JP2005232398A - Phosphor for luminescent element and electroluminescent element - Google Patents

Phosphor for luminescent element and electroluminescent element Download PDF

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JP2005232398A
JP2005232398A JP2004045884A JP2004045884A JP2005232398A JP 2005232398 A JP2005232398 A JP 2005232398A JP 2004045884 A JP2004045884 A JP 2004045884A JP 2004045884 A JP2004045884 A JP 2004045884A JP 2005232398 A JP2005232398 A JP 2005232398A
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phosphor
light emitting
light
particles
ferroelectric
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Toshiyuki Aoyama
俊之 青山
Masayuki Ono
雅行 小野
Shogo Nasu
昌吾 那須
Masaru Odagiri
優 小田桐
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Panasonic Holdings Corp
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Matsushita Electric Industrial Co Ltd
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Abstract

<P>PROBLEM TO BE SOLVED: To provide a phosphor for a luminescent element, having an improved luminous efficiency and a stable structure and to provide an EL element using the phosphor. <P>SOLUTION: The phosphor for the luminescent element, having an improved luminous efficiency and made proof against deterioration is obtained by coating the surfaces of phosphor particles comprising ultramicroparticles of a mean-particle diameter of 0.5 to 100 nm with a thin film made from a ferroelectric component. The electroluminescent element having a high luminous efficiency is obtained by using the phosphor. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

本発明は、発光素子用蛍光体、及びそれを用いたエレクトロルミネッセンス素子に関し、さらに詳しくは、蛍光体微粒子の表面を強誘電体成分からなる薄膜で被覆した発光素子用蛍光体、及びそれを用いたエレクトロルミネッセンス素子に関するものである。   The present invention relates to a phosphor for a light emitting device and an electroluminescence device using the same, and more specifically, a phosphor for a light emitting device in which the surface of phosphor fine particles is coated with a thin film made of a ferroelectric component, and the phosphor The present invention relates to an electroluminescent element.

発光素子用蛍光体は、電気や電子線、紫外線等によって励起されて蛍光を発するため、平板ディスプレイパネルやＣＲＴ、また、平面光源等様々な用途に利用されている。   Since the phosphor for light emitting element emits fluorescence when excited by electricity, an electron beam, ultraviolet rays, or the like, it is used for various applications such as a flat display panel, a CRT, and a flat light source.

例えば、電気を用いて発光させるエレクトロルミネッセンス素子（以下、ＥＬ素子という）は大別すると、有機材料に直流電圧を印加することにより、電子とホールを再結合させて発光する有機ＥＬ素子と、無機材料に交流電圧を印加して発光物質の電子を衝突励起させて発光する無機ＥＬ素子がある。そして、後者の無機ＥＬ素子は薄膜型ＥＬ素子と分散型ＥＬ素子に大別される。この分散型ＥＬ素子は消費電力が少なく、製造が比較的簡単であるといった利点がある反面、輝度が低いという欠点がある。   For example, electroluminescent elements that emit light using electricity (hereinafter referred to as EL elements) can be broadly divided into organic EL elements that emit light by recombining electrons and holes by applying a direct current voltage to organic materials, and inorganic elements. There is an inorganic EL element that emits light by applying an alternating voltage to a material to excite and excite electrons of a luminescent material. And the latter inorganic EL element is divided roughly into a thin film type EL element and a dispersion type EL element. This distributed EL element has the advantages of low power consumption and relatively simple manufacturing, but has the disadvantage of low brightness.

分散型ＥＬ素子の輝度を向上させるためには、その発光効率を向上させる必要があり、そのために発光素子用蛍光体の粒子サイズをナノサイズ化する検討がなされている。現在、一般に用いられている分散型ＥＬ素子用の代表的な発光素子用蛍光体は硫化亜鉛に金属を付活したものであるが、その粒径は数μｍ〜数十μｍである。しかし、例えば、特許文献１には、粒子サイズを０．５〜１００ｎｍにすることで発光効率を向上させることが提案されている。   In order to improve the luminance of the dispersion-type EL element, it is necessary to improve the light emission efficiency. For this purpose, studies have been made to reduce the particle size of the phosphor for the light-emitting element to nanosize. At present, a typical phosphor for a light-emitting element that is generally used for a dispersion-type EL element is obtained by activating a metal in zinc sulfide, and its particle size is several μm to several tens μm. However, for example, Patent Document 1 proposes to improve luminous efficiency by setting the particle size to 0.5 to 100 nm.

一方、代表的な発光素子用蛍光体である金属を付活した硫化亜鉛は水分に弱いという欠点を有しており、大気中の水分によって劣化するために、分散型ＥＬ素子全体を防湿フィルムで覆った構造や、例えば特許文献２に開示されるように硫化亜鉛を窒化金属等で被覆することが提案されている。また、例えば特許文献３には、ＰｂＴｉＯ3で硫化亜鉛を被覆する構造が提案されており、そして、ＰｂＴｉＯ3は強誘電体のため分散型ＥＬ素子として電圧をかけた際に、硫化亜鉛へ印加される電圧が実効的に向上し、輝度が向上する利点も挙げられている。
特開２００３−１７３８７８号公報 特開２００２−２４１７５３号公報 特開２００１−１８５３５８号公報 On the other hand, zinc sulfide activated with a metal, which is a typical phosphor for a light-emitting element, has a disadvantage that it is weak against moisture. Since it deteriorates due to moisture in the atmosphere, the entire dispersion type EL element is covered with a moisture-proof film. It has been proposed to cover zinc sulfide with metal nitride or the like as disclosed in, for example, Patent Document 2. The application, for example, Patent Document 3, has been proposed a structure covering the zinc sulfide in PbTiO 3, and, when a voltage is applied as a dispersion type EL element for PbTiO 3 ferroelectric, the zinc sulfide The advantage is that the applied voltage is effectively improved and the luminance is improved.
JP 2003-173878 A JP 2002-241753 A JP 2001-185358 A

