JPS64323B2 - - Google Patents
Info
- Publication number
- JPS64323B2 JPS64323B2 JP58124163A JP12416383A JPS64323B2 JP S64323 B2 JPS64323 B2 JP S64323B2 JP 58124163 A JP58124163 A JP 58124163A JP 12416383 A JP12416383 A JP 12416383A JP S64323 B2 JPS64323 B2 JP S64323B2
- Authority
- JP
- Japan
- Prior art keywords
- silicon carbide
- substrate
- film
- gas
- methylhydrodiene
- 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
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 18
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 18
- 239000000758 substrate Substances 0.000 claims description 18
- 239000011248 coating agent Substances 0.000 claims description 12
- 238000000576 coating method Methods 0.000 claims description 12
- 229920000548 poly(silane) polymer Polymers 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000004033 plastic Substances 0.000 claims description 5
- 229920003023 plastic Polymers 0.000 claims description 5
- 238000000354 decomposition reaction Methods 0.000 claims description 4
- 239000011521 glass Substances 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 238000007740 vapor deposition Methods 0.000 claims description 3
- 239000000919 ceramic Substances 0.000 claims description 2
- 238000000151 deposition Methods 0.000 claims description 2
- 239000002023 wood Substances 0.000 claims 1
- 238000000034 method Methods 0.000 description 22
- 239000007789 gas Substances 0.000 description 20
- 239000000463 material Substances 0.000 description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 9
- 238000005260 corrosion Methods 0.000 description 9
- 230000007797 corrosion Effects 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000005299 abrasion Methods 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 7
- 229910052710 silicon Inorganic materials 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 239000010703 silicon Substances 0.000 description 6
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 5
- 239000007858 starting material Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 4
- 150000004756 silanes Chemical class 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 239000012159 carrier gas Substances 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- -1 various windows Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 238000004026 adhesive bonding Methods 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- YGZSVWMBUCGDCV-UHFFFAOYSA-N chloro(methyl)silane Chemical compound C[SiH2]Cl YGZSVWMBUCGDCV-UHFFFAOYSA-N 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001343 alkyl silanes Chemical class 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- KQHIGRPLCKIXNJ-UHFFFAOYSA-N chloro-methyl-silylsilane Chemical compound C[SiH]([SiH3])Cl KQHIGRPLCKIXNJ-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- PZPGRFITIJYNEJ-UHFFFAOYSA-N disilane Chemical compound [SiH3][SiH3] PZPGRFITIJYNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229940050176 methyl chloride Drugs 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920000555 poly(dimethylsilanediyl) polymer Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound 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
