JPH0454209B2 - - Google Patents
Info
- Publication number
- JPH0454209B2 JPH0454209B2 JP58165506A JP16550683A JPH0454209B2 JP H0454209 B2 JPH0454209 B2 JP H0454209B2 JP 58165506 A JP58165506 A JP 58165506A JP 16550683 A JP16550683 A JP 16550683A JP H0454209 B2 JPH0454209 B2 JP H0454209B2
- Authority
- JP
- Japan
- Prior art keywords
- electrode
- display
- counter electrode
- electrochromic
- display element
- 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
- 239000002184 metal Substances 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000004065 semiconductor Substances 0.000 claims description 7
- 239000000758 substrate Substances 0.000 claims description 5
- 230000002093 peripheral effect Effects 0.000 claims 1
- 239000000463 material Substances 0.000 description 13
- 239000004020 conductor Substances 0.000 description 11
- 239000011521 glass Substances 0.000 description 9
- 230000006866 deterioration Effects 0.000 description 6
- 239000000975 dye Substances 0.000 description 5
- 239000010408 film Substances 0.000 description 5
- 238000006722 reduction reaction Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000003566 sealing material Substances 0.000 description 4
- 229910006404 SnO 2 Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- 229910000679 solder Inorganic materials 0.000 description 3
- 230000004075 alteration Effects 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 230000002411 adverse Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- -1 halogen ions Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000011356 non-aqueous organic solvent Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 150000003219 pyrazolines Chemical class 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000003115 supporting electrolyte Substances 0.000 description 1
- 230000002123 temporal effect Effects 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
Classifications
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect
- G02F1/153—Constructional details
- G02F1/155—Electrodes
Description
【発明の詳細な説明】
産業上の利用分野
本発明は時計、計測器、家電機器などの各種表
示用として利用されるエレクトロクロミツク表示
素子に関するものである。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to an electrochromic display element used for various displays such as watches, measuring instruments, and home appliances.
従来例の構成とその問題点
液晶と比較してエレクトロクロミツクデイスプ
レイは視角依存性がなく、色が明かるく、鮮明で
あるという特徴がある。エレクトロクロミツク材
料としては、無機物としてはWO3がよく知られ
ている、有機物としてはビオローゲンが最もよく
知られており、その他ピラゾリンやアントラキノ
ン類などの色素が知られている。Conventional configurations and their problems Compared to liquid crystal displays, electrochromic displays have no viewing angle dependence, and their colors are bright and clear. As electrochromic materials, WO 3 is well known as an inorganic material, viologen is the most well known as an organic material, and other pigments such as pyrazolines and anthraquinones are also known.
WO3は透明電極上に蒸着法などにより薄膜が
形成されて、対極間に電解液や誘電体膜などが設
けられることによつて素子が形成される。WO3
の実用上の問題点としては、表示寿命のほかに、
表示セグメント間の色ムラ、着色の色の種類がブ
ルー系の一色である。また、対極の反応のため
に、特に対極材料に工夫がいる、反射板等も素子
の中に組み込まなければならないという問題があ
る。ビオローゲン系などの有機色素は主に、還元
で発色し、それを酸化すると消色状態にもどる。
ビオローゲン系の色素の問題点として、発色状態
の色素が不溶化するものを利用するわけである
が、その場合、可溶と不溶の可逆性に問題があ
り、つまり、表示寿命が短いという問題がある。
また、これらの色素の還元と酸化反応にはハロゲ
ンイオンが関与しており、このイオンが透明電極
に悪影響を及ぼす場合があり、かつ消費電力が大
きいという問題がある。以上のように、液晶表示
素子と比較してエレクトロクロミツク表示素子の
実用上の問題は、表示寿命とともに応答速度であ
る。本出願人は前にエレクトロクロミツク材料と
してスチリル類似化合物の一種である色素を用い
たエレクトロクロミツク表示素子を提案した。そ
のエレクトロクロミツク表示素子の基本構造を第
１図にしめす。１はガラス基板、２は表示極、３
は対極、４は封着材、５は表示可能物質をしめ
す。ガラス基板１は少くとも一方が透明である材
料であればよい。表示極２、及び対極３の電極材
料としては、In2O3やSnO2のような透明電極が用
いられる。面積としては表示極２の方が対極３よ
り小さい。封着材４としてはエポキシ樹脂や低融
点ガラスや半田などが使われる。表示可能物質５
としては色素を非水系有機溶媒に支持電解質とと
もに溶解した溶液である。かかる素子構造におい
