JP2739803B2 - Inorganic thin film EL device - Google Patents
Inorganic thin film EL deviceInfo
- Publication number
- JP2739803B2 JP2739803B2 JP4358049A JP35804992A JP2739803B2 JP 2739803 B2 JP2739803 B2 JP 2739803B2 JP 4358049 A JP4358049 A JP 4358049A JP 35804992 A JP35804992 A JP 35804992A JP 2739803 B2 JP2739803 B2 JP 2739803B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- inorganic thin
- thin film
- light
- metal
- 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.)
- Expired - Fee Related
Links
- 239000010409 thin film Substances 0.000 title claims description 24
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 17
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 11
- -1 rare earth compound Chemical class 0.000 claims description 9
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 8
- 239000011701 zinc Substances 0.000 claims description 8
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 6
- 229910052731 fluorine Inorganic materials 0.000 claims description 6
- 239000011737 fluorine Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 229910052693 Europium Inorganic materials 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 229910052771 Terbium Inorganic materials 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 3
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 3
- 229910052772 Samarium Inorganic materials 0.000 claims description 3
- 229910052775 Thulium Inorganic materials 0.000 claims description 3
- 239000011575 calcium Substances 0.000 claims description 3
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims description 3
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 claims description 3
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 3
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 claims description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 2
- 229910052691 Erbium Inorganic materials 0.000 claims description 2
- 229910052689 Holmium Inorganic materials 0.000 claims description 2
- 229910052779 Neodymium Inorganic materials 0.000 claims description 2
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052790 beryllium Inorganic materials 0.000 claims description 2
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 229910052793 cadmium Inorganic materials 0.000 claims description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 claims description 2
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 claims description 2
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052740 iodine Inorganic materials 0.000 claims description 2
- 239000011630 iodine Substances 0.000 claims description 2
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 claims description 2
- 229910052712 strontium Inorganic materials 0.000 claims description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 2
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 12
- 239000000758 substrate Substances 0.000 description 11
- 239000004065 semiconductor Substances 0.000 description 10
- 239000008188 pellet Substances 0.000 description 6
- 229910052984 zinc sulfide Inorganic materials 0.000 description 6
- 238000010894 electron beam technology Methods 0.000 description 5
- 239000010408 film Substances 0.000 description 5
- 229910004261 CaF 2 Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000012190 activator Substances 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 description 2
- TYIZUJNEZNBXRS-UHFFFAOYSA-K trifluorogadolinium Chemical compound F[Gd](F)F TYIZUJNEZNBXRS-UHFFFAOYSA-K 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- BHHYHSUAOQUXJK-UHFFFAOYSA-L zinc fluoride Chemical compound F[Zn]F BHHYHSUAOQUXJK-UHFFFAOYSA-L 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 description 1
- 108091006149 Electron carriers Proteins 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- KUKHGSCDQCAFMM-UHFFFAOYSA-L difluoroerbium Chemical compound F[Er]F KUKHGSCDQCAFMM-UHFFFAOYSA-L 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 238000005566 electron beam evaporation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 238000002488 metal-organic chemical vapour deposition Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229920003227 poly(N-vinyl carbazole) Polymers 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- QGJSAGBHFTXOTM-UHFFFAOYSA-K trifluoroerbium Chemical compound F[Er](F)F QGJSAGBHFTXOTM-UHFFFAOYSA-K 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Electroluminescent Light Sources (AREA)
- Luminescent Compositions (AREA)
Description
【0001】[0001]
【産業上の利用分野】本発明は、無機蛍光体を用いた無
機薄膜エレクトロルミネッセンス素子(以下、EL素子
という。)に関し、さらに詳しくは、平面光源やディス
プレイ等に利用される無機蛍光体を用いた無機薄膜EL
素子に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an inorganic thin-film electroluminescence device (hereinafter referred to as an EL device) using an inorganic phosphor, and more particularly, to an inorganic phosphor used for a flat light source or a display. Inorganic thin film EL
Related to the element.
