JPS6360282A - Method for coating substrate surface by plasma vapor deposition - Google Patents
Method for coating substrate surface by plasma vapor depositionInfo
- Publication number
- JPS6360282A JPS6360282A JP20294386A JP20294386A JPS6360282A JP S6360282 A JPS6360282 A JP S6360282A JP 20294386 A JP20294386 A JP 20294386A JP 20294386 A JP20294386 A JP 20294386A JP S6360282 A JPS6360282 A JP S6360282A
- Authority
- JP
- Japan
- Prior art keywords
- reaction vessel
- substrate
- plasma
- metals
- gas
- 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.)
- Granted
Links
- 239000000758 substrate Substances 0.000 title claims abstract description 36
- 238000000576 coating method Methods 0.000 title claims description 36
- 239000011248 coating agent Substances 0.000 title claims description 32
- 238000000034 method Methods 0.000 title claims description 17
- 238000007740 vapor deposition Methods 0.000 title 1
- 238000006243 chemical reaction Methods 0.000 claims abstract description 43
- 229910052751 metal Inorganic materials 0.000 claims abstract description 11
- 239000002184 metal Substances 0.000 claims abstract description 11
- 150000002739 metals Chemical class 0.000 claims abstract description 9
- 230000000737 periodic effect Effects 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 239000007789 gas Substances 0.000 claims description 25
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 16
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 229910021529 ammonia Inorganic materials 0.000 claims description 7
- 239000001569 carbon dioxide Substances 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 6
- 230000008021 deposition Effects 0.000 claims description 6
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 4
- 239000000853 adhesive Substances 0.000 abstract description 2
- 230000001070 adhesive effect Effects 0.000 abstract description 2
- 239000000919 ceramic Substances 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract 1
- 239000004071 soot Substances 0.000 description 7
- 238000005240 physical vapour deposition Methods 0.000 description 6
- 239000004215 Carbon black (E152) Substances 0.000 description 5
- 238000005229 chemical vapour deposition Methods 0.000 description 5
- 238000000151 deposition Methods 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 150000002430 hydrocarbons Chemical class 0.000 description 5
- 230000008018 melting Effects 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910002090 carbon oxide Inorganic materials 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000011810 insulating material Substances 0.000 description 2
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 2
- 238000009832 plasma treatment Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910003074 TiCl4 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910001315 Tool steel Inorganic materials 0.000 description 1
- QUWBSOKSBWAQER-UHFFFAOYSA-N [C].O=C=O Chemical compound [C].O=C=O QUWBSOKSBWAQER-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 108010011222 cyclo(Arg-Pro) Proteins 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 238000005121 nitriding Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005496 tempering Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
Landscapes
- Chemical Vapour Deposition (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
この発明は、プラズマ化学反応により、被処理基体の表
面部に、耐摩耗性を向上させる酸炭窒化物を被覆形成す
る、プラズマ蒸着式基体表面被覆方法に関する。[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a plasma-deposited substrate in which an oxycarbonitride that improves wear resistance is coated on the surface of the substrate by a plasma chemical reaction. This invention relates to a surface coating method.
金属、セラミックス等の基体表面に、耐摩耗性に優れた
高融点化合物の被覆を形成する方法としては、従来、化
学的蒸着法（以下ＣＶＤ法という。Chemical vapor deposition (hereinafter referred to as CVD) is a conventional method for forming a coating of a high melting point compound with excellent wear resistance on the surface of a substrate such as metal or ceramic.
）及び物理的蒸着法（以下ＰＶＤ法という。）が知られ
ている。) and physical vapor deposition method (hereinafter referred to as PVD method) are known.
