JPS6353294A - Production of iridium oxide film - Google Patents
Production of iridium oxide filmInfo
- Publication number
- JPS6353294A JPS6353294A JP19666986A JP19666986A JPS6353294A JP S6353294 A JPS6353294 A JP S6353294A JP 19666986 A JP19666986 A JP 19666986A JP 19666986 A JP19666986 A JP 19666986A JP S6353294 A JPS6353294 A JP S6353294A
- Authority
- JP
- Japan
- Prior art keywords
- iridium
- oxide film
- substrate
- iridium oxide
- conductive substrate
- 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
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 229910000457 iridium oxide Inorganic materials 0.000 title claims abstract description 21
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 239000000758 substrate Substances 0.000 claims abstract description 22
- VNVQLDDPGAWSSB-UHFFFAOYSA-H iridium(3+);trisulfate Chemical compound [Ir+3].[Ir+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O VNVQLDDPGAWSSB-UHFFFAOYSA-H 0.000 claims abstract description 11
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims 1
- 239000010408 film Substances 0.000 description 29
- 238000000034 method Methods 0.000 description 7
- 238000000151 deposition Methods 0.000 description 6
- 229910052741 iridium Inorganic materials 0.000 description 6
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 6
- 230000008021 deposition Effects 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- 238000004040 coloring Methods 0.000 description 4
- 238000004042 decolorization Methods 0.000 description 4
- 238000002834 transmittance Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005562 fading Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000005240 physical vapour deposition Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 101100202463 Schizophyllum commune SC14 gene Proteins 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 238000002048 anodisation reaction Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 239000010409 thin film Substances 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
- 238000007740 vapor deposition Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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、少なくとも表面に電子伝導廿を有する材料の
表面上に、交流電解析出法によってエレクトロクロミッ
ク性（以下ＥＣ性と略す）を有する酸化イリジウム被膜
を製造する方法に関する。Detailed Description of the Invention [Industrial Field of Application] The present invention provides an oxidized material having electrochromic properties (hereinafter abbreviated as EC properties) by alternating current electrolytic deposition on the surface of a material having electron conductivity at least on the surface. The present invention relates to a method of manufacturing an iridium coating.
従来、酸化イリジウム膜は、ＥＣ性を示すことが知られ
ており、これを使用した素子も数多く提案されている。Conventionally, it has been known that iridium oxide films exhibit EC properties, and many devices using the same have been proposed.
Ｅ（Ｊとしての酸化イリジウム膜は、／）応等が速い、
２）化学的に安定である。３）駆動寿命が長い１等の利
点がありＷＯ２膜と共に有望視されている。E (Iridium oxide film as J is /) etc. is fast,
2) Chemically stable. 3) It has the advantage of long driving life and is considered promising along with the WO2 film.
酸化イリジウム膜の形成方法としては、通常、スパッタ
法、蒸着法などいわゆるＰＶＤ法が用いられ、例えば■
初めにイリジウム金属の薄膜を得た後、酸化＝囲気での
焼成、陽極酸化等の酸化処理を施す方法（例えば、Ｓ、
にｏｔｔｅｓｔｅｌｄｓ 、Ａｐｐｌ。As a method for forming an iridium oxide film, a so-called PVD method such as a sputtering method or a vapor deposition method is usually used.
A method in which a thin film of iridium metal is first obtained and then subjected to oxidation treatment such as oxidation = firing in an ambient atmosphere, anodization, etc. (for example, S,
ottestelds, Appl.
ＰｈｙＳ、ＬｅｔｔｅｒＳ、３Ｊ 、 ２０１ （／り
７ｒ）） 、■酸素雰 ″囲気下のスパッタ法により、
膜付けを行う方法（例えば、全弁ら、真空、第２７巻、
第３号（７９ざＩＩ）グア）等が知られている。PhyS, LetterS, 3J, 201 (/7r)), ■By sputtering method under oxygen atmosphere,
Methods for film attachment (for example, Zenben et al., Vacuum, Vol. 27,
No. 3 (79za II) Gua), etc. are known.