例えば、特許文献１に開示されているように、発光素子用蛍光体の粒子サイズを微小化して、発光効率を向上させる場合、粒子サイズが小さくなるということはそれだけ粒子の反応性が高まることであり、例えば、ＦＥＤ（フィールドエミッションディスプレイ）のような真空系の発光素子に用いる場合には問題にならなくとも、分散型ＥＬ素子等に用いる際には発光素子用蛍光体が硫化亜鉛のように構造が不安定な蛍光体の場合、その蛍光体の劣化が加速されることが容易に推測され、発光素子としての実用性に問題がある。   For example, as disclosed in Patent Document 1, when the particle size of the phosphor for a light emitting element is reduced to improve the light emission efficiency, the particle size becomes smaller because the reactivity of the particle is increased accordingly. For example, even if it is not a problem when used for a vacuum-type light emitting device such as an FED (field emission display), the phosphor for the light emitting device is used as zinc sulfide when used for a dispersion type EL device or the like. In the case of a phosphor having an unstable structure, it is easily estimated that deterioration of the phosphor is accelerated, and there is a problem in practicality as a light emitting element.

また、例えば、特許文献２に開示されているように、発光素子用蛍光体粒子を窒化金属等で被覆する場合、硫化亜鉛等の蛍光体の構造の安定性は増加するが、発光効率の向上は望めない。さらに、特許文献３に開示されているように、強誘電体であるＰｂＴｉＯ3で発光素子用蛍光体を被覆する場合には発光効率の向上は多少望めるが、粒子サイズを微小化するほどの効果は望めず、また、鉛を用いているので環境問題が発生する。また、特許文献２、特許文献３に記載の発光素子用蛍光体の粒径は数十μｍであり、微小な発光素子用蛍光体への適用は困難である。 Further, for example, as disclosed in Patent Document 2, when the phosphor particles for light emitting element are coated with metal nitride or the like, the stability of the structure of the phosphor such as zinc sulfide increases, but the luminous efficiency is improved. Can't hope. Furthermore, as disclosed in Patent Document 3, when the phosphor for a light emitting device is coated with a ferroelectric material, PbTiO 3 , an improvement in the light emission efficiency can be expected to some extent, but the effect of reducing the particle size can be achieved. Can not be expected, and because lead is used, environmental problems occur. In addition, the particle size of the phosphor for a light emitting element described in Patent Document 2 and Patent Document 3 is several tens of μm, and it is difficult to apply to a minute phosphor for a light emitting element.

本発明は、上記の課題に鑑みてなされたものであり、発光効率が向上し、かつ構造が安定であり、そして、環境に与える影響の少ない発光素子用蛍光体と、その発光素子用蛍光体を用いたＥＬ素子を提供するものである。   The present invention has been made in view of the above-mentioned problems, and has improved luminous efficiency, stable structure, and less impact on the environment, and a phosphor for the light emitting element. An EL element using the above is provided.

本発明は、平均粒径が０．５ｎｍ〜１００ｎｍの超微粒子からなる蛍光体粒子の表面を強誘電体成分からなる薄膜で被覆したことを特徴とする発光素子用蛍光体である。   The present invention is a phosphor for a light emitting device, characterized in that the surface of phosphor particles made of ultrafine particles having an average particle diameter of 0.5 nm to 100 nm is coated with a thin film made of a ferroelectric component.

さらに、前記強誘電体成分は、少なくとも２種類の金属元素からなる複合金属酸化物であることを特徴とする。   Further, the ferroelectric component is a complex metal oxide composed of at least two kinds of metal elements.

また、前記強誘電体成分は、Ｃａ、Ｓｒ、Ｂａから選ばれた少なくとも一つの金属元素からなる第１の成分と、Ｔｉ、Ｚｒのうち、少なくとも一つの金属元素からなる第２の成分からなる複合金属酸化物であることを特徴とする。   The ferroelectric component includes a first component made of at least one metal element selected from Ca, Sr, and Ba, and a second component made of at least one metal element of Ti and Zr. It is a composite metal oxide.

さらに、前記強誘電体成分からなる薄膜は、平均膜厚が０．５ｎｍ〜１００ｎｍであることを特徴とする。   Furthermore, the thin film made of the ferroelectric component has an average film thickness of 0.5 nm to 100 nm.

また、前記超微粒子からなる蛍光体粒子は金属元素が付活された硫化亜鉛であることを特徴とする。   The phosphor particles made of ultrafine particles are characterized by being zinc sulfide activated with a metal element.

さらに、本発明のエレクトロルミネッセンス素子は、少なくとも一方が透光性を有する１対の電極間に、発光層を有するエレクトロルミネッセンス素子であって、前記発光層を構成する発光素子用蛍光体は上記のいずれかの発光素子用蛍光体であることを特徴とする。   Furthermore, the electroluminescent element of the present invention is an electroluminescent element having a light emitting layer between a pair of electrodes, at least one of which has translucency, and the phosphor for a light emitting element constituting the light emitting layer is as described above. It is a phosphor for any light emitting element.

本発明の発光素子用蛍光体は、平均粒径が０．５ｎｍ〜１００ｎｍの超微粒子からなる蛍光体粒子の表面を強誘電体成分からなる薄膜で被覆したものであり、蛍光体粒子を超微粒子にすることで発光効率を向上させるとともに、蛍光体粒子の表面を強誘電体成分で被覆することにより、蛍光体粒子の劣化を防止するとともに、分散型ＥＬ素子に用いた際の蛍光体粒子への実効的な電圧を上げることで発光効率をさらに上昇することができる。   The phosphor for light emitting device of the present invention is obtained by coating the surface of phosphor particles made of ultrafine particles having an average particle diameter of 0.5 nm to 100 nm with a thin film made of a ferroelectric component. In addition to improving the luminous efficiency and covering the surface of the phosphor particles with a ferroelectric component, the phosphor particles are prevented from deteriorating and to the phosphor particles when used in the dispersion-type EL element. The luminous efficiency can be further increased by increasing the effective voltage.