ＣＶＤ法では、高融点化合物の被覆の形成が、９００〜
１２００°Ｃで行われるため、基体が薄物あるいは絹物
等のように変形を起こし易い形状のものである場合とか
、融点の低い材質のものである場合とかには、適用でき
ないという制限があった。また、このＣＶＤ法を工具鋼
に適用するときは、その処理温度が高いので、基体の硬
さが低下し、真空炉等によって再焼入れ、焼戻しする必
要があり、処理コストが嵩むという問題点があった。In the CVD method, the formation of a coating of a high melting point compound is
Because it is carried out at 1200°C, there are limitations in that it cannot be applied when the substrate is of a shape that easily deforms, such as thin or silk, or when it is made of a material with a low melting point. . Furthermore, when this CVD method is applied to tool steel, the processing temperature is high, which reduces the hardness of the base material and requires re-quenching and tempering in a vacuum furnace, which increases processing costs. there were.
一方、ＰＶＤ法では、高融点化合物の被覆を２００〜ｓ
ｏｏ’ｃという低温で行うことができるため、種々の用
途において実用化されている。しかしながら、ＰＶＤ法
は、１０”Ｔｏｒｒ以下という高真空の処理圧力である
から、蒸発した金属等が一定方向のみにしか飛散せず、
基体の一方向しか良好な被覆ができない。つまり、つき
まわりが悪い。そのため、基体を自公転させなければな
らず、コーティングコストが高くなり、応用範囲が狭い
という問題点があった。また、ＰＶＤ法で形成した被覆
は、ＣＶＤ法で形成した被覆より一般的に密着性が悪い
といわれている。On the other hand, in the PVD method, coating with a high melting point compound is performed for 20~s.
Since it can be carried out at a low temperature of oo'c, it has been put to practical use in various applications. However, since the PVD method uses a high vacuum processing pressure of 10" Torr or less, evaporated metal etc. are only scattered in a certain direction.
Good coverage can only be achieved in one direction of the substrate. In other words, it's not easy to get around. Therefore, the substrate must be rotated around its axis, resulting in high coating costs and a narrow range of application. Furthermore, it is said that coatings formed by PVD methods generally have poorer adhesion than coatings formed by CVD methods.
そこで、ＣＶＤ法とＰＶＤ法の長所だけを取り入れたプ
ラズマＣＶＤ法が開発されている（特公昭５９−１３５
８６号公報参照）。これは、従来より多く使われている
イオン窒化法と同じ原理によるものであり、反応容器に
流すガスの中に金属ハロゲン化物等を存在せしめるだけ
で、低温でつきまわりが優れている被覆が形成できるこ
とを特徴としている。Therefore, a plasma CVD method has been developed that incorporates only the advantages of CVD and PVD methods (Japanese Patent Publication No. 59-135
(See Publication No. 86). This is based on the same principle as the ion nitriding method, which has been widely used in the past. By simply allowing metal halides, etc. to be present in the gas flowing into the reaction vessel, a coating with excellent throwing power at low temperatures is formed. It is characterized by what it can do.
このプラズマＣＶＤ法により基体にＴｉＣＮ（Ｔ ｉ
Ｃ１Ｎｙ ； Ｘ ＋ Ｙ≦１）等の炭窒化物で被覆
する場合は、窒素の供給源として窒素ガスあるいはアン
モニアガスが用いられており、プラズマ化学反応上には
問題はない。一方、炭素の供給源としてはＣＨａ 、Ｃ
ｚ Ｈａ等の炭化水素系ガスが用いられる。この炭化水
素系ガスは、ＣＶＤ法のような高温域ではよく反応し、
基体と炭化物被覆の密着性は良好であり、煤の発生も殆
どない。しかしながら、プラズマＣＶＤ法のような低温
域では、この炭化水素系ガスガ十分に反応しなかったり
、煤を発生するため、基体と炭窒化物被覆膜の密着性は
悪（、反応容器内を煤で汚すこともあり、実用化には問
題があった。By this plasma CVD method, TiCN (Ti
When coating with a carbonitride such as C1Ny; On the other hand, carbon sources include CHa, C
A hydrocarbon gas such as zHa is used. This hydrocarbon gas reacts well in high temperature ranges such as in CVD methods,
The adhesion between the substrate and the carbide coating is good, and there is almost no soot generation. However, in low-temperature ranges such as plasma CVD, this hydrocarbon gas does not react sufficiently or generates soot, resulting in poor adhesion between the substrate and the carbonitride coating (and soot inside the reaction vessel). There was a problem with practical use as it could get dirty.