【0002】[0002]
【従来の技術】無機薄膜EL素子は、フラットパネルデ
ィスプレイ或いは平面光源として注目され、これまで
に、ZnS,CaS,SrS等の少なくとも1つを母材
とし、Mn,Tb,Sn,Ce,Eu,Sm,Tm等の
少なくとも1つを発光中心として5wt%以下の量ドー
プした無機蛍光体が用いられている。これらのうち、橙
色蛍光体としては、ZnS:Mnが研究され、その輝
度、寿命などの特性が優れているため、フラットパネル
ディスプレイとして利用されている。また、緑色発光蛍
光体についてはZnS:Tbなど、亜鉛硫化物の研究が
広く行われている。その他の母体として、青色発光蛍光
体としてはSrS:Ce、赤色発光蛍光体としてはCa
S:Eu、緑色発光蛍光体としてはCaS:Ceなど、
アルカリ土類金属硫化物からなる蛍光体も盛んに研究さ
れている。2. Description of the Related Art Inorganic thin-film EL elements have attracted attention as flat panel displays or flat light sources. Until now, at least one of ZnS, CaS, SrS and the like has been used as a base material, and Mn, Tb, Sn, Ce, Eu, and Eu have been used. An inorganic phosphor doped with at least one of Sm, Tm and the like as an emission center in an amount of 5 wt% or less is used. Of these, ZnS: Mn has been studied as an orange phosphor, and is used as a flat panel display because of its excellent properties such as brightness and life. As for the green light emitting phosphor, research on zinc sulfide such as ZnS: Tb has been widely conducted. Other base materials include SrS: Ce as a blue light-emitting phosphor and Ca as a red light-emitting phosphor.
S: Eu, green light emitting phosphor such as CaS: Ce,
Phosphors composed of alkaline earth metal sulfides have also been actively studied.
【0003】また、蛍光体の発光メカニズムについて
は、遷移金属(Mn)は直接、母体の電子が衝突して発
光するものであるのに対して、希土類元素では母体のバ
ンドギャップに対応するエネルギーが遷移して発光する
割合が大きくなる。アルカリ土類金属の硫化物は、その
バンドギャップエネルギーが4.3〜4.4eVであ
り、ZnSも3.6eVと少なく、高エネルギーが必要
となる青色〜紫外の発光を得るためには、バンドギャッ
プエネルギーが小さい。したがって、青色〜紫外の発光
を得るために、高バンドギャップエネルギーを持つZn
F2 :Gd(7〜8eV)を母体としたり(J.J.
A.P.vol.10B.(1991)pp.L181
5−l1816)、CaF2 :Euを母体とする(Ap
pl.Phys.Lett.41.1982.P.46
2)ことが研究されている。[0003] Regarding the light emission mechanism of a phosphor, transition metal (Mn) emits light by direct collision of a parent electron, whereas the energy corresponding to the band gap of the parent element is rare earth element. The ratio of light emission after transition increases. Alkaline earth metal sulfides have a band gap energy of 4.3 to 4.4 eV, a small amount of ZnS of 3.6 eV, and have a band gap in order to obtain blue to ultraviolet light that requires high energy. The gap energy is small. Therefore, in order to obtain blue to ultraviolet light emission, Zn having a high band gap energy
F 2 : Gd (7 to 8 eV) as a base material (JJ.
A. P. vol. 10B. (1991) pp. L181
5-11816), with CaF 2 : Eu as the parent (Ap
pl. Phys. Lett. 41.1982. P. 46
2) is being studied.
【0004】[0004]
【発明が解決しようとする課題】ところで、ZnS:M
nを除き、これらの硫化物を用いた無機蛍光体は、その
発光輝度、効率、寿命がフラットパネルディスプレイ或
いは平面光源として利用するために十分でなく、現在実
用的なカラーフラットパネルディスプレイは形成されて
いない。本発明は、以上述べたような従来の事情に対処
してなされたものであって、その目的は、実用レベルで
フルカラー表示の可能な無機薄膜EL素子を提供するこ
とにある。By the way, ZnS: M
Except for n, inorganic phosphors using these sulfides have insufficient luminous brightness, efficiency, and lifetime to be used as flat panel displays or flat light sources, and currently practical color flat panel displays are formed. Not. The present invention has been made in view of the above-described conventional circumstances, and an object of the present invention is to provide an inorganic thin film EL device capable of performing full-color display at a practical level.