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/32—Carbides
- C23C16/325—Silicon carbide
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
- Chemical Vapour Deposition (AREA)
- Surface Treatment Of Glass (AREA)
Description
本発明は表面被覆膜、特には耐久性、耐摩耗
性、耐熱性、耐蝕性、接着性、ガス不透過性のす
ぐれた炭化けい素被覆膜の製造方法に関するもの
である。
近年、各種電気機器のハウジングや表示器、各
種機能フイルム、建材、化粧板、玩具、装飾品な
どには多くのプラスチツク材が使用されている
が、このプラスチツク材はその表面がいわゆる有
機結合をした高分子量体とされていることから、
耐久性、耐摩耗性、耐熱性、耐蝕性、接着性、ガ
ス不透過性に劣るという本質的な欠点があつた。
また、窓ガラス、各種ウインドウ、メガネ、各種
電気機器の保護材として使用されているガラス質
材料には耐摩耗性（硬度）が劣り、強度にも限界
があるという不利があり、鉄、アルミニウム、銅
など各種方面に広く使用されている金属材料には
耐摩耗性、接着性、耐蝕性、耐薬品性に劣るとい
う欠点がある。
したがつて、これらの素材については各種の保
護方法が採られており、プラスチツクについては
その素材に各種の添加剤を添加して成形するか、
その成形品に塗料を塗布したり、異種のフイルム
を接着あるいはサンドイツチする方法が、またガ
ラス質物、セラミツクス系についてはプラスチツ
クフイルムを接着またはサンドイツチするか、塗
料の塗布という方法が行なわれており、金属の保
護については塗料の塗布、その表面を化学的にま
たは物理的に処理するか、その表面に保護材を溶
射するという方法が採られているが、これらは必
ずしも充分満足すべき結果を与えるものではなか
つた。
そのため、これら基材の表面保護は耐酸化性、
耐蝕性、耐熱性、耐熱衝撃性、低熱膨張性で、そ
れ自体が高硬度（高密度）である炭化けい素で被
覆するという方法が提案されており、例えばシ
リコン結晶をターゲツトとして炭素源に炭化水素
ガスを用いたスパツタリング方法（特公昭56−
26640号公報、特開昭56−40284号公報参照）、
シリコン蒸気をイオン化し、炭素基体の表面に膜
を形成させるイオンブレーテイング法（特公昭55
−18678号公報参照）、シランまたはハロゲン化
シランガスと炭化水素ガスとの混合ガスを熱分解
させる方法（特開昭57−116200号公報、特開昭57
−118082号公報参照）、炭素表面上で前記シラ
ンガスを熱分解させる方法（特公昭47−48120号
公報参照）、シリコン基板上で炭化水素ガスを
分解反応させる方法（特公昭56−26640号公報参
照）、さらには水素化シラン、アルキルシラン
またはハロゲン化シランと炭化水素ガスとをプラ
ズマ気相沈積法（以下CVD法という）で処理す
る方法（特開昭57−27914号公報、特開昭57−
22112号公報、特開昭57−200215号公報参照）な
どが知られている。しかし、この〜の方法は
高温が必要とされ、各元素のクラスターができや
すいし、均質な膜が得られにくく、成膜速度も遅
いという不利があるほか、熱膨張の相違によつて
室温に戻したときに皮膜にクラツクが発生し易
く、接着強度も劣るという欠点があり、このの
プラズマCVD法にはその始発原料としてモノシ
ラン（SiH4）を使用するとそれが非常に発火性
の高いものであるため取扱いに厳重な注意が必要
とされるほか、コストが高くなるという不利があ
るし、ハロゲン化シランを使用するとプラズマに
よつて塩酸や塩素が発生するためその処理に難点
が生じるほか反応速度が遅いという欠点があり、
またシリコン源と炭素源が異なるためにこの推積
速度を早めるとこれらの反応速度の相違からSiお
よびＣのクラスターが発生し、均質な膜が得られ
ないという不都合があつた。
本発明はこのような不利を解決した基体表面に
炭化けい素皮膜の形成させる方法に関するもので
あり、これは一般式（CH3）aSibHc（こゝに１＜ｂ
＜４、2b＋１≧ａ≧１、2b＋１≧ｃ≧１、ａ＋
ｃ＝2b＋２）で示されるメチルハイドロジエン
ポリシラン類の少なくとも１種の分解により発生
する炭化けい素を基体上に堆積させることを特徴
とするものである。
これを説明すると、本発明者らはさきにメチル
ハイドロジエンシラン化合物を始発材料とし、プ
ラズマCVD法で処理すれば高純度で均一な炭化
けい素膜を得ることができるということを見出す
と共に、特にメチルハイドロジエンジシラン、ま
たは−トリシランを使用すれば非常に大きい生長
速度で均質な炭化けい系膜を得ることができると
いうことを確認した（特願昭58−4695号参照）。
本発明はこの知見にもとづいて、メチルハイドロ
ジエンポリシランを始発材料とし、これをプラズ
マCVD法で処理し、こゝに発生した炭化けい素
を基体上に堆積させると、耐久性、耐摩耗性、耐
熱性、耐蝕性、接着性、ガス不透過性のすぐれた
表面被覆膜が得られるという本発明者らの確認に
よりなされたものである。
本発明に使用されるメチルハイドロジエンポリ
シランは前記した一般式（CH3）aSibHcで示され
るものであり、これには
The present invention relates to a method for producing a surface coating film, particularly a silicon carbide coating film having excellent durability, abrasion resistance, heat resistance, corrosion resistance, adhesiveness, and gas impermeability. In recent years, many plastic materials have been used for the housings and displays of various electrical devices, various functional films, building materials, decorative laminates, toys, decorations, etc., but these plastic materials have so-called organic bonds on their surfaces. Since it is considered to be a high molecular weight substance,
It had the essential disadvantage of being inferior in durability, abrasion resistance, heat resistance, corrosion resistance, adhesiveness, and gas impermeability.
