JPH0668476B2 - Thin film moisture sensitive element - Google Patents
Thin film moisture sensitive elementInfo
- Publication number
- JPH0668476B2 JPH0668476B2 JP22032885A JP22032885A JPH0668476B2 JP H0668476 B2 JPH0668476 B2 JP H0668476B2 JP 22032885 A JP22032885 A JP 22032885A JP 22032885 A JP22032885 A JP 22032885A JP H0668476 B2 JPH0668476 B2 JP H0668476B2
- Authority
- JP
- Japan
- Prior art keywords
- thin film
- sensitive element
- film
- moisture
- plasma
- 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 - Lifetime
Links
- 239000010409 thin film Substances 0.000 title claims description 39
- 239000010408 film Substances 0.000 claims description 20
- 239000000758 substrate Substances 0.000 claims description 19
- 229920000642 polymer Polymers 0.000 claims description 15
- 150000001350 alkyl halides Chemical class 0.000 claims description 8
- -1 nitrogen-containing organosilicon compound Chemical class 0.000 claims description 5
- 238000000034 method Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 230000007797 corrosion Effects 0.000 description 6
- 238000005260 corrosion Methods 0.000 description 6
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 5
- 229910052737 gold Inorganic materials 0.000 description 5
- 239000010931 gold Substances 0.000 description 5
- GZUXJHMPEANEGY-UHFFFAOYSA-N bromomethane Chemical compound BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 229920002120 photoresistant polymer Polymers 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- KAHVZNKZQFSBFW-UHFFFAOYSA-N n-methyl-n-trimethylsilylmethanamine Chemical compound CN(C)[Si](C)(C)C KAHVZNKZQFSBFW-UHFFFAOYSA-N 0.000 description 3
- 229920006254 polymer film Polymers 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 2
- 238000011835 investigation Methods 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229940102396 methyl bromide Drugs 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 150000003377 silicon compounds Chemical class 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- WGGNJZRNHUJNEM-UHFFFAOYSA-N 2,2,4,4,6,6-hexamethyl-1,3,5,2,4,6-triazatrisilinane Chemical compound C[Si]1(C)N[Si](C)(C)N[Si](C)(C)N1 WGGNJZRNHUJNEM-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 229910000792 Monel Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- WAIPAZQMEIHHTJ-UHFFFAOYSA-N [Cr].[Co] Chemical compound [Cr].[Co] WAIPAZQMEIHHTJ-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- SIOVKLKJSOKLIF-UHFFFAOYSA-N bis(trimethylsilyl)acetamide Chemical compound C[Si](C)(C)OC(C)=N[Si](C)(C)C SIOVKLKJSOKLIF-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910001026 inconel Inorganic materials 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- HVTICUPFWKNHNG-UHFFFAOYSA-N iodoethane Chemical compound CCI HVTICUPFWKNHNG-UHFFFAOYSA-N 0.000 description 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- VXAPDXVBDZRZKP-UHFFFAOYSA-N nitric acid phosphoric acid Chemical compound O[N+]([O-])=O.OP(O)(O)=O VXAPDXVBDZRZKP-UHFFFAOYSA-N 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000004043 responsiveness Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000003631 wet chemical etching Methods 0.000 description 1
Landscapes
- Investigating Or Analyzing Materials By The Use Of Fluid Adsorption Or Reactions (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、薄膜感湿素子に関する。更に詳しくは、耐環
境性にすぐれ、しかも特に電極部分での耐久性が良好な
薄膜感湿素子に関する。TECHNICAL FIELD The present invention relates to a thin film moisture sensitive element. More specifically, the present invention relates to a thin film moisture-sensitive element having excellent environment resistance and particularly good durability in the electrode portion.
空気中の相対湿度の制御は、精密工業、食品工業、繊維
工業、ビル管理上などで大変重要であり、それを検知す
る感湿素子としては、従来次のような材料を用いたもの
が知られている。Controlling the relative humidity in the air is very important for precision industry, food industry, textile industry, building management, etc., and as a moisture sensing element for detecting it, conventionally, the following materials are used. Has been.