て、表示寿命を決める要因は、表示可能物質５な
どに含まれる不純物などによるものなどいくつか
の要因があるが、対極３材料の電気化学反応によ
る変質も１つの要因になつている。すなわち表示
極２及び対極３を形成する透明電極はIn2O3等の
ような金属酸化物であるため、還元反応をうけや
すく、還元反応によつて、Ｏ原子の離脱があつ
て、溶液内の成分を酸化したりして表示寿命に悪
影響を及ぼす。電流値が大きいほど電極は還元を
うけやすい。特に対極３の変質が問題となる。そ
こで対極３の電流密度の分布を調べたところ、第
１図にしめした、Ａ，Ｂ，Ｃの領域に分けた場
合、全電流のうちＡの領域がしめる割り合いが70
％、Ｂの領域が 20％、Ｃの領域が10％程度とな
り、Ａ領域が著しく還元され表示寿命の劣化がみ
られた。 A thin film of WO 3 is formed on a transparent electrode by vapor deposition or the like, and an electrolytic solution, a dielectric film, etc. are provided between the counter electrodes to form an element. WO 3
In addition to the display life, practical problems include:
The color unevenness between display segments and the type of coloring are a single blue color. Further, due to the reaction of the counter electrode, there are problems in that the material of the counter electrode must be specially designed and a reflector plate or the like must be incorporated into the element. Organic pigments such as viologen-based pigments mainly develop color through reduction, and return to their decolorized state when oxidized.
The problem with viologen-based dyes is that they use dyes that become insolubilized in the coloring state, but in that case, there is a problem with the reversibility of soluble and insoluble, which means that the display life is short. .
Further, halogen ions are involved in the reduction and oxidation reactions of these dyes, and there are problems in that these ions may have an adverse effect on the transparent electrode and that power consumption is large. As described above, the practical problems of electrochromic display elements compared to liquid crystal display elements are display life and response speed. The present applicant has previously proposed an electrochromic display element using a dye, which is a type of styryl-like compound, as an electrochromic material. The basic structure of the electrochromic display element is shown in Figure 1. 1 is a glass substrate, 2 is a display pole, 3
4 indicates a counter electrode, 4 indicates a sealing material, and 5 indicates a displayable substance. The glass substrate 1 may be made of a material in which at least one side is transparent. As electrode materials for the display electrode 2 and the counter electrode 3, transparent electrodes such as In 2 O 3 and SnO 2 are used. In terms of area, the display electrode 2 is smaller than the counter electrode 3. As the sealing material 4, epoxy resin, low melting point glass, solder, etc. are used. Displayable substances 5
This is a solution in which a dye is dissolved in a non-aqueous organic solvent together with a supporting electrolyte. In such an element structure, there are several factors that determine the display life, such as impurities contained in the displayable substance 5, etc., but alteration of the counter electrode 3 material due to electrochemical reaction is also one of the factors. . In other words, since the transparent electrodes forming the display electrode 2 and the counter electrode 3 are made of metal oxides such as In 2 O 3 , they are susceptible to reduction reactions, and the reduction reaction causes O atoms to be released and It may oxidize the components of the product and have a negative effect on the display life. The larger the current value, the more easily the electrode is subject to reduction. In particular, the alteration of the counter electrode 3 becomes a problem. Therefore, when we investigated the current density distribution of the counter electrode 3, we found that when divided into regions A, B, and C as shown in Figure 1, the ratio of region A to the total current is 70%.