【0005】[0005]
【課題を解決するための手段】本発明者は、第IIb族金
属フッ素化物に希土類元素を添加すると、紫外から赤外
までの範囲の発光が得られるという知見を得、この知見
に基づいて本発明を完成するに至った。本発明の無機薄
膜EL素子は、第II族金属のフッ素化物に希土類元素ま
たはその化合物を添加した組成物より形成された発光層
を有し、該発光層中の第II族金属のフッ素化物が、式:
M1+x F2-y (ただし、Mは第II族金属を表わし、xは
0.001〜0.9を表わし、yは0.001〜1.8
を表わす。)で示されることを特徴とする。Means for Solving the Problems The present inventor has found that when a rare earth element is added to a fluoride of a Group IIb metal, light emission in the range from ultraviolet to infrared can be obtained. The invention has been completed. The inorganic thin film EL device of the present invention has a light emitting layer formed from a composition obtained by adding a rare earth element or a compound thereof to a fluoride of a group II metal, and a fluoride of the group II metal in the light emitting layer is used. ,formula:
M 1 + x F 2-y (where M represents a Group II metal, x represents 0.001 to 0.9, and y represents 0.001 to 1.8
Represents ).
【0006】以下、本発明の無機薄膜EL素子について
詳細に説明する。本発明において、発光層は、無機蛍光
体として、第II族金属のフッ素化物に希土類元素または
その化合物を添加した組成物より形成され、そして形成
された発光層中において、第II族金属のフッ素化物は、
上記式で示されるように、第II族金属の含有量が化学量
論的組成比からずれて多くなっている。その結果、発光
層におけるエレクトロンキャリアーの濃度を増加させる
ことが可能になり、したがって、ホールの注入層を設け
ることができる。本発明において、第II族金属とフッ素
との組成比、すなわち、上記式中のxおよびyの好まし
い範囲は、それぞれx=0.2〜0.6、y=0.4〜
1.2である。Hereinafter, the inorganic thin film EL device of the present invention will be described in detail. In the present invention, the light-emitting layer is formed from a composition obtained by adding a rare earth element or a compound thereof to a fluoride of a group II metal as an inorganic phosphor, and in the formed light-emitting layer, fluorine of a group II metal is used. The monsters
As shown by the above formula, the content of the Group II metal increases from the stoichiometric composition ratio. As a result, the electron carrier concentration in the light emitting layer can be increased, and therefore, a hole injection layer can be provided. In the present invention, the composition ratio of Group II metal and fluorine, that is, the preferred ranges of x and y in the above formula are x = 0.2 to 0.6 and y = 0.4 to respectively.
1.2.
【0007】本発明において、第II族金属としては、カ
ドミウム、亜鉛、ストロンチウム、カルシウム、バリウ
ムおよびベリリウムがあげられ、これらの金属の少なく
とも一種のフッ素化物が使用できる。In the present invention, the Group II metals include cadmium, zinc, strontium, calcium, barium and beryllium, and at least one fluoride of these metals can be used.
【0008】また、上記第II族金属のフッ素化物に添加
される希土類元素としては、セリウム、プラセオジウ
ム、ネオジウム、サマリウム、ユウロピウム、ガドリニ
ウム、テルビウム、ジスプロシウム、ホルミウム、エル
ビウム、ツリウムおよびイッテルビウムがあげられ、そ
れら希土類元素および希土類化合物の少なくとも一種が
添加される。希土類化合物としては、弗素、塩素、臭
素、よう素および酸素のうち少なくとも1つを含む化合
物が使用される。本発明において使用することができる
希土類化合物の具体例としては、例えば、弗化ガドリニ
ウム、弗化エルビウム、酸化ネオジウム等があげられ
る。The rare earth element added to the fluoride of the Group II metal includes cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium and ytterbium. At least one of a rare earth element and a rare earth compound is added. As the rare earth compound, a compound containing at least one of fluorine, chlorine, bromine, iodine and oxygen is used. Specific examples of the rare earth compound that can be used in the present invention include gadolinium fluoride, erbium fluoride, neodymium oxide, and the like.