（１）Se、Ge、Siなどの金属あるいは半導体 （２）Sn、Fe、Tiなどの金属の酸化物 （３）Al2O3などの多孔質金属酸化物 （４）LiClなどの電解質塩 （５）有機または無機材料からなる高分子膜 しかしながら、これらの各種材料を用いた感湿素子は、
いずれも保守が大変であったり、あるいは信頼性や応答
性に問題があるなど、満足される状態にはない。(1) Metals or semiconductors such as Se, Ge, Si (2) Oxides of metals such as Sn, Fe, Ti (3) Porous metal oxides such as Al 2 O 3 (4) Electrolyte salts such as LiCl ( 5) Polymer film made of organic or inorganic material However, the humidity sensitive element using these various materials is
None of them are in a satisfactory condition, because maintenance is difficult, or there are problems with reliability and responsiveness.
例えば、上記（２）の金属酸化物を用いる場合には、そ
れの成形にプレスや焼結が行われるが、均質なプレスが
困難であったりあるいは焼成時の割れなどの問題がみら
れる。また、工程上では問題なく成形されても、感湿素
子が水分の脱吸着に起因する抵抗変化を利用する性質
上、水分の影響で粒界から破壊が生ずるため、耐久性、
換言すれば信頼性にも問題がある。For example, when the metal oxide of the above (2) is used, pressing and sintering are performed to form the metal oxide, but there are problems such as difficulty in homogeneous pressing and cracking during firing. Further, even if molded without problems in the process, due to the nature of the humidity-sensitive element to utilize the resistance change due to the desorption of moisture, because the destruction from the grain boundary under the influence of moisture, durability,
In other words, there is also a problem with reliability.
また、上記（５）の高分子膜を用いた場合には、材料面
では廉価であるものの、溶剤などの薬品による劣化や信
頼性の低下などの問題がみられる。Further, when the polymer film of the above (5) is used, although it is inexpensive in terms of materials, there are problems such as deterioration due to chemicals such as solvents and deterioration of reliability.
こうした問題点を避け、特に電極材料として耐食性にす
ぐれたものを求めて種々検討を行なった結果、本出願人
は先に、絶縁性基板上に好ましくはスパッタリング法に
より形成させた耐食性被加工金属薄膜にフォトレジスト
パターンを形成させた後、電解エッチングして得られる
耐食性くし型電極を湿度センサーに用いることが好適で
あることを見出している（特願昭59-270,456号、特開昭
61−148871号）。As a result of various investigations in order to avoid such problems and particularly to obtain a material having excellent corrosion resistance as an electrode material, the present applicant previously found that the corrosion-resistant metal thin film to be processed is preferably formed on the insulating substrate by the sputtering method. It has been found that it is suitable to use a corrosion-resistant comb-shaped electrode obtained by electrolytically etching after forming a photoresist pattern on a humidity sensor (Japanese Patent Application No. 59-270,456, Japanese Patent Laid-Open No. Sho 59-270456).
61-148871).
その後、本出願人はかかる耐食性くし型電極を用いた薄
膜感湿素子のなお一層の改善を図った結果、絶縁性基板
上に形成させた導電性くし型電極の表面を高分子薄膜、
一般には含窒素有機けい素化合物のプラズマ重合膜で覆
い、更にこれをハロゲン化アルキルで処理することによ
り、耐環境性にすぐれ、しかも応答性の良好な薄膜感湿
素子を得ることに成功した（特願昭60-40,786号、特開
昭61−200454号）。かかる薄膜感湿素子の一態様が、図
面の第２図に平面図として示されており、絶縁性基板11
上に導電性くし型電極12,12′が形成され、その表面を
プラズマ重合膜13が覆っており、各取出電極14,14′に
は半田付けあるいは銀ペースト15,15′によりリード線1
6,16′が取り付けられている。After that, the present applicant has further improved the thin film moisture sensitive element using such a corrosion-resistant comb-shaped electrode, as a result, the surface of the conductive comb-shaped electrode formed on the insulating substrate is a polymer thin film,
In general, by covering it with a plasma-polymerized film of a nitrogen-containing organosilicon compound and further treating it with an alkyl halide, we succeeded in obtaining a thin film moisture-sensitive element with excellent environmental resistance and good response ( Japanese Patent Application No. 60-40,786, Japanese Patent Laid-Open No. 61-200454). One mode of such a thin film moisture sensitive element is shown in plan view in FIG.