また、本発明のエレクトロルミネッセンス素子は、発光効率の高い、すなわち消費電力の少ない発光素子を得ることができる。   In addition, the electroluminescence element of the present invention can provide a light-emitting element with high emission efficiency, that is, low power consumption.

（実施の形態１）
図１は本発明の実施の形態１に係る発光素子用蛍光体の模式断面図である。この発光素子用蛍光体１は超微粒子からなる蛍光体粒子１１の表面を強誘電体１２によって被覆したものである。 (Embodiment 1)
FIG. 1 is a schematic cross-sectional view of a phosphor for a light-emitting element according to Embodiment 1 of the present invention. This phosphor 1 for light emitting element is obtained by coating the surface of phosphor particles 11 made of ultrafine particles with a ferroelectric 12.

超微粒子からなる蛍光体粒子１１の構成材料は特に限定されないが、代表的なものとしては、硫化亜鉛、硫化カルシウム、硫化ストロンチウム等のII−VI族化合物蛍光体や、ＣａＧａ2Ｓ4、ＳｒＧａ2Ｓ4、ＢａＧａ2Ｓ4等のチオガレート系蛍光体、また、ＢａＡｌ2Ｓ4等のチオアルミネート蛍光体、さらに、Ｇａ2Ｏ3、Ｙ2Ｏ3、ＣａＯ、ＧｅＯ2、ＳｎＯ2等の金属酸化物蛍光体、また、Ｚｎ2ＳｉＯ4、Ｚｎ2ＧｅＯ4、ＺｎＧａ2Ｏ4、ＣａＧａ2Ｏ4、Ｙ4ＧｅＯ8、Ｙ2ＧｅＯ5や（Ｇａ2Ｏ3−Ａｌ2Ｏ3）、（ＣａＯ−Ｇａ2Ｏ3）、（Ｙ2Ｏ3−ＧｅＯ2）等の多元酸化物蛍光体等が挙げられる。これらの蛍光体にはそれぞれ、Ｍｎ、Ｃｕ、Ｐｒ、Ｎｄ、Ｓｍ、Ｔｂ、Ｄｙ、Ｈｏ、Ｅｒ、Ｔｍ、Ｃｅ、Ｔｉ、Ｃｒ、Ａｌ等の金属元素から選ばれる少なくとも１種類の元素が付活されている。また、この付活される元素はＣｌのような非金属元素やＴｂＦ3やＰｒＦ3といったフッ化物でもよく、また、これらのうち２種類以上を同時に付活しても何ら問題はない。なお、これらの構成材料のうち硫化亜鉛に金属元素を付活したものが合成しやすく、使いやすいために好ましい。 The constituent material of the phosphor particles 11 made of ultrafine particles is not particularly limited, but representative examples include II-VI group compound phosphors such as zinc sulfide, calcium sulfide, strontium sulfide, CaGa 2 S 4 , SrGa 2. Thiogallate phosphors such as S 4 and BaGa 2 S 4 , thioaluminate phosphors such as BaAl 2 S 4 , and metals such as Ga 2 O 3 , Y 2 O 3 , CaO, GeO 2 and SnO 2 Oxide phosphors, Zn 2 SiO 4 , Zn 2 GeO 4 , ZnGa 2 O 4 , CaGa 2 O 4 , Y 4 GeO 8 , Y 2 GeO 5 , (Ga 2 O 3 —Al 2 O 3 ), ( Examples thereof include multi-element oxide phosphors such as (CaO—Ga 2 O 3 ) and (Y 2 O 3 —GeO 2 ). Each of these phosphors is activated by at least one element selected from metal elements such as Mn, Cu, Pr, Nd, Sm, Tb, Dy, Ho, Er, Tm, Ce, Ti, Cr, and Al. Has been. The activated element may be a non-metallic element such as Cl or a fluoride such as TbF 3 or PrF 3, and there is no problem if two or more of these elements are activated simultaneously. Of these constituent materials, zinc sulfide activated with a metal element is preferred because it is easy to synthesize and is easy to use.

前記超微粒子からなる蛍光体粒子１１において、超微粒子化して発光効率を向上させるには、平均粒子サイズを、０．５ｎｍ〜１００ｎｍにすることが望ましく、好ましくは１ｎｍ〜６０ｎｍ、さらに好ましくは２ｎｍ〜２０ｎｍがよい。   In the phosphor particles 11 composed of the ultrafine particles, in order to improve the luminous efficiency by making ultrafine particles, the average particle size is desirably 0.5 nm to 100 nm, preferably 1 nm to 60 nm, more preferably 2 nm to 20 nm is preferable.

次に、超微粒子からなる蛍光体粒子１１の表面を被覆する強誘電体１２は強誘電体特性を示すものであるならば特に限定はされないが、少なくとも２種類の金属元素からなる複合金属酸化物であることが好ましく、特にＣａ、Ｓｒ、Ｂａから選ばれた少なくとも一つの金属元素からなる第１の成分と、Ｔｉ、Ｚｒのうち、少なくとも一つの金属元素からなる第２の成分からなる複合酸化物であることが好ましい。この複合酸化物として具体的にはＢａＴｉＯ3、ＳｒＴｉＯ3、ＣａＴｉＯ3、Ｓｒ（Ｚｒ、Ｔｉ）Ｏ3等が挙げられる。 Next, the ferroelectric 12 covering the surface of the phosphor particles 11 made of ultrafine particles is not particularly limited as long as it exhibits ferroelectric properties, but is a composite metal oxide made of at least two kinds of metal elements. In particular, a composite oxidation comprising a first component comprising at least one metal element selected from Ca, Sr and Ba, and a second component comprising at least one metal element of Ti and Zr. It is preferable that it is a thing. Specific examples of the composite oxide include BaTiO 3 , SrTiO 3 , CaTiO 3 , Sr (Zr, Ti) O 3 and the like.