この発明は、プラズマ化学反応により、密着性の優れた
酸炭窒化物を基体表面に形成する方法を提供して、かか
る問題を解決することを目的とする。An object of the present invention is to provide a method for forming an oxycarbonitride with excellent adhesion on the surface of a substrate by a plasma chemical reaction, thereby solving this problem.
この発明は、上記の目的を達成するために、プラズマＣ
ＶＤ法の炭素供給源として、炭化水素系ガスの代わりに
、−酸化炭素又は二酸化炭素を用いることによって、基
体との密着性の優れた被覆を形成する方法を提供する。In order to achieve the above object, this invention
A method of forming a coating with excellent adhesion to a substrate is provided by using -carbon oxide or carbon dioxide instead of a hydrocarbon gas as a carbon source in the VD method.
すなわち、この発明は、Ｓｉ、Ｂ、Ａｎ！、周期律表の
４Ａ、５Ａ、６Ａ族金属の化合物のうちの１種と水素と
窒素又はアンモニアあるいは窒素及びアンモニアと一酸
化炭素又は二酸化炭素とを主成分とするガスを反応容器
に導入し、その反応容器の内圧力を０．０１〜１０Ｔｏ
ｒｒにし、被処理基体を１００〜１０００°Ｃに加熱す
るとともに、反応容器内にプラズマを発生させ、プラズ
マ化学反応させることによって、被処理基体表面に、Ｓ
ｉ、 Ｂ、 Ａ１＋周期律表の４Ａ、５Ａ、６Ａ族金属
の１種の酸炭窒化物を形成することを特徴とするプラズ
マ蒸着式基体表面被覆方法に係る。That is, this invention provides Si, B, An! , introducing into a reaction vessel a gas whose main components are one of the compounds of metals of groups 4A, 5A, and 6A of the periodic table, hydrogen, nitrogen or ammonia, or nitrogen and ammonia, and carbon monoxide or carbon dioxide; The internal pressure of the reaction vessel is 0.01 to 10To
rr, and heat the substrate to 100 to 1000°C, generate plasma in the reaction vessel, and cause a plasma chemical reaction to inject S onto the surface of the substrate.
The present invention relates to a plasma deposition substrate surface coating method characterized by forming an oxycarbonitride of metals of groups 4A, 5A, and 6A of the periodic table.
ここで、形成される被覆膜の特性に影響する各因子につ
いて、それぞれ説明する。Here, each factor that influences the characteristics of the coating film to be formed will be explained.
（イ）反応ガスについて まず、反応容器に導入するガスは、Ｓｉ、Ｂ。(b) Regarding reaction gas First, the gases introduced into the reaction vessel are Si and B.
Ａｌ、周期律表の４Ａ、５Ａ、６Ａ族金属の化合物（以
下ソースガスという。）のうちの１種と水素と窒素又は
アンモニアあるいは窒素及びアンモニアと一酸化炭素又
は二酸化炭素とを主成分とする。これらの混合ガスは、
モル比で、ソースガス：水素：窒素又はアンモニアニー
酸化炭素二酸化炭素＝１：５〜２００ ： １〜１００
：０．２５〜５０に制御するのがよい。The main components are Al, one of the compounds of metals in groups 4A, 5A, and 6A of the periodic table (hereinafter referred to as source gas), hydrogen, nitrogen or ammonia, or nitrogen and ammonia, and carbon monoxide or carbon dioxide. . These mixed gases are
In molar ratio, source gas: hydrogen: nitrogen or ammonia annealed carbon carbon dioxide = 1:5-200: 1-100
: It is good to control it to 0.25-50.
その理由は、この値をはずすと、密着性及び均一性が悪
く、しかも硬さ９色の良好な被覆膜は得られないことに
ある。The reason is that if this value is exceeded, adhesion and uniformity are poor, and a good coating film with a hardness of 9 colors cannot be obtained.
