JPH04270780A - Electroluminescent fluorescent material - Google Patents
Electroluminescent fluorescent materialInfo
- Publication number
- JPH04270780A JPH04270780A JP3031170A JP3117091A JPH04270780A JP H04270780 A JPH04270780 A JP H04270780A JP 3031170 A JP3031170 A JP 3031170A JP 3117091 A JP3117091 A JP 3117091A JP H04270780 A JPH04270780 A JP H04270780A
- Authority
- JP
- Japan
- Prior art keywords
- phosphor
- gold
- activator
- zinc sulfide
- copper
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000463 material Substances 0.000 title abstract description 4
- 229910052984 zinc sulfide Inorganic materials 0.000 claims abstract description 36
- 239000005083 Zinc sulfide Substances 0.000 claims abstract description 35
- 229910052737 gold Inorganic materials 0.000 claims abstract description 30
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000012190 activator Substances 0.000 claims abstract description 19
- 239000011159 matrix material Substances 0.000 claims abstract description 6
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 59
- 239000010931 gold Substances 0.000 claims description 29
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 28
- 239000010949 copper Substances 0.000 claims description 19
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 17
- 229910052802 copper Inorganic materials 0.000 claims description 17
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 5
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 5
- 229910052794 bromium Inorganic materials 0.000 claims description 5
- 239000000460 chlorine Substances 0.000 claims description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 4
- 238000005401 electroluminescence Methods 0.000 abstract description 3
- 238000004020 luminiscence type Methods 0.000 abstract description 2
- 238000013329 compounding Methods 0.000 abstract 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 26
- 239000008367 deionised water Substances 0.000 description 20
- 229910021641 deionized water Inorganic materials 0.000 description 20
- 239000010453 quartz Substances 0.000 description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 18
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 12
- 238000010304 firing Methods 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 239000002245 particle Substances 0.000 description 10
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 239000011230 binding agent Substances 0.000 description 6
- -1 histo Chemical compound 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 239000011787 zinc oxide Substances 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- 239000003822 epoxy resin Substances 0.000 description 5
- 230000002706 hydrostatic effect Effects 0.000 description 5
- 229920000647 polyepoxide Polymers 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 229910001629 magnesium chloride Inorganic materials 0.000 description 4
- 150000004685 tetrahydrates Chemical class 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 3
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 3
- 229910001626 barium chloride Inorganic materials 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000007873 sieving Methods 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910000365 copper sulfate Inorganic materials 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- NYZGMENMNUBUFC-UHFFFAOYSA-N P.[S-2].[Zn+2] Chemical compound P.[S-2].[Zn+2] NYZGMENMNUBUFC-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- XEIPQVVAVOUIOP-UHFFFAOYSA-N [Au]=S Chemical compound [Au]=S XEIPQVVAVOUIOP-UHFFFAOYSA-N 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 229910001514 alkali metal chloride Inorganic materials 0.000 description 1
- 229910001617 alkaline earth metal chloride Inorganic materials 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000001553 barium compounds Chemical class 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000003081 coactivator Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 235000019256 formaldehyde Nutrition 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910001631 strontium chloride Inorganic materials 0.000 description 1
- AHBGXTDRMVNFER-UHFFFAOYSA-L strontium dichloride Chemical compound [Cl-].[Cl-].[Sr+2] AHBGXTDRMVNFER-UHFFFAOYSA-L 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
Landscapes
- Electroluminescent Light Sources (AREA)
- Luminescent Compositions (AREA)
Abstract
Description
【０００１】［発明の目的］[Object of the invention]
【０００２】0002
【産業上の利用分野】本発明は分散型の電場発光（以下
、ＥＬで表示する）素子に関し、特にそのＥＬ蛍光体に
関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a distributed electroluminescent (hereinafter referred to as EL) device, and particularly to an EL phosphor thereof.
【０００３】0003
【従来の技術】分散型のＥＬ蛍光体は、これを誘電物質
中に分散し、その両側に電極を配置して、少なくとも一
方の電極を透明電極で構成してこの電極間に交流電圧を
印加することにより発光する。したがって表示素子等に
用いることができる。[Prior Art] Dispersed EL phosphors are made by dispersing them in a dielectric material, disposing electrodes on both sides of the material, at least one of which is a transparent electrode, and applying an alternating current voltage between the electrodes. It emits light by doing so. Therefore, it can be used for display elements and the like.
【０００４】かかるＥＬ蛍光体として、硫化亜鉛（Ｚｎ
Ｓ）を母体とし、これに付活剤として銅およびハロゲン
Ｘ（塩素Ｃｌまたは臭素Ｂｒ）を導入したＺｎＳ：Ｃｕ
、Ｘ が一般的に用いられている。As such an EL phosphor, zinc sulfide (Zn
ZnS:Cu which uses S) as a matrix and introduces copper and halogen X (chlorine Cl or bromine Br) into it as an activator
, X are commonly used.
【０００５】しかし、従来この種の蛍光体を用いて製作
された分散型ＥＬは、他の表示素子に比べて明るさや寿
命がかなり悪いため、種々の改良がなされている。[0005] However, conventionally, dispersed ELs manufactured using this type of phosphor have considerably poorer brightness and lifespan than other display elements, and various improvements have therefore been made.
【０００６】一般に硫化亜鉛系のＥＬ蛍光体は、高温相
である六方晶型（ウルツァイト構造）の結晶粒子をまず
作り、次いで低温相である立方晶型（ジンクブレンド構
造）に変換するとＥＬ特性のよい蛍光体が得られること
が、「半導体光物性」高木・山田著（株式会社産報）に
記載されている。In general, in zinc sulfide-based EL phosphors, the EL properties are improved by first producing hexagonal crystal grains (wurtzite structure), which is a high-temperature phase, and then converting them to a cubic crystal structure (zinc blend structure), which is a low-temperature phase. The fact that a good phosphor can be obtained is described in "Semiconductor Photophysical Properties" by Takagi and Yamada (Sanpo Co., Ltd.).