In addition, glass materials used as protective materials for window glass, various windows, glasses, and various electrical devices have the disadvantage of poor abrasion resistance (hardness) and limited strength. Metal materials such as copper, which are widely used in various fields, have the disadvantage of being inferior in wear resistance, adhesion, corrosion resistance, and chemical resistance. Therefore, various protection methods are adopted for these materials, such as adding various additives to plastics and molding them, or
For molded products, methods include applying paint, gluing or sandwiching different types of films, and for glassy and ceramic materials, gluing or sandwiching plastic films, or applying paint. For protection, methods are used such as applying paint, treating the surface chemically or physically, or thermally spraying a protective material on the surface, but these methods do not always give fully satisfactory results. It wasn't. Therefore, the surface protection of these base materials is oxidation resistant,
A method has been proposed in which silicon carbide is coated with silicon carbide, which has corrosion resistance, heat resistance, thermal shock resistance, low thermal expansion, and is itself highly hard (high density). Sputtering method using hydrogen gas
26640, JP-A-56-40284),
Ion blating method (Special Publication Act 1987) in which silicon vapor is ionized and a film is formed on the surface of a carbon substrate.
-18678 Publication), a method of thermally decomposing a mixed gas of silane or halogenated silane gas and hydrocarbon gas (Japanese Unexamined Patent Application Publication No. 116200/1983,
-118082), a method of thermally decomposing the silane gas on a carbon surface (see Japanese Patent Publication No. 47-48120), a method of decomposing hydrocarbon gas on a silicon substrate (see Japanese Patent Publication No. 56-26640) ), and a method of treating hydrogenated silane, alkylsilane, or halogenated silane with hydrocarbon gas by plasma vapor deposition method (hereinafter referred to as CVD method) (JP-A-57-27914, JP-A-57-
22112, JP-A-57-200215, etc.) are known. However, this method requires high temperatures, tends to form clusters of each element, makes it difficult to obtain a homogeneous film, and has a slow film formation rate. The drawback is that the film tends to crack when it is put back together, and its adhesive strength is poor.The plasma CVD method uses monosilane (SiH 4 ) as its starting material because it is highly flammable. Because of this, strict care is required when handling it, and it also has the disadvantage of higher costs.When halogenated silanes are used, the plasma generates hydrochloric acid and chlorine, which makes processing difficult and slows down the reaction rate. The disadvantage is that it is slow,
Further, since the silicon source and the carbon source are different, if the estimated rate is accelerated, clusters of Si and C will be generated due to the difference in reaction rate, making it impossible to obtain a homogeneous film. The present invention relates to a method for forming a silicon carbide film on the surface of a substrate that solves these disadvantages, and is based on the general formula (CH 3 ) a Si b H c (where 1<b
<4, 2b+1≧a≧1, 2b+1≧c≧1, a+
The method is characterized in that silicon carbide generated by the decomposition of at least one type of methylhydrodiene polysilane represented by c=2b+2) is deposited on a substrate. To explain this, the present inventors first discovered that a highly pure and uniform silicon carbide film could be obtained by using a methylhydrogensilane compound as a starting material and treating it with a plasma CVD method. It has been confirmed that a homogeneous silicon carbide film can be obtained at a very high growth rate by using methylhydrodiene disilane or -trisilane (see Japanese Patent Application No. 1983-4695).