この場合、放電安定化あるいは反応制御用として、Ａｒ
、Ｈｅ、Ｎｅ等を導入してもよい。In this case, Ar is used for discharge stabilization or reaction control.
, He, Ne, etc. may be introduced.
（ロ）処理圧力について
処理圧力が０．０１未満では、複雑な形状の基体表面に
微細で緻密な組織を有する被覆膜を均一に形成すること
ができず、また、プラズマを直流電圧により発生する場
合に、その発生が困難となる。(b) Processing pressure If the processing pressure is less than 0.01, it will not be possible to uniformly form a coating film with a fine and dense structure on the complex-shaped substrate surface, and plasma will be generated by direct current voltage. When this happens, it becomes difficult for it to occur.
一方、処理圧力が１０Ｔｏｒｒを越えると、被覆膜は、
粗雑で密度の低い組織や柱状組織になり易い。On the other hand, when the processing pressure exceeds 10 Torr, the coating film becomes
It tends to become a coarse, low-density structure or a columnar structure.
そのため、この発明では、処理圧力を０．０１〜１ＱＴ
ｏｒｒの範囲とした。Therefore, in this invention, the processing pressure is 0.01 to 1QT.
The range was set as orr.
（ハ）処理温度について
基体温度が１００”Ｃ未満では、微細で緻密な被覆膜が
形成されず、基体と被覆膜との密着性が悪い。(c) Processing temperature If the substrate temperature is less than 100''C, a fine and dense coating film will not be formed and the adhesion between the substrate and the coating film will be poor.
一方、基体温度が１０００°Ｃを越えると、被覆膜は粗
雑な密度の低い組織や柱状組織になり、しかも基体の変
形が生じる。On the other hand, when the substrate temperature exceeds 1000° C., the coating film becomes a coarse structure with low density or a columnar structure, and the substrate is deformed.
そのため、この発明では、基体の温度を１００〜１００
０”Ｃの範囲とした。Therefore, in this invention, the temperature of the substrate is set at 100 to 100.
The range was 0"C.
（ニ）プラズマ発生について
プラズマ発生方法としては、直流電圧、高周波、マイク
ロ波等を用いればよい。それぞれの出力は、反応装置の
大きさ、基体表面積等によって変える必要がある。(d) Plasma generation As a plasma generation method, direct current voltage, high frequency, microwave, etc. may be used. Each output needs to be changed depending on the size of the reactor, the surface area of the substrate, etc.
この場合、プラズマは、化学反応を促進することと、基
体を加熱することの両方の役目をなす。In this case, the plasma serves both to promote the chemical reaction and to heat the substrate.
ただし、基体の加熱は、他にヒータを設けて行なうこと
とし、プラズマばあ（まで化学反応促進のために使う方
が、被覆膜の厚さ、密着性、物性をうまく制御すること
ができる。However, it is better to heat the substrate by installing an additional heater and using it to promote the chemical reaction using a plasma bath, which allows better control of the thickness, adhesion, and physical properties of the coating film. .
このように、プラズマＣＶＤ法の低温域処理でも、−酸
化炭素又は二酸化炭素は十分に反応し、煤を発生させる
ことはない。In this way, even in the low-temperature region treatment of the plasma CVD method, -carbon oxide or carbon dioxide reacts sufficiently and no soot is generated.
第１図に、この発明の方法で、Ｔ１ＣＮ○の被覆膜を基
体表面に形成するための装置の概略を示しである。FIG. 1 schematically shows an apparatus for forming a coating film of T1CN◯ on the surface of a substrate by the method of the present invention.