【０００７】従来、大粒子六方晶型の中間蛍光体を作り
これを高圧に加えて（熱処理も含む）処理し、大粒子立
方晶型硫化亜鉛蛍光体にして長寿命のＥＬ蛍光体を得る
方法が知られている（特開昭６１−２９６０８５ ）。
この他に、ＥＬ蛍光体に酸化亜鉛等の金属酸化物を混合
し熱処理した後、酸処理し、蛍光体粒子表面にエッチピ
ット状の穴を形成して、輝度寿命特性の向上を図る方法
も知られている（特願昭６２−２９６１３４）。 ま
た、焼成前に少量のバリウム化合物を添加して長寿命化
を図る方法（特開昭６１−１８８４８４ ）や、付活剤
の銅および共付活剤の臭素の添加量を最適化して長寿命
蛍光体を得る方法（特開昭５７−１４５１７４ ）も知
られている。Conventionally, a large particle hexagonal crystal type intermediate phosphor is prepared and then treated under high pressure (including heat treatment) to produce a large particle cubic crystal type zinc sulfide phosphor to obtain a long-life EL phosphor. is known (Japanese Patent Application Laid-Open No. 61-296085). Another method is to mix a metal oxide such as zinc oxide into the EL phosphor, heat treat it, and then treat it with an acid to form etch pit-like holes on the surface of the phosphor particles to improve the brightness life characteristics. It is known (Japanese Patent Application No. 62-296134). In addition, we have proposed a method to extend the life by adding a small amount of barium compound before firing (Japanese Patent Application Laid-open No. 61-188484), and by optimizing the amount of copper as an activator and bromine as a co-activator. A method for obtaining a phosphor (Japanese Unexamined Patent Publication No. 57-145174) is also known.
【０００８】また，硫化亜鉛の蛍光体に銅と金を入れる
ことも以前から知られている。例えば、東芝レビュー３
３巻６ 号５１５ ページにはブラウン管用の蛍光体と
して愛称“Ｇ＆Ｇ”として知られているＺｎＳ：Ｃｕ、
Ａｕ、Ａｌが報告されている。この蛍光体は金を導入す
ることにより、発光色を長波長にずらして、白色を出す
ときの電流比を均一化することを目的にしたものである
。It has also been known for some time to incorporate copper and gold into zinc sulfide phosphors. For example, Toshiba Review 3
Volume 3, No. 6, Page 515 describes ZnS:Cu, nicknamed “G&G” as a phosphor for cathode ray tubes.
Au and Al have been reported. The purpose of this phosphor is to shift the emission color to a longer wavelength by introducing gold, thereby making the current ratio uniform when emitting white light.
【０００９】ＥＬ蛍光体に金を導入することもいくつか
提案がなされている。例えば、（Ｚｎ，Ｃｄ）（Ｓ ，
Ｓｅ）に付活剤として銀，銅，鉛，マンガン，スカンジ
ウム，ガリウム，インジウム，燐，ひそ，金，アンチモ
ン，塩素，臭素，アルミニウム等を含み，蛍光体粒子表
面に銅または金濃度が内部より高くなるように硫酸銅や
塩化金水溶液に浸漬処理する方法、または銅や金を蛍光
体粒子表面に蒸着する方法が知られている（英国特許７
８２，０９５ と７８２，０９６ ）。 また、銅と
金とアルミニウムで活性化した硫化亜鉛蛍光体も知られ
ている（英国特許７８２，０９７ ）。 しかし，蛍
光体粒子表面を硫化銅、硫化金で被覆する方法はＥＬ発
光させるためには必要であるが、発光の一部がこの表面
で吸収され発光特性が低下する問題点を有する。[0009] Several proposals have been made to introduce gold into EL phosphors. For example, (Zn, Cd)(S,
Se) contains silver, copper, lead, manganese, scandium, gallium, indium, phosphorus, histo, gold, antimony, chlorine, bromine, aluminum, etc. as an activator, and the concentration of copper or gold on the surface of the phosphor particles is higher than that from the inside. A method of immersing copper sulfate or gold chloride in an aqueous solution to increase the height of the phosphor particles, or a method of vapor depositing copper or gold on the surface of the phosphor particles are known (UK Patent No. 7).
82,095 and 782,096). Zinc sulfide phosphors activated with copper, gold and aluminum are also known (British Patent No. 782,097). However, although the method of coating the surface of the phosphor particles with copper sulfide or gold sulfide is necessary for EL emission, it has the problem that part of the emitted light is absorbed by this surface, resulting in a decrease in the luminescent properties.
【００１０】硫化亜鉛系のＥＬ蛍光体の劣化機構につい
ては、未だ完全に理解されていないが、第一に、周囲に
ある湿気（水、炭酸ガス等）との反応による蛍光体の分
解、第二に、蛍光体粒子内部の活性剤である銅イオンの
移動拡散による非発光化の二つの大きな要因がある。第
一の要因に対しては、蛍光体粒子表面に湿気防止表面処
理の提案がいくつか成されており、また、ＥＬパネル製
造時、この湿気については十分注意がなされており、現
在では蛍光体自体の改良を目的とした第二の要因がより
重要になってきている。液晶等の表示素子のバックライ
トにはこの青緑発光のＺｎＳ：Ｃｕ、Ｘ 蛍光体とこの
青緑発光を吸収して赤色発光する有機染料とを一緒にし
た蛍光層をもつ白色発光ＥＬパネルが広く用いられてい
る。[0010] The deterioration mechanism of zinc sulfide-based EL phosphors is still not completely understood, but first, the phosphor decomposes due to reaction with surrounding moisture (water, carbon dioxide, etc.) Secondly, there are two major causes of non-emission due to movement and diffusion of copper ions, which are activators inside the phosphor particles. Regarding the first factor, several proposals have been made for moisture-preventing surface treatments on the surface of the phosphor particles, and due attention has been paid to this moisture when manufacturing EL panels, and currently phosphor particles are The second factor, aimed at improving itself, is becoming more important. The backlights of display elements such as liquid crystals use white-emitting EL panels that have a fluorescent layer that combines this blue-green-emitting ZnS:Cu,X phosphor with an organic dye that absorbs this blue-green light and emits red light. Widely used.
