PRODUCTION OF CARBON FILMS

Abstract: Disclosed is a method for preparing pyrolytic carbon films with highly ordered graphite structure at relatively low temperature comprising thermal decomposing an organic compounds introduced by a carrier gas into a reaction chamber to deposit the carbon films onto a single-crystalline substrate. The present invention also is to provide a method for preparing graphite intercalation compounds with metal or metal compounds consisting of a simultaneous thermal decomposition of two kinds of starting materials, modified CVD (Chemical vapor deposition) method in which hydrocar­ bon as a source material for the host graphite and other organometal reagents or metal halides for guest metal species or metal compound are decomposed at a same time in a reactor in order to intercalate the metal species or metal compound into carbon being depositing on the substrate. Further, the present invention is to provide a doped carbon film which is capable of P-type or N-type according to kinds of dopant species obtained by partial substitution of dopants for carbon atoms which constitute graphite hexagonal net layer during the growth of carbon films, through simul­ taneous thermal decomposition of two kinds of source materials for carbon films and for dopant to be substituted.

Description: The present invention relates to a process for preparing a pyrolitic carbon film. The graphite has such unique properties associated with its layer structure as anisotropies in thermal and electrical conductivity. However, the synthesis of graphite is required extreme conditions of pressure and temperature due to the fact that it has inaccessible melting point and the extremely low sublimation pressure. For example, so called HOPG is prepared by decomposing a gaseous hydrocarbon (e.g. methane) at 2,000°C and then hot pressing the resulting pyrolytic material at still higher temperature. It is now well known that most carboneceous materials are well graphitized when they are subjected to a heat treatment at higher temperature above 2,500°C. On the other hand, there have been many efforts to prepare pyrolytic carbons, at the low decomposition temperature utilizing dehydrogenation, dehydrohalogenation, decarbonic acid, dehydration of selected hydrocarbons. However, carbon deposits thus obtained are of so poorly ordered state that they are insufficient to provide anisotropic materials or device. There also has been known carbon fiber which is obtained by heat treatment of fibrous polymer compound at high temperature. These carbon fibers are widely used for structural materials, but their unstableness in physical properties debases the usefulness for new electronic materials or device utilizing anisotropic electrical and thermal conductivity due to lack of reproducibility. JP-A-59 232 904 describes a method for preparing a pyrolytic carbon film, wherein diethynylbenzene, together with a carrier gas, is introduced into a reaction chamber, is thermally decomposed at a temperature of preferably about 600 to 1000 °C and the carbon film is deposited onto different substrates, e.g. a quartz substrate. The present invention is to provides a method for preparing pyrolytic carbon films with highly ordered graphite structure at relatively low temperature. The method comprises thermal decomposition of benzene introduced by a carrier gas into a reaction chamber to deposit the carbon films onto a single-crystalline substrate. The Figure shows a schematical view of the apparatus for preparing the pyrolytic carbon film of the present invention. Benzene employed in the present invention as a starting material is generally decomposed approximately at 1,000°C. A method for supplying benzene includes bubbling method, vaporization method, sublimation method and the like. The carrier gas used to introduce benzene into the reaction chamber is hydrogen or an inert gas, such as argon, nitrogen. When the bubbling method for supplytig benzene is employed, hydrogen or argon is preferable for the carrier gas. The establishment of low temperature growth of pyrolytic carbon films provides practical utilization of its anisotropic properties to new electronic material. The single-crystalline substrate includes silicon, sapphire, silicon carbide (including alpha-type and beta-type), boron nitride, kish graphite, high orientation graphite and the like, which is required to have no modification at about 1,000°C. The following example illustrates the present invention, but it is not construed as limiting the present invention. Example In the Fig., benzene is selected as a starting material and the bubbling method using argon as carrier gas is employed for the preparation of pyrolytic carbon films. The low pressure CVD can also be achieved with the apparatus shown in the Fig. This method can provide carbon films in uniform thickness compared with bubbling method under atmospheric pressure. Benzene moleculars are introduces by bubbling method of the carrier gas into a quartz reaction tube 4 through a pyrex glass tube 3 from a feed stock 1 wherein benzene purified through vacuum distillation is accommodated. Supply rate of benzene is determined by valve 5 which regulates the flow rate of Ar bubbling gas in which benzene vapor is saturated. In order to supply benzene strictly at constant rate of several mmol/hour, the feed stock is kept at constant temperature. The benzene partial concentration is controlled by another Ar gas flow through pyrex tube 6. A piece of single-crystalline substrate, placed at the center position on the pedestol 7, is heated up to 1,000°C by the heating furnace 8 around the reaction tube 4. Thus benzene molecules led into the reaction tube 4 are thermally decomposed at 1,000°C and the carbon deposit having luster are formed on the single-crystalline substrate. The remaining vapor led to the reaction tube 4 is discharged outside 10 through a discharge pipe 9. The density of carbon deposits obtained were determined to be 2.1±0.1g/cm² by the float method using a mixture of carbon tetrachloride and methane dibromide. Infrared spectrum of the carbon films did not show the existence of -CH, -CH₂ and -CH₃.

Claims: Process for preparing pyrolytic carbon film having a highly ordered graphite structure which comprises introducing benzene together with a carrier gas into a reaction chamber, thermally decomposing said benzene at a temperature up to 1000 °C, and depositing the carbon film onto a single-crystalline substrate.

Inventors: HIGASHIGAKI, YOSHIYUKI, INOGUCHI, TOSHIO, NAKAJIMA, SHIGEO, SUZUKI, TOMONARI, YOSHIMOTO, YOSHIKASU
Applicants: SHARP KABUSHIKI KAISHA
Application year: 1986
Main classification: C23C16
IPC codes: C30B25, C23C16, C01B31