JPH0230755A - Carbon-based coating film - Google Patents
Carbon-based coating filmInfo
- Publication number
- JPH0230755A JPH0230755A JP17785188A JP17785188A JPH0230755A JP H0230755 A JPH0230755 A JP H0230755A JP 17785188 A JP17785188 A JP 17785188A JP 17785188 A JP17785188 A JP 17785188A JP H0230755 A JPH0230755 A JP H0230755A
- Authority
- JP
- Japan
- Prior art keywords
- carbon
- nitrogen
- film
- plasma
- substrate
- 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.)
- Pending
Links
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 44
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 239000011248 coating agent Substances 0.000 title abstract description 19
- 238000000576 coating method Methods 0.000 title abstract description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 61
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 31
- 239000000758 substrate Substances 0.000 claims abstract description 26
- 239000001257 hydrogen Substances 0.000 claims abstract description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000005268 plasma chemical vapour deposition Methods 0.000 claims abstract description 7
- 239000011521 glass Substances 0.000 claims abstract description 6
- 229910052751 metal Inorganic materials 0.000 claims abstract description 5
- 239000002184 metal Substances 0.000 claims abstract description 5
- 239000000919 ceramic Substances 0.000 claims abstract description 4
- 239000011347 resin Substances 0.000 claims abstract description 4
- 229920005989 resin Polymers 0.000 claims abstract description 4
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract 3
- 238000000034 method Methods 0.000 abstract description 10
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 9
- 239000000126 substance Substances 0.000 abstract description 7
- 229930195733 hydrocarbon Natural products 0.000 abstract description 6
- 150000002430 hydrocarbons Chemical class 0.000 abstract description 6
- 239000004215 Carbon black (E152) Substances 0.000 abstract description 3
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 abstract description 2
- 239000007858 starting material Substances 0.000 abstract 3
- 239000003575 carbonaceous material Substances 0.000 abstract 1
- 239000010408 film Substances 0.000 description 61
- 239000007789 gas Substances 0.000 description 26
- 230000001681 protective effect Effects 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 19
- 239000010410 layer Substances 0.000 description 15
- 239000002994 raw material Substances 0.000 description 12
- 230000005611 electricity Effects 0.000 description 8
- 108091008695 photoreceptors Proteins 0.000 description 8
- 230000003068 static effect Effects 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- 238000002834 transmittance Methods 0.000 description 7
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 6
- 239000005977 Ethylene Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000012159 carrier gas Substances 0.000 description 4
- 230000005684 electric field Effects 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000004642 Polyimide Substances 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 229910021417 amorphous silicon Inorganic materials 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 239000004020 conductor Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 229920001721 polyimide Polymers 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 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
- 238000009825 accumulation Methods 0.000 description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 229910003460 diamond Inorganic materials 0.000 description 2
- 239000010432 diamond Substances 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000009832 plasma treatment Methods 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- 239000011241 protective layer Substances 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
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- -1 alkalis Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 230000005672 electromagnetic field Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 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
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical class ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Abstract
Description
【発明の詳細な説明】
「発明の利用分野」
本発明は、ガラス、金属、セラミックス、有機樹脂等の
表面に耐機械的ストレス、静電気対策を同時に解決する
ことを目的としてコーティングされる、赤外および可視
域に透明な炭素を主成分とする被膜に関するものである
。Detailed Description of the Invention "Field of Application of the Invention" The present invention relates to an infrared ray material coated on the surface of glass, metal, ceramics, organic resin, etc. for the purpose of simultaneously solving mechanical stress resistance and static electricity countermeasures. The present invention also relates to a coating mainly composed of carbon that is transparent in the visible range.
「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, metals, plastics, and resins with a film that is harder than those soft materials is effective against mechanical stresses such as abrasion and scratches. be.
そのような膜としては、Ａ ｆ ｚ Ｏ３、ＴｉＮ、Ｂ
Ｎ、ＷＣ，Ｓ ｉ Ｃ，Ｓ ｉ ！Ｎ４．５ｉＯｚ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Ｊ （昭和５６年特許願第１４６９３０号）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
には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。Such films include A f z O3, TiN, B
N, WC, S i C, S i! Composite J having an inorganic film such as N4.5iOz and a carbon film (Patent Application No. 146930 of 1982) filed by the present inventor is known. However, the above-mentioned known protective film has already been It has a high electrical resistivity, easily generates static electricity, and tends to attract dirt and dust in the atmosphere to its surface. When used in composite materials that utilize static electricity by applying an electric field to the surface of the protective film, charge accumulates in the protective film, which has a high electrical resistance, resulting in the problem that the expected performance cannot be achieved for a long period of 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。One possible way to solve such problems is to add a conductive substance to the known film.
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。In this case, the added conductive substance becomes a light absorption center,
Light absorption occurs in the known protective film, making it unsuitable for applications requiring transparency in the infrared and visible ranges.
さらに、前記既知の保護膜は成膜過程の条件にもよるが
、内部応力が蓄積され、膜のビーリングが発生する問題
もあった。したがって膜厚をうずくする、前記保護膜と
下地材料の間に密着性の向上を目的とした中間層を設け
る等の対策が必要となるが、膜厚の低下は耐機械ストレ
スの低下を意味し、中間層の存在はプロセス増加による
コスト高の問題が発生ずる。Furthermore, depending on the conditions of the film forming process, the known protective film has a problem in that internal stress is accumulated and the film becomes peeled. Therefore, it is necessary to take measures such as reducing the film thickness or providing an intermediate layer between the protective film and the underlying material to improve adhesion, but a reduction in the film thickness means a reduction in mechanical stress resistance. However, the presence of an intermediate layer raises the problem of increased costs due to increased processes.
「発明の構成」
本発明は、以上述べた問題を解決し、保護膜としての耐
機械ストレス、静電気に由来する問題点、透明性を同時
に満足する被膜として炭素を主成分とする被膜に窒素ま
たは水素と窒素を０．１〜５０原子パーセント添加する
ことを特徴とする被膜を提供することを目的とする。
本発明による被膜は炭素の原料としてメタン（ＣＨ，）
、エタン（ＣｚＨｉ）、エチレン（Ｃ２Ｈ４） 、アセ
チレン（Ｃｚ Ｈｚ ）等の炭化水素をプラズマ中に導
入し、前記炭素原料を分解、励起し、所定の基板上に堆
積させることによって形成することができる。この時、
同時に窒素の原料としてＮＨ，、ＮＦ、、等の窒化物を
プラズマ中に導入して窒素を添加する。``Structure of the Invention'' The present invention solves the above-mentioned problems and provides a film that is mainly composed of carbon with nitrogen or It is an object of the present invention to provide a coating characterized in that 0.1 to 50 atomic percent of hydrogen and nitrogen are added.
The coating according to the present invention uses methane (CH,) as the carbon source.
It can be formed by introducing hydrocarbons such as , ethane (CzHi), ethylene (C2H4), acetylene (CzHz), etc. into plasma, decomposing and exciting the carbon raw material, and depositing it on a predetermined substrate. . At this time,
At the same time, nitrides such as NH, NF, etc. are introduced into the plasma as nitrogen raw materials to add nitrogen.
添加量は、窒素を含む物質の流量によって制御すること
ができる。ここで、炭素を含む原料ガスとして、前記炭
化水素の他にＣＦ、、ＣＨ、Ｆ ２等のフッ化炭素、Ｃ
Ｃ１４等の塩化炭素、ＣＨ：＋Ｂｒ等の臭化炭化水素を
用いてもよい。The amount added can be controlled by the flow rate of the nitrogen-containing substance. Here, as the raw material gas containing carbon, in addition to the above-mentioned hydrocarbons, fluorocarbons such as CF, CH, F2, etc.
Carbon chlorides such as C14 and brominated hydrocarbons such as CH:+Br may also be used.
本発明による被膜は、以上述べたような原料物質、すな
わち炭素原料物質と窒素材料を同時にプラズマ反応室に
導入し、この時ハロゲン系原料物質の流量を調整するこ
とによって被膜の窒素添加■を制御することができる。The film according to the present invention is produced by introducing the above-mentioned raw materials, that is, a carbon raw material and a nitrogen material into a plasma reaction chamber at the same time, and controlling nitrogen addition to the film by adjusting the flow rate of the halogen-based raw material. can do.
窒素添加量は導電率、透過率、硬度の違いとして観測さ
れる。以下に窒素原料物質の流量を変えた時の導電率の
変化の実験結果をしめず。The amount of nitrogen added is observed as a difference in conductivity, transmittance, and hardness. Below are the experimental results of changes in conductivity when the flow rate of the nitrogen source material was changed.
例えば窒素原料物質としてＮＨ，を用いる。炭素原料物
質としてエチレンを用い、エチレンの流１ｌ１０５ｅｃ
、反応圧力１０Ｐａ、投入電力密度０．０８Ｗ／ｃｍ２
とした。第１図に示すようにＮＩＰ、の量が増すに従い
、導電率が高くなっている。For example, NH is used as the nitrogen source material. Using ethylene as carbon raw material, ethylene stream 1l105ec
, reaction pressure 10 Pa, input power density 0.08 W/cm2
And so. As shown in FIG. 1, as the amount of NIP increases, the conductivity increases.
また、第２図に示すようにＮＨ，流量が増すに従い透過
率は高くなる。さらに第３図に示すようにＮＨ，流量が
増すに従い硬度は低下する。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。Furthermore, as shown in FIG. 2, the transmittance increases as the NH flow rate increases. Further, as shown in FIG. 3, as the NH flow rate increases, the hardness decreases. A decrease in hardness means a decrease in internal stress.
本発明による被膜を用いれば、以上述べたように比較的
広い範囲にわたって被膜の導電率、硬さ、透過率を変え
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。By using the coating according to the present invention, the conductivity, hardness, and transmittance of the coating can be varied over a relatively wide range as described above. That is, the optimum characteristics required for various applications can be easily obtained at relatively low cost.
以上窒素原料物質の流量を変えることによって窒素添加
■を変えることを述べたが、もちろん放電時の投入電力
、反応圧力、放電容器の形、炭素原料物質流量等の放電
条件は一定である。また、これらの放電条件のうち１つ
もしくは２つ以上を変化させても、窒素添加量を変える
ことができる。It has been described above that nitrogen addition (2) is changed by changing the flow rate of the nitrogen raw material, but of course the discharge conditions such as the input power during discharge, reaction pressure, the shape of the discharge vessel, and the flow rate of the carbon raw material are constant. Furthermore, the amount of nitrogen added can be changed by changing one or more of these discharge conditions.
−例として、投入電力を変化させた場合の導電率の変化
を第４図に示す。すなわち、投入電力を増すに従い導電
率は高くなる。この場合も勿論、投入電力以外の放電パ
ラメータである反応圧力、放電容器の形、Ｎｌ！３流量
、Ｃ２Ｈ４流量等は一定である。- As an example, FIG. 4 shows the change in conductivity when the input power is changed. That is, as the input power increases, the conductivity increases. In this case, of course, the discharge parameters other than the input power are the reaction pressure, the shape of the discharge vessel, and Nl! 3 flow rate, C2H4 flow rate, etc. are constant.
以上述べたように、窒素を含む炭素を主成分とする被膜
の導電率、硬さ、透過率等の膜特性は、投入電力、反応
圧力、放電容器の形、炭素原料物質流量、窒素原料物質
流量等の放電パラメータを変えることにより、容易に、
安価に比較的広い範囲で変化させることができる。As mentioned above, the film properties such as electrical conductivity, hardness, and transmittance of a film whose main component is carbon containing nitrogen are determined by the input power, reaction pressure, the shape of the discharge vessel, the flow rate of the carbon raw material, and the nitrogen raw material. By changing discharge parameters such as flow rate,
It can be varied over a relatively wide range at low cost.
また本発明によ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、水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。ここに窒素がプラズマ中
に存在すると窒素と炭素は容易にＣ−Ｎ結合をつくり炭
素の未結合手は水素のみの場合よりも低減すると考えら
れる。すなわち、内部応力が低減されることになる。ま
た、内部応力の低下により膜のビーリングの発生が防止
されることも特徴の１つである。Furthermore, the coating according to the present invention is characterized by low internal stress. This is because the dangling bonds that normally exist in carbon are terminated with hydrogen, which relieves the attractive force of the dangling bonds and reduces internal stress.
Not all dangling bonds are terminated with hydrogen, and some dangling bonds remain in the film, which is considered to be one of the causes of internal stress. It is thought that when nitrogen is present in the plasma, nitrogen and carbon easily form a C--N bond, and the number of dangling bonds in carbon is reduced compared to when only hydrogen is present. In other words, internal stress is reduced. Another feature is that the reduction in internal stress prevents the occurrence of membrane beerling.
さらに、本発明による被膜は耐熱性の点においても優れ
ている。Furthermore, the coating according to the present invention is also excellent in terms of heat resistance.
また、本発明による被膜は堆積時の基板の温度が室温か
ら１５０″Ｃ以下の低温で成膜できることも特徴の１つ
である。これによりプラスチックス、樹脂等の有機物、
セレン半導体等高温にできない基板上にも成膜すること
ができる。Another feature of the film according to the present invention is that it can be formed at a low temperature of the substrate during deposition, from room temperature to 150''C or less.
Films can also be formed on substrates that cannot be heated to high temperatures, such as selenium semiconductors.
「実施例１」
第５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。"Example 1" FIG. 5 shows an outline of a plasma CVD apparatus for forming carbon or a coating mainly composed of carbon according to 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、反応性気体である炭化水
素気体例えばメタン、エチレンを（３）より、窒素を含
む気体例えばＮＨ，を（４）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Ｏ■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 used as a carrier gas (2), a hydrocarbon gas as a reactive gas such as methane or ethylene is used as a (3), and a gas containing nitrogen as a gas such as NH is as a (4). After passing through a valve (6) and a flow meter (7), it is introduced into the reaction system (8) through a nozzle (9). Before reaching this nozzle, it is effective to preactivate the reactive gas by applying microwave energy at O₂ for excitation of the reactive gas.
反応系（８）には第１の電極（１１）、第２の電極０２
）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
）、０２１間には高周波電源面、マツチングトランス０
４）、直流バイアス電源θつより電気エネルギが加えら
れ、プラズマが発生ずる。排気系０６）は圧力調整バル
ブθり、ターボ分子ポンプ０８）、ロータリーポンプ０
９）をへて不要気体を排気する。反応性気体には、反応
空間Ｑ（Ｄにおける圧力が０．００１〜ｌ０Ｔｏｒｒ代
表的には０．０１〜ＩＴｏｒｒＯ下で高周波もしくは直
流によるエネルギにより０．１〜５に−のエネルギが加
えられる。The reaction system (8) includes a first electrode (11) and a second electrode 02.
) was established. In this case, the condition (first electrode area/second electrode area) <1 was satisfied. A pair of electrodes (11
), 021 has a high frequency power supply plane and matching transformer 0.
4) Electrical energy is applied from the DC bias power supply θ, and plasma is generated. The exhaust system 06) includes a pressure adjustment valve θ, a turbo molecular pump 08), and a rotary pump 0.
9) to exhaust unnecessary gas. Energy of 0.1 to 5 - is applied to the reactive gas by high frequency or direct current energy under a pressure in the reaction space Q (D) of 0.001 to 10 Torr, typically 0.01 to ITorr.
特に励起源がＩ Ｇ Ｈ□以上、例えば２．４５ＧＨ２
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０．１〜５０ＭＨ２例えば１３．５６Ｍ
Ｈ，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, if the excitation source is IGH□ or higher, for example 2.45GH2
At a frequency of 0.1 to 50 MH2, for example, 13.56 M
At the H frequency, C-C bonds and C=C bonds are decomposed to create -C-C- bonds, and the unpaired bonds of carbon collide with each other to form covalent bonds, creating a stable diamond structure. It is possible to have a structure that locally has
直流バイアスは一２００〜６００Ｖ （実質的には一４
００〜＋４００Ｖ）を加える。なぜなら、直流バイアス
が零のときは自己バイアスが一２００Ｖ（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 is -200 to 600V (substantially -4
00~+400V). This is because when the DC bias is zero, the self-bias has a voltage of 1200V (with the second electrode at the ground level).
また実験条件は、高周波エネルギー６０Ｗ、圧力０．０
１５Ｔｏｒｒ、エチレンの流ｆｆｌｌｏＯ３ＣＣＭ、Ｎ
Ｈ，の流量１１００５ＣＣ基板温度を室温、成膜時間３
０分で行った。The experimental conditions were: high frequency energy 60W, pressure 0.0
15Torr, ethylene flowfflloO3CCM, N
H, flow rate 11005CC, substrate temperature at room temperature, film formation time 3
It took 0 minutes.
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窒素を含んだ炭素を生成させ
た。さらにこの電磁エネルギは５０ｗ〜ｌｋｗを供給し
、単位面積あたり００３〜３ｗ／ｃ４のプラズマエネル
ギーを加えた。この窒素を含んだ炭素の透過率は第６図
に示すように６００ｎｍ以上の波長域では９５％以上の
透過であり、４００ｎＩ１１でも５０％以上透過のほぼ
透明な膜が得られた。ビッカース硬度は１０００〜２５
００ｋｇ／ｍであり、あまり硬くはないが内部応力は１
０ ’ｄｙｎ／ｃｎ＋”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°Ｃに加
熱した恒温槽（空気）中に１時間放置したものの表面も
変化が見られず化学的、熱的に安定なｎりを得ることが
できた。As described above, nitrogen-containing carbon having an amorphous structure or a microcrystalline structure with a large number of C--C bonds formed on the formation surface was generated by plasma. Further, this electromagnetic energy was supplied at 50w to lkw, and plasma energy of 003 to 3w/c4 per unit area was added. As shown in FIG. 6, the transmittance of this nitrogen-containing carbon was 95% or more in the wavelength range of 600 nm or more, and even at 400 nI11, a nearly transparent film with 50% or more transmission was obtained. Vickers hardness is 1000-25
00kg/m, and although it is not very hard, the internal stress is 1
It was extremely small, less than 0 'dyn/cn+''.Even if it was immersed in chemicals such as acids, alkalis, and organic solvents for one hour at room temperature, as far as the surface was observed under a 400x optical microscope, no particles were observed. No change was observed, and no change was observed on the surface after leaving it in a constant temperature bath (air) heated to 500°C for 1 hour, making it possible to obtain chemically and thermally stable n.
「実施例２」
第７図に本発明にて用いた磁場印加可能なマイクロ波プ
ラズマＣＶＤ装置を示す。"Example 2" FIG. 7 shows a microwave plasma CVD apparatus capable of applying a magnetic field used in the present invention.
同図において、この装置は減圧状態に保持可能なプラズ
マ発生空間（１）、補助空間（２）、磁場を発生する電
磁石（５）、（５”）およびその電源（２５）、マイク
ロ波発振器（４）、排気系を構成するターボ分子ポンプ
（７）、ロータリーポンプ０／Ｄ、圧力調整バルブ（！
Ｉ）、基板ホルダ（１０’）、被膜形成用物体００）、
マイクロ波導入窓Ｇ５）、ガス系（６）、（７）、（８
）、水冷系０８）、（１８’）ハロゲンランプＱΦ、反
射鏡（２１）、加熱用空間（３）より構成されている。In the figure, this device includes a plasma generation space (1) that can be maintained in a reduced pressure state, an auxiliary space (2), an electromagnet (5) that generates a magnetic field (5") and its power source (25), a microwave oscillator ( 4), turbomolecular pump (7), rotary pump 0/D, and pressure adjustment valve (!) that make up the exhaust system.
I), substrate holder (10'), film forming object 00),
Microwave introduction window G5), gas system (6), (7), (8
), a water cooling system 08), (18') a halogen lamp QΦ, a reflecting mirror (21), and a heating space (3).
まず薄膜形成用物体００）を基板ホルダ（１０°）上に
設置し、ゲート弁θωよりプラズマ発生空間（１）に配
設する。この実施例では基板は珪素ウェハを用いた。こ
の基板ホルダ（１０°）はマイクロ波および電磁場をで
きるだけ乱さないようにするためステンレス製とした。First, a thin film forming object 00) is placed on a substrate holder (10°) and placed in a plasma generation space (1) via a gate valve θω. In this example, a silicon wafer was used as the substrate. This substrate holder (10°) was made of stainless steel in order to avoid disturbing the microwave and electromagnetic fields as much as possible.
そしてここに正の電圧を加えるべくバイアス電圧を印加
し、成膜スピードを上げることは有効である。It is effective to apply a bias voltage here to apply a positive voltage to increase the film formation speed.
作製工程として、まずこれら全体をターボ分子ポンプ０
７）、ロータリーポンプ圓により、１×ｌＯ’Ｔｏｒｒ
以下に真空排気する。次に非生成物気体（分解反応後置
体を構成しない気体）例えば水素（６）を１１００５Ｃ
Ｃガス系（７）を通してプラズマ発生領域（１）に導入
し、この圧力を３０Ｔｏ ｒ ｒとする。外部より２．
４５０Ｈ２の周波数のマイクロ波をＩＫＷの強さで加え
る。マグネット（５）、（５”）を水冷ＯｔＤ、（１８
’）で磁場約２にガウスを磁石（５）、（５’）より印
加して、高密度プラズマをプラズマ発 主空間（１）に
て発生させる。この高密度プラズマ領域より高エネルギ
を持つ非生成物気体または電子が基板ホルダ（１０’）
上の物体００）の表面上に到り、表面を清浄にする。As a manufacturing process, firstly, all of these were assembled using a turbo molecular pump 0.
7), 1×lO'Torr by rotary pump circle
Evacuate as follows. Next, a non-product gas (a gas that does not constitute a post-decomposition reaction body), for example, hydrogen (6), is added to 11005C.
It is introduced into the plasma generation region (1) through the C gas system (7), and the pressure is set at 30 Torr. From the outside 2.
Microwaves with a frequency of 450H2 are applied at an intensity of IKW. Magnets (5), (5”) are water-cooled OtD, (18
A magnetic field of about 2 Gauss is applied from the magnets (5) and (5') to generate high-density plasma in the plasma generation space (1). From this high-density plasma region, non-product gas or electrons with high energy are transferred to the substrate holder (10').
reach the surface of the object 00) above and clean the surface.
次にこの反応系に水素とガス系（７）より生成物気体（
分解・反応後置体を構成する気体）例えばＣＩ＋、とＮ
ＩＰ、とを１：１の気体濃度比としその総流堵を３０Ｓ
ＣＣＭの流量で導入する。キャリアガスの水素／炭化物
基体−３０〜０（この場合は２）とした。この炭素の水
素化物はアセチレン（Ｃ２１１、）、メチルアルコール
（ＣＩ（３０Ｈ）、エチルアルコール（Ｃ２Ｈ５Ｏｆ（
）でもよい。Next, a product gas (
Gases constituting post-decomposition/reaction bodies) For example, CI+, and N
IP, and the gas concentration ratio of 1:1, the total flow is 30S
Introduce at a flow rate of CCM. Carrier gas hydrogen/carbide base -30 to 0 (2 in this case). This carbon hydride is acetylene (C211), methyl alcohol (CI(30H)), ethyl alcohol (C2H5Of(
) is also fine.
かくして高エネルギに励起された炭素原子が生成され、
基板ホルダ（１０’）上の物体θＯ）（ここでは珪素基
板を用いた）上にこの炭素が堆積し、０゜１〜１００μ
ｍの厚さの窒素が添加された炭素膜を形成させることが
できた。In this way, highly energetically excited carbon atoms are produced,
This carbon is deposited on the object θO) (here, a silicon substrate is used) on the substrate holder (10'), and
It was possible to form a nitrogen-doped carbon film with a thickness of m.
本発明方法が応用される炭素膜は、耐摩耗材であり、か
つ耐すべりやすさを表面に必要とする電気部品、耐化学
薬品性を有する化学器具に特に有効である。The carbon film to which the method of the present invention is applied is a wear-resistant material and is particularly effective for electrical parts whose surfaces require slip resistance and chemical instruments having chemical resistance.
「実施例３」
第８図は本発明のプラズマ処理方法を実施するための大
型プラズマ処理装置の概要を示す。また第９図は第８図
のＡ−Ａ’での縦断面を右方向よりみた状態を示してい
る。"Embodiment 3" FIG. 8 shows an outline of a large-scale plasma processing apparatus for carrying out the plasma processing method of the present invention. Further, FIG. 9 shows a vertical cross section taken along line AA' in FIG. 8, viewed from the right.
図面において、プラズマ処理装置の反応容器（７）はロ
ード用予備室（７−１）、アンロード用予備室（７２）
とを有し、それぞれの間はゲート弁（１４−２）、（１
４−３）および大気との間はデー１−弁（１４−１）、
（１４４）即ち０４）で仕切られている。In the drawing, the reaction vessel (7) of the plasma processing apparatus is divided into a loading preliminary chamber (7-1) and an unloading preliminary chamber (72).
and a gate valve (14-2), (1
4-3) and the atmosphere is a day 1 valve (14-1),
(144), that is, 04).
反応空間（６）では基体（ｌ−）、（１−２）・・（１
−ｍ）即ち（１）がホルダ（２−１）、（２−２） ・
・・（２−ｎ）即ち（２）上に配設されている。この基
体（１）は一方の面にのみプラズマ処理をする構成であ
る。しかし基体の表面および裏面に同時にプラズマ処理
をせんとする場合はホルダ（２）に穴をあけ、この穴に
基体を挾んで配設すればよい。In the reaction space (6), the substrates (l-), (1-2)...(1
-m) That is, (1) is the holder (2-1), (2-2)
... (2-n), that is, it is arranged on (2). This substrate (1) has a configuration in which only one surface is subjected to plasma treatment. However, if the front and back surfaces of the substrate are to be subjected to plasma treatment at the same time, a hole may be made in the holder (2) and the substrate may be placed between the holes.
この実施例において、第１の電圧が交番電圧であるため
ホルダが板状のアルミニウム、ニッケル等の導体であり
、その両面に図面に示す如く、ガラス、シリコン基板、
セラミックス等の絶縁体の基体を配設させ得る。このホ
ルダ間の間隔（３１−１）、（３１−２）、・・・・（
３１−ｎ−１）は互いに等しくまたは概略等しくせしめ
、それぞれの基体上の処理の程度が同じ（成膜では膜厚
、膜質が同じ）程度（平均値に対し±２０％以内のバラ
ツキ）となるようにした。ロード室（１７−１）、アン
ロード室（１７−２）においては、基体およびホルダは
空間の節約のため間隔（３２−１）、（３２−２）・・
・（３２−ｎ−１）を反応空間での間隔に比べて狭くし
た。またこれらホルダはガイドレール（９）にハング（
引っ掛け）されて保持させてあり、ガイドレール（９）
よりホルダに電流を流しホルダまたは電極を第３の電極
とし得るよう構成させた。In this embodiment, since the first voltage is an alternating voltage, the holder is a plate-shaped conductor such as aluminum or nickel, and as shown in the drawing, the holder is made of a plate-shaped conductor such as glass, silicon substrate, etc.
A substrate of an insulating material such as ceramics may be provided. The spacing between these holders (31-1), (31-2), ... (
31-n-1) are made equal or approximately equal to each other, and the degree of processing on each substrate is the same (film thickness and film quality are the same in film formation) (variation within ±20% from the average value). I did it like that. In the loading chamber (17-1) and the unloading chamber (17-2), the substrate and the holder are spaced at intervals (32-1), (32-2), etc. to save space.
- (32-n-1) was made narrower than the interval in the reaction space. These holders can also be hung on the guide rail (9) (
The guide rail (9)
The configuration is such that the holder or the electrode can be used as the third electrode by passing a current through the holder.
ガス系００）において、キャリアガスである水素または
アルゴンガスを（１０−１）より、反応性気体である炭
化水素気体、例えばメタン、エチレンを（１０２）より
、窒素の原料ガス例えばＮＨｆｆを（１０−３）より、
またエツチング用気体である例えば酸素または酸素化物
気体を（１０−４）より、バルブ（２８）、流■計（２
９）をへて反応系（３０）中にノズル（２５）より導入
される。In the gas system 00), a carrier gas of hydrogen or argon gas is added to (10-1), a reactive gas such as a hydrocarbon gas such as methane or ethylene is added to (102), and a nitrogen raw material gas such as NHff is added to (10-1). -3) From
In addition, an etching gas such as oxygen or an oxygenate gas is supplied from (10-4) through a valve (28) and a flow meter (2).
9) and is introduced into the reaction system (30) through a nozzle (25).
反応系（３０）は、筒構造体（８）、（８′）（四角の
枠構造を有する）を有し、また第９図に示す如く、この
第８図における前方（第９図における左側）および後方
（第９図の右側）には一対の第１および第２の電極（３
）、（３゛）を全屈メツシュで構成せしめる。基体の温
度は一１００°Ｃ（冷却手段を設けた場合）〜１５０°
Ｃの温度に成就させた。またホルダ（２）は第３の電極
を構成し、反応容器（７）とは電気的に絶縁される。こ
のホルダに保持されて基体（１１）、（１−２）、・・
・（１−ｎ）即ち（１）を配設している。第１の交番電
圧が電源θ′７）よりホルダ（２）の第３の電極と第１
および第２の電極（３）、（３″）との間に印加させる
ようになっている。The reaction system (30) has cylindrical structures (8) and (8') (having a square frame structure), and as shown in FIG. 9, the front in FIG. 8 (the left side in FIG. ) and a pair of first and second electrodes (3
) and (3゛) are made up of fully bent meshes. The temperature of the substrate is -100°C (if a cooling means is provided) to 150°C
A temperature of C was achieved. Further, the holder (2) constitutes a third electrode and is electrically insulated from the reaction vessel (7). The bases (11), (1-2), etc. are held by this holder.
- (1-n), that is, (1) is provided. The first alternating voltage is applied from the power source θ'7) to the third electrode of the holder (2) and the first
and the second electrodes (3), (3'').
さらに第２の電源θωよりマツチングトランスθＯを介
して、第１の交番電界よりより高い周波数の第２の交番
電圧が一対の電極（３）、（３″）に（４）、に（４゛
）をへて印加される。Furthermore, a second alternating voltage having a higher frequency than the first alternating electric field is applied from the second power supply θω to the pair of electrodes (3), (3″) through the matching transformer θO to the pair of electrodes (3), (3″), (4), (4). )).
このマツチングトランスは、対称型または概略対称型の
出力を有し、一端（４）および他端（４′）は−対の第
１および第２の電極（３）、（３″）にそれぞれに連結
されている。またトランスの出力側中点（５）には第１
の交番電圧θηが印加されている。第２の交番電圧は１
〜５ Ｇ Ｈｚ例えば１３．５６ＭＨ，の周波数の高周
波電界を印加し、第１の交番電圧は１〜５００に夏Ｉ２
例えば５０ＫＨ２の周波数の交番電界を印加した。This matching transformer has a symmetrical or approximately symmetrical output, with one end (4) and the other end (4') connected to a pair of first and second electrodes (3), (3''), respectively. Also, at the midpoint (5) on the output side of the transformer, the
An alternating voltage θη of θη is applied. The second alternating voltage is 1
A high frequency electric field with a frequency of ~5 GHz, e.g. 13.56 MHz, is applied, and the first alternating voltage is 1~500 MHz
For example, an alternating electric field with a frequency of 50 KH2 was applied.
かくして反応空間にプラズマ（６）が発生する。排気系
ＱＯは、圧力調整バルブ（２１）、ターボ分子ポンプ（
２２）、ロータリーポンプ（２３）をへて不要気体を排
気する。Plasma (6) is thus generated in the reaction space. The exhaust system QO includes a pressure adjustment valve (21), a turbo molecular pump (
22), exhausting unnecessary gas through a rotary pump (23).
これらの反応性気体は、反応空間（６）で０．００１〜
１．０Ｔｏｒｒ例えば０．０５”ｌ’ｏｒｒとし、この
筒構造体（８）、（８゛）は直方体状を有し、例えば中
ＩＧＯｃｍ、奥行き４０ｃｍ、縦１６０ｃｍとした。These reactive gases are present in the reaction space (6) at a concentration of 0.001 to
1.0 Torr, for example, 0.05''l'orr, and the cylindrical structures (8), (8') have a rectangular parallelepiped shape, for example, medium IGO cm, depth 40 cm, and length 160 cm.
また反応容器（７）の内壁面に付着しないようプラズマ
が反応空間（６）より外部（６０）にもれないよう筒構
造体（８）、（８″）を設けている。Further, cylindrical structures (8) and (8'') are provided to prevent plasma from leaking from the reaction space (6) to the outside (60) so as not to adhere to the inner wall surface of the reaction vessel (7).
一対の電極は有効面積１２０ｃｍ口とするため、１５０
ｃ＋＋＋口とした。かかる空間において１．０〜３０Ｋ
Ｗ（単位面積あたり０．０４〜１．３に／ｃ％）例えば
１０ＫＷ（単位面積あたり０．４４Ｗ／ｃｒＭのプラズ
マエネルギ）の第２の高周波電圧を加える。さらに第１
の交番電圧による交流バイアスは、被形成面上に一２０
０〜６００Ｖ （例えばその出力は５００Ｗ）となるよ
う５０ＫＨ２の周波数で３ＫＷの出力を加えた。The pair of electrodes has an effective area of 120 cm, so 150 cm
c++++ mouth. 1.0-30K in such space
A second high frequency voltage of W (0.04-1.3/c% per unit area), for example 10 KW (plasma energy of 0.44 W/crM per unit area) is applied. Furthermore, the first
An alternating current bias due to an alternating voltage of 120
An output of 3KW was applied at a frequency of 50KH2 so that the voltage ranged from 0 to 600V (for example, the output was 500W).
勿論、この直方体の筒構造体の高さを２０ｃｍ〜５ｍま
た電極の一辺を３０ｃｍ〜３１ｍとしてもよい。Of course, the height of this rectangular parallelepiped cylindrical structure may be 20 cm to 5 m, and the side of the electrode may be 30 cm to 31 m.
