US20170247786A1 - 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 - Google Patents
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 Download PDFInfo
- Publication number
- US20170247786A1 US20170247786A1 US15/519,885 US201515519885A US2017247786A1 US 20170247786 A1 US20170247786 A1 US 20170247786A1 US 201515519885 A US201515519885 A US 201515519885A US 2017247786 A1 US2017247786 A1 US 2017247786A1
- Authority
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- United States
- Prior art keywords
- carbonitride film
- metalloid
- metal
- film
- producing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 0 *N=C(N(*)*)N(*)* Chemical compound *N=C(N(*)*)N(*)* 0.000 description 5
- YWXFXJSMNBZQLK-UHFFFAOYSA-N CN(C)C(=N[Si](C)(C)C)N(C)C.[H]N([H])C(=N[Si](C)(C)C)N([H])[H].[H]N=C(N(C(C)C)C(C)C)N(C(C)C)C(C)C.[H]N=C(N(C)CC)N(C)CC.[H]N=C(N([H])C(C)(C)C)N([H])C(C)(C)C.[H]N=C(N([H])C1CC1)N([H])C1CC1.[H]N=C(N([H])C1CCCC1)N([H])C1CCCC1 Chemical compound CN(C)C(=N[Si](C)(C)C)N(C)C.[H]N([H])C(=N[Si](C)(C)C)N([H])[H].[H]N=C(N(C(C)C)C(C)C)N(C(C)C)C(C)C.[H]N=C(N(C)CC)N(C)CC.[H]N=C(N([H])C(C)(C)C)N([H])C(C)(C)C.[H]N=C(N([H])C1CC1)N([H])C1CC1.[H]N=C(N([H])C1CCCC1)N([H])C1CCCC1 YWXFXJSMNBZQLK-UHFFFAOYSA-N 0.000 description 1
- RXQWJHXUSOAZJG-UHFFFAOYSA-N C[Si](C)(C)N=C(N([Si](C)(C)C)[Si](C)(C)C)N([Si](C)(C)C)[Si](C)(C)C.[H]N(C(=N[Si](C)(C)C)N([H])[Si](C)(C)C)[Si](C)(C)C.[H]N([H])C(=N[Si](C)(C)C)N([H])[Si](C)(C)C.[H]N=C(N(C)C)N(C)C.[H]N=C(N([H])[H])N([H])[Si](C)(C)C.[H]N=C(N([H])[Si](C)(C)C)N([H])[Si](C)(C)C.[H]N=C(N([Si](C)(C)C)[Si](C)(C)C)N([Si](C)(C)C)[Si](C)(C)C Chemical compound C[Si](C)(C)N=C(N([Si](C)(C)C)[Si](C)(C)C)N([Si](C)(C)C)[Si](C)(C)C.[H]N(C(=N[Si](C)(C)C)N([H])[Si](C)(C)C)[Si](C)(C)C.[H]N([H])C(=N[Si](C)(C)C)N([H])[Si](C)(C)C.[H]N=C(N(C)C)N(C)C.[H]N=C(N([H])[H])N([H])[Si](C)(C)C.[H]N=C(N([H])[Si](C)(C)C)N([H])[Si](C)(C)C.[H]N=C(N([Si](C)(C)C)[Si](C)(C)C)N([Si](C)(C)C)[Si](C)(C)C RXQWJHXUSOAZJG-UHFFFAOYSA-N 0.000 description 1
- UCVRPTHUALFXQY-UHFFFAOYSA-N [H]N(C(=NC(C)(C)C)N(C)C)C(C)(C)C.[H]N(C(=NC(C)C)N(C)C)C(C)C.[H]N(C(=N[Si](C)(C)C)N(C)C)[Si](C)(C)C.[H]N(C)C(=NC)N(C)C.[H]N=C(N([H])C(C)C)N([H])C(C)C.[H]N=C(N1CC1)N1CC1.[H]N=C(N1CCCC1)N1CCCC1 Chemical compound [H]N(C(=NC(C)(C)C)N(C)C)C(C)(C)C.[H]N(C(=NC(C)C)N(C)C)C(C)C.[H]N(C(=N[Si](C)(C)C)N(C)C)[Si](C)(C)C.[H]N(C)C(=NC)N(C)C.[H]N=C(N([H])C(C)C)N([H])C(C)C.[H]N=C(N1CC1)N1CC1.[H]N=C(N1CCCC1)N1CCCC1 UCVRPTHUALFXQY-UHFFFAOYSA-N 0.000 description 1
- ADSQJKRXYFGBAI-UHFFFAOYSA-N [H]N([H])C1=NC=CC=N1.[H]N([H])C1=NC=CN1.[H]N=C(N([H])C)N([H])C.[H]N=C(N([H])[H])N([H])[H].[H]N=C1N([H])C=CN1[H].[H]N=C1N([H])CCCN1[H].[H]N=C1N([H])CCN1[H] Chemical compound [H]N([H])C1=NC=CC=N1.[H]N([H])C1=NC=CN1.[H]N=C(N([H])C)N([H])C.[H]N=C(N([H])[H])N([H])[H].[H]N=C1N([H])C=CN1[H].[H]N=C1N([H])CCCN1[H].[H]N=C1N([H])CCN1[H] ADSQJKRXYFGBAI-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
- C23C8/28—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases more than one element being applied in one step
- C23C8/30—Carbo-nitriding
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/36—Carbonitrides
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/448—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for generating reactive gas streams, e.g. by evaporation or sublimation of precursor materials
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45523—Pulsed gas flow or change of composition over time
- C23C16/45525—Atomic layer deposition [ALD]
- C23C16/45553—Atomic layer deposition [ALD] characterized by the use of precursors specially adapted for ALD
Definitions
- 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.