%, the area B was about 20%, the area C was about 10%, and the area A was significantly reduced, resulting in a deterioration of the display life.
このようなエレクトロクロミツク表示素子にお
いて、表示極２と対極３間に直流電圧を表示極２
が＋側になるように、印加すると発色濃度と電流
の時間に対する変化は第２図のようになる。ａは
印加電圧、ｂは発色濃度、ｃは電流値の時間的変
化を示す。第２図ｂに示した、発色濃度が飽和に
達するまでの時間t1を短くして応答速度を速くす
ることが必要である。 In such an electrochromic display element, a DC voltage is applied between the display electrode 2 and the counter electrode 3.
When the voltage is applied so that the voltage is on the + side, the color density and the current change over time are as shown in FIG. a represents the applied voltage, b represents the color density, and c represents the temporal change in current value. It is necessary to shorten the time t1 until the color density reaches saturation, as shown in FIG. 2b, to increase the response speed.
発明の目的
本発明は上記従来の問題点を解決するもので、
エレクトロクロミツク表示素子の応答速度と表示
寿命を改善することを目的とする。Purpose of the invention The present invention solves the above-mentioned conventional problems.
The purpose is to improve the response speed and display life of electrochromic display elements.
発明の構成
本発明は上記目的を達成するもので、少なくと
も一方が透明で、互いに対向して設けられた２枚
の基板の一方に表示電極、他方に対極を設け、前
記対極が電気伝導度の異なる、半導体膜と金属膜
とで形成されていることを特徴とするエレクトロ
クロミツク表示素子を提供するものである。Structure of the Invention The present invention achieves the above object, and consists of two substrates, at least one of which is transparent and provided facing each other, a display electrode is provided on one side, and a counter electrode is provided on the other. The present invention provides an electrochromic display element characterized in that it is formed of different semiconductor films and metal films.
実施例の説明
以下に本発明の実施例を図面とともに説明す
る。第３図は本発明の一実施例であるエレクトロ
クロミツク表示素子の断面図を示す。DESCRIPTION OF EMBODIMENTS Examples of the present invention will be described below with reference to the drawings. FIG. 3 shows a sectional view of an electrochromic display element which is an embodiment of the present invention.
図において１はガラス板、２はIn2O3やSnO2の
ような透明電極からなる表示極、４はエポキシ樹
脂や低融点ガラスや半田などからなる封着材、５
は表示可能物質でエレクトロクロミツク物質を含
む溶液又は表示極２の表面に設けられたエレクト
ロクロミツク膜と電解質との組合せよりなる。本
実施例の特徴は対極の構造にある。すなわち対極
が低電気伝導物質よりなる電極６と高電気伝導物
質よりなる電極７とから構成されており、表示極
２に対向するガラス板１に表示極２の領域を包含
するように表示極より大きい面積の低電気伝導物
質よりなる電極６を設け、その周縁に低電気伝導
物質よりなる電極６に隣接して高電気伝導物質よ
りなる電極７を設けてある。低電気伝導物質とし
てはIn2O3，SnO2のような半導体の金属酸化物を
用い、高電気伝導物質としては金属を用いる。金
属としては、Au，Ag，Pt，Cu，Alなどが用い
られる。このような対極構成とすると、Ａの領域
が占める電流の割り合いが50％以下となり、集中
的にＡ領域の電極が変質することは改善でき、表
示寿命をのばすことができた。また、第２図ｂに
示す発色濃度が飽和に達するまでの時間ｔを短縮
して応答速度を上げるには、第２図ｃに示す電流
の立ち上がりを急峻にすることが効果的である
が、低電気伝導物質に隣接して高電気伝導物質を
配することによりこの電流の立ち上がりをより急
峻にすることができ、応答速度を上げることがで
きる。高電気伝導物質よりなる電極７は人間の目
に入らない領域で用いるのもよい方法と考えられ
る。 In the figure, 1 is a glass plate, 2 is a display electrode made of a transparent electrode such as In 2 O 3 or SnO 2 , 4 is a sealing material made of epoxy resin, low melting point glass, solder, etc., and 5 is a sealing material made of epoxy resin, low melting point glass, solder, etc.