また、強誘電体１２は、膜厚が薄いほうが電界効果は高まるが、欠陥が生じると蛍光体の保護性能が低下するため、欠陥が生じない膜厚である必要があり、このため平均膜厚は、通常０．５ｎｍ〜１００ｎｍであり、より好ましくは１ｎｍ〜６０ｎｍ、さらに好ましくは２ｎｍ〜３０ｎｍがよい。   In addition, although the electric field effect is enhanced as the thickness of the ferroelectric 12 is smaller, the protective performance of the phosphor is reduced when a defect occurs, so that it is necessary to have a thickness that does not cause a defect. Is usually 0.5 nm to 100 nm, more preferably 1 nm to 60 nm, and even more preferably 2 nm to 30 nm.

本発明の発光素子用蛍光体の合成方法は特に限定はされないが、共沈法やゾル−ゲル法、逆ミセル法等の溶液系の合成方法が微粒子の合成と微粒子への強誘電体の被覆を行なうのに適している。   The method for synthesizing the phosphor for the light-emitting device of the present invention is not particularly limited, but solution-based synthesis methods such as coprecipitation method, sol-gel method, and reverse micelle method are used for fine particle synthesis and coating of the ferroelectric material on the fine particles. Suitable for performing.

（実施の形態２）
次に、本発明の実施の形態２に係るエレクトロルミネッセンス素子２の一例を図２に模式断面図で示す。このＥＬ素子は透明基板２１、透明電極２２、発光層２３、絶縁体層２４、背面電極２５、背面板２６からなり、透明基板２１の上に透明電極２２が設けられ、その上に順に発光層２３、絶縁体層２４、背面電極２５、背面板２６が設けられた構成からなっている。２７は交流電源であり、前記透明電極２２と背面電極２５との間に交流電圧を引加し、発光層２３を発光させる。 (Embodiment 2)
Next, an example of the electroluminescence element 2 according to Embodiment 2 of the present invention is shown in a schematic cross-sectional view in FIG. The EL element includes a transparent substrate 21, a transparent electrode 22, a light emitting layer 23, an insulator layer 24, a back electrode 25, and a back plate 26. The transparent electrode 22 is provided on the transparent substrate 21, and the light emitting layer is sequentially formed thereon. 23, an insulator layer 24, a back electrode 25, and a back plate 26 are provided. Reference numeral 27 denotes an AC power source, which applies an AC voltage between the transparent electrode 22 and the back electrode 25 to cause the light emitting layer 23 to emit light.

透明基板２１は光を透過する材質と厚さであれば特にその材質や厚さともに限定されず、例えば、材質としてはポリエチレンテレフタレートやポリエチレン、ポリプロピレン、ポリイミド、ポリアミド等の高分子材やガラス、石英等を用いることができる。   The material and thickness of the transparent substrate 21 are not particularly limited as long as the material and thickness transmit light. For example, the material is a polymer material such as polyethylene terephthalate, polyethylene, polypropylene, polyimide, polyamide, glass, quartz, and the like. Etc. can be used.

透明電極２２は導電性でかつ光を透過する材質と厚さであれば特にその材質や厚さともに限定されず、例えば材質としては、ＩＴＯやＺｎＯ等の金属酸化物や、Ａｕ、Ａｇ、Ａｌ等の金属、ポリアニリン、ポリピロール、ＰＥＤＯＴ／ＰＳＳ、ポリチオフェン等の高分子材等を用いることができる。   The material and thickness of the transparent electrode 22 are not particularly limited as long as they are conductive and transmit light. For example, the material may be a metal oxide such as ITO or ZnO, Au, Ag, or Al. Etc., high molecular materials such as polyaniline, polypyrrole, PEDOT / PSS, polythiophene, and the like can be used.

また、発光層２３は上記実施の形態１で説明した発光素子用蛍光体１が用いられ、その製法は特に限定はされないが、発光素子用蛍光体１をバインダに分散させて塗布する方法が簡便である。バインダには例えばシアノエチルセルロース、ポリフッ化ビニリデン等が挙げられる。塗布する方法としては例えば、スピンコート法、インクジェット法、スクリーン印刷法、バーコート法、ディップコート法等が挙げられる。発光層２３の膜厚は、通常２０〜８００００ｎｍであり、好ましくは５０〜４００００ｎｍである。   The light emitting layer 23 uses the phosphor 1 for light emitting element described in the first embodiment, and the manufacturing method is not particularly limited. However, a method of applying the phosphor 1 for light emitting element dispersed in a binder is simple. It is. Examples of the binder include cyanoethyl cellulose and polyvinylidene fluoride. Examples of the coating method include spin coating, ink jet, screen printing, bar coating, and dip coating. The thickness of the light emitting layer 23 is usually 20 to 80,000 nm, preferably 50 to 40,000 nm.

前記絶縁体層２４は通常無機物もしくは高分子材に無機物を分散させたものからなり、例えば無機物としては、ＳｉＯ2、Ｓｉ3Ｎ4、ＳｉＯＮ、Ａｌ2Ｏ3、Ｙ2Ｏ3、ＢａＴｉＯ3、ＳｒＴｉＯ3、ＣａＴｉＯ3等が挙げられる。そして、これらは混合物であってもよく、また２種類以上を積層させたものでもよい。高分子材に無機物を分散させる場合の高分子材は非導電性高分子材であれば特に限定はされないが、例えば発光層２３と同様にシアノエチルセルロースやポリフッ化ビニリデン、他にもポリスチレン系や、ポリビニルピリジン系等種々の高分子材を用いることができる。また、分散させる無機物に関しては、絶縁性を有しておれば特に限定されるものではないが、例えば前述の無機物の微粒子を用いることができる。 The insulator layer 24 is usually made of an inorganic material or a polymer material in which an inorganic material is dispersed. Examples of the inorganic material include SiO 2 , Si 3 N 4 , SiON, Al 2 O 3 , Y 2 O 3 , BaTiO 3 , SrTiO 3, CaTiO 3, and the like. These may be a mixture, or may be a laminate of two or more. The polymer material in the case where the inorganic substance is dispersed in the polymer material is not particularly limited as long as it is a non-conductive polymer material. For example, cyanoethyl cellulose and polyvinylidene fluoride as well as the light emitting layer 23, other polystyrene-based materials, Various polymer materials such as polyvinyl pyridine can be used. Further, the inorganic material to be dispersed is not particularly limited as long as it has insulating properties. For example, the above-mentioned inorganic fine particles can be used.