- metal carbonitride films or carbonitride films in which carbon exists in metalloid nitride films 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).
- an inorganic nitrogen gas such as ammonia
- a hydrocarbon gas such as acetylene
- isopropylamine is used as a source of carbon and nitrogen (carbonitriding agent)
- 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.
- 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):
- 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.
- 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.
- 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):
- 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 24 a and a nitrogen source 25 a from a metal or metalloid source supplying section 24 and a nitrogen source supplying section 25 , respectively, provided in the reaction chamber 21 .
- a metal or metalloid source 24 a and a nitrogen source 25 a 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).
- CVD Chemical Vapor Deposition process
- ALD Atomic Layer Deposition
- a guanidine compound needs to be vaporized in order to form a film on a film formation object.
- 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.
- aliphatic hydrocarbons include, for example, hexane, methylcyclohexane, ethylcyclohexane, and octane.
- aromatic hydrocarbons include, for example, toluene.
- ethers include, for example, tetrahydrofuran and dibutyl ether.
- 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.
- the film formation temperature in the present invention refers to the temperature of the film formation object during film formation.
- the guanidine compound is represented by the foregoing 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.
- Metal Source or Metalloid Source 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.
- metal halide examples include trichloroaluminum, tribromoaluminum, trifluoroaluminum, triiodoaluminum, tetrabromotitanium, tetrachlorotitanium, tetrafluorotitanium, tetraiodotitanium, tetrabromozirconium, tetrachlorozirconium, tetrafluorozirconium, tetraiodozirconium, tetrabromohafnium, tetrachlorohafnium, tetrafluorohafnium, tetraiodohafnium, pentachlorotantalum, pentachloromolybdenum, hexafluoromolybdenum, bis(cyclopentadienyl)dichloromolybdenum, hexachlorotungsten, hex
- metalloid halide examples 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.
- 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.
- XPS X-ray Photoelectron Spectroscopy
- 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: SiO 2 /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: SiO 2 /Si Substrate temperature: 250° C. Internal pressure in reaction system: 3990 Pa Vapor deposition time; 60 min.
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Chemical Vapour Deposition (AREA)
- Formation Of Insulating Films (AREA)
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014243722 | 2014-12-02 | ||
| JP2014-243722 | 2014-12-02 | ||
| PCT/JP2015/081014 WO2016088500A1 (ja) | 2014-12-02 | 2015-11-04 | 金属炭窒化膜又は半金属炭窒化膜の製造方法、金属炭窒化膜又は半金属炭窒化膜及び金属炭窒化膜又は半金属炭窒化膜の製造装置 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US20170247786A1 true US20170247786A1 (en) | 2017-08-31 |
Family
ID=56091452
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US15/519,885 Abandoned US20170247786A1 (en) | 2014-12-02 | 2015-11-04 | 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 |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US20170247786A1 (ja) |
| JP (1) | JP6361048B2 (ja) |
| KR (1) | KR20170091090A (ja) |
| CN (1) | CN107109642A (ja) |
| TW (1) | TW201634732A (ja) |
| WO (1) | WO2016088500A1 (ja) |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4434149B2 (ja) * | 2006-01-16 | 2010-03-17 | 東京エレクトロン株式会社 | 成膜方法、成膜装置及び記憶媒体 |
| US8142847B2 (en) * | 2007-07-13 | 2012-03-27 | Rohm And Haas Electronic Materials Llc | Precursor compositions and methods |
| JP5064296B2 (ja) * | 2008-05-21 | 2012-10-31 | 東京エレクトロン株式会社 | シリコン炭窒化膜の形成方法および形成装置 |
| JP6371223B2 (ja) * | 2012-12-21 | 2018-08-08 | 国立研究開発法人理化学研究所 | ｇ−Ｃ３Ｎ４フィルムの製造方法およびその利用 |
-
2015
- 2015-11-04 KR KR1020177013000A patent/KR20170091090A/ko unknown
- 2015-11-04 US US15/519,885 patent/US20170247786A1/en not_active Abandoned
- 2015-11-04 CN CN201580058152.XA patent/CN107109642A/zh active Pending
- 2015-11-04 WO PCT/JP2015/081014 patent/WO2016088500A1/ja active Application Filing
- 2015-11-04 JP JP2016562355A patent/JP6361048B2/ja not_active Expired - Fee Related
- 2015-12-01 TW TW104140207A patent/TW201634732A/zh unknown
Also Published As
| Publication number | Publication date |
|---|---|
| JP6361048B2 (ja) | 2018-07-25 |
| WO2016088500A1 (ja) | 2016-06-09 |
| CN107109642A (zh) | 2017-08-29 |
| TW201634732A (zh) | 2016-10-01 |
| JPWO2016088500A1 (ja) | 2017-05-25 |
| KR20170091090A (ko) | 2017-08-08 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| AS | Assignment |
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