JPH0790588A - Production of nitrigen containing carbon film - Google Patents
Production of nitrigen containing carbon filmInfo
- Publication number
- JPH0790588A JPH0790588A JP5238573A JP23857393A JPH0790588A JP H0790588 A JPH0790588 A JP H0790588A JP 5238573 A JP5238573 A JP 5238573A JP 23857393 A JP23857393 A JP 23857393A JP H0790588 A JPH0790588 A JP H0790588A
- Authority
- JP
- Japan
- Prior art keywords
- nitrigen
- graphite
- carbon film
- reaction
- temp
- 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.)
- Granted
Links
Abstract
Description
【０００１】[0001]
【産業上の利用分野】この発明は、窒素含有炭素膜の製
造方法に関するものである。さらに詳しくは、この発明
は、エレクトロニクス、バイオマテリアル等の分野にお
いて有用な、高機能性薄膜の提供を可能とする、新しい
窒素含有のグラファイト状炭素膜の製造方法に関するも
のである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a nitrogen-containing carbon film. More specifically, the present invention relates to a method for producing a novel nitrogen-containing graphite-like carbon film, which makes it possible to provide a highly functional thin film useful in the fields of electronics, biomaterials and the like.
【０００２】[0002]
【従来の技術とその課題】従来より、エレクトロニク
ス、バイオマテリアル等の分野においては、高機能性薄
膜の検討が精力的に進められており、さらに新たな物性
を備えた高機能性薄膜の創出への期待が寄せられてい
る。このような新しい物性を備えた高機能性薄膜のひと
つとして、異種原子をインターカレーションした炭素薄
膜や、異種原子によって一部の炭素原子を置換したグラ
ファイト厚膜が注目されている。2. Description of the Related Art Conventionally, in the fields of electronics, biomaterials, etc., high-performance thin films have been energetically studied, and to create high-performance thin films with new physical properties. Is expected. As one of the highly functional thin films having such new physical properties, a carbon thin film in which heteroatoms are intercalated and a graphite thick film in which some carbon atoms are replaced by heteroatoms are attracting attention.
【０００３】この異種原子置換炭素膜、特にグラファイ
ト状炭素膜についてもその物性について基礎的な研究が
進められている。現在までのところ、この異種原子置換
グラファイト状炭素膜については、ホウ素置換グラファ
イト（ＢｘＣ）やＢＮ置換グラファイト（ＢｘＣｙＮ）
が報告されている。Basic studies on the physical properties of this heteroatom-substituted carbon film, especially the graphite-like carbon film, are also underway. So far, this heteroatom-substituted graphite-like carbon film has been used for boron-substituted graphite (BxC) and BN-substituted graphite (BxCyN).
Has been reported.
【０００４】たとえば、ＢＮ置換グラファイトについて
は、ＢＣｌ3 ／ＣＣｌ4 ／Ｎ2 ／Ｈ 2 を高温（２０００
℃）で、または、ＢＣｌ3 ／ＣＨ3 ＣＮを８００℃で反
応させて合成することや高温高圧下でグラファイト中に
Ｂを拡散させることなどが報告されている。しかしなが
ら、これまでの異種原子置換グラファイト状炭素膜は、
一般的に高温高圧での合成反応によって形成されている
ため、他種の異種原子置換薄膜の製造にはまったく適し
ていないという問題がある。また、１０００℃前後の反
応でも、ＨＣｌのような反応の腐食性ガスが発生すると
いう問題があり、反応副生成物としての腐食性ガスに装
置が耐えられるようにしなければならず、排ガス処理の
ための設備も大がかりなものとなるという欠点があっ
た。For example, regarding BN-substituted graphite
Is BCl3/ CClFour/ N2/ H 2High temperature (2000
℃) or BCl3/ CH3Counter CN at 800 ℃
Reaction and synthesis in graphite under high temperature and high pressure
It has been reported that B is diffused. But Naga
So far, the heteroatom-substituted graphite-like carbon film is
Generally formed by synthetic reaction at high temperature and high pressure
Therefore, it is perfectly suitable for the production of other kinds of heteroatom-substituted thin films.
