JPH0230761A - Composite body having film composed principally of carbon - Google Patents
Composite body having film composed principally of carbonInfo
- Publication number
- JPH0230761A JPH0230761A JP63177849A JP17784988A JPH0230761A JP H0230761 A JPH0230761 A JP H0230761A JP 63177849 A JP63177849 A JP 63177849A JP 17784988 A JP17784988 A JP 17784988A JP H0230761 A JPH0230761 A JP H0230761A
- Authority
- JP
- Japan
- Prior art keywords
- film
- carbon
- halogen element
- halogen
- added
- 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 39
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 239000002131 composite material Substances 0.000 title claims abstract description 13
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 43
- 150000002367 halogens Chemical class 0.000 claims abstract description 43
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 12
- 239000001257 hydrogen Substances 0.000 claims abstract description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000758 substrate Substances 0.000 claims abstract description 8
- 239000011521 glass Substances 0.000 claims abstract description 5
- 239000011347 resin Substances 0.000 claims abstract description 5
- 229920005989 resin Polymers 0.000 claims abstract description 5
- 239000000919 ceramic Substances 0.000 claims abstract description 4
- 229910052751 metal Inorganic materials 0.000 claims abstract description 4
- 239000002184 metal Substances 0.000 claims abstract description 4
- 238000005268 plasma chemical vapour deposition Methods 0.000 claims abstract description 4
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract 2
- 239000002994 raw material Substances 0.000 abstract description 13
- 238000006243 chemical reaction Methods 0.000 abstract description 10
- 230000005611 electricity Effects 0.000 abstract description 5
- 230000003068 static effect Effects 0.000 abstract description 5
- 238000000034 method Methods 0.000 abstract description 4
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract 2
- 239000000853 adhesive Substances 0.000 abstract 1
- 230000001070 adhesive effect Effects 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 31
- 239000011248 coating agent Substances 0.000 description 13
- 238000000576 coating method Methods 0.000 description 13
- 230000001681 protective effect Effects 0.000 description 13
- 108091008695 photoreceptors Proteins 0.000 description 10
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 9
- 229910052731 fluorine Inorganic materials 0.000 description 9
- 239000011737 fluorine Substances 0.000 description 9
- 238000002834 transmittance Methods 0.000 description 9
- 239000007789 gas Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000004215 Carbon black (E152) 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
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic 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
- 229910052717 sulfur Inorganic materials 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 229910011208 Ti—N Inorganic materials 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 150000003842 bromide salts Chemical class 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 210000004209 hair Anatomy 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000004694 iodide salts Chemical class 0.000 description 1
- 150000002500 ions Chemical class 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
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 230000002040 relaxant effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 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を有する複合体に関
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 composite material having a coating mainly composed of carbon that is transparent in the visible range.
また同時に基板と被膜との間の密着性を向上させた被膜
を有する複合体に関するものである。The present invention also relates to a composite having a coating that improves the adhesion between the substrate and the coating.
