JPH0143296B2 - - Google Patents
Info
- Publication number
- JPH0143296B2 JPH0143296B2 JP55050657A JP5065780A JPH0143296B2 JP H0143296 B2 JPH0143296 B2 JP H0143296B2 JP 55050657 A JP55050657 A JP 55050657A JP 5065780 A JP5065780 A JP 5065780A JP H0143296 B2 JPH0143296 B2 JP H0143296B2
- Authority
- JP
- Japan
- Prior art keywords
- thin film
- electrode
- metal oxide
- transition metal
- transparent electrode
- 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
Links
- 239000010409 thin film Substances 0.000 claims description 22
- 239000004020 conductor Substances 0.000 claims description 8
- 229910000314 transition metal oxide Inorganic materials 0.000 claims description 8
- 239000011521 glass Substances 0.000 claims description 5
- 239000010416 ion conductor Substances 0.000 claims description 5
- 239000000758 substrate Substances 0.000 claims description 4
- 239000008151 electrolyte solution Substances 0.000 claims description 2
- 239000012769 display material Substances 0.000 claims 1
- 239000000463 material Substances 0.000 description 9
- 150000001768 cations Chemical class 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 238000004042 decolorization Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910000906 Bronze Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000010974 bronze Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000011532 electronic conductor Substances 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 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
- G02F1/1514—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 characterised by the electrochromic material, e.g. by the electrodeposited material
- G02F1/1523—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 characterised by the electrochromic material, e.g. by the electrodeposited material comprising inorganic material
- G02F1/1524—Transition metal compounds
Landscapes
- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Nonlinear Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Electrochromic Elements, Electrophoresis, Or Variable Reflection Or Absorption Elements (AREA)
- Devices For Indicating Variable Information By Combining Individual Elements (AREA)
Description
【発明の詳細な説明】
本発明は電気化学的な酸化還元反応に基づく表
示素子（エレクトロクロミツク表示体＝ECD）
の特性改良に関し、特に応答スピードの向上を計
つたものである。[Detailed description of the invention] The present invention is a display element (electrochromic display = ECD) based on an electrochemical redox reaction.
The aim is to improve the characteristics of the system, particularly the response speed.
第１図は遷移金属酸化物（例えば、WO3）を
用いたECDの構成を示した図である。１は表示
極側のガラス基板であり、酸化スズ、又は、酸化
インジウムの透明電極２が内面にコートされてい
る。３はマスク蒸着によつてパターン化がなされ
た遷移金属酸化物の薄膜である。４は多孔性のセ
ラミツク板であり、表示の白色背景となる。５は
カーボンを主体としたプレス成形電極であり、集
電体６が取りつけられている。７は成形加工され
たガラスの器であり、前記表示極側の基板と接着
されている。また、表示セルの内部にはプロピレ
ンカーボネイトに１モルの過塩素酸リチウムを溶
かした電解液８が充填されている。 FIG. 1 is a diagram showing the structure of an ECD using a transition metal oxide (for example, WO 3 ). Reference numeral 1 denotes a glass substrate on the display electrode side, the inner surface of which is coated with a transparent electrode 2 made of tin oxide or indium oxide. 3 is a transition metal oxide thin film patterned by mask vapor deposition. 4 is a porous ceramic plate, which serves as the white background of the display. 5 is a press-molded electrode mainly made of carbon, to which a current collector 6 is attached. Reference numeral 7 denotes a molded glass container, which is bonded to the substrate on the display electrode side. Further, the inside of the display cell is filled with an electrolytic solution 8 in which 1 mole of lithium perchlorate is dissolved in propylene carbonate.
さて、このような表示セルに於て、表示極であ
る透明電極２と、カーボンの対極５の間に表示極
がマイナス、対極がプラスの電圧を印加すると、
表示極側の酸化物薄膜に還元反応が起き、着色す
る。また、逆に表示極をプラス、対極をマイナス
にして酸化物薄膜に酸化反応を起すと、消色が行
なわれる。これをWO3の場合化学式で表わすと
次のようになる。 Now, in such a display cell, when a negative voltage is applied to the display electrode and a positive voltage is applied to the counter electrode between the transparent electrode 2, which is the display electrode, and the carbon counter electrode 5,
A reduction reaction occurs in the oxide thin film on the display electrode side, causing it to become colored. Conversely, if the display electrode is set to positive and the counter electrode is set to negative, an oxidation reaction is caused in the oxide thin film, and the color is erased. In the case of WO 3 , this can be expressed as a chemical formula as follows.
WO3＋xM+＋xe-MxWO3
但し、Ｍ＝Ｈ、Li、Na etc
即ち、酸化タングステン薄膜中にエレクトロン
とカチオンの注入がなされることによつて、タン
グステンブロンズが形成され、これが着色体とな
る。従つて、この反応がすみやかに可逆的に行な
われるもの程、表示の応答スピードが速くなる。
現在の所、この応答は着色、消色ともに１秒前後
かかり、表示素子として実用上満足のできるもの
ではない。本発明はこの点に留意し、改良を試み
たものである。 WO 3 +xM + +xe - MxWO 3 However, M=H, Li, Na etc. That is, by injecting electrons and cations into the tungsten oxide thin film, tungsten bronze is formed, which becomes a colored body. Therefore, the more quickly and reversibly this reaction occurs, the faster the display response speed will be.
At present, this response takes about 1 second for both coloring and decoloring, which is not practically satisfactory as a display element. The present invention takes this point into consideration and attempts to improve it.
まず、ECDの応答を改良する上で考えねばな
らないことは、着消色の反応の律速が何によつて
生じるかである。本発明者はこの原因として、１
つは電解液中、あるいは、回体薄膜中のイオンの
拡散スピードであると考える。また、もう１つは
薄膜−電解液、あるいは、薄膜−電極間の化学
的、あるいは、電気的な障壁であると考えた。従
つて、応答スピードの改良の手段としては前者の
因に対してはガチオンとしてイオン半径の小さい
電解質を用いること、あるいは、拡散が浅くても
充分な発色が得られるEC材料を選ぶこと、さら
には、薄膜の幾何学的形状の改良によつて反応面
積を増すことが有効であると考えた。また、後者
の因に対する対策としてはデバイスとしての導電
性を増すこと、外部供給エネルギーを増すこと、
さらには、触媒等の添加によつて果面でのバリア
を低くすること等が有効である。しかし、これら
の対策の中にはECDの寿命の面から即取り入れ
ることの難しいものもある。そこで、本発明では
現在の大きく変えることなく改良して、応答スピ
ードの向上を得ようとするものである。 First, in order to improve the response of ECD, we must consider what is the rate-limiting factor for the coloring/decoloring reaction. The inventor believes that this is due to 1.
The first factor is considered to be the diffusion speed of ions in the electrolyte or the rotating body thin film. We also thought that the other reason is a chemical or electrical barrier between the thin film and the electrolyte, or between the thin film and the electrode. Therefore, as a means of improving the response speed, for the former reason, it is necessary to use an electrolyte with a small ionic radius as a cation, or to select an EC material that can produce sufficient color even if the diffusion is shallow. We considered that it would be effective to increase the reaction area by improving the geometry of the thin film. In addition, countermeasures against the latter cause include increasing the conductivity of the device, increasing externally supplied energy,
Furthermore, it is effective to lower the barrier on the fruit surface by adding a catalyst or the like. However, some of these measures are difficult to implement immediately due to the longevity of the ECD. Therefore, the present invention attempts to improve the response speed without making any major changes to the current system.
第２図は本発明によるEC薄膜を模式的に示し
た図である。即ち、遷移金属酸化物の薄膜９の上
に電子、あるいは、イオンの良導体１０を薄く重
ね、さらに、その上に先の金属酸化物を重ねると
いうようにして、EC材料と伝導体の多層薄膜を
形成し、表示部とするものである。各層の膜厚は
数10〜数100Åとし、全体の透過率は70〜90％と
なるようにコントロールする。このようにして得
たEC薄膜は従来の遷移金属酸化物薄膜が絶縁体
であつたのに対し、電子の良導体として働き、ま
た、イオン伝導体を重ねた場合にはイオンの良導
体として働く。つまり、ECの発消色に必要な電
子、あるいは、カチオンがすみやかにEC材料中
に注入、あるいは、脱出が可能となり応答スピー
ドが向上する。特に、積層した薄膜の各々が網目
状に重なるようなハイポーラスな膜を重ねた場合
にはEC材料と伝導材料が複雑に重なり、その効
果が大きい。 FIG. 2 is a diagram schematically showing an EC thin film according to the present invention. That is, a thin film 9 of a transition metal oxide is layered with a good conductor 10 of electrons or ions, and then the metal oxide is layered on top of that, thereby forming a multilayer thin film of EC material and conductor. It is used as a display section. The thickness of each layer is controlled to be several tens to hundreds of angstroms, and the overall transmittance is controlled to be 70 to 90%. While conventional transition metal oxide thin films are insulators, the EC thin film thus obtained acts as a good conductor of electrons, and when layered with an ion conductor, acts as a good conductor of ions. In other words, the electrons or cations necessary for EC color development and decolorization can be quickly injected into or escaped from the EC material, improving response speed. In particular, when highly porous films in which the laminated thin films overlap in a mesh pattern are stacked, the EC material and the conductive material overlap in a complicated manner, which has a large effect.
本発明に用いる電子伝導体としては貴金属類を
始めとする電気化学的に安定な金属材料がよい。
特に、Pd、Pt、Ir等は水素の吸蔵が高く、プロ
トンの供給源としての働きもある。即ち、この場
合にはEC材料中へ内部からカチオン注入がなさ
れる為、応答スピードの向上が著しい。また、イ
オン伝導体としてはLi3N、LiIなどが使用でき、
WO3を用いたECDではLixWO3の形成に開与が
あると思われる。 The electron conductor used in the present invention is preferably an electrochemically stable metal material such as noble metals.