このようなＰＶＤ法では、繁雑な操作を必要とするため
、生産性が悪く、大面積にわたって均一な被膜を作成す
ることが困難であり、かつ大型で高価な装置を必要とす
るためｔ！！造コストが割高となる等の問題点があった
。Such PVD methods require complicated operations, resulting in poor productivity, difficulty in creating a uniform film over a large area, and the need for large and expensive equipment. ! There were problems such as relatively high manufacturing costs.
また、直流電解析出法によって酸化イリジウム膜が得ら
れることが知られている（゛例えば、合方ら、電気化学
会講演（／Ｉｒ！ 、秋季大会））。It is also known that an iridium oxide film can be obtained by direct current electrolytic deposition (for example, Agata et al., Lecture at the Electrochemical Society of Japan (/Ir!, Fall Meeting)).
しかしながら上記直流電解析出法により得られた膜は透
過率の変化幅が小さく、特に消色時に消え残りがあると
いう問題点を有していた。However, the film obtained by the above-mentioned DC electrolytic deposition method has the problem that the range of change in transmittance is small, and in particular, there is some residual color left after decoloring.
本発明は、生産性が高く、且つ大面積にわたって均一で
あり、良好なＥＣ性を示す酸化イリジウム被膜の製造方
法を提供することを目的とする。An object of the present invention is to provide a method for producing an iridium oxide film that is highly productive, uniform over a large area, and exhibits good EC properties.
本発明は、硫酸イリジウムを含む水溶液に少なくとも表
面に導電性を有する導電性基板と対極を入れ、導電性基
板の極性を交互に反転しながら導電性基板および対極間
に電圧を印加して該導電性基板上に酸化イリジウム被膜
を形成させている。In the present invention, a conductive substrate having conductivity at least on the surface and a counter electrode are placed in an aqueous solution containing iridium sulfate, and a voltage is applied between the conductive substrate and the counter electrode while alternately reversing the polarity of the conductive substrate to conduct the conductive substrate. An iridium oxide film is formed on a transparent substrate.
前記水溶液に添加するＦＡ酸イリジウムとしては、無水
物である工ｒ２（ＳＯ４）３ が消色時に消え歿りの少
ないＥＣ膜が得られやすいので好ましい。又硫酸イリジ
ウムの濃度を２〜ｒｗｔ％とすることが、すぐれたＥＣ
特性の酸化イリジウム膜を得るために望ましい。As the iridium FA acid added to the aqueous solution, it is preferable to use the anhydride iridium 2(SO4)3 since it is easy to obtain an EC film with less fading during decoloring. Also, setting the concentration of iridium sulfate to 2 to rwt% provides excellent EC.
desirable for obtaining iridium oxide films with specific properties.
析出時の分極電圧（正、負共に）は、印加電圧時の電流
密度が２０〜．１ｍＡ／ｉとなるように設定するのが好
ましく、特に、電流密度がＪ Ｏ−Ｊ ＯｍＡ／ｃｒ７
Ｉのとき、良好なＥＣ性を得ることができる。The polarization voltage (both positive and negative) during deposition is such that the current density at the time of applied voltage is 20~. It is preferable to set the current density to 1 mA/i, especially when the current density is J O-J OmA/cr7
When I, good EC properties can be obtained.
このように、極性を反転することにより、導電性の基板
が、カソード時にはイリジウム金属の析出が起こり、ア
ノード時には酸化が起こり、酸化イリジウム被膜を形成
する。極性はＯ，１〜３０秒間隔、望ましくは１〜１０
秒間隔で反転することが均質な膜を得るために好ましい
。By reversing the polarity in this manner, the conductive substrate undergoes iridium metal deposition at the cathode and oxidation at the anode to form an iridium oxide film. Polarity: O, 1-30 second intervals, preferably 1-10
Inversion every second is preferred to obtain a homogeneous film.