Conductive comb-shaped electrodes 12 and 12 'are formed on the upper surface of the electrode, and the surface thereof is covered with a plasma-polymerized film 13.The lead electrodes 1 and 14' are soldered or silver pastes 15 and 15 'to the lead electrodes 1 and 14'.
6, 16 'are attached.
ところで、従来から知られている各種の感湿素子におい
ては、耐久性の点から電極材料としては最も耐食性の良
好な金や白金が多く使用されている。しかるに、これら
の電極材料は、薄膜電極として使われる場合基板との密
着性が悪く、剥れ易いため、クロムなど基板との密着性
の良好な材料の薄膜を中間層として形成させている。By the way, in various conventionally known moisture-sensitive elements, gold or platinum, which has the best corrosion resistance, is often used as an electrode material from the viewpoint of durability. However, when these electrode materials are used as thin film electrodes, they have poor adhesion to the substrate and are easily peeled off, so that a thin film of a material having good adhesion to the substrate such as chromium is formed as the intermediate layer.
しかしながら、このような構造をとっても、元来基板と
クロム、クロムと金、白金との間の密着力はそれ程大き
くはないため、過酷な条件下、例えば湿度センサーのよ
うに水分の多い状態で使用される素子では、信頼性の面
での不安があったり、耐久性の点でも問題がみられたり
する。However, even with such a structure, the adhesion between the substrate and chrome, chrome and gold, and platinum is not so large originally, so it can be used under harsh conditions, such as a humidity sensor where there is a lot of water. In such devices, there are concerns about reliability, and there are problems with durability.
前記の如き本出願人の提案に係る薄膜感湿素子の場合に
は、耐環境性や応答性の点では所期の効果が十分得られ
たものの、くし型電極部分の耐久性の点では、上記従来
の公知技術と同様に問題がみられ、その点でのなお一層
の改善が求められた。In the case of the thin film moisture-sensitive element according to the applicant's proposal as described above, although the desired effect was sufficiently obtained in terms of environmental resistance and response, in terms of the durability of the comb-shaped electrode portion, As with the above-mentioned conventional known techniques, there are problems, and further improvement in this respect has been demanded.
本発明者は、かかる新たな課題の解決方法を求めて検討
を重ねた結果、その表面に導電性くし型電極を形成させ
る絶縁性基板を予め高分子薄膜で被覆しておいて用いる
ことにより、上記課題が効果的に解決されることを見出
した。The present inventor, as a result of repeated investigations to find a solution to such a new problem, by using an insulating substrate for forming a conductive comb-shaped electrode on the surface thereof in advance coated with a polymer thin film, It has been found that the above problems can be effectively solved.
〔問題点を解決するための手段〕および〔作用〕 従って、本発明は薄膜感湿素子に係り、この薄膜感湿素
子は、高分子薄膜で被覆された絶縁性基板の被覆面上に
形成させた導電性くし型電極の表面を、ハロゲン化アル
キルで表面処理された高分子薄膜で覆ってなる。[Means for Solving the Problems] and [Operation] Therefore, the present invention relates to a thin film moisture sensitive element, which is formed on a coated surface of an insulating substrate coated with a polymer thin film. The surface of the conductive comb-shaped electrode is covered with a thin polymer film surface-treated with an alkyl halide.
絶縁性基板としては、一般にガラス、石英、アルミナな
どが用いられるが、感湿素子の環境への温度追従性が更
に良好なことが望まれる場合などには、やはり先に本出
願人によって提案されているシリコン基板表面を酸化し
て形成させた絶縁膜（特願昭60-122,548号、特開昭61−
281958号）なども用いることができる。As the insulating substrate, glass, quartz, alumina, etc. are generally used. However, when it is desired that the humidity-sensitive element has better temperature followability to the environment, it has been proposed by the present applicant. Insulating film formed by oxidizing the surface of a silicon substrate (Japanese Patent Application No. 60-122,548, Japanese Patent Laid-Open No. 61-
No. 281958) can also be used.