「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、ＡｌｇＯ：＋、Ｔｉ−Ｎ、ｔ３
Ｎ、Ｗ Ｃ，Ｓ ｉ Ｃ，Ｓ ｉ ３Ｎ４．５ｉｆｔ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）
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 AlgO:+, Ti-N, t3
Inorganic films such as N, W C, S i C, S i 3N4.5ift, etc., and "composite with carbon film" filed by the present inventor (Patent Application No. 146930 of 1982)
It has been known. However, the above-mentioned known protective film
It already has a high electrical resistivity, tends to generate static electricity, and tends to attract dirt and dust in the atmosphere to its surface. In addition, when used in composite materials that actively apply an electric field and utilize static electricity, such as photoreceptors used in electrophotographic processes, charges accumulate in the protective film with high electrical resistance. However, there was a problem that the expected performance could not 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、膜のピーリングが発生する問題
もあった。したがって膜厚をうすすくする、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する。Furthermore, depending on the conditions of the film forming process, the known protective film has the problem of accumulation of internal stress and peeling of the film. Therefore, it is necessary to take measures such as thinning the film thickness or providing an intermediate layer between the protective film and the underlying material to improve adhesion, but a reduction in film thickness means a reduction in mechanical stress resistance. However, the presence of an intermediate layer causes 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、透明性及び密
着性を同時に満足する被膜として炭素を主成分とする被
膜にハロゲン元素または水素とハロゲン元素を添加し、
該ハロゲン元素の濃度が堆積された膜の厚さ方向に沿っ
て分布をもっことを特徴とする被膜を有する複合体を提
供することを目的とする。"Structure of the Invention" The present invention solves the above-mentioned problems, and provides a film mainly composed of carbon as a film that satisfies mechanical stress resistance as a protective film, problems arising from static electricity, transparency, and adhesion at the same time. Adding a halogen element or hydrogen and a halogen element to
The object of the present invention is to provide a composite having a film characterized in that the concentration of the halogen element is distributed along the thickness direction of the deposited film.
本発明による被膜は炭素の原料としてメタン（ｃｔｒ、
）、エタン（ＣｚＨ６）、エチレン（Ｃ２Ｌ）、アセチ
レン（Ｃ，Ｈ，） 、ベンゼン（Ｃ４Ｈ６）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、同時にハロゲン元素の原料としてＮ
Ｆ、、ＳＦ、、ＷＦ６等のフン化物、ＣＣ１，等の塩化
物、ＣＨ，Ｂｒ等の臭化物又は、ヨウ化物をプラズマ中
に導入してＦ、Ｃ１、Ｂｒ、Ｔ等のハロゲン元素を添加
する。The coating according to the present invention uses methane (ctr,
), ethane (CzH, It can be formed by At this time, at the same time, N is used as a raw material for the halogen element.
Fluorides such as F, SF, WF6, chlorides such as CC1, bromides such as CH, Br, or iodides are introduced into the plasma to add halogen elements such as F, C1, Br, T, etc. .
添加量は、ハロゲン元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ＣＦ４、ＣＨ１Ｆ’１等のフッ化
炭素、Ｃｃ １．等の塩化炭素、ＣＨ，Ｂ ｒ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 substance containing the halogen element. Here, in addition to the above-mentioned hydrocarbons, fluorocarbons such as CF4 and CH1F'1, Cc1. Carbon chloride such as, brominated hydrocarbon such as CH, Br, etc. may also be used.
しかしながら、ハロゲン元素としては、プラズマ反応室
内壁の腐蝕の問題からフッ素化物が最も利用しやすい。However, as the halogen element, fluoride is most easily used due to the problem of corrosion of the walls of the plasma reaction chamber.
また、ハロゲン元素添加量制御の点から炭素原料物質と
してはフッ素を含まない炭化水素が有効である。In addition, from the viewpoint of controlling the amount of halogen element added, hydrocarbons that do not contain fluorine are effective as the carbon raw material.
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ハロゲン元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ハロゲン元素添加量を制御す
るものである。The film according to the present invention can be produced by introducing the above-mentioned raw materials, that is, a carbon raw material and a halogen element material into a plasma reaction chamber at the same time, and adjusting the flow rate of the halogen-based raw material at this time to adjust the amount of halogen element added to the film. It controls the
ハロゲン元素添加量は導電率、透過率、硬度の違いとし
て観測される。以下にハロゲン元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す。The amount of halogen added is observed as a difference in conductivity, transmittance, and hardness. The experimental results of changes in electrical conductivity when changing the flow rate of the halogen element raw material are shown below.
ハロゲン元素原料物質としてＮＦ、を用いた。NF was used as a halogen element raw material.
