JPH04174824A - Electrochromic display manufacturing method - Google Patents
Electrochromic display manufacturing methodInfo
- Publication number
- JPH04174824A JPH04174824A JP2301052A JP30105290A JPH04174824A JP H04174824 A JPH04174824 A JP H04174824A JP 2301052 A JP2301052 A JP 2301052A JP 30105290 A JP30105290 A JP 30105290A JP H04174824 A JPH04174824 A JP H04174824A
- Authority
- JP
- Japan
- Prior art keywords
- layer
- particles
- electrochromic display
- substrate
- ecd
- 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.)
- Pending
Links
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 8
- 239000002245 particle Substances 0.000 claims abstract description 23
- 239000000758 substrate Substances 0.000 claims abstract description 12
- 238000004040 coloring Methods 0.000 claims abstract description 9
- 239000011248 coating agent Substances 0.000 claims 1
- 238000000576 coating method Methods 0.000 claims 1
- 230000004044 response Effects 0.000 abstract description 8
- 239000010410 layer Substances 0.000 description 16
- 238000000034 method Methods 0.000 description 13
- 239000000463 material Substances 0.000 description 9
- 239000011882 ultra-fine particle Substances 0.000 description 9
- 239000010419 fine particle Substances 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 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
- 239000011230 binding agent Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007787 long-term memory Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明はエレクトロクロミックディスプレイ（以下ＥＣ
Ｄと記す）に関し、詳しくは、電極基板上にＷＯ３微粒
子材料を含有する薄層を有するエレクトロクロミックデ
ィスプレイの作製方法に関する。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to electrochromic displays (hereinafter referred to as EC).
Specifically, the present invention relates to a method for producing an electrochromic display having a thin layer containing WO3 fine particle material on an electrode substrate.
［従来の技術］
ＥＣＤには、電圧印加による酸化還元反応によって物質
の色が可逆的に変化する現象が利用され、他の電子デイ
スプレィと比べると、表示容量と応答速度の点で劣って
いるが、下記の利点がある。[Prior Art] ECD utilizes the phenomenon in which the color of a substance changes reversibly through redox reactions caused by voltage application, and is inferior to other electronic displays in terms of display capacity and response speed. , has the following advantages.
（１）長期間にわたるメモリー性、
（２）視角依存性がないこと、
（３）駆動電圧が低いこと、
（４）外部光に妨げられないこと、
などであり、種々のＥＣ材料について研究が行われてい
る。(1) long-term memory, (2) no viewing angle dependence, (3) low driving voltage, and (4) no interference from external light, etc., and research has been conducted on various EC materials. It is being done.
現在のところＷＯ３膜が有望であり、一部実用化が始ま
りつつある。Currently, WO3 membranes are promising, and some are beginning to be put into practical use.
膜の製法としては、加熱蒸着、スパッタリングなどの一
般的な真空成膜法のほか、大気圧下で行なえる比較的簡
単な作業性のよい方法として、微粒子材料を塗布する方
法が注目されている。As for film manufacturing methods, in addition to general vacuum film forming methods such as heated evaporation and sputtering, the method of applying fine particle materials is attracting attention as a relatively simple method that can be performed under atmospheric pressure and has good workability. .
これまでの研究から、着色反応が起こるのは電極基板と
直接接している粒子、及びこれに接触している粒子のみ
で、電解液中に孤立した粒子は着色が起こらないこと、
さらに密度の小さな膜の方が電荷移動の可逆性が向上す
ることなどがわかっている。From previous research, we have found that the coloring reaction occurs only in particles that are in direct contact with the electrode substrate, and particles that are in contact with this, and that particles isolated in the electrolyte do not become colored.
Furthermore, it is known that the reversibility of charge transfer is improved in films with lower density.
上述のことから、微粒子を用いた着色を考えた場合、粒
径が小さいものほど相互の接触の機会が増え、着色の効
率が向上し、また膜（ＥＣ材料層）としての比表面積が
大きいほど表示素子としての応答速度が速くなる。From the above, when considering coloring using fine particles, the smaller the particle size, the more opportunities for mutual contact and the higher the coloring efficiency, and the larger the specific surface area as a film (EC material layer). The response speed of the display element becomes faster.
したがって、微粒子の塗布方法や塗布条件にも増して、
用いる微粒子自体の特性（粒径、形状、比表面積など）
によって、ＥＣＤとしての表示品質が左右されることに
なる。Therefore, in addition to the method and conditions for applying fine particles,
Characteristics of the fine particles used (particle size, shape, specific surface area, etc.)
This will affect the display quality of the ECD.
Ｃ発明が解決しようとする課題］
すなわち、本発明はＥＣ材料層の形成において、ＷＯ３
超微粒子材料の塗布による方法を用いることによって、
高表示品質０ＥＣＤを提供しようとするものである。Problems to be Solved by Invention C] That is, the present invention solves the problem of WO3 in forming an EC material layer.
By using the method of applying ultrafine particle material,
This is intended to provide high display quality 0ECD.
［課題を解決するための手段］
上記課題を解決するための本発明の構成は基板上にＷＯ
Ｊを含有する発色層を有するエレクトロクロミックディ
スプレイの作製方法において、粒径０．１μＳ以下のＷ
Ｏ３超微粒子を塗布することにより、ＷＯ３層を形成す
るエレクトロクロミックディスプレイの作製方法である
。[Means for Solving the Problems] The structure of the present invention for solving the above problems is to
In the method for producing an electrochromic display having a coloring layer containing J, W with a particle size of 0.1 μS or less is used.
This is a method for producing an electrochromic display in which a WO3 layer is formed by applying ultrafine O3 particles.
本発明の方法で作製されるＥＣＤの一例を図面を参照し
て具体的に説明すると、まず第１図に、一般的な液体型
のＥＣＤの構成を示す。ＥＣＤは基本的には、透明電極
１．８／Ｗ０３層３／電解液４（白色反射層７）／対向
電極６よりなる構成を持つ。An example of an ECD manufactured by the method of the present invention will be specifically described with reference to the drawings. First, FIG. 1 shows the configuration of a general liquid type ECD. The ECD basically has a structure consisting of a transparent electrode 1.8/W03 layer 3/electrolytic solution 4 (white reflective layer 7)/counter electrode 6.
電解液４としては、炭酸プロピレン（Ｐ Ｃ）、γ−ブ
チロラクトンなどの非水溶媒に、ＬｉＣｌ０＋、ＬｉＢ
Ｆ４などのＬｉ塩をＬｓｏｌ／ｉ程度溶かしたものが用
いられる。As the electrolytic solution 4, LiCl0+, LiB
A solution of Li salt such as F4 to approximately Lsol/i is used.
対向電極６には、ＷＯ３膜、カーボンのほか、カーボン
にＭ ｎ Ｏ２またはＦｅ錯体などを混合し、応答性能
、信頼性の向上を図った材料が用いられる。The counter electrode 6 is made of a WO3 film, carbon, or a material in which carbon is mixed with MnO2 or an Fe complex to improve response performance and reliability.
反射層７は、表示の背景を与えるために必要で、通常の
素子では対向電極６を隠蔽する働きもする。この目的の
ために、ＴｉＯ２、Ａｌ２Ｏ３などの材料が粉末が多孔
質板の形で電解液中に設置される。The reflective layer 7 is necessary to provide a background for display, and also serves to hide the counter electrode 6 in a normal device. For this purpose, powders of materials such as TiO2, Al2O3 are placed in the electrolyte in the form of porous plates.
透明電極５には、ＩＴＯか、アンチモンまたはフッ素を
ドープしたＳｎＯ２膜が使用される。For the transparent electrode 5, ITO, antimony, or fluorine-doped SnO2 film is used.
ＩＴＯの場合には、電気化学的に還元されるのを防ぐた
めに、５ｉ０２などの絶縁性の保護層２がこの電極の露
出した部分に形成される。In the case of ITO, an insulating protective layer 2, such as 5i02, is formed on the exposed parts of this electrode to prevent electrochemical reduction.
Ｍ１図に示す表基板Ｉと裏基板８とは、その中に反射板
７と対向電極６とを挟持した形で組立てられ、周辺はエ
ポキシ樹脂などでシールされる。その後、電解液が注入
され、注入孔が封止される。A front substrate I and a back substrate 8 shown in FIG. M1 are assembled with a reflecting plate 7 and a counter electrode 6 sandwiched therein, and the periphery is sealed with epoxy resin or the like. Thereafter, an electrolytic solution is injected and the injection hole is sealed.
本発明のＷＯ３膜の形成にはＷＯ３微粒子が用いられる
。ＷＯ３微粒子の粒径は小さいほどよく、本発明におい
ては粒径０．１μ麿以下、好ましくは０，０５μ層以下
、さらに好ましくは０．０３μ■以下のＷＯ３超微粒子
が用いられる。WO3 fine particles are used to form the WO3 film of the present invention. The smaller the particle size of the WO3 fine particles, the better, and in the present invention, WO3 ultrafine particles with a particle size of 0.1 μm or less, preferably 0.05 μm or less, more preferably 0.03 μm or less are used.
ＷＯ３超微粒子の形状は球状またはこれに近いものが好
ましく、粒径分布についてはシャープのものが好ましい
。以上のような条件を満たすＷＯｙ超微粒子を用いるこ
とにより、電極基板上に塗布層を形成した場合、粒子間
相互の接触の機会が多く、密に充填された、しかも層と
しての比表面積が大きな粒子層の形成が可能となり、し
たがって、着色効率が高く、応答速度の速いＥＣＤの作
製が可能となる。The shape of the WO3 ultrafine particles is preferably spherical or close to spherical, and the particle size distribution is preferably sharp. By using WOy ultrafine particles that meet the above conditions, when a coating layer is formed on an electrode substrate, there are many opportunities for mutual contact between particles, and the layer is densely packed and has a large specific surface area. It becomes possible to form a particle layer, and therefore, it becomes possible to produce an ECD with high coloring efficiency and fast response speed.
本発明におけるＷＯｓ超微粒子の塗布方法としては、Ｗ
Ｏ３超微粒子を適当な分散媒に分散させ、電極基板にス
ピンコードしてもよいし、またはディッピングなどの方
法によってもよい。The method for applying WOs ultrafine particles in the present invention includes W
The O3 ultrafine particles may be dispersed in a suitable dispersion medium and spin-coated onto the electrode substrate, or may be carried out by a method such as dipping.
また、アルコールやポリマーなとのいわゆるバインダー
中に混合して、スクリーン印刷などの印刷法によって塗
布してもよい。このような方法でＷＯ３超微粒子材料を
塗布した後、前記ＷＯ３微粒子層は適当な温度で乾燥ま
たは焼成されて形成される。Alternatively, it may be mixed in a so-called binder such as alcohol or polymer and applied by a printing method such as screen printing. After applying the WO3 ultrafine particle material in this manner, the WO3 fine particle layer is formed by drying or firing at an appropriate temperature.
次に本発明を実施例によって具体的に説明する。Next, the present invention will be specifically explained using examples.
［実施例］
ＷＯ３粒子として、平均粒径０．０３μ■粒径分布のシ
ャープな球状のＷＯ３超微粒子を用いた。[Example] As the WO3 particles, sharp spherical WO3 ultrafine particles with an average particle size of 0.03 μm and a particle size distribution were used.
これをメタノールに分散させ、ＩＴＯ透明電極を設けた
基板上にスピンコードにより塗布し、続いて２００℃、
３０分の熱処理を行い、Ｗ ０３層を形成した。This was dispersed in methanol and applied onto a substrate with an ITO transparent electrode using a spin cord, followed by heating at 200°C.
Heat treatment was performed for 30 minutes to form a W 03 layer.
これを用い、第１図のような構成のＥＣＤを作製し、着
色時のコントラストを評価するため、一定光度の光源で
照明を行ない、リニアリティのよい工業用テレビカメラ
を用いて反射光強度を測定した。Using this, we created an ECD with the configuration shown in Figure 1, and in order to evaluate the contrast during coloring, we illuminated it with a light source of a constant luminous intensity and measured the reflected light intensity using an industrial television camera with good linearity. did.
ＷＯ２層を蒸着により形成した以外は同様の構成で作製
したリファレンスＥＣＤと比較したところ、コントラス
トは約１１０％、応答時間は約９５％であった。When compared with a reference ECD manufactured with the same configuration except that the WO2 layer was formed by vapor deposition, the contrast was about 110% and the response time was about 95%.
比較例
Ｗｏｏ１粒子として、平均粒径３μ麿の粉砕法によるＷ
Ｏ３粒子を用い、実施例と同様の測定をしたところ、リ
ファレンスＥＣＤと比較し、コントラストは約９０％、
応答時間は約９５％であった。As Comparative Example Woo1 particles, W obtained by the pulverization method with an average particle size of 3 μm
When measurements were made in the same manner as in the example using O3 particles, the contrast was approximately 90% compared to the reference ECD.
Response time was approximately 95%.
［発明の効果］
以上説明したように本発明０ＥＣＤの作製方法は、ＷＯ
２を用いたＥＣＤにおいて、粒径０．１μ−以下、好ま
しくは０．０５μｍ以下、さらに好ましくは０．０３μ
−以下のＷＯ３超微粒子を塗布することによりＷＯ２層
を形成することを特徴とし、従来の真空成膜法に比べて
、大気圧下で行なえ、しかも工程が簡単な作業性のよい
方法であり、これにより、高表示品質のＥＣＤを提供で
きる。[Effect of the invention] As explained above, the method for producing the 0ECD of the present invention is described in WO
In ECD using 2, the particle size is 0.1 μm or less, preferably 0.05 μm or less, more preferably 0.03 μm.
- It is characterized by forming a WO2 layer by applying the following WO3 ultrafine particles, and is an easy-to-work method that can be performed under atmospheric pressure and has a simple process, compared to conventional vacuum film-forming methods. This makes it possible to provide an ECD with high display quality.
第１図は本発明のＥＣＤの一具体例を説明するための断
面の模式図である。
１・・・表基板、２・・・５ｉＯｚ層、３・・・ＷＯ２
層、４・・・電解液、５・・・ＩＴＯ１８・・・対向電
極、７・・・反射板、８・・・裏基板、９・・・シール
材、１０・・・Ａｇトランスファー。FIG. 1 is a schematic cross-sectional view for explaining a specific example of the ECD of the present invention. 1...Top substrate, 2...5iOz layer, 3...WO2
Layer, 4... Electrolyte, 5... ITO18... Counter electrode, 7... Reflector, 8... Back substrate, 9... Sealing material, 10... Ag transfer.
Claims (1)
クトロクロミックディスプレイの作製方法において、粒
径０．１μｍ以下のＷＯ＿３超微粒子を塗布することに
より、ＷＯ＿３層を形成することを特徴とするエレクト
ロクロミックディスプレイの作製方法。(1) A method for producing an electrochromic display having a coloring layer containing WO_3 on a substrate, which comprises forming a WO_3 layer by coating ultrafine WO_3 particles with a particle size of 0.1 μm or less. How to make a display.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2301052A JPH04174824A (en) | 1990-11-08 | 1990-11-08 | Electrochromic display manufacturing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2301052A JPH04174824A (en) | 1990-11-08 | 1990-11-08 | Electrochromic display manufacturing method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04174824A true JPH04174824A (en) | 1992-06-23 |
Family
ID=17892285
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2301052A Pending JPH04174824A (en) | 1990-11-08 | 1990-11-08 | Electrochromic display manufacturing method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04174824A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006208862A (en) * | 2005-01-28 | 2006-08-10 | Ricoh Co Ltd | Display element and reflection type display |
-
1990
- 1990-11-08 JP JP2301052A patent/JPH04174824A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006208862A (en) * | 2005-01-28 | 2006-08-10 | Ricoh Co Ltd | Display element and reflection type display |
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