JPH0458158B2 - - Google Patents
Info
- Publication number
- JPH0458158B2 JPH0458158B2 JP61052473A JP5247386A JPH0458158B2 JP H0458158 B2 JPH0458158 B2 JP H0458158B2 JP 61052473 A JP61052473 A JP 61052473A JP 5247386 A JP5247386 A JP 5247386A JP H0458158 B2 JPH0458158 B2 JP H0458158B2
- Authority
- JP
- Japan
- Prior art keywords
- film
- light
- emitting layer
- activating material
- activating
- 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 - Lifetime
Links
- 239000000463 material Substances 0.000 claims description 24
- 239000010408 film Substances 0.000 claims description 20
- 230000003213 activating effect Effects 0.000 claims description 19
- 239000010409 thin film Substances 0.000 claims description 5
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 229910052976 metal sulfide Inorganic materials 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- 229910052693 Europium Inorganic materials 0.000 claims description 3
- 229910052772 Samarium Inorganic materials 0.000 claims description 3
- 229910052771 Terbium Inorganic materials 0.000 claims description 3
- 229910052775 Thulium Inorganic materials 0.000 claims description 3
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 239000011159 matrix material Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 238000004544 sputter deposition Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 229910021645 metal ion Inorganic materials 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000000295 emission spectrum Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002488 metal-organic chemical vapour deposition Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 230000004913 activation Effects 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005090 crystal field Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005566 electron beam evaporation Methods 0.000 description 1
- 239000002784 hot electron Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000000927 vapour-phase epitaxy Methods 0.000 description 1
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は薄膜EL素子に関するもので、特に発
光層母体材料として混合物質を用いることによつ
て、発光色の調整を行ない、同時に発光ムラが少
なく安定な素子を得るものである。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a thin-film EL device, and in particular, by using a mixed substance as a matrix material for the emitting layer, the color of emitted light can be adjusted, and at the same time unevenness in emitted light can be prevented. The purpose is to obtain a stable element with a small amount of oxidation.
従来技術では、付活物質を変えて発光色を変え
ることが一般に行なわれていて、発光色の調整は
特開昭54−155789号公報に記載のように、付活物
質を変えた発光層を積層して用いたり、或いは発
光色の異なる複数のEL素子を積み重ねて用いた
りしていた。しかし、母体材料と付活物質におけ
る金属イオン半径の食い違いのために、付活物質
の最適な混合濃度がきわめて低く、また母体材料
中に付活物質を均一に分散させることが困難であ
つた。
In conventional technology, it is common practice to change the emitted light color by changing the activating material, and the emitting color can be adjusted by using a light emitting layer with a different activating material, as described in Japanese Patent Application Laid-Open No. 155789/1989. They have been used in stacked layers, or in stacks of multiple EL elements that emit light of different colors. However, due to the difference in metal ion radius between the base material and the activating material, the optimal mixing concentration of the activating material is extremely low, and it has been difficult to uniformly disperse the activating material in the base material.
従来技術では、付活物質を変えることによつて
発光色を変えることが一般に行なわれており、発
光色の調整は、複数の付活物質混入や、発光色の
異なる発光層又はEL素子の積層によつて実現さ
れていた。しかし、母体材料の金属Zn、Ca、Sr、
Baと、付活物質Mn、Tb、Tm、Sm、Ce、Eu、
Pr等とのイオン半径の食い違いのため、付活物
質の最適な混合濃度はきわめて低く、均一な拡散
をさせることが困難であつた。本発明の目的は、
この困難を除いて付活物質の均一拡散を容易にす
ることにより発光ムラを少なくし安定な素子を
得、同時に発光色の調整を可能とすることにあ
る。
In conventional technology, the color of emitted light is generally changed by changing the activating material, and the color of emitted light can be adjusted by mixing multiple activating materials or stacking emitting layers or EL elements with different emitting colors. It was realized by. However, the base material metals Zn, Ca, Sr,
Ba and activating materials Mn, Tb, Tm, Sm, Ce, Eu,
Due to the discrepancy in ionic radius with Pr, etc., the optimal mixed concentration of the activating material was extremely low, making it difficult to achieve uniform diffusion. The purpose of the present invention is to
The object of the present invention is to eliminate this difficulty and facilitate the uniform diffusion of the activating material, thereby reducing uneven light emission and obtaining a stable element, and at the same time making it possible to adjust the color of the emitted light.
本発明の薄膜EL素子は、少なくとも一方が光
透過性を有する電極の間に、絶縁膜、発光層及び
絶縁膜を順に積層してなるものであつて、発光層
が、ZnS、CaS、SrS及びBaSから選ばれた二種
類以上の金属硫化物と、Mn、Tm、Tb、Sm、
Pr、Eu及びCeから選ばれた付活物質とを有する
ものである。そして、硫化物の金属のイオン半径
が、付活物質のイオン半径を間にはさむ形で選択
されることを特徴とする。
The thin film EL device of the present invention is formed by laminating an insulating film, a light-emitting layer, and an insulating film in this order between electrodes, at least one of which is transparent. Two or more metal sulfides selected from BaS, Mn, Tm, Tb, Sm,
It has an activating material selected from Pr, Eu and Ce. The method is characterized in that the ionic radius of the metal sulfide is selected to sandwich the ionic radius of the activating material.
発光層母体材料として用いられる硫化物の金属
イオン半径は、それぞれZn2+0.74Å、Ca2+0.09
Å、Sr2+1.12Å、Ba2+1.34Åであつて、付活物質
の金属イオン半径は、例えば、Mn2+0.80Å、
Tm3+0.87Å、Tb3+0.92Å、Sm3+0.96Å、
Pr3+1.01Å、Eu2+1.09Å、Ce3+1.03Åである。こ
のように、これら付活物質の金属イオン半径はい
ずれもZnとBaの中間にあるため、ZnS、CaS、
SrS、BaSのうちから付活物質のイオン半径を間
にはさむ形（例えばZn2+＜Mn2+＜Ba2+）で、２
種以上の混合母体物質を選択して膜を作製した場
合、これら付活物質を容易に混合膜中の異種金属
硫化物格子間に取り込む（例えば（CaS）−Ce−
（SrS）などの形）ため、より多量の付活物質を
安定に混入することが可能となる。又、膜中の結
晶場の変化に由来して、発光中心の励起を行なう
ホツトエレクトロンのエネルギー分布を変え得る
ため、母体混合比を変えることによつて発光色を
変えることが可能となる。
The metal ion radius of the sulfide used as the host material for the emissive layer is Zn 2+ 0.74 Å and Ca 2+ 0.09 Å, respectively.
Å, Sr 2+ 1.12 Å, Ba 2+ 1.34 Å, and the metal ion radius of the activating material is, for example, Mn 2+ 0.80 Å,
Tm 3+ 0.87Å, Tb 3+ 0.92Å, Sm 3+ 0.96Å,
Pr 3+ 1.01 Å, Eu 2+ 1.09 Å, Ce 3+ 1.03 Å. In this way, the metal ion radius of these activating materials is between Zn and Ba, so ZnS, CaS,
SrS or BaS, with the ionic radius of the activation material in between (for example, Zn 2+ < Mn 2+ < Ba 2+
When a film is prepared by selecting a mixed matrix material of more than one species, these activating materials can be easily incorporated between the different metal sulfide lattices in the mixed film (for example, (CaS)-Ce-
(forms such as SrS)), it is possible to stably incorporate a larger amount of activating material. Furthermore, because the energy distribution of hot electrons that excite the luminescent center can be changed due to changes in the crystal field in the film, it is possible to change the emission color by changing the matrix mixing ratio.
以下、本発明の一実施例を第１図により説明す
る。第１図はCaS−SrSの混合膜に、Ceを付加し
た発光層を持つ二重絶縁薄膜EL素子の断面図で
ある。コーニング＃7059ガラス基板１上に、ITO
透明電極２を膜厚2000Å程度で形成する。次に、
Ta2O5、10wt％SiO2からなる厚さ5000Åの第１
絶縁層３をスパツタリング法で形成し、その上に
（Ca、Sr）Ｓ：Ceの発光層４をスパツタリング法
で形成する（原子数比Ca：Sr：Ce＝50：50：
１）。ここで、イオン半径はCa＜Ce＜Srである。
その上にTa2O5・10wt％SiO2からなる厚さ5000
Åの第２絶縁層５をスパツタリング法で形成す
る。その上に、2000Å厚のAl膜６を背部電極と
して蒸着する。Al−ITO間に1KHz、200V正弦波
を印加することにより発光が得られる。
An embodiment of the present invention will be described below with reference to FIG. FIG. 1 is a cross-sectional view of a double insulating thin film EL device having a light-emitting layer made of a CaS-SrS mixed film with Ce added thereto. ITO on Corning #7059 glass substrate 1
The transparent electrode 2 is formed with a film thickness of about 2000 Å. next,
A 5000 Å thick first layer consisting of Ta 2 O 5 and 10 wt% SiO 2
An insulating layer 3 is formed by a sputtering method, and a light emitting layer 4 of (Ca, Sr)S:Ce is formed thereon by a sputtering method (atomic ratio Ca:Sr:Ce=50:50:
1). Here, the ionic radius is Ca<Ce<Sr.
On top of that, a thickness of 5000 consisting of Ta2O5・10wt% SiO2
A second insulating layer 5 having a thickness of .ANG. is formed by sputtering. A 2000 Å thick Al film 6 is deposited thereon as a back electrode. Light emission can be obtained by applying a 1KHz, 200V sine wave between Al and ITO.
第２図は、本実施例素子と、CaS：Ce、SrS：
Ceをそれぞれ発光層に用いた素子との、発光ス
ペクトルの比較である。７はCaS：Ce、８は本
実施例、９はSrS：Ceの発光層の素子により実現
されるスペクトルであり、本実施例の素子は
CaS：Ce、SrS：Ceの中間の発色を示す。 Figure 2 shows the device of this example, CaS:Ce, SrS:
This is a comparison of the emission spectra with devices using Ce in their respective light-emitting layers. 7 is a spectrum realized by a device with a light emitting layer of CaS:Ce, 8 is a spectrum of this example, and 9 is a spectrum realized by a device with a light emitting layer of SrS:Ce, and the device of this example is
Shows a color intermediate between CaS:Ce and SrS:Ce.
本実施例の発光層は、２元スパツタリング法を
用いた膜であるが、それ以外に、２元電子ビーム
蒸着法や、MBE法、気相成長法、MOCVD法を
用いて混合母体の発光層を形成することが可能で
ある。又、Ｆ、Ｐ、Clなどの共付活剤を適宜用い
ることによつて輝度の向上が得られる点は、従来
技術と同様である。 The light-emitting layer in this example is a film formed using a binary sputtering method, but other methods may also be used to form a light-emitting layer of a mixed matrix using a binary electron beam evaporation method, an MBE method, a vapor phase epitaxy method, or an MOCVD method. It is possible to form Further, as in the prior art, brightness can be improved by appropriately using a co-activator such as F, P, or Cl.
MOCVD法やMBE法など、単原子膜作製技術
を用いて第３図のような混合膜を作成した場合、
スパツタリング法やEB蒸着法と比較して、飛躍
的な輝度向上が得られる。 When a mixed film like the one shown in Figure 3 is created using monoatomic film manufacturing technology such as MOCVD or MBE,
Compared to the sputtering method and EB evaporation method, a dramatic improvement in brightness can be obtained.
第３図は、上記方法で作製する発光層（Zn、
Ca）Ｓ：Mnの模式図であり、１０はＳ原子、１
１はZn原子、１２はMn原子、１３はCa原子に対
応している。ここで、イオン半径はZn＜Mn＜Ca
である。上記の単原子膜作製技術により膜を作製
した場合は、混合膜を単結晶的に成長させること
が可能になるために、スパツタリング法やEB蒸
着法で混合膜を作製した場合に生じた、混合によ
る結晶性の低下と、それに伴う輝度低下が生じ
ず、良好なEL素子を得ることができる。 Figure 3 shows the light-emitting layer (Zn,
Ca) S:Mn schematic diagram, where 10 is an S atom, 1
1 corresponds to a Zn atom, 12 to a Mn atom, and 13 to a Ca atom. Here, the ionic radius is Zn<Mn<Ca
It is. When a film is fabricated using the above-mentioned monoatomic film fabrication technology, it is possible to grow the mixed film in a single-crystal manner, so that the mixture that occurs when the mixed film is fabricated using the sputtering method or the EB evaporation method can be avoided. Therefore, a good EL element can be obtained without a decrease in crystallinity due to oxidation and a corresponding decrease in brightness.
本発明によれば、混合母体の混合比を変えるこ
とにより、発光色を変えることが可能である。同
時に、従来より多量の付活物質を安定に混入する
ことが可能となり、発光ムラが少なく、安定な発
光素子が得られる。
According to the present invention, it is possible to change the luminescent color by changing the mixing ratio of the mixed matrix. At the same time, it becomes possible to stably incorporate a larger amount of activating material than before, and a stable light-emitting element with less uneven light emission can be obtained.
第１図は本発明の一実施例として挙げた二重絶
縁EL素子の断面図、第２図は本発明素子と単一
母体物質を用いた素子との発光スペクトルの比較
線図、第３図は他の実施例による混合膜の形成図
である。
１……コーニング＃7059ガラス基板、２……
ITO電極、３……Ta2O5・10wt％SiO絶縁膜、４
……（Ca、Sr）Ｓ：Ce発光層、５……Ta2O5・
10wt％SiO2絶縁膜、６……Al電極、７……
CaS：Ce発光層を用いた素子の発光スペクトル。
Figure 1 is a cross-sectional view of a double-insulated EL element as an example of the present invention, Figure 2 is a comparison diagram of the emission spectra of the element of the present invention and an element using a single matrix material, and Figure 3. FIG. 3 is a diagram showing the formation of a mixed film according to another example. 1... Corning #7059 glass substrate, 2...
ITO electrode, 3...Ta 2 O 5・10wt% SiO insulation film, 4
...(Ca, Sr)S: Ce luminescent layer, 5...Ta 2 O 5・
10wt% SiO 2 insulating film, 6... Al electrode, 7...
Emission spectrum of a device using a CaS:Ce emissive layer.
Claims (1)
に、絶縁膜、発光層及び絶縁膜を順に積層してな
る薄膜EL素子において、 前記発光層が、ZnS、CaS、SrS及びBaSから
選ばれた二種類以上の金属硫化物と、Mn、Tm、
Tb、Sm、Pr、Eu及びCeから選ばれた付活物質
とを有し、 前記硫化物の金属のイオン半径が、前記付活物
質のイオン半径を間にはさむ形で選択されること
を特徴とする薄膜EL素子。[Claims] 1. A thin-film EL device comprising an insulating film, a light-emitting layer, and an insulating film stacked in this order between electrodes, at least one of which is optically transparent, wherein the light-emitting layer includes ZnS, CaS, SrS, or Two or more metal sulfides selected from BaS, Mn, Tm,
and an activating material selected from Tb, Sm, Pr, Eu, and Ce, and characterized in that the ionic radius of the metal of the sulfide is selected such that the ionic radius of the activating material is sandwiched therebetween. Thin-film EL device.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61052473A JPS62211897A (en) | 1986-03-12 | 1986-03-12 | Thin film el device |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61052473A JPS62211897A (en) | 1986-03-12 | 1986-03-12 | Thin film el device |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62211897A JPS62211897A (en) | 1987-09-17 |
| JPH0458158B2 true JPH0458158B2 (en) | 1992-09-16 |
Family
ID=12915688
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61052473A Granted JPS62211897A (en) | 1986-03-12 | 1986-03-12 | Thin film el device |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62211897A (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6319797A (en) * | 1986-07-14 | 1988-01-27 | 東ソー株式会社 | Thin film el device |
| RU2108355C1 (en) * | 1997-01-17 | 1998-04-10 | Институт неорганической химии СО РАН | Inorganic pigment on the base of sulfide of metal and method for its production |
| JP2002231151A (en) * | 2001-01-30 | 2002-08-16 | Hitachi Ltd | Image display device |
| US8089015B2 (en) * | 2008-05-01 | 2012-01-03 | Dell Products L.P. | Keyboard with integrated electroluminescent illumination |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61260593A (en) * | 1985-05-15 | 1986-11-18 | 富士通株式会社 | Manufacture of el thin film |
-
1986
- 1986-03-12 JP JP61052473A patent/JPS62211897A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61260593A (en) * | 1985-05-15 | 1986-11-18 | 富士通株式会社 | Manufacture of el thin film |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62211897A (en) | 1987-09-17 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |