JPH0623433B2 - Method for producing carbon-based coating - Google Patents
Method for producing carbon-based coatingInfo
- Publication number
- JPH0623433B2 JPH0623433B2 JP26196788A JP26196788A JPH0623433B2 JP H0623433 B2 JPH0623433 B2 JP H0623433B2 JP 26196788 A JP26196788 A JP 26196788A JP 26196788 A JP26196788 A JP 26196788A JP H0623433 B2 JPH0623433 B2 JP H0623433B2
- Authority
- JP
- Japan
- Prior art keywords
- bond
- gas
- carbon
- nitrogen
- film
- 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
- 229910052799 carbon Inorganic materials 0.000 title claims description 41
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims description 38
- 239000011248 coating agent Substances 0.000 title claims description 31
- 238000000576 coating method Methods 0.000 title claims description 31
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 56
- 239000007789 gas Substances 0.000 claims description 45
- 229910052757 nitrogen Inorganic materials 0.000 claims description 29
- 229910052731 fluorine Inorganic materials 0.000 claims description 23
- 239000011737 fluorine Substances 0.000 claims description 22
- 229910052739 hydrogen Inorganic materials 0.000 claims description 20
- 239000001257 hydrogen Substances 0.000 claims description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 150000002431 hydrogen Chemical class 0.000 claims description 6
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 21
- 230000001681 protective effect Effects 0.000 description 19
- 238000000034 method Methods 0.000 description 14
- 239000010410 layer Substances 0.000 description 13
- 239000000758 substrate Substances 0.000 description 12
- 239000002131 composite material Substances 0.000 description 10
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 10
- 230000005611 electricity Effects 0.000 description 8
- 230000003068 static effect Effects 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 6
- 238000012546 transfer Methods 0.000 description 6
- 238000002834 transmittance Methods 0.000 description 6
- 230000007423 decrease Effects 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 108091008695 photoreceptors Proteins 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000004642 Polyimide Substances 0.000 description 3
- 229910021417 amorphous silicon Inorganic materials 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 229920001721 polyimide Polymers 0.000 description 3
- 239000011241 protective layer Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910003460 diamond Inorganic materials 0.000 description 2
- 239000010432 diamond Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 229910052711 selenium Inorganic materials 0.000 description 2
- 239000011669 selenium Substances 0.000 description 2
- 239000007779 soft material Substances 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- -1 C 2 F 6 Chemical compound 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 241000283986 Lepus Species 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 238000001259 photo etching Methods 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002040 relaxant effect Effects 0.000 description 1
- 238000006748 scratching Methods 0.000 description 1
- 230000002393 scratching effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 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
- 239000007787 solid Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
Landscapes
- Photoreceptors In Electrophotography (AREA)
- Chemical Vapour Deposition (AREA)
Description
【発明の詳細な説明】 「発明の利用分野」 本発明は、炭素を主成分とする被膜のプラズマCVD 法に
よる作製方法を提供するものであり、その出発材料の気
体として、C-F 結合を有する第１の気体およびC-N 結合
を有する第２の気体を少なくとも含み、かつプラズマCV
D 中に-50 〜-2000Vのバイアスを被形成面を有する複合
体上に印加しつつ、プラズマCVD を行う方法に関するも
のである。DETAILED DESCRIPTION OF THE INVENTION “Field of Use of the Invention” The present invention provides a method for producing a coating film containing carbon as a main component by a plasma CVD method. Plasma CV containing at least one gas and a second gas having a CN bond
The present invention relates to a method of performing plasma CVD while applying a bias of −50 to −2000 V in D onto a composite having a formation surface.
「従来の技術」 ガラス、金属、プラスチックス、樹脂等の比較的柔らか
い材料の表面を、それら柔らかい材料よりも硬い膜でコ
ーティングすることは、摩耗、ひっかき等の機械的スト
レスに対して有効である。"Prior Art" Coating the surface of relatively soft materials such as glass, metal, plastics, and resins with a film harder than those soft materials is effective against mechanical stress such as abrasion and scratching. .
そのような膜としては、Al2O3,TiN,BN,WC,SiC,Si3N4,Si
O2等の無機膜および、本発明人の出願による「炭素被膜
を有する複合体」（昭和56年特許願第146930号（特開昭
58-42428））が知られている。しかしながら、上記既知
の保護膜は、既して電気的に高い抵抗率をもち、静電気
が発生しやすく、雰囲気中のゴミやチリをその表面に吸
着しやすい性質があった。また、電子写真プロセスに用
いられる感光体等のように積極的に電界をかけ、静電気
を利用するような複合材料に用いた場合などは、電気抵
抗の高い保護膜に電荷が蓄積されてしまい、期待される
性能が長期にわたり発揮できない問題があった。Examples of such films include Al 2 O 3 , TiN, BN, WC, SiC, Si 3 N 4 and Si.
Inorganic film such as O 2 and “composite having carbon coating” filed by the present inventor (Japanese Patent Application No. 146930 (1981)
58-42428)) is known. However, the known protective film already has a high electrical resistivity, tends to generate static electricity, and tends to adsorb dust and dust in the atmosphere onto the surface thereof. In addition, when an electric field is positively applied like a photoconductor used in an electrophotographic process and used in a composite material that uses static electricity, charges are accumulated in a protective film having high electric resistance, There was a problem that the expected performance could not be exhibited for a long time.
そのような問題を解決する方法として前記既知膜中に導
電性物質を添加する方法が考えられる。この場合、添加
された導電性物質が光の吸収中心となり、前記既知の保
護膜中での光の吸収が発生して、赤外および可視域での
透光性を必要とする応用に適用できなくなる。As a method for solving such a problem, a method of adding a conductive substance to the known film can be considered. In this case, the added conductive substance becomes an absorption center of light, and absorption of light in the known protective film occurs, which can be applied to applications requiring translucency in the infrared and visible regions. Disappear.
従来かかる方法を実施するため、C2H4とNF3,NH3との反
応を用いて窒素が添加された炭素を主成分とするプラズ
マCVD 法がある。しかしこの場合、成膜された膜中には
弗素および窒素が添加されるが、これらはN-F 結合また
はN-H 結合を有しつつも、主成分である炭素とC-F 結
合、C-N 結合を十分安定して構成させることができな
い。そのためにこの表面に長時間摩擦を与えた場合、ま
た静電複写機感光ドラムの保護層として用いる場合、窒
素(N) および弗素(F) が脱気し、電気抵抗の増加という
不良および信頼性の低下がおきてしまった。このため電
気抵抗が、初期においても、また105 〜107 回もその表
面に摩擦を与えても、また加熱処理をしても、１×106
〜５×1013Ωcmの所定の値を安定に有し、かつ、いかな
る還元雰囲気でも安定な物性を有する炭素を主成分とす
る被膜の作製方法が求められていた。In order to carry out such a method conventionally, there is a plasma CVD method containing nitrogen-added carbon as a main component by using a reaction between C 2 H 4 and NF 3 , NH 3 . However, in this case, although fluorine and nitrogen are added to the formed film, they have a NF bond or an NH bond, but sufficiently stabilize carbon, CF bond, and CN bond which are the main components. Can't be configured. Therefore, when this surface is rubbed for a long time, or when it is used as a protective layer for the photoconductor drum of an electrostatic copying machine, nitrogen (N) and fluorine (F) are degassed, resulting in an increase in electrical resistance. Has fallen. Therefore, the electric resistance is 1 × 10 6 even when the surface is rubbed or heat-treated at the initial stage or 10 5 to 10 7 times.
There has been a demand for a method of producing a coating film containing carbon as a main component, which has a predetermined value of 5 × 10 13 Ωcm stably and is stable in any reducing atmosphere.
「発明の構成」 本発明の目的は、以上述べた問題を解決し、保護膜とし
ての耐機器ストレス、静電気に由来する問題点、透明性
を同時に満足ことである。"Structure of the Invention" An object of the present invention is to solve the above-mentioned problems and simultaneously satisfy the device stress resistance as a protective film, the problems derived from static electricity, and the transparency.
そのため、炭素を主成分とする被膜にハロゲン元素であ
る弗素とＶ価の不純物である窒素、さらに必要に応じて
架橋体としての水素とを0.1 〜50原子％添加し、該C-F
結合を有する弗素とC-N 結合を有する窒素もしくはこれ
らに加えて水素が添加された炭素を主成分とする被膜を
基体表面に形成する。これに際し、プラズマCVD 法に用
いる出発材料としての基体中に、予めC-F 結合を有する
第１の基体と、C-N 結合を予め有する第２の気体とを用
いる場合、またこれら第１および第２の気体と水素また
はC-H 結合を有する第３の気体とを用いて成膜するとと
もに、この成膜中に被形成面を有する基体に対し、-50
〜-2000Vの自己または外部からの直流バイアス電圧を印
加しつつ実施することを特徴としている。Therefore, 0.1 to 50 atomic% of fluorine, which is a halogen element, nitrogen which is a V-valent impurity, and hydrogen, which is a cross-linking body, are added to the coating film containing carbon as a main component, and the CF is added.
A film mainly composed of fluorine having a bond and nitrogen having a CN bond or carbon to which hydrogen is added to these is formed on the surface of the substrate. In this case, when the first substrate having a CF bond in advance and the second gas having a CN bond in advance are used in the substrate as the starting material used in the plasma CVD method, and the first and second gases are used. And a third gas having a hydrogen or CH bond are used to form a film, and a base having a surface to be formed during the film formation is -50
It is characterized in that it is carried out while applying a DC bias voltage of -2000 V to itself or from the outside.
本発明による複合体に用いるC-F 結合を有する炭素の原
料として、CF4,C2F6,C3F8,CHF3,CH2F2,CH3Fより選ばれ
た少なくとも１種の気体を用いる。At least one gas selected from CF 4 , C 2 F 6 , C 3 F 8 , CHF 3 , CH 2 F 2 and CH 3 F is used as a raw material of carbon having a CF bond used in the composite according to the present invention. To use.
またC-N 結合を有する第２の気体としては、 N(CH3)3,N(C2H5)3,HN(C2H5)2,H2N(CH3),HN(C2H5)2,H2N
(C2H5)より選ばれた第２の気体を用いる。さらにこれら
に加えてC-H 結合を有する第３の気体を用いる。即ち既
に記したC-H 結合を有する第１または第２の気体または
これに加えて、C2H4,CH4,C2H2,C3H8,C2H6より選ばれた
少なくとも１種または水素(H2)であって、これら第１、
第２、第３の気体は0.001 〜10torrの圧力で気体として
提供し、これらを用いて炭素を主成分とする被膜をプラ
ズマCVD 法で生ぜしめる。The second gas having a CN bond is N (CH 3 ) 3 , N (C 2 H 5 ) 3 , HN (C 2 H 5 ) 2 , H 2 N (CH 3 ), HN (C 2 H 5 ) 2 , H 2 N
A second gas selected from (C 2 H 5 ) is used. In addition to these, a third gas having a CH bond is used. That is, the above-mentioned first or second gas having a CH bond or at least one selected from C 2 H 4 , CH 4 , C 2 H 2 , C 3 H 8 and C 2 H 6 in addition to this. Or hydrogen (H 2 ), these first,
The second and third gases are provided as gases at a pressure of 0.001 to 10 torr, and these are used to form a coating film containing carbon as the main component by the plasma CVD method.
本発明による被膜は、以上述べたような原料物質、すな
わちC-F 結合を有する炭素原料物質とC-N 結合を有する
窒素の原料物質とを同時にプラズマ反応室に導入し、こ
の時第１の気体と第２の気体との流量を調整することに
よって、被膜中へのC-F 結合量およびC-N 結合を有する
窒素の添加量を制御することができる。In the coating film according to the present invention, the above-mentioned raw material, that is, the carbon raw material having a CF bond and the nitrogen raw material having a CN bond are simultaneously introduced into the plasma reaction chamber. It is possible to control the amount of CF bond and the amount of nitrogen having CN bond added to the film by adjusting the flow rate with the gas.
本発明方法で作られたC-F 結合およびC-N 結合の添加量
は、導電率（逆数は比抵抗）、透過率、硬度の違いとし
て観測される。以下に第１の気体と第２の気体の流量を
変えた時の導電率の変化の実験結果を示す。The added amount of CF bond and CN bond produced by the method of the present invention is observed as a difference in conductivity (reciprocal is specific resistance), transmittance, and hardness. The experimental results of the change in conductivity when the flow rates of the first gas and the second gas are changed are shown below.
第１の気体として弗化炭素、例えばC2F6を用いた。また
第２の気体として、トリメチルアミン(N(CH3)3)を用い
た。Carbon fluoride, such as C 2 F 6, was used as the first gas. Trimethylamine (N (CH 3 ) 3 ) was used as the second gas.
この気体は、-124℃にて固体、沸点3.2 〜3.8 ℃、密度
0.6709、300Kにおいて2000mHg のベーパープレッシァを
有する気体である。This gas is a solid at -124 ° C, boiling point 3.2-3.8 ° C, density
It is a gas with a vapor pressure of 2000mHg at 0.6709 and 300K.
さらに第３の気体としてエチレン(C2H4)を用いた。C2F6
の流量100SCCM 、エチレンの流量100SCCMとし、さらにN
(CH3)3 の流量を可変とした。反応圧力0.1torr 、投入
電力密度0.08W/cm2(50W)とした。第１図に示すようにN
(CH3)3 の量が増すに従い、比抵抗が低くなっている。
また、第２図にバイアス電圧とビッカース硬度との関係
を示す。図面において、N(CH3)3 の流量が増すに従い、
ビッカース硬度が小さくなり、また同じくバイアス電圧
を大きくすると大きくなる。硬度が低下するということ
は、すなわち、内部応力が低下することを意味する。Further, ethylene (C 2 H 4 ) was used as the third gas. C 2 F 6
Flow rate of 100 SCCM, ethylene flow rate of 100 SCCM, and N
The flow rate of (CH 3 ) 3 was made variable. The reaction pressure was 0.1 torr and the input power density was 0.08 W / cm 2 (50 W). N as shown in FIG.
The resistivity decreases as the amount of (CH 3 ) 3 increases.
Further, FIG. 2 shows the relationship between the bias voltage and Vickers hardness. In the drawing, as the flow rate of N (CH 3 ) 3 increases,
The Vickers hardness decreases, and also increases with increasing bias voltage. A decrease in hardness means a decrease in internal stress.
以上述べたように、比較的広い範囲にわたって被膜の比
抵抗、硬さ、透過率等を変えることができる。すなわち
種々の応用に要求される最適特性が比較的安価に容易に
得ることができる。As described above, the specific resistance, hardness, transmittance, etc. of the coating can be changed over a relatively wide range. That is, the optimum characteristics required for various applications can be easily obtained at a relatively low cost.
またC-F 結合とC-N 結合またはC-F 結合とC-N 結合とC-
H 結合を有して弗素と窒素と水素が添加された炭素を主
成分とする被膜は、内部応力が小さいという特徴があ
る。これは、通常炭素中に存在する未結合手（ダングリ
ングボンド）には、弗素がターミネートされ、未結合手
の引力を緩和することにより内部応力を低減させるが、
未結合手すべてに弗素または水素がターミネートされる
わけではなく、多少の未結合手が膜中に残っており、こ
れが内部応力の原因の１つと考えられる。ここに水素よ
りも反応性の高い弗素が初期気体の状態でC-F 結合を有
し、さらに電気的導電性を示すための窒素も初期気体の
状態でC-N 結合を有する。このＣとＮは元素周期表で隣
に位置するため単にプラズマ中では十分に分解し、それ
ぞれが独立した気体の場合、安定して炭素と結合するこ
とができない。しかしN(CH3)3 を用いると、N-C 結合は
すでに有し、このCH3 のＨとC-F 結合を有するＦとは互
いに結合してHFを生じ、残った炭素同士がSP3 結合を作
りやすくなる。その結果、初めて価電子制御がなされた
炭素を主成分とする被膜を作り得る。Also, CF bond and CN bond or CF bond and CN bond and C-
A film containing H, H, and nitrogen as a main component to which fluorine, nitrogen, and hydrogen have been added is characterized by having a small internal stress. This is because fluorine is terminated in dangling bonds, which are usually present in carbon, and the internal stress is reduced by relaxing the attractive force of dangling bonds.
Not all dangling bonds are terminated with fluorine or hydrogen, and some dangling bonds remain in the film, which is considered to be one of the causes of internal stress. Fluorine, which is more reactive than hydrogen, has a CF bond in the initial gas state, and nitrogen, which exhibits electrical conductivity, also has a CN bond in the initial gas state. Since C and N are located next to each other in the periodic table of the elements, they are simply decomposed sufficiently in plasma, and when they are independent gases, they cannot stably bond with carbon. However, when N (CH 3 ) 3 is used, it already has an NC bond, and H of CH 3 and F having a CF bond are bonded to each other to generate HF, and the remaining carbons easily form an SP 3 bond. Become. As a result, it is possible to form a coating film containing carbon as a main component for which valence electron control is performed for the first time.
弗素と窒素または、弗素と窒素と水素が添加された炭素
を主成分とする被膜は、耐熱性のてにおいても優れてい
る。The coating film containing fluorine and nitrogen or carbon to which fluorine, nitrogen and hydrogen are added as a main component is also excellent in heat resistance.