これらの絶縁性基板の表面上に被覆される高分子薄膜と
しては、通常有機けい素化合物のプラズマ重合膜が用い
られ、このプラズマ重合膜は感湿膜としても作用する。
プラズマ重合される単量体としては、例えばトリメチル
シリルジメチルアミン、トリエチルシラザン、ヘキサメ
チルジシラザン、ヘキサメチルシクロトリシラザン、ビ
ス（トリメチルシリル）アセトアミドなどの含窒素有機
けい素化合物が好んで用いられ、これは必要に応じてア
ンモニアとの混合物として用いることもできる。これら
の有機けい素化合物プラズマ重合膜以外の高分子薄膜と
しては、例えばポリスチレン、ポリフッ化ビニリデン、
ポリ塩化ビニルなどの熱可塑性樹脂薄膜が挙げられる。As the polymer thin film coated on the surface of these insulating substrates, a plasma polymerized film of an organic silicon compound is usually used, and this plasma polymerized film also functions as a moisture sensitive film.
As the monomer to be plasma-polymerized, for example, nitrogen-containing organosilicon compounds such as trimethylsilyldimethylamine, triethylsilazane, hexamethyldisilazane, hexamethylcyclotrisilazane, and bis (trimethylsilyl) acetamide are preferably used. If necessary, it can also be used as a mixture with ammonia. Polymer thin films other than these organic silicon compound plasma polymerized films include, for example, polystyrene, polyvinylidene fluoride,
A thermoplastic resin thin film such as polyvinyl chloride may be used.
このようにして、好ましくはプラズマ重合法により厚さ
約0.2〜0.6μｍ程度の高分子薄膜を絶縁性基板面上に被
覆させた後、その被覆面上に導電性くし型電極を形成さ
せることが行われる。導電性くし型電極の形成に際して
は、まずこの絶縁膜上に、ステンレススチール、ハステ
ロイＣ、インコネル、モネル、金などの耐食性金属や
銀、アルミニウムなどの電極形成材料金属をスパッタリ
ング法、イオンプレーティング法などにより、約0.1〜
0.5μｍ程度の厚さの薄膜が形成され、次にそこにフォ
トレジストパターンを形成させる。In this manner, preferably, the polymer thin film having a thickness of about 0.2 to 0.6 μm is coated on the surface of the insulating substrate by the plasma polymerization method, and then the conductive comb-shaped electrode is formed on the coated surface. Done. In forming the conductive comb-shaped electrode, first, a corrosion-resistant metal such as stainless steel, Hastelloy C, Inconel, Monel, or gold, or an electrode forming material metal such as silver or aluminum is sputtered or ion-plated on the insulating film. , Etc.
A thin film having a thickness of about 0.5 μm is formed, and then a photoresist pattern is formed thereon.
例えばアルミニウムの場合には、このようにして形成さ
れた電極形成材料金属薄膜へのフォトレジストパターン
の形成は、周知のフォトリソグラフ工程を適用すること
によって行われる。即ち、金属薄膜上にフォトレジスト
コーティングを行ない、そこにくし型電極のパターンの
陰画または陽画を焼付けたガラス乾板を重ね、光照射に
よる焼付けおよび現像によって行われる。この後、湿式
化学エッチングが行われるが、エッチング液としては、
リン酸‐硫酸‐無水クロム酸‐水（重量比65:15:5:15）
混合液、BHF（フッ酸系）、塩化第２鉄水溶液、硝酸、
リン酸‐硝酸混合液などが用いられる。For example, in the case of aluminum, the photoresist pattern is formed on the electrode forming material metal thin film thus formed by applying a well-known photolithography process. That is, a photoresist is coated on the metal thin film, a glass plate having a negative or positive image of the pattern of the comb-shaped electrode is baked thereon, and the film is baked and developed by light irradiation. After this, wet chemical etching is performed.
Phosphoric acid-sulfuric acid-chromic anhydride-water (weight ratio 65: 15: 5: 15)
Mixed solution, BHF (hydrofluoric acid type), ferric chloride aqueous solution, nitric acid,
A phosphoric acid-nitric acid mixed solution or the like is used.
