JPH0427690B2 - - Google Patents
Info
- Publication number
- JPH0427690B2 JPH0427690B2 JP61277517A JP27751786A JPH0427690B2 JP H0427690 B2 JPH0427690 B2 JP H0427690B2 JP 61277517 A JP61277517 A JP 61277517A JP 27751786 A JP27751786 A JP 27751786A JP H0427690 B2 JPH0427690 B2 JP H0427690B2
- Authority
- JP
- Japan
- Prior art keywords
- carbon
- gas
- carbon film
- producing
- present
- 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 claims description 37
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 34
- 239000007789 gas Substances 0.000 claims description 14
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 229910003460 diamond Inorganic materials 0.000 claims description 6
- 239000010432 diamond Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 6
- 239000004215 Carbon black (E152) Substances 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 229930195733 hydrocarbon Natural products 0.000 claims description 5
- 150000002430 hydrocarbons Chemical class 0.000 claims description 5
- 239000012535 impurity Substances 0.000 claims description 5
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 4
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims 2
- 239000000758 substrate Substances 0.000 description 10
- 239000011521 glass Substances 0.000 description 8
- 239000000919 ceramic Substances 0.000 description 5
- 239000002131 composite material Substances 0.000 description 5
- 150000001721 carbon Chemical class 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 230000005284 excitation Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
Landscapes
- Chemical Vapour Deposition (AREA)
- Formation Of Insulating Films (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
Description
【発明の詳細な説明】
本発明は、プラズマCVD法によりダイヤモン
ド構造を有する炭素被膜を作製する方法に関す
る。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a carbon film having a diamond structure by plasma CVD.
本発明は、かかる炭素または炭素を主成分とす
る被膜をガラス、金属またはセラミツクスの表面
にコーテイングすることにより、ガラス板の補強
材、また機械的ストレスに対する保護材を得んと
している複合体の作製方法に関する。 The present invention aims to produce a composite material which is intended to serve as a reinforcing material for a glass plate and as a protective material against mechanical stress by coating the surface of glass, metal or ceramics with such carbon or a film mainly composed of carbon. Regarding the method.
本発明は、アセチレン、メタンのような炭化水
素気体をプラズマ雰囲気中に導入し分解せしめる
ことにより、Ｃ−Ｃ結合を作り、結果としてグラ
フアイトのような導電性または不良導電性の炭素
を作るのではなく、光学的にエネルギバンド巾
（Egという）が2.0eV以上、好ましくは2.6〜
4.5eVを有する単結晶ダイヤモンドに類似のダイ
ヤモンド構造を有する絶縁性の炭素を形成するこ
とを特徴としている。さらにこの本発明の炭素
は、その硬度も4500Kg／mm2以上、代表的には6500
Kg／mm2というダイヤモンド類似の硬さを有する。
そしてその結晶学的構造は５〜200〓の大きさの
微結晶性を有している。またこの炭素は水素、ハ
ロゲン元素が25モル％以下の量を同時に含有して
いる。 The present invention creates C-C bonds by introducing a hydrocarbon gas such as acetylene or methane into a plasma atmosphere and decomposing it, resulting in the creation of conductive or poorly conductive carbon such as graphite. Rather, the optical energy band width (called Eg) is 2.0eV or more, preferably 2.6~
It is characterized by the formation of insulating carbon with a diamond structure similar to single crystal diamond with a voltage of 4.5eV. Furthermore, the carbon of the present invention has a hardness of 4500 Kg/mm 2 or more, typically 6500 Kg/mm 2 or more.
It has a hardness of Kg/mm 2 similar to diamond.
Its crystallographic structure has microcrystallinity with a size of 5 to 200 mm. Further, this carbon simultaneously contains hydrogen and halogen elements in an amount of 25 mol% or less.
また本発明の炭素に価またはＶ価の不純物を
５モル％以下に添加し、ＰまたはＮ型の導電型を
有せしめ得る。 Further, the carbon of the present invention can be made to have P or N type conductivity by adding valence or V valence impurities to 5 mol % or less.
本発明は、この炭素を形成させる際の基板に加
える温度を150〜450℃とし、従来より知られた
CVD法において用いられる基板の温度に比べ500
〜1500℃も低い温度で形成したことを他の特徴と
する。 In the present invention, the temperature applied to the substrate when forming this carbon is 150 to 450 degrees Celsius, which is different from conventionally known methods.
