Coating processes – With pretreatment of the base – Preapplied reactant or reaction promoter or hardener
Reexamination Certificate
1999-04-27
2001-07-10
Jones, Deborah (Department: 1775)
Coating processes
With pretreatment of the base
Preapplied reactant or reaction promoter or hardener
C148S283000, C205S205000, C205S210000, C205S258000, C427S305000, C427S253000, C427S255170, C427S255390, C427S328000, C427S404000, C427S405000, C428S469000, C428S936000, C428S938000
Reexamination Certificate
active
06258411
ABSTRACT:
BACKGROUND OF THE INVENTION
The present invention relates to an industrial material with fluorine passivated film and process of manufacturing the same, and more particularly to an industrial material such as metal, ceramics or plastics whose surface has a film passivated by fluoridation and which is preferably applicable to a manufacturing field of semiconductors, and to a process of manufacturing the above industrial material.
In general, in the process of manufacturing semiconductors, specific gases of high reactivity and corrosiveness such as BCl
3
, SiF
4
, WF
4
, or the like are used, and therefore hydrolysis occurs under the atmosphere of moisture, resulting in generation of highly corrosive acid such as hydrogen chloride, hydrogen fluoride or the like. Accordingly, when using some metal material such as aluminum or aluminum alloy as storage containers, pipelines, reaction chambers and the like for treating the above gases, there unavoidably arises a serious problem that such metal material is caused to corrode easily.
Recently, semiconductor devices have been small-sized to improve integration thereof, and various researches and developments have been made so that semiconductor devices are small-sized in the range of 1 &mgr;m to submicron of smaller than 0.2 &mgr;m may be put into practical use.
In order to improve the integration of semiconductor devices, it is necessary for semiconductors to be manufactured by the process which is kept at low temperature and with high selectivity in terms of material of substrate, thus a highly purified process atmosphere is required. In the case where an apparatus necessary for such a highly purified process atmosphere corrodes slightly, impurities produced as a result of such corrosion may be mixed with wafer of semiconductor devices, resulting in deterioration of quality of film and making it impossible to achieve accuracy of fine processing. Consequently, reliability essential for ultra-fine semiconductor devices, i.g., ULSI is lowered.
Further, in the field of excimer laser using a laser containing rare gases such as argon, krypton or xenon, or halogen gases together with rare gases, a laser oscillator is caused to corrode by fluorine due to corrosion of inside of the apparatus, thus shortening the life of the apparatus.
Furthermore, in the apparatus for treating particular halogen gas such as RIE performing directional chemical etching which is used for manufacturing integrated circuits, or CVD performing chemical vacuum evaporation to precipitate a film of reaction product by feeding a volatile compound of material to be precipitated onto the substrate and then pyrolysis or reaction thereof, the employed gas is reacted with moisture absorbed on metal surface or oxidation film of metal surface, thus generating secondary corrosive gas and resulting in secondary pollution of atmosphere in the apparatus.
In order to solve the above drawbacks, conventionally, a grounding film is formed on the metal surface by means of electroplating, vacuum evaporation or sputtering or the like, fluorine passivated film is formed on the grounding film of the metal surface, thereby preventing the metal surface from being corroded by the above-mentioned secondary corrosive gas. Such technology is disclosed in, for example, the Laid-Open patent publications No. 2-175855, No. 2-263972.
However, since the semiconductor manufacturing apparatuses, the excimer laser, and pipes attached to the apparatuses have mostly complicated shape, the grounding film cannot be uniformly formed on the inside surface of the apparatuses by means of electroplating, vacuum evaporation or sputtering or the like. Consequently, the fluorine passivated film cannot be formed on the grounding film, sufficient corrosion resistance to corrosive gas of the halogen series cannot be obtained.
Further, in the field of manufacturing semiconductors, in the case of where phosphorus is exposed on the metal surface, there occurs doping upon sputtering. Therefore, it is necessary not to expose phosphorus on the metal surface.
On the other hand, in the process of manufacturing semiconductors, nonmetal material such as plastics, ceramics or the like besides the above-mentioned metal material is used. When using the nonmetal material in the process of manufacturing semiconductors, it is necessary to form fluorine passivated film on the surface of the material to prevent gas from being released from the surface of the material or to obtain conductivity. Incidentally, in case of plastics, the fluorine passivated film must be also formed on the surface of the material from the viewpoint of corrosion resistance.
SUMMARY OF THE INVENTION
It is therefore an object of the present invention to provide an industrial material with fluorine passivated film which can extremely improve corrosion resistance to corrosive gas in metal material or plastics and can prevent gas from being released from the surface of the material and obtain conductivity, and which is effectively applicable to the field of manufacturing semiconductors.
Another object of the present invention is to provide a process of manufacturing the above industrial material with fluorine passivated film.
According to one aspect of the present invention, there is provided an industrial material comprising: a substrate; a nickel alloy film formed on the substrate and containing nickel, semimetal and/or other metal whose fluoride becomes a volatile compound; a fluorine passivated film formed at least on a surface of the nickel alloy film in such a manner that the fluorine passivated film contains nickel and does not contain said other metal or the semimetal, and satisfies stoichiometric ratio.
According to the above industrial material, the nickel alloy film comprising nickel, other metal such as tungsten or semimetal such as phosphorus, boron is formed on the substrate comprising metal such as pure metal or alloy thereof, or nonmetal such as plastics or ceramics as grounding treatment prior to forming a fluorine passivated film, and the fluorine passivated film is formed on the nickel alloy film, thereby forming extremely stable nickel alloy film by the action of said other metal such as tungsten or semimetal such as phosphorus, boron which form an alloy film together with nickel. Further, a thick and stable fluorine passivated film can be formed by the action of said other metal or semimetal contained in the nickel alloy film.
Further, when forming the fluorine passivated film, nickel contained in the nickel alloy film reacts with fluorine, and said other metal such as tungsten or semimetal such as phosphorus, boron contained in the alloy plating film reacts with fluorine. Said other metal such as tungsten or semimetal such as phosphorus, boron, and fluorine form a volatile compound (fluoride) having a low boiling point, and then the volatile compound is sublimated and discharged. Therefore, said other metal such as phosphorus, boron, tungsten, or semimetal is not contained at least on the surface of the fluorine passivated film, the fluorine passivated film is applicable to the industrial material in semiconductor manufacturing field without any bad influence.
According to another aspect of the present invention, there is provided a process of manufacturing an industrial material comprising the steps of: performing grounding treatment of a surface of a substrate; forming a nickel alloy film on the surface of the substrate, the nickel alloy film comprising nickel, semimetal and/or other metal; and forming a fluorine passivated film on the nickel alloy film.
With the above process, in the case where the nickel alloy film comprising nickel, semimetal and/or other metal is formed by, especially, electroless plating, a plating film having uniform thickness is formed of the apparatuses or pipes having very complicated shapes.
REFERENCES:
patent: 4397812 (1983-08-01), Mallory, Jr.
patent: 5009963 (1991-04-01), Ohmi et al.
patent: 0352061 (1990-01-01), None
patent: 59-13065 (1984-01-01), None
Chiba Kazuo
Ishigaki Kenji
Kikuyama Hirohisa
Maeno Matagoro
Mikasa Yutaka
Jones Deborah
Koehler Robert R.
Mitsubisi Aluminum Company, Ltd.
Quinn Charles N.
Saul Ewing LLP
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