JPH0349988B2 - - Google Patents
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- Publication number
- JPH0349988B2 JPH0349988B2 JP5771884A JP5771884A JPH0349988B2 JP H0349988 B2 JPH0349988 B2 JP H0349988B2 JP 5771884 A JP5771884 A JP 5771884A JP 5771884 A JP5771884 A JP 5771884A JP H0349988 B2 JPH0349988 B2 JP H0349988B2
- Authority
- JP
- Japan
- Prior art keywords
- transition metal
- oxide film
- mol
- film
- solution
- 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
- 238000000576 coating method Methods 0.000 claims description 26
- 239000000243 solution Substances 0.000 claims description 26
- 229910052723 transition metal Inorganic materials 0.000 claims description 26
- 239000007864 aqueous solution Substances 0.000 claims description 23
- 239000002253 acid Substances 0.000 claims description 22
- 239000011248 coating agent Substances 0.000 claims description 22
- 150000003624 transition metals Chemical class 0.000 claims description 20
- 229910000314 transition metal oxide Inorganic materials 0.000 claims description 18
- -1 transition metal salt Chemical class 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 6
- 238000005342 ion exchange Methods 0.000 claims description 5
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 3
- 239000003729 cation exchange resin Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 2
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical group O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 claims description 2
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 claims description 2
- 239000010408 film Substances 0.000 description 42
- 238000000034 method Methods 0.000 description 15
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 9
- 229910001887 tin oxide Inorganic materials 0.000 description 9
- 239000011521 glass Substances 0.000 description 8
- 239000007788 liquid Substances 0.000 description 6
- 239000002585 base Substances 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 4
- 238000009833 condensation Methods 0.000 description 4
- 230000005494 condensation Effects 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 229910001935 vanadium oxide Inorganic materials 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000006482 condensation reaction Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 2
- 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 2
- 239000011368 organic material Substances 0.000 description 2
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910001930 tungsten oxide Inorganic materials 0.000 description 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-L Oxalate Chemical compound [O-]C(=O)C([O-])=O MUBZPKHOEPUJKR-UHFFFAOYSA-L 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 229920001429 chelating resin Polymers 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- AAQNGTNRWPXMPB-UHFFFAOYSA-N dipotassium;dioxido(dioxo)tungsten Chemical compound [K+].[K+].[O-][W]([O-])(=O)=O AAQNGTNRWPXMPB-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000010981 drying operation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 description 1