is a displayable substance and is made of a solution containing an electrochromic substance or a combination of an electrochromic film provided on the surface of the display electrode 2 and an electrolyte. The feature of this embodiment lies in the structure of opposite electrodes. That is, the counter electrode is composed of an electrode 6 made of a low electrically conductive material and an electrode 7 made of a highly electrically conductive material. An electrode 6 made of a low electrical conductivity material having a large area is provided, and an electrode 7 made of a high electrical conductivity material is provided adjacent to the electrode 6 made of a low electrical conductivity material at the periphery thereof. A semiconductor metal oxide such as In 2 O 3 or SnO 2 is used as the low electrical conductivity material, and a metal is used as the high electrical conductivity material. Au, Ag, Pt, Cu, Al, etc. are used as the metal. With such a counter electrode configuration, the proportion of the current occupied by the region A was 50% or less, and the concentrated deterioration of the electrode in the A region could be prevented, and the display life could be extended. Furthermore, in order to shorten the time t until the color density reaches saturation as shown in Fig. 2b and increase the response speed, it is effective to make the rise of the current steep as shown in Fig. 2c. By arranging a high electrical conductivity material adjacent to a low electrical conductivity material, the rise of this current can be made steeper, and the response speed can be increased. It is also considered a good method to use the electrode 7 made of a highly electrically conductive material in an area where it cannot be seen by the human eye.
第４図に本発明は第２の実施例のエレクトロク
ロミツク表示素子の断面図を示す。 FIG. 4 shows a sectional view of an electrochromic display element according to a second embodiment of the present invention.
本実施例は対極の構成が異なる以外は第１の実
施例とまつたく同じ構造である。すなわちガラス
板１上に低電気伝導物質よりなる電極６を形成
し、表示極２の直下を含む表示極２を包含する領
域を除いた領域に高電気伝導物質よりなる電極８
を設けて対極を構成している。この場合も第１の
実施例と同様に対極における電流密度の分布を均
一にし、局所的な対極の変質による表示寿命の劣
化を防止することができ、また、応答速度も向上
することができる。 This embodiment has exactly the same structure as the first embodiment except that the configuration of the counter electrode is different. That is, an electrode 6 made of a low electrically conductive material is formed on the glass plate 1, and an electrode 8 made of a highly electrically conductive material is formed on the glass plate 1, and an electrode 8 made of a highly electrically conductive material is formed in the area excluding the area including the display electrode 2, including directly below the display electrode 2.
is set up to form the opposite pole. In this case as well, as in the first embodiment, it is possible to make the current density distribution at the counter electrode uniform, prevent deterioration of display life due to local deterioration of the counter electrode, and improve response speed.
第５図は本発明の第３の実施例であるエレクト
ロクロミツク表示素子の断面図である。本実施例
は低電気伝導物質よりなる電極６上全面に高電気
伝導物質よりなる電極８が設けられたもので、第
２の実施例の高電気伝導物質を表示極２の直下に
まで広げて配したもので、この実施例に対してよ
り応答速度を向上することができる。 FIG. 5 is a sectional view of an electrochromic display element according to a third embodiment of the present invention. In this embodiment, an electrode 8 made of a highly electrically conductive material is provided on the entire surface of an electrode 6 made of a low electrically conductive material, and the highly electrically conductive material of the second embodiment is extended to just below the display electrode 2. The response speed can be further improved compared to this embodiment.
