JPS62162367A - Composite having carbon coat - Google Patents
Composite having carbon coatInfo
- Publication number
- JPS62162367A JPS62162367A JP61277520A JP27752086A JPS62162367A JP S62162367 A JPS62162367 A JP S62162367A JP 61277520 A JP61277520 A JP 61277520A JP 27752086 A JP27752086 A JP 27752086A JP S62162367 A JPS62162367 A JP S62162367A
- Authority
- JP
- Japan
- Prior art keywords
- carbon
- composite
- substrate
- pin junction
- wear
- 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
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
Abstract
Description
【発明の詳細な説明】
本発明は、ガラス、金属またはセラミックス上に炭素被
膜をコーティングしようとするものであり、特にアセチ
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、
結果としてグラファ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、光学的エネルギバンド中（
Ｅｇという）が２． ＯｅＶ以上、好ましくは２．６〜
４．５ｅＶを有するダイヤモンドに類似の絶縁性の炭素
を形成することを特徴としている。DETAILED DESCRIPTION OF THE INVENTION The present invention attempts to coat glass, metal, or ceramics with a carbon film, and in particular, by introducing a hydrocarbon gas such as acetylene or methane into a plasma atmosphere and decomposing it. , make a C-C bond,
As a result, rather than making carbon conductive or poorly conductive like graphite, it is
Eg) is 2. OeV or more, preferably 2.6~
It is characterized by the formation of insulating carbon similar to diamond with a voltage of 4.5 eV.
本発明はこの炭素に■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る。In the present invention, this carbon contains 5 mol% of valent or V-valent impurities.
It is added below to have P or N type conductivity.
さらにこの本発明の炭素は、その硬度も４５００Ｋｇ／
ｍｍ”以上、代表的には６５００Ｋｇ／ｍｍ”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
造はアモルファス（非晶質）または５〜２００人の大き
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。Furthermore, the carbon of the present invention has a hardness of 4500 kg/
It has a hardness similar to that of diamond, typically 6,500 Kg/mm. Its crystallographic structure is amorphous or microcrystalline with a size of 5 to 200 people. Further, this carbon simultaneously contains hydrogen and halogen elements in an amount of 25 mol % or less.
さらに本発明の炭素は珪素がＳｉ／Ｃ≦０．２５の濃度
に添加されたいわゆる炭素を主成分とする炭素をも意味
する。Furthermore, the carbon of the present invention also means carbon whose main component is so-called carbon to which silicon is added at a concentration of Si/C≦0.25.
本発明はこれらの炭素（以下本発明においては単に炭素
という）をガラス、金属またはセラミックス上に設けた
複合体を設けたものである。The present invention provides a composite body in which these carbons (hereinafter simply referred to as carbon in the present invention) are provided on glass, metal, or ceramics.
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°C, which is 500 to 1500°C compared to the temperature of the substrate used in the conventional CVD method.
Another feature is that it was formed at a low temperature.
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７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ァ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, the present invention eliminates boron, which is a valent impurity, to this carbon.
．． By adding phosphorus, a heptavalent impurity, to a concentration of 0.1 to 5 mol% and providing N-type carbon, P-type carbon is added to a concentration of 1 to 5 mol%. Another feature is that the carbon on the upper surface of this substrate has semiconductivity due to valence electron control, which is different from that of 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 a PIN junction or NIP bond on this substrate.
By providing carbon with a junction, it is characterized by having semiconductor characteristics having diode characteristics.
さらに本発明の複合体はバルブ、耐磨耗材料、またはＰ
ＩＮ型を有する半導体としての装置例えば受光または発
光素子への応用が可能である。Further, the composite of the present invention may be used as a valve, wear-resistant material, or P.
It is possible to apply it to a device as an IN type semiconductor, such as a light receiving or light emitting device.
以下に図面に従っ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 Figure 1 shows plasma CVD for forming carbon of the present invention.
An overview of the device is shown.
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
、キャリアガスを水素またはへリュームにより（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７価の不純物、例えばジボランまたはフ
ォ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。In the drawing, a hydrocarbon gas, such as acetylene, which is a reactive gas, is introduced from (8) through a valve and a flow meter (5) into an excitation chamber (4) in the reaction system. Furthermore, if necessary, the carrier gas is supplied with hydrogen or helium (7) through a valve and a flow meter (6), and similarly reaches the excitation chamber. If a valent or heptavalent impurity, such as diborane or phosphin, is to be introduced here, it may be added to the system in the same manner.