炭素原料物質としてエチレンを用い、エチレンの流ＩＩ
ＱｓｃｃＭ、反応圧力１０Ｐａ、投入電力密度０．０８
Ｗ／ｃｍ”とした。第１図に示すようにＮＦ３の量が増
すに従い、導電率が高くなっている。また、第２図に示
すようにＮＦ、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Ｎ Ｆ ３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。Using ethylene as carbon feedstock material, ethylene stream II
QsccM, reaction pressure 10 Pa, input power density 0.08
W/cm". As shown in FIG. 1, as the amount of NF3 increases, the conductivity increases. Also, as shown in FIG. 2, as the flow rate of NF increases, the transmittance increases. Further, as shown in Fig. 3, as the N F 3 flow rate increases, the hardness decreases.The decrease in hardness means that the internal stress decreases.
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。As described above, the conductivity, hardness, and transmittance of the coating can be varied over a relatively wide range.
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。That is, the optimum characteristics required for various applications can be easily obtained at relatively low cost.
以上ハロゲン元素原料物質の流量を変えることによって
ハロゲン元素添加量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、ハ
ロゲン元素添加■を変えることができる。It has been described above that the amount of halogen element added can be changed by changing the flow rate of the halogen element raw material, but of course the discharge conditions such as input power, reaction pressure, discharge vessel shape, carbon raw material flow rate, etc. during discharge are constant. . Moreover, the halogen element addition (2) can also be changed by changing one or more of these discharge conditions.
一例として、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、Ｎ Ｆ ３流
■、Ｃ２Ｈ，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 as well, of course, the discharge parameters other than the input power, such as the reaction pressure, the shape of the discharge vessel, the N F3 flow, C2H, and the flow rate, are constant.
以上述べたように、ハロゲン元素または水素とハロゲン
元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、ハロゲン元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 conductivity, hardness, and transmittance of a film whose main component is a halogen element or carbon containing hydrogen and a halogen element are determined by the input power, reaction pressure, the shape of the discharge vessel, and the carbon raw material. By changing discharge parameters such as the material flow rate and the halogen element raw material flow rate, it can be easily and inexpensively changed over a relatively wide range.
本発明は前記ハロゲン元素が添加された炭素を主成分と
する被膜の諸特性を、膜厚方向に沿って変化させ、所望
の膜特性を得ることのできる複合体を得るものである。The present invention is to obtain a composite that can obtain desired film characteristics by changing the various properties of the film mainly composed of carbon to which a halogen element has been added, along the film thickness direction.
またハロゲン元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。Furthermore, a coating mainly composed of carbon to which a halogen element is added is characterized by low internal stress.
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。ここに水素よりも反応性の高い
ハロゲン元素、例えばフッ素がプラズマ中に存在すると
フッ素と炭素は容易にＣ−Ｆ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。This is because the dangling bonds that normally exist in carbon are terminated with hydrogen and reduce the internal stress by relaxing the attractive force of the dangling bonds. Rather, some dangling bonds remain in the film, and this is thought to be one of the causes of internal stress. It is thought that if a halogen element, such as fluorine, which is more reactive than hydrogen, is present in the plasma, the fluorine and carbon will easily form a C--F bond, and the number of dangling bonds in carbon will be 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、ハロゲン元素が添加された炭素を主成分とする
被膜は耐熱性の点においても優れている。Furthermore, a film containing carbon as a main component to which a halogen element is added is also excellent in terms of heat resistance.
また、ハロゲン元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。Further, one of the characteristics of a film mainly composed of carbon to which a halogen element is added is that it can be formed at a deposition temperature of the substrate at a low temperature ranging from room temperature to 150° C. or less. This allows film formation even on substrates that cannot be heated to high temperatures, such as organic materials such as plastics and resins, and selenium semiconductors.
また、ハロゲン元素が添加された炭素を主成分とする被
膜は透光性も良い。例えば、フッ素を含んだ炭素の透過
率を第６図に示す。図面に示すように６００ｎｓ＋以上
の波長域では９５％以上の透過であり、４００ｎｍでも
５０％以上透過のほぼ透明な膜が得らる。Furthermore, a film mainly composed of carbon to which a halogen element is added has good light transmission. For example, the transmittance of carbon containing fluorine is shown in FIG. As shown in the drawing, a nearly transparent film with a transmission of 95% or more in the wavelength range of 600 ns+ or more, and a transmission of 50% or more even at 400 nm can be obtained.