【００１１】[0011]
【発明が解決しようとする課題】以上述べたように、現
行の分散型ＥＬ蛍光体は種々の工夫により寿命特性は改
良されているが、まだ他の表示素子に比較して必ずしも
十分ではない。As described above, although the life characteristics of current dispersed EL phosphors have been improved through various efforts, they are still not necessarily sufficient compared to other display elements.
【００１２】したがって本発明の目的は、高い電場発光
輝度をもち、発光色のＣＩＥｙ値の低い、かつ寿命特性
の良好な分散型ＥＬ蛍光体を提供することにある。[0012] Accordingly, an object of the present invention is to provide a dispersed EL phosphor having high electroluminescence brightness, a low CIEy value of emitted light color, and good lifetime characteristics.
【００１３】［発明の構成］[Configuration of the invention]
【００１４】[0014]
【課題を解決するための手段】本発明の蛍光体は、上記
従来の英国特許の提案とは蛍光体の構造組成が原理的に
異なり、金を導入して電場発光輝度を向上させると共に
、寿命特性も良好で、かつ発光色を短波長にシフトする
ことを見出だしたことに基づくものである。すなわち本
発明の蛍光体は、硫化亜鉛を母体として，これに付活剤
として銅，第１の共付活剤として塩素，臭素の少なくと
も一種，第２の共付活剤として金を硫化亜鉛 １モルに
対して， １×１０−５グラム原子以上１２×１０−５
グラム原子以下含有することを特徴とする。[Means for Solving the Problems] The phosphor of the present invention is fundamentally different from the above-mentioned conventional proposal in the British patent in terms of its structural composition. This is based on the discovery that it has good characteristics and shifts the emission color to shorter wavelengths. That is, the phosphor of the present invention uses zinc sulfide as a matrix, copper as an activator, at least one of chlorine and bromine as a first co-activator, and gold as a second co-activator. For moles, 1 x 10-5 gram atoms or more 12 x 10-5
It is characterized by containing less than gram atoms.
【００１５】本発明の特徴である第２の共付活剤として
使用する金は、硫化亜鉛 １モルに対して １×１０−
５グラム原子以上１２×１０−５グラム原子以下含有す
る。 １×１０−５グラム原子より少なくなると輝度・
寿命が低下し、１２×１０−５を越えると、輝度が低下
し、またＣＩＥｙ値も大きくなる。The amount of gold used as the second co-activator, which is a feature of the present invention, is 1×10− per mol of zinc sulfide.
Contains at least 5 gram atoms and at most 12 x 10-5 gram atoms. When it becomes less than 1 x 10-5 gram atoms, the brightness
When the lifetime decreases and exceeds 12×10 −5 , the brightness decreases and the CIEy value also increases.
【００１６】また、本発明に付活剤として使用される銅
の濃度を高くするとＥＬ蛍光体の寿命特性は一般に向上
する。しかし、発光色の色度ＣＩＥｙ値が高くなり、青
緑から緑色方向にシフトする結果、赤色有機染料を混合
して使用される白色発光ＥＬパネルの白色が黄緑色味が
かかり好ましくない。好ましい銅の濃度は ５×１０−
４から ２．０×１０−３グラム原子／ＺｎＳ １モル
の範囲である。Furthermore, increasing the concentration of copper used as an activator in the present invention generally improves the lifetime characteristics of the EL phosphor. However, as the chromaticity CIEy value of the emitted light increases and shifts from blue-green to green, the white color of a white-emitting EL panel that is used with a mixture of red organic dye becomes yellow-green, which is undesirable. The preferred copper concentration is 5×10−
It ranges from 4 to 2.0 x 10-3 gram atoms/mol of ZnS.
【００１７】本発明の蛍光体は、一例として以下のよう
な方法で作ることができる。The phosphor of the present invention can be produced by the following method, for example.
【００１８】硫化亜鉛粉末に所定の量の硫酸銅および塩
化金酸を脱イオン水に投入してスラリー状にして十分よ
く混合して乾燥器に入れて乾燥する。次に、この混合物
にアルカリ金属塩化物、アルカリ土類金属塩化物をフラ
ックスとして５〜１５％ 混合する。この混合物を石英
ルツボに充填して、蓋をして１１００〜１２００℃、３
〜８ 時間空気中で焼成する。焼成後、ルツボより焼
成物を取り出し、脱イオン水で数回洗浄し、濾過した後
乾燥する。このようにして得られた六方晶型中間蛍光体
をゴム袋に入れ、ラバープレス装置で０．５ 〜 ２．
０ｔ／ｃｍ２ の静水圧で数分間加圧して立方晶型に変
換する。このときゴム袋に水が入らないようにすること
が必要である。ゴム袋より取り出し、酸化亜鉛等の金属
酸化物を数重量％混合して石英ルツボに充填して、蓋を
して６００ 〜８００ ℃、１ 〜２ 時間空気中で焼
成する。焼成後、ルツボより焼成物を取り出し、脱イオ
ン水に分散して塩酸を加えｐＨを１ 〜３ に保ちなが
ら約３０分間撹拌して酸処理した後、脱イオン水で数回
洗浄して本発明の蛍光体を製造することができる。Zinc sulfide powder, predetermined amounts of copper sulfate and chloroauric acid are added to deionized water to form a slurry, mixed thoroughly, and dried in a dryer. Next, 5 to 15% of an alkali metal chloride and an alkaline earth metal chloride are mixed as a flux into this mixture. This mixture was filled into a quartz crucible, covered with a lid, and heated to 1100-1200℃ for 3
Bake in air for ~8 hours. After firing, the fired product is removed from the crucible, washed several times with deionized water, filtered, and dried. The hexagonal intermediate phosphor thus obtained was placed in a rubber bag and heated to 0.5 to 2.