これらの反応性気体は２．４５ＧＩＩｚのマイクロ波に
よる電磁エネルギにより０．１〜５に−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る
。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１３．５
６Ｍ１ｌｚ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
、゛加える電磁エネルギが小さい場合はアモルファス構
造の炭素が生成される。他方、この電磁エネルギを強く
加えた場合は５〜２００人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得る。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０．００１〜１０ｔｏ
ｒｒ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１Ｇ
ＩＩｚ以上の周波数にあっては、Ｃ−Ｈ結合より水素を
分離し、０．１〜５０ＭＩＩｚ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 are activated, decomposed or reacted in an excitation chamber by applying an energy of 0.1 to 5 - by microwave electromagnetic energy of 2.45 GIIz. Furthermore, this reactive gas is heated in a heating furnace (9) in a reactor (1).
) to 150-450°C, and further heated to 13.5°C.
It is reacted and polymerized by the high frequency energy (2) of 6M1lz to produce carbon having a large number of C--C bonds. At this time, if the applied electromagnetic energy is small, carbon with an amorphous structure is produced. On the other hand, if this electromagnetic energy is strongly applied, diamond-shaped microcrystalline carbon with a size of 5 to 200 people can be produced. This reaction is carried out by heating the heater (11) with the power source (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 0.001 to 10to
rr is typically maintained at 0.1 to 0.5 torr, and a plasma state is generated in the reaction chamber (1) by the energy of microwaves (3) and high frequency waves (2). Especially 1G
At frequencies above IIz, hydrogen is separated from the C-H bond, and at frequencies from 0.1 to 50 MIIz, C=
Decomposes C bonds and C=C bonds, creates >C-C< bonds or -C-C- bonds, and causes the unpaired bonds of carbon to collide with each other to covalently bond, creating a stable diamond structure. Ta.
かくしてガラス、金属、セラミッ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。In this way, carbon, particularly carbon containing 25 mol % or less of hydrogen in carbon, or carbon having a conductivity type of P, I or N type, was formed on a substrate having a surface made of glass, metal or ceramics.
実施例２
第２図（＾）は第１図の製造装置により作られた複合体
の一例である。第２図（Ａ）はガラスの上にＰまたはＮ
型の導電型を有する炭素膜を形成させた。この電気伝導
率は１０” 〜１０−”（０ｃｍ） −’を有し、自動
車の窓の内表面に設けて、ここに電流を０、Ｏ１〜ＩＡ
流すことにより発熱せしめ、雨等の環境による曇どめを
実施せしめた。Example 2 FIG. 2 (^) is an example of a composite manufactured by the manufacturing apparatus shown in FIG. 1. Figure 2 (A) shows P or N on the glass.
A carbon film having the same conductivity type was formed. It has an electrical conductivity of 10" to 10-"(0cm)-', and is installed on the inner surface of a car window, where a current of 0, O1 to IA is applied.
By flushing, it generates heat and prevents fogging caused by rain or other environmental conditions.
これは自動車のみならず、多くの分野においてその応用
が可能である。This can be applied not only to automobiles but also to many other fields.
実施例３
第２図（Ｂ）は実施例１を用いた本発明方法によってこ
の炭素（２２）を基板（２０）の表面全面に形成したも
のである。かかる炭素を板状の基板のみならず任意の形
状を有する基体（２０）にも形成して、複合体とし得る
。更にこの複合体は切さく機の歯、耐摩耗性表面を有せ
しめる金属またはセラミックの表面とし得る。Example 3 In FIG. 2(B), this carbon (22) was formed on the entire surface of a substrate (20) by the method of the present invention using Example 1. Such carbon can be formed not only on a plate-shaped substrate but also on a base (20) having an arbitrary shape to form a composite. Additionally, the composite may be a cutting machine tooth, a metal or ceramic surface providing a wear-resistant surface.
実施例４
第２図（Ｃ）は実施例１の作製方法によって得られた炭
素を用いた複合体の例である。即ち円錐状の穴があけら
れた被形成面を有するセラミックまたは金属の基板の表
面に炭素（２２）を０．１〜３μの厚さに設けである。Example 4 FIG. 2(C) is an example of a composite using carbon obtained by the manufacturing method of Example 1. That is, carbon (22) is provided to a thickness of 0.1 to 3 .mu.m on the surface of a ceramic or metal substrate having a surface on which conical holes are formed.