この方法によれば、金属チタン源としてＴｉＣ１，を用
い、そのＴ ｉＣ１ａを入れたソースタンク７を、ソー
スタンク加熱用ヒータ８により加熱し、気体の状態のＴ
ｚ ＣＩ ４をソースガス用流量計５を通して反応容
器１３に供給する。その場合、ソースタンク７、ソース
タンク加熱用ヒータ８、及びソースガス用流量計５は、
一定の温度に保持された恒温槽６に収納されている。こ
の恒温槽５は、−旦気体になったＴ ｉＣ１＜を液化さ
せないためのものである。According to this method, TiC1 is used as a source of metallic titanium, a source tank 7 containing TiC1a is heated by a source tank heating heater 8, and T in a gaseous state is heated.
z CI 4 is supplied to the reaction vessel 13 through the source gas flow meter 5. In that case, the source tank 7, the source tank heater 8, and the source gas flow meter 5 are
It is housed in a constant temperature bath 6 maintained at a constant temperature. This constant temperature bath 5 is provided to prevent T iC1<, which has become a gas, from being liquefied.
上記ＴｉＣＬガスは、Ｈｚ 、Ｎｔ又はＮＨ。The above TiCL gas is Hz, Nt or NH.
あるいは窒素及びＮ Ｈ３、ＣＯとともに反応容器に送
られるようになっている。この際、必要に応じて、Ａ
ｒ ｒ Ｈｅ ＋ Ｎ ｅ等を添加してもよい。Alternatively, it is sent to the reaction vessel together with nitrogen, NH3, and CO. At this time, if necessary,
r r He + Ne, etc. may be added.
Ｃ源としてＣＯを用いる主たる理由は、ＣＨ。The main reason for using CO as a C source is CH.
、ＣｚＨｔ等の炭化水素系ガスに比べて煤の発生が殆ど
なく、その添加量を多くできることにある。Compared to hydrocarbon gases such as , CzHt, etc., soot is hardly generated, and the amount of soot added can be increased.
そのことにより、密着性の良好な被覆膜ができるととも
に、蒸着速度も増すことができる。また、ＣＯを用いる
理由は、その分子式より理解できるように、分子の中に
Ｏを持っているので、その添加量、処理条件等によって
は、形成される被覆膜中にＯが入り、酸炭窒化物被覆膜
ができる。実際には、少量の炭窒化物を生成する。なお
、炭素供給源として二酸化炭素の使用も可能である。As a result, a coating film with good adhesion can be obtained, and the deposition rate can also be increased. In addition, the reason for using CO is that, as can be understood from its molecular formula, it has O in its molecules, so depending on the amount added, processing conditions, etc., O may enter the coating film that is formed. A carbonitride coating is formed. In fact, it produces small amounts of carbonitrides. Note that carbon dioxide can also be used as a carbon supply source.
反応容器１３内には、導入ガスを一定流量として流し、
真空ポンプ９によって排気する場合、図中のコンダクタ
ンスパルプ１４を調節することによって、反応容器１３
内は０． ０１〜１０Ｔｏｒｒの適当な値に保つ。Introduced gas is flowed into the reaction vessel 13 at a constant flow rate,
When evacuating with the vacuum pump 9, the reaction vessel 13 can be evacuated by adjusting the conductance pulp 14 in the figure.
Inside is 0. Keep it at an appropriate value of 01 to 10 Torr.
前記Ｔｉ ＣＩ４＋ Ｈｚ 、Ｎｚ又はＮ Ｈ３あるい
はＮｔ及びＮＨ，Ｊ、Ｃｏを主成分とするガスは、反応
容器１３内でプラズマとなり、そのプラズマ内で基体１
０の表面にＴ ｉ ＣＮ Ｏの被覆膜を形成させる。The gas whose main components are TiCI4+ Hz, Nz, NH3, or Nt and NH, J, and Co becomes plasma in the reaction vessel 13, and the substrate 1 is heated within the plasma.
A coating film of T i CN O is formed on the surface of the substrate.