It is converted into a cubic crystal form by applying a hydrostatic pressure of 0 t/cm2 for several minutes. At this time, it is necessary to prevent water from entering the rubber bag. The mixture is taken out of the rubber bag, mixed with several weight percent of a metal oxide such as zinc oxide, and filled into a quartz crucible, covered with a lid, and fired in air at 600 to 800°C for 1 to 2 hours. After firing, the fired product is taken out from the crucible, dispersed in deionized water, added with hydrochloric acid and stirred for about 30 minutes while maintaining the pH at 1 to 3 for acid treatment, and then washed several times with deionized water to obtain the present invention. phosphors can be produced.
【００１９】[0019]
【作用】図１は硫化亜鉛ＺｎＳ １モルに対して銅を
９．２ ×１０−４グラム原子導入し、共付活剤として
金を導入したとき蛍光体の輝度と金の濃度の関係を示し
たものである。
図２は蛍光体の発光色度ＣＩＥｙ値と金の濃度の関
係を示したものである。図３は蛍光体の寿命と金の濃度
との関係を示したものである。[Operation] Figure 1 shows the relationship between the brightness of the phosphor and the concentration of gold when 9.2 x 10-4 gram atoms of copper are introduced into 1 mole of zinc sulfide (ZnS) and gold is introduced as a co-activator. It is something that FIG. 2 shows the relationship between the emission chromaticity CIEy value of the phosphor and the gold concentration. FIG. 3 shows the relationship between the lifetime of the phosphor and the gold concentration.
【００２０】ここで、蛍光体の輝度・色度・寿命は、こ
の蛍光体を用いたＥＬパネルとして測定したものである
。すなわち、蛍光体にエポキシ樹脂をバインダーとして
、蛍光体とバインダーの体積比を７：３ として、透明
電極上に蛍光層を形成し、ＥＬ素子を作成する。このＥ
Ｌ素子に５００Ｈｚ の交流電圧を加え、蛍光層の電場
が２×１０４ Ｖ／ｃｍのときの輝度および色度を測定
し蛍光体の輝度・色度とする。また、寿命はＥＬ素子を
デシケータに入れて、４ｋＨｚの交流電圧を加えたとき
初期輝度が半減する時間で定義した。この寿命は通常の
５００Ｈｚ の交流電圧を加えたときの輝度半減時間の
約１／１０の強制寿命である。[0020] Here, the brightness, chromaticity, and lifespan of the phosphor were measured for an EL panel using this phosphor. That is, an EL element is produced by forming a fluorescent layer on a transparent electrode using a fluorescent substance and an epoxy resin as a binder, and setting the volume ratio of the fluorescent substance and the binder to 7:3. This E
An AC voltage of 500 Hz is applied to the L element, and the luminance and chromaticity are measured when the electric field of the phosphor layer is 2×10 4 V/cm, and these are taken as the luminance and chromaticity of the phosphor. Further, the life span was defined as the time required for the initial brightness to be halved when the EL element was placed in a desiccator and an alternating current voltage of 4 kHz was applied. This life span is about 1/10 of the luminance half-life when a normal 500 Hz AC voltage is applied.
【００２１】図１から図３より明らかなように、金の導
入量がＺｎＳ １モルに対して、１×１０−５グラム原
子より多くなると輝度・寿命が向上していくことが分か
る。また、ＣＩＥｙ値は小さくなって上述の赤色の有機
染料を混合して得られる白色の色純度は高いものである
。しかし、金の導入量が １２ ×１０−５を越えると
、寿命については問題ないが、輝度は低下し、またＣＩ
Ｅｙ値が大きくなり好ましくない。As is clear from FIGS. 1 to 3, it can be seen that when the amount of gold introduced is greater than 1×10 −5 gram atoms per mole of ZnS, the brightness and lifetime are improved. Further, the CIEy value is small, and the color purity of the white color obtained by mixing the above-mentioned red organic dye is high. However, if the amount of gold introduced exceeds 12
The Ey value becomes large, which is not preferable.
【００２２】[0022]
【実施例】次に、本発明について以下の実施例でさらに
詳細に説明する。EXAMPLES Next, the present invention will be explained in more detail with reference to the following examples.