前記絶縁体層２４に用いる絶縁物は誘電率が高いほうが好ましく、前述の無機物の中ではＳｒＴｉＯ3やＢａＴｉＯ3等が誘電率が高いために好ましい。絶縁体層２４の膜厚は通常５０〜８００００ｎｍであり、好ましくは１００〜５００００ｎｍである。また、背面電極２５側からも光を取り出す場合、すなわち両面から発光させる場合は、絶縁体層２４及び背面電極２５並びに背面板２６は発光波長に対して透明な材料で構成する。 The insulator used for the insulator layer 24 preferably has a high dielectric constant, and among the inorganic substances described above, SrTiO 3 and BaTiO 3 are preferable because of their high dielectric constant. The film thickness of the insulator layer 24 is usually 50 to 80000 nm, preferably 100 to 50000 nm. When light is extracted also from the back electrode 25 side, that is, when light is emitted from both sides, the insulator layer 24, the back electrode 25, and the back plate 26 are made of a material that is transparent to the emission wavelength.

なお、背面電極２５は導電性であれば特に限定されず、例えば材質としては、ＩＴＯやＺｎＯ等の金属酸化物や、Ａｕ、Ａｇ、Ａｌ、Ｃｕ等の金属、ポリアニリン、ポリピロール、ＰＥＤＯＴ／ＰＳＳ等の高分子材や、カーボン等を用いることができる。また、背面電極２５側から光を取り出す場合には、発光波長に対して透明な電極材料、例えば透明電極２２と同様の材料で構成すればよい。   The back electrode 25 is not particularly limited as long as it is conductive. For example, the material is a metal oxide such as ITO or ZnO, a metal such as Au, Ag, Al, or Cu, polyaniline, polypyrrole, PEDOT / PSS, or the like. These polymer materials, carbon and the like can be used. Further, when extracting light from the back electrode 25 side, it may be made of an electrode material that is transparent to the emission wavelength, for example, the same material as the transparent electrode 22.

前記背面板２６は背面電極２５を保護するためにカバーするものであり、そのため絶縁性であることが好ましい。また、特に材質と厚さともに限定されず、例えば、材質としてはポリエチレンテレフタレートやポリエチレン、ポリプロピレン、ポリイミド、ポリアミド、ナイロン等の高分子材やガラス、石英、セラミックス等を用いることができる。この背面板２６の形成方法としては、例えば、スピンコート法、インクジェット法、スクリーン印刷法、バーコート法、ディップコート法等の塗布でもって形成してもよく、また、例えば高分子フィルムやガラス基板を張り合わせて形成してもよい。また、例えばＵＶ硬化樹脂を塗布し、これをＵＶ光にて硬化させてもよい。   The back plate 26 covers the back electrode 25 to protect it, and is therefore preferably insulative. In addition, the material and thickness are not particularly limited. For example, the material may be a polymer material such as polyethylene terephthalate, polyethylene, polypropylene, polyimide, polyamide, nylon, glass, quartz, ceramics, or the like. As a method for forming the back plate 26, for example, the back plate 26 may be formed by applying a spin coating method, an ink jet method, a screen printing method, a bar coating method, a dip coating method, or the like, for example, a polymer film or a glass substrate. May be formed by laminating. Further, for example, a UV curable resin may be applied and cured with UV light.

なお、上記において、背面板２６側からのみ光を取り出す場合は、透明電極２２と透明基板２１の少なくともいずれか一方を不透明材料から構成すればよい。   In the above description, when light is extracted only from the back plate 26 side, at least one of the transparent electrode 22 and the transparent substrate 21 may be made of an opaque material.

（実施の形態３）
ここで、発光層２３として本発明の発光素子用蛍光体を用いたＥＬ素子の構成は上記実施の形態２で説明したものに限られるものではなく、例えば図３の（ａ）〜（ｅ）に実施の形態３−ａ〜３−ｅとして模式断面で示す構成からなるものであってもよく、また、ここに図示していない他の構成からなるものであってもよく、特にＥＬ素子の構造には限定されない。 (Embodiment 3)
Here, the structure of the EL element using the phosphor for light emitting element of the present invention as the light emitting layer 23 is not limited to that described in the second embodiment, and for example, (a) to (e) in FIG. Embodiments 3-a to 3-e may have a configuration shown in a schematic cross-section, or may have another configuration not shown here, particularly of an EL element. The structure is not limited.

上記実施の形態３−ａ〜３−ｅにおいて、図２に示した実施の形態２のＥＬ素子と同一構成部分には同一符号が附してあり、その各構成体の説明は省略する。   In the above-described Embodiments 3-a to 3-e, the same components as those of the EL element of Embodiment 2 shown in FIG. 2 are denoted by the same reference numerals, and description of each component will be omitted.

