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WO2010032679A1 - Material used for forming nickel-containing film and method for manufacturing the nickel-containing film - Google Patents

Material used for forming nickel-containing film and method for manufacturing the nickel-containing film Download PDF

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Publication number
WO2010032679A1
WO2010032679A1 PCT/JP2009/065851 JP2009065851W WO2010032679A1 WO 2010032679 A1 WO2010032679 A1 WO 2010032679A1 JP 2009065851 W JP2009065851 W JP 2009065851W WO 2010032679 A1 WO2010032679 A1 WO 2010032679A1
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Prior art keywords
nickel
film
containing film
forming material
confirmed
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PCT/JP2009/065851
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French (fr)
Japanese (ja)
Inventor
隆典 青木
孝充 小林
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Resonac Holdings Corp
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Showa Denko KK
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Priority to JP2010529734A priority Critical patent/JPWO2010032679A1/en
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    • H10P14/43—
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • 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
    • C23C16/06—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 metallic material
    • C23C16/18—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 metallic material from metallo-organic compounds
    • 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
    • C23C16/42—Silicides
    • H10D64/01316—

Definitions

  • the present invention relates to a nickel-containing film forming material and a method for producing a nickel-containing film. More specifically, the present invention relates to a nickel-containing film forming material used for film formation by chemical vapor deposition (CVD) and a method for producing a nickel-containing film using the material.
  • CVD chemical vapor deposition
  • a silicide film is formed on the diffusion layer of the gate electrode, the source or the drain, thereby further reducing the resistance.
  • introduction of a nickel silicide film having a resistance lower than that of a titanium silicide film or a cobalt silicide film has been studied.
  • This nickel silicide film has been formed by a sputtering method so far.
  • a sputtering method there is a concern about physical damage to the semiconductor element, and uniform film formation is difficult.
  • CVD chemical vapor deposition
  • CVD is a method of depositing a film on a silicon substrate by volatilizing a film forming material and flowing it in a gas state and utilizing a chemical reaction in a reactor.
  • CVD can be performed at a low temperature by film formation under reduced pressure, but the conditions for film formation vary greatly depending on the film forming material used.
  • a characteristic required for the film forming material used at this time includes a high vapor pressure.
  • the formed nickel-containing film contains carbon. There was a problem that was likely to remain. When carbon remains, for example, the resistance value of the nickel-containing film tends to increase.
  • tetrakis (trifluorophosphine) nickel is less likely to remain carbon in the nickel-containing film formed due to the weak interaction between nickel and the unshared electron pair of the phosphorus trifluorophosphine ligand,
  • HF was produced as a by-product due to cleavage of the PF bond of the ligand during film formation.
  • the formed nickel-containing film tends to be damaged.
  • the present invention is intended to solve the problems associated with the prior art as described above, and provides a nickel-containing film forming material in which carbon does not easily remain in a formed nickel-containing film and HF is not easily produced as a by-product. There is to do. Furthermore, it is providing the nickel containing film forming material whose nickel containing film is a nickel film or a nickel silicide film.
  • Another object of the present invention is to provide a method for producing a nickel-containing film using the nickel-containing film forming material. Furthermore, it is providing the manufacturing method of the nickel containing film whose nickel containing film is a nickel film or a nickel silicide film.
  • the present inventors can form a stable film by CVD using a nickel-containing film forming material containing a nickel complex in which two or more specific ligands are coordinated. At the same time, it has been found that carbon is unlikely to remain in the formed nickel-containing film, and that HF is hardly produced as a by-product during film formation. Furthermore, the present inventors have found that the nickel-containing film forming material is suitable for forming a nickel silicide film. The nickel-containing film forming material of the present invention has not yet been reported.
  • the present invention relates to the following.
  • the ligands are of two types, PF 3 and PF 2 R 1 (where R 1 is H, an alkyl group having 1 to 6 carbon atoms, or a phenyl group) [1] The nickel-containing film-forming material described in 1.
  • the type of the ligand is PF 3 and PF 2 NR 4 R 5 (wherein R 4 and R 5 are each independently H, an alkyl group having 1 to 6 carbon atoms, or a phenyl group).
  • the nickel-containing film forming material according to [1] which is two types of the above.
  • the Si source of the nickel silicide film is Si a H 2a + 2 (where a is an integer of 1 to 3) or R b SiH 4-b (where b is an integer of 1 to 3) And R represents an alkyl group having 1 to 3 carbon atoms.)
  • the nickel-containing film-forming material according to [12] which is at least one silicon compound represented by the structural formula:
  • a stable nickel-containing film can be formed by CVD, carbon is unlikely to remain in the formed nickel-containing film, and HF is hardly generated as a by-product during film formation. That is, by using the nickel-containing film forming material of the present invention, a good nickel-containing film and further a good nickel silicide film can be easily formed by CVD.
  • the nickel-containing film forming material of the present invention contains at least one nickel complex having four specific ligands, and the type of the ligand is CO, PF 3 , PF 2 (CF 3 ), PF (CF 3) 2, P (CF 3 ) 3, PF 2 R 1, PFR 2 R 3, PF 2 NR 4 R 5, P (CF 3) 2 CH 2 CH 2 P (CF 3) 2 and P (CF 3) 2 CF 2 CF 2 P (CF 3 ) 2 (wherein R 1 to R 5 are each independently H, an alkyl group having 1 to 6 carbon atoms or a phenyl group, and P (CF 3 ) 2 CH 2 CH 2 P (CF 3 ) 2 and P (CF 3 ) 2 CF 2 CF 2 P (CF 3 ) 2 are equivalent to two ligands.) It is said.
  • Examples of the ligand include CO, PF 3 , PF 2 (CF 3 ), PF (CF 3 ) 2 , P (CF 3 ) 3 , and PF 2 R 1 (where R 1 is H, carbon number) 1 to 6 alkyl groups or phenyl groups), PFR 2 R 3 (wherein R 2 and R 3 are each independently H, an alkyl group having 1 to 6 carbon atoms or a phenyl group), PF 2 NR 4 R 5 (wherein R 4 and R 5 are each independently H, an alkyl group having 1 to 6 carbon atoms or a phenyl group), preferably CO, PF 3 , PF 2 (CF 3 ), PF (CF 3 ) 2 , P (CF 3 ) 3 , PF 2 R 1 (where R 1 is H, an alkyl group having 1 to 6 carbon atoms or a phenyl group), PF 2 NR 4 R 5 (wherein R 4 and R 5 are each independently H, an alkyl group having 1 to 6
  • the vapor pressure of the nickel complex tends to increase.
  • a nickel complex has high volatility, it can be suitably used for a film forming method in which a film forming material is volatilized, for example, CVD.
  • the nickel-containing film forming material of the present invention includes, for example, a nickel complex in which the types of the ligands are CO and PF 3 .
  • a nickel complex in which the types of the ligands are CO and PF 3 .
  • the nickel complex include Ni (CO) 3 (PF 3 ), Ni (CO) 2 (PF 3 ) 2 or Ni (CO) (PF 3 ) 3 .
  • the vapor pressure tends to increase.
  • a nickel complex has high volatility, it can be suitably used for a film forming method in which a film forming material is volatilized, for example, CVD.
  • the nickel-containing film forming material of the present invention includes, for example, a nickel complex whose ligands are CO and PF 2 (CF 3 ).
  • a nickel complex whose ligands are CO and PF 2 (CF 3 ).
  • the nickel complex include Ni (CO) 2 (PF 2 (CF 3 )) 2 or Ni (CO) (PF 2 (CF 3 )) 3 .
  • the vapor pressure tends to increase.
  • a nickel complex has high volatility, it can be suitably used for a film forming method in which a film forming material is volatilized, for example, CVD.
  • the nickel-containing film forming material of the present invention includes, for example, a nickel complex in which the ligands are CO and PF (CF 3 ) 2 .
  • the nickel complex include Ni (CO) 2 (PF (CF 3 ) 2 ) 2 or Ni (CO) (PF (CF 3 ) 2 ) 3 .
  • the vapor pressure tends to increase.
  • such a nickel complex has high volatility, it can be suitably used for a film forming method in which a film forming material is volatilized, for example, CVD.
  • the nickel-containing film forming material of the present invention includes, for example, a nickel complex in which the types of the ligands are CO and P (CF 3 ) 3 .
  • a nickel complex in which the types of the ligands are CO and P (CF 3 ) 3 .
  • the nickel complex include Ni (CO) 2 (P (CF 3 ) 3 ) 2 or Ni (CO) (P (CF 3 ) 3 ) 3 .
  • the vapor pressure tends to increase.
  • a nickel complex has high volatility, it can be suitably used for a film forming method in which a film forming material is volatilized, for example, CVD.
  • the nickel-containing film forming material of the present invention includes, for example, Ni (CO) 2 (P (CF 3 ) 2 CH 2 CH 2 P (CF 3 ) 2 ). With such a nickel complex, the vapor pressure tends to increase. Moreover, since such a nickel complex has high volatility, it can be suitably used for a film forming method in which a film forming material is volatilized, for example, CVD.
  • the nickel-containing film forming material of the present invention includes, for example, Ni (CO) 2 (P (CF 3 ) 2 CF 2 CF 2 P (CF 3 ) 2 ).
  • Ni (CO) 2 (P (CF 3 ) 2 CF 2 CF 2 P (CF 3 ) 2 Ni (CO) 2 (P (CF 3 ) 2 CF 2 CF 2 P (CF 3 ) 2 ).
  • the vapor pressure tends to increase.
  • a nickel complex has high volatility, it can be suitably used for a film forming method in which a film forming material is volatilized, for example, CVD.
  • the nickel-containing film forming material of the present invention includes, for example, a nickel complex in which the type of the ligand is PF 3 and PF 2 (CF 3 ).
  • Specific examples of the nickel complex include Ni (PF 3 ) 2 (PF 2 (CF 3 )) 2 or Ni (PF 3 ) 3 (PF 2 (CF 3 )).
  • the vapor pressure tends to increase.
  • such a nickel complex has high volatility, it can be suitably used for a film forming method in which a film forming material is volatilized, for example, CVD.
  • the type of the ligand is PF 3 and PF 2 R 1 (where R 1 is H, an alkyl group having 1 to 6 carbon atoms, or a phenyl group).
  • R 1 is preferably CH 3 , C 2 H 5 , C 3 H 7 , C 4 H 9 , cyclo-C 6 H 11 or C 6 H 5 .
  • nickel complex examples include Ni (PF 3 ) 2 (PF 2 (CH 3 )) 2 , Ni (PF 3 ) (PF 2 (CH 3 )) 3 , Ni (PF 3 ) 3 (PF 2 (C 2 H 5 )), Ni (PF 3 ) 2 (PF 2 (C 2 H 5 )) 2 , Ni (PF 3 ) 2 (PF 2 (C 3 H 7 )) 2 , Ni (PF 3 ) (PF 2 (C 3 H 7 )) 3 , Ni (PF 3 ) 3 (PF 2 (cyclo-C 6 H 11 )) or Ni (PF 3 ) 3 (PF 2 (C 6 H 5 )).
  • the vapor pressure tends to increase.
  • a nickel complex has high volatility, it can be suitably used for a film forming method in which a film forming material is volatilized, for example, CVD.
  • the type of the ligand is PF 3 and PFR 2 R 3 (wherein R 2 and R 3 are each independently H, an alkyl group having 1 to 6 carbon atoms, or Represents a phenyl group).
  • R 2 and R 3 are preferably each independently CH 3 , C 2 H 5 , C 3 H 7 , C 4 H 9 , cyclo-C 6 H 11 or C 6 H 5 .
  • nickel complex examples include Ni (PF 3 ) 3 (PF (CH 3 ) (C 2 H 5 )), Ni (PF 3 ) 2 (PF (CH 3 ) (C 2 H 5 )) 2 , Ni (PF 3 ) (PF (CH 3 ) (C 2 H 5 )) 3 and the like.
  • PF 3 ) 3 PF (CH 3 ) (C 2 H 5 )
  • Ni (PF 3 ) 2 PF (CH 3 ) (C 2 H 5 )
  • Ni (PF 3 ) (PF (CH 3 ) (C 2 H 5 )) 3 Ni (PF 3 ) (PF (CH 3 ) (C 2 H 5 )) 3 and the like.
  • the nickel-containing film-forming material of the present invention has, for example, the types of the ligands PF 3 and PF 2 NR 4 R 5 (wherein R 4 and R 5 are each independently H, alkyl having 1 to 6 carbon atoms) A nickel complex which is a group or a phenyl group.
  • R 4 and R 5 are preferably each independently H, CH 3 , C 2 H 5 , C 3 H 7 , C 4 H 9 , cyclo-C 6 H 11 or C 6 H 5 .
  • nickel complex examples include Ni (PF 3 ) 2 (PF 2 NH 2 ) 2 , Ni (PF 3 ) 3 (PF 2 NH (CH 3 )), Ni (PF 3 ) 2 (PF 2 NH (CH 3 )) 2 , Ni (PF 3 ) (PF 2 NH (CH 3 )) 3 , Ni (PF 3 ) 3 (PF 2 NH (C 2 H 5 )), Ni (PF 3 ) 3 (PF 2 NH (C 3 H 7 )), Ni (PF 3 ) 3 (PF 2 NH (C 4 H 9 )) or Ni (PF 3 ) 3 (PF 2 N (C 2 H 5 ) 2 ).
  • the vapor pressure tends to increase.
  • a nickel complex has high volatility, it can be suitably used for a film forming method in which a film forming material is volatilized, for example, CVD.
  • a nickel-containing film forming material containing at least one kind of nickel complex as described above When a nickel-containing film forming material containing at least one kind of nickel complex as described above is used, carbon does not easily remain in the formed nickel-containing film, and HF is hardly generated as a by-product during film formation. In particular, a stable nickel-containing film can be easily formed by CVD.
  • the nickel-containing film forming material of the present invention can also contain two or more of the above nickel complexes.
  • the nickel-containing film forming material of the present invention can also contain a rare gas such as helium, neon, argon or krypton.
  • the method for producing the nickel complex contained in the nickel-containing film forming material of the present invention can be produced by a known method.
  • it can be produced by ligand exchange with a ligand of a nickel complex intended for tetracarbonyl nickel or dicyclopentadienyl nickel.
  • the nickel complex can be purified by a known method as necessary.
  • the purification method include distillation or adsorption.
  • the nickel-containing film forming material of the present invention is preferably used for film formation by CVD, but is not limited to CVD as long as it is a film forming method using vapor of the nickel-containing film forming material.
  • the method for producing a nickel-containing film of the present invention forms a film by chemical vapor deposition (CVD) using the nickel-containing film forming material.
  • various CVDs that decompose the nickel complex as a Ni source can be used. That is, as various types of CVD, thermal CVD that thermally decomposes, photo CVD that decomposes by heat and light, plasma CVD that activates and decomposes by plasma, laser-assisted CVD that activates and decomposes by laser, and active by ion beam For example, ion beam assisted CVD for photolysis and photolysis. These various types of CVD can be used as a method for forming a nickel-containing film.
  • the reaction pressure when forming the nickel-containing film is preferably 0.0013 to 101.3 kPa, more preferably 0.013 to 101.3 kPa, and still more preferably 0.13 to 101.3 kPa.
  • the reaction temperature is preferably 50 to 800 ° C, more preferably 100 to 500 ° C.
  • the nickel-containing film formed using the nickel-containing film forming material of the present invention is preferably a nickel film or a nickel silicide film.
  • the nickel film or nickel silicide film must use the nickel complex as a Ni source.
  • the Si source of the nickel silicide film is preferably Si a H 2a + 2 (where a is an integer of 1 to 3) or R b SiH 4-b (where b is an integer of 1 to 3). And R represents an alkyl group having 1 to 3 carbon atoms.), And more preferably a silane, disilane, trisilane, methylsilane, dimethylsilane, trimethylsilane, Ethylsilane, diethylsilane, and triethylsilane.
  • the Si source of the nickel silicide film the vapor pressure tends to increase.
  • various types of CVD for decomposing the nickel complex as a Ni source can be used. That is, as various types of CVD, thermal CVD that thermally decomposes, photo CVD that decomposes by heat and light, plasma CVD that activates and decomposes by plasma, laser-assisted CVD that activates and decomposes by laser, and active by ion beam For example, ion beam assisted CVD for photolysis and photolysis. These various types of CVD can be used for forming a nickel film or a nickel silicide film. Also, when the silicon compound that is the Si source of the nickel silicide film is decomposed, various types of CVD can be used in the same manner.
  • the reaction pressure when forming the nickel film or nickel silicide film is preferably 0.0013 to 101.3 kPa, more preferably 0.013 to 101.3 kPa, and still more preferably 0.13 to 101.3 kPa.
  • the reaction temperature is preferably 50 to 800 ° C, more preferably 100 to 500 ° C.
  • Ni or Si is likely to be reduced.
  • the reducing agent include hydrogen.
  • the collected colorless liquid was analyzed by GC-MS (HP 6890 made by HP / JMS-AUTOMASSII made by JEOL), ICP-AES (VISTA-PRO made by SII) and an organic element analyzer (CHNS-932 made by LECO).
  • PF 3 ) 2 PF 2 (CF 3 )) 2 was confirmed (17 g, yield 83%).
  • the collected colorless liquid was analyzed by GC-MS (HP 6890 made by HP / JMS-AUTOMASSII made by JEOL), ICP-AES (VISTA-PRO made by SII) and an organic element analyzer (CHNS-932 made by LECO). CO) 2 (P (CF 3 ) 2 CH 2 CH 2 P (CF 3 ) 2 ) (16 g, 48% yield).
  • the collected colorless liquid was analyzed by GC-MS (HP 6890 made by HP / JMS-AUTOMASSII made by JEOL), ICP-AES (VISTA-PRO made by SII) and an organic element analyzer (CHNS-932 made by LECO). CO) 2 (P (CF 3 ) 2 CF 2 CF 2 P (CF 3 ) 2 ) (25 g, yield 65%).