【００２３】実施例１
硫化亜鉛粉末５００ｇと硫酸銅５水和物１．５ｇと塩化
金酸４水和物０．１ｇに脱イオン水を加えてスラリー状
態にして混合し、これを １５０℃で１２時間乾燥する
。次に、この混合物に塩化ナトリウム１０ｇ 、塩化マ
グネシウム１５ｇ 、塩化ストロンチウム１５ｇ を十
分に混合して石英ルツボに充填し、蓋をしてこれを１１
５０℃、 ６時間空気中で焼成する。
焼成後、石英ルツボより焼成物を取り出し脱イオン水で
５回洗浄し、濾過した後、 １５０℃で１２時間乾燥
する。このようにして得られた銅・金・塩素付活した中
間蛍光体２００ｇをゴム袋に入れ、ラバープレス装置で
１ｔ／ｃｍ２ の静水圧で ３分間加圧した。このと
きゴム袋に水が入らないようにすることが必要である。
次に、ゴム袋より取り出した加圧処理した蛍光体１００
ｇに酸化亜鉛５ｇを混合して、石英ルツボに入れ蓋をし
て、 ７５０℃、 １時間空気中で焼成する。焼成後、
石英ルツボより焼成物を取り出し、脱イオン水に分散し
て塩酸を加えｐＨを１．５ に保ちながら３０分間撹拌
洗浄処理、次いで脱イオン水で ５回洗浄後、濾過、乾
燥、ふるい工程を経て本発明の蛍光体が得られる。この
蛍光体は化学分析の結果、銅は １．２×１０−３ｇ
原子／ＺｎＳ １モル、金は ４．７×１０−５ｇ 原
子／ＺｎＳ １モル導入されているものであり、この蛍
光体にエポキシ樹脂をバインダーとして、ＥＬ素子を作
製する。この輝度は従来の金を含まないＥＬ蛍光体の１
２０％と高く、発光色のＣＩＥｙ値は０．０２小さくよ
り青味の強い緑色発光を示すものであり、４ｋＨｚの交
流電圧を加えたとき初期輝度が半減する時間で定義され
る寿命は従来の金を含まない蛍光体が２００時間である
のに対して、 ４００時間であり、輝度寿命特性の優れ
たものである。実施例２
硫化亜鉛粉末５００ｇと硫酸銅５水和物１．０ｇと塩化
金酸４水和物０．０９ｇ に脱イオン水を加えてスラリ
ー状態にして混合し、これを １５０℃で１２時間乾燥
する。次に、この混合物に塩化カリウム１０ｇ 、塩化
マグネシウム１５ｇ 、塩化バリウム１５ｇ を十分に
混合して石英ルツボに充填し、蓋をしてこれを１１５０
℃、 ６時間空気中で焼成する。焼成後、石英ルツボよ
り焼成物を取り出し脱イオン水で ５回洗浄し、濾過し
た後、 １５０℃で１２時間乾燥する。このようにして
得られた銅・金・塩素付活した中間蛍光体２００ｇをゴ
ム袋に入れ、ラバープレス装置で １ｔ／ｃｍ２ の静
水圧で ３分間加圧した。このときゴム袋に水が入らな
いようにすることが必要である。次に、ゴム袋より取り
出した加圧処理した蛍光体１００ｇに酸化亜鉛５ｇを混
合して、石英ルツボに入れ蓋をして、 ７５０℃、 １
時間空気中で焼成する。
焼成後、石英ルツボより焼成物を取り出し、脱イオン水
に分散して塩酸を加えｐＨを１．５ に保ちながら３０
分間撹拌洗浄処理、次いで脱イオン水で５回洗浄後、濾
過、乾燥、ふるい工程を経て本発明の蛍光体が得られる
。この蛍光体は化学分析の結果、銅は ７．８×１０−
４ｇ 原子／ＺｎＳ １モル、金は ４．３×１０−５
ｇ 原子／ＺｎＳ １モル導入されているものであり、
この蛍光体にエポキシ樹脂をバインダーとして、ＥＬ素
子を作製する。この輝度は従来の金を含まないＥＬ蛍光
体の１１０％と高く、発光色のＣＩＥｙ値は０．０１５
小さくより青味の強い緑色発光を示すものであり、４
ｋＨｚの交流電圧を加えたとき初期輝度が半減する時間
で定義される寿命は従来の金を含まない蛍光体が １６
０時間であるのに対して、 ３１０時間であり、輝度寿
命特性の優れたものである。Example 1 Deionized water was added to 500 g of zinc sulfide powder, 1.5 g of copper sulfate pentahydrate, and 0.1 g of chloroauric acid tetrahydrate to form a slurry, which was then mixed at 150°C. Dry for 12 hours. Next, 10 g of sodium chloride, 15 g of magnesium chloride, and 15 g of strontium chloride were thoroughly mixed with this mixture, filled into a quartz crucible, and the crucible was covered with a lid.
Bake in air at 50°C for 6 hours. After firing, the fired product was taken out of the quartz crucible, washed five times with deionized water, filtered, and dried at 150°C for 12 hours. 200 g of the copper-gold-chlorine activated intermediate phosphor thus obtained was placed in a rubber bag and pressurized for 3 minutes at a hydrostatic pressure of 1 t/cm 2 using a rubber press device. At this time, it is necessary to prevent water from entering the rubber bag. Next, the pressure-treated phosphor 100 taken out from the rubber bag
g and 5 g of zinc oxide are mixed, placed in a quartz crucible, covered, and fired in air at 750°C for 1 hour. After firing,
The fired product was removed from the quartz crucible, dispersed in deionized water, added hydrochloric acid, and stirred and washed for 30 minutes while keeping the pH at 1.5.Then, after washing five times with deionized water, it was filtered, dried, and sieved. The phosphor of the present invention is obtained. Chemical analysis of this phosphor revealed that the copper content was 1.2 x 10-3g.
Atom/1 mole of ZnS and gold are introduced at 4.7×10 −5 g atoms/1 mole of ZnS, and an EL element is produced by using this phosphor with an epoxy resin as a binder. This brightness is higher than that of conventional gold-free EL phosphors.
The CIEy value of the emitted light color is 0.02, which is as high as 20%, and the CIEy value of the emitted light is 0.02, indicating a more bluish green light emitted. It has excellent brightness life characteristics, with a lifespan of 400 hours compared to 200 hours for phosphors that do not contain gold. Example 2 Deionized water was added to 500 g of zinc sulfide powder, 1.0 g of copper sulfate pentahydrate, and 0.09 g of chloroauric acid tetrahydrate, mixed to form a slurry, and this was dried at 150°C for 12 hours. do. Next, this mixture was thoroughly mixed with 10 g of potassium chloride, 15 g of magnesium chloride, and 15 g of barium chloride, filled into a quartz crucible, covered with a lid, and heated to 1150 g.
Cake in air for 6 hours. After firing, the fired product was taken out of the quartz crucible, washed five times with deionized water, filtered, and dried at 150°C for 12 hours. 200 g of the copper-gold-chlorine activated intermediate phosphor thus obtained was placed in a rubber bag and pressurized for 3 minutes at a hydrostatic pressure of 1 t/cm 2 using a rubber press device. At this time, it is necessary to prevent water from entering the rubber bag. Next, 100 g of the pressurized phosphor taken out from the rubber bag was mixed with 5 g of zinc oxide, placed in a quartz crucible, covered with a lid, and heated at 750°C.