穴（２３） 、 （２３’）をインクジェット又は光通
信用の石英の紡錘ジグに用いる場合、０．０５〜５μの
大きさを有し、かつこの穴が耐摩耗性を必要とするため
、かかる複合体はきわめて好都合であった。この炭素を
コーティングしないものに比べて、１０２〜１０’倍も
の耐久性を有していた。When the holes (23) and (23') are used in a quartz spindle jig for inkjet or optical communication, they have a size of 0.05 to 5μ, and these holes require wear resistance. The complex was extremely convenient. The durability was 102 to 10' times higher than that without carbon coating.
実施例５
第２図（ロ）は実施例１に示される方法で形成される炭
素を用いた本発明の他の複合体の実施例を示す。即ち基
板（２０）上にＰＩＮ接合をまたは旧Ｐ接合を有する価
電子制御用の炭素を設けたものである。即ちＰまたはＮ
型の炭素半導体（２５）、Ｉ型の炭素、ＮまたはＰ型の
炭素半導体（２７）よりなる炭素半導体（２４）である
。このＰまたはＮ型の炭素層は０．０１〜５モル％例え
ば１〜３モル％の濃度にホウ素またはリンを添加した。Example 5 FIG. 2(b) shows an example of another composite of the present invention using carbon formed by the method shown in Example 1. That is, carbon for controlling valence electrons having a PIN junction or a former P junction is provided on the substrate (20). i.e. P or N
The carbon semiconductors (24) include a type carbon semiconductor (25), an I type carbon semiconductor, and an N or P type carbon semiconductor (27). This P or N type carbon layer is doped with boron or phosphorus at a concentration of 0.01 to 5 mol%, for example 1 to 3 mol%.
これは（２８）の部分にリフトオフ用の材料を選択的に
設け、全面に形成した後、リフトオフを第３図の製造方
法と同様の方法を用いて得たものである。本発明は基板
の全面に炭素を形成してもまたＰＮ接合またはその他の
構造を設けてもよい。This was obtained by selectively providing a material for lift-off in the portion (28) and forming it on the entire surface, and then using a method similar to the manufacturing method shown in FIG. 3 to perform lift-off. In the present invention, carbon may be formed on the entire surface of the substrate, or a PN junction or other structure may be provided.
この半導体のうち、炭素層（２６）のエネルギバンド巾
は他の炭素層（２５） 、 （２７）に比べて小さく、
珪素またはゲルマニュームを添加して形成し、ここに電
極（２９）を設け、縦方向に電流を基板との間に流すこ
とにより炭素の発光素子を基板上に集積化して設けるこ
とができた。かかる発光素子とする複合体にあっては、
基板はステンレス等の導体であることが必要である。こ
の場合、炭素層（２５）、炭素層（２７）はエネルギバ
ンド巾が２．６〜４．５ｅＶであり、また炭素Ｎ （２
６）は２〜３ｅＶとすることによって白色または緑、青
等の色の発光素子を基板上に設けることができた。Among these semiconductors, the energy band width of the carbon layer (26) is smaller than that of the other carbon layers (25) and (27).
By adding silicon or germanium, providing an electrode (29) thereon, and passing a current between the substrate and the substrate in the vertical direction, a carbon light emitting element could be integrated and provided on the substrate. In such a composite body as a light emitting element,
The substrate must be made of a conductor such as stainless steel. In this case, the carbon layer (25) and the carbon layer (27) have an energy band width of 2.6 to 4.5 eV, and carbon N (2
In 6), by setting the voltage to 2 to 3 eV, it was possible to provide white, green, blue, or other colored light emitting elements on the substrate.
炭素被膜の選択的な除去方法として、基板全面に設けら
れた炭素に対し、酸化物雰囲気中にてレーザ光を選択的
にコンピュータ制御により行い、不要の部分の炭素を酸
化して炭酸ガスとして放出して除去する。このレーザ光
による選択エツチングは実施例２〜５に対しても、その
工業的応用に関して任意に用いることができる。As a method for selectively removing the carbon film, laser light is selectively applied to the carbon provided on the entire surface of the substrate in an oxide atmosphere under computer control, and the unnecessary carbon is oxidized and released as carbon dioxide gas. and remove it. This selective etching using laser light can also be used in Examples 2 to 5 as desired for industrial applications.