このような極性の反転を数秒間隔で繰り返し行うと、イ
リジウム金属の非常に薄い層（７０−１０ｍオーダ）で
反応が起こり、十分に酸化された酸化イリジウム被膜が
得られる。これにより、直流電解析出法によって得られ
る酸化イリジウム膜に比べ消色時の消え残りが解消され
、消色時に十分高い透過率が得られる。また、膜厚を十
分厚くすることにより、着色時に十分な吸収が得られる
。When such polarity reversals are repeated at intervals of several seconds, a reaction occurs in a very thin layer (on the order of 70-10 m) of iridium metal, resulting in a fully oxidized iridium oxide film. As a result, as compared to an iridium oxide film obtained by direct current electrolytic deposition, there is no residual fade during decolorization, and a sufficiently high transmittance can be obtained during decolorization. Furthermore, by making the film thick enough, sufficient absorption can be obtained during coloring.
得られた膜の分光スペクトルは、はぼ可視域全体にわた
って、吸収を有することからシャッター効果が大きいこ
とがわかる。The spectrum of the obtained film shows absorption throughout the entire visible range, indicating that the shutter effect is large.
まず、純水１００ｍ１ｌに対して、硫酸イリジウムＩｒ
２（ＳＣ１４）２を添加し、Ｊｗｔ％の硫酸イリジウム
溶液を作成し、析出浴とした。First, for 100ml of pure water, iridium sulfate, Ir.
2(SC14)2 was added to prepare a Jwt% iridium sulfate solution, which was used as a precipitation bath.
導電性基板として、透明導電膜であるインジウム、スズ
酸化物膜（以下ＩＴＯ膜と略称する）付ガラス基板を、
対極としてｐｔはくを使用する。As a conductive substrate, a glass substrate with an indium and tin oxide film (hereinafter abbreviated as ITO film), which is a transparent conductive film, was used.
A PT foil is used as the counter electrode.
ＩＴＯ膜付膜付側板側Ｓ、Ｏ（Ｖ）の電圧を６秒間、そ
の後−２，０（Ｖ）の電圧を３秒間印加する。電圧波形
を第１図に示す。A voltage of S, O (V) on the ITO film-coated side plate side is applied for 6 seconds, and then a voltage of -2.0 (V) is applied for 3 seconds. The voltage waveform is shown in FIG.
この操作を１０分間繰り返した。得られた膜は、約１１
００ｎ テあった。ＯＡ；ｍｏｌ／ｌのＨ２ＳＯ４水溶
液の電解質、白金対極および上記酸化イリジウム膜つき
ガラス基板を用いて簡易ＥＣセルを作成し、両電極間に
士ハＳ （Ｖ）の電圧を印加し、該ＥＣセルの光学応答
を測定した。着消色時の分光スペクトルを第２図に示す
。また、印加電圧変化時の波長乙３２、にｎｍの光の透
過率の時間変化を第３図に示す。This operation was repeated for 10 minutes. The obtained membrane had a thickness of about 11
00n It happened. A simple EC cell was prepared using an electrolyte of OA; mol/l H2SO4 aqueous solution, a platinum counter electrode, and the above-mentioned glass substrate with an iridium oxide film. The optical response was measured. Fig. 2 shows the spectrum when coloring and decoloring. Further, FIG. 3 shows the time change in the transmittance of light at a wavelength of 32 nm when the applied voltage changes.
第２図および第３図から消色時の透過率は十分高く、早
い応答が得られていることがわがる。It can be seen from FIGS. 2 and 3 that the transmittance during decolorization is sufficiently high and a fast response is obtained.
また、析出浴作製後、容器に移し、室内に７０日間保存
後、上記同様にして析出を行ったが得られた膜の特性は
ほとんど同じであった。この事がら析出浴はほとんど経
時的に変化せず、安定であることがわかった。Further, after the precipitation bath was prepared, it was transferred to a container and stored indoors for 70 days, and then precipitation was performed in the same manner as above, but the properties of the obtained film were almost the same. This indicates that the precipitation bath hardly changes over time and is stable.
本発明によれば、実施例からも明らかなとうりＥＣ素子
を作成した際消色時の透過性が、十分高い酸化イリジウ
ム被膜を作成することができる。又本発明によれば大面
積にわたり、均一な膜を安価に形成することができ、更
に析出条件を制御することにより得られる被膜の膜淳を
正確に制御することもできる。According to the present invention, when an EC element is produced, an iridium oxide film having sufficiently high transparency during decolorization can be produced, as is clear from the Examples. Further, according to the present invention, a uniform film can be formed over a large area at low cost, and furthermore, by controlling the deposition conditions, the thickness of the resulting film can be accurately controlled.