発明の効果
以上要するに本発明は少なくとも一方が透明
で、互いに対向して設けられた２枚の基板の一方
に表示電極、他方に対極を設け、前記対極が電気
伝導度の異なる、半導体膜と金属膜とで形成され
ていることを特徴とするエレクトロクロミツク表
示素子を提供するもので、対向電極の変質による
表示寿命の劣化を防止するとともに応答速度の改
善をはかることができる。Effects of the Invention In summary, the present invention provides two substrates, at least one of which is transparent, provided facing each other, a display electrode is provided on one side, and a counter electrode is provided on the other. The present invention provides an electrochromic display element characterized in that it is formed of a film, and can prevent deterioration of display life due to deterioration of the counter electrode and improve response speed.
第１図は従来のエレクトロクロミツク表示素子
の断面図、第２図は印加電圧、発色濃度、電流の
時間に対する変化を示す図、第３図、第４図及び
第５図は本発明の実施例であるエレクトロクロミ
ツク表示素子の断面図である。
１……ガラス板、２……表示極、４……封着
剤、５……表示可能物質、６……低電気伝導物質
からなる電極、７，８……高電気伝導物質からな
る電極。
FIG. 1 is a cross-sectional view of a conventional electrochromic display element, FIG. 2 is a diagram showing changes in applied voltage, color density, and current over time, and FIGS. 3, 4, and 5 are diagrams showing the implementation of the present invention. 1 is a cross-sectional view of an example electrochromic display element; FIG. DESCRIPTION OF SYMBOLS 1...Glass plate, 2...Display electrode, 4...Sealing agent, 5...Displayable material, 6...An electrode made of a low electrically conductive material, 7, 8...An electrode made of a highly electrically conductive material.
Claims (1)
けられた２枚の基板の一方に表示電極、他方に対
極を設け、前記対極が電気伝導度の異なる、半導
体膜と金属膜とで形成されていることを特徴とす
るエレクトロクロミツク表示素子。 ２ 表示電極に対向して半導体膜を設け、前記半
導体膜に隣接して金属膜を設けたことを特徴とす
る特許請求の範囲第１項記載のエレクトロクロミ
ツク表示素子。 ３ 半導体膜上の周縁部に金属膜を設けたことを
特徴とする特許請求の範囲第１項記載のエレクト
ロクロミツク表示素子。 ４ 半導体膜上全面に金属膜を設けたことを特徴
とする特許請求の範囲第１項記載のエレクトロク
ロミツク表示素子。[Claims] 1. A semiconductor film and a metal film, at least one of which is transparent, and a display electrode and a counter electrode are provided on one of two substrates facing each other, and the counter electrode has different electrical conductivity. An electrochromic display element comprising: 2. An electrochromic display element according to claim 1, characterized in that a semiconductor film is provided opposite to the display electrode, and a metal film is provided adjacent to the semiconductor film. 3. The electrochromic display element according to claim 1, characterized in that a metal film is provided on the peripheral portion of the semiconductor film. 4. The electrochromic display element according to claim 1, characterized in that a metal film is provided over the entire surface of the semiconductor film.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16550683A JPS6057324A (en) | 1983-09-08 | 1983-09-08 | Electrochromic display element |
| US06/647,490 US4660939A (en) | 1983-09-08 | 1984-09-05 | Electrochromic display device |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16550683A JPS6057324A (en) | 1983-09-08 | 1983-09-08 | Electrochromic display element |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6057324A JPS6057324A (en) | 1985-04-03 |
| JPH0454209B2 true JPH0454209B2 (en) | 1992-08-28 |
Family
ID=15813682
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP16550683A Granted JPS6057324A (en) | 1983-09-08 | 1983-09-08 | Electrochromic display element |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6057324A (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58139129A (en) * | 1982-02-12 | 1983-08-18 | Matsushita Electric Ind Co Ltd | Electrochromic display element |
-
1983
- 1983-09-08 JP JP16550683A patent/JPS6057324A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58139129A (en) * | 1982-02-12 | 1983-08-18 | Matsushita Electric Ind Co Ltd | Electrochromic display element |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6057324A (en) | 1985-04-03 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |