METHOD FOR PRODUCING METAL CARBONITRIDE FILM OR METALLOID CARBONITRIDE FILM, METAL CARBONITRIDE FILM OR METALLOID CARBONITRIDE FILM, AND APPARATUS FOR PRODUCING METAL CARBONITRIDE FILM OR METALLOID CARBONITRIDE FILM

Abstract

Provided is a method and apparatus that can form a metal carbonitride film or a metalloid carbonitride film at low temperature. 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.

Description

TECHNICAL FIELD

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.

BACKGROUND ART

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).

CITATION LIST

Patent Literature

• Patent Literature 1: JP-A-2007-189173
• Patent Literature 2: JP-A-2009-283587

SUMMARY OF INVENTION

Technical Problem

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.

Solution to Problem

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.

Advantageous Effects of Invention

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.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 is a schematic view showing an apparatus for producing a metal carbonitride film or a metalloid carbonitride film according to one embodiment of the present invention.

DESCRIPTION OF EMBODIMENTS

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 FIG. 1, a film 26 is formed by supplying, to a film formation object 23 placed on a placement section 22 provided in a reaction chamber 21 of an apparatus 20 for producing a metal carbonitride film or a metalloid carbonitride film, a metal or metalloid source 24a and a nitrogen source 25a from a metal or metalloid source supplying section 24 and a nitrogen source supplying section 25, respectively, provided in the reaction chamber 21. No particular limitation is placed on the method for producing a metal carbonitride film or a metalloid carbonitride film. A metal carbonitride film or a metalloid carbonitride film can be produced, for example, by vapor deposition, such as the CVD process (Chemical Vapor Deposition process; hereinafter, referred to as the CVD process) or the ALD (Atomic Layer Deposition; hereinafter, referred to as the ALD process).

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.

EXAMPLES

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.

Examples 1 to 3

Vapor Deposition Test; Production of Silicon Carbonitride Films

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.

	TABLE 1
		Characteristics of Silicon
	Film Formation Conditions	Carbonitride Film
Example 1	Guanidine compound: (9)	Film thickness: 300 nm
	Vaporization temperature of guanidine compound: 30° C.	XPS analysis; silicon carbonitride
	Flow rate of Ar carrier for guanidine compound:	film
	5 ml/min.
	Silicon source; hexachlorodisilane
	Vaporization temperature of hexachlorodisilane: 30° C.
	Flow rate of Ar carrier for hexachlorodisilane: 5 ml/min.
	Substrate material: SiO2/Si
	Substrate temperature: 500° C.
	Internal pressure in reaction system: 3990 Pa
	Vapor deposition time; 60 min.
Example 2	Guanidine compound: (9)	Film thickness: 100 nm
	Vaporization temperature of guanidine compound: 30° C.	XPS analysis; silicon carbonitride
	Flow rate of Ar carrier for guanidine compound:	film
	5 ml/min.
	Silicon source; hexachlorodisilane
	Vaporization temperature of hexachlorodisilane: 30° C.
	Flow rate of Ar carrier for hexachlorodisilane: 5 ml/min.
	Substrate material: SiO2/Si
	Substrate temperature: 350° C.
	Internal pressure in reaction system: 3990 Pa
	Vapor deposition time; 60 min.
Example 3	Guanidine compound: (9)	Film thickness: 30 nm
	Vaporization temperature of guanidine compound: 30° C.	XPS analysis; silicon carbonitride
	Flow rate of Ar carrier for guanidine compound:	film
	5 ml/min.
	Silicon source: hexachlorodisilane
	Vaporization temperature of hexachlorodisilane: 30° C.
	Flow rate of Ar carrier for hexachlorodisilane: 5 ml/min.
	Substrate material: SiO2/Si
	Substrate temperature: 250° C.
	Internal pressure in reaction system: 3990 Pa
	Vapor deposition time; 60 min.

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.

REFERENCE SIGNS LIST

• 20 apparatus for producing a metal carbonitride film or a metalloid carbonitride film
• 21 reaction chamber
• 22 placement section
• 23 film formation object
• 24 metal or metalloid source supplying section
• 24a metal or metalloid source
• 25 nitrogen source supplying section
• 25a nitrogen source
• 26 film

Claims

1. A method for producing a metal carbonitride film or a metalloid carbonitride film, the method comprising forming a metal carbonitride film or a metalloid carbonitride film 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.

2. The method for producing a metal carbonitride film or a metalloid carbonitride film according to claim 1, wherein a silicon carbonitride film is formed as the metalloid carbonitride film.

3. The method for producing a metal carbonitride film or a metalloid carbonitride film according to claim 1, wherein a guanidine compound solution containing at least one solvent selected from the group consisting of aliphatic hydrocarbons, aromatic hydrocarbons, and ethers is used as the nitrogen source.

4. The method for producing a metal carbonitride film or a metalloid carbonitride film according to claim 1, wherein a metal halide or a metalloid halide is used as the metal source or the metalloid source.

5. The method for producing a metal carbonitride film or a metalloid carbonitride film according to claim 1, wherein a film formation temperature for the metal carbonitride film or the metalloid carbonitride film is below 600° C.

6. The method for producing a metal carbonitride film or a metalloid carbonitride film according to claim 5, wherein the film formation temperature for the metal carbonitride film or the metalloid carbonitride film is below 550° C.

7. The method for producing a metal carbonitride film or a metalloid carbonitride film according to claim 6, wherein the film formation temperature for the metal carbonitride film or the metalloid carbonitride film is not more than 500° C.

8. A metal carbonitride film or metalloid carbonitride film obtained by the method for producing a metal carbonitride film or a metalloid carbonitride film according to claim 1.

9. An apparatus for producing a metal carbonitride film or a metalloid carbonitride film, the apparatus being for use in the method for producing a metal carbonitride film or a metalloid carbonitride film according to claim 1, the apparatus comprising:

a reaction chamber including a placement section in which a film formation object is to be placed;

a metal or metalloid source supplying section that supplies the metal source or the metalloid source into the reaction chamber; and

a nitrogen source supplying section that supplies the nitrogen source into the reaction chamber.