- 235000015393 sodium molybdate Nutrition 0.000 description 1
- 239000011684 sodium molybdate Substances 0.000 description 1
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
- C23C18/1208—Oxides, e.g. ceramics
- C23C18/1216—Metal oxides
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Surface Treatment Of Glass (AREA)
- Chemically Coating (AREA)
Description
【発明の詳細な説明】
ａ 産業上の利用分野
本発明は、ガラス、セラミツクス、金属、有機
材料などの基材の表面に遷移金属酸化物膜を形成
させる方法に関し、特に大面積に均一な膜が形成
出来る遷移金属酸化物膜の製造方法に関する。
ｂ 従来技術
遷移金属の酸化物は従来エレクトロクロミツク
特性（以下EC特性と略称）を示すことが知られ
ており、これら薄膜を使用したEC素子も数多く
提案されている。
この様な遷移金属酸化物膜の形成方法として
は、蒸着法スパツタ法などの真空法により作成さ
れるが、これら真空法は生産性が悪く又大面積の
均一膜が得にくく、又これら真空法により得られ
た膜のEC特性の応答速度が遅いなどの欠点があ
つた。
本発見者らはこれら技術の欠点を補なうため
に、遷移金属酸イオンと修酸イオンを含む溶液を
電解還元して遷移金属を含むオキザライト錯体溶
液を作成し、該溶液に被覆すべき基材を浸漬する
ことにより、基材表面に遷移金属酸化物膜を形成
する方法（以下析出法と略称）を考案した。（特
開昭58−172231）
上記方法によれば大面積の均一膜が簡単に得ら
れ、応答速度の速いWo3等の被膜が得られるとい
う利点があつたが、オキザライト錯体溶液の化学
的安定性が比較的不安定であり、再現性良く被膜
が得にくいという欠点があつた。又上記方法では
V2O5膜が得られにくく、又得られた膜もEC特性
は示すものの非常に応答が遅いという欠点があつ
た。
V2O5膜は通常の真空法においても製造される
が、その応答は約30分と非常に遅いものであつ
た。（電子通信学会論文誌、Vol.J65−Ｃ、629、
８（1982）Susumu Sato他）
ｃ 発見の目的
本発明は、大面積にわたつて均一であり、EC
素子として使用するのに好ましい特性を持つた遷
移金属酸化物膜の製造方法を提供すること、特に
応答の早いV2O5膜が得られる遷移金属酸化物膜
の製造方法を提供することをその目的とする。
ｄ 発見の構成
本発明は、遷移金属酸又はその縮合物の遷移金
属酸としての濃度が0.1〜５モル／である塗布
用溶液を、基材表面に塗布した後乾燥させて遷移
金属酸化物膜とする遷移金属酸化物膜の製造方法
である。
本発明に使用する遷移金属酸としては、バナジ
ン酸、タングステン酸、モリブデン酸等があげら
れる。これらの遷移金属酸水溶液は、例えば上記
遷移金属酸塩水溶液をカチオン交換樹脂を用いて
樹脂中の水素イオン（H+）と塩中のカチオンと
をイオン交換することにより得られる。遷移金属
酸塩としては、イオン交換可能な塩の範囲で任意
に選ぶことが出来、Li、Na、Ｋなどのアルカリ
金属塩、Mg、Caなどの２価金属塩などが使用出
来る。遷移金属酸水溶液は、その後の操作の都合
上0.05モル／以上の濃度のものが好ましい。
0.05モル／未満の水溶液では0.1〜５モル／
の濃度である塗布溶液を作成するための濃縮に時
間を要するため好ましくない。
遷移金属酸水溶液をイオン交換を用いて作成す
る場合の遷移金属酸塩の水溶液としては、0.05〜
0.5モル／の濃度が好ましい。0.5モル／より
高い濃度の水溶液は、遷移金属酸塩の水への溶解
度が低いため得られにくく、又0.05モル／未満
の濃度の水溶液ではイオン交換するだけでは0.05
モル／未満の濃度の遷移金属酸の水溶液しか得
られないためである。
上記方法などで作成された遷移金属酸水溶液で
例えば0.05〜0.1モル／の濃度であり、塗布に
必要な濃度（粘度）を有しない場合、又は0.5モ
ル／以上の濃度の塗布液を調整する場合は、例
えば真空エバポレーターなどを用いて0.1〜５モ
ル／に濃縮される。
遷移金属酸水溶液は、この様に濃縮されること
により遊離酸の縮合反応が進められて水溶液全体
がより高い粘度を持つた遷移金属酸およびその縮
合物との混合物又は縮合物の溶液となる。
遷移金属酸の縮合度はその水溶液濃度、水溶液
温度などに依存し、水溶液濃度が高くなるほど縮
合が進み粘度が増加する。粘度が適度に増加した
遷移金属酸又はその縮合物の水溶液は基材表面に
付着して適度な水溶液の被膜を作る。
この様に基材表面で適度な膜厚を保つ粘度に調
整された塗布用溶液は、はけぬり法、デイツピン
グ法、スクリーンプリント法などの塗布方法によ
つてガラス、セラミツクス、プラスチツク、金属
などからなる基材表面に塗布することが出来る。
塗布用溶液中の遷移金属酸の縮合度は溶液の濃
度に依存するが、又時間と共に進行するものであ
る。しかしながら塗布用溶液は揮発等による濃縮
等がなければ、１週間程度の保存使用も可能であ
つた。
塗布に使用される塗布液としては遷移金属酸に
還算して0.1〜５モル／の濃度の遷移金属酸又
は遷移金属酸縮合物の水溶液が好ましい。５モ
ル／よりも高濃度の液体では、縮合反応が進み
すぎて塗布法による溶液膜形成が困難であり、又
0.1モル／よりも低い濃度では、塗布法により
連続的に均一の厚みを持つた溶液膜の得られる粘
度の液体が得られない。
基材表面に塗布された塗布用液体は、乾燥され
ることにより縮合が促進され、最終的に遷移金属
酸化物膜となる。乾燥の操作としては室内におけ
る乾燥手段であつても、又加熱による乾燥手段で
あつてもかまわない。しかしながら100℃以上の
温度で急激に加熱すると基材表面の塗布液が沸騰
して膜表面に泡が発生するため好ましくない。室
