JPS63210916A - Electrochromic material and electrochromic element - Google Patents
Electrochromic material and electrochromic elementInfo
- Publication number
- JPS63210916A JPS63210916A JP62046114A JP4611487A JPS63210916A JP S63210916 A JPS63210916 A JP S63210916A JP 62046114 A JP62046114 A JP 62046114A JP 4611487 A JP4611487 A JP 4611487A JP S63210916 A JPS63210916 A JP S63210916A
- Authority
- JP
- Japan
- Prior art keywords
- oxide
- film
- color
- coloring
- hydroxide
- 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
- 239000000463 material Substances 0.000 title claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 15
- 229910052751 metal Inorganic materials 0.000 claims abstract description 13
- 239000002184 metal Substances 0.000 claims abstract description 13
- 229910052741 iridium Inorganic materials 0.000 claims abstract description 10
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 4
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 16
- 230000001590 oxidative effect Effects 0.000 claims description 10
- 230000009467 reduction Effects 0.000 claims description 6
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 4
- 229910000457 iridium oxide Inorganic materials 0.000 claims 4
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 claims 3
- 238000002834 transmittance Methods 0.000 abstract description 12
- 230000004044 response Effects 0.000 abstract description 5
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 abstract description 5
- 239000007787 solid Substances 0.000 abstract description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 229910052593 corundum Inorganic materials 0.000 abstract description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract description 3
- 230000002441 reversible effect Effects 0.000 abstract description 2
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 abstract description 2
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 abstract 4
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 abstract 4
- 238000009413 insulation Methods 0.000 abstract 1
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 abstract 1
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 abstract 1
- 230000002035 prolonged effect Effects 0.000 abstract 1
- 238000004040 coloring Methods 0.000 description 38
- 230000003647 oxidation Effects 0.000 description 13
- 238000007254 oxidation reaction Methods 0.000 description 13
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 11
- 239000002131 composite material Substances 0.000 description 10
- 239000008188 pellet Substances 0.000 description 9
- 238000004544 sputter deposition Methods 0.000 description 8
- 238000006722 reduction reaction Methods 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 238000001704 evaporation Methods 0.000 description 5
- 230000008020 evaporation Effects 0.000 description 5
- 230000007334 memory performance Effects 0.000 description 5
- 230000003287 optical effect Effects 0.000 description 5
- 238000000053 physical method Methods 0.000 description 5
- 239000011787 zinc oxide Substances 0.000 description 5
- 230000008859 change Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 150000004679 hydroxides Chemical class 0.000 description 4
- 230000004043 responsiveness Effects 0.000 description 4
- 230000003595 spectral effect Effects 0.000 description 4
- 230000007423 decrease Effects 0.000 description 3
- 230000006870 function Effects 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000004973 liquid crystal related substance Substances 0.000 description 3
- 230000015654 memory Effects 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000007740 vapor deposition Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000004793 poor memory Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000005546 reactive sputtering Methods 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000007743 anodising Methods 0.000 description 1
- 238000005422 blasting Methods 0.000 description 1
- 238000010549 co-Evaporation Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 230000004313 glare Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- SKRWFPLZQAAQSU-UHFFFAOYSA-N stibanylidynetin;hydrate Chemical compound O.[Sn].[Sb] SKRWFPLZQAAQSU-UHFFFAOYSA-N 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- -1 zoi and LatOi Chemical class 0.000 description 1
Landscapes
- Electrochromic Elements, Electrophoresis, Or Variable Reflection Or Absorption Elements (AREA)
- Devices For Indicating Variable Information By Combining Individual Elements (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は酸化発色型エレクトロクロミック材料および防
眩ミラー等に応用可能な当該材料を利用した全固体エレ
クトロクロミック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 oxidative color-forming electrochromic material and an all-solid-state electrochromic device using the material, which can be applied to anti-glare mirrors and the like.
電気信号により光学的性質を制御する光学機能素子のう
ち現在量も広く普及しているものに液晶表示素子（ＬＣ
）がある、しかし１表示素子として利用する場合、像の
二重写り、視認性の悪さ等の欠点が以前から指摘されて
いた。一方ＬＣ素子の可視光透重過制御性を利用しいわ
ゆる調光膜として応用しようとする動きも活発であり９
反射鏡と組み合わせた液晶防眩ミラーがすでに実用化さ
れている。この場合、前述の像の二重写り、視認性の悪
さに加え、液晶そのものの可視光透過率が低く、非防眩
時に反射率が低く暗いとの不具合が指摘されてきた。Among the optical functional elements whose optical properties are controlled by electrical signals, liquid crystal display elements (LC) are currently widely used.
), but when used as a single display element, drawbacks such as double images and poor visibility have long been pointed out. On the other hand, there is also an active movement to utilize the visible light transmission weight controllability of LC elements and apply them as so-called light control films9.
Liquid crystal anti-glare mirrors combined with reflective mirrors have already been put into practical use. In this case, in addition to the above-mentioned double image and poor visibility, problems have been pointed out that the visible light transmittance of the liquid crystal itself is low, and the reflectance is low and dark when not anti-glare.
一方電気信号により調光機能を示す光学機能素子の一つ
にエレクトロクロミック（ＥＣ）素子がある。電気化学
反応により着色・消色を繰り返すＥＣ素子の歴史は非常
に古い。しかし今日現在。On the other hand, an electrochromic (EC) element is one of the optical functional elements that exhibits a dimming function using an electrical signal. EC elements, which repeat coloring and decoloring through electrochemical reactions, have a very long history. But as of today.
溶液型素子は実用化されているが、全固体型ＥＣ素子は
実用化には至っていない。しかし、全固体型ＥＣ素子も
その後の改良研究により長寿命化。Although solution-type devices have been put into practical use, all-solid-state EC devices have not yet been put into practical use. However, all-solid-state EC elements also had a longer lifespan through subsequent improvement research.
安定化が行われ、ＥＣ防眩ミラーとして実用化の試みが
なされている。全固体ＥＣ防眩ミラーはＥＣ防眩ミラー
に比べ像の二重写りもなく視認性も良好であるが、応答
性が悪い、全固体ＥＣを構成する膜の着色により非防眩
時のミラー反射率がＬＣミラーに比べ必ずしも高くはな
らない、また。It has been stabilized and attempts are being made to put it into practical use as an EC anti-glare mirror. Compared to EC anti-glare mirrors, all-solid EC anti-glare mirrors have better visibility with no double images, but they have poor responsiveness and the coloring of the film that makes up all-solid EC causes mirror reflection when not anti-glare. The ratio is not necessarily higher than that of an LC mirror.
メモリー性が悪い、すなわち着色後放置すると短時間に
消色してしまう等の欠点があった。これらの特性を左右
する要因は膜を構成する酸化発色型エレクトロクコミッ
ク層の特性にある。通常この酸化発色型ＥＣ層として最
も広く利用されている材料にイリジウム（Ｉｒ）がある
。このＩｒ化合物膜の作製法としては従来、陽極酸化法
９反応性蒸着法１反応性イオンブレーティング法５反応
性スパッタ法等が用いられている。可視光透過率。There were drawbacks such as poor memory properties, that is, the color would fade in a short time if left undisturbed after coloring. The factors that influence these properties are the properties of the oxidative color-forming electrocomic layer that constitutes the film. Iridium (Ir) is usually the most widely used material for this oxidation coloring type EC layer. Conventionally, methods for producing this Ir compound film include anodic oxidation, reactive vapor deposition, reactive ion blasting, and reactive sputtering. Visible light transmittance.
着色・消色応答性、メモリー性ともに陽極酸化法で作製
したＩｒ酸化物または水酸化物が最も優れている。しか
し陽極酸化法そのものが大面積基板への処理に不適であ
り、また、全固体ＥＣセルを構成する還元発色層、誘電
体層を物理的成膜法（蒸着、スパッタ、イオンブレーテ
ィング等）により作製する都合上２．生産性、コストの
面からもＩｒ化合物（つまり酸化物または水酸化物）を
物理的手法により作製することが強く望まれていた。Ir oxide or hydroxide produced by anodizing is the best in both coloring/decoloring response and memory properties. However, the anodic oxidation method itself is unsuitable for processing large-area substrates, and the reduction coloring layer and dielectric layer that make up the all-solid-state EC cell are formed using physical film-forming methods (evaporation, sputtering, ion blating, etc.). 2. Due to manufacturing reasons. From the viewpoint of productivity and cost, it has been strongly desired to produce Ir compounds (that is, oxides or hydroxides) by physical methods.
しかし物理的手法により作製したＩｒ酸化物または水酸
化物膜は種々の手法を駆使しても着色・消色応答性が不
充分で高い可視光透過率も得られず。However, Ir oxide or hydroxide films prepared by physical methods have insufficient coloring/decoloring response and cannot obtain high visible light transmittance even if various methods are used.
メモリー性も劣っていた。また、特開昭６１．−１２３
８１９号では、物理的手法によってＩｒの酸化物または
水酸化物を酸化亜鉛（ＺｎＯ）、酸化スズ（Ｓｎｏｗ）
またはＩ Ｔ Ｏ（Ｉｎｄｉｕ＋ｗ−Ｔｉｎ−Ｏｘｉｄ
ｅ）等の導電性物質中に分散させたＥＣ材料を作製し、
これを用いたＥＣ素子を作製している。しかし、このＥ
Ｃ素子もメーモリー性にやや劣っており、上記特性のす
べてを満足させるものではなかった。Memory performance was also poor. Also, JP-A-61. -123
In No. 819, Ir oxides or hydroxides are converted into zinc oxide (ZnO), tin oxide (Snow) by physical methods.
or I T O (Indiu+w-Tin-Oxid
e) Create an EC material dispersed in a conductive substance such as
An EC device using this is being manufactured. However, this E
The C element also had somewhat poor memory properties, and did not satisfy all of the above characteristics.
本発明は物理的成膜法により可視光透過率９着色・消色
応答性、メモリー性のいずれにおいても優れている全固
体ＥＣ素子を得るためにＥＣ素子を構成する酸化型発色
層の改良を目的とする。上記特性のうち、特に、メモリ
ー性の向上を図るために鋭意努力を重ねた。その中で１
本発明者等はＩｒの酸化物または水酸化物を分散させる
受容体として導電性のＳｎＯ□やＺｎＯ□やＩＴＯに代
えて絶縁性を有するＡ／ｚＣ＋＋ｃｒｚＯ：＋＋Ｂｆｚ
０３等の３価金属の酸化物に着目した。そして、該酸化
物中にＩｒの酸化物を分散させた酸化発色層を用いたＥ
Ｃ素子を作製した。その結果、該ＥＣ素子は上記特性の
すべてにおいて優れていることが確かめられた。The present invention aims to improve the oxidized coloring layer constituting the EC device in order to obtain an all-solid-state EC device with excellent visible light transmittance (9) in both coloring/decoloring response and memory performance using a physical film-forming method. purpose. Among the above characteristics, we have made extensive efforts to improve memory performance in particular. Among them, 1
The present inventors used insulating A/zC++crzO:++Bfz instead of conductive SnO□, ZnO□, or ITO as a receptor for dispersing Ir oxides or hydroxides.
We focused on oxides of trivalent metals such as 03. Then, E
A C element was manufactured. As a result, it was confirmed that the EC element was excellent in all of the above characteristics.
本発明は、ｌｒならびにＩｒの酸化物または水酸化物と
Ａ１２０ｚ＋ Ｃｒｚ（ｈ＋ ＢｉｚＯｚ等の３価の金
属の酸化物とからなることを特徴とする酸化発色型エレ
クトロクロミック材料および該エレクトロクロミック材
料を用いた全固体エレクトロクロミック素子に関するも
のである。The present invention provides an oxidative color-forming electrochromic material characterized by comprising an oxide or hydroxide of lr and Ir and an oxide of a trivalent metal such as A120z+Crz(h+BizOz), and an electrochromic material using the electrochromic material. This relates to all-solid-state electrochromic devices.
本発明は極めて微細な１ｒならびにＩｒの酸化物または
水酸化物を分散させる受容体としてこれまで用いられて
きたＳｎＯ□、 ＺｎＯ□またはＩＴＯ等の導電性物質
に代えて絶縁性を有するＡｌ２Ｏ３，Ｃｒ ２ｏ１３ｉ
ｚｏｉ、ＬａｔＯｉ等の３価金属の酸化物を用いること
により可視光透過性を高め１次式に示す着色・消色可逆
反応をスムーズに進むようにして１着色・消色応答性を
向上させた。また、絶縁性の受容体をｒ ｒ （ＯＨ）
ｌｌ＋ｘ （ＯＨ）−（透明）
；： Ｉ ｒ （ＯＨ） ｆｉ＋＊ ＋ Ｘ ｅ−（ダ
ークブルー）
使用したためＥＣ素子の絶縁抵抗が導電性のＳｎＯ□等
を用いた場合の数にΩ／ ｃｎｌから１０”Ω／ｄと大
きくなり電流の漏れ量が著しく減少し９着色後。The present invention uses insulating Al2O3, Cr instead of conductive substances such as SnO□, ZnO□ or ITO, which have been used hitherto as receptors for dispersing extremely fine 1r and Ir oxides or hydroxides. 2o13i
By using oxides of trivalent metals such as zoi and LatOi, the visible light transmittance is increased and the reversible coloring and decoloring reaction shown in the linear equation proceeds smoothly, thereby improving the coloring and decoloring responsiveness. In addition, the insulating receptor is r r (OH)
ll+x (OH)- (transparent) ;: I r (OH) fi+* + After coloring 9, the current leakage amount was significantly reduced as it increased to 10”Ω/d.
回路を遮断し放置した場合の消色までの時間が長くなり
、メモリー性が著しく向上した。したがって、全固体Ｅ
Ｃ膜の防眩ミラー等への応用・実用化の可能性が高まっ
た。When the circuit is cut off and the color is left unused, it takes longer to erase the color, and the memory performance has been significantly improved. Therefore, the total solid E
The possibility of application and practical use of the C film to anti-glare mirrors has increased.
以下本発明の実施態様について説明する。Embodiments of the present invention will be described below.
本発明の実施態様にかかる全固体ＥＣ素子（反射型）の
断面構造を第１図により説明する。基板１１は通常透明
なガラスまたは樹脂であり、その形状は平面板または曲
面板であっても良く、電気信号によりその光学特性の変
化する酸化発色型ＥＣ層１３．還元発色型ＥＣ層１５お
よび誘電体層１４を保持するとともに表示面としての役
割を有する。層１２および層１６は電気信号を印加する
電極である。反射型の場合１層１２が透明導電膜であり
１層１６は反射鏡を兼ねた電極膜である。The cross-sectional structure of an all-solid-state EC element (reflection type) according to an embodiment of the present invention will be explained with reference to FIG. The substrate 11 is usually transparent glass or resin, and its shape may be a flat plate or a curved plate, and includes an oxidation coloring type EC layer 13 whose optical properties change according to an electric signal. It holds the reduction coloring type EC layer 15 and the dielectric layer 14 and also serves as a display surface. Layer 12 and layer 16 are electrodes that apply electrical signals. In the case of a reflective type, one layer 12 is a transparent conductive film, and one layer 16 is an electrode film that also serves as a reflecting mirror.
また、透過型の場合層は９層１６と共に透明導電膜から
成る。ここで６透明導電膜を形成する材料としてはＩ
Ｔ Ｏ（Ｉｎｄｉｕｍ−Ｔｉｎ−Ｏｘｉｄｅ）＋ Ａ
Ｔ Ｏ（Ａｎｔｉｍｏｎｙ−Ｔｉｎ−Ｏｘｉｄｅ）、
Ｚ Ａ Ｏ（Ｚｉｎｃ−Ａｌｕｍｉｎｉｕｍ−Ｏｘｉ
ｄｅ）等を使用することができる。また反射膜を形成す
る材料としては通常光学反射率の高いＡｅ、Ａｇ、Ｉｎ
、Ｓｎ等の金属または合金を使用することができる。酸
化発色型ＥＣ層１３としてはｆｒｉｚが用いられ１通常
その膜厚は１００人〜２０００人程度である。また、還
元発色型ＥＣ層１５としてはＷＯ３ｌＭｏ０＝、 Ｖｚ
Ｏｓ、Ｒｅ０ｚ等が用いられ、その膜厚は通常２０００
人〜１００００人程度である。Further, in the case of a transmission type, the nine layers 16 are made of a transparent conductive film. Here, the material for forming the 6 transparent conductive film is I.
T O (Indium-Tin-Oxide) + A
T O (Antimony-Tin-Oxide),
Z A O (Zinc-Aluminum-Oxi
de) etc. can be used. In addition, the materials for forming the reflective film are usually Ae, Ag, and In, which have high optical reflectance.
, Sn, or other metals or alloys can be used. Friz is used as the oxidation coloring type EC layer 13, and its film thickness is usually about 100 to 2000 layers. Further, as the reduction coloring type EC layer 15, WO3lMo0=, Vz
Os, Re0z, etc. are used, and the film thickness is usually 2000 mm.
Approximately 10,000 to 10,000 people.
さらに誘電体層１４としてはＴａｚ０５＋ＳｉＯ２，Ｔ
ｉ０ｚ＋ＮｂｚＯｓ＋Ａｈ０３＋Ｚｒｏｔ、Ｈｆ０ｚ＋
ＹｚＯｓ等が用いられその膜厚は大吉２０００人〜１０
０００人程度である。第１図に示すＥＣ素子で電極１２
．１６間に印加される電界により誘電体層１４中に含ま
れる１１□０が電気分解し Ｈ＋およびＯＨ−を生ずる
。このＨ”およびＯＨ−とＥＣＪｉ１５およびＥＣ層１
３との酸化・還元反応によってＥＣ層１５．１３を形成
する材料の吸光特性が変化し１着色・消色等の可視光透
過率制御が行われる。ちなみに反射型ＥＣ膜を防眩ミラ
ーとして利用する場合１着色により防眩状態となり消色
により非防眩状態となる。Further, as the dielectric layer 14, Taz05+SiO2,T
i0z+NbzOs+Ah03+Zrot, Hf0z+
YzOs etc. are used and the film thickness is Daikichi 2000 ~ 10
Approximately 000 people. The electrode 12 of the EC element shown in FIG.
．． Due to the electric field applied between the dielectric layers 16 and 16, 11□0 contained in the dielectric layer 14 is electrolyzed to generate H+ and OH-. This H" and OH- and ECJi15 and EC layer 1
The light absorption characteristics of the material forming the EC layer 15.13 change due to the oxidation/reduction reaction with the EC layer 15, 13, and visible light transmittance control such as coloring and decoloring is performed. Incidentally, when the reflective EC film is used as an anti-glare mirror, it becomes an anti-glare state when it is colored with one color, and becomes a non-glare state when it is decolored.
本発明の実施態様にかかる酸化発色物質であるＩｒなら
びにｌｒの酸化物または水酸化物の受容体としては、可
視域で透明なＡ１ｚ０３．ＣｒｔＯｚ＋ＲｉｔＯｓ＋Ｌ
ａＪｓ＋５ＣＪ１等の３価の金属酸化物を用いる。これ
らはいずれも絶縁体である。As the receptor for the oxide or hydroxide of Ir and lr, which are oxidized color-forming substances according to the embodiments of the present invention, A1z03. CrtOz+RitOs+L
A trivalent metal oxide such as aJs+5CJ1 is used. All of these are insulators.
一方１ｒは通常、金属、酸化物または水酸化物の状態と
考えられるが、可視域で物理的手法により透明にするこ
とはかなり困難である。また、エレクトロクロミック膜
として機能させる為には少なくとも酸化物または水酸化
物の形で２００Å以上の膜厚が必要である。着色・消色
時のλ＝５００ｎｍ（視感度が最も高い）に於ける分光
反射率比（コントラスト比）を大きく得ようとすればＩ
ｒ酸化物または水酸化物の厚さを増加させることが必要
であるが逆に消色時の分光反射率の低下を招（、ところ
が本発明の上記受容体中にＩｒを分散させることにより
９等量のＩｒ酸化物または水酸化物だけから成る膜に比
べ可視光透過率を向上させることができる。On the other hand, 1r is usually considered to be in the state of metal, oxide, or hydroxide, but it is quite difficult to make it transparent in the visible range by physical methods. Further, in order to function as an electrochromic film, it is necessary to have a film thickness of at least 200 Å in the form of an oxide or hydroxide. If you want to obtain a large spectral reflectance ratio (contrast ratio) at λ = 500 nm (highest visibility) during coloring and decoloring, I
It is necessary to increase the thickness of the r oxide or hydroxide, but this results in a decrease in the spectral reflectance during decolorization (however, by dispersing Ir in the receptor of the present invention, Visible light transmittance can be improved compared to a film made of only an equal amount of Ir oxide or hydroxide.
本発明の実施態様の酸化発色型ＥＣ層はＩｒを金属、酸
化物、水酸化物の形で上記受容体の中に５〜５０ａｔ％
分散させたものである。Ｉｒ１ｌが５０ａｔ％より多い
と着色量が増大し、光の透過率が著しく悪くなる。逆に
５ａｔ％以下であると実用上必要な着色量が得られなく
なる。また９層の厚さは２００〜２０００人の範囲で選
ばれる。２０００人より厚いと酸化発色現象がイオンの
拡散反応によって律速されるため、その応答性が低下し
、 ゛実用上致命的な欠陥となる。また、２００人よ
り薄いとｌｒ量が少なくなって実用上必要とされる着色
量が得られなくなるとともに、酸化発色過程における膜
の損傷が激しく実用的な耐久性を失うこととなる。The oxidative color-forming EC layer of the embodiment of the present invention contains 5 to 50 at% Ir in the form of metal, oxide, or hydroxide in the receptor.
It is dispersed. When Ir1l is more than 50 at%, the amount of coloring increases and the light transmittance becomes significantly worse. On the other hand, if it is less than 5 at%, it will not be possible to obtain a practically necessary amount of coloring. The thickness of the nine layers is selected within the range of 200 to 2,000 people. If it is thicker than 2,000 mm, the rate of oxidation color development is determined by the ion diffusion reaction, resulting in a decrease in responsiveness, which is a fatal defect in practical use. On the other hand, if the thickness is less than 200, the amount of lr decreases, making it impossible to obtain the amount of coloring required for practical use, and the film is severely damaged during the oxidative coloring process, resulting in a loss of practical durability.
実際にはＩｒ量と膜厚とは相互に関連し、上記範囲内で
それぞれ最適値が決定される。すなわち。In reality, the amount of Ir and the film thickness are mutually related, and their respective optimum values are determined within the above ranges. Namely.
膜厚が大で着色量が著しく大きくなった場合にはＩｒ量
を減らして調整する必要があり、逆に膜厚を薄くした場
合はＩｒ量を増やして着色量を大きくする必要がある。If the film thickness is large and the amount of coloring becomes significantly large, it is necessary to reduce the amount of Ir for adjustment, and conversely, when the film thickness is made thin, it is necessary to increase the amount of Ir to increase the amount of coloring.
本発明の実施態様のｌｒ等と３価金属酸化物との複合酸
化発色層の形成は通常の物理的成膜法によって行うこと
ができる。Ｉｒは金属、酸化物または水酸化物の形での
入手は通常難しく、物理的手法以外では分散膜を形成さ
せることは困難である。物理的成膜法としては５例えば
金属１ｒターゲツトまたは蒸発源であるペレットとＡ７
．Ｏ，、ＢｉｚＯｚ＋ｃｒｚＯ：＋１ａｚＯｔ＋５Ｃｚ
Ｏ＋＋ＹｚＯ：＋等の酸化物ターゲ・ノドまたはペレッ
トとを０□またはＨ２０雰囲気中で同時スパッタ法、同
時蒸着法または同時イオンブレーティング法等により形
成することができる。膜中のＩｒ量はＩｒターゲットま
たはベレ・ノドおよび酸化物ターゲットまたはペレット
への投入電力を制御することにより調整できる。さらに
複合酸化発色膜の厚さ方向にＩｒ量を変化させることも
成膜過程でのＩｒおよび酸化物ターゲットまたはペレッ
トへの投入電力を変化させることにより可能となる。ま
たＩｒと上記酸化物との複合ターゲットまたはペレット
を用いれば同時成膜法を用いなくともスパッタ法、蒸着
法、イオンブレーティング法により所定のＩｒを含有す
る複合酸化発色層を形成できる。Formation of the composite oxidation color forming layer of lr etc. and trivalent metal oxide in the embodiment of the present invention can be performed by a normal physical film forming method. Ir is usually difficult to obtain in the form of metal, oxide, or hydroxide, and it is difficult to form a dispersed film using other than physical methods. As a physical film forming method, for example, a metal 1r target or a pellet as an evaporation source and A7 are used.
．． O,, BizOz+crzO:+1azOt+5Cz
An oxide target such as O++YzO:+ or pellets can be formed by a simultaneous sputtering method, a simultaneous vapor deposition method, a simultaneous ion blating method, etc. in an 0□ or H20 atmosphere. The amount of Ir in the film can be adjusted by controlling the power input to the Ir target or beret and the oxide target or pellet. Furthermore, it is possible to change the amount of Ir in the thickness direction of the composite oxide coloring film by changing the power input to Ir and the oxide target or pellet during the film formation process. Furthermore, if a composite target or pellets of Ir and the above-mentioned oxides is used, a composite oxide coloring layer containing a predetermined amount of Ir can be formed by sputtering, vapor deposition, or ion-blating without using a simultaneous film-forming method.