この実施の形態３−ａ〜３−ｅが実施の形態２と異なるところは、各構成体の積層形態であり、実施の形態２に対する積層形態の相違点は、まず、図３（ａ）の実施の形態３−ａは背面板２６を有しない構成であり、図３（ｂ）の実施の形態３−ｂは透明電極２２と発光層２３との間にさらに透明材料からなる絶縁体層２４を設けた構成であり、図３（ｃ）の実施の形態３−ｃは透明電極２２と発光層２３との間にさらに透明材料からなる絶縁体層２４を設け、かつ背面板２６を有しない構成であり、図３（ｄ）の実施の形態３−ｄは絶縁体層２４を有しない構成であり、さらに図３（ｅ）の実施の形態３−ｅは絶縁体層２４と背面板２６をともに有しない構成である。   The difference between Embodiments 3-a to 3-e and Embodiment 2 is the stacked form of each component, and the difference between the stacked forms with respect to Embodiment 2 is that in FIG. The embodiment 3-a has a configuration without the back plate 26, and the embodiment 3-b of FIG. 3B further includes an insulator layer 24 made of a transparent material between the transparent electrode 22 and the light emitting layer 23. In the embodiment 3-c of FIG. 3C, an insulator layer 24 made of a transparent material is further provided between the transparent electrode 22 and the light emitting layer 23, and the back plate 26 is not provided. 3D, the embodiment 3-d in FIG. 3D does not have the insulator layer 24, and the embodiment 3-e in FIG. 3E has the insulator layer 24 and the back plate 26. It is the structure which does not have both.

なお、これらにおいても両面から光を取り出す場合は、発光層２３の上に積層される絶縁体層２４、背面電極２５、背面板２６を透明材料で構成すればよく、また背面電極２５側からのみ光を取り出す場合は、発光層２３の上に積層されている各構成体を透明材料で構成し、かつ発光層２３の下方側の積層構成体のうち、少なくとも１つの構成体を不透明材料で構成すればよい。   In these cases, when light is extracted from both sides, the insulating layer 24, the back electrode 25, and the back plate 26 laminated on the light emitting layer 23 may be made of a transparent material, and only from the back electrode 25 side. When taking out light, each structure laminated | stacked on the light emitting layer 23 is comprised with a transparent material, and at least 1 structure is comprised with an opaque material among the laminated structures below the light emitting layer 23. do it.

（実施例１）
以下に、本発明についてさらに具体的に説明する。なお、本発明はここに説明する実施例１に限定されるものではない。 (Example 1)
Hereinafter, the present invention will be described more specifically. The present invention is not limited to the first embodiment described here.

（発光素子用蛍光体の製造）
この実施例１では逆ミセル法を用い、蛍光体粒子としてＺｎＳ：Ｍｎ、強誘電体としてＢａＴｉＯ3からなる発光素子用蛍光体１の合成例である。 (Manufacture of phosphors for light-emitting elements)
In Example 1, a reverse micelle method is used, and a phosphor 1 for a light-emitting element made of ZnS: Mn as a phosphor particle and BaTiO 3 as a ferroelectric is a synthesis example.

溶媒として、ヘプタン１００ｍｌに界面活性剤としてスルホこはく酸ジイソオクチルナトリウム１２ｇをマグネチックスターラーを用いて溶解したものを用いた。この溶液に純水３．５ｇを加え、超音波を用いたホモジナイザ-で攪拌し、逆ミセル溶液を作成した。この逆ミセル溶液８０ｍｌをとりわけ、これに１ｍｏｌ／ｌの酢酸亜鉛溶液０．５ｍｌと１ｍｏｌ／ｌの酢酸マンガン溶液０．０５ｍｌを加え、マグネチックスターラーを用いて攪拌し、亜鉛・マンガン逆ミセル溶液を作成した。   As a solvent, 100 ml of heptane dissolved in 12 g of diisooctyl sulfosuccinate sodium as a surfactant using a magnetic stirrer was used. To this solution, 3.5 g of pure water was added and stirred with a homogenizer using ultrasonic waves to prepare a reverse micelle solution. Add 80 ml of this reverse micelle solution, in particular 0.5 ml of 1 mol / l zinc acetate solution and 0.05 ml of 1 mol / l manganese acetate solution, and stir using a magnetic stirrer. Created.

また、残りの逆ミセル溶液２０ｍｌに、１ｍｏｌ／ｌの硫化ナトリウム溶液を０．６ｍｌ加え、マグネチックスターラーを用いて攪拌し、硫黄逆ミセル溶液を作成した。   Further, 0.6 ml of 1 mol / l sodium sulfide solution was added to the remaining 20 ml of reverse micelle solution, and the mixture was stirred using a magnetic stirrer to prepare a sulfur reverse micelle solution.

そして、前記亜鉛・マンガン逆ミセル溶液に硫黄逆ミセル溶液を加え、攪拌することによりＺｎＳ：Ｍｎ逆ミセル溶液を作成した。   And the sulfur reverse micelle solution was added to the said zinc * manganese reverse micelle solution, and the ZnS: Mn reverse micelle solution was created by stirring.

次に、前記ＺｎＳ：Ｍｎ逆ミセル溶液に、ジメトキシバリウム溶液とテトラメトキシチタン溶液をモル比で１対１の割合で加え、逆ミセル溶液内で反応させる。この溶液を５５００ｒｐｍの回転数で遠心分離を行い、その分離した粒子を６０℃の温度で乾燥を行なった。その後、乾燥後の粒子を窒素雰囲気中で１０００℃の温度で１時間加熱を行なった。   Next, a dimethoxybarium solution and a tetramethoxytitanium solution are added at a molar ratio of 1: 1 to the ZnS: Mn reverse micelle solution and reacted in the reverse micelle solution. This solution was centrifuged at a rotational speed of 5500 rpm, and the separated particles were dried at a temperature of 60 ° C. Thereafter, the dried particles were heated in a nitrogen atmosphere at a temperature of 1000 ° C. for 1 hour.

これにより、ＺｎＳ：Ｍｎを中心核として表面を強誘電体であるＢａＴｉＯ3で被覆された発光素子用蛍光体１を製造した。 As a result, the phosphor 1 for a light-emitting device having ZnS: Mn as a central core and the surface coated with BaTiO 3 which is a ferroelectric was manufactured.