There is a problem not. In addition, the anti-
However, if a corrosive gas of reaction such as HCl is generated,
There is a problem that the corrosive gas as a reaction by-product
Of the exhaust gas treatment
There is a drawback that the equipment for
It was
【０００５】このため、従来の技術をもってしても、窒
素等の他の異種原子を置換したグラファイト状炭素膜の
製造には至っていないのが実情である。この発明は、以
上の通りの事情に鑑みてなされたものであり、従来の方
法の欠点を解消し、異種原子として窒素を含有するグラ
ファイト状炭素膜の新しい製造方法を提供することを目
的としている。For this reason, even with the conventional technique, the fact is that a graphite-like carbon film in which other heteroatoms such as nitrogen have been replaced has not been produced yet. The present invention has been made in view of the above circumstances, and an object thereof is to solve the drawbacks of the conventional methods and to provide a new method for producing a graphite-like carbon film containing nitrogen as a heteroatom. .
【０００６】[0006]
【課題を解決するための手段】この発明は、上記の課題
を解決するものとして、含窒素環状有機化合物を化学気
相蒸着することを特徴としている。つまり、この発明に
おいては、従来のように高温高圧合成方法を採用するこ
となく、また、反応副生物としてＨＣｌ等の腐食性化合
物を発生させることなく化学気相蒸着（ＣＶＤ）するこ
とに大きな特徴がある。In order to solve the above problems, the present invention is characterized by chemical vapor deposition of a nitrogen-containing cyclic organic compound. In other words, the present invention has a great feature that chemical vapor deposition (CVD) is performed without using a high-temperature high-pressure synthesis method as in the past and without generating a corrosive compound such as HCl as a reaction by-product. There is.
【０００７】この場合の原料物質は、ピロール、イミダ
ゾール、ピリジン、ピペリジン、トリアゾール、テトラ
ゾール等の含窒素環状有機化合物の適宜なものを用いる
ことができる。そして、これら原料物質にはＨＣｌ等の
腐食性化合物を生成させる塩素等の元素を含有しないも
のを用いることとする。また、反応には、キャリアガス
として、Ａｒ，Ｈｅ，Ｎｅ等の反応しにくい不活性気体
が好ましく使用される。反応温度は通常６００〜１００
０℃程度の温度が採用される。また、反応は、常圧、減
圧下に行うのが好ましく、成膜速度は、０．１〜５０Å
／ｓｅｃ程度とするのが好ましい。基板として各種の固
体、たとえば石英、ガラス、Ｎｉ，Ｐｔ，Ｓｉ，その他
のものを適宜に採用する。As the raw material in this case, an appropriate nitrogen-containing cyclic organic compound such as pyrrole, imidazole, pyridine, piperidine, triazole, tetrazole, etc. can be used. Then, as these raw material substances, those which do not contain an element such as chlorine which produces a corrosive compound such as HCl are used. Further, in the reaction, an inert gas such as Ar, He, Ne or the like which is hard to react is preferably used as a carrier gas. The reaction temperature is usually 600 to 100
A temperature of about 0 ° C is adopted. The reaction is preferably carried out under normal pressure and reduced pressure, and the film formation rate is 0.1 to 50Å
/ Sec is preferable. As the substrate, various solids such as quartz, glass, Ni, Pt, Si and others are appropriately adopted.
【０００８】もちろん、この発明においては、熱ＣＶＤ
法、減圧ＣＶＤ法、プラズマＣＶＤ法、光ＣＶＤ法等の
様々な手段としての各種のＣＶＤ法を用いることができ
る。以下実施例を示し、さらに詳しくこの発明について
説明する。Of course, in the present invention, thermal CVD
Method, low pressure CVD method, plasma CVD method, optical CVD method, and various other CVD methods can be used. The present invention will be described in more detail with reference to the following examples.
【０００９】[0009]
【実施例】石英反応管内において、原料の環状含窒素複
素環化合物を温度制御しつつ気化させ、キャリアガス
（Ａｒ等）により基板上の反応域に導入し、基板上に薄
膜を生成させた。原料には環状ヘテロ化合物であるピロ
ールを用い、キャリアガスとしてＡｒを用い、その流量
は３００ｃｃ／ｍｉｎとした。反応温度は６００，７５
０，８００，１０００℃とした。Example In a quartz reaction tube, a cyclic nitrogen-containing heterocyclic compound as a raw material was vaporized while controlling the temperature and introduced into a reaction region on a substrate by a carrier gas (Ar or the like) to form a thin film on the substrate. Pyrrole, which is a cyclic hetero compound, was used as a raw material, Ar was used as a carrier gas, and the flow rate was 300 cc / min. Reaction temperature is 600,75
The temperature was 0,800,1000 ° C.
【００１０】図１はこの実施例で用いた薄膜生成装置の
概略図である。石英管内にはＮｉ基板と原料物質として
のピロールを置き、基板を炉により所定の温度に加熱
し、また原料ピロールをヒーターにより気化温度程度に
加熱し、石英管内にＡｒガスを流入させた。１時間後、
上記の各反応温度において、Ｎｉ基板上に厚さ約１〜５
μｍの灰色の薄膜が得られた。FIG. 1 is a schematic diagram of a thin film forming apparatus used in this embodiment. A Ni substrate and a pyrrole as a raw material were placed in a quartz tube, the substrate was heated to a predetermined temperature by a furnace, the raw pyrrole was heated to a vaporization temperature by a heater, and Ar gas was introduced into the quartz tube. One hour later,
At each of the above reaction temperatures, the thickness of the Ni substrate is about 1 to 5
A gray thin film of μm was obtained.
【００１１】各反応温度で生成した薄膜をＸ線回折によ
り解析したところ、７５０℃以上で生成した膜では、グ
ラファイト状の層状構造が確認された。すなわち、この
Ｘ線回折による強度は、図２に示した通りであり、これ
から求めたＸ線回折ｄ値は、表１に示した通りであっ
た。反応温度６００℃で生成された膜ではＸ線回折のピ
ークは見られず、グラファイトは生成していないのに対
し、７５０℃以上では格子面間隔ｄ値〜３．３５Ａが得
られ、グラファイト状構造の膜が生成していることがわ
かった。Ｘ線の回折の半値幅は７５０℃のものでは１．
０ｄｅｇとやや広く、結晶性がまだ乱れがあるのに対
し、蒸着感度が高くなると半値幅は小さくなり、結晶性
が良くなることが確かめられた。When the thin film formed at each reaction temperature was analyzed by X-ray diffraction, a graphite-like layered structure was confirmed in the film formed at 750 ° C. or higher. That is, the intensity by this X-ray diffraction was as shown in FIG. 2, and the X-ray diffraction d value obtained from this was as shown in Table 1. No X-ray diffraction peak was observed in the film formed at a reaction temperature of 600 ° C., and no graphite was formed, whereas a lattice spacing d value of ˜3.35 A was obtained at 750 ° C. or higher, indicating a graphite-like structure. It was found that the film was formed. The full width at half maximum of the X-ray diffraction is 1.50 at 750 ° C.
It was confirmed that while the crystallinity is still disordered with a wide range of 0 deg, the half-width becomes smaller and the crystallinity becomes better as the deposition sensitivity becomes higher.
【００１２】さらに、この生成された薄膜をＸ線光電子
分光法（ＸＰＳ）により、Ｎ濃度、Ｃエネルギー状態、
および、Ｎエネルギー状態を確認した。表１に例示した
ように、反応温度８００℃のときに、Ｎ濃度は最大の１
５ａｔｍ％にも及び反応温度が上昇するにしたがいＮ濃
度は減少し、また反応温度が下降してもＮ濃度は減少し
た。Further, the produced thin film was analyzed by X-ray photoelectron spectroscopy (XPS) to obtain N concentration, C energy state,
And the N energy state was confirmed. As illustrated in Table 1, when the reaction temperature is 800 ° C., the N concentration is 1
The N concentration decreased as the reaction temperature increased to 5 atm%, and the N concentration decreased even when the reaction temperature decreased.
【００１３】このことから、各反応温度で生成された薄
膜のＣ／Ｎを求めると、表１に例示したように、８００
℃で生成した薄膜のＣ／Ｎは４．６、７５０℃で生成し
た薄膜のＣ／Ｎは１３．８であった。From this fact, the C / N of the thin film produced at each reaction temperature was calculated to be 800 as shown in Table 1.
The C / N of the thin film formed at ° C was 4.6, and the C / N of the thin film formed at 750 ° C was 13.8.
【００１４】[0014]
【表１】 [Table 1]
【００１５】さらに、Ｘ線光電子分光法（ＸＰＳ）によ
り解析した各結合エネルギーの強度は、Ｃ1sスペクトル
を用いた場合においては、たとえば図３に例示したよう
に、グラファイトに近い２８４．５ｅＶの結合エネルギ
ーにおいて、その強度のピークが見られた。図４は、Ｎ
1sのスペクトルを例示したものである。Further, the intensity of each binding energy analyzed by X-ray photoelectron spectroscopy (XPS) is 284.5 eV, which is close to that of graphite as shown in FIG. 3, when the C 1s spectrum is used. At energy, a peak of that intensity was seen. FIG. 4 shows N
It is an example of the spectrum of 1s .
【００１６】以上の例と同様にして、ピロールに代えて
イミダゾール、トリアゾール、テトラゾール、ピリジ
ン、ピリミジンの各々を原料として気相蒸着させた。ピ
ロールの場合と同様に格子面間隔としてグラファイト近
似の、窒素含有膜が得られた。In the same manner as in the above example, each of imidazole, triazole, tetrazole, pyridine and pyrimidine was used as a raw material in place of pyrrole, and vapor deposition was performed. As in the case of pyrrole, a nitrogen-containing film having a lattice spacing similar to that of graphite was obtained.
【００１７】[0017]
【発明の効果】以上詳しく説明した通り、この発明によ
り窒素含有グラファイト状炭素薄膜の作成が可能となっ
た。As described in detail above, the present invention enables the production of a nitrogen-containing graphite-like carbon thin film.
【図１】この発明の実施例における薄膜生成装置の概略
図である。FIG. 1 is a schematic view of a thin film forming apparatus according to an embodiment of the present invention.
【図２】この発明の実施例におけるＸ線回折角と強度の
関係を示した関係図である。FIG. 2 is a relationship diagram showing a relationship between an X-ray diffraction angle and intensity in an example of the present invention.
【図３】この発明の実施例における結合エネルギー（Ｃ
IS）と−温度毎の強度の関係を示した関係図である。FIG. 3 shows the binding energy (C
It is a relationship diagram showing the relationship between IS ) and the strength for each temperature.
【図４】この発明の実施例における結合エネルギー（Ｎ
IS）と温度毎の強度の関係を示した関係図である。FIG. 4 shows the binding energy (N
It is a relationship diagram showing the relationship between IS ) and the strength for each temperature.
───────────────────────────────────────────────────── フロントページの続き (71)出願人 592194406 大木 芳正 神奈川県相模原市大野台３−30−２ (71)出願人 593178007 吉村 進 神奈川県横浜市緑区鴨志田町529−18 (72)発明者 松井 丈雄 東京都町田市小川１−12−３ 町田コープ タウン20−202 (72)発明者 湯田坂 雅子 神奈川県川崎市多摩区南生田５−８−４− 202 (72)発明者 菊地 理恵 神奈川県大和市つきみ野２−１−６−303 (72)発明者 大木 芳正 神奈川県相模原市大野台３−30−２ (72)発明者 吉村 進 神奈川県横浜市緑区鴨志田529−18 ─────────────────────────────────────────────────── ─── Continuation of the front page (71) Applicant 592194406 Yoshimasa Oki 3-30-2 Onodai, Sagamihara-shi, Kanagawa (71) Applicant 593178007 Susumu Yoshimura 529-18 Kamoshida-cho, Midori-ku, Yokohama-shi, Kanagawa (72) Inventor Matsui Takeo Tokyo 1-12-3 Ogawa, Machida, Tokyo 20-202 Machida Coop Town (72) Inventor Masako Yudasaka 5-8-4-202 Minami Ikuta, Tama-ku, Kawasaki City, Kanagawa Prefecture (72) Rie Kikuchi Yamato, Kanagawa Prefecture 2-1-6-303 Tsukimino, Ichi (72) Yoshimasa Oki 3-30-2 Onodai, Sagamihara-shi, Kanagawa Prefecture (72) Inventor Susumu Yoshimura 529-18 Kamoshida, Midori-ku, Yokohama-shi, Kanagawa Prefecture
Claims (2)
気相蒸着によりグラファイト状窒素含有炭素膜を製造す
ることを特徴とする窒素含有炭素膜の製造方法。1. A method for producing a nitrogen-containing carbon film, which comprises producing a graphite-like nitrogen-containing carbon film by chemical vapor deposition using a nitrogen-containing cyclic organic compound as a raw material.