【0009】本発明の無機薄膜EL素子において、上記
の材料を用いて発光層を形成するためには、加圧焼結
法、共付活剤、例えば、金或いは亜鉛等の低融点金属を
用いて加圧固着したペレットを用い、真空蒸着法、スパ
ッタ法、CVD法、MOCVD法などの気相法によって
形成することができる。本発明において、発光層を形成
する場合、基板温度、製膜雰囲気等を制御することによ
り、発光層中における第II族金属とフッ素の含有量を化
学量論的組成比からずらせることができる。In the inorganic thin film EL device of the present invention, in order to form a light emitting layer using the above materials, a pressure sintering method, a co-activator, for example, using a low melting point metal such as gold or zinc. It can be formed by a gas phase method such as a vacuum evaporation method, a sputtering method, a CVD method, and an MOCVD method using the pellets fixed by pressure. In the present invention, when forming the light emitting layer, the content of the Group II metal and fluorine in the light emitting layer can be shifted from the stoichiometric composition ratio by controlling the substrate temperature, the film formation atmosphere, and the like. .
【0010】本発明の無機薄膜素子は、上記発光層を有
するものであれば、その層構成は特に限定されるもので
はなく、例えば、図1および図2で示される構造を有す
るものをあげることができる。図1においては、絶縁性
基板1の上に、背面電極2、絶縁層3、発光層4、絶縁
層3および透明電極5を順次設けた構造を有し、図2に
おいては、透明基板6上に透明電極5、絶縁層3、発光
層4、絶縁層3および背面電極2を順次設けた構造を有
している。また、絶縁性基板の上に、背面電極、絶縁
層、半導体層、発光層、半導体層、絶縁層および透明電
極を順次設けた構造を有していてもよい。The layer structure of the inorganic thin-film element of the present invention is not particularly limited as long as it has the above-mentioned light-emitting layer. For example, an element having the structure shown in FIGS. Can be. 1 has a structure in which a back electrode 2, an insulating layer 3, a light emitting layer 4, an insulating layer 3, and a transparent electrode 5 are sequentially provided on an insulating substrate 1. In FIG. A transparent electrode 5, an insulating layer 3, a light emitting layer 4, an insulating layer 3, and a back electrode 2 are sequentially provided. Further, a structure may be employed in which a back electrode, an insulating layer, a semiconductor layer, a light emitting layer, a semiconductor layer, an insulating layer, and a transparent electrode are sequentially provided on an insulating substrate.
【0011】絶縁層としては、ZnF2 、CaF2 、M
gF2 、SiNx 、TaOx 、Al2 O3 、Y2 O3 、
PbTiO3 等を用いることができ、これらを二重にし
て用いてもよい。また、半導体層は、発光の輝度を向上
させるためのキャリアの注入層として作用する。これら
の半導体としては、水素化アモルファスシリコン、Ca
S,MgSなどのI−VII 化合物半導体、HgI2 など
のII−VI化合物半導体、AlAs,GaNなどのIII −
V化合物半導体、TiO2 、SnO2 などのIV−VI化合
物半導体、As2 O3 ,Bi2 O3 などのV−VI化合物
半導体、ポリビニルカルバゾール等の有機半導体があげ
られる。As the insulating layer, ZnF 2 , CaF 2 , M
gF 2 , SiN x , TaO x , Al 2 O 3 , Y 2 O 3 ,
PbTiO 3 or the like can be used, and these may be used in duplicate. Further, the semiconductor layer functions as a carrier injection layer for improving luminance of light emission. These semiconductors include hydrogenated amorphous silicon, Ca
I-VII compound semiconductors such as S and MgS; II-VI compound semiconductors such as HgI 2;
Examples thereof include V compound semiconductors, IV-VI compound semiconductors such as TiO 2 and SnO 2 , V-VI compound semiconductors such as As 2 O 3 and Bi 2 O 3, and organic semiconductors such as polyvinyl carbazole.