  • PF 2 NH (CH 3 ) was identified by FT-IR (Thermo-Nicolet AVATAR360 manufactured by Thermo Electron) and NMR (JEOL JNM-AL400).
  • 13 g of Ni (PF 3 ) 4 was placed in a 500 ml stainless steel pressure vessel, and 5.2 g of PF 2 NH (CH 3 ) was introduced and sealed. The container was then heated at 100 ° C. for 24 hours. After the reaction, a colorless liquid was separated by distillation.
  • the collected colorless liquid was analyzed by GC-MS (HP 6890 made by HP / JMS-AUTOMASSII made by JEOL), ICP-AES (VISTA-PRO made by SII) and an organic element analyzer (CHNS-932 made by LECO).
  • PF 3 ) 3 PF 2 NH (CH 3 ) was confirmed (9.0 g, yield 69%).
  • Example 1 ⁇ The Ni (CO) 3 (PF 3 ) Ni obtained by film formation evaluation Synthesis Example 1 (CO) 3 (PF 3) , using a differential thermogravimetric simultaneous measurement device (SII manufactured by TG / DTA6200), 500 It was 99.5 mass% when the volatilization rate when heated to ° C was determined. It has been found that there are very few volatile residues and it is suitable as a nickel-containing film-forming material.
  • Example 1-2 Nickel film formation using Ni (CO) 3 (PF 3 ) A nickel film was formed in the same manner as in Example 1-1 except that H 2 gas was used instead of the mixed gas of SiH 4 and H 2 . As a result, deposition of the film was confirmed on the substrate, and when the composition of the film was examined with an X-ray photoelectron analyzer (XPS) (AXIS-NOVA manufactured by KRATOS), the presence of nickel was confirmed. Moreover, almost no carbon was confirmed. Further, the film was confirmed to be a nickel film by analysis with an X-ray diffractometer (XRD) (Rigaku RAD- ⁇ X). Moreover, almost no HF was confirmed in the analysis of the exhaust gas from the CVD apparatus. The exhaust gas was analyzed by FT-IR (Nicolet 380 manufactured by Thermo Electron).
  • Example 2 About ⁇ Ni (CO) 2 (PF 3) Ni obtained in 2 of film formation evaluation Synthesis Example 2 (CO) 2 (PF 3 ) 2, using a differential thermogravimetric simultaneous measurement device (SII manufactured by TG / DTA6200) The volatilization rate when heated to 500 ° C. was 99.2% by mass. It has been found that there are very few volatile residues and it is suitable as a nickel-containing film-forming material.
  • SII manufactured by TG / DTA6200
  • Example 2-1 ⁇ Ni (CO) 2 (PF 3) Ni obtained 2 nickel silicide film formed in Synthesis Example 2 using (CO) 2 (PF 3) 2 , except that used were formed in the same manner as in Example 1-1 Filmed.
  • XPS X-ray photoelectron analyzer
  • XIS-NOVA XIS-NOVA manufactured by KRATOS
  • XRD X-ray diffractometer
  • RAD- ⁇ X manufactured by Rigaku confirmed that this film was a nickel silicide film.
  • almost no HF was confirmed in the analysis of the exhaust gas from the CVD apparatus.
  • the exhaust gas was analyzed by FT-IR (Nicolet 380 manufactured by Thermo Electron).
  • Example 2-2 Nickel film formation using Ni (CO) 2 (PF 3 ) 2 A film was formed in the same manner as in Example 2-1, except that H 2 gas was used instead of the mixed gas of SiH 4 and H 2 . As a result, deposition of the film was confirmed on the substrate, and when the composition of the film was examined with an X-ray photoelectron analyzer (XPS) (AXIS-NOVA manufactured by KRATOS), the presence of nickel was confirmed. Moreover, almost no carbon was confirmed. Further, the film was confirmed to be a nickel film by analysis with an X-ray diffractometer (XRD) (Rigaku RAD- ⁇ X). Moreover, almost no HF was confirmed in the analysis of the exhaust gas from the CVD apparatus. The exhaust gas was analyzed by FT-IR (Nicolet 380 manufactured by Thermo Electron).
  • Example 3 About ⁇ Ni (CO) (PF 3 ) 3 Ni obtained by film formation evaluation Synthesis Example 3 (CO) (PF 3) 3 , using a differential thermogravimetric simultaneous measurement device (SII manufactured by TG / DTA6200), 500 It was 98.9 mass% when the volatilization rate when heated to ° C was determined. It has been found that there are very few volatile residues and it is suitable as a nickel-containing film-forming material.
  • Example 3-1 Nickel silicide film formation using Ni (CO) (PF 3 ) 3 A film was formed in the same manner as in Example 1-1 except that Ni (CO) (PF 3 ) 3 obtained in Synthesis Example 3 was used. . As a result, deposition of the film was confirmed on the substrate, and when the composition of the film was examined by an X-ray photoelectron analyzer (XPS) (AXIS-NOVA manufactured by KRATOS), the presence of nickel and silicon was confirmed. Moreover, almost no carbon was confirmed. Further, analysis by an X-ray diffractometer (XRD) (RAD- ⁇ X manufactured by Rigaku) confirmed that this film was a nickel silicide film. Moreover, almost no HF was confirmed in the analysis of the exhaust gas from the CVD apparatus. The exhaust gas was analyzed by FT-IR (Nicolet 380 manufactured by Thermo Electron).
  • FT-IR Nicolet 380 manufactured by Thermo Electron
  • Example 3-2 Nickel film formation using Ni (CO) (PF 3 ) 3
  • a film was formed in the same manner as in Example 3-1, except that H 2 gas was used instead of the mixed gas of SiH 4 and H 2 .
  • XPS X-ray photoelectron analyzer
  • AXIS-NOVA manufactured by KRATOS
  • the presence of nickel was confirmed.
  • almost no carbon was confirmed.
  • the film was confirmed to be a nickel film by analysis with an X-ray diffractometer (XRD) (Rigaku RAD- ⁇ X).
  • XRD X-ray diffractometer
  • almost no HF was confirmed in the analysis of the exhaust gas from the CVD apparatus.
  • the exhaust gas was analyzed by FT-IR (Nicolet 380 manufactured by Thermo Electron).
  • Example 4 Evaluation of film formation of Ni (CO) (PF 2 (CF 3 )) 3 carbonyltris (trifluoromethyldifluorophosphine) nickel About Ni (CO) (PF 2 (CF 3 )) 3 obtained in Synthesis Example 4
  • the volatilization rate when heated to 500 ° C. using a thermothermogravimetric simultaneous measurement apparatus (TG / DTA6200 manufactured by SII) was 99.1% by mass. It has been found that there are very few volatile residues and it is suitable as a nickel-containing film-forming material.
  • Example 4-1 ⁇ Ni (CO) (PF 2 (CF 3)) 3 was obtained with nickel silicide film formed in Synthesis Example 4 using Ni (CO) (PF 2 ( CF 3)) 3 was used, the first holding temperature of the raw material container A film was formed in the same manner as in Example 1-1 except that the temperature was set to 60 ° C. As a result, deposition of the film was confirmed on the substrate, and when the composition of the film was examined by an X-ray photoelectron analyzer (XPS) (AXIS-NOVA manufactured by KRATOS), the presence of nickel and silicon was confirmed. Moreover, almost no carbon was confirmed.
  • XPS X-ray photoelectron analyzer
  • XRD X-ray diffractometer
  • Example 4-2 Nickel film formation using Ni (CO) (PF 2 (CF 3 )) 3 Film formation was performed in the same manner as in Example 4-1, except that H 2 gas was used instead of the mixed gas of SiH 4 and H 2. did. As a result, deposition of the film was confirmed on the substrate, and when the composition of the film was examined with an X-ray photoelectron analyzer (XPS) (AXIS-NOVA manufactured by KRATOS), the presence of nickel was confirmed. Moreover, almost no carbon was confirmed. Further, the film was confirmed to be a nickel film by analysis with an X-ray diffractometer (XRD) (Rigaku RAD- ⁇ X). Moreover, almost no HF was confirmed in the analysis of the exhaust gas from the CVD apparatus. The exhaust gas was analyzed by FT-IR (Nicolet 380 manufactured by Thermo Electron).
  • Example 5 ⁇ Ni (CO) 2 (P (CF 3) 3) Ni obtained in 2 of film formation evaluation Synthesis Example 5 (CO) 2 (P ( CF 3) 3) for 2, differential thermogravimetric simultaneous measurement device (SII Using TG / DTA6200), the volatilization rate when heated to 500 ° C. was 99.5% by mass. It has been found that there are very few volatile residues and it is suitable as a nickel-containing film-forming material.
  • Example 5-1 ⁇ Ni (CO) 2 (P (CF 3) 3) 2 was obtained with nickel silicide film formed in Synthesis Example 5 using the Ni (CO) 2 (P ( CF 3) 3) 2 was used, the raw material container first A film was formed in the same manner as in Example 1-1 except that the holding temperature was 60 ° C. As a result, deposition of the film was confirmed on the substrate, and when the composition of the film was examined by an X-ray photoelectron analyzer (XPS) (AXIS-NOVA manufactured by KRATOS), the presence of nickel and silicon was confirmed. Moreover, almost no carbon was confirmed.
  • XPS X-ray photoelectron analyzer
  • XRD X-ray diffractometer
  • Example 5-2 Nickel film formation using Ni (CO) 2 (P (CF 3 ) 3 ) 2 The same process as in Example 5-1, except that H 2 gas was used instead of the mixed gas of SiH 4 and H 2. Filmed. As a result, deposition of the film was confirmed on the substrate, and when the composition of the film was examined with an X-ray photoelectron analyzer (XPS) (AXIS-NOVA manufactured by KRATOS), the presence of nickel was confirmed. Moreover, almost no carbon was confirmed. Further, the film was confirmed to be a nickel film by analysis with an X-ray diffractometer (XRD) (Rigaku RAD- ⁇ X). Moreover, almost no HF was confirmed in the analysis of the exhaust gas from the CVD apparatus. The exhaust gas was analyzed by FT-IR (Nicolet 380 manufactured by Thermo Electron).
  • Example 6 ⁇ Ni (PF 3) 2 ( PF 2 (CF 3)) Ni obtained in 2 of film formation evaluation Synthesis Example 6 (PF 3) 2 (PF 2 (CF 3)) for 2, the differential thermogravimetric simultaneous analysis device It was 99.0 mass% when the volatilization rate when heating to 500 degreeC was calculated
  • Example 6-1 ⁇ Ni (PF 3) 2 ( PF 2 (CF 3)) Ni (PF 3) obtained in the nickel silicide film formed Synthesis Example 6 using 2 2 using (PF 2 (CF 3)) 2, of the raw material container A film was formed in the same manner as in Example 1-1 except that the initial holding temperature was 60 ° C. As a result, deposition of the film was confirmed on the substrate, and when the composition of the film was examined by an X-ray photoelectron analyzer (XPS) (AXIS-NOVA manufactured by KRATOS), the presence of nickel and silicon was confirmed. Moreover, almost no carbon was confirmed.
  • XPS X-ray photoelectron analyzer
  • XRD X-ray diffractometer
  • Example 6-2 Nickel film formation using Ni (PF 3 ) 2 (PF 2 (CF 3 )) 2 Similar to Example 6-1 except that H 2 gas was used instead of the mixed gas of SiH 4 and H 2. A film was formed. As a result, deposition of the film was confirmed on the substrate, and when the composition of the film was examined with an X-ray photoelectron analyzer (XPS) (AXIS-NOVA manufactured by KRATOS), the presence of nickel was confirmed. Moreover, almost no carbon was confirmed. Further, the film was confirmed to be a nickel film by analysis with an X-ray diffractometer (XRD) (Rigaku RAD- ⁇ X). Moreover, almost no HF was confirmed in the analysis of the exhaust gas from the CVD apparatus. The exhaust gas was analyzed by FT-IR (Nicolet 380 manufactured by Thermo Electron).
  • Example 7 ⁇ Ni (CO) 2 (P (CF 3) 2 CH 2 CH 2 P (CF 3) 2) Ni obtained by film formation evaluation Synthesis Example 7 (CO) 2 (P (CF 3) 2 CH 2 CH 2 With respect to P (CF 3 ) 2 ), the volatilization rate when heated to 500 ° C. using a differential thermothermal gravimetric simultaneous measurement apparatus (TG / DTA 6200 manufactured by SII) was 98.9% by mass. It has been found that there are very few volatile residues and it is suitable as a nickel-containing film-forming material.
  • Example 7-1 Nickel silicide film formation using Ni (CO) 2 (P (CF 3 ) 2 CH 2 CH 2 P (CF 3 ) 2 ) Ni (CO) 2 (P (CF 3 ) 2 CH obtained in Synthesis Example 7
  • a film was formed in the same manner as in Example 1-1 except that 2 CH 2 P (CF 3 ) 2 ) was used and the initial holding temperature of the raw material container was set to 60 ° C.
  • XPS X-ray photoelectron analyzer
  • KRATOS X-ray photoelectron analyzer
  • XRD X-ray diffractometer
  • Example 7-2 Nickel film formation using Ni (CO) 2 (P (CF 3 ) 2 CH 2 CH 2 P (CF 3 ) 2 ) Except for using H 2 gas instead of the mixed gas of SiH 4 and H 2 A film was formed in the same manner as in Example 7-1.
  • XPS X-ray photoelectron analyzer
  • AXIS-NOVA manufactured by KRATOS
  • the presence of nickel was confirmed.
  • almost no carbon was confirmed.
  • the film was confirmed to be a nickel film by analysis with an X-ray diffractometer (XRD) (Rigaku RAD- ⁇ X).
  • XRD X-ray diffractometer
  • almost no HF was confirmed in the analysis of the exhaust gas from the CVD apparatus.
  • the exhaust gas was analyzed by FT-IR (Nicolet 380 manufactured by Thermo Electron).
  • Example 8 Film formation evaluation of Ni (CO) 2 (P (CF 3 ) 2 CF 2 CF 2 P (CF 3 ) 2 ) Ni (CO) 2 (P (CF 3 ) 2 CF 2 CF 2 obtained in Synthesis Example 8 With respect to P (CF 3 ) 2 ), the volatilization rate when heated to 500 ° C. using a differential thermothermal gravimetric simultaneous measurement apparatus (TG / DTA 6200 manufactured by SII) was 98.8% by mass. It has been found that there are very few volatile residues and it is suitable as a nickel-containing film-forming material.
  • Example 8-1 Nickel silicide film formation using Ni (CO) 2 (P (CF 3 ) 2 CF 2 CF 2 P (CF 3 ) 2 ) Ni (CO) 2 (P (CF 3 ) 2 CF obtained in Synthesis Example 8
  • a film was formed in the same manner as in Example 1-1 except that 2 CF 2 P (CF 3 ) 2 ) was used and the initial holding temperature of the raw material container was changed to 60 ° C.
  • XPS X-ray photoelectron analyzer
  • AXIS-NOVA manufactured by KRATOS
  • XRD X-ray diffractometer
  • Example 8-2 Nickel film formation using Ni (CO) 2 (P (CF 3 ) 2 CF 2 CF 2 P (CF 3 ) 2 ) Except for using a H 2 gas instead of a mixed gas of SiH 4 and H 2 A film was formed in the same manner as in Example 8-1. As a result, deposition of the film was confirmed on the substrate, and when the composition of the film was examined with an X-ray photoelectron analyzer (XPS) (AXIS-NOVA manufactured by KRATOS), the presence of nickel was confirmed. Moreover, almost no carbon was confirmed. Further, the film was confirmed to be a nickel film by analysis with an X-ray diffractometer (XRD) (Rigaku RAD- ⁇ X). Moreover, almost no HF was confirmed in the analysis of the exhaust gas from the CVD apparatus. The exhaust gas was analyzed by FT-IR (Nicolet 380 manufactured by Thermo Electron).
  • Example 9 ⁇ Ni (PF 3) 3 ( PF 2 NH (CH 3)) Ni (PF 3) obtained in the film formation evaluation Synthesis Example 9 of 3 (PF 2 NH (CH 3 )), the differential thermogravimetric simultaneous analysis device It was 99.0 mass% when the volatilization rate when heating to 500 degreeC was calculated
  • Example 9-1 ⁇ Ni (PF 3) 3 ( PF 2 NH (CH 3)) using a Ni obtained in the nickel silicide film formed in Synthesis Example 9 using (PF 3) 3 (PF 2 NH (CH 3)), the raw material container A film was formed in the same manner as in Example 1-1 except that the initial holding temperature was 60 ° C. As a result, deposition of the film was confirmed on the substrate, and when the composition of the film was examined by an X-ray photoelectron analyzer (XPS) (AXIS-NOVA manufactured by KRATOS), the presence of nickel and silicon was confirmed. Moreover, almost no carbon was confirmed.
  • XPS X-ray photoelectron analyzer
  • XRD X-ray diffractometer
  • Example 9-2 Nickel film formation using Ni (PF 3 ) 3 (PF 2 NH (CH 3 )) Similar to Example 9-1 except that H 2 gas was used instead of the mixed gas of SiH 4 and H 2. A film was formed. As a result, deposition of the film was confirmed on the substrate, and when the composition of the film was examined with an X-ray photoelectron analyzer (XPS) (AXIS-NOVA manufactured by KRATOS), the presence of nickel was confirmed. Moreover, almost no carbon was confirmed. Further, the film was confirmed to be a nickel film by analysis with an X-ray diffractometer (XRD) (Rigaku RAD- ⁇ X). Moreover, almost no HF was confirmed in the analysis of the exhaust gas from the CVD apparatus. The exhaust gas was analyzed by FT-IR (Nicolet 380 manufactured by Thermo Electron).
  • Example 10 ⁇ For Ni (PF 3) 3 (PF 2 N (C 2 H 5) 2) Ni obtained by film formation evaluation Synthesis Example 10 (PF 3) 3 (PF 2 N (C 2 H 5) 2), a differential The volatilization rate when heated to 500 ° C. using a thermothermogravimetric simultaneous measurement apparatus (TG / DTA6200 manufactured by SII) was 99.1% by mass. It has been found that there are very few volatile residues and it is suitable as a nickel-containing film-forming material.
  • TG / DTA6200 manufactured by SII thermothermogravimetric simultaneous measurement apparatus
  • Example 10-1 ⁇ Ni (PF 3) 3 ( PF 2 N (C 2 H 5) 2) was obtained with nickel silicide film formed Synthesis Example 10 using Ni (PF 3) 3 (PF 2 N (C 2 H 5) 2) A film was formed in the same manner as in Example 1-1 except that the initial holding temperature of the raw material container was changed to 60 ° C. As a result, deposition of the film was confirmed on the substrate, and when the composition of the film was examined by an X-ray photoelectron analyzer (XPS) (AXIS-NOVA manufactured by KRATOS), the presence of nickel and silicon was confirmed. Moreover, almost no carbon was confirmed.
  • XPS X-ray photoelectron analyzer
  • XRD X-ray diffractometer
  • Example 10-2 Nickel film formation using Ni (PF 3 ) 3 (PF 2 N (C 2 H 5 ) 2 )
  • Example 10-1 except that H 2 gas was used instead of the mixed gas of SiH 4 and H 2
  • XPS X-ray photoelectron analyzer
  • AXIS-NOVA manufactured by KRATOS
  • the presence of nickel was confirmed.
  • almost no carbon was confirmed.
  • the film was confirmed to be a nickel film by analysis with an X-ray diffractometer (XRD) (Rigaku RAD- ⁇ X).
  • XRD X-ray diffractometer
  • almost no HF was confirmed in the analysis of the exhaust gas from the CVD apparatus.
  • the exhaust gas was analyzed by FT-IR (Nicolet 380 manufactured by Thermo Electron).
  • XRD X-ray diffractometer

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Abstract

Provided is a nickel-containing film formation material used for forming by the CVD (chemical vapor deposition), a nickel-containing film in which carbon cannot easily remain and HF cannot easily be produced as a byproduct.  Furthermore, provided is a nickel-containing film formation material for forming a nickel-containing film as a nickel silicide film. The nickel-containing film formation material contains at least one type of nickel complex having four ligands.  The ligands include at least two types selected from a group consisting of: CO, PF3, PF2(CF3), PF(CF3)2, P(CF3)3, PF2R1, PFR2R3, PF2NR4R5, P(CF3)2CH2CH2P(CF3)2, and P(CF3)2CF2CF2P(CF3)2, (wherein R1 to R5 are respectively, H and an alkyl group or a phenyl group having 1 to 6 carbons; and P(CF3)2CH2CH2P(CF3)2 and P(CF3)2CF2CF2P(CF3)2 correspond to 2 ligands).

Description

ニッケル含有膜形成材料およびニッケル含有膜の製造方法Nickel-containing film forming material and method for producing nickel-containing film

　本発明は、ニッケル含有膜形成材料およびニッケル含有膜の製造方法に関する。より詳しくは、化学気相成長法（ＣＶＤ）による膜形成に用いられるニッケル含有膜形成材料および該材料を用いたニッケル含有膜の製造方法に関する。 The present invention relates to a nickel-containing film forming material and a method for producing a nickel-containing film. More specifically, the present invention relates to a nickel-containing film forming material used for film formation by chemical vapor deposition (CVD) and a method for producing a nickel-containing film using the material.

　現在、半導体デバイスにおける技術の進歩は著しく、更なる高速動作を可能とするために、高度化および微細化が急速に行われ、その為の材料開発が盛んに行われている。 At present, technological progress in semiconductor devices is remarkable, and in order to enable further high-speed operation, advancement and miniaturization are rapidly performed, and material development for that purpose is actively performed.

　配線材料には低抵抗材料が次々に導入され、ゲート電極、ソースまたはドレインの拡散層上へシリサイド膜を形成することにより、更なる低抵抗化が行われている。ここで使われているシリサイド膜として、チタンシリサイド膜またはコバルトシリサイド膜よりも低抵抗なニッケルシリサイド膜の導入が検討されている。 As the wiring material, low resistance materials are successively introduced, and a silicide film is formed on the diffusion layer of the gate electrode, the source or the drain, thereby further reducing the resistance. As a silicide film used here, introduction of a nickel silicide film having a resistance lower than that of a titanium silicide film or a cobalt silicide film has been studied.

　このニッケルシリサイド膜の形成は、これまでスパッタリング法により行われてきた。しかし、スパッタリング法は、半導体素子への物理的な損傷が懸念されると共に、均一な成膜が困難であることなどから、近年、化学気相成長法（以下「ＣＶＤ」とも記す。）による膜形成が検討されている。 This nickel silicide film has been formed by a sputtering method so far. However, in the sputtering method, there is a concern about physical damage to the semiconductor element, and uniform film formation is difficult. In recent years, a film formed by chemical vapor deposition (hereinafter also referred to as “CVD”) is used. Formation is being considered.

　ＣＶＤは、膜形成材料を揮発させてガス状態で流し、反応器内で化学反応を利用して、シリコン基板上に膜を堆積させる方法である。ＣＶＤは減圧下での成膜により、低温での成膜を行うことが出来るが、用いる膜形成材料の違いにより、成膜する際の条件が大きく異なる。このとき用いる膜形成材料に求められる特性として、高い蒸気圧を有することなどが挙げられる。 CVD is a method of depositing a film on a silicon substrate by volatilizing a film forming material and flowing it in a gas state and utilizing a chemical reaction in a reactor. CVD can be performed at a low temperature by film formation under reduced pressure, but the conditions for film formation vary greatly depending on the film forming material used. A characteristic required for the film forming material used at this time includes a high vapor pressure.

　これまでに提案されているニッケル含有膜形成材料の中で、高い蒸気圧を有する化合物として、ビス（アルキルシクロペンタジエニル）ニッケル（例えば、特許文献１参照）、シクロペンタジエニルアリルニッケル（例えば、特許文献２参照）、テトラキス（トリフルオロホスフィン）ニッケル（例えば、特許文献３参照）が報告されている。 Among the nickel-containing film forming materials that have been proposed so far, as a compound having a high vapor pressure, bis (alkylcyclopentadienyl) nickel (for example, see Patent Document 1), cyclopentadienylallylnickel (for example, Patent Document 2) and tetrakis (trifluorophosphine) nickel (for example, see Patent Document 3) have been reported.

　しかしながら、ビス（アルキルシクロペンタジエニル）ニッケルまたはシクロペンタジエニルアリルニッケルは、配位子であるシクロペンタジエニルの炭素とニッケルとの相互作用が強いために、形成されたニッケル含有膜に炭素が残存しやすいという課題があった。炭素が残存すると、例えば、ニッケル含有膜の抵抗値が増加する傾向がある。 However, since bis (alkylcyclopentadienyl) nickel or cyclopentadienylallylnickel has a strong interaction between the carbon of the cyclopentadienyl ligand and nickel, the formed nickel-containing film contains carbon. There was a problem that was likely to remain. When carbon remains, for example, the resistance value of the nickel-containing film tends to increase.

　また、テトラキス（トリフルオロホスフィン）ニッケルは、配位子であるトリフルオロホスフィンのリンの非共有電子対とニッケルとの相互作用が弱いために形成されたニッケル含有膜に炭素は残存しにくいが、膜形成時に配位子のＰ－Ｆ結合の開裂によるＨＦが副生するという課題があった。ＨＦが副生すると、形成されたニッケル含有膜を損傷する傾向がある。 In addition, tetrakis (trifluorophosphine) nickel is less likely to remain carbon in the nickel-containing film formed due to the weak interaction between nickel and the unshared electron pair of the phosphorus trifluorophosphine ligand, There was a problem that HF was produced as a by-product due to cleavage of the PF bond of the ligand during film formation. When HF is by-produced, the formed nickel-containing film tends to be damaged.

　そのため、ＣＶＤにより形成したニッケル含有膜に炭素が残存しにくく、かつＨＦが副生しにくい材料の開発が望まれている。 Therefore, it is desired to develop a material in which carbon does not easily remain in a nickel-containing film formed by CVD and HF is not easily generated as a by-product.

特開２００３－３２８１３０号公報JP 2003-328130 A 特開２００５－９３７３２号公報JP 2005-93732 A 特開２００６－４５６４９号公報JP 2006-45649 A

　本発明は、上記のような従来技術に伴う問題を解決しようとするものであって、形成されたニッケル含有膜に炭素が残存しにくく、かつＨＦが副生しにくいニッケル含有膜形成材料を提供することにある。さらには、ニッケル含有膜がニッケル膜またはニッケルシリサイド膜であるニッケル含有膜形成材料を提供することにある。 The present invention is intended to solve the problems associated with the prior art as described above, and provides a nickel-containing film forming material in which carbon does not easily remain in a formed nickel-containing film and HF is not easily produced as a by-product. There is to do. Furthermore, it is providing the nickel containing film forming material whose nickel containing film is a nickel film or a nickel silicide film.

　また、本発明の他の目的は、上記ニッケル含有膜形成材料を用いたニッケル含有膜の製造方法を提供することにある。さらには、ニッケル含有膜がニッケル膜またはニッケルシリサイド膜であるニッケル含有膜の製造方法を提供することにある。 Another object of the present invention is to provide a method for producing a nickel-containing film using the nickel-containing film forming material. Furthermore, it is providing the manufacturing method of the nickel containing film whose nickel containing film is a nickel film or a nickel silicide film.

　本発明者らは上記課題に対する検討を行った結果、特定の配位子が２種以上配位したニッケル錯体を含むニッケル含有膜形成材料を用いれば、ＣＶＤにより安定な膜を形成することができるとともに、形成されたニッケル含有膜に炭素が残存しにくいこと、ならびに膜形成時にＨＦが副生しにくいことを見出した。さらに、前記ニッケル含有膜形成材料がニッケルシリサイド膜形成に適していることを見出した。本発明のニッケル含有膜形成材料は、いまだ報告されていない。 As a result of studying the above problems, the present inventors can form a stable film by CVD using a nickel-containing film forming material containing a nickel complex in which two or more specific ligands are coordinated. At the same time, it has been found that carbon is unlikely to remain in the formed nickel-containing film, and that HF is hardly produced as a by-product during film formation. Furthermore, the present inventors have found that the nickel-containing film forming material is suitable for forming a nickel silicide film. The nickel-containing film forming material of the present invention has not yet been reported.

　すなわち、本発明は以下に関する。 That is, the present invention relates to the following.

　[１]配位子を４個有するニッケル錯体を少なくとも１種含むニッケル含有膜形成材料であって、前記配位子の種類が、ＣＯ、ＰＦ3、ＰＦ2（ＣＦ3）、ＰＦ（ＣＦ3）2、Ｐ（ＣＦ3）3、ＰＦ2Ｒ1、ＰＦＲ2Ｒ3、ＰＦ2ＮＲ4Ｒ5、Ｐ（ＣＦ3）2ＣＨ2ＣＨ2Ｐ（ＣＦ3）2およびＰ（ＣＦ3）2ＣＦ2ＣＦ2Ｐ（ＣＦ3）2からなる群（ただし、Ｒ1～Ｒ5は各々独立に、Ｈ、炭素数１～６のアルキル基またはフェニル基であり、Ｐ（ＣＦ3）2ＣＨ2ＣＨ2Ｐ（ＣＦ3）2およびＰ（ＣＦ3）2ＣＦ2ＣＦ2Ｐ（ＣＦ3）2は、配位子２個分に相当する。）より選ばれる２種以上であることを特徴とするニッケル含有膜形成材料。 [1] A nickel-containing film forming material containing at least one nickel complex having four ligands, wherein the type of the ligand is CO, PF 3 , PF 2 (CF 3 ), PF (CF 3 ) 2 , P (CF 3 ) 3 , PF 2 R 1 , PFR 2 R 3 , PF 2 NR 4 R 5 , P (CF 3 ) 2 CH 2 CH 2 P (CF 3 ) 2 and P (CF 3 ) 2 A group consisting of CF 2 CF 2 P (CF 3 ) 2 (wherein R 1 to R 5 are each independently H, an alkyl group having 1 to 6 carbon atoms, or a phenyl group; P (CF 3 ) 2 CH 2 CH 2 P (CF 3 ) 2 and P (CF 3 ) 2 CF 2 CF 2 P (CF 3 ) 2 are equivalent to two ligands.) Nickel-containing film forming material.

　[２]前記配位子の種類が、ＣＯおよびＰＦ3の２種である[１]に記載のニッケル含有膜形成材料。 [2] The nickel-containing film forming material according to [1], wherein the ligands are two types, CO and PF 3 .

　[３]前記配位子の種類が、ＣＯおよびＰＦ2（ＣＦ3）の２種である[１]に記載のニッケル含有膜形成材料。 [3] The nickel-containing film forming material according to [1], wherein the ligands are two types, CO and PF 2 (CF 3 ).

　[４]前記配位子の種類が、ＣＯおよびＰＦ（ＣＦ3）2の２種である[１]に記載のニッケル含有膜形成材料。 [4] The nickel-containing film forming material according to [1], wherein the ligands are two types, CO and PF (CF 3 ) 2 .

　[５]前記配位子の種類が、ＣＯおよびＰ（ＣＦ3）3の２種である[１]に記載のニッケル含有膜形成材料。 [5] The nickel-containing film-forming material according to [1], wherein the ligand is of two types, CO and P (CF 3 ) 3 .

　[６]前記配位子の種類が、ＰＦ3およびＰＦ2（ＣＦ3）の２種である[１]に記載のニッケル含有膜形成材料。 [6] The nickel-containing film-forming material according to [1], wherein the types of the ligand are two types, PF 3 and PF 2 (CF 3 ).

　[７]前記配位子の種類が、ＰＦ3およびＰＦ2Ｒ1（ただし、Ｒ1は、Ｈ、炭素数１～６のアルキル基またはフェニル基である。）の２種である[１]に記載のニッケル含有膜形成材料。 [7] The ligands are of two types, PF 3 and PF 2 R 1 (where R 1 is H, an alkyl group having 1 to 6 carbon atoms, or a phenyl group) [1] The nickel-containing film-forming material described in 1.

　[８]前記配位子の種類が、ＰＦ3およびＰＦ2ＮＲ4Ｒ5（ただし、Ｒ4およびＲ5は各々独立に、Ｈ、炭素数１～６のアルキル基またはフェニル基である。）の２種である[１]に記載のニッケル含有膜形成材料。 [8] The type of the ligand is PF 3 and PF 2 NR 4 R 5 (wherein R 4 and R 5 are each independently H, an alkyl group having 1 to 6 carbon atoms, or a phenyl group). The nickel-containing film forming material according to [1], which is two types of the above.

　[９]前記ニッケル錯体が、Ｎｉ（ＣＯ）2（Ｐ（ＣＦ3）2ＣＨ2ＣＨ2Ｐ（ＣＦ3）2）である[１]に記載のニッケル含有膜形成材料。 [9] The nickel-containing film forming material according to [1], wherein the nickel complex is Ni (CO) 2 (P (CF 3 ) 2 CH 2 CH 2 P (CF 3 ) 2 ).

　[１０]前記ニッケル錯体が、Ｎｉ（ＣＯ）2（Ｐ（ＣＦ3）2ＣＦ2ＣＦ2Ｐ（ＣＦ3）2）である[１]に記載のニッケル含有膜形成材料。 [10] The nickel-containing film forming material according to [1], wherein the nickel complex is Ni (CO) 2 (P (CF 3 ) 2 CF 2 CF 2 P (CF 3 ) 2 ).

　[１１]化学気相成長法（ＣＶＤ）による膜形成に用いられる[１]～[１０]のいずれかに記載のニッケル含有膜形成材料。 [11] The nickel-containing film forming material according to any one of [1] to [10], which is used for film formation by chemical vapor deposition (CVD).

　[１２]ニッケル含有膜が、ニッケル膜またはニッケルシリサイド膜である[１]～[１１] のいずれかに記載のニッケル含有膜形成材料。 [12] The nickel-containing film forming material according to any one of [1] to [11], wherein the nickel-containing film is a nickel film or a nickel silicide film.