温で乾燥させても付着力の良好な膜が得られる
が、60℃以上の温度で乾燥させるのが能率上好ま
しい。
以下に本発明の実施例を説明する。
ｅ 実施例
実施例 １
濃度1/10モル／のメタバナジン酸ナトリウム
（NaVo3）水溶液100mlをカチオン交換樹脂（ア
ンバーライトIR−20）と接触させ、Naイオンを
水素イオン（H+）とイオン交換した。次いで、
イオン交換後の溶液を真空エバポレータで濃縮し
１／５モル／のバナジン酸モノマーの水溶液を作
成した。この時の溶液は淡黄色で幾分粘性のある
状態であつた。この溶液を酸化スズ被覆ガラス
（SnO2膜厚＝2000Å）の表面に刷毛塗り法で塗布
し、60℃で20分間乾燥した処、酸化スズ膜表面に
黄色の被膜形成が認められた。形成された被膜の
一部をカミソリ刃で削り落し、タリサーフで被膜
の厚味を測定した処1400Åであつた。
その後この黄色の被膜をXMAで分析した処、
成分的にはバナジウム、酸素のみであり、かつ赤
外反射スペクトルでＶ−Ｏ結合の存在が認められ
たことから、この黄色の被膜は酸化バナジウムの
被膜であると考えられた。更にこの酸化バネジウ
ム被覆ガラスの一部を１モル／の濃度の過塩素
酸リチウム（LiClO4）のプロピレンカーボネー
ト液中に浸漬し、これと平行に白金電極も浸漬し
た上で、酸化バナジウム被覆ガラス中の酸化ス
ズ、白金電極の間に２ボルト（Ｖ）の直流電圧を
加えた。酸化スズをカソードとした場合、酸化バ
ナジウム膜は数秒で黄色から青緑色に変り、酸化
スズをアノードとした場合青緑色から黄色に戻る
というエレクトロクロミツク特性が認められた。
本実施例によつて得られたV2O5膜は、従来真
空法で得られているV2O5膜と較べると飛躍的に
エレクトロクロミツク特性が改善されている。
実施例 ２
濃度1/10モル／のタングステン酸カリウム
（K2WO4）水溶液を出発液とし、実施例１と同様
の方法で1/5モル／の塗布用溶液を作成した後、
酸化スズ被覆ガラス上に酸化タングステン被膜
（約1400Å厚）を形成した。次いで実施例１と同
様の方法で酸化タングステン被膜のエレクトロク
ロミツク特性を調べた処、酸化スズ膜をカソード
とした時に青色に、アノードとした時に無色透明
に可逆的に変るのが認められた。
実施例 ３
濃度1/10モル／のモリブデン酸ナトリウム
（Na2MoO4）水溶液を出発液とし、実施例１と
同様の方法で1/5モル／塗布用溶液を作成した
後酸化スズ被覆ガラス上に酸化モリブデン被覆
（約1400Å厚）を形成した。次いで実施例１と同
様の方法で酸化モリブデン被膜のエレクトロクロ
ミツク特性を調べた処、酸化スズ膜をカソードと
した時に青色に、アノードとした時に無色透明に
可逆的に変るのが認められた。
ｆ 発明の効果
実施例からもあきらかな様に本発明によれば、
他の成膜法においては良好なエレクトロクロミツ
ク特性を持つた膜が得られにくいV2O5膜であつ
ても、良好なエレクトロクロミツク特性を示す膜
が製造出来ている。
又析出法と比べて塗布液が非常に安定であるた
め、再現よく安定して遷移金属酸化物膜が得られ
る。 Detailed Description of the Invention a. Field of Industrial Application The present invention relates to a method for forming a transition metal oxide film on the surface of a base material such as glass, ceramics, metal, or organic material, and particularly relates to a method for forming a transition metal oxide film on the surface of a base material such as glass, ceramics, metal, or organic material. The present invention relates to a method for producing a transition metal oxide film that can form a transition metal oxide film. b. Prior Art Transition metal oxides are conventionally known to exhibit electrochromic characteristics (hereinafter abbreviated as EC characteristics), and many EC devices using these thin films have been proposed. Such transition metal oxide films are formed by vacuum methods such as vapor deposition and sputtering, but these vacuum methods have poor productivity and are difficult to obtain uniform films over a large area. The film obtained by this method had drawbacks such as slow response speed of EC characteristics. In order to compensate for the shortcomings of these techniques, the present discoverers created an oxalite complex solution containing a transition metal by electrolytically reducing a solution containing a transition metal acid ion and an oxalate ion, and coated the solution with the base to be coated. We devised a method for forming a transition metal oxide film on the surface of a substrate by immersing the material (hereinafter abbreviated as the precipitation method). (Japanese Unexamined Patent Publication No. 58-172231) The above method has the advantage that a uniform film with a large area can be easily obtained and a film such as Wo 3 with a fast response speed can be obtained, but the chemical stability of the oxalite complex solution is The drawbacks were that the properties were relatively unstable and it was difficult to obtain a film with good reproducibility. Also, in the above method