Bake in air for an hour. After firing, the fired product was taken out from the quartz crucible, dispersed in deionized water, and added with hydrochloric acid to keep the pH at 1.5.
The phosphor of the present invention is obtained by a stirring washing treatment for a minute, followed by washing five times with deionized water, followed by filtration, drying and sieving steps. As a result of chemical analysis, this phosphor has a copper content of 7.8 x 10-
4g atoms/1 mole of ZnS, gold is 4.3 x 10-5
g atoms/1 mole of ZnS is introduced,
An EL element is produced by using this phosphor with an epoxy resin as a binder. This brightness is 110% higher than that of conventional EL phosphors that do not contain gold, and the CIEy value of the luminescent color is 0.015.
It emits a smaller and more bluish green light, and 4
Conventional gold-free phosphors have a lifespan defined as the time it takes for the initial brightness to halve when a kHz AC voltage is applied.16
It has excellent brightness life characteristics, with a brightness life of 310 hours compared to 0 hours.
【００２４】実施例３
硫化亜鉛粉末５００ｇと硫酸銅５水和物１．２ｇと塩化
金酸４水和物０．１５ｇ に脱イオン水を加えてスラリ
ー状態にして混合し、これを １５０℃で１２時間乾燥
する。次に、この混合物に塩化リチウム１０ｇ 、塩化
マグネシウム１５ｇ 、塩化バリウム１５ｇ を十分に
混合して石英ルツボに充填し、蓋をしてこれを１１５０
℃、 ６時間空気中で焼成する。焼成後、石英ルツボよ
り焼成物を取り出し脱イオン水で ５回洗浄し、濾過し
た後、 １５０℃で１２時間乾燥する。このようにして
得られた銅・金・塩素付活した中間蛍光体２００ｇをゴ
ム袋に入れ、ラバープレス装置で １ｔ／ｃｍ２ の静
水圧で ３分間加圧した。このときゴム袋に水が入らな
いようにすることが必要である。次に、ゴム袋より取り
出した加圧処理した蛍光体１００ｇに酸化亜鉛５ｇを混
合して、石英ルツボに入れ蓋をして、 ７５０℃、 １
時間空気中で焼成する。
焼成後、石英ルツボより焼成物を取り出し、脱イオン水
に分散して塩酸を加えｐＨを１．５ に保ちながら３０
分間撹拌洗浄処理、次いで脱イオン水で５回洗浄後、濾
過、乾燥、ふるい工程を経て本発明の蛍光体が得られる
。この蛍光体は化学分析の結果、銅は ９．４×１０−
４ｇ 原子／ＺｎＳ １モル、金は ７．１×１０−５
ｇ 原子／ＺｎＳ １モル導入されているものであり、
この蛍光体にエポキシ樹脂をバインダーとして、ＥＬ素
子を作製する。この輝度は従来の金を含まないＥＬ蛍光
体の１２５％と高く、発光色のＣＩＥｙ値は０．０３小
さくより青味の強い緑色発光を示すものであり、４ｋＨ
ｚの交流電圧を加えたとき初期輝度が半減する時間で定
義される寿命は従来の金を含まない蛍光体が １６０時
間であるのに対して、 ３１０時間であり、輝度寿命特
性の優れたものである。Example 3 Deionized water was added to 500 g of zinc sulfide powder, 1.2 g of copper sulfate pentahydrate, and 0.15 g of chloroauric acid tetrahydrate to form a slurry, which was mixed at 150°C. Dry for 12 hours. Next, this mixture was thoroughly mixed with 10 g of lithium chloride, 15 g of magnesium chloride, and 15 g of barium chloride, filled into a quartz crucible, covered with a lid, and heated to 1150 g.
Cake in air for 6 hours. After firing, the fired product was taken out of the quartz crucible, washed five times with deionized water, filtered, and dried at 150°C for 12 hours. 200 g of the copper-gold-chlorine activated intermediate phosphor thus obtained was placed in a rubber bag and pressurized for 3 minutes at a hydrostatic pressure of 1 t/cm 2 using a rubber press device. At this time, it is necessary to prevent water from entering the rubber bag. Next, 100 g of the pressurized phosphor taken out from the rubber bag was mixed with 5 g of zinc oxide, placed in a quartz crucible, covered with a lid, and heated at 750°C.
Bake in air for an hour. After firing, the fired product was taken out from the quartz crucible, dispersed in deionized water, and added with hydrochloric acid to keep the pH at 1.5.
The phosphor of the present invention is obtained by a stirring washing treatment for a minute, followed by washing five times with deionized water, followed by filtration, drying and sieving steps. As a result of chemical analysis, this phosphor has a copper content of 9.4 x 10-
4g atoms/1 mole of ZnS, gold is 7.1×10-5
g atoms/1 mole of ZnS is introduced,
An EL element is produced by using this phosphor with an epoxy resin as a binder. This luminance is 125% higher than that of conventional EL phosphors that do not contain gold, and the CIEy value of the emitted light color is 0.03 smaller, emitting green light with a stronger bluish tinge, and is 4kHz.
The lifespan, defined as the time for the initial brightness to halve when an alternating current voltage of It is.
