Patent Application
20170247786
The present invention relates to a method for producing a metal carbonitride film or a metalloid carbonitride film using a guanidine compound, a metal carbonitride film or a metalloid carbonitride film, and an apparatus for producing a metal carbonitride film or a metalloid carbonitride film.
Recently, in the field of semiconductors, electronic components, and the like, much research and development has been done on highly chemical-resistant “metal carbonitride films or carbonitride films in which carbon exists in metalloid nitride films”. As methods for producing a metal carbonitride film or a metalloid carbonitride film, there are known, for example, a method for producing it by combining an inorganic nitrogen gas, such as ammonia, and a hydrocarbon gas, such as acetylene (see Patent Literature 1) and a method in which isopropylamine is used as a source of carbon and nitrogen (carbonitriding agent) (see Patent Literature 2).
However, the methods for producing a metal carbonitride film or a metalloid carbonitride film according to Patent Literatures 1 and 2 have a problem that a metal carbonitride film or a metalloid carbonitride film has a high film formation temperature.
A principal object of the present invention is to provide a method and apparatus that can form a metal carbonitride film or a metalloid carbonitride film at low temperature.
In a method for producing a metal carbonitride film or a metalloid carbonitride film according to the present invention, a metal carbonitride film or a metalloid carbonitride film is formed by supplying onto a film formation object a nitrogen source and a metal source or a metalloid source, the nitrogen source containing a guanidine compound represented by the following general formula (1):
where a plurality of Rs are the same or different, each represent a hydrogen atom, a linear, branched or cyclic alkyl group of 1 to 5 carbon atoms or a trialkylsilyl group of 1 to 9 carbon atoms, and, depending on circumstances, bond to each other to form a ring.
A metal carbonitride film or a metalloid carbonitride film according to the present invention is one obtained by the method for producing a metal carbonitride film or a metalloid carbonitride film according to the present invention.
An apparatus for producing a metal carbonitride film or a metalloid carbonitride film according to the present invention is an apparatus for producing a metal carbonitride film or a metalloid carbonitride film for use in the method for producing a metal carbonitride film or a metalloid carbonitride film according to the present invention. The apparatus for producing a metal carbonitride film or a metalloid carbonitride film according to the present invention includes a reaction chamber, a metal or metalloid source supplying section, and a nitrogen source supplying section. The reaction chamber includes a placement section in which a film formation object is to be placed. The metal or metalloid source supplying section supplies the metal source or the metalloid source into the reaction chamber. The nitrogen source supplying section supplies the nitrogen source into the reaction chamber.
According to the present invention, it is possible to provide a method and apparatus that can form a metal carbonitride film or a metalloid carbonitride film at low temperature.
In a method for producing a metal carbonitride film or a metalloid carbonitride film according to this embodiment, a metal carbonitride film or a metalloid carbonitride film is formed by supplying onto a film formation object a nitrogen source and a metal source or a metalloid source, the nitrogen source containing a guanidine compound represented by the following general formula (1):
where a plurality of Rs are the same or different, each represent a hydrogen atom, a linear, branched or cyclic alkyl group of 1 to 5 carbon atoms or a trialkylsilyl group of 1 to 9 carbon atoms, and, depending on circumstances, bond to each other to form a ring. Specifically, as shown in
In the CVD process and the ALD process, a guanidine compound needs to be vaporized in order to form a film on a film formation object. For example, only a guanidine compound may be supplied into a vaporizing chamber and vaporized therein or a guanidine compound solution in which a guanidine compound is diluted in a solvent may be supplied to the vaporizing chamber and vaporized therein.
Examples of the solvent for the guanidine compound solution include aliphatic hydrocarbons, aromatic hydrocarbons, and ethers. These solvents may be used alone or in combinations of some of them.
Specific examples of aliphatic hydrocarbons include, for example, hexane, methylcyclohexane, ethylcyclohexane, and octane.
Specific examples of aromatic hydrocarbons include, for example, toluene.
Specific examples of ethers include, for example, tetrahydrofuran and dibutyl ether.
