JPS6333595A - Electrodeposited iridium oxide film - Google Patents
Electrodeposited iridium oxide filmInfo
- Publication number
- JPS6333595A JPS6333595A JP61173653A JP17365386A JPS6333595A JP S6333595 A JPS6333595 A JP S6333595A JP 61173653 A JP61173653 A JP 61173653A JP 17365386 A JP17365386 A JP 17365386A JP S6333595 A JPS6333595 A JP S6333595A
- Authority
- JP
- Japan
- Prior art keywords
- iridium oxide
- solution
- electrodeposition
- film
- anode
- 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 description 17
- 229910000457 iridium oxide Inorganic materials 0.000 title claims description 17
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 18
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 25
- 238000004070 electrodeposition Methods 0.000 claims description 20
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 239000008139 complexing agent Substances 0.000 claims description 4
- 238000000151 deposition Methods 0.000 claims description 2
- 230000008021 deposition Effects 0.000 claims description 2
- 150000002504 iridium compounds Chemical class 0.000 claims 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 abstract description 10
- 229910000029 sodium carbonate Inorganic materials 0.000 abstract description 5
- 229910021639 Iridium tetrachloride Inorganic materials 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract 1
- 235000017550 sodium carbonate Nutrition 0.000 abstract 1
- 239000010408 film Substances 0.000 description 27
- 239000010409 thin film Substances 0.000 description 7
- 238000005868 electrolysis reaction Methods 0.000 description 6
- 239000011521 glass Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- CALMYRPSSNRCFD-UHFFFAOYSA-J tetrachloroiridium Chemical compound Cl[Ir](Cl)(Cl)Cl CALMYRPSSNRCFD-UHFFFAOYSA-J 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000005546 reactive sputtering Methods 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D9/00—Electrolytic coating other than with metals
- C25D9/04—Electrolytic coating other than with metals with inorganic materials
- C25D9/06—Electrolytic coating other than with metals with inorganic materials by anodic processes
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electrochromic Elements, Electrophoresis, Or Variable Reflection Or Absorption Elements (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明はイリジウム酸化物薄膜に係り、特に製造コウト
の低減に好適なイリジウム酸化物電析膜に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to an iridium oxide thin film, and particularly to an iridium oxide electrodeposited film suitable for reducing production cost.
［従来の技術］
従来、エレクトロクロミンク物質として知られるイリジ
ウム酸化物薄膜は、リアクティブスパッタ（Ｕ、Ｓ、Ｐ
、４，２５８，９８４）やイオンブレーティング（特開
昭５４−３１７６３）などの真空技術によって形成され
てきた。[Prior Art] Conventionally, an iridium oxide thin film known as an electrochromic material has been produced by reactive sputtering (U, S, P
, 4,258,984) and ion blating (Japanese Unexamined Patent Publication No. 54-31763).
［発明が解決しようとする問題点］
しかし、これらの方法は、真空技術を使用しているため
、薄膜形成のコストが高い。このため。[Problems to be Solved by the Invention] However, since these methods use vacuum technology, the cost of forming a thin film is high. For this reason.
より低コストでイリジウム酸化物薄膜を形成する技術の
開発が望まれていた。It has been desired to develop a technique for forming iridium oxide thin films at lower cost.
本発明の目的は、簡便な方法でイリジウム酸化物薄膜を
形成する技術を提供することにある。An object of the present invention is to provide a technique for forming an iridium oxide thin film using a simple method.
［問題点を解決するための手段］
上記目的は、イリジウム酸化物薄膜を電析によって形成
することによって、達成される。[Means for Solving the Problems] The above object is achieved by forming an iridium oxide thin film by electrodeposition.
硫酸イリジウム（Ｉｒ （ＳＯ２）２）や四塩化イリジ
ウム（ＩｒＣＱ４）のＰＨが１附近の酸性水溶液に１対
の電極を浸漬し、適当な電流密度で電解すると陰極側に
茶褐色の被膜を析出させることが出来る。A pair of electrodes is immersed in an acidic aqueous solution of iridium sulfate (Ir (SO2)2) or iridium tetrachloride (IrCQ4) with a pH of around 1, and electrolysis is performed at an appropriate current density to deposit a brownish-brown film on the cathode side. I can do it.
例えば、５ｇ／Ｑの四塩化イリジウムのｐＨが１．０の
溶液を用意し、液温を２５℃、電析電流導度を２ ｍ
Ａ ／ ａｌ、電析時間を３０分とし、透明導電膜をコ
ートしたガラス基板を陰極側として電解すると、透明導
電膜上に茶褐色の被膜が析出する。しかし、この条件で
電析した被膜は不均一で色むらが生じる。For example, prepare a solution of 5 g/Q iridium tetrachloride with a pH of 1.0, set the solution temperature to 25°C, and set the electrodeposition current conductivity to 2 m
A/al, when the electrodeposition time was set to 30 minutes and the glass substrate coated with a transparent conductive film was used as the cathode side, electrolysis was performed, and a brownish-brown film was deposited on the transparent conductive film. However, the coating deposited under these conditions is non-uniform and has uneven color.