この場合、基体１０を陰極とし、反応容器１３を陽極と
し、直流電圧を印加することによりプラズマが発生する
。ここで、基体（陰極）１０と反応容器（陽極）１３と
は、絶縁材１２によって電気的に絶縁されている。この
場合、プラズマの発生だけで被覆膜を形成すると、プラ
ズマによるスパッタリング効果により、蒸着速度が小さ
くなるため、反応容器１３外側にヒータ１１を設けて基
体１０の加熱をすることにより、プラズマ出力を押さえ
ることができるので、蒸着速度を増すことができるとと
もに、均一な被覆もできる。In this case, plasma is generated by applying a DC voltage to the substrate 10 as a cathode and the reaction vessel 13 as an anode. Here, the base body (cathode) 10 and the reaction vessel (anode) 13 are electrically insulated by an insulating material 12. In this case, if a coating film is formed only by generating plasma, the deposition rate will be reduced due to the sputtering effect of the plasma. Therefore, by providing a heater 11 outside the reaction vessel 13 to heat the substrate 10, the plasma output can be reduced. Since it can be held down, the deposition rate can be increased and uniform coating can be achieved.
ここでは、プラズマの発生手段としては、直流電圧以外
に、高周波、マイクロ波等を利用してもよく、また、ヒ
ータを反応容器の内側に設置するようにしてもよい。Here, as a means for generating plasma, in addition to direct current voltage, high frequency waves, microwaves, etc. may be used, and a heater may be installed inside the reaction vessel.
この実施例の実施手順は、凡そ次の通りである。The implementation procedure of this example is approximately as follows.
（ｉ）被処理品を治具の上に載置し、反応容器内の適切
な位置に配置する。(i) Place the item to be processed on the jig and place it at an appropriate position within the reaction vessel.
（ｉｉ ）反応容器内を１０−’Ｔｏｒｒ以下に排気す
る。(ii) Evacuate the inside of the reaction vessel to 10-'Torr or less.
（ｉｉｉ） Ｈｚ、 Ａ ｒ又はＨｚ＋Ａｒを０．０１
〜１０Ｔｏｒｒの必要値になるように反応容器内に導入
する。(iii) Hz, Ar or Hz+Ar 0.01
The required value of ~10 Torr is introduced into the reaction vessel.
（ｉｖ）直流電圧、高周波、マイクロ波等により反応容
器内にプラズマを発生させ、被処理品表面をスパッター
クリーニングし、その後、処理温度に加熱する。この場
合、加熱手段として、ヒータを併用すれば均一な加熱が
できるとともに、プラズマ出力を適正に制御し蒸着速度
を上げることができる。(iv) Plasma is generated in the reaction vessel by direct current voltage, high frequency, microwave, etc. to perform sputter cleaning on the surface of the article to be treated, and then heated to a treatment temperature. In this case, if a heater is used as a heating means, uniform heating can be achieved, and the plasma output can be appropriately controlled to increase the deposition rate.
（Ｖ）Ｓ ｉ、Ｂ、Ａｌ並びに周期律表の４Ａ。(V) Si, B, Al and 4A of the periodic table.
５Ａ及び６Ａ族の金属化合物の１０種のガス状物質とＮ
２又はＮＨ，あるいはＮ２及びＮＨ，とＣＯ又はＣＯ２
とを反応容器に導入し、それらのガスと、Ｈｚ、Ａｒと
の比率を一定値に制御し、更に０．０１〜１０Ｔｏｒｒ
の処理圧力に保ち、必要時間プラズマ処理する。10 gaseous substances of group 5A and 6A metal compounds and N
2 or NH, or N2 and NH, and CO or CO2
were introduced into the reaction vessel, and the ratios of these gases and Hz and Ar were controlled to constant values, and the temperature was further increased from 0.01 to 10 Torr.
Maintain the treatment pressure at 100 mL and perform plasma treatment for the required time.
（ＶＩ）その後、Ｈｚを除いた他のガスの供給とプラズ
マ出力、ヒータ出力とを中止し、反応容器内圧力を０．
０１ ＝ １０Ｔｏｒｒに保って冷却する。(VI) After that, the supply of other gases except Hz, the plasma output, and the heater output are stopped, and the pressure inside the reaction vessel is reduced to 0.
01 = Maintained at 10 Torr and cooled.
