JPH0790588A - Production of nitrigen containing carbon film - Google Patents

Abstract

PURPOSE:To form a nitrigen containing graphite-like carbon thin film by chemical vapor depositing a nitrigen-containing cyclic organic compound without applying a high temp. high pressure synthesis method. CONSTITUTION:This graphite-like nitrigen containing carbon film is formed on a substrate by evaporating the cyclic nitrigen-containing heterocyclic compound under the control of the temp. and introducing into a reaction zone with a carrier gas. An adequete material of phrrole, imidazole, pyridine, pyperidine, triazol, tetrazol or the like is used as the raw material. A hardly reactive inert gas such as Ar, He, Ne is used as the carrier gas. The reaction temp. is usually 600-1000 deg.C.

Description

Detailed Description of the Invention

[0001]

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]

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.

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.

For example, regarding BN-substituted graphite
Is BCl₃/ CCl_Four/ 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

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]

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.

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.

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]

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.

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.

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.

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.

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]

[Table 1]

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 .

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]

As described in detail above, the present invention enables the production of a nitrogen-containing graphite-like carbon thin film.

[Brief description of drawings]

FIG. 1 is a schematic view of a thin film forming apparatus according to an embodiment of the present invention.

FIG. 2 is a relationship diagram showing a relationship between an X-ray diffraction angle and intensity in an example of the present invention.

FIG. 3 shows the binding energy (C
It is a relationship diagram showing the relationship between _IS ) and the strength for each temperature.

FIG. 4 shows the binding energy (N
It is a relationship diagram showing the relationship between _IS ) and the strength for each temperature.

 ─────────────────────────────────────────────────── ─── 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)

[Claims] 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. 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.