［作用］
上述の電析膜の不均一性は、電析液が酸性であるため、
陰極側で水素が発生し易く、電析効率が低いことによる
と推定できる６
ところが、上記電析液ら炭酸ナトリウムを加えて液性を
アルカリ性とすると、電析効率に著しく向上する。アル
カリ性の電析液では１００μＡ／ｄ以下という低い電流
密度で電析が可能になる。[Effect] The above-mentioned non-uniformity of the deposited film is due to the acidity of the electrodepositing solution.
It is presumed that this is because hydrogen is easily generated on the cathode side and the electrodeposition efficiency is low.6 However, when sodium carbonate is added to the above electrodeposition solution to make the liquid alkaline, the electrodeposition efficiency is significantly improved. With an alkaline electrodepositing solution, electrodeposition can be performed at a low current density of 100 μA/d or less.
さらに、この場合、陰極に茶褐色の被膜が析出するとと
もに陽極に使用した透明導電膜にもブルーブラックの被
膜が析出した。陰極に析出した被膜は析出メカニズムか
らＩｒ（ＯＨ） と考えられ、４−δ
陽極に析出した被膜はＩｒ（ＯＨ） と考えられ４−
δ
る。Furthermore, in this case, a brownish-brown film was deposited on the cathode, and a blue-black film was also deposited on the transparent conductive film used for the anode. The film deposited on the cathode is thought to be Ir(OH) based on the precipitation mechanism, and the film deposited on the anode is thought to be Ir(OH).
δru.
陽極に析出するブルーブラックの被膜の厚さは電析液の
ＰＨに大きく依存する。すなわち、電析液のｐＨが８未
満の場合には１００μＡ／ｃｄ程度の電流密度では電析
されない。The thickness of the blue-black film deposited on the anode largely depends on the pH of the electrolyte. That is, if the pH of the electrodepositing solution is less than 8, electrodeposition will not occur at a current density of about 100 μA/cd.
また、アルカリ性電析液は放置することにより、液性が
変化し、電析効率が変化するという性質を有する。この
電析液の経時変化を防ぐためには錯化剤を電析液に添加
するのが有効である。例えば。Furthermore, the alkaline electrodepositing solution has the property that when it is left to stand, the liquid properties change and the electrodeposition efficiency changes. In order to prevent this deterioration of the electrodeposition solution over time, it is effective to add a complexing agent to the electrodeposition solution. for example.
錯化剤としてシュウ酸を添加すると、電析液は暗い茶色
から、濃い紫に変化する。この紫色の電析液は安定な溶
液であり、ｐＨの経時変化が少なく、電析効率の変動も
小さい。。When oxalic acid is added as a complexing agent, the color of the deposit changes from dark brown to deep purple. This purple electrodeposition solution is a stable solution, with little change in pH over time and little variation in electrodeposition efficiency. .
また、陰極に析出した茶褐色の電析被膜は、電極でアニ
オンを放出することにより無色になり、アニオンの注入
により再び茶褐色に変化する。全く同様の変化が陽極に
析出したブルーブラックの電析被膜に認められる。この
場合にはブルーブラック−無色の変化が起きる。従って
、これらの被膜はエレクトロクロミンク表示・素子に応
用できる。Further, the brown electrodeposited film deposited on the cathode becomes colorless by releasing anions at the electrode, and changes to brown again by injection of anions. Exactly the same change is observed in the blue-black electrodeposited film deposited on the anode. In this case a blue-black-colorless change occurs. Therefore, these films can be applied to electrochromic displays/devices.
［実施例］
以下、本発明の内容を具体的実施例でより詳細に説明す
る。[Examples] Hereinafter, the contents of the present invention will be explained in more detail with reference to specific examples.
実施例１
５ ｇ ／ ＱのＩｒＣｌ２４を含む溶液を１００ｍＡ
調整した。この溶液に少量のカセイソーダ水溶液を加え
、ｐＨを１．０とした。こり溶液を、シート抵抗が１０
Ω／ｄの酸化イリジウム主成分とする透明導電膜でコー
トしたガラス基板を陰極、金線を陽極、電析電流密度を
２ ｍ Ａ ／ ａｄとし、２５℃で３０分間電解した
。その結果、陰極の透明導電膜上に茶褐色の被膜が電析
された。しかし、電析被膜は不均一な膜であり、著しい
色むらがあった。Example 1 A solution containing 5 g/Q of IrCl24 was heated at 100 mA.