本発明はこのような諸特性を有する炭素を主成分はする
被膜性のハロゲン元素含有■をその膜厚方向に沿って変
化させることにより、これらハロゲン元素が添加された
炭素を主成分とする被膜の有する利点をさらに増やし、
有用な複合体を得ようとするものである。The present invention is capable of producing a film mainly composed of carbon to which these halogen elements are added, by changing the halogen element-containing film having the above-mentioned characteristics along the film thickness direction. further increase the benefits of
The aim is to obtain useful complexes.
以下、−Ｃ的な被膜作成方法を述べる。A method for producing a -C film will be described below.
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。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.
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、ハロゲン
元素を含む気体例えばＮＦ、を（４）よりパルプ（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００で加えて予め活性化さ
廿ることは有効である。In the drawing, in the doping system (1), hydrogen as a carrier gas is added to (2), a hydrocarbon gas such as methane or ethylene is added to (3) as a reactive gas, and a gas containing a halogen element such as NF is added to (4). ) than pulp (6)
, is introduced into the reaction system (8) through a nozzle (9) through a flowmeter (7). Before reaching this nozzle, it is advantageous to preactivate the reactive gas by applying microwave energy at 000 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）く１の条件を満たすようにした。一対の電極（１１
）、θり間には高周波電源０■、マツチングトランス０
７０、直流バイアス電源０５）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０ωは圧力調整バル
ブ０７）、ターボ分子ポンプ側、ロータリーポンプθつ
をへて不要気体を排気する。反応性気体には、反応空間
Ｑａｌにおける圧力が０．００１〜ｌ０Ｔｏｒｒ代表的
には０．０１〜ＩＴｏｒｒの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, condition 1 (first electrode area/second electrode area) was satisfied. A pair of electrodes (11
), 0 high frequency power supply, 0 matching transformer between θ interval
70, electrical energy is applied from the DC bias power supply 05) to generate plasma. The exhaust system 0ω exhausts unnecessary gas through the pressure regulating valve 07), the turbo molecular pump side, and the rotary pump θ. 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 Qal of 0.001 to 10 Torr, typically 0.01 to ITorr.
特に励起源がＩＧＨ，以上、例えば２．４５Ｇ【■２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１３．５６ＭＨ
２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 is at a frequency of IGH or above, for example 2.45G [■2], hydrogen is separated from the C-H bond, and the frequency source is 0.1 to 50MH2, for example 13.56MH.
At frequency 2, 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 covalently bond, creating a stable diamond structure. It may have a locally formed structure.
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).
代表的な被膜の作成条件は、高周波エネルギー６０Ｗ、
圧力０．０１５Ｔｏ ｒ ｒ、炭素源、例えばエチレン
の流ｆｆｌｌｏＯ３ｃｃＭ、基板温度は室温である。ハ
ロゲン元素源、例えばＮＦ、の流■は０．０１〜３００
３ＣＣＭの範囲で変化させた。Typical film creation conditions are high frequency energy of 60W,
The pressure is 0.015 Torr, the flow of carbon source, eg ethylene, fflOO3 ccM, and the substrate temperature is room temperature. The flow rate of the halogen element source, e.g. NF, is 0.01 to 300.
It was varied within a range of 3CCM.
以下、実施例に従って更に詳しく述べる。The following will be described in more detail according to examples.