（エレクトロルミネッセンス素子の製造）
透明基板２１ならびに透明電極２２には、ＰＥＴフィルムにＩＴＯがスパッタリングされたＩＴＯフィルムを用いた。発光層２３には上記実施例１で製造した発光素子用蛍光体１をシアノエチルセルロースに混合、かつ分散し、スクリーン印刷法を用いて上記透明電極２２上に塗布し、その塗布後に１２０℃の温度で乾燥を行なったものを用いた。 (Manufacture of electroluminescence elements)
As the transparent substrate 21 and the transparent electrode 22, an ITO film obtained by sputtering ITO onto a PET film was used. In the light emitting layer 23, the phosphor 1 for a light emitting device manufactured in Example 1 is mixed and dispersed in cyanoethyl cellulose, and coated on the transparent electrode 22 by using a screen printing method. What was dried in step 1 was used.

絶縁体層２４にはＢａＴｉＯ3の微粒子を前記発光層２３と同様にシアノエチルセルロースに混合、かつ分散し、スクリーン印刷法にて発光層２３上に塗布し、そして塗布後に１２０℃の温度で乾燥を行なったものを用いた。 In the insulator layer 24, fine particles of BaTiO 3 are mixed and dispersed in cyanoethyl cellulose in the same manner as the light emitting layer 23, and are coated on the light emitting layer 23 by a screen printing method and dried at a temperature of 120 ° C. after the coating. What was done was used.

また、背面電極２５はカーボンペーストをスクリーン印刷法にて絶縁体層２４の上に塗布した。背面板２６はポリイミド系感光樹脂を背面電極２５の上に塗布し、これを感光して硬化を行なうことにより得た。   For the back electrode 25, carbon paste was applied on the insulator layer 24 by screen printing. The back plate 26 was obtained by applying a polyimide-based photosensitive resin on the back electrode 25, and exposing and curing it.

（比較例）
ここで、上記実施例１により製造したエレクトロルミネッセンス素子に対する比較例を説明する。 (Comparative example)
Here, the comparative example with respect to the electroluminescent element manufactured by the said Example 1 is demonstrated.

この比較例は、前述の実施例１と同様の方法でＺｎＳ：Ｍｎ逆ミセル溶液を作成し、この溶液をそのまま何も添加せずに５５００ｒｐｍの回転数で遠心分離を行い、その分離した粒子を６０℃の温度で乾燥を行なった。そして、この乾燥後の粒子を窒素雰囲気中で１０００℃の温度で１時間加熱を行い、被膜のないＺｎＳ：Ｍｎの発光素子用蛍光体を製造した。この被膜のないＺｎＳ：Ｍｎの発光素子用蛍光体を用いて、上記実施例１と同様の方法でエレクトロルミネッセンス素子を製造した。   In this comparative example, a ZnS: Mn reverse micelle solution was prepared in the same manner as in Example 1 described above, and the solution was centrifuged at 5500 rpm without adding any solution. Drying was performed at a temperature of 60 ° C. The dried particles were heated in a nitrogen atmosphere at a temperature of 1000 ° C. for 1 hour to produce a ZnS: Mn phosphor for a light emitting device without a coating. An electroluminescent device was produced in the same manner as in Example 1 using the phosphor for ZnS: Mn light emitting device without the coating.

上記の方法により製造した実施例１ならびに比較例のエレクトロルミネッセンス素子の発光スペクトルを図４に示す。Ａは実施例１により製造した素子の発光スペクトルであり、Ｂは上記比較例により製造した素子の発光スペクトルである。   FIG. 4 shows emission spectra of the electroluminescent elements of Example 1 and Comparative Example manufactured by the above method. A is the emission spectrum of the device manufactured according to Example 1, and B is the emission spectrum of the device manufactured according to the comparative example.

この図４から明らかなように、本発明におけるエレクトロルミネッセンス素子は比較例のエレクトロルミネッセンス素子よりもＥＬ強度が強く、発光効率が向上していることが分かる。   As can be seen from FIG. 4, the electroluminescence element of the present invention has a higher EL intensity and improved luminous efficiency than the electroluminescence element of the comparative example.

本発明に係る発光素子用蛍光体は平均粒径が０．５ｎｍ〜１００ｎｍの超微粒子からなる蛍光体粒子の表面を強誘電体成分からなる薄膜で被覆することで、発光効率の向上と、蛍光体粒子の劣化を防止することができ、特に分散型ＥＬ素子用の蛍光体として有用である。   The phosphor for a light-emitting device according to the present invention covers the surface of phosphor particles made of ultrafine particles having an average particle size of 0.5 nm to 100 nm with a thin film made of a ferroelectric component, thereby improving luminous efficiency and fluorescence. Deterioration of body particles can be prevented, and it is particularly useful as a phosphor for a dispersion type EL device.

また、本発明の蛍光体粒子を用いたＥＬ素子は、超微粒子の表面を強誘電体成分からなる薄膜で被覆された発光素子用蛍光体を用いることで、発光効率の高い、すなわち消費電力の少ない発光素子として有用である。   In addition, the EL device using the phosphor particles of the present invention uses a phosphor for a light emitting device in which the surface of ultrafine particles is coated with a thin film made of a ferroelectric component. It is useful as a small number of light emitting elements.

本発明の実施の形態１における発光素子用蛍光体の模式断面図Schematic cross-sectional view of the phosphor for light-emitting element in Embodiment 1 of the present invention 本発明の実施の形態２におけるエレクトロルミネッセンス素子の模式断面図Schematic cross-sectional view of the electroluminescence element in the second embodiment of the present invention （ａ）〜（ｅ）は本発明の実施の形態３−ａ〜３−ｅにおけるエレクトロルミネッセンス素子の模式断面図(A)-(e) is typical sectional drawing of the electroluminescent element in Embodiment 3-a-3-e of this invention 本発明の実施例１で製造したエレクトロルミネッセンス素子と比較例として製造した素子の発光スペクトルを示す図The figure which shows the emission spectrum of the electroluminescent element manufactured in Example 1 of this invention, and the element manufactured as a comparative example.