又、本発明は、従来の真空法などの製゛造法とくらべて
大規模な設備を必要とせず、析出浴が経時的にほとんど
変化しないため、安定して膜の供給が可能であり、高い
生産性が期待される。In addition, the present invention does not require large-scale equipment compared to conventional production methods such as vacuum methods, and since the precipitation bath hardly changes over time, it is possible to stably supply the film. High productivity is expected.
第１図は、本発明実施例にて電極間に印加した電圧およ
び時間変化を示す図、第２図および第３図は実施例にて
作成した酸化イリジウム膜を使用したＥＣ素子の着消色
時の分光スペクトルを示す図および着消色速度を示す図
である。
第１図Fig. 1 is a diagram showing the voltage applied between the electrodes and the change over time in an example of the present invention, and Figs. 2 and 3 are coloring and decoloring of an EC element using an iridium oxide film prepared in an example. FIG. 2 is a diagram showing a spectroscopic spectrum at a certain time and a diagram showing a coloring/fading speed. Figure 1
Claims (4)
面に導電性を有する導電性基板と前記導電性基板表面に
電流を流すために必要な対極を浸漬し、前記導電性基板
の極性を交互に反転しながら導電性基板および対極間に
電圧を印加して前記導電性基板の表面上に酸化イリジウ
ム被膜を析出させる酸化イリジウム被膜の製造方法。(1) In an aqueous solution containing iridium sulfate, a conductive substrate having at least conductivity on its surface and a counter electrode necessary for passing a current through the surface of the conductive substrate are immersed, and the polarity of the conductive substrate is alternately reversed. A method for producing an iridium oxide film, in which an iridium oxide film is deposited on the surface of the conductive substrate by applying a voltage between the conductive substrate and a counter electrode.
＿２（ＳＯ＿４）＿３で表わされる無水硫酸イリジウム
を溶かした水溶液である特許請求の範囲第１項記載の酸
化イリジウム被膜の製造方法。(2) The aqueous solution containing iridium sulfate has the chemical formula Ir
The method for producing an iridium oxide film according to claim 1, which is an aqueous solution in which anhydrous iridium sulfate represented by _2(SO_4)_3 is dissolved.
る特許請求の範囲第１項又は第２項記載の酸化イリジウ
ム被膜の製造方法。(3) The method for producing an iridium oxide film according to claim 1 or 2, wherein the amount of iridium sulfate added is 1 to 5 wt%.
に反転させる特許請求の範囲第１項ないし第３項記載の
酸化イリジウム被膜の製造方法。(4) The method for producing an iridium oxide film according to claims 1 to 3, wherein the polarity of the conductive substrate is alternately reversed at intervals of 0.1 to 30 seconds.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19666986A JPS6353294A (en) | 1986-08-22 | 1986-08-22 | Production of iridium oxide film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19666986A JPS6353294A (en) | 1986-08-22 | 1986-08-22 | Production of iridium oxide film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6353294A true JPS6353294A (en) | 1988-03-07 |
Family
ID=16361623
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP19666986A Pending JPS6353294A (en) | 1986-08-22 | 1986-08-22 | Production of iridium oxide film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6353294A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5356574A (en) * | 1992-09-22 | 1994-10-18 | Petoca, Ltd. | Process for producing pitch based activated carbon fibers and carbon fibers |
| JP2014152341A (en) * | 2013-02-05 | 2014-08-25 | Tanaka Kikinzoku Kogyo Kk | Anode electrolytic plating method of iridium oxide coating |
-
1986
- 1986-08-22 JP JP19666986A patent/JPS6353294A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5356574A (en) * | 1992-09-22 | 1994-10-18 | Petoca, Ltd. | Process for producing pitch based activated carbon fibers and carbon fibers |
| JP2014152341A (en) * | 2013-02-05 | 2014-08-25 | Tanaka Kikinzoku Kogyo Kk | Anode electrolytic plating method of iridium oxide coating |
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