In vapor-depositing a metal carbonitride film or a metalloid carbonitride film using a guanidine compound, for example, the internal pressure in the reaction chamber 21 is preferably 1 Pa to 200 kPa and more preferably 10 Pa to 110 kPa. The film formation temperature is preferably below 600° C., more preferably below 550° C., and still more preferably not more than 500° C. The film formation temperature is preferably not less than 100° C. and more preferably not less than 200° C. The temperature for vaporizing the guanidine compound is preferably 0° C. to 180° C. and more preferably 10° C. to 100° C. The content of gas of the guanidine compound in the amount of gas to be supplied into the reaction chamber 21 is preferably 0.1% to 99% by volume and more preferably 0.5% to 95% by volume.
Note that the film formation temperature in the present invention refers to the temperature of the film formation object during film formation.
(Guanidine Compound)
The guanidine compound is represented by the foregoing general formula (1). In the general formula (1), a plurality of Rs are the same or different and each represent a hydrogen atom, a linear, branched or cyclic alkyl group of 1 to 5 carbon atoms or a trialkylsilyl group of 1 to 9 carbon atoms.
Examples of the linear, branched or cyclic alkyl group of 1 to 5 carbon atoms include, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, a pentyl group, a cyclopropyl group, a cyclobutyl group, and a cyclopentyl group.
Examples of the trialkylsilyl group of 1 to 9 carbon atoms include, for example, a trimethylsilyl group, a triethylsilyl group, a dimethylethylsilyl group, and a methyldiethylsilyl group.
The plurality of Rs may bond to each other to form a ring and examples of the ring to be formed include, for example, saturated or unsaturated rings of 2 to 10 carbon atoms.
Specific examples of the guanidine compound that is preferably used include, for example, guanidine compounds represented by Formulae (2) to (29) below. These guanidine compounds may be used alone or in combinations of two or more of them.
(Metal Source or Metalloid Source)
The metal source or metalloid source that is preferably used is, for example, a metal halide or a metalloid halide.
Examples of the metal halide include trichloroaluminum, tribromoaluminum, trifluoroaluminum, triiodoaluminum, tetrabromotitanium, tetrachlorotitanium, tetrafluorotitanium, tetraiodotitanium, tetrabromozirconium, tetrachlorozirconium, tetrafluorozirconium, tetraiodozirconium, tetrabromohafnium, tetrachlorohafnium, tetrafluorohafnium, tetraiodohafnium, pentachlorotantalum, pentachloromolybdenum, hexafluoromolybdenum, bis(cyclopentadienyl)dichloromolybdenum, hexachlorotungsten, hexafluorotungsten, dibromocobalt, dichlorocobalt, difluorocobalt, diiodocobalt, dibromonickel, dichloronickel, diiodonickel, dibromomanganese, dichloromanganese, difluoromanganese, diiodomanganese, monobromocopper, dibromocopper, monochlorocopper, dichlorocopper, difluorocopper, diiodocopper, tribromogallium, trichlorogallium, trifluorogallium, triiodogallium, tribromobismuth, trichlorobismuth, trifluorobismuth, triiodobismuth, tribromoruthenium, trichlororuthenium, trifluororuthenium, trichlororhodium, dibromoplatinum, dichloroplatinum, tetrachloroplatinum, diiodoplatinum, dibromopalladium, dichloropalladium, diiodopalladium, triiodoruthenium, benzenedichlororuthenium, dibromozinc, dichlorozinc, difluorozinc, and diiodozinc.
Examples of the metalloid halide include tetrachlorosilane, tetrafluorosilane, hexachlorodisilane, chloropentamethyldisilane, dichlorotetramethyldisilane, monochlorosilane, dichlorosilane, trichlorosilane, tetrabromogermanium, tetrachlorogermanium, tetraiodogermanium, tribromoboron, trichloroboron, trifluoroboron, and triiodoboron.
The method for producing a metal carbonitride film or a metalloid carbonitride film according to the present invention is suitable particularly for producing a silicon carbonitride film.
Next, the present invention will be described in concrete terms with reference to examples but the scope of the present invention is not limited to these examples.
Each film was formed on a 20 mm×20 mm substrate by the CVD process using the guanidine compound shown in Table 1 under the conditions shown in Table 1. Furthermore, the formed film was analyzed by XPS (X-ray Photoelectron Spectroscopy) to identify the film.
It can be seen from the above results that with the use of a guanidine compound, a silicon carbonitride film can be produced at low temperature.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2014-243722 | Dec 2014 | JP | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/JP2015/081014 | 11/4/2015 | WO | 00 |