以上の説明より明らかな如く、本発明はガラス、金属ま
たはセラミック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ィングして設けたものである。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.
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 seen in many other examples, the applications of this composite are immeasurable, especially when this carbon is heated to 450°C.
It is characterized by its extremely high hardness and excellent adhesion to the substrate.
本発明におけるセラミックはアルミナ、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
っては、ステンレス、モリブデン、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。As the ceramic in the present invention, alumina, zirconia, or any material to which a rare earth element such as carbon or lanthanum is added can be used. Furthermore, as for metals, any material such as stainless steel, molybdenum, tungsten, etc. that can withstand temperatures of at least 300 to 450° C. can be used. 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。
第２図（＾）〜（Ｄ）は本発明の複合体の実施例を示す
。FIG. 1 shows an outline of a manufacturing apparatus for manufacturing carbon of the present invention on a surface to be formed. FIGS. 2(^) to (D) show examples of composites of the present invention.
Claims (1)
主成分とすることを特徴とする炭素被膜を有する複合体
。 ２、特許請求の範囲第１項において、ＰまたはＮ型半導
体に比べてＩ型半導体は小さいエネルギバンド巾は有す
ることを特徴とする炭素被膜を有する複合体。 ３、特許請求の範囲第１項において、ＰおよびＮ型半導
体は２．６〜４．５ｅＶの光学的エネルギバンド巾を有
し、Ｉ型半導体は２〜３ｅＶのエネルツギバンド巾を有
することを特徴とする炭素被膜を有する複合体。 ４、特許請求の範囲第１項において、炭素は微結晶性を
有することを特徴とする炭素被膜を有する複合体。[Claims] 1. A composite having a PIN or NIP junction and a carbon coating characterized by containing carbon as a main component. 2. A composite material having a carbon film according to claim 1, wherein the I-type semiconductor has a smaller energy band width than the P- or N-type semiconductor. 3. Claim 1 states that the P and N type semiconductors have an optical energy band width of 2.6 to 4.5 eV, and the I type semiconductor has an energy band width of 2 to 3 eV. A composite material with a characteristic carbon coating. 4. A composite body having a carbon coating according to claim 1, wherein the carbon has microcrystalline properties.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61277520A JPS62162367A (en) | 1986-11-19 | 1986-11-19 | Composite having carbon coat |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61277520A JPS62162367A (en) | 1986-11-19 | 1986-11-19 | Composite having carbon coat |
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 (1)
| Publication Number | Publication Date |
|---|---|
| JPS62162367A true JPS62162367A (en) | 1987-07-18 |
Family
ID=17584736
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61277520A Pending JPS62162367A (en) | 1986-11-19 | 1986-11-19 | Composite having carbon coat |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62162367A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002033497A (en) * | 2000-07-14 | 2002-01-31 | Nihon University | Solar cell and panel thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS53143180A (en) * | 1977-05-18 | 1978-12-13 | Energy Conversion Devices Inc | Amorphous semiconductor structure and method of producing same |
| JPS5464981A (en) * | 1977-10-12 | 1979-05-25 | Energy Conversion Devices Inc | High temperature amorphous semiconductor member and method of producing same |
| JPS5511329A (en) * | 1978-07-08 | 1980-01-26 | Shunpei Yamazaki | Semiconductor device |
| JPS5513938A (en) * | 1978-07-17 | 1980-01-31 | Shunpei Yamazaki | Photoelectronic conversion semiconductor device and its manufacturing method |
-
1986
- 1986-11-19 JP JP61277520A patent/JPS62162367A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS53143180A (en) * | 1977-05-18 | 1978-12-13 | Energy Conversion Devices Inc | Amorphous semiconductor structure and method of producing same |
| JPS5464981A (en) * | 1977-10-12 | 1979-05-25 | Energy Conversion Devices Inc | High temperature amorphous semiconductor member and method of producing same |
| JPS5511329A (en) * | 1978-07-08 | 1980-01-26 | Shunpei Yamazaki | Semiconductor device |
| JPS5513938A (en) * | 1978-07-17 | 1980-01-31 | Shunpei Yamazaki | Photoelectronic conversion semiconductor device and its manufacturing method |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002033497A (en) * | 2000-07-14 | 2002-01-31 | Nihon University | Solar cell and panel thereof |
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