本実施例の複合酸化発色膜の作製は金属１ｒとＡＺｚＯ
：＋＋ＢｉｚＯ：＋ＣｒｚＯ：＋、５ＣｚＯｔｌａ２０
ｔ＋ＹｚＯｚ等の酸化物とを０□雰囲気中で室温基板（
コーニングガラス階７０５９）上に反応性スパッタ法ま
たは反応性共蒸着法により行った。複合膜の組成はＩｒ
ターゲットまたは蒸発源であるペレットおよび＾Ｚ２０
３．ＢｉＺＯ３＋ Ｃｒ２０３１５ｃｚＯ）、 Ｌａ２
Ｏ３＋ ｙ２ｏ３クーゲットまたは蒸発源への投入電力
を調整し行った。膜厚は触針法により測り１組成はＸ線
マイクロアナライザーおよびオージェ分析により定量し
た。このようにして作製した膜の分光透過率は通常の分
光光度計により測定した。またＩｒターゲットおよびＡ
ｌ２０ｙターゲツトへの投入電力を成膜時間とともに連
続的または断続的に変化させることにより本発明の複合
酸化発色膜の厚さ方向に対しＩｒの分布を自在に制御で
きる。The composite oxidation coloring film of this example was prepared using metal 1r and AZzO.
:++BizO:+CrzO:+, 5CzOtla20
t + oxide such as YzOz on a room temperature substrate (
It was carried out on Corning Glass Floor 7059) by reactive sputtering or reactive co-evaporation. The composition of the composite film is Ir
Pellets and ^Z20 that are targets or evaporation sources
3. BiZO3+ Cr20315czO), La2
The power input to the O3+ y2o3 cuget or evaporation source was adjusted. The film thickness was measured by a stylus method, and the composition was determined by an X-ray microanalyzer and Auger analysis. The spectral transmittance of the film thus produced was measured using a conventional spectrophotometer. Also, Ir target and A
By continuously or intermittently changing the power input to the l20y target with the film forming time, the distribution of Ir in the thickness direction of the composite oxidation color forming film of the present invention can be freely controlled.
一本実施例の複合酸化発色膜のＥＣ特性は第１図にその
断面構造を示す反射型全固体ＥＣ素子の形で評価した。The EC characteristics of the composite oxidation color forming film of this example were evaluated in the form of a reflective all-solid-state EC device whose cross-sectional structure is shown in FIG.
まず透明ガラス基板１１上に透明導電膜１２としてＩＴ
Ｏを約２０００人の厚さに真空蒸着し、続いて本発明の
複合酸化発色膜１３を上述の方法で２００−２０００人
の厚さに形成し。First, IT is applied as a transparent conductive film 12 on a transparent glass substrate 11.
O was vacuum-deposited to a thickness of about 2000 nm, and then the composite oxide coloring film 13 of the present invention was formed to a thickness of 200 to 2000 nm by the method described above.
さらに誘電体層１４としてＴａｚＯｓを約４０００人の
厚さに真空蒸着し、還元発色膜１５として一〇。Furthermore, TazOs was vacuum-deposited as a dielectric layer 14 to a thickness of about 4,000 mm, and a reduction coloring film 15 was formed as a layer of 10 mm.
を約４０００人の厚さに真空蒸着し、最後に反射鏡兼電
極としてＡ１を約４０００人蒸着し１反射型全固体ＥＣ
素子とした。なお、 Ｔａ２０５＋ＷＯｚ膜はいずれも
酸化物ペレットを用い電子ビーム加熱。was vacuum-deposited to a thickness of approximately 4000 mm, and finally A1 was evaporated to a thickness of approximately 4000 mm as a reflector and electrode to form a reflective all-solid-state EC.
It was named Element. Note that both Ta205+WOz films were heated by electron beam using oxide pellets.
真空蒸着法により作製した。なお酸化発色層１３゜誘電
体層１４．還元発色層１５の積層順を上記実施例と逆に
して素子を形成することは当然可能で事実同一の効果が
得られた。また素子作製中基板の加熱は行わなかった。Manufactured by vacuum evaporation method. Note that the oxidized coloring layer 13.dielectric layer 14. It is of course possible to form an element by reversing the stacking order of the reduction color forming layer 15 from that of the above embodiment, and in fact the same effect could be obtained. Further, the substrate was not heated during device fabrication.
本実施例のＥＣ素子の着消色特性は以下の手順で評価し
た。The coloring and fading characteristics of the EC element of this example were evaluated using the following procedure.
第１図に示す素子の透明導電膜１２とＡ１反射膜１６と
の間に±１．５ボルトの直流電圧を０．２１１ｚの周期
で５００回印加し、活性化後着色時および消色時の分光
反射率を測定しそれらの比から以下の式で定義されるコ
ントラスト比を求めた。A DC voltage of ±1.5 volts was applied 500 times at a period of 0.211z between the transparent conductive film 12 and the A1 reflective film 16 of the device shown in FIG. The spectral reflectance was measured and the contrast ratio defined by the following formula was determined from the ratio thereof.