It was difficult to obtain a V 2 O 5 film, and although the obtained film showed EC characteristics, it had the disadvantage of a very slow response. V 2 O 5 films can also be produced using the usual vacuum method, but the response time was very slow, taking about 30 minutes. (Journal of the Institute of Electronics and Communication Engineers, Vol. J65-C, 629,
8 (1982) Susumu Sato et al.) c. Purpose of Discovery The present invention is uniform over a large area and
It is an object of the present invention to provide a method for producing a transition metal oxide film that has favorable characteristics for use as a device, and in particular to provide a method for producing a transition metal oxide film that provides a V 2 O 5 film with a quick response. purpose. d Structure of the Discovery The present invention is directed to forming a transition metal oxide film by applying a coating solution having a concentration of a transition metal acid or a condensate thereof as a transition metal acid from 0.1 to 5 mol per mol onto the surface of a substrate and then drying the coating solution. This is a method for producing a transition metal oxide film. Examples of transition metal acids used in the present invention include vanadate, tungstic acid, and molybdic acid. These transition metal acid aqueous solutions can be obtained, for example, by ion-exchanging the hydrogen ions (H + ) in the resin with the cations in the salt in the transition metal salt aqueous solution using a cation exchange resin. The transition metal salt can be arbitrarily selected from the range of ion-exchangeable salts, such as alkali metal salts such as Li, Na, and K, and divalent metal salts such as Mg and Ca. The transition metal acid aqueous solution preferably has a concentration of 0.05 mol/or more for convenience of subsequent operations.
0.1 to 5 mol/for aqueous solutions less than 0.05 mol/
It is not preferable because it takes time to concentrate to create a coating solution with a concentration of . When creating a transition metal acid aqueous solution using ion exchange, the transition metal acid aqueous solution should be 0.05~
A concentration of 0.5 mol/mole is preferred. Aqueous solutions with concentrations higher than 0.5 mol/mole are difficult to obtain due to the low solubility of transition metal salts in water, and aqueous solutions with concentrations lower than 0.05 mol/mole/mole/mole are difficult to obtain by ion exchange alone.