【0012】本発明の無機薄膜EL素子は、キャリア濃
度が高いため、駆動する電圧として直流または低周波の
交流を使用することができ、特に直流が好ましく、回路
設計が容易になるという利点がある。Since the inorganic thin film EL device of the present invention has a high carrier concentration, a direct current or a low frequency alternating current can be used as a driving voltage. Particularly, a direct current is preferable, and there is an advantage that circuit design becomes easy. .
【0013】本発明の無機薄膜EL素子においては、無
機蛍光体よりなる発光層が強いEL発光強度を示し、そ
して、その発光は、添加される希土類元素の種類によっ
て種々変化する。例えば、ガドリニウムを添加すること
によって紫色光が、プラセオジウムを添加することによ
って青色光が、テルビウムを添加することによって緑色
光が、また、ユウロピウムを添加することによって橙色
光が得られる。したがって、添加する希土類元素または
希土類化合物を換えることによって種々の発光色を得る
ことが可能であり、フルカラー化が可能になる。In the inorganic thin-film EL device of the present invention, the light-emitting layer composed of an inorganic phosphor exhibits a high EL light-emitting intensity, and the light emission varies variously depending on the type of the rare-earth element added. For example, adding gadolinium gives purple light, adding praseodymium gives blue light, adding terbium gives green light, and adding europium gives orange light. Therefore, various emission colors can be obtained by changing the rare earth element or the rare earth compound to be added, and full color can be obtained.
【0014】[0014]
【実施例】実施例1 弗化ガドリニウム10wt%を弗化亜鉛89wt%に混
入し、共付活剤としてAu1wt%を加えて800kg
/cm2 にて加圧固着し、蒸着用ペレットとした。この
ペレットを用いて、図1に示す層構成の無機薄膜EL素
子を作製した。すなわち、絶縁性基板上1に形成された
Al電極上2に、Ta2 O5 を電子ビームで2000オ
ングストロームの厚さに蒸着して絶縁層3を形成し、そ
の後、上記手順で得られたペレットを基板温度120℃
において電子ビームで蒸着して、厚さ7000オングス
トロームの無機蛍光層よりなる発光層4を形成した。S
EMEPMA測定によれば、Zn:Fの比が1.2:
1.8となっていた。また、この膜導電率を測定したと
ころ、基板温度200℃で成膜したもの(Zn:F=
1:2)に比べて2桁上昇した。その上にTa2 O5 を
電子ビームで2000オングストロームの厚さに蒸着し
て絶縁層3を形成し、さらにITOからなる透明電極膜
5を1000オングストロームの厚さに蒸着した。以上
のようにして得られた無機薄膜EL素子の発光特性を調
べたところ、312nm付近にピークをもつ、紫外の発
光が0.01mW/cm2 の強度で得られた。EXAMPLE 1 800 kg by mixing 10 wt% of gadolinium fluoride with 89 wt% of zinc fluoride and adding 1 wt% of Au as a co-activator.
/ Cm 2 to form a pellet for vapor deposition. Using the pellets, an inorganic thin film EL device having a layer configuration shown in FIG. 1 was produced. That is, on an Al electrode 2 formed on an insulating substrate 1, Ta 2 O 5 is vapor-deposited with an electron beam to a thickness of 2000 angstroms to form an insulating layer 3, and then the pellet obtained by the above procedure is formed. The substrate temperature is 120 ° C
Then, the light emitting layer 4 made of an inorganic fluorescent layer having a thickness of 7000 Å was formed by electron beam evaporation. S
According to the EMEPMA measurement, the Zn: F ratio was 1.2:
It was 1.8. When the film conductivity was measured, a film formed at a substrate temperature of 200 ° C. (Zn: F =
1: 2). On top of that, Ta 2 O 5 was vapor-deposited with an electron beam to a thickness of 2000 Å to form an insulating layer 3, and a transparent electrode film 5 made of ITO was vapor-deposited to a thickness of 1000 Å. When the emission characteristics of the inorganic thin film EL device obtained as described above were examined, ultraviolet emission having a peak at around 312 nm was obtained at an intensity of 0.01 mW / cm 2 .