「応用例１」
実施例１．２および３のいずれかの方法もしくは、その
複数を組み合わせた方法により、電子写真のプロセスに
用いられる感光体に、本発明による炭素を主成分とした
被膜を応用した場合の例を以下に述べる。"Application Example 1" A coating mainly composed of carbon according to the present invention is applied to a photoreceptor used in an electrophotographic process by any of the methods of Examples 1.2 and 3, or a combination of them. An example of this case is described below.
第１０図は、本発明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２００μｍ厚さのＰ
ＥＴシート（１）上に厚さ６００人のＡＩ蒸着層（２）
、中間Ｎ（３）をはさんで０．６〜１゜２μｍの電荷発
生層を（４）を設け、本発明による保護膜（６）、約２
０μｍ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
。あらかじめ、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。FIG. 10 shows the structure of a photoreceptor to which a coating mainly composed of carbon according to the present invention is applied. Approximately 200μm thick P
AI vapor deposition layer (2) with a thickness of 600 people on the ET sheet (1)
, a charge generation layer (4) with a thickness of 0.6 to 1°2 μm is provided across an intermediate N (3), and a protective film (6) according to the present invention is formed with a thickness of about 2 μm.
When light (7) is incident through the charge transfer layer (5) of 0 μm, it is absorbed by the charge generation layer, and electron-hole pairs are generated. If the charge transfer layer or the protective layer is negatively charged in advance, holes generated in the charge generation layer move through the charge transfer layer only in areas where light is incident, neutralizing the negative charges.
この時、電荷発生層で生成された電子は中間層を通って
Ａ１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。At this time, electrons generated in the charge generation layer pass through the intermediate layer, reach the A1 deposited layer, and are discharged. The negative charge remaining in the area where no light was incident then adsorbs toner and is transferred to the transfer paper, forming an image on the transfer paper depending on whether or not light is incident.
ここで形成された保護層は本発明を用いたものであり、
Ｎ Ｈ，流猾によりその比抵抗を１０１１〜１０’（０
ｃｍ）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。The protective layer formed here uses the present invention,
N H, the specific resistance is 1011 ~ 10' (0
cm). Therefore, there is no lateral movement of charged charges that occurs because the specific resistance is too low, and the boundaries of the areas where light is incident are clear without blurring. Therefore, the transferred image was also clear.
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が、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長期に渡り良
質の転写像を得ることができた。Furthermore, if the specific resistance is too high, charges will gradually accumulate in the protective film due to repeated use, making it impossible to remove used toner and causing the transfer paper to become black. Since the resistivity was controlled to such an extent that no accumulation occurred, it was possible to obtain high-quality transferred images over a long period of time without such a phenomenon.
また、ここで用いた保護膜の透過率は５００ｎｍ以上の
波長域で８０％以上であり、４００ｎｍ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。Further, the transmittance of the protective film used here was 80% or more in a wavelength range of 500 nm or more, and 60% or more in a wavelength range of 400 nm or more. Therefore, the photoreceptor of this practical example was sufficiently usable even in the visible light range.
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°ζいることは言うまでもない。Of course, it goes without saying that 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、シート状怒光体を曲率半径
１０ａｕｅまで曲げても、保護膜にクシツクの発生は見
られず、また、ピーリングも生じなかった。Furthermore, the protective film used here had reduced internal stress and good adhesion. That is, even when the sheet-like photoreflector was bent to a radius of curvature of 10 aue, no scratches were 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。In this embodiment, a sheet-like organic photoreceptor has been described as a photoreceptor, but the protective film according to the present invention can be similarly constructed for a drum-shaped organic photoreceptor, an amorphous silicon photoreceptor, and a selenium photoreceptor. The effect of this can be obtained.
「応用例２」
代表的なサーマルプリントヘッド構造を第１１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
る窒素を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。"Application Example 2" A typical thermal print head structure is shown in FIG. A glaze (2) is formed on an insulating substrate (1), a protruding glaze (3) is formed on the part corresponding to the heating element at the same time as the glaze (2), and then a heating element (4) is formed on the substrate (11).
) and an electrical conductor (5) are sequentially laminated, then a heating element portion (21) is formed on the protruding glaze using a known photolithography technique, and finally a nitrogen-containing layer according to the present invention is formed. Protective film with carbon as the main component (6)
Formed as.
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、本応用例で用
いた保護膜（６）は応用例１で形成した保護膜と同様の
特性を有し、ＮＨ，流量を制御することによりビッカー
ス硬度２０００ｋｇ／ｍｍ”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。The protective film usually used 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 application example has the same characteristics as the protective film formed in application example 1, and by controlling the NH and flow rate, the Vickers hardness can be reduced. A hard film of 2000 kg/mm" or more can be formed. Therefore, a film thickness of about 1 μm is sufficient for practical use.
また、本応用例で用いた保護膜は内部応力が１０”ｄｙ
ｎ／ｃｍ”と小さ（密着性も良好であり、５００°Ｃ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。In addition, the protective film used in this application example has an internal stress of 10" dy
n/cm" (adhesion was also good, and it was confirmed that the heat resistance test at 500°C for 1 hour (in air) was also good.
さらに、１０１６ΩＣ−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、
また、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, the specific resistance of about 1016 ΩC- is convenient for static electricity countermeasures, and can reduce dirt and dust that can cause scratches.
Furthermore, the influence of static electricity on electronic circuits could be reduced.
本応用例では既知の発熱体（４）を用いたが、本発明に
よる窒素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、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１０
３〜１０’Ωｃｍとなようにすれば、この被膜を発熱体
として用いることができる。In this application example, a known heating element (4) was used, but it is also possible to use the coating mainly composed of carbon containing nitrogen according to the present invention as the heating element. That is, the film is formed under film forming conditions that increase the concentration of nitrogen, and the resistivity of the film is reduced to 10.
If the resistance is 3 to 10' Ωcm, this film can be used as a heating element.
「応用例３」
本応用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１゛２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。``Application Example 3'' In this application example, the film containing carbon as the main component of the present invention is applied to a contact type image sensor to form a film containing carbon as the main component having the structure shown in FIG. 1-2.