Based on this knowledge, the present invention uses methylhydrodienepolysilane as a starting material, processes it by plasma CVD, and deposits the silicon carbide generated on the substrate to improve durability, wear resistance, This was made based on the inventors' confirmation that a surface coating film with excellent heat resistance, corrosion resistance, adhesiveness, and gas impermeability can be obtained. The methylhydrodiene polysilane used in the present invention is represented by the above-mentioned general formula (CH 3 ) a Si b H c , which includes:
【式】【formula】
【式】
などが例示されるが、これはその単独または２種
以上の混合物であつてもよい。このメチルハイド
ロジエンポリシランは１分子中にけい素原子と炭
素原子とを同時に含有するものであるため、この
分解により発生する炭化けい素を堆積させた皮膜
は均質であり、その膜の成長速度がモノシランを
使用した場合にくらべて数倍以上早いという有利
性が与えられる。なお、このメチルハイドロジエ
ンポリシランの製造法は公知であり、これはポリ
ジメチルシランを350℃以上で熱分解するか、ま
たはメチルクロライドと金属けい素との反応によ
るメチルクロロシランの直接合成時に副生するメ
チルクロロジシランの還元によつて得ることがで
きる。
本発明方法の実施にはこのメチルハイドロジエ
ンポリシランをプラズマCVD法で処理すればよ
いが、これにはまず処理すべき基体を反応室内に
載置したのち、この反応室内を0.01〜５トルに減
圧し、こゝにキヤリヤーガスとしての水素、ヘリ
ウム、アルゴンガスと共にメチルハイドロジエン
ポリシランを導入してから、この系内に高周波電
力を印加してプラズマを発生させればよい。この
反応温度は基体の耐熱温度によつて調節する必要
があるが、これは100℃以上、好ましくは150℃以
上とすることがよい。しかし、これを150℃以下
とすると得られる炭化けい素被膜中にSiH2結合
に起因する2090cm-1の吸収が生じ、耐久性、耐熱
性の点で問題となるおそれがあるので、この場合
にはキヤリヤーガスと原料としてのメチルハイド
ロジエンポリシランの供給を停止して、炭素源、
窒素源、酸素源となるガス体だけを供給し、この
温度で20分以上エージングすることがよく、これ
によればかゝる不利を除去することができる。な
お、この反応温度の上限は700℃以下とすること
がよいが、経済的見地とこれが高すぎると基体と
被覆膜との熱膨張係数の差で均一で稠密な膜が得
られなくなるおそれがあるので、基材の種類にも
よるが500℃以下とすることが好ましい。
本発明の方法では、前記したようにこのメチル
ハイドロジエンポリシランが炭素原子とけい素原
子を同時に保有しており、その比率も変化させる
ことができるので、この反応系に他の炭素源、け
い素源となるガス体を添加する必要はないが、上
記したエージング用などに使用する炭素源として
はメタン、エタンなど、窒素源としては窒素ガ
ス、アンモニアガス、N2H4などが、また酸素源
としては酸素ガス、水蒸気などを、さらにこれら
の混合ガスとしてはCO、CO2、N2O、CH3OHな
どを使用すればよい。
本発明の方法による炭化けい素被覆膜の膜厚は
目的によつて異なるけれども、被覆膜に強度が必
要とされるときにはこれを数ミクロンから数十ミ
クロンとし、強度を必要とせず耐久性、表面硬
度、ガス不透過性、接着性などの改良が目的とさ
れる場合には数ミクロン以下としてもよい。ま
た、この炭化けい素被覆の炭素とけい素の原子比
は始発材料として使用するメチルハイドロジエン
ポリシランの構造、すなわちそのけい素原子と炭
素原子の総合比により変化するが、これは本発明
の目的からは任意とされ、どのような比であつて
もよい。
本発明の方法で形成される炭化けい素被覆膜は
各種素材の改質に有用とされるものであり、これ
は例えば窒化けい素、サイアロン、ムライトなど
のセラミツクの潤滑性改良、表面保護用として、
鉄鉱、非鉄金属類、合金製品などの防錆、表面強
化のための表面処理用として、また太陽熱コレク
ター、太陽光発電用表管、板、各種ICなどのよ
うな電機、電子部品の表面保護用として利用する
ことができるほか、各種プラスチツク、ガラス類
の強化、接着性改良、ガス透過性改良などを目的
とする表面処理にも広く使用することができる。
つぎに本発明方法の実施例をあげる。
実施例 １
反応装置内に100mm×50mm×１mmの第１表に掲
記した基体を載置してから系内を５×10-2トルに
まで減圧し、ついでヒーターを使用して基体を第
２表に示した温度にまで加熱した。
つぎに、この反応室内に所定の温度に予熱した
第１表に掲記した各種のメチルハイドロジエンポ
リシランをキヤリヤーガスとしてのアルゴンと水
素との３：１の混合ガスと共に導入し、こゝに
13.56MHzの高周波電力（50W）を印加してプラ
ズマを発生させてこのポリシランの分解により生
成した炭化けい素を基体上に堆積させたのち、
こゝに得られた基体について耐蝕性、耐摩耗性、
耐熱性を下記の方法で測定したところ、第１表に
併記したとおりの結果が得られた。
なお、この第１表には比較のため、始発材料と
してモノシランとメタンの混合ガスを使用して同
様に処理したもの、また未処理の各基材について
の試験結果を併記した。
（耐蝕性）
濃フツ酸と濃硝酸の１：１の混合液に室温で２
時間浸漬後、その状態をしらべた。
（耐摩耗性）
表面状態がビツカース硬度で1500Kg／mm2以上で
あるかどうかをしらべた。
（耐熱性）
400℃で８時間加熱したのちの膜の状態を電子
顕微鏡で観察した。[Formula] is exemplified, but it may be used alone or as a mixture of two or more thereof. Since this methylhydrodiene polysilane contains both silicon atoms and carbon atoms in one molecule, the film deposited with silicon carbide generated by this decomposition is homogeneous, and the growth rate of the film is slow. This has the advantage of being several times faster than when monosilane is used. The method for producing methylhydrodiene polysilane is known, and is produced by thermally decomposing polydimethylsilane at 350°C or higher, or by producing methylchlorosilane as a by-product during the direct synthesis of methylchlorosilane by reacting methyl chloride with metal silicon. It can be obtained by reduction of methylchlorodisilane. To carry out the method of the present invention, this methylhydrodiene polysilane may be treated by the plasma CVD method, but first, the substrate to be treated is placed in a reaction chamber, and then the pressure in the reaction chamber is reduced to 0.01 to 5 torr. However, after introducing methylhydrogenpolysilane together with hydrogen, helium, and argon gases as carrier gases, high-frequency power is applied to the system to generate plasma. This reaction temperature needs to be adjusted depending on the heat resistance temperature of the substrate, and is preferably 100°C or higher, preferably 150°C or higher. However, if the temperature is lower than 150℃, absorption of 2090cm -1 due to SiH 2 bonds will occur in the resulting silicon carbide film, which may cause problems in terms of durability and heat resistance. The carrier gas and the supply of methylhydrodiene polysilane as a raw material are stopped, and the carbon source,