弗素と窒素または弗素と窒素と水素が添加された炭素を
主成分とする被膜は、堆積的の基板の温度が室温から45
0 ℃以下の好ましくは室温〜150 ℃の低温で成膜できる
ことも特徴の１つである。従って、複合体の基体とし
て、プラスチックス、有機感光樹脂等の有機物、セレン
半導体等、高温にできないものでも構成することができ
る。A film mainly composed of carbon to which fluorine and nitrogen or fluorine, nitrogen and hydrogen are added has a deposition substrate temperature from room temperature to 45 ° C.
One of the features is that the film can be formed at a temperature of 0 ° C. or lower, preferably at a low temperature of room temperature to 150 ° C. Therefore, the substrate of the composite can be composed of plastics, organic materials such as organic photosensitive resins, selenium semiconductors, and other materials that cannot be heated to a high temperature.
以下図面に従って作製方法を述べる。The manufacturing method will be described below with reference to the drawings.
第３図は本発明に用いた弗素と窒素または弗素と窒素と
水素が添加された炭素を主成分とする被膜を形成するた
めのプラズマCVD 装置の概要を示す。FIG. 3 shows an outline of a plasma CVD apparatus for forming a film containing carbon containing fluorine and nitrogen or fluorine, nitrogen and hydrogen as a main component used in the present invention.
図面において、ドーピング系(1)において、キャリアガ
スである水素を(2)より、C-F 結合を有する第１の反応
性気体である炭化水素気体例えばC2F6を(3)より、C-N
結合を有する気体例えばN(CH3)3 を(4)より、C-H 結合
を有する気体、例えばC2H4を(5) より、バルブ(6)、流
量計(7)をへて反応系(8)中にノズル(9)より導入され
る。このノズルに至る前に、反応性気体の励起用にマイ
クロ波エネルギを(10)で加えて予め活性化させることは
有効である。In the drawing, in the doping system (1), hydrogen as a carrier gas is obtained from (2), and a hydrocarbon gas which is a first reactive gas having a CF bond, such as C 2 F 6 is obtained from (3), CN
A gas having a bond such as N (CH 3 ) 3 from (4), a gas having a CH bond, such as C 2 H 4 from (5), a valve (6), a flow meter (7), and a reaction system ( It is introduced into nozzle 8) through nozzle (9). Before reaching this nozzle, it is effective to add microwave energy at (10) to excite the reactive gas and preactivate it.
反応系(8)には第１の電極(11)、第２の電極(12)を設け
た。この場合（第１の電極面積／第２の電極面積）＜１
の条件を満たすようにした。一対の電極(11),(12) 間に
は高周波電源(13)、マッチングトランス(14)、直流バイ
アス電源(15)より電気エネルギが加えられ、プラズマが
発生する。排気系(16)は圧力調整バルブ(17)、ターボ分
子ポンプ(18)、ロータリーポンプ(19)をへて不要気体を
排気する。反応性気体には、反応空間(20)における圧力
が0.001 〜10torr代表的には0.01〜1torr の下で高周波
もしくは直流によるエネルギにより0.05〜１KWのエネル
ギが加えられる。The reaction system (8) was provided with a first electrode (11) and a second electrode (12). In this case (first electrode area / second electrode area) <1
I met the condition of. Electric energy is applied between the pair of electrodes (11) and (12) from the high frequency power supply (13), the matching transformer (14) and the DC bias power supply (15), and plasma is generated. The exhaust system (16) exhausts unnecessary gas through the pressure control valve (17), the turbo molecular pump (18) and the rotary pump (19). Energy of 0.05 to 1 KW is applied to the reactive gas by high frequency or direct current energy under the pressure of 0.001 to 10 torr, typically 0.01 to 1 torr in the reaction space (20).
特に励起源が1GHz以上、例えば2.45GHz の周波数にあっ
ては、Ｃ−Ｈ結合より水素を分離し、さらに周波数源が
0.1〜50MHz 例えば13.56MHzの周波数にあってはＣ−Ｃ
結合、Ｃ＝Ｃ結合を分解し、−Ｃ−Ｃ−結合を作り、炭
素の不対結合手同志を互いに衝突させて共有結合させ、
安定なダイヤモンド構造を局部的に有した構造とさせ得
る。In particular, when the excitation source has a frequency of 1 GHz or higher, for example, 2.45 GHz, hydrogen is separated from the CH bond, and the frequency source is
0.1 to 50MHz For example, if the frequency is 13.56MHz, CC
Bond, C = C bond is decomposed, -C-C- bond is formed, and unpaired carbon bonds of carbon atoms are made to collide with each other to form a covalent bond,
The structure may have a stable diamond structure locally.
直流バイアスは+200〜-1800Vを実験では加える。なぜな
ら、直流バイアスが零のときは自己バイアスが-200V
（第２の電極を接地レベルとして）を有しているためで
ある。DC bias of +200 to -1800V is applied in the experiment. Because the self-bias is -200V when the DC bias is zero.
This is because it has (with the second electrode as a ground level).
基板に対してはバイアス電圧が-50 〜-2000V好ましくは
-100〜-1000Vにおいて、ビッカース硬度も大きくさせる
ことができることがわかった。このバイアス電圧は、単
に13.56MHzの周波数の高周波電圧を加え、被形成面を有
する基板が直流的に接地されていたり、また一対の電極
の形状異方性を与えることによる自己バイアスを加えな
い場合、炭素を主成分とする被膜ができてもビッカース
硬度は300Kg/mm2 以下と、いわゆるDLC(ダイヤモンド状
炭素)として成膜することができない。特に電気伝導度
を制御する材料として窒素を用いた場合、このバイアス
電圧は成膜された炭素を主成分とする被膜に安定で高い
信頼性を有せしめるために、きわめて重要な用件であ
る。The bias voltage for the substrate is -50 to -2000V, preferably
It was found that Vickers hardness can be increased at -100 to -1000V. This bias voltage is obtained by simply applying a high frequency voltage of 13.56MHz, when the substrate having the surface to be formed is grounded in direct current, or when self-bias is not applied by giving the shape anisotropy of the pair of electrodes. Even if a coating film containing carbon as a main component is formed, the Vickers hardness is 300 Kg / mm 2 or less, and it cannot be formed as so-called DLC (diamond-like carbon). In particular, when nitrogen is used as the material for controlling the electric conductivity, this bias voltage is a very important requirement in order to make the deposited film containing carbon as a main component stable and highly reliable.
以上のようにして、プラズマにより被形成面上にＣ−Ｃ
結合を多数形成したアモルファス構造または微結晶構造
を有するアモルファス構造のC-F 結合を有する弗素とC-
N 結合を有する窒素またはこれらに加えてC-H 係合を有
する水素を含んだ炭素を生成させた。この電磁エネルギ
は50ｗ〜１KWを供給し、単位面積あたり0.03〜3W/cm2の
プラズマエネルギを加えた。この弗素と窒素とを予め結
合した炭素の透過率は第４図に示すように600 ｎｍ以上
の波長域では95％以上の透過であり、400 ｎｍでも50％
以上透過のほぼ透明な膜が得られた。また、膜の内部応
力は内素と窒素を含まない膜に比べて1/10以下と非常に
小さなものであった。酸やアルカリ、有機溶剤等の薬品
に室温にて１時間浸しておいても、その表面を400 倍の
光学顕微鏡で観察する限りでは変化は見られず、また、
500 ℃に加熱した恒温槽（空気）中に１時間放置したも
のの、表面に変化が見られず、化学的、熱的に安定な膜
を得ることができた。As described above, C-C is formed on the surface to be formed by the plasma.
Fluorine and C- with a CF bond having an amorphous structure having a large number of bonds or an amorphous structure having a microcrystalline structure
Nitrogen with N-bonds or hydrogen-containing carbons with CH2-engagement in addition to these were generated. The electromagnetic energy supplied was 50 w to 1 KW, and plasma energy of 0.03 to 3 W / cm 2 was applied per unit area. As shown in Fig. 4, the transmittance of carbon that is a combination of fluorine and nitrogen is 95% or more in the wavelength range of 600 nm or more, and 50% even at 400 nm.
As a result, a transparent and almost transparent film was obtained. The internal stress of the film was 1/10 or less compared to the film containing neither nitrogen nor nitrogen. Even if it is soaked in a chemical such as an acid, an alkali, or an organic solvent at room temperature for 1 hour, no change is seen as long as the surface is observed with a 400 × optical microscope.
After being left in a constant temperature oven (air) heated to 500 ° C for 1 hour, no change was observed on the surface and a chemically and thermally stable film could be obtained.
特にこの炭素を主成分とする被膜を用いた感光ドラムと
して、これに紙を105 〜106 枚(A4 版)こすっても、そ
の電気抵抗、透過率に変化がないというきわめて安定な
膜であることがわかった。In particular, as a photosensitive drum that uses this carbon-based coating, it is an extremely stable film that does not change its electrical resistance or transmittance even when it is rubbed with 10 5 to 10 6 sheets (A4 size) of paper. I knew it was.
以上述べた作製方法はあくまで一例であり、従来より良
く知られているグロー放電プラズマであっても、アーク
放電プラズマであっても、また、ECR(電子サイクロトロ
ン共鳴)を用いたプラズマであってもよい。The above-described manufacturing method is merely an example, and it may be glow discharge plasma, arc discharge plasma, or plasma using ECR (electron cyclotron resonance), which is well known in the art. Good.
以下実施例に従って本発明を応用した複合体についてさ
らに詳しく述べる。The composite to which the present invention is applied will be described in more detail below with reference to Examples.
「実施例１」 電子写真のプロセスに用いられる感光体に、本発明によ
る複合体を応用した場合の例を以下に述べる。[Example 1] An example in which the composite according to the present invention is applied to a photoreceptor used in an electrophotographic process will be described below.
第５図は、本発明による炭素を主成分とした被膜を応用
した場合の感光体の構造を示す。約200 μｍ厚さのPET
シート(1)上に厚さ600 ÅのAl蒸着層(2)、中間層(3)を
はさんで0.6〜1.2 μｍの電荷発生層を(4)を設け、本発
明による保護膜(6)、約20μｍの電荷移動層(5)を通して
光(7)が入射すると、前記電荷発生層で吸収され、電子
正孔対が生成される。予め、電荷移動層もしくは保護層
を負に帯電させておけば、光入射のあった領域のみ電荷
発生層で生成された正孔が電荷移動層を移動し、帯電さ
れた負電荷を中和させる。この時、電荷発生層で生成さ
れた電子は、中間層を通ってAl蒸着層に達し、排出され
る。光入射のなかった領域に残った負電荷は、その後ト
ナーを吸着し、転写紙に転写されて、光入射の有無に応
じた像を転写紙上に形成することとなる。FIG. 5 shows the structure of a photoreceptor when the coating film containing carbon as a main component according to the present invention is applied. PET with a thickness of about 200 μm
A protective film (6) according to the present invention is provided on the sheet (1) by providing a 600 Å-thick Al vapor-deposited layer (2) and an intermediate layer (3) with a charge generation layer of 0.6 to 1.2 μm (4). When light (7) enters through the charge transfer layer (5) of about 20 μm, it is absorbed in the charge generation layer and electron-hole pairs are generated. If the charge transfer layer or the protective layer is negatively charged in advance, the holes generated in the charge generation layer move in the charge transfer layer only in the region where light is incident, and neutralize the charged negative charge. . At this time, the electrons generated in the charge generation layer reach the Al vapor deposition layer through the intermediate layer and are discharged. The negative charge remaining in the area where no light is incident then adsorbs the toner and is transferred to the transfer paper to form an image on the transfer paper depending on whether light is incident.