コントラスト比＝ｌｏｇＣ消色時反射率／着色時反射率
）
また着色・消色応答性は±１．５ボルトの印加周期を０
．５１１ｚ（１抄着色／１秒消色）と変化させコントラ
スト比を評価した。さらに素子のメモリー性は１．５ボ
ルトを５秒間印加し着色させた後、電極１２．１６間を
開放し初期着色量の８０％迄自然消色する迄の時間τを
計測した。τの長い程メモリー性は良好となる。Contrast ratio = logC reflectance when decoloring/reflectance when coloring
．． 511z (coloring for 1 paper/decoloring for 1 second) and evaluated the contrast ratio. Furthermore, the memory property of the device was determined by applying 1.5 volts for 5 seconds to color the device, then opening the gap between the electrodes 12 and 16, and measuring the time τ until the color naturally faded to 80% of the initial coloring amount. The longer τ is, the better the memory performance is.
表は以下に示す実施例１〜２１．比較例１〜４で作製し
た酸化発色膜の着色・消色応答性等の特性を調べた結果
を示したものである。The table shows Examples 1 to 21 shown below. This figure shows the results of examining the characteristics of the oxidized coloring films prepared in Comparative Examples 1 to 4, such as coloring and decoloring responsiveness.
実施例１〜３： ＩｒターゲットとＡ４０３ターゲツト
を用いて０□雰囲気中で同時ス
バッタ法により成膜した。膜厚
は７００人一定とし、投入電力
を調整して膜中のＩｒ量を変化
させた。Examples 1 to 3: Films were formed by simultaneous sputtering in a 0□ atmosphere using an Ir target and an A403 target. The film thickness was kept constant for 700 people, and the amount of Ir in the film was varied by adjusting the input power.
実施例４〜６：Ｉ「ペレットとＡｌＯ３ペレットを用い
て０２雰囲気中で同時蒸着法
によって成膜した。膜厚は７０
０人一定とし、投入電力を調整
し、Ｉｒ量を変化させた。Examples 4 to 6: Films were formed by simultaneous evaporation in an 02 atmosphere using I pellets and AlO3 pellets.The film thickness was kept constant at 700, the input power was adjusted, and the amount of Ir was varied.
実施例７〜１６：ＩｒターゲットとＢｔｚＯｚ＋Ｃｒｚ
Ｏｚ、ＬａｚＯ＋ｔＳｃｚＯｚ またはＹ２Ｏ３ターゲ
ットとを用いて０２雰囲気中で
同時スパッタ法によって成膜し
た。膜厚は７００人一定とし。Examples 7-16: Ir target and BtzOz+Crz
A film was formed by simultaneous sputtering in a 02 atmosphere using Oz, LazO+tSczOz or Y2O3 targets. The film thickness is fixed at 700 people.
各酸化物について投入電力を調 整し、膜中のｔｒ量を変化させ た。Check the input power for each oxide. and change the amount of tr in the film. Ta.
実施例１７〜１９：ＩｒターゲットとＡｌ０−ｓターゲ
ットを用いて０□雰囲気中で同
時スパッタ法によって成膜した。Examples 17 to 19: Films were formed by simultaneous sputtering in an atmosphere of 0□ using an Ir target and an Al0-s target.
膜中のＩｒ量を７．２ａｔ％一定と し膜厚を変化させた。The amount of Ir in the film is kept constant at 7.2 at%. The film thickness was changed.
実施例２０〜２１：Ｉｒターゲットとへ！０．夕一ゲン
トを用いて０２雰囲気中で同
時スパッタ法によって成膜した。Examples 20-21: To Ir target! 0. A film was formed by simultaneous sputtering using Yuichi Ghent in an 02 atmosphere.
膜厚を７００人一定とし、投入 電力を変化させ、膜中のＩｒｌ を第２図に示すように厚さ方向 に変化させた。Injected with a constant film thickness of 700 people. By changing the power, Irl in the membrane in the thickness direction as shown in Figure 2. changed to.
比較例１〜２：ターゲットをＩｒとし、０□雰囲気中で
スパッタしＩｒとＩｒの
酸化物からなる膜を形成させた。Comparative Examples 1 and 2: Using Ir as a target, sputtering was performed in an atmosphere of 0□ to form a film made of Ir and an oxide of Ir.
比較例３〜４：ターゲットをＩｒとＺｎＯまたはＳｎＯ
２とし、０２雰囲気中で同時ス
パッタし、 ＺｎＯ等の中に］ｒと
Ｉｒの酸化物を分散させた膜を
形成した。Comparative Examples 3 to 4: Ir and ZnO or SnO as targets
2 and simultaneously sputtered in a 02 atmosphere to form a film in which oxides of r and Ir were dispersed in ZnO or the like.
これらの実施例、比較例の結果から、酸化発色型ＥＣ材
として３価金属の酸化物中に［ｒの酸化物も分散させた
ものを用いるとＩｒの酸化物のみからなるもの、あるい
はＺｎＯやＳｎＯ□中にＩｒの酸化物を分散させたもの
と比較して可視光透過率。From the results of these Examples and Comparative Examples, it is clear that if an oxidative color-forming EC material in which an oxide of [r is also dispersed in an oxide of a trivalent metal is used, a material consisting only of an oxide of Ir, or a material consisting of only an oxide of Ir, or a material such as ZnO or Visible light transmittance compared to that of Ir oxide dispersed in SnO□.
