結果物を粉砕及び２次焼成する工程と、を含むことを特徴とす
る蛍光体の製造方法。 (A) forming a mixture of an alkaline earth metal precursor compound, Eu precursor compound, acid, Si 3 N 4 powder and chelate compound in a gel state;
(B) drying and primary firing the mixture obtained in the step (a);
(C) A method for producing a phosphor, comprising a step of pulverizing and secondary firing the resultant product of the step (b).
（ＮＯ３）２，ＢａＣｌ２，ＳｒＣＯ３，ＳｒＯ，Ｓｒ（ＮＯ３）２，ＳｒＣｌ２，Ｃａ
ＣＯ３，ＣａＯ，Ｃａ（ＮＯ３）２およびＣａＣｌ２からなる群から選ばれる少なくとも
１種である、請求項２２に記載の蛍光体の製造方法。 In the step (a), the alkaline earth metal precursor compound is BaCO 3 , BaO, Ba.
(NO 3 ) 2 , BaCl 2 , SrCO 3 , SrO, Sr (NO 3 ) 2 , SrCl 2 , Ca
The method for producing a phosphor according to claim 22, wherein the phosphor is at least one selected from the group consisting of CO 3 , CaO, Ca (NO 3 ) 2 and CaCl 2 .
ｕＣｌ３からなる群から選ばれる少なくとも１種である、請求項２２に記載の蛍光体の製
造方法。 In the step (a), the Eu precursor compounds are Eu 2 O 3 , Eu (NO 3 ) 3 and E
The method for producing a phosphor according to claim 22, wherein the phosphor is at least one selected from the group consisting of uCl 3 .
酸および酒石酸からなる群から選ばれる少なくとも１種である、請求項２２に記載の蛍光
体の製造方法。 The phosphor according to claim 22, wherein in the step (a), the acid is at least one selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid, acetic acid, butyric acid, palmitic acid, oxalic acid, and tartaric acid. Method.
請求項２２に記載の蛍光体の製造方法。 In the step (a), the acid has a concentration of 0.1 to 10 mol / l in the mixture.
The manufacturing method of the fluorescent substance of Claim 22.
ジアミン四酢酸からなる群から選ばれる少なくとも１種である、請求項２２に記載の蛍光
体の製造方法。 The method for producing a phosphor according to claim 22, wherein in the step (a), the chelate compound is at least one selected from the group consisting of citric acid, glycine, urea, and ethylenediaminetetraacetic acid.
２２に記載の蛍光体の製造方法。 The method for manufacturing a phosphor according to claim 22, wherein the primary firing step of the step (b) is performed at 300 to 700 ° C in an air atmosphere.
間にＮＨ３、Ｈ２及びＮ２の混合ガス、またはＮＨ３、Ｈ２及びＮ２の混合ガス雰囲気下
で行う、請求項２２に記載の蛍光体の製造方法。 Wherein (c) 2 primary firing NH process to between 10 to 100 hours to no 1300 1700 ° C. 3, a mixed gas of H 2 and N 2 steps, or NH 3, H 2 and a mixed gas atmosphere of N 2 at The manufacturing method of the fluorescent substance of Claim 22 performed.
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| KR1020080050995A KR20090019677A (en) | 2007-08-21 | 2008-05-30 | Oxy nitride phosphor, white light emitting device including oxy nitride phosphor and method for preparing phosphor |
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