この発明を更に具体的に実施すると、次のようになる。A more specific implementation of this invention is as follows.
被処理品としては、直径１５ｕ、高さ５０ｍの寸法の５
ＫＤＩＩ、５ＫＤ６１，５ＫＨ５１゜５ＵＳ３０４の鋼
材それぞれ用い、第１図に示した装置にＴ ｉ ＣＮＯ
の被覆膜を以下の手１ｕｌｌで形成した。The item to be processed is a 5 piece with a diameter of 15u and a height of 50m.
KDII, 5KD61, 5KH51゜5US304 steel materials were used, and T i CNO was installed in the equipment shown in Figure 1.
A coating film of 1 ull was formed in the following manner.
まず、被処理品を反応容器内治具に配置した後に、反応
容器内を１０−”Ｔｏｒｒに減圧し、その後、ガス成分
比でＡｒ ：Ｈｚ ＝１ ： １の混合ガスを、反応容
器内がＩ Ｔｏｒｒになるように制御して導入した。First, after placing the product to be treated in a jig inside the reaction vessel, the pressure inside the reaction vessel is reduced to 10-” Torr, and then a mixed gas with a gas component ratio of Ar:Hz = 1:1 is added to the inside of the reaction vessel. The temperature was controlled to be 1 Torr.
そして、被処理品を陰極とし反応容器を陽極として、６
００ｖの直流電圧を印加するとともに、外部ヒータによ
り、被処理品温度を４００°Ｃに保持し、３０分間被処
理品表面をプラズマによりスパッタークリーニングした
。Then, with the product to be treated as a cathode and the reaction vessel as an anode, 6
While applying a DC voltage of 00 V, the temperature of the article to be treated was maintained at 400° C. using an external heater, and the surface of the article to be treated was sputter-cleaned using plasma for 30 minutes.
次に、外部ヒータの出力を増して、被処理品を５５０”
Ｃに昇温し、その後、ガス成分比でＴｉＣｌ４ ：Ｈ
ｚ ：Ｎｚ ：ＣＯ：Ａｒ＝１ ： ８３：４：４
：８の混合ガスを反応容器内が２ Ｔｏｒｒになるよう
に導入し、３時間プラズマ処理を続行した。Next, increase the output of the external heater and heat the product to 550”.
After that, the gas component ratio was increased to TiCl4:H
z:Nz:CO:Ar=1:83:4:4
A mixed gas of :8 was introduced so that the pressure inside the reaction vessel was 2 Torr, and the plasma treatment was continued for 3 hours.
この結果、厚さ６μｍの均一なＴ ｉ ＣＮＯと若干の
Ｔ１ＣＮの被覆膜が、それぞれの被処理品表面に形成さ
れたことが確認された。As a result, it was confirmed that a uniform coating film of 6 μm thick of T i CNO and a small amount of T1CN was formed on the surface of each processed article.
この実施例は、基体表面にＴｉ ＣＮＯの被覆膜を形成
する場合であるが、Ｔｉ以外の例えばＳｉ。In this example, a coating film of Ti CNO is formed on the surface of the substrate, but a coating film other than Ti, such as Si, is used.
Ｂ、ＡＩ、周期律表の４Ａ、５Ａ、６Ａ族金属の酸炭窒
化物の被覆膜を形成することも勿論可能である。Of course, it is also possible to form a coating film of oxycarbonitrides of B, AI, and metals of groups 4A, 5A, and 6A of the periodic table.
この発明によれば、低温でも煤を発生させることなく、
反応容器内で一酸化炭素又は二酸化炭素が十分に反応し
て、複雑な基体に酸炭化物の被覆膜を、緻密で均一にし
かも密着性よく形成することができる。According to this invention, no soot is generated even at low temperatures,
Carbon monoxide or carbon dioxide reacts sufficiently in the reaction vessel, and a dense, uniform, and highly adhesive coating film of oxycarbide can be formed on a complex substrate.