In particular, Pd, Pt, Ir, etc. have a high hydrogen storage capacity and also function as a proton supply source. That is, in this case, since cations are injected into the EC material from within, the response speed is significantly improved. In addition, Li 3 N, LiI, etc. can be used as ion conductors.
In ECD using WO 3 , the formation of LixWO 3 seems to be a contributing factor.
以上の説明で明らかなように本発明は固体EC
薄膜の電子伝導性、あるいは、カチオン伝導性を
増すことを第１主願とし、さらに、EC材料中へ
のイオンの拡散深さの軽減、あるいは、反応面積
の拡大を計つたものである。ことに、EC材料と
電子伝導体又はイオン伝導体とを交互に積層する
とき、積層した薄膜の各々を網目状に重ねたの
で、電解液との接触面積即ち反応面積が大巾に拡
大される。そのためにECの発消色に必要な電子
あるいはカチオンのEC材料中への注入、脱出の
反応が活発に促進されるので応答スピードを向上
させることができる。ちなみに、金属材料として
Pd、EC材料をWO3としたECセル（構成は第１
図と同様）に於て、最高0.1sの応答スピードを得
ており、本発明が有効であることが確認されてい
る。従つて、本発明によれば従来にないECDの
応答スピードが得られ、表示素子として一層の応
用展開が計れるものである。 As is clear from the above explanation, the present invention is a solid EC
The primary objective is to increase the electron conductivity or cation conductivity of thin films, and also to reduce the depth of ion diffusion into the EC material or expand the reaction area. In particular, when EC materials and electron conductors or ionic conductors are alternately laminated, each of the laminated thin films is overlapped in a mesh pattern, so the contact area with the electrolyte, that is, the reaction area, is greatly expanded. . For this reason, the reaction of injecting and escaping electrons or cations into and out of the EC material, which are necessary for EC color development and decolorization, is actively promoted, and the response speed can be improved. By the way, as a metal material
EC cell with Pd and EC material as WO 3 (configuration is 1st
(Similar to the figure), a maximum response speed of 0.1 s was obtained, confirming that the present invention is effective. Therefore, according to the present invention, an unprecedented ECD response speed can be obtained, and further applications as a display element can be expected.
第１図は固体薄膜を用いたECDの構成例であ
る。第２図は本発明によるECDの表示部の模式
図である。
図中の番号、１……ガラス基板、２……透明電
極、３……EC薄膜、４……セラミツク板、５…
…カーボン対極、６……集電体、７……ガラス容
器、８……電解液、９……遷移金属酸化物、１０
……電子、又は、イオン伝導体。
Figure 1 shows an example of the configuration of an ECD using a solid thin film. FIG. 2 is a schematic diagram of the display section of the ECD according to the present invention. Numbers in the figure: 1... Glass substrate, 2... Transparent electrode, 3... EC thin film, 4... Ceramic plate, 5...
... Carbon counter electrode, 6 ... Current collector, 7 ... Glass container, 8 ... Electrolyte, 9 ... Transition metal oxide, 10
...electronic or ionic conductor.
Claims (1)
明電極上にパターン化して形成された遷移金属酸
化物の薄膜と、前記透明電極と対向する側に配置
された集電体を有する電極と、前記透明電極と前
記薄膜と前記電極に接するよう充填された電解液
とを備えたエレクトロクロミツク表示体におい
て、前記遷移金属酸化物と電子伝導体、あるいは
前記遷移金属酸化物とイオン伝導体の薄層を交互
に網目状に重ねたことを特徴とするエレクトロク
ロミツク表示体。1. A transparent electrode formed on a glass substrate, a thin film of a transition metal oxide patterned and formed on the transparent electrode, and an electrode having a current collector disposed on a side facing the transparent electrode, In an electrochromic display comprising the transparent electrode, the thin film, and an electrolytic solution filled in contact with the electrode, a thin film of the transition metal oxide and an electron conductor, or a thin film of the transition metal oxide and an ionic conductor is provided. An electrochromic display material characterized by alternating layers arranged in a mesh pattern.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5065780A JPS56147129A (en) | 1980-04-17 | 1980-04-17 | Electrochromic display body |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5065780A JPS56147129A (en) | 1980-04-17 | 1980-04-17 | Electrochromic display body |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS56147129A JPS56147129A (en) | 1981-11-14 |
| JPH0143296B2 true JPH0143296B2 (en) | 1989-09-20 |
Family
ID=12865014
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5065780A Granted JPS56147129A (en) | 1980-04-17 | 1980-04-17 | Electrochromic display body |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS56147129A (en) |
-
1980
- 1980-04-17 JP JP5065780A patent/JPS56147129A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS56147129A (en) | 1981-11-14 |
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