「実施例１」
第７図は、ハロゲン元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の感光体の構造を示す。約２００
μｍｑさのＰＥＴシート（１）上に厚さ６００人のＡ１
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（力
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。この時、電荷発生層で生成された
電子は中間層を通って１蒸着層に達し、排出される。"Example 1" FIG. 7 shows the structure of a photoreceptor in which a film mainly composed of carbon to which a halogen element is added is applied. Approximately 200
600mm thick A1 on μmq PET sheet (1)
0.6 to 1.2 across the vapor deposited layer (2) and intermediate layer (3)
A charge generation layer (4) with a thickness of μm is provided, and when light (force) is incident through the protective film (6) according to the present invention and a charge transfer layer (5) with a thickness of about 20 μm, it is absorbed by the charge generation layer, and electron-hole pairs are formed. If the charge transfer layer or protective layer is negatively charged in advance, the holes generated in the charge generation layer will move through the charge transfer layer only in the area where light is incident, discharging the negative charges. At this time, the electrons generated in the charge generation layer pass through the intermediate layer, reach one deposited layer, and are discharged.
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。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３ｆｆＪｆｆｌは本発明を用いたも
のであり、前記装置を用いて、前記−船釣な条件にて被
膜を作成した。初めの２分間はＮＦ、流量を０、ＩＳＣ
ＣＭ以下として第１の層を形成し、その後２０分間はＮ
Ｆ３流■を１１００５ＣＣとし°ζ第２の層を形成した
。第１の層と第２の層のＭ厚は各々０．０２１ノー、１
μｍであった。この複合被膜の比抵抗、透光性、硬さ、
内部応力等の特性はその膜厚の大きさから、殆ど第２の
層の特性で決定される。ところが、密着性に関しては感
光層と被膜の界面即ち第１の居の特性が大きく影客する
。フッ素を添加した場合はしない時に比べて密着性は良
くないから、第一の層の存在により複合被膜の密着性は
かなり改善される。The film formed here was formed using the present invention, and the film was created using the above-mentioned apparatus under the above-mentioned conditions. For the first 2 minutes, NF, flow rate 0, ISC
Form the first layer below CM, then apply N for 20 minutes.
A second layer was formed using F3 stream (1) at 11005 CC. The M thickness of the first layer and the second layer is 0.021 and 1, respectively.
It was μm. The specific resistance, translucency, hardness,
Characteristics such as internal stress are determined mostly by the characteristics of the second layer due to its film thickness. However, the adhesion is greatly affected by the characteristics of the interface between the photosensitive layer and the coating, that is, the first bond. Since adhesion is not as good when fluorine is added as compared to when it is not added, the presence of the first layer significantly improves the adhesion of the composite coating.
該複合被膜の比抵抗は第２の層で決まり、１０’〜１０
９（Ωｃｍ）であった。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。The specific resistance of the composite coating is determined by the second layer and is between 10' and 10'.
It was 9 (Ωcm). 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.
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
像を得るごとができた。Therefore, the transferred image was also clear. Additionally, if the specific resistance is too high, charges will gradually accumulate on the protective film due to repeated use, making it impossible to remove used toner.
The phenomenon that the transfer paper becomes black occurs, but since the protective film according to the present invention has a resistivity controlled to such an extent that no charge is accumulated, this phenomenon does not occur, and high-quality transferred images can be obtained for a long period of time. Ta.
また、保護膜の透過率も第２の層で決まり、５００ｎ１
１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。In addition, the transmittance of the protective film is determined by the second layer, and is 500n1
It was 80% or more in a wavelength range of 1 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
る耐久性が向上していることは言うまでもないが、更に
第３の層として、フッ素の含有量を少なくした層を構成
すると、表面は−より硬くなる。Of course, it goes without saying that durability against mechanical stress such as abrasion resistance and scratch resistance is improved, but when a third layer with a lower fluorine content is constructed, the surface becomes more It becomes hard.
更に、内部応力は第２の層で決まり、フッ素が多く添加
されているため、内部応力は緩和され、密着性も良いも
のであった。即し、シート状感光体を曲率半径１０ｍｍ
まで曲げても、保護膜にクランクの発生は見られず、ま
た、ピーリングも生じなかった。Furthermore, since the internal stress was determined by the second layer and a large amount of fluorine was added, the internal stress was relaxed and the adhesion was good. Therefore, the sheet-like photoreceptor has a radius of curvature of 10 mm.