500° compared to the substrate temperature used in the CVD method.
Another feature is that it was formed at temperatures as low as ~1500℃.
また本発明はこの炭素に価の不純物であるホ
ウ素を0.1〜５モル％の濃度に添加し、Ｐ型の炭
素を設け、またＶ価の不純物であるリンを同様に
0.1〜５モル％の濃度に添加し、Ｎ型の炭素を設
けることにより、この基板上面の炭素をグラフア
イト構造とは異なる価電子制御による半導電性を
有せしめたことを他の特徴としている。 In addition, in the present invention, boron, which is a valent impurity, is added to this carbon at a concentration of 0.1 to 5 mol% to provide P-type carbon, and phosphorus, which is a V-valent impurity, is added to the carbon at a concentration of 0.1 to 5 mol%.
Another feature is that by adding N-type carbon at a concentration of 0.1 to 5 mol%, the carbon on the upper surface of the substrate has semiconductivity due to valence electron control, which is different from the graphite structure. .
さらに本発明は、この基板上にPIN接合または
NIP接合を有する炭素を設けることにより、ダイ
オード特性を有する半導体的特性を有せしめるこ
とを特徴としている。 Furthermore, the present invention provides PIN bonding or
By providing carbon with an NIP junction, it is characterized in that it has semiconductor characteristics with diode characteristics.
また本発明は基板特にガラスまたはセラミツク
を用い、その後この基板の一部を選択的に除去し
てインクジエツトノズル、光通信用石英ガラスの
引き出し用ノズルとして設けるものである。 Further, the present invention uses a substrate, particularly glass or ceramic, and then selectively removes a portion of the substrate to provide an inkjet nozzle or a nozzle for extracting quartz glass for optical communication.
また本発明は、ガラス基板上に選択的に炭素被
膜を設け、電子ビーム露光装置または紫外線の露
光装置のフオトマスクとして用いることを他の特
徴としている。 Another feature of the present invention is that a carbon film is selectively provided on a glass substrate and used as a photomask for an electron beam exposure device or an ultraviolet exposure device.
さらに本発明の複合体はバルブ、耐磨耗材料、
またはPIN型を有する半導体としての装置例えば
受光または発光素子への反応が可能である。 Furthermore, the composite of the present invention can be used as a valve, wear-resistant material,
Alternatively, it is possible to react to a device as a semiconductor having a PIN type, such as a light receiving or light emitting element.
以下に図面に従つて本発明に用いられた複合体
またはその複合体の作製方法を記す。 The composite used in the present invention and the method for producing the composite will be described below according to the drawings.
実施例 １
第１図は本発明の炭素を形成するためのプラズ
マCVD装置の概要を示す。Example 1 FIG. 1 shows an outline of a plasma CVD apparatus for forming carbon according to the present invention.
図面において反応性気体である炭化水素気体、
例えばアセチレンが８よりバルブ、流量計５をへ
て反応系中の励起室４に導入される。さらに必要
に応じて、キヤリアガスを水素またはヘリユーム
により７よりバルブ、流量計６をへて同様に励起
室に至る。ここに価またはＶ価の不純物、例え
ばジボランまたはフオスヒンを導入する場合はさ
らに同様にこの系に加えればよい。 hydrocarbon gas, which is a reactive gas in the drawing;
For example, acetylene is introduced from 8 through a valve and a flow meter 5 into an excitation chamber 4 in the reaction system. Further, if necessary, the carrier gas is supplied with hydrogen or helium from 7 through a valve and a flow meter 6 to reach the excitation chamber in the same manner. When introducing a valent or V-valent impurity, such as diborane or phoschin, it may be added to the system in the same manner.