符号の説明Explanation of symbols

１ 発光素子用蛍光体
２ エレクトロルミネッセンス素子
１１ 蛍光体粒子
１２ 強誘電体
２１ 透明基板
２２ 透明電極
２３ 発光層
２４ 絶縁体層
２５ 背面電極
２６ 背面板
２７ 交流電源 DESCRIPTION OF SYMBOLS 1 Phosphor for light emitting elements 2 Electroluminescent element 11 Phosphor particle 12 Ferroelectric material 21 Transparent substrate 22 Transparent electrode 23 Light emitting layer 24 Insulator layer 25 Back electrode 26 Back plate 27 AC power supply

Claims (6)

平均粒径が０．５ｎｍ〜１００ｎｍの超微粒子からなる蛍光体粒子の表面を強誘電体成分からなる薄膜で被覆したことを特徴とする発光素子用蛍光体。 A phosphor for a light emitting device, characterized in that the surface of phosphor particles comprising ultrafine particles having an average particle diameter of 0.5 nm to 100 nm is coated with a thin film comprising a ferroelectric component. 前記強誘電体成分は、少なくとも２種類の金属元素からなる複合金属酸化物であることを特徴とする請求項１に記載の発光素子用蛍光体。 The phosphor for a light emitting device according to claim 1, wherein the ferroelectric component is a composite metal oxide composed of at least two kinds of metal elements. 前記強誘電体成分は、Ｃａ、Ｓｒ、Ｂａから選ばれた少なくとも一つの金属元素からなる第１の成分と、Ｔｉ、Ｚｒのうち、少なくとも一つの金属元素からなる第２の成分からなる複合金属酸化物であることを特徴とする請求項２に記載の発光素子用蛍光体。 The ferroelectric component is a composite metal composed of a first component composed of at least one metal element selected from Ca, Sr and Ba and a second component composed of at least one metal element selected from Ti and Zr. The phosphor for a light emitting device according to claim 2, wherein the phosphor is an oxide. 前記強誘電体成分からなる薄膜は、平均膜厚が０．５ｎｍ〜１００ｎｍであることを特徴とする請求項１乃至請求項３のいずれかに記載の発光素子用蛍光体。 The phosphor for a light-emitting element according to any one of claims 1 to 3, wherein the thin film made of the ferroelectric component has an average film thickness of 0.5 nm to 100 nm. 前記超微粒子からなる蛍光体粒子は金属元素が付活された硫化亜鉛であることを特徴とする請求項１乃至請求項４のいずれかに記載の発光素子用蛍光体。 The phosphor for a light emitting device according to any one of claims 1 to 4, wherein the phosphor particles made of the ultrafine particles are zinc sulfide activated with a metal element. 少なくとも一方が透光性を有する１対の電極間に、発光層を有するエレクトロルミネッセンス素子であって、前記発光層を構成する発光素子用蛍光体は請求項１乃至請求項５のいずれかに記載の発光素子用蛍光体であることを特徴とするエレクトロルミネッセンス素子。 6. The phosphor for a light-emitting element, which is an electroluminescent element having a light-emitting layer between a pair of electrodes, at least one of which has a light-transmitting property, and that constitutes the light-emitting layer. An electroluminescent element characterized by being a phosphor for a light emitting element.
JP2004045884A 2004-02-23 2004-02-23 Phosphor for luminescent element and electroluminescent element Pending JP2005232398A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2022032916A (en) * 2020-08-11 2022-02-25 延世大學校産學協力團 Material in which piezoelectricity and luminescent are synchronized, and element containing them

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JPH04178486A (en) * 1990-11-09 1992-06-25 Sumitomo Chem Co Ltd Production of water-resistant fluophor
JPH06200245A (en) * 1992-12-28 1994-07-19 Toyo Alum Kk Dielectric-coated material and its production
JPH06203957A (en) * 1993-10-22 1994-07-22 Nissan Motor Co Ltd Manufacture of dispersion type el panel
JPH0992467A (en) * 1995-09-28 1997-04-04 Toshiba Corp Distributed type electroluminescent element
JPH0992167A (en) * 1995-09-19 1997-04-04 Toshiba Corp Fluorescent surface
JP2001185358A (en) * 1999-12-27 2001-07-06 Yazaki Corp Encapsulated fluorescent particle for electroluminescence and el display panel, and manufacturing method for the same
JP2003511548A (en) * 1998-08-31 2003-03-25 アメリカ合衆国 Cathodoluminescent phosphor with coating
JP2005120117A (en) * 2003-10-14 2005-05-12 Sumitomo Electric Ind Ltd Phosphor, and porous body and filter obtained using the same

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04178486A (en) * 1990-11-09 1992-06-25 Sumitomo Chem Co Ltd Production of water-resistant fluophor
JPH06200245A (en) * 1992-12-28 1994-07-19 Toyo Alum Kk Dielectric-coated material and its production
JPH06203957A (en) * 1993-10-22 1994-07-22 Nissan Motor Co Ltd Manufacture of dispersion type el panel
JPH0992167A (en) * 1995-09-19 1997-04-04 Toshiba Corp Fluorescent surface
JPH0992467A (en) * 1995-09-28 1997-04-04 Toshiba Corp Distributed type electroluminescent element
JP2003511548A (en) * 1998-08-31 2003-03-25 アメリカ合衆国 Cathodoluminescent phosphor with coating
JP2001185358A (en) * 1999-12-27 2001-07-06 Yazaki Corp Encapsulated fluorescent particle for electroluminescence and el display panel, and manufacturing method for the same
JP2005120117A (en) * 2003-10-14 2005-05-12 Sumitomo Electric Ind Ltd Phosphor, and porous body and filter obtained using the same

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2022032916A (en) * 2020-08-11 2022-02-25 延世大學校産學協力團 Material in which piezoelectricity and luminescent are synchronized, and element containing them
JP7083987B2 (en) 2020-08-11 2022-06-14 延世大學校産學協力團 Materials with synchronized piezoelectricity and luminescence and elements containing them

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