第１２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
用いて積層させエキシマレーザ−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ー素
子（３４）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２．０μｍの厚さに形成した。As shown in FIG. 12, electrodes and amorphous silicon are laminated on a transparent glass substrate (33) using a known plasma CVD method, and the electrodes and amorphous silicon layer are processed using an excimer laser to form a photosensor element (34). ), then transparent polyimide (35)
is applied using a known spinner method to create a contact image sensor.
was created. Thereafter, a protective film (36) with a thickness of 2.0 μm was formed on the transparent 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２５００
Ｋｇ／ｍｓ”であり、また比抵抗はｌＸｌ０’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。The Vickers hardness of the protective film was measured and was 2500.
Kg/ms'', and the specific resistance was lXl0'Ωcm.The formed carbon film had a hardness similar to that of diamond on the surface on which it was formed and on the surface, and an appropriate electrical insulation property as a countermeasure against static electricity. As a result, the above layer is not scratched by irregularities on the document surface or the metal fittings of the stapler, and even if static electricity is generated due to friction between the document and the protective film, it is possible to prevent the accumulation of static electricity. In addition, it was possible to suppress the electrical influence on the optical sensor element and to prevent the contamination of impurities in the translucent polyimide.
「効果」
以上述べたように本発明は窒素または水素と窒素が添加
された炭素を主成分とする被膜であり、該被膜は窒素添
加量により、容易にしかも安価に該被膜の硬度、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
応力は小さく回着性の良いものである。"Effects" As stated above, the present invention is a film whose main component is nitrogen or hydrogen and carbon to which nitrogen is added. In addition, the internal stress of the coating is small and the reversibility is good.
本発明による窒素または水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場合、応用例に述べたとう
り、本発明による炭素を主成分とする被膜を応用しなか
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。When applying the coating mainly composed of carbon to which nitrogen or hydrogen and nitrogen are added according to the present invention, as described in the application example, compared to the case where the coating mainly composed of carbon according to the present invention is not applied. It was possible to significantly improve the lifespan and reliability of the composite.
第１図はＮ Ｈｘ流量と導電率の関係を示す。
第２図はＮＨ３流量と透過率の関係を示す。
第３図はＮ Ｈｘ流量と硬度の関係を示す。
第４図は投入電力と導電率の関係を示す。
第５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６図は窒素を含んだ炭素の透過率を示す。
第７図は本発明にて用いた磁場印加可能なマイクロ波プ
ラズマＣＶＤ装置を示す。
第８図は本発明のプラズマ処理方法を実施するための大
型プラズマ処理装置の概要を示す。
第９図は第８図のＡ−Ａ″での縦断面を右方向よりみた
状態を示している。
第１Ｏ図は、本発明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１１図は代表的なサーマルプリントヘッド構造を示す
。
第１２図は密着型イメージセンサに本発明の炭素を主成
分とする被膜を通用したものである。FIG. 1 shows the relationship between NHx flow rate and conductivity. FIG. 2 shows the relationship between NH3 flow rate and permeability. FIG. 3 shows the relationship between NHx flow rate and hardness. FIG. 4 shows the relationship between input power and conductivity. FIG. 5 shows an outline of a plasma CVD apparatus for forming carbon or a film containing carbon as a main component according to the present invention. FIG. 6 shows the transmittance of carbon containing nitrogen. FIG. 7 shows a microwave plasma CVD apparatus capable of applying a magnetic field used in the present invention. FIG. 8 shows an outline of a large-scale plasma processing apparatus for carrying out the plasma processing method of the present invention. FIG. 9 shows a vertical cross section taken along line A-A'' in FIG. 8, viewed from the right. FIG. Fig. 11 shows a typical thermal print head structure. Fig. 12 shows a contact type image sensor in which the film containing carbon as a main component of the present invention is applied.
Claims (1)
、プラズマＣＶＤ（化学気相成長法）法を用いて、作成
された炭素を主成分とする被膜において該炭素を主成分
とする被膜には、窒素または水素と窒素が含有されてい
ることを特徴とする炭素を主成分とする被膜。In a film whose main component is carbon, which is created using plasma CVD (chemical vapor deposition) on a substrate such as glass, metal, ceramics, organic resin, etc. , a carbon-based film characterized by containing nitrogen or hydrogen and nitrogen.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17785188A JPH0230755A (en) | 1988-07-17 | 1988-07-17 | Carbon-based coating film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17785188A JPH0230755A (en) | 1988-07-17 | 1988-07-17 | Carbon-based coating film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0230755A true JPH0230755A (en) | 1990-02-01 |
Family
ID=16038210
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP17785188A Pending JPH0230755A (en) | 1988-07-17 | 1988-07-17 | Carbon-based coating film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0230755A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5277748A (en) * | 1992-01-31 | 1994-01-11 | Canon Kabushiki Kaisha | Semiconductor device substrate and process for preparing the same |
| US5597738A (en) * | 1993-12-03 | 1997-01-28 | Kulite Semiconductor Products, Inc. | Method for forming isolated CMOS structures on SOI structures |
| US5845837A (en) * | 1995-12-28 | 1998-12-08 | Itt Automotive, Inc. | Polymer-based material for carbon deposition during brazing operations |
-
1988
- 1988-07-17 JP JP17785188A patent/JPH0230755A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5277748A (en) * | 1992-01-31 | 1994-01-11 | Canon Kabushiki Kaisha | Semiconductor device substrate and process for preparing the same |
| US5597738A (en) * | 1993-12-03 | 1997-01-28 | Kulite Semiconductor Products, Inc. | Method for forming isolated CMOS structures on SOI structures |
| US5845837A (en) * | 1995-12-28 | 1998-12-08 | Itt Automotive, Inc. | Polymer-based material for carbon deposition during brazing operations |
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