ここで形成された保護層は、本発明の用いたものであ
り、N(CH3)3 の流量によりその比抵抗を１×106 〜５
×1013（Ωcm）好ましくは１×108 〜５×1011（Ωcm）
に制御されたものである。従って、比抵抗が低すぎる為
に発生する帯電電荷の横方向の移動がなく、光入射のあ
った領域の境界はぼけることなくはっきりとしている。
依って、転写された像も鮮明なものであった。また、比
抵抗が高すぎれば、繰り返し使用により徐々に保護膜に
電荷が蓄積され、使用済のトナーが除去されなくなり、
転写紙が黒くなるという現象が起こる。The protective layer formed here is the one used in the present invention and has a specific resistance of 1 × 10 6 to 5 depending on the flow rate of N (CH 3 ) 3.
× 10 13 (Ωcm), preferably 1 × 10 8 to 5 × 10 11 (Ωcm)
It is controlled by. Therefore, since the specific resistance is too low, there is no lateral movement of the charged electric charge, and the boundary of the region where the light is incident is clear without blurring.
Therefore, the transferred image was also clear. Also, if the specific resistance is too high, electric charge is gradually accumulated in the protective film due to repeated use, and used toner cannot be removed,
The phenomenon that the transfer paper turns black occurs.
本発明による保護膜は、電荷が蓄積されない程度の比抵
抗に制御されているため、そのような現象もなく、C2H4
とNF3を用いたものでは２×104 枚の複写で像ながれが
みられたが、本発明方法では１×105 〜１×106 枚(A4
版相当)を複写しても像ながれは観察されず、長期に渡
り良質の転写像を得ることができた。Since the protective film according to the present invention is controlled to have a specific resistance that does not accumulate charges, no C 2 H 4
With NF 3 and NF 3 , image flow was observed in copying 2 × 10 4 sheets, but with the method of the present invention, 1 × 10 5 to 1 × 10 6 sheets (A4
No image streaks were observed even when the (corresponding plate) was copied, and a good quality transferred image could be obtained for a long period of time.
また、ここで用いた保護膜の透過率は500 ｎｍ以上の波
長域で80％以上であり、400 ｎｍ以上の波長域で60％以
上であった。従って、本実用例の感光体は可視光域にお
いても十分使用可能なものであった。The transmittance of the protective film used here was 80% or more in the wavelength range of 500 nm or more, and 60% or more in the wavelength range of 400 nm or more. Therefore, the photoconductor of this practical example was sufficiently usable even in the visible light region.
勿論、耐摩耗性，耐引っ掻き等の機械的ストレスに対す
る耐久性が向上していることは言うまでもない。Needless to say, durability against mechanical stress such as abrasion resistance and scratch resistance is improved.
更に、ここで用いた保護膜は内部応力が低減され密着性
も良いものであった。即ち、シート状感光体を曲率半径
10mmまで曲げても、保護膜にクラックの発生は見られ
ず、また、ピーリングも生じなかった。Furthermore, the protective film used here had low internal stress and good adhesion. That is, the radius of curvature of the sheet-shaped photoreceptor is
Even when bent to 10 mm, no crack was observed in the protective film and no peeling occurred.
以上、本実施例では感光体としてシート状有機感光体に
ついて述べたが、ドラム状有機感光体、アモルファスシ
リコン感光体、セレン感光体についても同様に本発明に
よる保護膜を構成することができ、同様の効果が得られ
る。Although the sheet-shaped organic photoconductor is described as the photoconductor in the present embodiment, the protective film according to the present invention can be similarly configured for the drum-shaped organic photoconductor, the amorphous silicon photoconductor, and the selenium photoconductor. The effect of is obtained.
「実施例２」 代表的なサーマルプリントヘッド構造を第６図に示す。
絶縁基板(1)上にグレーズ(2)を形成し、グレーズ(2)と
同時に発熱体部にあたる部分に突起したグレーズ(3)を
形成し、次に基板(11)上に発熱体(4)と電気導電体(5)と
を順次積層し、その後公知のフォトリソグラフィー技術
を用いて、突起したグレーズの上に発熱体素子部(21)を
形成し、最後に本発明による弗素と窒素または弗素と窒
素と水素をC-F 結合、C-N 結合を有して含んだ炭素を主
成分とする被膜を保護膜(6)として形成した。Example 2 A typical thermal print head structure is shown in FIG.
The glaze (2) is formed on the insulating substrate (1), the glaze (2) and the protruding glaze (3) are formed at the same time as the heating element, and then the heating element (4) is formed on the substrate (11). And the electric conductor (5) are sequentially laminated, and then a known photolithography technique is used to form the heating element part (21) on the protruding glaze, and finally, the fluorine and nitrogen or fluorine according to the present invention is used. A film containing carbon as a main component containing nitrogen and hydrogen with CF bonds and CN bonds was formed as the protective film (6).
通常用いられる保護膜は窒化珪素膜等の無機膜であり、
その膜厚は５μｍと大きいものであるが、本実施例で用
いた保護膜(6)は実施例１で形成した保護膜と同様の特
性を有し、N(CH3)3 の流量を制御することにより、ビッ
カース硬度2000Kg/mm2以上の硬い膜を形成することがで
きる。そのため、膜厚１μｍ程度の被膜で実用に際して
は十分である。A commonly used protective film is an inorganic film such as a silicon nitride film,
Although the film thickness is as large as 5 μm, the protective film (6) used in this example has the same characteristics as the protective film formed in Example 1, and the flow rate of N (CH 3 ) 3 is controlled. By doing so, a hard film having a Vickers hardness of 2000 Kg / mm 2 or more can be formed. Therefore, a film having a film thickness of about 1 μm is sufficient for practical use.
また、本実施例で用いた保護膜は、内部応力が109dyn/c
m2以下と小さく密着性も良好であり、500 ℃において１
時間（空気中）の耐熱試験でも良好であることを確認し
た。The protective film used in this example has an internal stress of 10 9 dyn / c.
It is as small as m 2 or less and has good adhesion.