This is because only an aqueous solution of a transition metal acid having a concentration of less than mol/molar can be obtained. When a transition metal acid aqueous solution prepared by the above method has a concentration of, for example, 0.05 to 0.1 mol/2, and does not have the concentration (viscosity) necessary for coating, or when preparing a coating solution with a concentration of 0.5 mol/or more is concentrated to 0.1 to 5 mol/ml using, for example, a vacuum evaporator. By concentrating the transition metal acid aqueous solution in this manner, the condensation reaction of the free acid proceeds, and the entire aqueous solution becomes a mixture with the transition metal acid and its condensate or a solution of the condensate having a higher viscosity. The degree of condensation of a transition metal acid depends on the concentration of the aqueous solution, the temperature of the aqueous solution, etc., and as the concentration of the aqueous solution increases, condensation progresses and the viscosity increases. An aqueous solution of a transition metal acid or a condensate thereof having an appropriately increased viscosity adheres to the surface of the substrate to form a coating of an appropriate aqueous solution. Coating solutions adjusted to a viscosity that maintains an appropriate film thickness on the surface of substrates can be applied to glass, ceramics, plastics, metals, etc. by coating methods such as brushing, dipping, and screen printing. It can be applied to the surface of the base material. The degree of condensation of the transition metal acid in the coating solution depends on the concentration of the solution, but also progresses with time. However, the coating solution could be stored and used for about one week unless it was concentrated due to volatilization or the like. The coating liquid used for coating is preferably an aqueous solution of a transition metal acid or a transition metal acid condensate having a concentration of 0.1 to 5 mol/concentration based on the transition metal acid. If the concentration of the liquid is higher than 5 mol/mol, the condensation reaction will proceed too much and it will be difficult to form a solution film by the coating method.
If the concentration is lower than 0.1 mol/mol/l, it is not possible to obtain a liquid with a viscosity that allows a continuous solution film of uniform thickness to be obtained by the coating method. The coating liquid applied to the surface of the base material is dried to promote condensation and finally form a transition metal oxide film. The drying operation may be performed indoors or by heating. However, rapid heating at a temperature of 100° C. or higher is not preferable because the coating liquid on the surface of the substrate boils and bubbles are generated on the surface of the film. Although a film with good adhesion can be obtained by drying at room temperature, it is preferable to dry at a temperature of 60° C. or higher in terms of efficiency. Examples of the present invention will be described below. e Examples Example 1 100 ml of an aqueous solution of sodium metavanadate (NaVo 3 ) with a concentration of 1/10 mole was brought into contact with a cation exchange resin (Amberlite IR-20), and Na ions were ion-exchanged with hydrogen ions (H + ). . Then,
The solution after ion exchange was concentrated using a vacuum evaporator to prepare a 1/5 mol/aqueous solution of vanadate monomer. The solution at this time was pale yellow and somewhat viscous. This solution was applied to the surface of tin oxide coated glass (SnO 2 film thickness = 2000 Å) using a brush coating method and dried at 60°C for 20 minutes, and a yellow film was observed to form on the surface of the tin oxide film. A portion of the formed coating was scraped off with a razor blade, and the thickness of the coating was measured using Talysurf and was found to be 1400 Å. After that, this yellow film was analyzed by XMA, and