It was adjusted. A small amount of caustic soda aqueous solution was added to this solution to adjust the pH to 1.0. The stiffness solution has a sheet resistance of 10
Electrolysis was carried out at 25° C. for 30 minutes using a glass substrate coated with a transparent conductive film mainly composed of iridium oxide of Ω/d as a cathode, a gold wire as an anode, and a deposition current density of 2 mA/ad. As a result, a brown coating was deposited on the transparent conductive film of the cathode. However, the electrodeposited film was non-uniform and had significant color unevenness.
実施例２
５ ｇ ／ ＱのＩｒＣＱ＋と５ ｇ ／ Ｑのシュウ
酸を含む溶液を１００ｍＡ調整した。この溶液に炭酸ナ
トリウムを少量ずつ添加し５．液のｐＨを１０．０とし
た。この溶液を、シート抵抗が１０Ω／ｄの酸化イリジ
ウムを主成分とする透明導電膜でコートしたガラス基板
を陰極、金線を陽極、電析電流密度を１５０μＡ／ａｔ
とし、２５℃で３０分間電解した。その結果、陰極の透
明導電膜上に茶褐色の被膜が０．１μｍ被着された。電
析被膜は均一で色むらもなかった。実施例１との比較か
ら明らかなように、アルカリ電析液によれば、均一な電
析膜が低電流密度で得られる。Example 2 A solution containing 5 g/Q of IrCQ+ and 5 g/Q of oxalic acid was adjusted to 100 mA. 5. Add sodium carbonate little by little to this solution. The pH of the liquid was set to 10.0. A glass substrate coated with a transparent conductive film mainly composed of iridium oxide with a sheet resistance of 10 Ω/d was used as the cathode, a gold wire was used as the anode, and the electrodeposition current density was 150 μA/at.
Then, electrolysis was carried out at 25°C for 30 minutes. As a result, a brown coating of 0.1 μm was deposited on the transparent conductive film of the cathode. The electrodeposited film was uniform and had no uneven color. As is clear from the comparison with Example 1, a uniform electrodeposited film can be obtained at a low current density using the alkaline electrodepositing solution.
実施例３
実施例２と同様に５ｇ／ｕのｒｒｃＩ１４と５ｇ／Ｑの
シュウ酸を含む溶液を１００ｍ１２調整した。Example 3 In the same manner as in Example 2, 100 ml of a solution containing 5 g/u of rrcI14 and 5 g/Q of oxalic acid was prepared.
この溶液に炭酸ナトリウムを少量ずつ添加し、液のｐＨ
を１０．０とした。この溶液を、シート抵抗が１０Ω／
Ｊの酸イリジウムを主成分とする透明導電膜でコートし
たガラス基板を陽極、全線を陰極、電析電流密度を６０
μＡ／ｃｉとし、２５℃で３０分間電解した。その結果
、陽極の透明導電膜上にブルーブラックの被膜が０．２
５μｍ被着された。電析被膜は均一で色むらがなかった
。Add sodium carbonate little by little to this solution to adjust the pH of the solution.
was set to 10.0. This solution has a sheet resistance of 10Ω/
The glass substrate coated with a transparent conductive film mainly composed of acid iridium of J was used as an anode, all the wires were used as a cathode, and the electrodeposition current density was 60.
Electrolysis was carried out at 25° C. for 30 minutes at μA/ci. As a result, a blue-black film of 0.2
A thickness of 5 μm was deposited. The electrodeposited film was uniform and had no uneven color.
実施例４
実施例２と同様に５ｇ／ＱのＩｒＣｌ２４と５ｇ／Ｑの
シュウ酸を含む溶液を１００ ｍ Ｑ調整した。Example 4 In the same manner as in Example 2, a solution containing 5 g/Q of IrCl24 and 5 g/Q of oxalic acid was adjusted to 100 mQ.
この溶液に炭酸ナトリウムを少量ずつ添加し。Add sodium carbonate little by little to this solution.
ｐｕを変えて陽極側に電析した。すなわち、ＰＨの異な
る溶液を、シート抵抗が１ｏΩ／ｃｄの酸化イリジウム
を主成分とする透明導電膜でコートしたガラス基板を゛
陽極、金線を陰極、電析電流密度を６０μＡ／ａｌとし
、２５℃で３０分間電解した。Electrodeposition was performed on the anode side with different pu. That is, a glass substrate coated with a transparent conductive film mainly composed of iridium oxide with a sheet resistance of 1 oΩ/cd was coated with solutions with different pH values, the anode was the anode, the gold wire was the cathode, the electrodeposition current density was 60 μA/al, and 25 Electrolysis was carried out at ℃ for 30 minutes.
その結果、第１図に示すようにＰＨが７．０以下では、
全く電析されなかった。しかし、アルカリ性溶液ではｐ
Ｈが増すにしたがい電析膜の膜厚も増加することが明ら
かとなった。とくにｐＨ８，０以上の場合が好ましい。As a result, as shown in Figure 1, when the pH is below 7.0,
There was no electrodeposition at all. However, in alkaline solution p
It became clear that as H increased, the thickness of the deposited film also increased. Particularly preferred is a pH of 8.0 or higher.