【0015】実施例2 弗化エルビウム10wt%を弗化カドミウム90wt%
に混入し、800kg/cm2 にて加圧焼結し、蒸着用
ペレットとした。このペレットを用いて、図2に示す層
構成の無機薄膜EL素子を作製した。すなわち、ガラス
よりなる透明基板6上に形成されたITOからなる透明
導電5の上に、CaF2 を電子ビームによって蒸着して
厚さ2000オングストロームの絶縁層3を形成し、そ
の後、上記手順で得られたペレットを用い、基板温度1
50°Cで電子ビームによって蒸着し、厚さ7000オ
ングストロームの無機蛍光層よりなる発光層4を形成し
た。SEMEPMA測定により、この発光層4は、Cd
とFの比が1.5:1.3となっていた。また、この発
光層の導電率を測定したところ、基板温度200℃で成
膜したもの(Zn:F=1:2)に比べて1桁上昇し
た。その上にCaF2 を電子ビームによって蒸着して、
厚さ2000オングストロームの絶縁層3を形成し、さ
らに、Alよりなる背面電極2を1000オングストロ
ームの厚さに蒸着した。以上のようにして得られた無機
薄膜EL素子の発光特性を調べたところ、緑色の発光が
0.01mW/cm2 の強度で得られた。[0015] The 10wt% Example 2 fluoride erbium fluoride Kad Mi Umm 90wt%
And sintered under pressure at 800 kg / cm 2 to obtain pellets for vapor deposition. Using the pellets, an inorganic thin film EL device having a layer configuration shown in FIG. 2 was produced. That is, on a transparent conductive material 5 made of ITO formed on a transparent substrate 6 made of glass, CaF 2 is vapor-deposited by an electron beam to form an insulating layer 3 having a thickness of 2000 angstroms. Substrate temperature 1
Emission was performed by an electron beam at 50 ° C. to form a light-emitting layer 4 composed of an inorganic fluorescent layer having a thickness of 7000 Å. According to the SEMEPMA measurement, the light emitting layer 4 was found to have Cd
And F had a ratio of 1.5: 1.3. When the conductivity of the light emitting layer was measured, it was increased by one digit as compared with that of the film formed at a substrate temperature of 200 ° C. (Zn: F = 1: 2). CaF 2 is deposited thereon by an electron beam,
An insulating layer 3 having a thickness of 2000 angstroms was formed, and a back electrode 2 made of Al was deposited to a thickness of 1000 angstroms. When the light emission characteristics of the inorganic thin film EL device obtained as described above were examined, green light was emitted at an intensity of 0.01 mW / cm 2 .
【0016】[0016]
【発明の効果】本発明の無機薄膜EL素子は、上記の構
成の無機蛍光体よりなる発光層を有するから、従来のも
のよりも高輝度かつ長寿命で広範囲な波長領域の光を発
光し得るものとすることができる。したがって、本発明
の無機薄膜EL素子は、ディスプレイ等の平面光源とし
て極めて有用であり、その実用価値は高い。The inorganic thin-film EL device of the present invention has a light-emitting layer composed of the inorganic phosphor having the above-described structure, and can emit light in a wide wavelength range with higher luminance and longer life than the conventional device. Things. Therefore, the inorganic thin film EL element of the present invention is extremely useful as a flat light source for a display or the like, and its practical value is high.
【図1】 本発明の無機薄膜EL素子の一例の模式的断
面図である。FIG. 1 is a schematic sectional view of an example of an inorganic thin film EL device of the present invention.
【図2】 本発明の無機薄膜EL素子の他の一例の模式
的断面図である。FIG. 2 is a schematic sectional view of another example of the inorganic thin film EL device of the present invention.