絶縁性基板の被覆面上に形成させた導電性くし型電極
は、更にその表面が感湿特性にすぐれた高分子薄膜、一
般には前記と同様の含窒素有機けい素化合物のプラズマ
重合膜によって覆われる。The conductive comb-shaped electrode formed on the coated surface of the insulating substrate is further covered with a polymer thin film excellent in moisture-sensitive property, generally a plasma-polymerized film of the same nitrogen-containing organosilicon compound as described above. Be seen.
このプラズマ重合膜は、電気抵抗が高く、通常は絶縁性
の薄膜であるが、その表面を臭化メチル、臭化エチル、
ヨウ化メチル、ヨウ化エチルなどのハロゲン化アルキル
のガスと接触させると、その抵抗値を下げることができ
る。これは、化学反応や拡散現象により、膜中に臭素や
ヨウ素が取り込まれ、そのために導電性が改善されるた
めと考えられる。This plasma polymerized film has a high electric resistance and is usually an insulating thin film, but its surface is treated with methyl bromide, ethyl bromide,
Contact with an alkyl halide gas such as methyl iodide or ethyl iodide can reduce the resistance value. It is considered that this is because bromine and iodine are incorporated into the film due to a chemical reaction and a diffusion phenomenon, which improves conductivity.
図面の第１図は、本発明に係る薄膜感湿素子の一態様を
示すそれの断面図であり、絶縁性基板１の面上に高分子
薄膜２が被覆され、その被覆面上に形成させた導電性く
し型電極3,3′の表面は、ハロゲン化アルキルで表面処
理された高分子薄膜４によって覆われている。FIG. 1 of the drawings is a cross-sectional view showing an embodiment of a thin film moisture sensitive element according to the present invention, in which a polymer thin film 2 is coated on the surface of an insulating substrate 1 and formed on the coated surface. The surface of the conductive comb-shaped electrodes 3, 3'is covered with a polymer thin film 4 surface-treated with an alkyl halide.
導電性くし型電極が密着性よく絶縁性基板上に形成され
るため、それから作製される薄膜感湿素子は、信頼性お
よび耐久性の点ですぐれている。Since the conductive comb-shaped electrode is formed on the insulating substrate with good adhesion, the thin film moisture-sensitive element manufactured from it is excellent in reliability and durability.
次に、実施例について本発明を説明する。 Next, the present invention will be described with reference to examples.
実施例 絶縁性基板としてガラスプレートを用い、その面上にト
リメチルシリルジメチルアミンのプラズマ重合膜（厚さ
500Å）を形成させた。次に、金電極のパターニング法
として一般に行われているリフトオフ法によって、電極
幅500μｍ、電極間隔250μｍのくし型電極を形成させ
た。Example A glass plate was used as an insulating substrate, and a plasma-polymerized film of trimethylsilyldimethylamine (thickness
500 Å) was formed. Next, a comb-shaped electrode having an electrode width of 500 μm and an electrode interval of 250 μm was formed by a lift-off method generally used as a patterning method for gold electrodes.
このリフトオフ法では、上記プラズマ重合膜の面上にス
ピンコーターを用いてポジ型レジストを塗布し、80℃で
120分間のプレベークを行なった後、マスクを用いて紫
外線による密着露出を行ない、次いで現像してくし型電
極の反転したパターンを形成させ、更にそこに厚さ2000
Åの金を蒸着させ、最後にアセトン浸漬して残りのレジ
ストを剥離させることにより、くし型電極の形成が行わ
れた。In this lift-off method, a positive type resist is applied on the surface of the above-mentioned plasma polymerized film using a spin coater, and the temperature is increased to 80 ° C.
After pre-baking for 120 minutes, contact exposure with ultraviolet rays was performed using a mask, and then development was performed to form a pattern in which the comb-shaped electrodes were reversed, and then a thickness of 2000
A comb-shaped electrode was formed by vapor-depositing Å gold and finally immersing in acetone to peel off the remaining resist.