［発明の効果］
以上に述べたように、本発明のイリジウム酸化物薄膜は
簡便な方法で形成でき、イリジウム酸化物を用いた製品
の低価格化に効果がある。[Effects of the Invention] As described above, the iridium oxide thin film of the present invention can be formed by a simple method, and is effective in reducing the cost of products using iridium oxide.
第１図は、本発明を説明するための図である。 FIG. 1 is a diagram for explaining the present invention.
Claims (1)
析により析出させてなることを特徴とするイリジウム酸
化物電析膜。 ２、上記アルカリ性水溶液はｐＨが８．０以上である特
許請求の範囲第１項記載のイリジウム酸化物電析膜。 ３、上記析出は陽極側に電析により析出させてなること
を特徴とする特許請求の範囲第１項記載のイリジウム酸
化物電析膜。 ４、上記水溶液が錯化剤を含む溶液であることを特徴と
する特許請求の範囲第１項、第２項又は第３項記載のイ
リジウム酸化物電析膜。 ５、上記錯化剤がシュウ酸であることを特徴とする特許
請求の範囲第４項記載のイリジウム酸化物電析膜。[Claims] 1. An electrodeposited iridium oxide film, characterized in that it is deposited by electrodeposition from an alkaline aqueous solution containing an iridium compound. 2. The iridium oxide electrodeposited film according to claim 1, wherein the alkaline aqueous solution has a pH of 8.0 or more. 3. The iridium oxide electrodeposited film according to claim 1, wherein the deposition is performed by electrodeposition on the anode side. 4. The iridium oxide electrodeposited film according to claim 1, 2 or 3, wherein the aqueous solution is a solution containing a complexing agent. 5. The iridium oxide electrodeposited film according to claim 4, wherein the complexing agent is oxalic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61173653A JPS6333595A (en) | 1986-07-25 | 1986-07-25 | Electrodeposited iridium oxide film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61173653A JPS6333595A (en) | 1986-07-25 | 1986-07-25 | Electrodeposited iridium oxide film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6333595A true JPS6333595A (en) | 1988-02-13 |
Family
ID=15964602
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61173653A Pending JPS6333595A (en) | 1986-07-25 | 1986-07-25 | Electrodeposited iridium oxide film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6333595A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007238990A (en) * | 2006-03-07 | 2007-09-20 | Osaka City | Composition for electrolytically forming silver oxide film |
-
1986
- 1986-07-25 JP JP61173653A patent/JPS6333595A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007238990A (en) * | 2006-03-07 | 2007-09-20 | Osaka City | Composition for electrolytically forming silver oxide film |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5209980A (en) | Transparent counterelectrodes | |
| US5215821A (en) | Solid-state electrochromic device with proton-conducting polymer electrolyte and Prussian blue counterelectrode | |
| JPH0676940U (en) | Transparent electrochromic articles | |
| JP2617641B2 (en) | Solid-state electrochromic articles | |
| JPH0127158B2 (en) | ||
| GB2071151A (en) | Trivalent chromium electroplating | |
| JPS6333595A (en) | Electrodeposited iridium oxide film | |
| JP3148882B2 (en) | Method for producing zinc oxide film | |
| CN110389479A (en) | For coating the electrodeposition process and electrochromic device of electrochomeric films | |
| Shahizuan et al. | Influence of pH solution on the electrodeposition of tungsten oxide (WO3) films onto indium tin oxide (ITO)-glass substrate | |
| US4536260A (en) | Thin film cadmium selenide electrodeposited from selenosulphite solution | |
| CN108389936A (en) | The surface treatment method of TCO conductive materials on a kind of solar cell | |
| JPH0127405B2 (en) | ||
| JPS62177528A (en) | Electrodeposited tungsten oxide thin film | |
| JP2625006B2 (en) | Method for producing mixed valence transition metal complex film | |
| JPH07157892A (en) | Electroplating method | |
| CN216210367U (en) | Electrode for electrochemical deposition of electrochromic functional layer | |
| KR100838271B1 (en) | Process of manufacturing transparent counter electrode of dye sensitized solar cell | |
| JPS60228698A (en) | Production of molybdenum oxide film | |
| JP3536210B2 (en) | Electrosynthesis of ceramic thin films | |
| US20220035215A1 (en) | High-efficiency electrodeposition for coating electrochromic films | |
| JPS63163431A (en) | Electrochromic display element | |
| JPH01243035A (en) | Production of electrochromic display device | |
| JPH036288A (en) | Electrodeposited iridium oxide film | |
| JPS62297824A (en) | Light transmission variable element |