これらの反応性気体は2.45GHzのマイクロ波に
よる電磁エネルギにより0.1〜5Kwのエネルギを
加えられ、励起室にて活性化、分解または反応さ
せられてＣ−Ｃ結合を生成した。さらにこの反応
性気体は反応炉１にて加熱炉９により150〜450℃
に加熱させ、さらに13.56MHzの高周波エネルギ
２により反応、重合され、Ｃ−Ｃ結合を多数形成
した炭素を生成する。この際、加える高周波やマ
イクロ波の電磁エネルギが小さい場合はアモルフ
アス構造の炭素が生成される。このため本発明方
法ではこの電磁エネルギを強く加え、５〜200〓
の大きさのダイヤモンド形状の微結晶性を有する
炭素を生成させる。この反応は電源１３によりヒ
ータ１１を加熱し、さらにその上の基板１０を加
熱して行う。そしてこの基板の上面に被膜として
反応生成物の炭素被膜が形成される。反応後の不
要物は排気口１２よりロータリーポンプを経て排
気される。反応室１は0.001〜10torr代表的には
0.1〜0.5torrに保持されており、マイクロ波３、
高周波２のエネルギにより反応室１内はプラズマ
状態が生成される。特に1GHz以上の周波数にあ
つては、Ｃ−Ｈ結合より水素を分離し、0.1〜
50MHzの周波数にあつてはＣ≡Ｃ結合、Ｃ＝Ｃ結
合を分解し、Ｃ−Ｃ結合または−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有
せしめた。 These reactive gases were applied with 0.1 to 5 Kw of electromagnetic energy by microwaves at 2.45 GHz, and activated, decomposed or reacted in an excitation chamber to form C--C bonds. Furthermore, this reactive gas is heated to a temperature of 150 to 450°C in a heating furnace 9 in a reactor 1.
The carbon is heated to , and then reacted and polymerized by high frequency energy 2 of 13.56 MHz to produce carbon having many C--C bonds. At this time, if the applied high frequency or microwave electromagnetic energy is small, carbon with an amorphous structure is produced. Therefore, in the method of the present invention, this electromagnetic energy is strongly applied to
This produces diamond-shaped microcrystalline carbon with a size of . This reaction is carried out by heating the heater 11 with the power supply 13 and further heating the substrate 10 thereon. Then, a carbon film of the reaction product is formed as a film on the upper surface of this substrate. Unwanted substances after the reaction are exhausted from the exhaust port 12 via a rotary pump. Reaction chamber 1 is typically 0.001 to 10 torr.
It is maintained at 0.1 to 0.5 torr, and microwave 3,
A plasma state is generated within the reaction chamber 1 by the energy of the high frequency wave 2 . In particular, at frequencies above 1 GHz, hydrogen is separated from the C-H bond, and 0.1~
At a frequency of 50MHz, C≡C bonds and C=C bonds are decomposed, C-C bonds or -C-C- bonds are created, and unpaired carbon bonds are collided with each other to form covalent bonds. It has a stable diamond structure.
かくしてガラス、金属、セラミツクスよりなる
被形成面を有する基板上に炭素特に炭素中に水素
を25モル％以下含有する炭素またＰ、ＩまたはＮ
型の導電型を有する炭素を形成させた。 Thus, carbon, especially carbon containing 25 mol% or less of hydrogen, P, I or N, is applied onto a substrate having a surface made of glass, metal or ceramics.
Carbon having a conductivity type of the type was formed.
以上の説明より明らかな如く、本発明はガラ
ス、金属またはセラミツクスの表面または内部に
炭素または炭素を主成分とした被膜をコーテイン
グして設けたものである。この複合体は他の多く
の実施例にみられる如く、その応用は計り知れな
いものであり、特にこの炭素が450℃以下の低温
で形成され、その硬度また基板に対する密着性が
きわめて優れているのが特徴である。 As is clear from the above description, the present invention provides a film in which carbon or a film containing carbon as a main component is coated on the surface or inside of glass, metal, or ceramic. As seen in many other examples, the applications of this composite are immeasurable, especially since this carbon is formed at a low temperature of 450°C or less, and its hardness and adhesion to substrates are extremely excellent. It is characterized by
本発明におけるセラミツクはアルミナ、ジルコ
ニア、またはそれらに炭素またはランタン等の希
土類元素が添加された任意の材料を用いることが
できる。また金属にあつては、ステンレス、モリ
ブテン、タングステン等の少なくとも300〜450℃
の温度に耐えられる材料ならばすべてに応用可能
である。またガラスは石英のみならずソーダガラ
ス等に対しても被膜化が可能であり、その応用は
きわめて広い。 The ceramic used in the present invention may be alumina, zirconia, or any material to which a rare earth element such as carbon or lanthanum is added. For metals, stainless steel, molybdenum, tungsten, etc. must be heated to at least 300 to 450℃.