Since the components were only vanadium and oxygen, and the presence of a V--O bond was observed in the infrared reflection spectrum, this yellow film was considered to be a vanadium oxide film. Further, a part of this vanadium oxide-coated glass was immersed in a propylene carbonate solution containing lithium perchlorate (LiClO 4 ) at a concentration of 1 mol/mole, a platinum electrode was also immersed in parallel, and then a part of the vanadium oxide-coated glass was immersed in a propylene carbonate solution containing lithium perchlorate (LiClO 4 ) at a concentration of 1 mol/mole. A DC voltage of 2 volts (V) was applied between the tin oxide and platinum electrodes. When tin oxide was used as the cathode, the vanadium oxide film turned from yellow to blue-green in a few seconds, and when tin oxide was used as the anode, the color changed from blue-green to yellow, which is an electrochromic property. The V 2 O 5 film obtained in this example has significantly improved electrochromic properties compared to the V 2 O 5 film obtained by conventional vacuum methods. Example 2 Using a potassium tungstate (K 2 WO 4 ) aqueous solution with a concentration of 1/10 mol/ as a starting solution, a 1/5 mol/coating solution was prepared in the same manner as in Example 1, and then
A tungsten oxide film (approximately 1400 Å thick) was formed on tin oxide coated glass. Next, the electrochromic properties of the tungsten oxide film were examined in the same manner as in Example 1, and it was observed that the tin oxide film reversibly changed to blue when used as a cathode, and to colorless and transparent when used as an anode. Example 3 Using a sodium molybdate (Na 2 MoO 4 ) aqueous solution with a concentration of 1/10 mol/ as a starting solution, a 1/5 mol/coating solution was prepared in the same manner as in Example 1, and then coated on tin oxide coated glass. A molybdenum oxide coating (approximately 1400 Å thick) was formed on the surface. Next, the electrochromic properties of the molybdenum oxide film were examined in the same manner as in Example 1, and it was observed that the tin oxide film reversibly changed to blue when used as a cathode, and to colorless and transparent when used as an anode. f. Effect of the invention As is clear from the examples, according to the present invention,
Even with V 2 O 5 films, which are difficult to obtain with other film-forming methods, films with good electrochromic properties can be produced. Furthermore, since the coating liquid is very stable compared to the precipitation method, a transition metal oxide film can be obtained stably with good reproducibility.
Claims (1)
ての濃度が0.1〜５モル／である塗布用溶液を、
基材表面に塗布した後乾燥させて遷移金属酸化物
膜とする遷移金属酸化物膜の製造方法。 ２ 塗布用溶液が、遷移金属酸塩の水溶液をカチ
オン交換樹脂によりイオン交換を行ない作成した
ものであるか又はそれらを濃縮したものである特
許請求の範囲第１項記載の遷移金属酸化物膜の製
造方法。 ３ 遷移金属酸がバナジン酸、タングステン酸、
モリブデン酸、又はこれらの混合物である特許請
求の範囲第１項又は第２項記載の遷移金属酸化物
膜の製造方法。[Claims] 1. A coating solution having a concentration of a transition metal acid or a condensate thereof as a transition metal acid of 0.1 to 5 mol/
A method for producing a transition metal oxide film, which comprises coating the surface of a base material and drying it to obtain a transition metal oxide film. 2. The transition metal oxide film according to claim 1, wherein the coating solution is prepared by ion-exchanging an aqueous solution of a transition metal salt with a cation exchange resin, or is concentrated. Production method. 3 The transition metal acids are vanadate, tungstic acid,
The method for producing a transition metal oxide film according to claim 1 or 2, wherein the transition metal oxide film is molybdic acid or a mixture thereof.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5771884A JPS60200971A (en) | 1984-03-26 | 1984-03-26 | Production of transition metallic oxide film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5771884A JPS60200971A (en) | 1984-03-26 | 1984-03-26 | Production of transition metallic oxide film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60200971A JPS60200971A (en) | 1985-10-11 |
| JPH0349988B2 true JPH0349988B2 (en) | 1991-07-31 |
Family
ID=13063722
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5771884A Granted JPS60200971A (en) | 1984-03-26 | 1984-03-26 | Production of transition metallic oxide film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60200971A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2024129738A (en) * | 2023-03-13 | 2024-09-27 | Jsr株式会社 | Film formation method |
-
1984
- 1984-03-26 JP JP5771884A patent/JPS60200971A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60200971A (en) | 1985-10-11 |
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