It is preferable to supply only gases serving as nitrogen and oxygen sources and to perform aging at this temperature for 20 minutes or more, thereby eliminating such disadvantages. Note that the upper limit of this reaction temperature is preferably 700°C or less, but from an economic standpoint, if this is too high, there is a risk that a uniform and dense film may not be obtained due to the difference in thermal expansion coefficient between the substrate and the coating film. Therefore, the temperature is preferably 500°C or less, although it depends on the type of substrate. In the method of the present invention, as mentioned above, this methylhydrodiene polysilane simultaneously contains carbon atoms and silicon atoms, and the ratio can be changed, so other carbon sources and silicon sources are added to the reaction system. Although it is not necessary to add gases that will be Oxygen gas, water vapor, etc. may be used, and CO, CO 2 , N 2 O, CH 3 OH, etc. may be used as the mixed gas. Although the thickness of the silicon carbide coating film obtained by the method of the present invention varies depending on the purpose, when strength is required for the coating film, the thickness is set from several microns to several tens of microns, and durability is not required. If the purpose is to improve surface hardness, gas impermeability, adhesion, etc., the thickness may be several microns or less. In addition, the atomic ratio of carbon to silicon in this silicon carbide coating varies depending on the structure of the methylhydrodiene polysilane used as the starting material, that is, the overall ratio of silicon atoms to carbon atoms. is arbitrary and may be any ratio. The silicon carbide coating film formed by the method of the present invention is said to be useful for modifying various materials, such as improving the lubricity of ceramics such as silicon nitride, sialon, and mullite, and for surface protection. As,
For surface treatment to prevent rust and strengthen the surface of iron ore, non-ferrous metals, alloy products, etc., and for surface protection of electrical and electronic components such as solar collectors, solar power generation tubes, plates, and various ICs. In addition, it can be widely used in surface treatments for the purpose of strengthening various plastics and glasses, improving adhesion, and improving gas permeability.
Next, examples of the method of the present invention will be given. Example 1 A substrate of 100 mm x 50 mm x 1 mm listed in Table 1 was placed in a reactor, the pressure inside the system was reduced to 5 x 10 -2 torr, and then a heater was used to transfer the substrate to a second reactor. It was heated to the temperature indicated in the table. Next, various methylhydrodiene polysilanes listed in Table 1, which had been preheated to a predetermined temperature, were introduced into the reaction chamber together with a 3:1 mixed gas of argon and hydrogen as a carrier gas.
After applying 13.56MHz high frequency power (50W) to generate plasma and depositing silicon carbide produced by decomposition of this polysilane on the substrate,
The obtained substrate has corrosion resistance, abrasion resistance,
When the heat resistance was measured by the method below, the results shown in Table 1 were obtained. For comparison, Table 1 also shows test results for base materials treated in the same manner using a mixed gas of monosilane and methane as the starting material, and for untreated base materials. (Corrosion resistance) Add 2 ml to a 1:1 mixture of concentrated hydrofluoric acid and concentrated nitric acid at room temperature.