It was confirmed that the heat resistance test in time (in air) was also good.
さらに、1010Ωcm程度の比抵抗は静電気対策に好都合で
あり、傷の発生原因となるゴミや塵を低減でき、静電気
の電子回路に及ぼす影響も低減することができた。Furthermore, a specific resistance of about 10 10 Ωcm is convenient as a countermeasure against static electricity, and it is possible to reduce dust and dirt that cause scratches, and reduce the influence of static electricity on electronic circuits.
本応用例では既知の発熱体(4)を用いたが、本発明によ
るC-F 結合とC-N 結合とを含む炭素を主成分とする被膜
を発熱体として用いることも可能である。即ち、弗素と
窒素の濃度が高くなるような成膜条件で被膜を作成し
て、被膜の比抵抗を103 〜104 Ωｃｍにすれば、この被
膜を発熱体として用いることができる。Although the known heating element (4) is used in this application example, it is also possible to use, as the heating element, the coating film containing carbon having a CF bond and a CN bond according to the present invention as a main component. That is, if a coating film is formed under the film forming conditions such that the concentrations of fluorine and nitrogen are high and the specific resistance of the coating film is 10 3 to 10 4 Ωcm, this coating film can be used as a heating element.
「実施例３」 本実施例は、密着型イメージセンサに本発明の炭素を主
成分とする被膜を適用し、第７図に示す構造の炭素を主
成分とする被膜を形成したものである。"Example 3" In this example, a coating containing carbon as a main component of the present invention was applied to a contact image sensor to form a coating containing carbon having a structure shown in FIG.
第７図に示すように、透明ガラス基板(33)上に電極及び
アモルファスシリコンを公知のプラズマCVD 法を用いて
積層させ、フォトエッチング法により電極及びアモルフ
ァスシリコンの層を加工することにより光センサ素子(3
4)を形成させた後、透光性ポリイミド(35)を公知のスピ
ンナー法で塗布し密着型イメージセンサを作製した。そ
の後、上記イメージセンサの透光性ポリイミド(35)上に
実施例１で述べた方法により、保護膜(36)を2.0 μｍの
厚さに形成した。As shown in FIG. 7, an optical sensor element is formed by stacking an electrode and amorphous silicon on a transparent glass substrate (33) by a known plasma CVD method, and processing the electrode and the amorphous silicon layer by a photoetching method. (3
After forming 4), the translucent polyimide (35) was applied by a known spinner method to fabricate a contact image sensor. After that, the protective film (36) was formed to a thickness of 2.0 μm on the translucent polyimide (35) of the image sensor by the method described in Example 1.
前記保護膜のビッカース硬度を測定したところ2500Kg/m
m2であり、また比抵抗は１×108 Ωcmであった。形成さ
れた炭素被膜は、被形成面上と表面とにダイヤモンド類
似の硬さと静電気対策にとって適度な電気絶縁性とを有
しているため、原稿面上の凹凸やホチキスの金具等によ
り上記の層に傷が付くこともなく、また原稿と保護膜と
の間の摩擦により静電気が生じても、静電気の蓄積を防
ぐことができた。また光センサー素子への電気的影響を
抑えると共に、透光性ポリイミド中の不純物が混入する
ことを防止できた。When the Vickers hardness of the protective film was measured, it was 2500 Kg / m.
m 2 and the specific resistance was 1 × 10 8 Ωcm. Since the formed carbon coating has hardness similar to diamond on the surface to be formed and the surface and an electric insulating property suitable for static electricity countermeasures, the above-mentioned layer is formed by unevenness on the original surface or staple metal fittings. It was possible to prevent the accumulation of static electricity even if the static electricity was generated due to the friction between the original and the protective film. Further, it was possible to suppress the electrical influence on the optical sensor element and prevent the impurities in the translucent polyimide from being mixed.
「効果」 以上述べたように、本発明はC-F 結合とC-N 結合または
これらに加えてC-H 結合を有する炭素を主成分とする被
膜を有する複合体であり、該被膜は弗素の添加量により
排水性表面とし、窒素の添加量によって比抵抗を制御す
ることにより、容易にしかも安価に該被膜の排水性また
は親水性の程度、硬度、透光性、比抵抗を変化させるこ
とができ、加えて該被膜の内部応力は小さく、密着性の
良いものである。[Effects] As described above, the present invention is a composite having a coating mainly composed of carbon having a CF bond and a CN bond or a CH bond in addition to these, and the coating has a drainage property depending on the amount of fluorine added. By controlling the specific resistance by the amount of nitrogen added to the surface, it is possible to easily and inexpensively change the degree of drainage or hydrophilicity, hardness, translucency, and specific resistance of the coating film. The internal stress of the coating is small and the adhesion is good.
本発明によるハロゲン元素と窒素または水素とハロゲン
元素と窒素が添加された炭素を主成分とする被膜を応用
した複合体において、実施例に述べた通り、本発明にお
いては、C-N 結合を有する気体の使用料がNH3,NF3 を用
いる場合の約1/20で同じ比抵抗を作ることができ、イオ
ン化率（活性不純物量／添加した不純物量）を20倍も大
きい。As described in the examples, in the composite to which the coating film containing carbon containing halogen element and nitrogen or hydrogen, halogen element and nitrogen added according to the present invention is applied, in the present invention, a gas having a CN bond is used. The same specific resistance can be made at about 1/20 of the case of using NH 3 and NF 3 , and the ionization rate (active impurity amount / added impurity amount) is 20 times larger.
そして炭素を主成分とする被膜を適用しなかった場合に
比べ、該複合体の寿命および信頼性を格段に向上させる
ことができた。The life and reliability of the composite could be significantly improved as compared with the case where the coating film containing carbon as the main component was not applied.