It can be applied to any material that can withstand this temperature. Further, glass can be coated not only on quartz but also on soda glass, etc., and its applications are extremely wide.
第１図は本発明の炭素を被形成面上に作製する
製造装置の概要を示す。
FIG. 1 shows an outline of a manufacturing apparatus for manufacturing carbon of the present invention on a surface to be formed.
Claims (1)
体とを反応系に導入し、1GHz以上の周波数のマ
イクロ波及び0.1〜50MHzの高周波の電磁エネル
ギーを前記混合気体に供給してプラズマ化し、ダ
イヤモンド構造の結晶を有する炭素被膜を被膜形
成面上に形成することを特徴とする炭素被膜の作
製方法。 ２ 炭化水素気体がアセチレン又はメタンである
特許請求の範囲第１項に記載の炭素被膜の作製方
法。 ３ 炭化水素気体と水素又はヘリユームの混合気
体と価又はＶ価の不純物気体とを反応系に導入
し、1GHz以上のマイクロ波及び0.1〜50MHzの高
周波の電磁エネルギーを前記混合気体に供給して
プラズマ化し、Ｐ型又はＮ型のダイヤモンド構造
の結晶を有する炭素被膜を被膜形成面上に形成す
ることを特徴とする炭素被膜の作製方法。 ４ 炭化物気体がアセチレン又はメタンである特
許請求の範囲第３項に記載の炭素被膜の作製方
法。[Claims] 1. A gas mixture of hydrocarbon gas and hydrogen or helium is introduced into a reaction system, and microwaves with a frequency of 1 GHz or more and electromagnetic energy with a high frequency of 0.1 to 50 MHz are supplied to the gas mixture to generate a plasma. 1. A method for producing a carbon film, which comprises forming a carbon film having diamond-structured crystals on a film-forming surface. 2. The method for producing a carbon film according to claim 1, wherein the hydrocarbon gas is acetylene or methane. 3. A mixed gas of hydrocarbon gas, hydrogen or helium, and a valent or V-valent impurity gas are introduced into the reaction system, and microwaves of 1 GHz or more and high frequency electromagnetic energy of 0.1 to 50 MHz are supplied to the mixed gas to generate plasma. 1. A method for producing a carbon film, which comprises forming a carbon film having P-type or N-type diamond structure crystals on a film-forming surface. 4. The method for producing a carbon film according to claim 3, wherein the carbide gas is acetylene or methane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27751786A JPS62167885A (en) | 1986-11-19 | 1986-11-19 | Production of composite body having carbon film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27751786A JPS62167885A (en) | 1986-11-19 | 1986-11-19 | Production of composite body having carbon film |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP56146930A Division JPS5848428A (en) | 1981-09-17 | 1981-09-17 | Compound material having carbon film and manufacture therefor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62167885A JPS62167885A (en) | 1987-07-24 |
| JPH0427690B2 true JPH0427690B2 (en) | 1992-05-12 |
Family
ID=17584698
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP27751786A Granted JPS62167885A (en) | 1986-11-19 | 1986-11-19 | Production of composite body having carbon film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62167885A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5470661A (en) * | 1993-01-07 | 1995-11-28 | International Business Machines Corporation | Diamond-like carbon films from a hydrocarbon helium plasma |
| JPH07161646A (en) * | 1993-12-13 | 1995-06-23 | Nec Corp | Formation of polycrystalline film |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5328576A (en) * | 1976-08-13 | 1978-03-16 | Nat Res Dev | Surface coating process with cargonaceous material and apparatus therefor |
| JPS5578524A (en) * | 1978-12-10 | 1980-06-13 | Shunpei Yamazaki | Manufacture of semiconductor device |
-
1986
- 1986-11-19 JP JP27751786A patent/JPS62167885A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5328576A (en) * | 1976-08-13 | 1978-03-16 | Nat Res Dev | Surface coating process with cargonaceous material and apparatus therefor |
| JPS5578524A (en) * | 1978-12-10 | 1980-06-13 | Shunpei Yamazaki | Manufacture of semiconductor device |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62167885A (en) | 1987-07-24 |
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