Even when the protective film was bent to a certain extent, no cranking was observed, and no peeling occurred.
以上、本実施例では感光体としてシート状有機怒光体に
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 present embodiment has described a sheet-like organic photoreceptor as a photoreceptor, 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. A similar effect can be obtained.
また、サーマルプリントヘッドや密着型イメージセンサ
−のようなガラス若しくはセラミックスのような基板の
上に形成しても同様に密着性の良い良質な保護膜を構成
することができる。Further, even when formed on a substrate such as glass or ceramics such as a thermal print head or a contact type image sensor, a high-quality protective film with good adhesion can be constructed.
「実施例２」
ＩＣチップの高信頼化のために採用されるリードフレー
上へのワイヤーボンド後の被膜形成に本発明を適用した
場合、ＩＣチップ上のアルミパッドに溶着された金線の
剥がれの原因となる被膜中の内部応力の対策に極めて有
効である。"Example 2" When the present invention is applied to the formation of a film after wire bonding on a lead fly adopted to improve the reliability of an IC chip, the gold wire welded to the aluminum pad on the IC chip peels off. It is extremely effective in countering internal stress in the coating that causes
フッ素の多く含まれている第１の層を１ｒＩ記一般的な
作成条件に於いてＣ，Ｈ，とＮＦ、の流■比を１：１と
して、厚さ０．６μｍの被膜を作成した。The first layer containing a large amount of fluorine was prepared under typical conditions, with a flow ratio of C, H, and NF of 1:1 to form a film with a thickness of 0.6 μm.
この第１の層は内部応力がｌ Ｏ７ｄｙｎ／ｃｍ”と非
常に小さなものである。第１の層作成の後、第２の層を
前記一般的な作成条件に於いてＣ２Ｈ，とＮＦ３の流量
比を１００：１として、厚さ０．１μｍの被膜を作成し
た。この第２の層はりビッカース硬度２０００ｋｇ／ｍ
ｍ”以上の硬い膜であり化学的に安定なものである。依
って、本実施例に述べたような被膜をリードフレー上へ
のワイヤーボンド後の被膜に適用すると、第１の層が応
力を緩和することによりＩＣチップ上のアルミパッドに
溶着された金線の剥がれが防止でき、同時に第２の層が
水やアルカリイオン等の不純物の浸入を防止するため、
ＩＣの信頼性を格段に向上させることができた。This first layer has a very small internal stress of lO7dyn/cm. After the first layer is formed, the second layer is formed under the general conditions described above with a flow rate of C2H and NF3. A coating with a thickness of 0.1 μm was prepared using a ratio of 100:1. This second layer had a Vickers hardness of 2000 kg/m.
It is a hard film with a hardness of more than m" and is chemically stable. Therefore, when a film like the one described in this example is applied to the lead fly after wire bonding, the first layer will be free from stress. By alleviating this, the gold wire welded to the aluminum pad on the IC chip can be prevented from peeling off, and at the same time, the second layer prevents impurities such as water and alkali ions from entering.
We were able to significantly improve the reliability of the IC.
「効果」
以上述べたように本発明はハロゲン元素または水素とハ
ロゲン元素が添加された炭素を主成分とする被膜におい
て、該被膜中のハロゲン元素量を厚さ方向に沿って分布
をもたせることにより、本来有用性の高い高硬度、高透
光性、比抵抗可変化性、低内部応力等の膜特性の欠点を
補うことによりさらに工業上利用価値の高い複合体とす
ることができ、本発明を応用した場合の複合体の寿命お
よび信頼性を格段に向上させることができた。"Effects" As described above, the present invention provides a film whose main component is halogen element or carbon to which hydrogen and halogen element are added, by making the amount of halogen element in the film distributed along the thickness direction. By compensating for the disadvantages of film properties such as high hardness, high light transmittance, variable specific resistance, and low internal stress, which are originally highly useful, a composite with even higher industrial utility value can be obtained, and the present invention We were able to significantly improve the lifespan and reliability of the composite when it was applied.