1…絶縁性基板、2…背面電極、3…絶縁層、4…発光
層、5…透明電極、6…透明基板。DESCRIPTION OF SYMBOLS 1 ... Insulating substrate, 2 ... Back electrode, 3 ... Insulating layer, 4 ... Light emitting layer, 5 ... Transparent electrode, 6 ... Transparent substrate.
Claims (5)
たはその化合物を添加した組成物より形成された発光層
を有し、該発光層中の第II族金属のフッ素化物が、式:
M1+x F2-y (ただし、Mは第II族金属を表わし、xは
0.001〜0.9を表わし、yは0.001〜1.8
を表わす。)で示されることを特徴とする無機薄膜EL
素子。1. A light-emitting layer formed from a composition obtained by adding a rare earth element or a compound thereof to a fluoride of a group II metal, wherein the fluoride of the group II metal in the light-emitting layer has a formula:
M 1 + x F 2-y (where M represents a Group II metal, x represents 0.001 to 0.9, and y represents 0.001 to 1.8
Represents Inorganic thin film EL characterized by the following:
element.
ロンチウム、カルシウム、バリウムおよびベリリウムよ
りなる群から選択された少なくとも一種の元素からなる
請求項1記載の無機薄膜EL素子。2. The inorganic thin-film EL device according to claim 1, wherein the Group II metal comprises at least one element selected from the group consisting of cadmium, zinc, strontium, calcium, barium, and beryllium.
ム、プラセオジウム、ネオジウム、サマリウム、ユウロ
ピウム、ガドリニウム、テルビウム、ジスプロシウム、
ホルミウム、エルビウム、ツリウムおよびイッテルビウ
ムよりなる群から選択された少なくとも一種であること
を特徴とする請求項1記載の無機薄膜EL素子。3. The method according to claim 1, wherein the rare earth element added is cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium,
2. The inorganic thin film EL device according to claim 1, wherein the device is at least one selected from the group consisting of holmium, erbium, thulium, and ytterbium.
素、臭素、ヨウ素および酸素よりなる群から選択された
少なくとも1つの元素を含む請求項1記載の無機薄膜E
L素子。4. The inorganic thin film E according to claim 1, wherein the rare earth compound to be added contains at least one element selected from the group consisting of fluorine, chlorine, bromine, iodine and oxygen.
L element.
化物である請求項1記載の無機薄膜EL素子。 5. The fluorinated compound of Group II metal is fluorine of zinc.
The inorganic thin film EL device according to claim 1, which is a compound.
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP4358049A JP2739803B2 (en) | 1992-12-25 | 1992-12-25 | Inorganic thin film EL device |
US08/136,770 US5625255A (en) | 1992-12-25 | 1993-10-15 | Inorganic thin film electroluminescence device |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP4358049A JP2739803B2 (en) | 1992-12-25 | 1992-12-25 | Inorganic thin film EL device |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH06203961A JPH06203961A (en) | 1994-07-22 |
JP2739803B2 true JP2739803B2 (en) | 1998-04-15 |
Family
ID=18457277
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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JP4358049A Expired - Fee Related JP2739803B2 (en) | 1992-12-25 | 1992-12-25 | Inorganic thin film EL device |
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JP (1) | JP2739803B2 (en) |
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KR100537349B1 (en) | 1996-06-26 | 2006-02-28 | 오스람 게젤샤프트 미트 베쉬랭크터 하프퉁 | Light-emitting semiconductor component with luminescence conversion element |
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JPS5141687A (en) * | 1974-10-07 | 1976-04-08 | Matsushita Electric Ind Co Ltd | Denpahatsukoban |
PL93896B1 (en) * | 1974-10-10 | 1977-06-30 | ||
JPH0696862A (en) * | 1992-09-14 | 1994-04-08 | Fuji Xerox Co Ltd | Inorganic thin film el element |
JP2605570B2 (en) * | 1992-12-25 | 1997-04-30 | 富士ゼロックス株式会社 | Inorganic thin film EL device |
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1992
- 1992-12-25 JP JP4358049A patent/JP2739803B2/en not_active Expired - Fee Related
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