第１図はこの発明の方法の実施に用いる装置の概略図で
あり、図中、１はＨ２流量計、２はＡｒ流量計、３はＮ
２流量計、４はＣＯ流量計、５はソースガス用流量計、
６は恒温槽、７はソースタンク、８はソースタンク加熱
用ヒータ、９は真空ポンプ、１０は基体、１１はヒータ
、１２は絶縁材、１３は反応容器、１４はコンダクタン
スバルブである。FIG. 1 is a schematic diagram of the apparatus used to carry out the method of the present invention, in which 1 is an H2 flowmeter, 2 is an Ar flowmeter, and 3 is an N2 flowmeter.
2 flowmeter, 4 CO flowmeter, 5 source gas flowmeter,
6 is a constant temperature bath, 7 is a source tank, 8 is a heater for heating the source tank, 9 is a vacuum pump, 10 is a substrate, 11 is a heater, 12 is an insulating material, 13 is a reaction vessel, and 14 is a conductance valve.
Claims (1)
金属の化合物のうちの１種と水素と窒素又はアンモニア
あるいは窒素及びアンモニアと一酸化炭素又は二酸化炭
素とを主成分とするガスを反応容器に導入し、その反応
容器の内圧力を０．０１〜１０Ｔｏｒｒにし、被処理基
体を１００〜１０００゜Ｃに加熱するとともに、反応容
器内にプラズマを発生させ、プラズマ化学反応させるこ
とによって、被処理基体表面に、Ｓｉ、Ｂ、Ａｌ、周期
律表の４Ａ、５Ａ、６Ａ族金属の１種の酸炭窒化物を形
成することを特徴とするプラズマ蒸着式基体表面被覆方
法。(1) The main components are Si, B, Al, one of the compounds of group 4A, 5A, and 6A metals of the periodic table, hydrogen, nitrogen or ammonia, or nitrogen and ammonia, and carbon monoxide or carbon dioxide. Introducing gas into a reaction vessel, setting the internal pressure of the reaction vessel to 0.01 to 10 Torr, heating the substrate to be processed to 100 to 1000°C, and generating plasma in the reaction vessel to cause a plasma chemical reaction. A method for coating a surface of a substrate by plasma deposition, characterized in that an oxycarbonitride of Si, B, Al, or one of the metals of groups 4A, 5A, and 6A of the periodic table is formed on the surface of a substrate to be treated.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20294386A JPS6360282A (en) | 1986-08-29 | 1986-08-29 | Method for coating substrate surface by plasma vapor deposition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20294386A JPS6360282A (en) | 1986-08-29 | 1986-08-29 | Method for coating substrate surface by plasma vapor deposition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6360282A true JPS6360282A (en) | 1988-03-16 |
| JPH0119469B2 JPH0119469B2 (en) | 1989-04-11 |
Family
ID=16465729
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP20294386A Granted JPS6360282A (en) | 1986-08-29 | 1986-08-29 | Method for coating substrate surface by plasma vapor deposition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6360282A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7264668B2 (en) * | 2001-10-16 | 2007-09-04 | The Chinese University Of Hong Kong | Decorative hard coating and method for manufacture |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5389804A (en) * | 1977-01-19 | 1978-08-08 | Mitsubishi Metal Corp | Covered supethard alloy product and its preparation |
| JPS6036665A (en) * | 1984-04-13 | 1985-02-25 | Mitsubishi Metal Corp | Method for coating surface of substrate with metallic nitride |
-
1986
- 1986-08-29 JP JP20294386A patent/JPS6360282A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5389804A (en) * | 1977-01-19 | 1978-08-08 | Mitsubishi Metal Corp | Covered supethard alloy product and its preparation |
| JPS6036665A (en) * | 1984-04-13 | 1985-02-25 | Mitsubishi Metal Corp | Method for coating surface of substrate with metallic nitride |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7264668B2 (en) * | 2001-10-16 | 2007-09-04 | The Chinese University Of Hong Kong | Decorative hard coating and method for manufacture |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0119469B2 (en) | 1989-04-11 |
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