このようにして得られた、ガラスプレートの被覆面上に
形成されたくし型電極の表面を、更にトリメチルシリル
ジメチルアミンのプラズマ重合膜（厚さ2000Å）で覆っ
た後、60℃の臭化メチル蒸気と48時間接触処理させた。The surface of the comb-shaped electrode formed on the coated surface of the glass plate thus obtained was further covered with a plasma-polymerized film of trimethylsilyldimethylamine (thickness 2000 Å), and then treated with methyl bromide vapor at 60 ° C. Contact treatment was carried out for 48 hours.
リード線を銀ペースト付けして作製した感湿素子につい
て、その感湿特性を測定したところ、絶縁性基板上に直
ちに導電性くし型電極を形成させたものと比較して同等
の性能が得られ、長期の高湿度雰囲気中においても性能
の低下はみられなかった。また、くし型電極を形成させ
るリフトオフ法において、不良品の発生が認められない
ということは、密着性が良好なためと考えられる。Moisture sensitive characteristics of the moisture sensitive element made by attaching the lead wire to silver paste were measured, and it was found that the same performance was obtained as compared with the case where the conductive comb-shaped electrode was immediately formed on the insulating substrate. The performance was not deteriorated even in a long-term high-humidity atmosphere. In addition, in the lift-off method for forming the comb-shaped electrode, the fact that no defective product is found is considered to be due to good adhesion.
第１図は、本発明に係る薄膜感湿素子の一態様の断面図
である。また、第２図は、本出願人によって先に提案さ
れた薄膜感湿素子の平面図である。 （符号の説明） １……絶縁性基板 ２……高分子薄膜 ３……導電性くし型電極 ４……ハロゲン化アルキルで表面処理された高分子薄膜FIG. 1 is a sectional view of one mode of the thin film moisture sensitive element according to the present invention. FIG. 2 is a plan view of the thin film moisture sensitive element previously proposed by the present applicant. (Explanation of symbols) 1 ... Insulating substrate 2 ... Polymer thin film 3 ... Conductive comb-shaped electrode 4 ... Polymer thin film surface-treated with alkyl halide
Claims (4)
面上に形成させた導電性くし型電極の表面を、ハロゲン
化アルキルで表面処理された高分子薄膜で覆ってなる薄
膜感湿素子。1. A thin film moisture-sensitive film obtained by covering the surface of a conductive comb-shaped electrode formed on a coated surface of an insulating substrate coated with a polymer thin film with a polymer thin film surface-treated with an alkyl halide. element.
合膜である特許請求の範囲第１項記載の薄膜感湿素子。2. The thin film moisture sensitive element according to claim 1, wherein the polymer thin film on the surface of the insulating substrate is a plasma polymerized film.
子薄膜が導電性くし型電極の表面に形成させたプラズマ
重合膜をハロゲン化アルキルで表面処理したものである
特許請求の範囲第１項または第２項記載の薄膜感湿素
子。3. The polymer thin film surface-treated with an alkyl halide is a plasma-polymerized film formed on the surface of a conductive comb electrode, which is surface-treated with an alkyl halide. The thin film moisture-sensitive element according to item 2.
のプラズマ重合膜である特許請求の範囲第２項または第
３項記載の薄膜感湿素子。4. The thin film moisture sensitive element according to claim 2, wherein the plasma polymerized film is a plasma polymerized film of a nitrogen-containing organosilicon compound.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22032885A JPH0668476B2 (en) | 1985-10-04 | 1985-10-04 | Thin film moisture sensitive element |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22032885A JPH0668476B2 (en) | 1985-10-04 | 1985-10-04 | Thin film moisture sensitive element |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6280543A JPS6280543A (en) | 1987-04-14 |
| JPH0668476B2 true JPH0668476B2 (en) | 1994-08-31 |
Family
ID=16749419
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP22032885A Expired - Lifetime JPH0668476B2 (en) | 1985-10-04 | 1985-10-04 | Thin film moisture sensitive element |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0668476B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100913319B1 (en) * | 2007-07-06 | 2009-08-21 | 전자부품연구원 | Humidity sensor and its manufacturing method |
-
1985
- 1985-10-04 JP JP22032885A patent/JPH0668476B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6280543A (en) | 1987-04-14 |
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