本発明方法は第３図に示したプラズマCVD 装置に限定さ
れることはない。重要なことは、初期状態において、C-
F 結合およびC-N 結合を有する気体を用いることおよび
負の直流バイアスを基板に自励的または人為的に加える
こと、さらにこれに加えてC-H 結合またはH2を同時に添
加することである。またプラズマCVD 中は0.001 〜10to
rr、好ましくは0.01〜0.1torr とした。また基板温度は
室温〜450 ℃である。The method of the present invention is not limited to the plasma CVD apparatus shown in FIG. What is important is that in the initial state, C-
The use of gases with F and CN bonds and the self-excited or artificial application of a negative DC bias to the substrate, as well as the simultaneous addition of CH or H 2 bonds. During plasma CVD, 0.001-10to
rr, preferably 0.01 to 0.1 torr. The substrate temperature is room temperature to 450 ° C.
第１図はN(CH3)3 の流量と比抵抗の関係を示す。 第２図はバイアス電圧とビッカース硬度の関係を示す。 第３図は本発明の炭素または炭素を主成分とする被膜を
形成するためのプラズマCVD 装置の概要を示す。 第４図は弗素と窒素と水素を含んだ炭素の透過率を示
す。 第５図は、本発明による炭素を主成分とした被膜を応用
した場合の感光体の構造を示す。 第６図は代表的なサーマルプリントヘッド構造を示す。 第７図は密着型イメージセンサに本発明の炭素を主成分
とする被膜を適用したものである。Figure 1 shows the relationship between the flow rate of N (CH 3 ) 3 and the specific resistance. FIG. 2 shows the relationship between bias voltage and Vickers hardness. FIG. 3 shows an outline of a plasma CVD apparatus for forming carbon or a coating film containing carbon as a main component of the present invention. FIG. 4 shows the transmittance of carbon containing fluorine, nitrogen and hydrogen. FIG. 5 shows the structure of a photoreceptor when the coating film containing carbon as a main component according to the present invention is applied. FIG. 6 shows a typical thermal printhead structure. FIG. 7 shows the contact type image sensor to which the coating film containing carbon of the present invention as a main component is applied.
フロントページの続き (72)発明者 石田 典也 神奈川県厚木市長谷398番地 株式会社半 導体エネルギー研究所内 (72)発明者 鈴木 邦夫 神奈川県厚木市長谷398番地 株式会社半 導体エネルギー研究所内 審査官 木梨 貞男 (56)参考文献 特開 昭63−210010（ＪＰ，Ａ)Front page continuation (72) Inventor Noriya Ishida 398 Hase, Atsugi City, Kanagawa Prefecture, Semiconducting Energy Laboratory Co., Ltd. Sadao (56) Reference JP-A-63-210010 (JP, A)
Claims (2)
を有する第２の気体または前記第１および第２の気体に
加えて水素またはC-H 結合を有する第３の気体を混合せ
しめ、-50 〜-2000Vの自己バイアスまたは外部バイアス
を印加しつつプラズマ化学反応をせしめることにより、
被形成面上に窒素と弗素がC-N 結合およびC-F 結合を有
して添加された炭素を主成分とする被膜を形成すること
を特徴とする炭素を主成分とする被膜の作製方法。1. A first gas having a CF bond and a second gas having a CN bond or a mixture of hydrogen or a third gas having a CH bond in addition to the first and second gases, By causing plasma chemical reaction while applying self bias or external bias of 50 to -2000V,
A method for producing a carbon-based film, comprising forming a carbon-based film to which nitrogen and fluorine have a CN bond and a CF bond and is added on the surface to be formed.
を有する第１の気体は、CF4,C2F6,C3F8,CHF3, CH2F2,CH
3Fより選ばれた少なくとも１種の気体、C-N 結合を有す
る第２の気体はN(CH3)3,N(C2H5)3,HN(CH3)2,H2N(CH3),N
H(C2H5)2, H2N(C2H5)より選ばれた少なくとも１種の気
体、また、水素(H2)またはC-H 結合を有する気体は前記
第１または第２の気体であって、かつC-H 結合を有する
気体またはC2H4,CH4, C2H2,C3H8より選ばれた第３の気
体よりなり、圧力0.001 〜10torrにおいて気体状態を呈
する気体よりなることを特徴とする炭素を主成分とする
被膜の作製方法。2. The first gas having a CF bond according to claim 1, is CF 4 , C 2 F 6 , C 3 F 8 , CHF 3 , CH 2 F 2 , CH.
At least one gas selected from 3 F and the second gas having a CN bond are N (CH 3 ) 3 , N (C 2 H 5 ) 3 , HN (CH 3 ) 2 , H 2 N (CH 3 ), N
At least one gas selected from H (C 2 H 5 ) 2 and H 2 N (C 2 H 5 ) and the gas having hydrogen (H 2 ) or CH bond is the first or second gas. And a gas having a CH bond or a third gas selected from C 2 H 4 , CH 4 , C 2 H 2 and C 3 H 8 and having a gas state at a pressure of 0.001 to 10 torr. A method for producing a coating film containing carbon as a main component, wherein
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26196788A JPH0623433B2 (en) | 1988-10-17 | 1988-10-17 | Method for producing carbon-based coating |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26196788A JPH0623433B2 (en) | 1988-10-17 | 1988-10-17 | Method for producing carbon-based coating |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02107773A JPH02107773A (en) | 1990-04-19 |
| JPH0623433B2 true JPH0623433B2 (en) | 1994-03-30 |
Family
ID=17369145
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP26196788A Expired - Lifetime JPH0623433B2 (en) | 1988-10-17 | 1988-10-17 | Method for producing carbon-based coating |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0623433B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2599642B2 (en) * | 1990-09-25 | 1997-04-09 | 株式会社半導体エネルギー研究所 | Copier |
| CN106906456B (en) * | 2017-01-23 | 2018-04-20 | 江苏菲沃泰纳米科技有限公司 | A kind of preparation method of the controllable coating of the degree of cross linking |
-
1988
- 1988-10-17 JP JP26196788A patent/JPH0623433B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH02107773A (en) | 1990-04-19 |
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