コントラスト比ならびにメモリー性ともに優れているこ
とが明らかである。It is clear that both the contrast ratio and memory properties are excellent.
なお、第１図に示す層構造を逆にしてＥＣ素子を作製す
ること、また、透過型とし調光機能膜として利用できる
ことは当然である。It goes without saying that the layer structure shown in FIG. 1 can be reversed to produce an EC element, and that it can also be made into a transmissive type and used as a light control function film.
第１図は本発明で用いた反射型全固体ＥＣ素子の断面構
造を示す説明図である。また、第２図は本発明の実施例
２０．２１で作製した複合酸化発色膜中のＩｒの分布状
態を示した説明図である。
１１・・・ガラス基板、１２・・・透明導電膜。
１３・・・酸化発色膜、１４・・・誘電体膜。FIG. 1 is an explanatory diagram showing the cross-sectional structure of the reflective all-solid-state EC element used in the present invention. Moreover, FIG. 2 is an explanatory diagram showing the distribution state of Ir in the composite oxidation coloring film produced in Examples 20 and 21 of the present invention. 11...Glass substrate, 12...Transparent conductive film. 13... Oxidation coloring film, 14... Dielectric film.
Claims (3)
化物とＡｌ＿２Ｏ＿３、Ｃｒ＿２Ｏ＿３、Ｂｉ＿２Ｏ＿
３、Ｙ＿２Ｏ＿３等の３価金属の酸化物とからなること
を特徴とする酸化発色型エレクトロクロミック材料。(1) Iridium and iridium oxide or hydroxide and Al_2O_3, Cr_2O_3, Bi_2O_
3. An oxidative color-forming electrochromic material comprising an oxide of a trivalent metal such as Y_2O_3.
は水酸化物および３価金属の酸化物が物理的成膜法によ
って形成された膜によって構成されたことを特徴とする
特許請求の範囲第（１）項記載の酸化発色型エレクトロ
クロミック材料。(2) Claim (1) characterized in that the iridium, the iridium oxide or hydroxide, and the trivalent metal oxide are constituted by a film formed by a physical film forming method. The oxidative color-forming electrochromic material described above.
層と誘電体からなる絶縁層と還元発色型エレクトロクロ
ミック層とを順次積層してなる全固体エレクトロクロミ
ック素子において、酸化発色型エレクトロクロミック層
がイリジウムまたはイリジウムの酸化物または水酸化物
とＡｌ＿２Ｏ＿３、Ｃｒ＿２Ｏ＿３、Ｂｉ＿２Ｏ＿３、
Ｙ＿２Ｏ＿３等の３価金属の酸化物とからなることを特
徴とする全固体エレクトロクロミック素子。(3) In an all-solid-state electrochromic device in which an oxidative color-forming electrochromic layer, an insulating layer made of a dielectric, and a reduction color-forming electrochromic layer are sequentially laminated between a pair of electrodes, the oxidative color-forming electrochromic layer is made of iridium. or iridium oxide or hydroxide and Al_2O_3, Cr_2O_3, Bi_2O_3,
An all-solid-state electrochromic device comprising an oxide of a trivalent metal such as Y_2O_3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62046114A JPS63210916A (en) | 1987-02-27 | 1987-02-27 | Electrochromic material and electrochromic element |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62046114A JPS63210916A (en) | 1987-02-27 | 1987-02-27 | Electrochromic material and electrochromic element |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63210916A true JPS63210916A (en) | 1988-09-01 |
Family
ID=12737973
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62046114A Pending JPS63210916A (en) | 1987-02-27 | 1987-02-27 | Electrochromic material and electrochromic element |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63210916A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1986043A3 (en) * | 2001-09-26 | 2009-06-10 | ChromoGenics AB | Electrochromic film and device comprising the same |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59228628A (en) * | 1983-06-10 | 1984-12-22 | Canon Inc | Entirely solid electrochromic element |
| JPS60263125A (en) * | 1984-06-11 | 1985-12-26 | Nippon Kogaku Kk <Nikon> | Electrochromic display device |
| JPS61241732A (en) * | 1985-04-18 | 1986-10-28 | Nippon Kogaku Kk <Nikon> | Two-color type electrochromic element |
| JPS61296380A (en) * | 1985-06-26 | 1986-12-27 | 株式会社ニコン | Manufacture of electrolytic acid thin film |
-
1987
- 1987-02-27 JP JP62046114A patent/JPS63210916A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59228628A (en) * | 1983-06-10 | 1984-12-22 | Canon Inc | Entirely solid electrochromic element |
| JPS60263125A (en) * | 1984-06-11 | 1985-12-26 | Nippon Kogaku Kk <Nikon> | Electrochromic display device |
| JPS61241732A (en) * | 1985-04-18 | 1986-10-28 | Nippon Kogaku Kk <Nikon> | Two-color type electrochromic element |
| JPS61296380A (en) * | 1985-06-26 | 1986-12-27 | 株式会社ニコン | Manufacture of electrolytic acid thin film |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1986043A3 (en) * | 2001-09-26 | 2009-06-10 | ChromoGenics AB | Electrochromic film and device comprising the same |
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