After soaking for a period of time, the condition was examined. (Abrasion resistance) We checked whether the surface condition had a Bitkers hardness of 1500 Kg/mm 2 or more. (Heat resistance) After heating at 400°C for 8 hours, the state of the film was observed using an electron microscope.
【表】
(注) ○…良、△…やゝ良、×…不良
実施例 ２
実施例１と同じ方法で第２表に掲記した基体を
処理し、基体上に2μｍの膜厚の炭化けい素被覆
膜を作つてから、これらについての耐蝕性、耐摩
耗性、接着性、ガス不透過性を下記の方法でしら
べたところ、第２表に示すとおりの結果が得られ
た。
なお、この第２表にはこのような処理を施して
いない基体についての物性を併記した。
（耐蝕性）…実施例１と同じ
（耐摩耗性）
表面状態をビツカース硬度が1000Kg／mm2以上で
あるかどうかをしらべた。
（接着性）
エポキシ樹脂を使用して、接着強度が60Kg／cm2
以上であるかどうかをしらべた。
（ガス不透過性）
酸素の透過率を測定し、ガス透過度が10c.c.／
m2・24時間・気圧以下であるかどうかをしらべ
た。[Table] (Note) ○...good, △...good, ×...bad Example 2 The substrate listed in Table 2 was treated in the same manner as in Example 1, and a silicon carbide film with a thickness of 2 μm was deposited on the substrate. After the raw coating films were prepared, their corrosion resistance, abrasion resistance, adhesion, and gas impermeability were examined using the methods described below, and the results shown in Table 2 were obtained. Note that Table 2 also lists the physical properties of the substrates that were not subjected to such treatment. (Corrosion resistance) Same as Example 1 (Abrasion resistance) The surface condition was examined to see if the Vickers hardness was 1000 Kg/mm 2 or more. (Adhesiveness) Adhesive strength is 60Kg/cm 2 using epoxy resin.
I checked to see if the above is true. (Gas impermeability) The oxygen permeability was measured and the gas permeability was 10c.c./
I checked whether it was below m 2 / 24 hours / atmospheric pressure.
【表】【table】
Claims (1)
＋１≧ａ≧１、2b＋１≧ｃ≧１、ａ＋ｃ＝2b＋
２）で示されるメチルハイドロジエンポリシラン
類の少なくとも１種の分解により発生する炭化け
い素を基体上に堆積させることを特徴とする表面
被覆膜の製造方法。 ２ 炭化けい素の被膜がプラズマ気相沈積法で堆
積される特許請求の範囲第１項記載の表面被覆膜
の製造方法。 ３ ガラス、金属、セラミツク、プラスチツク、
木材などの基材上にプラズマ気相沈積法で炭化け
い素被膜が堆積される特許請求の範囲第１項記載
の表面被覆膜の製造方法。[Claims] 1 General formula (CH 3 ) a Si b H c (where 1<b<4, 2b
+1≧a≧1, 2b+1≧c≧1, a+c=2b+
2) A method for producing a surface coating film, which comprises depositing silicon carbide generated by the decomposition of at least one methylhydrodiene polysilane on a substrate. 2. The method for producing a surface coating film according to claim 1, wherein the silicon carbide film is deposited by plasma vapor deposition. 3 Glass, metal, ceramic, plastic,
2. The method for producing a surface coating film according to claim 1, wherein the silicon carbide film is deposited on a substrate such as wood by plasma vapor deposition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58124163A JPS6016810A (en) | 1983-07-08 | 1983-07-08 | Formation of surface coating film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58124163A JPS6016810A (en) | 1983-07-08 | 1983-07-08 | Formation of surface coating film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6016810A JPS6016810A (en) | 1985-01-28 |
| JPS64323B2 true JPS64323B2 (en) | 1989-01-06 |
Family
ID=14878499
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58124163A Granted JPS6016810A (en) | 1983-07-08 | 1983-07-08 | Formation of surface coating film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6016810A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5041303A (en) * | 1988-03-07 | 1991-08-20 | Polyplasma Incorporated | Process for modifying large polymeric surfaces |
| JP2932604B2 (en) * | 1990-05-15 | 1999-08-09 | 東亞合成株式会社 | Method for manufacturing article having silicon carbide film |
| GB0509648D0 (en) * | 2005-05-12 | 2005-06-15 | Dow Corning Ireland Ltd | Plasma system to deposit adhesion primer layers |
-
1983
- 1983-07-08 JP JP58124163A patent/JPS6016810A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6016810A (en) | 1985-01-28 |
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