【００２５】実施例４
硫化亜鉛粉末５００ｇと硫酸銅５水和物１．４ｇと塩化
金酸４水和物０．２ｇに脱イオン水を加えてスラリー状
態にして混合し、これを １５０℃で１２時間乾燥する
。次に、この混合物に塩化ナトリウム１０ｇ 、塩化マ
グネシウム１５ｇ 、塩化バリウム１５ｇ を十分に混
合して石英ルツボに充填し、蓋をしてこれを１１５０℃
、 ６時間空気中で焼成する。焼成後、石英ルツボより
焼成物を取り出し脱イオン水で ５回洗浄し、濾過した
後、 １５０℃で１２時間乾燥する。このようにして得
られた銅・金・塩素付活した中間蛍光体２００ｇをゴム
袋に入れ、ラバープレス装置で １ｔ／ｃｍ２ の静水
圧で ３分間加圧した。このときゴム袋に水が入らない
ようにすることが必要である。次に、ゴム袋より取り出
した加圧処理した蛍光体１００ｇに酸化亜鉛５ｇを混合
して、石英ルツボに入れ蓋をして、 ７５０℃、 １時
間空気中で焼成する。
焼成後、石英ルツボより焼成物を取り出し、脱イオン水
に分散して塩酸を加えｐＨを１．５ に保ちながら３０
分間撹拌洗浄処理、次いで脱イオン水で ５回洗浄後、
濾過、乾燥、ふるい工程を経て本発明の蛍光体が得られ
る。この蛍光体は化学分析の結果、銅は １．１×１０
−３ｇ 原子／ＺｎＳ １モル、金は ９．５×１０−
５ｇ 原子／ＺｎＳ １モル導入されているものであり
、この蛍光体にエポキシ樹脂をバインダーとして、ＥＬ
素子を作製する。この輝度は従来の金を含まないＥＬ蛍
光体の１２５％と高く、発光色のＣＩＥｙ値は０．０３
小さくより青味の強い緑色発光を示すものであり、４ｋ
Ｈｚの交流電圧を加えたとき初期輝度が半減する時間で
定義される寿命は従来の金を含まない蛍光体が ２００
時間であるのに対して、 ４１０時間であり、輝度寿命
特性の優れたものである。Example 4 Deionized water was added to 500 g of zinc sulfide powder, 1.4 g of copper sulfate pentahydrate, and 0.2 g of chloroauric acid tetrahydrate to form a slurry, and the mixture was heated at 150°C. Dry for 12 hours. Next, this mixture was thoroughly mixed with 10 g of sodium chloride, 15 g of magnesium chloride, and 15 g of barium chloride, filled into a quartz crucible, covered with a lid, and heated to 1150°C.
, Bake in air for 6 hours. After firing, the fired product was taken out of the quartz crucible, washed five times with deionized water, filtered, and dried at 150°C for 12 hours. 200 g of the copper-gold-chlorine activated intermediate phosphor thus obtained was placed in a rubber bag and pressurized for 3 minutes at a hydrostatic pressure of 1 t/cm 2 using a rubber press device. At this time, it is necessary to prevent water from entering the rubber bag. Next, 5 g of zinc oxide was mixed with 100 g of the pressurized phosphor taken out from the rubber bag, placed in a quartz crucible, covered, and fired in air at 750° C. for 1 hour. After firing, the fired product was taken out from the quartz crucible, dispersed in deionized water, and added with hydrochloric acid to keep the pH at 1.5.
After washing with agitation for 5 minutes, followed by 5 washes with deionized water,
The phosphor of the present invention is obtained through filtration, drying, and sieving steps. As a result of chemical analysis, this phosphor has a copper content of 1.1×10
-3g atoms/1 mole of ZnS, gold is 9.5x10-
5g atoms/1 mole of ZnS is introduced, and by using epoxy resin as a binder to this phosphor, EL
Fabricate the element. This brightness is 125% higher than that of conventional EL phosphors that do not contain gold, and the CIEy value of the luminescent color is 0.03.
It emits a smaller, more bluish green light, and is 4K.
The lifetime, defined as the time for the initial brightness to decrease by half when an AC voltage of Hz is applied, is 200% for conventional gold-free phosphors.
410 hours, which means it has excellent brightness life characteristics.
【００２６】[0026]
【発明の効果】以上の実施例から明らかなように本発明
によれば、高い電場発光輝度をもち、発光色のＣＩＥｙ
値の低い、かつ寿命特性の良好な分散型ＥＬ蛍光体が実
現できる。Effects of the Invention As is clear from the above embodiments, the present invention has high electroluminescence brightness and CIEy luminescence color.
A dispersed EL phosphor with a low value and good lifetime characteristics can be realized.
【図面の簡単な説明】[Brief explanation of the drawing]
【図１】硫化亜鉛ＺｎＳ １ モルに対して銅を ９．
２×１０−４グラム原子導入し、共付活剤として金を導
入したとき蛍光体の輝度と金の輝度の関係を示したもの
である。FIG. 1: Copper per mole of zinc sulfide ZnS 9.
This figure shows the relationship between the luminance of the phosphor and the luminance of gold when 2×10 −4 gram atoms are introduced and gold is introduced as a coactivator.
【図２】蛍光体の発光色度ＣＩＥｙ値と金の濃度の関係
を示したものである。FIG. 2 shows the relationship between the emission chromaticity CIEy value of a phosphor and the gold concentration.
【図３】蛍光体の寿命と金の濃度の関係を示したもので
ある。FIG. 3 shows the relationship between the lifetime of a phosphor and the concentration of gold.