含まない原料を化学気相蒸着する請求項１の製造方法。2. The method according to claim 1, wherein the raw material containing no element that forms a corrosive compound such as chlorine is subjected to chemical vapor deposition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5238573A JP2898520B2 (en) | 1993-09-24 | 1993-09-24 | Method for producing nitrogen-containing carbon film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5238573A JP2898520B2 (en) | 1993-09-24 | 1993-09-24 | Method for producing nitrogen-containing carbon film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0790588A true JPH0790588A (en) | 1995-04-04 |
| JP2898520B2 JP2898520B2 (en) | 1999-06-02 |
Family
ID=17032231
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5238573A Expired - Lifetime JP2898520B2 (en) | 1993-09-24 | 1993-09-24 | Method for producing nitrogen-containing carbon film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2898520B2 (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008108009A1 (en) * | 2007-03-07 | 2008-09-12 | Tokyo Institute Of Technology | n-TYPE CARBON SEMICONDUCTOR FILM AND SEMICONDUCTOR DEVICE UTILIZING THE SAME |
| WO2008117855A1 (en) | 2007-03-28 | 2008-10-02 | Asahi Kasei Chemicals Corporation | Nitrogenous carbon material and process for producing the same |
| JP2011148686A (en) * | 2009-12-25 | 2011-08-04 | Toyota Central R&D Labs Inc | Amorphous carbon orientation film and method for forming the same |
| US8034976B2 (en) | 2005-09-30 | 2011-10-11 | Asahi Kasei Chemicals Corporation | Nitrogen-containing carbon material and method of producing the same |
| US8486565B2 (en) | 2007-03-28 | 2013-07-16 | Asahi Kasei Chemicals Corporation | Electrode, and lithium ion secondary battery, electric double layer capacitor and fuel cell using the same |
| CN104108708A (en) * | 2014-07-25 | 2014-10-22 | 深圳新宙邦科技股份有限公司 | Nitrogen-doped graphene and preparation method thereof |
| CN106185903A (en) * | 2016-07-15 | 2016-12-07 | 浙江大学 | A kind of method of ice crystal auxiliary preparation high flexibility graphene film |
-
1993
- 1993-09-24 JP JP5238573A patent/JP2898520B2/en not_active Expired - Lifetime
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8034976B2 (en) | 2005-09-30 | 2011-10-11 | Asahi Kasei Chemicals Corporation | Nitrogen-containing carbon material and method of producing the same |
| EP2527294A1 (en) | 2005-09-30 | 2012-11-28 | Asahi Kasei Chemicals Corporation | Nitrogen-containing carbon material and method of producing the same |
| WO2008108009A1 (en) * | 2007-03-07 | 2008-09-12 | Tokyo Institute Of Technology | n-TYPE CARBON SEMICONDUCTOR FILM AND SEMICONDUCTOR DEVICE UTILIZING THE SAME |
| WO2008117855A1 (en) | 2007-03-28 | 2008-10-02 | Asahi Kasei Chemicals Corporation | Nitrogenous carbon material and process for producing the same |
| US8092771B2 (en) | 2007-03-28 | 2012-01-10 | Asahi Kasei Chemicals Corporation | Nitrogen-containing carbon material and process for producing the same |
| US8486565B2 (en) | 2007-03-28 | 2013-07-16 | Asahi Kasei Chemicals Corporation | Electrode, and lithium ion secondary battery, electric double layer capacitor and fuel cell using the same |
| US8900754B2 (en) | 2007-03-28 | 2014-12-02 | Asahi Kasei Chemicals Corporation | Electrode, and lithium ion secondary battery, electric double layer capacitor and fuel cell using the same |
| JP2011148686A (en) * | 2009-12-25 | 2011-08-04 | Toyota Central R&D Labs Inc | Amorphous carbon orientation film and method for forming the same |
| CN104108708A (en) * | 2014-07-25 | 2014-10-22 | 深圳新宙邦科技股份有限公司 | Nitrogen-doped graphene and preparation method thereof |
| CN104108708B (en) * | 2014-07-25 | 2015-11-25 | 深圳新宙邦科技股份有限公司 | A kind of nitrogen-doped graphene and preparation method thereof |
| CN106185903A (en) * | 2016-07-15 | 2016-12-07 | 浙江大学 | A kind of method of ice crystal auxiliary preparation high flexibility graphene film |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2898520B2 (en) | 1999-06-02 |
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