第１図はＮＦ、流量と導電率の関係を示す。
第２図はＮＦユ流聞と透過率の関係を示す。
第３図はＮ Ｆ ｓ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図はフッ素を含んだ炭素の透過率を示す。
第７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。
ＮＦ３式 （ｓｃｃｔ−をン
ネ１図
／θθ
２ｖ ダ０
ＮＦ３直蓋（ＳＣ錯）
第２図
ＮＦａ
追撃Ｌ（Ｓここノイ９
役人ｔカ
（ｗ）
二欠髪（ｈｍ）
第乙図FIG. 1 shows the relationship between NF, flow rate, and conductivity. Figure 2 shows the relationship between NF Yu leakage and transmittance. FIG. 3 shows the relationship between N F s 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 fluorine. FIG. 7 shows the structure of a photoreceptor to which a coating mainly composed of carbon according to the present invention is applied. NF3 type (scct- 1 diagram/θθ 2v da 0 NF3 direct lid (SC complex) Figure 2 NFa Pursuit L (S Kokonoi 9 Official tka (w) Two missing hairs (hm) Figure Otsu
Claims (1)
プラズマＣＶＤ（化学気相成長法）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、ハロゲン元素または水素とハロゲン元素が含
有され、前記ハロゲン元素の濃度が堆積された膜の厚さ
方向に沿って分布をもつことを特徴とする炭素を主成分
とする被膜を有する複合体。In a carbon-based film created using plasma CVD (chemical vapor deposition) on a substrate such as glass, metal, ceramics, or organic resin, the carbon-based film contains a halogen element. Alternatively, a composite having a film mainly composed of carbon, which contains hydrogen and a halogen element, and wherein the concentration of the halogen element has a distribution along the thickness direction of the deposited film.
Priority Applications (9)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63177849A JPH0230761A (en) | 1988-07-17 | 1988-07-17 | Composite body having film composed principally of carbon |
| EP88307417A EP0304220B1 (en) | 1987-08-10 | 1988-08-10 | Thin film carbon material and method of depositing the same |
| CN88106060A CN1020477C (en) | 1987-08-10 | 1988-08-10 | Carbon material containing halogen and deposition method for same |
| KR1019880010194A KR930001013B1 (en) | 1987-08-10 | 1988-08-10 | Carbon material containing a halogen and deposition method for same |
| DE3852357T DE3852357T2 (en) | 1987-08-10 | 1988-08-10 | Thin film carbon material and method of application. |
| US07/380,328 US5238705A (en) | 1987-02-24 | 1989-07-17 | Carbonaceous protective films and method of depositing the same |
| US07/481,720 US5145711A (en) | 1987-08-10 | 1990-02-16 | Cyclotron resonance chemical vapor deposition method of forming a halogen-containing diamond on a substrate |
| US07/587,659 US5120625A (en) | 1987-08-10 | 1990-09-26 | Carbon material containing a halogen and deposition method for same |
| US07/725,896 US5230931A (en) | 1987-08-10 | 1991-07-01 | Plasma-assisted cvd of carbonaceous films by using a bias voltage |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63177849A JPH0230761A (en) | 1988-07-17 | 1988-07-17 | Composite body having film composed principally of carbon |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0230761A true JPH0230761A (en) | 1990-02-01 |
Family
ID=16038179
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63177849A Pending JPH0230761A (en) | 1987-02-24 | 1988-07-17 | Composite body having film composed principally of carbon |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0230761A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6080445A (en) * | 1997-02-20 | 2000-06-27 | Citizen Watch Co., Ltd. | Method of forming films over insulating material |
-
1988
- 1988-07-17 JP JP63177849A patent/JPH0230761A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6080445A (en) * | 1997-02-20 | 2000-06-27 | Citizen Watch Co., Ltd. | Method of forming films over insulating material |
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