Claims (1)
として銅，第１の共付活剤として塩素，臭素の少なくと
も一種，第２の共付活剤として金を硫化亜鉛 １モルに
対して， １×１０−５グラム原子以上１２×１０−５
グラム原子以下含有することを特徴とする電場発光蛍光
体。[Claim 1] Zinc sulfide as a matrix, copper as an activator, at least one of chlorine and bromine as a first co-activator, and gold as a second co-activator per mole of zinc sulfide. So, 1 x 10-5 gram atoms or more 12 x 10-5
An electroluminescent phosphor characterized by containing less than a gram atom.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3031170A JP2994058B2 (en) | 1991-02-27 | 1991-02-27 | Electroluminescent phosphor and display element |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3031170A JP2994058B2 (en) | 1991-02-27 | 1991-02-27 | Electroluminescent phosphor and display element |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04270780A true JPH04270780A (en) | 1992-09-28 |
| JP2994058B2 JP2994058B2 (en) | 1999-12-27 |
Family
ID=12323966
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3031170A Expired - Fee Related JP2994058B2 (en) | 1991-02-27 | 1991-02-27 | Electroluminescent phosphor and display element |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2994058B2 (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5702643A (en) * | 1996-04-24 | 1997-12-30 | Osram Sylvania Inc. | ZnS:Cu electroluminescent phosphor and method of making same |
| US5711898A (en) * | 1996-04-24 | 1998-01-27 | Osram Sylvania Inc. | Improved blue-green emitting ZnS:Cu,Cl electroluminescent phosphor and method of making same |
| US6682664B1 (en) | 2002-09-05 | 2004-01-27 | Osram Sylvania Inc. | High brightness orange-yellow-emitting electroluminescent phosphor and method of making |
| JP2006063317A (en) * | 2004-06-24 | 2006-03-09 | Fuji Photo Film Co Ltd | Electroluminescent phosphor |
| JP2007299607A (en) * | 2006-04-28 | 2007-11-15 | Fujifilm Corp | Inorganic dispersion-type electroluminescent element |
| JP2007299606A (en) * | 2006-04-28 | 2007-11-15 | Fujifilm Corp | Distributed type electroluminescence element |
| EP2090640A1 (en) | 2008-01-18 | 2009-08-19 | Fujifilm Corporation | Inorganic phosphor |
| RU2672708C2 (en) * | 2013-12-19 | 2018-11-19 | Бундесдруккерай Гмбх | Zinc-sulphide phosphor having photo- and electroluminescent properties, process for producing same, and security document, security feature and method for detecting same |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7422801B2 (en) | 2004-06-24 | 2008-09-09 | Fujifilm Corporation | Electroluminescent fluorescent substance |
| WO2006046564A1 (en) * | 2004-10-25 | 2006-05-04 | Fujifilm Corporation | Electroluminescence phosphor and el element using the same |
-
1991
- 1991-02-27 JP JP3031170A patent/JP2994058B2/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5702643A (en) * | 1996-04-24 | 1997-12-30 | Osram Sylvania Inc. | ZnS:Cu electroluminescent phosphor and method of making same |
| US5711898A (en) * | 1996-04-24 | 1998-01-27 | Osram Sylvania Inc. | Improved blue-green emitting ZnS:Cu,Cl electroluminescent phosphor and method of making same |
| US6682664B1 (en) | 2002-09-05 | 2004-01-27 | Osram Sylvania Inc. | High brightness orange-yellow-emitting electroluminescent phosphor and method of making |
| JP2006063317A (en) * | 2004-06-24 | 2006-03-09 | Fuji Photo Film Co Ltd | Electroluminescent phosphor |
| JP2007299607A (en) * | 2006-04-28 | 2007-11-15 | Fujifilm Corp | Inorganic dispersion-type electroluminescent element |
| JP2007299606A (en) * | 2006-04-28 | 2007-11-15 | Fujifilm Corp | Distributed type electroluminescence element |
| EP2090640A1 (en) | 2008-01-18 | 2009-08-19 | Fujifilm Corporation | Inorganic phosphor |
| RU2672708C2 (en) * | 2013-12-19 | 2018-11-19 | Бундесдруккерай Гмбх | Zinc-sulphide phosphor having photo- and electroluminescent properties, process for producing same, and security document, security feature and method for detecting same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2994058B2 (en) | 1999-12-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR100305405B1 (en) | Electroluminescence fluorescent-substance and organic-despersing type electroluminescent elememt using the one | |
| JP5813096B2 (en) | Phosphor for light emitting device, method for producing the same, and light emitting device using the same | |
| US5702643A (en) | ZnS:Cu electroluminescent phosphor and method of making same | |
| US20050189518A1 (en) | Method of producing a fluorescent particle | |
| JPH04270780A (en) | Electroluminescent fluorescent material | |
| JP4433793B2 (en) | Phosphor and light emitting device using the same | |
| US20050173675A1 (en) | Method of manufacturing a luminescent material | |
| US5711898A (en) | Improved blue-green emitting ZnS:Cu,Cl electroluminescent phosphor and method of making same | |
| JP2004331934A (en) | Fluorescent material and luminescent element using the same | |
| JP3904897B2 (en) | High-brightness electroluminescent phosphor and electroluminescent device using the same | |
| JP5014628B2 (en) | Phosphor, method of manufacturing the same, and lamp | |
| JP4786026B2 (en) | Long-life electroluminescent phosphor and electroluminescent device using the same | |
| JP2002188084A (en) | Red light-emitting phosphor and light-emitting apparatus using the same | |
| JP2004231770A (en) | Red light-emitting phosphor and light emitter | |
| JP4886221B2 (en) | Method for manufacturing light emitting device | |
| JPH04270779A (en) | Dispersion-type el fluorescent material | |
| JPH11172245A (en) | Electroluminescent phosphor and electroluminescent panel | |
| JP3673120B2 (en) | Electroluminescent phosphor and organic dispersion type electroluminescent device using the same | |
| JP4156915B2 (en) | Electroluminescent phosphor and organic dispersion type electroluminescent device using the same | |
| JPH026589A (en) | Electroluminescent phosphor and electroluminescent element | |
| JPH0794658B2 (en) | High color rendering fluorescent lamp | |
| JPS621778A (en) | Fluorescent material | |
| US3389089A (en) | Blue electroluminescent phosphor and method for its production | |
| JP5989775B2 (en) | Phosphor, method for manufacturing the same, and light emitting device using the same | |
| JPH02173086A (en) | Electroluminescent phosphor and electroluminescent element |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 19991005 |
|
| LAPS | Cancellation because of no payment of annual fees |