　[１３]前記ニッケルシリサイド膜のＳｉ源が、ＳｉaＨ2a+2（ただし、ａは１～３の整数である。）またはＲbＳｉＨ4-b（ただし、ｂは１～３の整数であり、Ｒは炭素数１～３のアルキル基を表す。）の構造式で示される少なくとも１種のケイ素化合物である[１２]に記載のニッケル含有膜形成材料。 [13] The Si source of the nickel silicide film is Si a H 2a + 2 (where a is an integer of 1 to 3) or R b SiH 4-b (where b is an integer of 1 to 3) And R represents an alkyl group having 1 to 3 carbon atoms.) The nickel-containing film-forming material according to [12], which is at least one silicon compound represented by the structural formula:

　[１４]前記ケイ素化合物が、シラン、ジシラン、トリシラン、メチルシラン、ジメチルシラン、トリメチルシラン、エチルシラン、ジエチルシランまたはトリエチルシランである[１３]に記載のニッケル含有膜形成材料。 [14] The nickel-containing film forming material according to [13], wherein the silicon compound is silane, disilane, trisilane, methylsilane, dimethylsilane, trimethylsilane, ethylsilane, diethylsilane, or triethylsilane.

　[１５] [１]～[１４]のいずれかに記載のニッケル含有膜形成材料を用いて、化学気相成長法（ＣＶＤ）によりニッケル含有膜を形成することを特徴とするニッケル含有膜の製造方法。 [15] Production of a nickel-containing film, characterized by forming a nickel-containing film by chemical vapor deposition (CVD) using the nickel-containing film-forming material according to any one of [1] to [14] Method.

　本発明によれば、ＣＶＤにより安定なニッケル含有膜を形成することができ、形成されたニッケル含有膜に炭素が残存しにくく、かつ膜形成時にＨＦが副生しにくい。すなわち、本発明のニッケル含有膜形成材料を用いることで、ＣＶＤにより良好なニッケル含有膜、さらには良好なニッケルシリサイド膜を容易に形成することができる。 According to the present invention, a stable nickel-containing film can be formed by CVD, carbon is unlikely to remain in the formed nickel-containing film, and HF is hardly generated as a by-product during film formation. That is, by using the nickel-containing film forming material of the present invention, a good nickel-containing film and further a good nickel silicide film can be easily formed by CVD.

ＣＶＤ装置の模式図である。It is a schematic diagram of a CVD apparatus.

　以下、本発明のニッケル含有膜形成材料について、詳細に説明する。 Hereinafter, the nickel-containing film forming material of the present invention will be described in detail.

　本発明のニッケル含有膜形成材料は、特定の配位子を４個有するニッケル錯体を少なくとも１種含み、前記配位子の種類が、ＣＯ、ＰＦ3、ＰＦ2（ＣＦ3）、ＰＦ（ＣＦ3）2、Ｐ（ＣＦ3）3、ＰＦ2Ｒ1、ＰＦＲ2Ｒ3、ＰＦ2ＮＲ4Ｒ5、Ｐ（ＣＦ3）2ＣＨ2ＣＨ2Ｐ（ＣＦ3）2およびＰ（ＣＦ3）2ＣＦ2ＣＦ2Ｐ（ＣＦ3）2からなる群（ただし、Ｒ1～Ｒ5は各々独立に、Ｈ、炭素数１～６のアルキル基またはフェニル基であり、Ｐ（ＣＦ3）2ＣＨ2ＣＨ2Ｐ（ＣＦ3）2およびＰ（ＣＦ3）2ＣＦ2ＣＦ2Ｐ（ＣＦ3）2は、配位子２個分に相当する。）より選ばれる２種以上であることを特徴としている。 The nickel-containing film forming material of the present invention contains at least one nickel complex having four specific ligands, and the type of the ligand is CO, PF 3 , PF 2 (CF 3 ), PF (CF 3) 2, P (CF 3 ) 3, PF 2 R 1, PFR 2 R 3, PF 2 NR 4 R 5, P (CF 3) 2 CH 2 CH 2 P (CF 3) 2 and P (CF 3) 2 CF 2 CF 2 P (CF 3 ) 2 (wherein R 1 to R 5 are each independently H, an alkyl group having 1 to 6 carbon atoms or a phenyl group, and P (CF 3 ) 2 CH 2 CH 2 P (CF 3 ) 2 and P (CF 3 ) 2 CF 2 CF 2 P (CF 3 ) 2 are equivalent to two ligands.) It is said.

　前記配位子の種類としては、ＣＯ、ＰＦ3、ＰＦ2（ＣＦ3）、ＰＦ（ＣＦ3）2、Ｐ（ＣＦ3）3、ＰＦ2Ｒ1（ただし、Ｒ1は、Ｈ、炭素数１～６のアルキル基またはフェニル基である。）、ＰＦＲ2Ｒ3（ただし、Ｒ2およびＲ3は各々独立に、Ｈ、炭素数１～６のアルキル基またはフェニル基である。）、ＰＦ2ＮＲ4Ｒ5（ただし、Ｒ4およびＲ5は各々独立に、Ｈ、炭素数１～６のアルキル基またはフェニル基である。）であることが好ましく、ＣＯ、ＰＦ3、ＰＦ2（ＣＦ3）、ＰＦ（ＣＦ3）2、Ｐ（ＣＦ3）3、ＰＦ2Ｒ1（ただし、Ｒ1は、Ｈ、炭素数１～６のアルキル基またはフェニル基である。）、ＰＦ2ＮＲ4Ｒ5（ただし、Ｒ4およびＲ5は各々独立に、Ｈ、炭素数１～６のアルキル基またはフェニル基である。）であることがより好ましい。このような配位子であると、ニッケル錯体の蒸気圧が高くなる傾向がある。また、このようなニッケル錯体は、揮発性が高くなるため、膜形成材料を揮発させて行う膜形成方法、例えばＣＶＤに好適に用いることができる。 Examples of the ligand include CO, PF 3 , PF 2 (CF 3 ), PF (CF 3 ) 2 , P (CF 3 ) 3 , and PF 2 R 1 (where R 1 is H, carbon number) 1 to 6 alkyl groups or phenyl groups), PFR 2 R 3 (wherein R 2 and R 3 are each independently H, an alkyl group having 1 to 6 carbon atoms or a phenyl group), PF 2 NR 4 R 5 (wherein R 4 and R 5 are each independently H, an alkyl group having 1 to 6 carbon atoms or a phenyl group), preferably CO, PF 3 , PF 2 (CF 3 ), PF (CF 3 ) 2 , P (CF 3 ) 3 , PF 2 R 1 (where R 1 is H, an alkyl group having 1 to 6 carbon atoms or a phenyl group), PF 2 NR 4 R 5 (wherein R 4 and R 5 are each independently H, an alkyl group having 1 to 6 carbon atoms, or a phenyl group). More preferably. With such a ligand, the vapor pressure of the nickel complex tends to increase. Moreover, since such a nickel complex has high volatility, it can be suitably used for a film forming method in which a film forming material is volatilized, for example, CVD.

　本発明のニッケル含有膜形成材料は、例えば、前記配位子の種類がＣＯおよびＰＦ3であるニッケル錯体を含む。該ニッケル錯体の好ましい具体例としては、Ｎｉ（ＣＯ）3（ＰＦ3）、Ｎｉ（ＣＯ）2（ＰＦ3）2またはＮｉ（ＣＯ）（ＰＦ3）3などが挙げられる。このようなニッケル錯体であると、蒸気圧が高くなる傾向がある。また、このようなニッケル錯体は、揮発性が高くなるため、膜形成材料を揮発させて行う膜形成方法、例えばＣＶＤに好適に用いることができる。 The nickel-containing film forming material of the present invention includes, for example, a nickel complex in which the types of the ligands are CO and PF 3 . Preferable specific examples of the nickel complex include Ni (CO) 3 (PF 3 ), Ni (CO) 2 (PF 3 ) 2 or Ni (CO) (PF 3 ) 3 . With such a nickel complex, the vapor pressure tends to increase. Moreover, since such a nickel complex has high volatility, it can be suitably used for a film forming method in which a film forming material is volatilized, for example, CVD.

　本発明のニッケル含有膜形成材料は、例えば、前記配位子の種類がＣＯおよびＰＦ2（ＣＦ3）であるニッケル錯体を含む。該ニッケル錯体の好ましい具体例としては、Ｎｉ（ＣＯ）2（ＰＦ2（ＣＦ3））2またはＮｉ（ＣＯ）（ＰＦ2（ＣＦ3））3などが挙げられる。このようなニッケル錯体であると、蒸気圧が高くなる傾向がある。また、このようなニッケル錯体は、揮発性が高くなるため、膜形成材料を揮発させて行う膜形成方法、例えばＣＶＤに好適に用いることができる。 The nickel-containing film forming material of the present invention includes, for example, a nickel complex whose ligands are CO and PF 2 (CF 3 ). Preferable specific examples of the nickel complex include Ni (CO) 2 (PF 2 (CF 3 )) 2 or Ni (CO) (PF 2 (CF 3 )) 3 . With such a nickel complex, the vapor pressure tends to increase. Moreover, since such a nickel complex has high volatility, it can be suitably used for a film forming method in which a film forming material is volatilized, for example, CVD.

　本発明のニッケル含有膜形成材料は、例えば、前記配位子の種類がＣＯおよびＰＦ（ＣＦ3）2であるニッケル錯体を含む。該ニッケル錯体の好ましい具体例としては、Ｎｉ（ＣＯ）2（ＰＦ（ＣＦ3）2）2またはＮｉ（ＣＯ）（ＰＦ（ＣＦ3）2）3などが挙げられる。このようなニッケル錯体であると、蒸気圧が高くなる傾向がある。また、このようなニッケル錯体は、揮発性が高くなるため、膜形成材料を揮発させて行う膜形成方法、例えばＣＶＤに好適に用いることができる。 The nickel-containing film forming material of the present invention includes, for example, a nickel complex in which the ligands are CO and PF (CF 3 ) 2 . Preferable specific examples of the nickel complex include Ni (CO) 2 (PF (CF 3 ) 2 ) 2 or Ni (CO) (PF (CF 3 ) 2 ) 3 . With such a nickel complex, the vapor pressure tends to increase. Moreover, since such a nickel complex has high volatility, it can be suitably used for a film forming method in which a film forming material is volatilized, for example, CVD.

　本発明のニッケル含有膜形成材料は、例えば、前記配位子の種類がＣＯおよびＰ（ＣＦ3）3であるニッケル錯体を含む。該ニッケル錯体の好ましい具体例としては、Ｎｉ（ＣＯ）2（Ｐ（ＣＦ3）3）2またはＮｉ（ＣＯ）（Ｐ（ＣＦ3）3）3などが挙げられる。このようなニッケル錯体であると、蒸気圧が高くなる傾向がある。また、このようなニッケル錯体は、揮発性が高くなるため、膜形成材料を揮発させて行う膜形成方法、例えばＣＶＤに好適に用いることができる。 The nickel-containing film forming material of the present invention includes, for example, a nickel complex in which the types of the ligands are CO and P (CF 3 ) 3 . Preferable specific examples of the nickel complex include Ni (CO) 2 (P (CF 3 ) 3 ) 2 or Ni (CO) (P (CF 3 ) 3 ) 3 . With such a nickel complex, the vapor pressure tends to increase. Moreover, since such a nickel complex has high volatility, it can be suitably used for a film forming method in which a film forming material is volatilized, for example, CVD.

　本発明のニッケル含有膜形成材料は、例えば、Ｎｉ（ＣＯ）2（Ｐ（ＣＦ3）2ＣＨ2ＣＨ2Ｐ（ＣＦ3）2）を含む。このようなニッケル錯体であると、蒸気圧が高くなる傾向がある。また、このようなニッケル錯体は、揮発性が高くなるため、膜形成材料を揮発させて行う膜形成方法、例えばＣＶＤに好適に用いることができる。 The nickel-containing film forming material of the present invention includes, for example, Ni (CO) 2 (P (CF 3 ) 2 CH 2 CH 2 P (CF 3 ) 2 ). With such a nickel complex, the vapor pressure tends to increase. Moreover, since such a nickel complex has high volatility, it can be suitably used for a film forming method in which a film forming material is volatilized, for example, CVD.

　本発明のニッケル含有膜形成材料は、例えば、Ｎｉ（ＣＯ）2（Ｐ（ＣＦ3）2ＣＦ2ＣＦ2Ｐ（ＣＦ3）2）を含む。このようなニッケル錯体であると、蒸気圧が高くなる傾向がある。また、このようなニッケル錯体は、揮発性が高くなるため、膜形成材料を揮発させて行う膜形成方法、例えばＣＶＤに好適に用いることができる。 The nickel-containing film forming material of the present invention includes, for example, Ni (CO) 2 (P (CF 3 ) 2 CF 2 CF 2 P (CF 3 ) 2 ). With such a nickel complex, the vapor pressure tends to increase. Moreover, since such a nickel complex has high volatility, it can be suitably used for a film forming method in which a film forming material is volatilized, for example, CVD.

　本発明のニッケル含有膜形成材料は、例えば、前記配位子の種類がＰＦ3およびＰＦ2（ＣＦ3）であるニッケル錯体を含む。該ニッケル錯体の好ましい具体例としては、Ｎｉ（ＰＦ3）2（ＰＦ2（ＣＦ3））2またはＮｉ（ＰＦ3）3（ＰＦ2（ＣＦ3））などが挙げられる。このようなニッケル錯体であると、蒸気圧が高くなる傾向がある。また、このようなニッケル錯体は、揮発性が高くなるため、膜形成材料を揮発させて行う膜形成方法、例えばＣＶＤに好適に用いることができる。 The nickel-containing film forming material of the present invention includes, for example, a nickel complex in which the type of the ligand is PF 3 and PF 2 (CF 3 ). Specific examples of the nickel complex include Ni (PF 3 ) 2 (PF 2 (CF 3 )) 2 or Ni (PF 3 ) 3 (PF 2 (CF 3 )). With such a nickel complex, the vapor pressure tends to increase. Moreover, since such a nickel complex has high volatility, it can be suitably used for a film forming method in which a film forming material is volatilized, for example, CVD.

　本発明のニッケル含有膜形成材料は、例えば、前記配位子の種類がＰＦ3およびＰＦ2Ｒ1（ただし、Ｒ1は、Ｈ、炭素数１～６のアルキル基またはフェニル基である。）であるニッケル錯体を含む。前記Ｒ1はＣＨ3、Ｃ2Ｈ5、Ｃ3Ｈ7、Ｃ4Ｈ9、cyclo-Ｃ6Ｈ11またはＣ6Ｈ5であることが好ましい。このようなニッケル錯体の具体例としては、Ｎｉ（ＰＦ3）2（ＰＦ2（ＣＨ3））2、Ｎｉ（ＰＦ3）（ＰＦ2（ＣＨ3））3、Ｎｉ（ＰＦ3）3（ＰＦ2（Ｃ2Ｈ5））、Ｎｉ（ＰＦ3）2（ＰＦ2（Ｃ2Ｈ5））2、Ｎｉ（ＰＦ3）2（ＰＦ2（Ｃ3Ｈ7））2、Ｎｉ（ＰＦ3）（ＰＦ2（Ｃ3Ｈ7））3、Ｎｉ（ＰＦ3）3（ＰＦ2（cyclo-Ｃ6Ｈ11））またはＮｉ（ＰＦ3）3（ＰＦ2（Ｃ6Ｈ5））が挙げられる。このようなニッケル錯体であると、蒸気圧が高くなる傾向がある。また、このようなニッケル錯体は、揮発性が高くなるため、膜形成材料を揮発させて行う膜形成方法、例えばＣＶＤに好適に用いることができる。 In the nickel-containing film forming material of the present invention, for example, the type of the ligand is PF 3 and PF 2 R 1 (where R 1 is H, an alkyl group having 1 to 6 carbon atoms, or a phenyl group). A nickel complex. R 1 is preferably CH 3 , C 2 H 5 , C 3 H 7 , C 4 H 9 , cyclo-C 6 H 11 or C 6 H 5 . Specific examples of such a nickel complex include Ni (PF 3 ) 2 (PF 2 (CH 3 )) 2 , Ni (PF 3 ) (PF 2 (CH 3 )) 3 , Ni (PF 3 ) 3 (PF 2 (C 2 H 5 )), Ni (PF 3 ) 2 (PF 2 (C 2 H 5 )) 2 , Ni (PF 3 ) 2 (PF 2 (C 3 H 7 )) 2 , Ni (PF 3 ) (PF 2 (C 3 H 7 )) 3 , Ni (PF 3 ) 3 (PF 2 (cyclo-C 6 H 11 )) or Ni (PF 3 ) 3 (PF 2 (C 6 H 5 )). . With such a nickel complex, the vapor pressure tends to increase. Moreover, since such a nickel complex has high volatility, it can be suitably used for a film forming method in which a film forming material is volatilized, for example, CVD.

　本発明のニッケル含有膜形成材料は、例えば、前記配位子の種類がＰＦ3およびＰＦＲ2Ｒ3（ただし、Ｒ2およびＲ3は各々独立に、Ｈ、炭素数１～６のアルキル基またはフェニル基を表す。）であるニッケル錯体を含む。Ｒ2およびＲ3は各々独立に、ＣＨ3、Ｃ2Ｈ5、Ｃ3Ｈ7、Ｃ4Ｈ9、cyclo-Ｃ6Ｈ11またはＣ6Ｈ5であることが好ましい。このようなニッケル錯体の具体例としては、Ｎｉ（ＰＦ3）3（ＰＦ（ＣＨ3）（Ｃ2Ｈ5））、Ｎｉ（ＰＦ3）2（ＰＦ（ＣＨ3）（Ｃ2Ｈ5））2、Ｎｉ（ＰＦ3）（ＰＦ（ＣＨ3）（Ｃ2Ｈ5））3等が挙げられる。このようなニッケル錯体であると、蒸気圧が高くなる傾向がある。また、このようなニッケル錯体は、揮発性が高くなるため、膜形成材料を揮発させて行う膜形成方法、例えばＣＶＤに好適に用いることができる。 In the nickel-containing film-forming material of the present invention, for example, the type of the ligand is PF 3 and PFR 2 R 3 (wherein R 2 and R 3 are each independently H, an alkyl group having 1 to 6 carbon atoms, or Represents a phenyl group). R 2 and R 3 are preferably each independently CH 3 , C 2 H 5 , C 3 H 7 , C 4 H 9 , cyclo-C 6 H 11 or C 6 H 5 . Specific examples of such a nickel complex include Ni (PF 3 ) 3 (PF (CH 3 ) (C 2 H 5 )), Ni (PF 3 ) 2 (PF (CH 3 ) (C 2 H 5 )) 2 , Ni (PF 3 ) (PF (CH 3 ) (C 2 H 5 )) 3 and the like. With such a nickel complex, the vapor pressure tends to increase. Moreover, since such a nickel complex has high volatility, it can be suitably used for a film forming method in which a film forming material is volatilized, for example, CVD.

　本発明のニッケル含有膜形成材料は、例えば、前記配位子の種類がＰＦ3およびＰＦ2ＮＲ4Ｒ5（ただし、Ｒ4およびＲ5は各々独立に、Ｈ、炭素数１～６のアルキル基またはフェニル基である。）であるニッケル錯体を含む。前記Ｒ4およびＲ5は各々独立に、Ｈ、ＣＨ3、Ｃ2Ｈ5、Ｃ3Ｈ7、Ｃ4Ｈ9、cyclo-Ｃ6Ｈ11またはＣ6Ｈ5であることが好ましい。このようなニッケル錯体の具体例としては、Ｎｉ（ＰＦ3）2（ＰＦ2ＮＨ2）2、Ｎｉ（ＰＦ3）3（ＰＦ2ＮＨ（ＣＨ3））、Ｎｉ（ＰＦ3）2（ＰＦ2ＮＨ（ＣＨ3））2、Ｎｉ（ＰＦ3）（ＰＦ2ＮＨ（ＣＨ3））3、Ｎｉ（ＰＦ3）3（ＰＦ2ＮＨ（Ｃ2Ｈ5））、Ｎｉ（ＰＦ3）3（ＰＦ2ＮＨ（Ｃ3Ｈ7））、Ｎｉ（ＰＦ3）3（ＰＦ2ＮＨ（Ｃ4Ｈ9））またはＮｉ（ＰＦ3）3（ＰＦ2Ｎ（Ｃ2Ｈ5）2）等が挙げられる。このようなニッケル錯体であると、蒸気圧が高くなる傾向がある。また、このようなニッケル錯体は、揮発性が高くなるため、膜形成材料を揮発させて行う膜形成方法、例えばＣＶＤに好適に用いることができる。 The nickel-containing film-forming material of the present invention has, for example, the types of the ligands PF 3 and PF 2 NR 4 R 5 (wherein R 4 and R 5 are each independently H, alkyl having 1 to 6 carbon atoms) A nickel complex which is a group or a phenyl group. R 4 and R 5 are preferably each independently H, CH 3 , C 2 H 5 , C 3 H 7 , C 4 H 9 , cyclo-C 6 H 11 or C 6 H 5 . Specific examples of such a nickel complex include Ni (PF 3 ) 2 (PF 2 NH 2 ) 2 , Ni (PF 3 ) 3 (PF 2 NH (CH 3 )), Ni (PF 3 ) 2 (PF 2 NH (CH 3 )) 2 , Ni (PF 3 ) (PF 2 NH (CH 3 )) 3 , Ni (PF 3 ) 3 (PF 2 NH (C 2 H 5 )), Ni (PF 3 ) 3 (PF 2 NH (C 3 H 7 )), Ni (PF 3 ) 3 (PF 2 NH (C 4 H 9 )) or Ni (PF 3 ) 3 (PF 2 N (C 2 H 5 ) 2 ). . With such a nickel complex, the vapor pressure tends to increase. Moreover, since such a nickel complex has high volatility, it can be suitably used for a film forming method in which a film forming material is volatilized, for example, CVD.

　上述したようなニッケル錯体を少なくとも１種含むニッケル含有膜形成材料を用いると、形成されたニッケル含有膜に炭素が残存しにくく、かつ膜形成時にＨＦが副生しにくい。特にＣＶＤにより安定なニッケル含有膜を容易に形成することができる。 When a nickel-containing film forming material containing at least one kind of nickel complex as described above is used, carbon does not easily remain in the formed nickel-containing film, and HF is hardly generated as a by-product during film formation. In particular, a stable nickel-containing film can be easily formed by CVD.

　本発明のニッケル含有膜形成材料は、上記の２種以上のニッケル錯体を含むことも可能である。また、本発明のニッケル含有膜形成材料は、ヘリウム、ネオン、アルゴンまたはクリプトンなどの希ガスを含むことも可能である。 The nickel-containing film forming material of the present invention can also contain two or more of the above nickel complexes. The nickel-containing film forming material of the present invention can also contain a rare gas such as helium, neon, argon or krypton.

　本発明のニッケル含有膜形成材料に含有するニッケル錯体の製造方法は、公知の方法によって製造することが可能である。例えば、テトラカルボニルニッケルまたはジシクロペンタジエニルニッケルなどを目的とするニッケル錯体の配位子との配位子交換により製造することが可能である。 The method for producing the nickel complex contained in the nickel-containing film forming material of the present invention can be produced by a known method. For example, it can be produced by ligand exchange with a ligand of a nickel complex intended for tetracarbonyl nickel or dicyclopentadienyl nickel.

　また、ニッケル錯体は、必要に応じて公知の方法によって精製することも可能である。精製の方法としては、例えば、蒸留または吸着などが挙げられる。 Further, the nickel complex can be purified by a known method as necessary. Examples of the purification method include distillation or adsorption.

　本発明のニッケル含有膜形成材料は、ＣＶＤによる膜形成に用いられることが好ましいが、ニッケル含有膜形成材料の蒸気を利用する成膜方法であればＣＶＤに限定されるものではない。 The nickel-containing film forming material of the present invention is preferably used for film formation by CVD, but is not limited to CVD as long as it is a film forming method using vapor of the nickel-containing film forming material.

　本発明のニッケル含有膜の製造方法は、上記ニッケル含有膜形成材料を用いて、化学気相成長法（ＣＶＤ）により膜形成する。 The method for producing a nickel-containing film of the present invention forms a film by chemical vapor deposition (CVD) using the nickel-containing film forming material.

　ニッケル含有膜の製造方法としては、Ｎｉ源である上記ニッケル錯体を分解する各種のＣＶＤを利用することができる。すなわち、各種のＣＶＤとして、熱的に分解する熱的ＣＶＤ、熱及び光により分解する光ＣＶＤ、プラズマで活性化し光分解するプラズマＣＶＤ、レーザーで活性化し光分解するレーザー補助ＣＶＤ、イオンビームで活性化し光分解するイオンビーム補助ＣＶＤなどが挙げられる。これらの各種ＣＶＤが、ニッケル含有膜の成膜方法として利用できる。 As a method for producing a nickel-containing film, various CVDs that decompose the nickel complex as a Ni source can be used. That is, as various types of CVD, thermal CVD that thermally decomposes, photo CVD that decomposes by heat and light, plasma CVD that activates and decomposes by plasma, laser-assisted CVD that activates and decomposes by laser, and active by ion beam For example, ion beam assisted CVD for photolysis and photolysis. These various types of CVD can be used as a method for forming a nickel-containing film.

　ニッケル含有膜を形成する際の反応圧力としては、０．００１３～１０１．３ｋＰａが好ましく、より好ましくは０．０１３～１０１．３ｋＰａ、さらに好ましくは０．１３～１０１．３ｋＰａである。また、反応温度としては、５０～８００℃が好ましく、さらに好ましくは１００～５００℃である。 The reaction pressure when forming the nickel-containing film is preferably 0.0013 to 101.3 kPa, more preferably 0.013 to 101.3 kPa, and still more preferably 0.13 to 101.3 kPa. The reaction temperature is preferably 50 to 800 ° C, more preferably 100 to 500 ° C.

　本発明のニッケル含有膜形成材料を用いて形成したニッケル含有膜としては、ニッケル膜またはニッケルシリサイド膜が好ましい。 The nickel-containing film formed using the nickel-containing film forming material of the present invention is preferably a nickel film or a nickel silicide film.

　ニッケル膜またはニッケルシリサイド膜は、上記ニッケル錯体をＮｉ源として用いることが必須である。また、ニッケルシリサイド膜のＳｉ源としては、好ましくはＳｉaＨ2a+2（ただし、ａは１～３の整数である。）またはＲbＳｉＨ4-b（ただし、ｂは１～３の整数であり、Ｒは炭素数１～３のアルキル基を表す。）の構造式で示される少なくとも１種のケイ素化合物であり、さらに好ましくは、シラン、ジシラン、トリシラン、メチルシラン、ジメチルシラン、トリメチルシラン、エチルシラン、ジエチルシラン、トリエチルシランである。このようなケイ素化合物をニッケルシリサイド膜のＳｉ源として用いると、蒸気圧が高くなる傾向がある。 The nickel film or nickel silicide film must use the nickel complex as a Ni source. The Si source of the nickel silicide film is preferably Si a H 2a + 2 (where a is an integer of 1 to 3) or R b SiH 4-b (where b is an integer of 1 to 3). And R represents an alkyl group having 1 to 3 carbon atoms.), And more preferably a silane, disilane, trisilane, methylsilane, dimethylsilane, trimethylsilane, Ethylsilane, diethylsilane, and triethylsilane. When such a silicon compound is used as the Si source of the nickel silicide film, the vapor pressure tends to increase.

　ニッケル膜またはニッケルシリサイド膜の製造方法としては、Ｎｉ源である上記ニッケル錯体を分解する各種のＣＶＤを利用することができる。すなわち、各種のＣＶＤとして、熱的に分解する熱的ＣＶＤ、熱及び光により分解する光ＣＶＤ、プラズマで活性化し光分解するプラズマＣＶＤ、レーザーで活性化し光分解するレーザー補助ＣＶＤ、イオンビームで活性化し光分解するイオンビーム補助ＣＶＤなどが挙げられる。これらの各種ＣＶＤが、ニッケル膜またはニッケルシリサイド膜の成膜に利用することができる。また、ニッケルシリサイド膜のＳｉ源である上記ケイ素化合物を分解する場合も同様の方法で各種のＣＶＤを利用することができる。 As a method for producing a nickel film or a nickel silicide film, various types of CVD for decomposing the nickel complex as a Ni source can be used. That is, as various types of CVD, thermal CVD that thermally decomposes, photo CVD that decomposes by heat and light, plasma CVD that activates and decomposes by plasma, laser-assisted CVD that activates and decomposes by laser, and active by ion beam For example, ion beam assisted CVD for photolysis and photolysis. These various types of CVD can be used for forming a nickel film or a nickel silicide film. Also, when the silicon compound that is the Si source of the nickel silicide film is decomposed, various types of CVD can be used in the same manner.

　ニッケル膜またはニッケルシリサイド膜を形成する際の反応圧力としては、０．００１３～１０１．３ｋＰａが好ましく、より好ましくは０．０１３～１０１．３ｋＰａ、さらに好ましくは０．１３～１０１．３ｋＰａである。また、反応温度としては、５０～８００℃が好ましく、さらに好ましくは１００～５００℃である。 The reaction pressure when forming the nickel film or nickel silicide film is preferably 0.0013 to 101.3 kPa, more preferably 0.013 to 101.3 kPa, and still more preferably 0.13 to 101.3 kPa. The reaction temperature is preferably 50 to 800 ° C, more preferably 100 to 500 ° C.

　本発明のニッケル含有膜形成材料を用いて製造するニッケル含有膜は、還元剤の存在下に製造すると、ＮｉまたはＳｉが還元されやすくなる。還元剤としては、例えば、水素などが挙げられる。 When a nickel-containing film produced using the nickel-containing film-forming material of the present invention is produced in the presence of a reducing agent, Ni or Si is likely to be reduced. Examples of the reducing agent include hydrogen.

　以下、本発明を実施例によって詳細に説明するが、本発明はこれらに限定されるものではない。 Hereinafter, the present invention will be described in detail by way of examples, but the present invention is not limited thereto.

　［合成例１］
　・Ｎｉ（ＣＯ）3（ＰＦ3）の合成
　この錯体は、Inorganic Chemistry vol.４、６５１（１９６５）に記載の方法に準じて合成した。まず、５００ｍｌステンレス製耐圧容器にＮｉ（ＣＯ）4　６．５ｇを入れ、ＰＦ3　２５ｇを導入して密閉した。その後、容器を１００℃で２時間加熱した。加熱後、蒸留により無色液体を分取した。分取した無色液体をＧＣ－ＭＳ（ＨＰ製ＨＰ６８９０／ＪＥＯＬ製ＪＭＳ－ＡｕｔｏｍａｓｓII）、ＩＣＰ－ＡＥＳ（ＳＩＩ製ＶＩＳＴＡ－ＰＲＯ）および有機元素分析装置（ＬＥＣＯ製ＣＨＮＳ－９３２）により分析したところ、Ｎｉ（ＣＯ）3（ＰＦ3）であることを確認した（２．８ｇ、収率３０％）。 [Synthesis Example 1]
Synthesis of Ni (CO) 3 (PF 3 ) This complex was synthesized according to the method described in Inorganic Chemistry vol. 4, 651 (1965). First, 6.5 g of Ni (CO) 4 was put into a 500 ml stainless steel pressure vessel, and 25 g of PF 3 was introduced and sealed. The container was then heated at 100 ° C. for 2 hours. After heating, a colorless liquid was collected by distillation. The separated colorless liquid was analyzed by GC-MS (HP 6890 made by HP / JMS-Automass II made by JEOL), ICP-AES (VISTA-PRO made by SII) and an organic element analyzer (CHNS-932 made by LECO). CO) 3 (PF 3 ) was confirmed (2.8 g, yield 30%).

　［合成例２］
　・Ｎｉ（ＣＯ）2（ＰＦ3）2の合成
　この錯体は、Inorganic Chemistry vol.４、６５１（１９６５）に記載の方法に準じて合成した。まず、５００ｍｌステンレス製耐圧容器にＮｉ（ＣＯ）4　６．５ｇを入れ、ＰＦ3　３７ｇを導入して密閉した。その後、容器を１００℃で２時間加熱した。加熱後、蒸留により無色液体を分取した。分取した無色液体をＧＣ－ＭＳ（ＨＰ製ＨＰ６８９０／ＪＥＯＬ製ＪＭＳ－ＡＵＴＯＭＡＳＳII）、ＩＣＰ－ＡＥＳ（ＳＩＩ製ＶＩＳＴＡ－ＰＲＯ）および有機元素分析装置（ＬＥＣＯ製ＣＨＮＳ－９３２）により分析したところ、Ｎｉ（ＣＯ）2（ＰＦ3）2であることを確認した（７．５ｇ、収率６８％）。 [Synthesis Example 2]
· Ni (CO) 2 (PF 3) 2 Synthesis This complex was synthesized according to the method described in Inorganic Chemistry vol.4,651 (1965). First, 6.5 g of Ni (CO) 4 was put in a 500 ml stainless steel pressure vessel, and 37 g of PF 3 was introduced and sealed. The container was then heated at 100 ° C. for 2 hours. After heating, a colorless liquid was collected by distillation. The collected colorless liquid was analyzed by GC-MS (HP 6890 made by HP / JMS-AUTOMASSII made by JEOL), ICP-AES (VISTA-PRO made by SII) and an organic element analyzer (CHNS-932 made by LECO). CO) 2 (PF 3 ) 2 was confirmed (7.5 g, yield 68%).

　［合成例３］
　・Ｎｉ（ＣＯ）（ＰＦ3）3の合成
　この錯体は、Inorganic Chemistry vol.４、６５１（１９６５）に記載の方法に準じて合成した。まず、５００ｍｌステンレス製耐圧容器にＮｉ（ＣＯ）4　６．５ｇを入れ、ＰＦ3　４９ｇを導入して密閉した。その後、容器を１００℃で２時間加熱した。加熱後、蒸留により無色液体を分取した。分取した無色液体をＧＣ－ＭＳ（ＨＰ製ＨＰ６８９０／ＪＥＯＬ製ＪＭＳ－ＡＵＴＯＭＡＳＳII）、ＩＣＰ－ＡＥＳ（ＳＩＩ製ＶＩＳＴＡ－ＰＲＯ）および有機元素分析装置（ＬＥＣＯ製ＣＨＮＳ－９３２）により分析したところ、Ｎｉ（ＣＯ）（ＰＦ3）3であることを確認した（７．８ｇ、収率５８％）。 [Synthesis Example 3]
Synthesis of Ni (CO) (PF 3 ) 3 This complex was synthesized according to the method described in Inorganic Chemistry vol. 4, 651 (1965). First, 6.5 g of Ni (CO) 4 was put in a 500 ml stainless steel pressure vessel, and 49 g of PF 3 was introduced and sealed. The container was then heated at 100 ° C. for 2 hours. After heating, a colorless liquid was collected by distillation. The collected colorless liquid was analyzed by GC-MS (HP 6890 made by HP / JMS-AUTOMASSII made by JEOL), ICP-AES (VISTA-PRO made by SII) and an organic element analyzer (CHNS-932 made by LECO). CO) (PF 3 ) 3 was confirmed (7.8 g, yield 58%).

　［合成例４］
　・Ｎｉ（ＣＯ）（ＰＦ2（ＣＦ3））3の合成
　この錯体は、Inorganic Chemistry vol.４、６５１（１９６５）に記載の方法に準じて合成した。まず、５００ｍｌステンレス製耐圧容器にＮｉ（ＣＯ）4　６．５ｇを入れ、ＰＦ2（ＣＦ3）　５８ｇを導入して密閉した。その後、容器を１００℃で３時間加熱した。加熱後、蒸留により無色液体を分取した。分取した無色液体をＧＣ－ＭＳ（ＨＰ製ＨＰ６８９０／ＪＥＯＬ製ＪＭＳ－ＡＵＴＯＭＡＳＳII）、ＩＣＰ－ＡＥＳ（ＳＩＩ製ＶＩＳＴＡ－ＰＲＯ）および有機元素分析装置（ＬＥＣＯ製ＣＨＮＳ－９３２）により分析したところ、Ｎｉ（ＣＯ）（ＰＦ2（ＣＦ3））3であることを確認した（１４ｇ、収率３５％）。 [Synthesis Example 4]
Synthesis of Ni (CO) (PF 2 (CF 3 )) 3 This complex was synthesized according to the method described in Inorganic Chemistry vol. 4, 651 (1965). First, 6.5 g of Ni (CO) 4 was put into a 500 ml stainless steel pressure vessel, and 58 g of PF 2 (CF 3 ) was introduced and sealed. The container was then heated at 100 ° C. for 3 hours. After heating, a colorless liquid was collected by distillation. The collected colorless liquid was analyzed by GC-MS (HP 6890 made by HP / JMS-AUTOMASSII made by JEOL), ICP-AES (VISTA-PRO made by SII) and an organic element analyzer (CHNS-932 made by LECO). CO) (PF 2 (CF 3 )) 3 was confirmed (14 g, yield 35%).

　［合成例５］
　・Ｎｉ（ＣＯ）2（Ｐ（ＣＦ3）3）2の合成
　この錯体は、Inorganic Chemistry vol.４、６５１（１９６５）に記載の方法に準じて合成した。まず、５００ｍｌステンレス製耐圧容器にＮｉ（ＣＯ）4　６．５ｇを入れ、Ｐ（ＣＦ3）3　１００ｇを導入して密閉した。その後、容器を１００℃で３時間加熱した。加熱後、蒸留により無色液体を分取した。分取した無色液体をＧＣ－ＭＳ（ＨＰ製ＨＰ６８９０／ＪＥＯＬ製ＪＭＳ－ＡＵＴＯＭＡＳＳII）、ＩＣＰ－ＡＥＳ（ＳＩＩ製ＶＩＳＴＡ－ＰＲＯ）および有機元素分析装置（ＬＥＣＯ製ＣＨＮＳ－９３２）により分析したところ、Ｎｉ（ＣＯ）2（Ｐ（ＣＦ3）3）2であることを確認した（１４ｇ、収率４６％）。 [Synthesis Example 5]
Synthesis of Ni (CO) 2 (P (CF 3 ) 3 ) 2 This complex was synthesized according to the method described in Inorganic Chemistry vol. 4, 651 (1965). First, 6.5 g of Ni (CO) 4 was put into a 500 ml stainless steel pressure vessel, and 100 g of P (CF 3 ) 3 was introduced and sealed. The container was then heated at 100 ° C. for 3 hours. After heating, a colorless liquid was collected by distillation. The collected colorless liquid was analyzed by GC-MS (HP 6890 made by HP / JMS-AUTOMASSII made by JEOL), ICP-AES (VISTA-PRO made by SII) and an organic element analyzer (CHNS-932 made by LECO). CO) 2 (P (CF 3 ) 3 ) 2 was confirmed (14 g, yield 46%).

　［合成例６］
　・Ｎｉ（ＰＦ3）2（ＰＦ2（ＣＦ3））2の合成
　この錯体は、Inorganic Chemistry vol.４、６５１（１９６５）に記載の方法に準じて合成した。まず、５００ｍｌステンレス製耐圧容器にＮｉ（ＰＦ2（ＣＦ3））4　２５ｇを入れ、ＰＦ3　５０ｇを導入して密閉した。その後、容器を１００℃で３週間加熱した。加熱後、蒸留により無色液体を分取した。分取した無色液体をＧＣ－ＭＳ（ＨＰ製ＨＰ６８９０／ＪＥＯＬ製ＪＭＳ－ＡＵＴＯＭＡＳＳII）、ＩＣＰ－ＡＥＳ（ＳＩＩ製ＶＩＳＴＡ－ＰＲＯ）および有機元素分析装置（ＬＥＣＯ製ＣＨＮＳ－９３２）により分析したところ、Ｎｉ（ＰＦ3）2（ＰＦ2（ＣＦ3））2であることを確認した（１７ｇ、収率８３％）。 [Synthesis Example 6]
Synthesis of Ni (PF 3 ) 2 (PF 2 (CF 3 )) 2 This complex was synthesized according to the method described in Inorganic Chemistry vol. 4, 651 (1965). First, 25 g of Ni (PF 2 (CF 3 )) 4 was placed in a 500 ml stainless steel pressure vessel, and 50 g of PF 3 was introduced and sealed. The container was then heated at 100 ° C. for 3 weeks. After heating, a colorless liquid was collected by distillation. The collected colorless liquid was analyzed by GC-MS (HP 6890 made by HP / JMS-AUTOMASSII made by JEOL), ICP-AES (VISTA-PRO made by SII) and an organic element analyzer (CHNS-932 made by LECO). PF 3 ) 2 (PF 2 (CF 3 )) 2 was confirmed (17 g, yield 83%).

　［合成例７］
　・Ｎｉ（ＣＯ）2（Ｐ（ＣＦ3）2ＣＨ2ＣＨ2Ｐ（ＣＦ3）2）の合成
　この錯体は、Journal of the American Chemical Society vol.８５、３５２２（１９６３）に記載の方法に準じて合成した。まず、窒素雰囲気下、１０００ｍｌフラスコに、脱水乾燥したジエチルエーテル　７００ｍｌおよびＮｉ（ＣＯ）4　１２ｇを入れ、Ｐ（ＣＦ3）2ＣＨ2ＣＨ2Ｐ（ＣＦ3）2　２６ｇを加えて、６０℃で２０時間撹拌した。反応後、蒸留により無色液体を分取した。分取した無色液体をＧＣ－ＭＳ（ＨＰ製ＨＰ６８９０／ＪＥＯＬ製ＪＭＳ－ＡＵＴＯＭＡＳＳII）、ＩＣＰ－ＡＥＳ（ＳＩＩ製ＶＩＳＴＡ－ＰＲＯ）および有機元素分析装置（ＬＥＣＯ製ＣＨＮＳ－９３２）により分析したところ、Ｎｉ（ＣＯ）2（Ｐ（ＣＦ3）2ＣＨ2ＣＨ2Ｐ（ＣＦ3）2）であることを確認した（１６ｇ、収率４８％）。 [Synthesis Example 7]
Synthesis of Ni (CO) 2 (P (CF 3 ) 2 CH 2 CH 2 P (CF 3 ) 2 ) This complex conforms to the method described in Journal of the American Chemical Society vol. 85, 3522 (1963). And synthesized. First, 700 ml of dehydrated and dried diethyl ether and 12 g of Ni (CO) 4 were placed in a 1000 ml flask under a nitrogen atmosphere, and 26 g of P (CF 3 ) 2 CH 2 CH 2 P (CF 3 ) 2 was added at 60 ° C. Stir for 20 hours. After the reaction, a colorless liquid was separated by distillation. The collected colorless liquid was analyzed by GC-MS (HP 6890 made by HP / JMS-AUTOMASSII made by JEOL), ICP-AES (VISTA-PRO made by SII) and an organic element analyzer (CHNS-932 made by LECO). CO) 2 (P (CF 3 ) 2 CH 2 CH 2 P (CF 3 ) 2 ) (16 g, 48% yield).

　［合成例８］
　・Ｎｉ（ＣＯ）2（Ｐ（ＣＦ3）2ＣＦ2ＣＦ2Ｐ（ＣＦ3）2）の合成
　この錯体は、Journal of the American Chemical Society vol.８５、３５２２（１９６３）に記載の方法に準じて合成した。まず、窒素雰囲気下、１０００ｍｌフラスコに、脱水乾燥したジエチルエーテル　７００ｍｌおよびＮｉ（ＣＯ）4　１２ｇを入れ、Ｐ（ＣＦ3）2ＣＦ2ＣＦ2Ｐ（ＣＦ3）2　３１ｇを加えて、６０℃で２１時間撹拌した。反応後、蒸留により無色液体を分取した。分取した無色液体をＧＣ－ＭＳ（ＨＰ製ＨＰ６８９０／ＪＥＯＬ製ＪＭＳ－ＡＵＴＯＭＡＳＳII）、ＩＣＰ－ＡＥＳ（ＳＩＩ製ＶＩＳＴＡ－ＰＲＯ）および有機元素分析装置（ＬＥＣＯ製ＣＨＮＳ－９３２）により分析したところ、Ｎｉ（ＣＯ）2（Ｐ（ＣＦ3）2ＣＦ2ＣＦ2Ｐ（ＣＦ3）2）であることを確認した（２５ｇ、収率６５％）。 [Synthesis Example 8]
Synthesis of Ni (CO) 2 (P (CF 3 ) 2 CF 2 CF 2 P (CF 3 ) 2 ) This complex conforms to the method described in Journal of the American Chemical Society vol. 85, 3522 (1963). And synthesized. First, under a nitrogen atmosphere, 700 ml of dehydrated and dried diethyl ether and 12 g of Ni (CO) 4 were placed in a 1000 ml flask, and 31 g of P (CF 3 ) 2 CF 2 CF 2 P (CF 3 ) 2 was added at 60 ° C. Stir for 21 hours. After the reaction, a colorless liquid was separated by distillation. The collected colorless liquid was analyzed by GC-MS (HP 6890 made by HP / JMS-AUTOMASSII made by JEOL), ICP-AES (VISTA-PRO made by SII) and an organic element analyzer (CHNS-932 made by LECO). CO) 2 (P (CF 3 ) 2 CF 2 CF 2 P (CF 3 ) 2 ) (25 g, yield 65%).

　［合成例９］
　・Ｎｉ（ＰＦ3）3（ＰＦ2ＮＨ（ＣＨ3））の合成
　この錯体は、Journal of the American Chemical Society vol.９３、１１３０（１９７１）を参考に配位子合成をした後、Inorganic Chemistry vol.４、６５１（１９６５）に記載の方法に準じて合成した。まず、５００ｍｌステンレス耐圧容器に、クロロジフルオロホスフィン　８．５ｇとメチルアミン　５．１ｇとを導入して密閉した。その後、室温で１５分間撹拌した。反応後、反応物を－９６℃でトラップし、ＰＦ2ＮＨ（ＣＨ3）　５．２ｇを得た。得られたＰＦ2ＮＨ（ＣＨ3）の同定は、ＦＴ－ＩＲ（サーモエレクトロン製Ｔｈｅｒｍｏ－Ｎｉｃｏｌｅｔ　ＡＶＡＴＡＲ３６０）およびＮＭＲ（ＪＥＯＬ製ＪＮＭ－ＡＬ４００）で行った。次に、５００ｍｌステンレス製耐圧容器にＮｉ（ＰＦ3）4　１３ｇを入れ、ＰＦ2ＮＨ（ＣＨ3）　５．２ｇを導入して密閉した。その後、容器を１００℃で２４時間加熱した。反応後、蒸留により無色液体を分取した。分取した無色液体をＧＣ－ＭＳ（ＨＰ製ＨＰ６８９０／ＪＥＯＬ製ＪＭＳ－ＡＵＴＯＭＡＳＳII）、ＩＣＰ－ＡＥＳ（ＳＩＩ製ＶＩＳＴＡ－ＰＲＯ）および有機元素分析装置（ＬＥＣＯ製ＣＨＮＳ－９３２）により分析したところ、Ｎｉ（ＰＦ3）3（ＰＦ2ＮＨ（ＣＨ3））であることを確認した（９．０ｇ、収率６９％）。 [Synthesis Example 9]
Synthesis of Ni (PF 3 ) 3 (PF 2 NH (CH 3 )) This complex was synthesized by ligand synthesis with reference to Journal of the American Chemical Society vol. 93, 1130 (1971), and then the organic chemistry vol. Synthesized according to the method described in .4, 651 (1965). First, 8.5 g of chlorodifluorophosphine and 5.1 g of methylamine were introduced into a 500 ml stainless steel pressure vessel and sealed. Then, it stirred at room temperature for 15 minutes. After the reaction, the reaction product was trapped at −96 ° C. to obtain 5.2 g of PF 2 NH (CH 3 ). The obtained PF 2 NH (CH 3 ) was identified by FT-IR (Thermo-Nicolet AVATAR360 manufactured by Thermo Electron) and NMR (JEOL JNM-AL400). Next, 13 g of Ni (PF 3 ) 4 was placed in a 500 ml stainless steel pressure vessel, and 5.2 g of PF 2 NH (CH 3 ) was introduced and sealed. The container was then heated at 100 ° C. for 24 hours. After the reaction, a colorless liquid was separated by distillation. The collected colorless liquid was analyzed by GC-MS (HP 6890 made by HP / JMS-AUTOMASSII made by JEOL), ICP-AES (VISTA-PRO made by SII) and an organic element analyzer (CHNS-932 made by LECO). PF 3 ) 3 (PF 2 NH (CH 3 )) was confirmed (9.0 g, yield 69%).

　［合成例１０］
　・Ｎｉ（ＰＦ3）3（ＰＦ2Ｎ（Ｃ2Ｈ5）2）の合成
　この錯体は、Journal of the American Chemical Society vol.９３、１１３０（１９７１）を参考に配位子合成をした後、Inorganic Chemistry vol.４、６５１（１９６５）に記載の方法に準じて合成した。まず、５００ｍｌステンレス製耐圧容器に、クロロジフルオロホスフィン　８．５ｇとジエチルアミン　１２ｇとを導入して密閉した。その後、室温で１５分間撹拌した。反応後、反応物を－９６℃でトラップし、ＰＦ2Ｎ（Ｃ2Ｈ5）2　９．１ｇを得た。同定は、ＦＴ－ＩＲ（サーモエレクトロン製Ｔｈｅｒｍｏ－Ｎｉｃｏｌｅｔ　ＡＶＡＴＡＲ３６０）およびＮＭＲ（ＪＥＯＬ製ＪＮＭ－ＡＬ４００）で行った。次に、５００ｍｌステンレス耐圧容器にＮｉ（ＰＦ3）4　１６ｇを入れ、ＰＦ2Ｎ（Ｃ2Ｈ5）2　９．１ｇを導入して密閉した。その後、容器を１００℃で２４時間加熱した。反応後、蒸留により無色液体を分取した。分取した無色液体をＧＣ－ＭＳ（ＨＰ製ＨＰ６８９０／ＪＥＯＬ製ＪＭＳ－ＡＵＴＯＭＡＳＳII）、ＩＣＰ－ＡＥＳ（ＳＩＩ製ＶＩＳＴＡ－ＰＲＯ）および有機元素分析装置（ＬＥＣＯ製ＣＨＮＳ－９３２）により分析したところ、Ｎｉ（ＰＦ3）3（ＰＦ2Ｎ（Ｃ2Ｈ5）2）であることを確認した（１３ｇ、収率７２％）。 [Synthesis Example 10]
Synthesis of Ni (PF 3 ) 3 (PF 2 N (C 2 H 5 ) 2 ) This complex was synthesized after ligand synthesis with reference to Journal of the American Chemical Society vol. 93, 1130 (1971). It was synthesized according to the method described in Inorganic Chemistry vol. 4, 651 (1965). First, 8.5 g of chlorodifluorophosphine and 12 g of diethylamine were introduced into a 500 ml stainless steel pressure vessel and sealed. Then, it stirred at room temperature for 15 minutes. After the reaction, the reaction product was trapped at −96 ° C. to obtain 9.1 g of PF 2 N (C 2 H 5 ) 2 . Identification was performed by FT-IR (Thermo Electron Thermo-Nicolet AVATAR360) and NMR (JEOL JNM-AL400). Next, 16 g of Ni (PF 3 ) 4 was placed in a 500 ml stainless steel pressure vessel, and 9.1 g of PF 2 N (C 2 H 5 ) 2 was introduced and sealed. The container was then heated at 100 ° C. for 24 hours. After the reaction, a colorless liquid was separated by distillation. The collected colorless liquid was analyzed by GC-MS (HP 6890 made by HP / JMS-AUTOMASSII made by JEOL), ICP-AES (VISTA-PRO made by SII) and an organic element analyzer (CHNS-932 made by LECO). PF 3 ) 3 (PF 2 N (C 2 H 5 ) 2 ) (13 g, yield 72%).

　［実施例１］
　・Ｎｉ（ＣＯ）3（ＰＦ3）の成膜評価
　合成例１で得たＮｉ（ＣＯ）3（ＰＦ3）について、示差熱熱重量同時測定装置（ＳＩＩ製　ＴＧ／ＤＴＡ６２００）を用いて、５００℃まで加熱した時の揮発率を求めたところ、９９．５質量％であった。揮発残渣が非常に少なく、ニッケル含有膜形成材料として適していることがわかった。 [Example 1]
· The Ni (CO) 3 (PF 3 ) Ni obtained by film formation evaluation Synthesis Example 1 (CO) 3 (PF 3) , using a differential thermogravimetric simultaneous measurement device (SII manufactured by TG / DTA6200), 500 It was 99.5 mass% when the volatilization rate when heated to ° C was determined. It has been found that there are very few volatile residues and it is suitable as a nickel-containing film-forming material.

　［実施例１－１］
　・Ｎｉ（ＣＯ）3（ＰＦ3）を用いたニッケルシリサイド膜形成
　図１に示したＣＶＤ装置を用いて、合成例１で得たＮｉ（ＣＯ）3（ＰＦ3）の成膜評価を行った。Ｎｉ（ＣＯ）3（ＰＦ3）を原料容器に入れ、その容器を３０℃に保持し、キャリアガスとしてヘリウムを１０ｍｌ／ｍｉｎ、Ｓｉ源としてＳｉＨ4とＨ2との混合ガス（ＳｉＨ4：Ｈ2＝（１：９）（容量比））を２０ｍｌ／ｍｉｎの流量で流し、反応容器に導入した。このとき、系内は２０ｋＰａに減圧され、反応容器内の基板温度は１５０～３５０℃であった。 [Example 1-1]
Formation of nickel silicide film using Ni (CO) 3 (PF 3 ) Using the CVD apparatus shown in FIG. 1, film formation evaluation of Ni (CO) 3 (PF 3 ) obtained in Synthesis Example 1 was performed. . Ni (CO) 3 (PF 3 ) is put in a raw material container, the container is kept at 30 ° C., helium is 10 ml / min as a carrier gas, and a mixed gas of SiH 4 and H 2 as a Si source (SiH 4 : H 2 = (1: 9) (volume ratio)) was flowed at a flow rate of 20 ml / min and introduced into the reaction vessel. At this time, the pressure in the system was reduced to 20 kPa, and the substrate temperature in the reaction vessel was 150 to 350 ° C.

　その結果、基板上に膜の堆積が確認され、Ｘ線光電子分析装置（ＸＰＳ）（ＫＲＡＴＯＳ製ＡＸＩＳ－ＮＯＶＡ）により膜の組成を調べたところ、ニッケルおよびケイ素の存在が確認された。また、炭素はほとんど確認されなかった。さらにＸ線回折装置（ＸＲＤ）（リガク製ＲＡＤ－γＸ）の分析から、この膜がニッケルシリサイド膜であることが確認された。また、ＣＶＤ装置からの排気ガスの分析でＨＦはほとんど確認されなかった。当該排気ガスの分析は、ＦＴ－ＩＲ（サーモエレクトロン製Ｎｉｃｏｌｅｔ３８０）で行った。 As a result, deposition of the film was confirmed on the substrate, and the composition of the film was examined with an X-ray photoelectron analyzer (XPS) (AXIS-NOVA manufactured by KRATOS), and the presence of nickel and silicon was confirmed. Moreover, almost no carbon was confirmed. Further, analysis by an X-ray diffractometer (XRD) (RAD-γX manufactured by Rigaku) confirmed that this film was a nickel silicide film. Moreover, almost no HF was confirmed in the analysis of the exhaust gas from the CVD apparatus. The exhaust gas was analyzed by FT-IR (Nicolet 380 manufactured by Thermo Electron).

　［実施例１－２］
　・Ｎｉ（ＣＯ）3（ＰＦ3）を用いたニッケル膜形成
　ＳｉＨ4とＨ2との混合ガスの代わりにＨ2ガスを用いた以外は実施例１－１と同様に成膜した。その結果、基板上に膜の堆積が確認され、Ｘ線光電子分析装置（ＸＰＳ）（ＫＲＡＴＯＳ製ＡＸＩＳ－ＮＯＶＡ）により膜の組成を調べたところ、ニッケルの存在が確認された。また、炭素はほとんど確認されなかった。さらにＸ線回折装置（ＸＲＤ）（リガク製ＲＡＤ－γＸ）の分析から、この膜がニッケル膜であることが確認された。また、ＣＶＤ装置からの排気ガスの分析でＨＦはほとんど確認されなかった。当該排気ガスの分析は、ＦＴ－ＩＲ（サーモエレクトロン製Ｎｉｃｏｌｅｔ３８０）で行った。 [Example 1-2]
Nickel film formation using Ni (CO) 3 (PF 3 ) A nickel film was formed in the same manner as in Example 1-1 except that H 2 gas was used instead of the mixed gas of SiH 4 and H 2 . As a result, deposition of the film was confirmed on the substrate, and when the composition of the film was examined with an X-ray photoelectron analyzer (XPS) (AXIS-NOVA manufactured by KRATOS), the presence of nickel was confirmed. Moreover, almost no carbon was confirmed. Further, the film was confirmed to be a nickel film by analysis with an X-ray diffractometer (XRD) (Rigaku RAD-γX). Moreover, almost no HF was confirmed in the analysis of the exhaust gas from the CVD apparatus. The exhaust gas was analyzed by FT-IR (Nicolet 380 manufactured by Thermo Electron).

　［実施例２］
　・Ｎｉ（ＣＯ）2（ＰＦ3）2の成膜評価
　合成例２で得たＮｉ（ＣＯ）2（ＰＦ3）2について、示差熱熱重量同時測定装置（ＳＩＩ製ＴＧ／ＤＴＡ６２００）を用いて、５００℃まで加熱した時の揮発率を求めたところ、９９．２質量％であった。揮発残渣が非常に少なく、ニッケル含有膜形成材料として適していることがわかった。 [Example 2]
About · Ni (CO) 2 (PF 3) Ni obtained in 2 of film formation evaluation Synthesis Example 2 (CO) 2 (PF 3 ) 2, using a differential thermogravimetric simultaneous measurement device (SII manufactured by TG / DTA6200) The volatilization rate when heated to 500 ° C. was 99.2% by mass. It has been found that there are very few volatile residues and it is suitable as a nickel-containing film-forming material.

　［実施例２－１］
　・Ｎｉ（ＣＯ）2（ＰＦ3）2を用いたニッケルシリサイド膜形成
　合成例２で得たＮｉ（ＣＯ）2（ＰＦ3）2を用いた以外は、実施例１－１と同様にして成膜した。その結果、基板上に膜の堆積が確認され、Ｘ線光電子分析装置（ＸＰＳ）（ＫＲＡＴＯＳ製ＡＸＩＳ－ＮＯＶＡ）により膜の組成を調べたところ、ニッケルおよびケイ素の存在が確認された。また、炭素はほとんど確認されなかった。さらにＸ線回折装置（ＸＲＤ）（リガク製ＲＡＤ－γＸ）の分析から、この膜がニッケルシリサイド膜であることが確認された。また、ＣＶＤ装置からの排気ガスの分析でＨＦはほとんど確認されなかった。当該排気ガスの分析は、ＦＴ－ＩＲ（サーモエレクトロン製Ｎｉｃｏｌｅｔ３８０）で行った。 [Example 2-1]
· Ni (CO) 2 (PF 3) Ni obtained 2 nickel silicide film formed in Synthesis Example 2 using (CO) 2 (PF 3) 2 , except that used were formed in the same manner as in Example 1-1 Filmed. As a result, deposition of the film was confirmed on the substrate, and when the composition of the film was examined by an X-ray photoelectron analyzer (XPS) (AXIS-NOVA manufactured by KRATOS), the presence of nickel and silicon was confirmed. Moreover, almost no carbon was confirmed. Further, analysis by an X-ray diffractometer (XRD) (RAD-γX manufactured by Rigaku) confirmed that this film was a nickel silicide film. Moreover, almost no HF was confirmed in the analysis of the exhaust gas from the CVD apparatus. The exhaust gas was analyzed by FT-IR (Nicolet 380 manufactured by Thermo Electron).

　［実施例２－２］
　・Ｎｉ（ＣＯ）2（ＰＦ3）2を用いたニッケル膜形成
　ＳｉＨ4とＨ2との混合ガスの代わりにＨ2ガスを用いた以外は実施例２－１と同様に成膜した。その結果、基板上に膜の堆積が確認され、Ｘ線光電子分析装置（ＸＰＳ）（ＫＲＡＴＯＳ製ＡＸＩＳ－ＮＯＶＡ）により膜の組成を調べたところ、ニッケルの存在が確認された。また、炭素はほとんど確認されなかった。さらにＸ線回折装置（ＸＲＤ）（リガク製ＲＡＤ－γＸ）の分析から、この膜がニッケル膜であることが確認された。また、ＣＶＤ装置からの排気ガスの分析でＨＦはほとんど確認されなかった。当該排気ガスの分析は、ＦＴ－ＩＲ（サーモエレクトロン製Ｎｉｃｏｌｅｔ３８０）で行った。 [Example 2-2]
Nickel film formation using Ni (CO) 2 (PF 3 ) 2 A film was formed in the same manner as in Example 2-1, except that H 2 gas was used instead of the mixed gas of SiH 4 and H 2 . As a result, deposition of the film was confirmed on the substrate, and when the composition of the film was examined with an X-ray photoelectron analyzer (XPS) (AXIS-NOVA manufactured by KRATOS), the presence of nickel was confirmed. Moreover, almost no carbon was confirmed. Further, the film was confirmed to be a nickel film by analysis with an X-ray diffractometer (XRD) (Rigaku RAD-γX). Moreover, almost no HF was confirmed in the analysis of the exhaust gas from the CVD apparatus. The exhaust gas was analyzed by FT-IR (Nicolet 380 manufactured by Thermo Electron).

　［実施例３］
　・Ｎｉ（ＣＯ）（ＰＦ3）3の成膜評価
　合成例３で得たＮｉ（ＣＯ）（ＰＦ3）3について、示差熱熱重量同時測定装置（ＳＩＩ製ＴＧ／ＤＴＡ６２００）を用いて、５００℃まで加熱した時の揮発率を求めたところ、９８．９質量％であった。揮発残渣が非常に少なく、ニッケル含有膜形成材料として適していることがわかった。 [Example 3]
About · Ni (CO) (PF 3 ) 3 Ni obtained by film formation evaluation Synthesis Example 3 (CO) (PF 3) 3 , using a differential thermogravimetric simultaneous measurement device (SII manufactured by TG / DTA6200), 500 It was 98.9 mass% when the volatilization rate when heated to ° C was determined. It has been found that there are very few volatile residues and it is suitable as a nickel-containing film-forming material.

　［実施例３－１］
　・Ｎｉ（ＣＯ）（ＰＦ3）3を用いたニッケルシリサイド膜形成
　合成例３で得たＮｉ（ＣＯ）（ＰＦ3）3を用いた以外は、実施例１－１と同様にして成膜した。その結果、基板上に膜の堆積が確認され、Ｘ線光電子分析装置（ＸＰＳ）（ＫＲＡＴＯＳ製ＡＸＩＳ－ＮＯＶＡ）により膜の組成を調べたところ、ニッケルおよびケイ素の存在が確認された。また、炭素はほとんど確認されなかった。さらにＸ線回折装置（ＸＲＤ）（リガク製ＲＡＤ－γＸ）の分析から、この膜がニッケルシリサイド膜であることが確認された。また、ＣＶＤ装置からの排気ガスの分析でＨＦはほとんど確認されなかった。当該排気ガスの分析は、ＦＴ－ＩＲ（サーモエレクトロン製Ｎｉｃｏｌｅｔ３８０）で行った。 [Example 3-1]
Nickel silicide film formation using Ni (CO) (PF 3 ) 3 A film was formed in the same manner as in Example 1-1 except that Ni (CO) (PF 3 ) 3 obtained in Synthesis Example 3 was used. . As a result, deposition of the film was confirmed on the substrate, and when the composition of the film was examined by an X-ray photoelectron analyzer (XPS) (AXIS-NOVA manufactured by KRATOS), the presence of nickel and silicon was confirmed. Moreover, almost no carbon was confirmed. Further, analysis by an X-ray diffractometer (XRD) (RAD-γX manufactured by Rigaku) confirmed that this film was a nickel silicide film. Moreover, almost no HF was confirmed in the analysis of the exhaust gas from the CVD apparatus. The exhaust gas was analyzed by FT-IR (Nicolet 380 manufactured by Thermo Electron).

　［実施例３－２］
　・Ｎｉ（ＣＯ）（ＰＦ3）3を用いたニッケル膜形成
　ＳｉＨ4とＨ2との混合ガスの代わりにＨ2ガスを用いた以外は実施例３－１と同様に成膜した。その結果、基板上に膜の堆積が確認され、Ｘ線光電子分析装置（ＸＰＳ）（ＫＲＡＴＯＳ製ＡＸＩＳ－ＮＯＶＡ）により膜の組成を調べたところ、ニッケルの存在が確認された。また、炭素はほとんど確認されなかった。さらにＸ線回折装置（ＸＲＤ）（リガク製ＲＡＤ－γＸ）の分析から、この膜がニッケル膜であることが確認された。また、ＣＶＤ装置からの排気ガスの分析でＨＦはほとんど確認されなかった。当該排気ガスの分析は、ＦＴ－ＩＲ（サーモエレクトロン製Ｎｉｃｏｌｅｔ３８０）で行った。 [Example 3-2]
Nickel film formation using Ni (CO) (PF 3 ) 3 A film was formed in the same manner as in Example 3-1, except that H 2 gas was used instead of the mixed gas of SiH 4 and H 2 . As a result, deposition of the film was confirmed on the substrate, and when the composition of the film was examined with an X-ray photoelectron analyzer (XPS) (AXIS-NOVA manufactured by KRATOS), the presence of nickel was confirmed. Moreover, almost no carbon was confirmed. Further, the film was confirmed to be a nickel film by analysis with an X-ray diffractometer (XRD) (Rigaku RAD-γX). Moreover, almost no HF was confirmed in the analysis of the exhaust gas from the CVD apparatus. The exhaust gas was analyzed by FT-IR (Nicolet 380 manufactured by Thermo Electron).

　［実施例４］
　・Ｎｉ（ＣＯ）（ＰＦ2（ＣＦ3））3カルボニルトリス（トリフルオロメチルジフルオロホスフィン）ニッケルの成膜評価
　合成例４で得たＮｉ（ＣＯ）（ＰＦ2（ＣＦ3））3について、示差熱熱重量同時測定装置（ＳＩＩ製ＴＧ／ＤＴＡ６２００）を用いて、５００℃まで加熱した時の揮発率を求めたところ、９９．１質量％であった。揮発残渣が非常に少なく、ニッケル含有膜形成材料として適していることがわかった。 [Example 4]
Evaluation of film formation of Ni (CO) (PF 2 (CF 3 )) 3 carbonyltris (trifluoromethyldifluorophosphine) nickel About Ni (CO) (PF 2 (CF 3 )) 3 obtained in Synthesis Example 4 The volatilization rate when heated to 500 ° C. using a thermothermogravimetric simultaneous measurement apparatus (TG / DTA6200 manufactured by SII) was 99.1% by mass. It has been found that there are very few volatile residues and it is suitable as a nickel-containing film-forming material.

　［実施例４－１］
　・Ｎｉ（ＣＯ）（ＰＦ2（ＣＦ3））3を用いたニッケルシリサイド膜形成
　合成例４で得たＮｉ（ＣＯ）（ＰＦ2（ＣＦ3））3を用い、原料容器の最初の保持温度を６０℃にした以外は、実施例１－１と同様にして成膜した。その結果、基板上に膜の堆積が確認され、Ｘ線光電子分析装置（ＸＰＳ）（ＫＲＡＴＯＳ製ＡＸＩＳ－ＮＯＶＡ）により膜の組成を調べたところ、ニッケルおよびケイ素の存在が確認された。また、炭素はほとんど確認されなかった。さらにＸ線回折装置（ＸＲＤ）（リガク製ＲＡＤ－γＸ）の分析から、この膜がニッケルシリサイド膜であることが確認された。また、ＣＶＤ装置からの排気ガスの分析でＨＦはほとんど確認されなかった。当該排気ガスの分析は、ＦＴ－ＩＲ（サーモエレクトロン製Ｎｉｃｏｌｅｔ３８０）で行った。 [Example 4-1]
· Ni (CO) (PF 2 (CF 3)) 3 was obtained with nickel silicide film formed in Synthesis Example 4 using Ni (CO) (PF 2 ( CF 3)) 3 was used, the first holding temperature of the raw material container A film was formed in the same manner as in Example 1-1 except that the temperature was set to 60 ° C. As a result, deposition of the film was confirmed on the substrate, and when the composition of the film was examined by an X-ray photoelectron analyzer (XPS) (AXIS-NOVA manufactured by KRATOS), the presence of nickel and silicon was confirmed. Moreover, almost no carbon was confirmed. Further, analysis by an X-ray diffractometer (XRD) (RAD-γX manufactured by Rigaku) confirmed that this film was a nickel silicide film. Moreover, almost no HF was confirmed in the analysis of the exhaust gas from the CVD apparatus. The exhaust gas was analyzed by FT-IR (Nicolet 380 manufactured by Thermo Electron).

　［実施例４－２］
　・Ｎｉ（ＣＯ）（ＰＦ2（ＣＦ3））3を用いたニッケル膜形成
　ＳｉＨ4とＨ2との混合ガスの代わりにＨ2ガスを用いた以外は実施例４－１と同様に成膜した。その結果、基板上に膜の堆積が確認され、Ｘ線光電子分析装置（ＸＰＳ）（ＫＲＡＴＯＳ製ＡＸＩＳ－ＮＯＶＡ）により膜の組成を調べたところ、ニッケルの存在が確認された。また、炭素はほとんど確認されなかった。さらにＸ線回折装置（ＸＲＤ）（リガク製ＲＡＤ－γＸ）の分析から、この膜がニッケル膜であることが確認された。また、ＣＶＤ装置からの排気ガスの分析でＨＦはほとんど確認されなかった。当該排気ガスの分析は、ＦＴ－ＩＲ（サーモエレクトロン製Ｎｉｃｏｌｅｔ３８０）で行った。 [Example 4-2]
Nickel film formation using Ni (CO) (PF 2 (CF 3 )) 3 Film formation was performed in the same manner as in Example 4-1, except that H 2 gas was used instead of the mixed gas of SiH 4 and H 2. did. As a result, deposition of the film was confirmed on the substrate, and when the composition of the film was examined with an X-ray photoelectron analyzer (XPS) (AXIS-NOVA manufactured by KRATOS), the presence of nickel was confirmed. Moreover, almost no carbon was confirmed. Further, the film was confirmed to be a nickel film by analysis with an X-ray diffractometer (XRD) (Rigaku RAD-γX). Moreover, almost no HF was confirmed in the analysis of the exhaust gas from the CVD apparatus. The exhaust gas was analyzed by FT-IR (Nicolet 380 manufactured by Thermo Electron).

　［実施例５］
　・Ｎｉ（ＣＯ）2（Ｐ（ＣＦ3）3）2の成膜評価
　合成例５で得たＮｉ（ＣＯ）2（Ｐ（ＣＦ3）3）2について、示差熱熱重量同時測定装置（ＳＩＩ製ＴＧ／ＤＴＡ６２００）を用いて、５００℃まで加熱した時の揮発率を求めたところ、９９．５質量％であった。揮発残渣が非常に少なく、ニッケル含有膜形成材料として適していることがわかった。 [Example 5]
· Ni (CO) 2 (P (CF 3) 3) Ni obtained in 2 of film formation evaluation Synthesis Example 5 (CO) 2 (P ( CF 3) 3) for 2, differential thermogravimetric simultaneous measurement device (SII Using TG / DTA6200), the volatilization rate when heated to 500 ° C. was 99.5% by mass. It has been found that there are very few volatile residues and it is suitable as a nickel-containing film-forming material.

　［実施例５－１］
　・Ｎｉ（ＣＯ）2（Ｐ（ＣＦ3）3）2を用いたニッケルシリサイド膜形成
　合成例５で得たＮｉ（ＣＯ）2（Ｐ（ＣＦ3）3）2を用い、原料容器の最初の保持温度を６０℃にした以外は、実施例１－１と同様にして成膜した。その結果、基板上に膜の堆積が確認され、Ｘ線光電子分析装置（ＸＰＳ）（ＫＲＡＴＯＳ製ＡＸＩＳ－ＮＯＶＡ）により膜の組成を調べたところ、ニッケルおよびケイ素の存在が確認された。また、炭素はほとんど確認されなかった。さらにＸ線回折装置（ＸＲＤ）（リガク製ＲＡＤ－γＸ）の分析から、この膜がニッケルシリサイド膜であることが確認された。また、ＣＶＤ装置からの排気ガスの分析でＨＦはほとんど確認されなかった。当該排気ガスの分析は、ＦＴ－ＩＲ（サーモエレクトロン製Ｎｉｃｏｌｅｔ３８０）で行った。 [Example 5-1]
· Ni (CO) 2 (P (CF 3) 3) 2 was obtained with nickel silicide film formed in Synthesis Example 5 using the Ni (CO) 2 (P ( CF 3) 3) 2 was used, the raw material container first A film was formed in the same manner as in Example 1-1 except that the holding temperature was 60 ° C. As a result, deposition of the film was confirmed on the substrate, and when the composition of the film was examined by an X-ray photoelectron analyzer (XPS) (AXIS-NOVA manufactured by KRATOS), the presence of nickel and silicon was confirmed. Moreover, almost no carbon was confirmed. Further, analysis by an X-ray diffractometer (XRD) (RAD-γX manufactured by Rigaku) confirmed that this film was a nickel silicide film. Moreover, almost no HF was confirmed in the analysis of the exhaust gas from the CVD apparatus. The exhaust gas was analyzed by FT-IR (Nicolet 380 manufactured by Thermo Electron).

　［実施例５－２］
　・Ｎｉ（ＣＯ）2（Ｐ（ＣＦ3）3）2を用いたニッケル膜形成
　ＳｉＨ4とＨ2との混合ガスの代わりにＨ2ガスを用いた以外は実施例５－１と同様に成膜した。その結果、基板上に膜の堆積が確認され、Ｘ線光電子分析装置（ＸＰＳ）（ＫＲＡＴＯＳ製ＡＸＩＳ－ＮＯＶＡ）により膜の組成を調べたところ、ニッケルの存在が確認された。また、炭素はほとんど確認されなかった。さらにＸ線回折装置（ＸＲＤ）（リガク製ＲＡＤ－γＸ）の分析から、この膜がニッケル膜であることが確認された。また、ＣＶＤ装置からの排気ガスの分析でＨＦはほとんど確認されなかった。当該排気ガスの分析は、ＦＴ－ＩＲ（サーモエレクトロン製Ｎｉｃｏｌｅｔ３８０）で行った。 [Example 5-2]
Nickel film formation using Ni (CO) 2 (P (CF 3 ) 3 ) 2 The same process as in Example 5-1, except that H 2 gas was used instead of the mixed gas of SiH 4 and H 2. Filmed. As a result, deposition of the film was confirmed on the substrate, and when the composition of the film was examined with an X-ray photoelectron analyzer (XPS) (AXIS-NOVA manufactured by KRATOS), the presence of nickel was confirmed. Moreover, almost no carbon was confirmed. Further, the film was confirmed to be a nickel film by analysis with an X-ray diffractometer (XRD) (Rigaku RAD-γX). Moreover, almost no HF was confirmed in the analysis of the exhaust gas from the CVD apparatus. The exhaust gas was analyzed by FT-IR (Nicolet 380 manufactured by Thermo Electron).

　［実施例６］
　・Ｎｉ（ＰＦ3）2（ＰＦ2（ＣＦ3））2の成膜評価
　合成例６で得たＮｉ（ＰＦ3）2（ＰＦ2（ＣＦ3））2について、示差熱熱重量同時測定装置（ＳＩＩ製ＴＧ／ＤＴＡ６２００）を用いて、５００℃まで加熱した時の揮発率を求めたところ、９９．０質量％であった。揮発残渣が非常に少なく、ニッケル含有膜形成材料として適していることがわかった。 [Example 6]
· Ni (PF 3) 2 ( PF 2 (CF 3)) Ni obtained in 2 of film formation evaluation Synthesis Example 6 (PF 3) 2 (PF 2 (CF 3)) for 2, the differential thermogravimetric simultaneous analysis device It was 99.0 mass% when the volatilization rate when heating to 500 degreeC was calculated | required using (TG / DTA6200 made from SII). It has been found that there are very few volatile residues and it is suitable as a nickel-containing film-forming material.

　［実施例６－１］
　・Ｎｉ（ＰＦ3）2（ＰＦ2（ＣＦ3））2を用いたニッケルシリサイド膜形成
　合成例６で得たＮｉ（ＰＦ3）2（ＰＦ2（ＣＦ3））2を用い、原料容器の最初の保持温度を６０℃にした以外は、実施例１－１と同様にして成膜した。その結果、基板上に膜の堆積が確認され、Ｘ線光電子分析装置（ＸＰＳ）（ＫＲＡＴＯＳ製ＡＸＩＳ－ＮＯＶＡ）により膜の組成を調べたところ、ニッケルおよびケイ素の存在が確認された。また、炭素はほとんど確認されなかった。さらにＸ線回折装置（ＸＲＤ）（リガク製ＲＡＤ－γＸ）の分析から、この膜がニッケルシリサイド膜であることが確認された。また、ＣＶＤ装置からの排気ガスの分析でＨＦはほとんど確認されなかった。当該排気ガスの分析は、ＦＴ－ＩＲ（サーモエレクトロン製Ｎｉｃｏｌｅｔ３８０）で行った。 [Example 6-1]
· Ni (PF 3) 2 ( PF 2 (CF 3)) Ni (PF 3) obtained in the nickel silicide film formed Synthesis Example 6 using 2 2 using (PF 2 (CF 3)) 2, of the raw material container A film was formed in the same manner as in Example 1-1 except that the initial holding temperature was 60 ° C. As a result, deposition of the film was confirmed on the substrate, and when the composition of the film was examined by an X-ray photoelectron analyzer (XPS) (AXIS-NOVA manufactured by KRATOS), the presence of nickel and silicon was confirmed. Moreover, almost no carbon was confirmed. Further, analysis by an X-ray diffractometer (XRD) (RAD-γX manufactured by Rigaku) confirmed that this film was a nickel silicide film. Moreover, almost no HF was confirmed in the analysis of the exhaust gas from the CVD apparatus. The exhaust gas was analyzed by FT-IR (Nicolet 380 manufactured by Thermo Electron).

　［実施例６－２］
　・Ｎｉ（ＰＦ3）2（ＰＦ2（ＣＦ3））2を用いたニッケル膜形成
　ＳｉＨ4とＨ2との混合ガスの代わりにＨ2ガスを用いた以外は実施例６－１と同様に成膜した。その結果、基板上に膜の堆積が確認され、Ｘ線光電子分析装置（ＸＰＳ）（ＫＲＡＴＯＳ製ＡＸＩＳ－ＮＯＶＡ）により膜の組成を調べたところ、ニッケルの存在が確認された。また、炭素はほとんど確認されなかった。さらにＸ線回折装置（ＸＲＤ）（リガク製ＲＡＤ－γＸ）の分析から、この膜がニッケル膜であることが確認された。また、ＣＶＤ装置からの排気ガスの分析でＨＦはほとんど確認されなかった。当該排気ガスの分析は、ＦＴ－ＩＲ（サーモエレクトロン製Ｎｉｃｏｌｅｔ３８０）で行った。 [Example 6-2]
Nickel film formation using Ni (PF 3 ) 2 (PF 2 (CF 3 )) 2 Similar to Example 6-1 except that H 2 gas was used instead of the mixed gas of SiH 4 and H 2. A film was formed. As a result, deposition of the film was confirmed on the substrate, and when the composition of the film was examined with an X-ray photoelectron analyzer (XPS) (AXIS-NOVA manufactured by KRATOS), the presence of nickel was confirmed. Moreover, almost no carbon was confirmed. Further, the film was confirmed to be a nickel film by analysis with an X-ray diffractometer (XRD) (Rigaku RAD-γX). Moreover, almost no HF was confirmed in the analysis of the exhaust gas from the CVD apparatus. The exhaust gas was analyzed by FT-IR (Nicolet 380 manufactured by Thermo Electron).

　［実施例７］
　・Ｎｉ（ＣＯ）2（Ｐ（ＣＦ3）2ＣＨ2ＣＨ2Ｐ（ＣＦ3）2）の成膜評価
　合成例７で得たＮｉ（ＣＯ）2（Ｐ（ＣＦ3）2ＣＨ2ＣＨ2Ｐ（ＣＦ3）2）について、示差熱熱重量同時測定装置（ＳＩＩ製ＴＧ／ＤＴＡ６２００）を用いて、５００℃まで加熱した時の揮発率を求めたところ、９８．９質量％であった。揮発残渣が非常に少なく、ニッケル含有膜形成材料として適していることがわかった。 [Example 7]
· Ni (CO) 2 (P (CF 3) 2 CH 2 CH 2 P (CF 3) 2) Ni obtained by film formation evaluation Synthesis Example 7 (CO) 2 (P (CF 3) 2 CH 2 CH 2 With respect to P (CF 3 ) 2 ), the volatilization rate when heated to 500 ° C. using a differential thermothermal gravimetric simultaneous measurement apparatus (TG / DTA 6200 manufactured by SII) was 98.9% by mass. It has been found that there are very few volatile residues and it is suitable as a nickel-containing film-forming material.

　［実施例７－１］
　・Ｎｉ（ＣＯ）2（Ｐ（ＣＦ3）2ＣＨ2ＣＨ2Ｐ（ＣＦ3）2）を用いたニッケルシリサイド膜形成
　合成例７で得たＮｉ（ＣＯ）2（Ｐ（ＣＦ3）2ＣＨ2ＣＨ2Ｐ（ＣＦ3）2）を用い、原料容器の最初の保持温度を６０℃にした以外は、実施例１－１と同様にして成膜した。その結果、基板上に膜の堆積が確認され、Ｘ線光電子分析装置（ＸＰＳ）（ＫＲＡＴＯＳ製ＡＸＩＳ－ＮＯＶＡ）により膜の組成を調べたところ、ニッケルおよびケイ素の存在が確認された。また、炭素はほとんど確認されなかった。さらにＸ線回折装置（ＸＲＤ）（リガク製ＲＡＤ－γＸ）の分析から、この膜がニッケルシリサイド膜であることが確認された。また、ＣＶＤ装置からの排気ガスの分析でＨＦはほとんど確認されなかった。当該排気ガスの分析は、ＦＴ－ＩＲ（サーモエレクトロン製Ｎｉｃｏｌｅｔ３８０）で行った。 [Example 7-1]
Nickel silicide film formation using Ni (CO) 2 (P (CF 3 ) 2 CH 2 CH 2 P (CF 3 ) 2 ) Ni (CO) 2 (P (CF 3 ) 2 CH obtained in Synthesis Example 7 A film was formed in the same manner as in Example 1-1 except that 2 CH 2 P (CF 3 ) 2 ) was used and the initial holding temperature of the raw material container was set to 60 ° C. As a result, deposition of the film was confirmed on the substrate, and when the composition of the film was examined by an X-ray photoelectron analyzer (XPS) (AXIS-NOVA manufactured by KRATOS), the presence of nickel and silicon was confirmed. Moreover, almost no carbon was confirmed. Further, analysis by an X-ray diffractometer (XRD) (RAD-γX manufactured by Rigaku) confirmed that this film was a nickel silicide film. Moreover, almost no HF was confirmed in the analysis of the exhaust gas from the CVD apparatus. The exhaust gas was analyzed by FT-IR (Nicolet 380 manufactured by Thermo Electron).

　［実施例７－２］
　・Ｎｉ（ＣＯ）2（Ｐ（ＣＦ3）2ＣＨ2ＣＨ2Ｐ（ＣＦ3）2）を用いたニッケル膜形成
　ＳｉＨ4とＨ2との混合ガスの代わりにＨ2ガスを用いた以外は実施例７－１と同様に成膜した。その結果、基板上に膜の堆積が確認され、Ｘ線光電子分析装置（ＸＰＳ）（ＫＲＡＴＯＳ製ＡＸＩＳ－ＮＯＶＡ）により膜の組成を調べたところ、ニッケルの存在が確認された。また、炭素はほとんど確認されなかった。さらにＸ線回折装置（ＸＲＤ）（リガク製ＲＡＤ－γＸ）の分析から、この膜がニッケル膜であることが確認された。また、ＣＶＤ装置からの排気ガスの分析でＨＦはほとんど確認されなかった。当該排気ガスの分析は、ＦＴ－ＩＲ（サーモエレクトロン製Ｎｉｃｏｌｅｔ３８０）で行った。 [Example 7-2]
Nickel film formation using Ni (CO) 2 (P (CF 3 ) 2 CH 2 CH 2 P (CF 3 ) 2 ) Except for using H 2 gas instead of the mixed gas of SiH 4 and H 2 A film was formed in the same manner as in Example 7-1. As a result, deposition of the film was confirmed on the substrate, and when the composition of the film was examined with an X-ray photoelectron analyzer (XPS) (AXIS-NOVA manufactured by KRATOS), the presence of nickel was confirmed. Moreover, almost no carbon was confirmed. Further, the film was confirmed to be a nickel film by analysis with an X-ray diffractometer (XRD) (Rigaku RAD-γX). Moreover, almost no HF was confirmed in the analysis of the exhaust gas from the CVD apparatus. The exhaust gas was analyzed by FT-IR (Nicolet 380 manufactured by Thermo Electron).

　［実施例８］
　・Ｎｉ（ＣＯ）2（Ｐ（ＣＦ3）2ＣＦ2ＣＦ2Ｐ（ＣＦ3）2）の成膜評価
　合成例８で得たＮｉ（ＣＯ）2（Ｐ（ＣＦ3）2ＣＦ2ＣＦ2Ｐ（ＣＦ3）2）について、示差熱熱重量同時測定装置（ＳＩＩ製ＴＧ／ＤＴＡ６２００）を用いて、５００℃まで加熱した時の揮発率を求めたところ、９８．８質量％であった。揮発残渣が非常に少なく、ニッケル含有膜形成材料として適していることがわかった。 [Example 8]
Film formation evaluation of Ni (CO) 2 (P (CF 3 ) 2 CF 2 CF 2 P (CF 3 ) 2 ) Ni (CO) 2 (P (CF 3 ) 2 CF 2 CF 2 obtained in Synthesis Example 8 With respect to P (CF 3 ) 2 ), the volatilization rate when heated to 500 ° C. using a differential thermothermal gravimetric simultaneous measurement apparatus (TG / DTA 6200 manufactured by SII) was 98.8% by mass. It has been found that there are very few volatile residues and it is suitable as a nickel-containing film-forming material.

　［実施例８－１］
　・Ｎｉ（ＣＯ）2（Ｐ（ＣＦ3）2ＣＦ2ＣＦ2Ｐ（ＣＦ3）2）を用いたニッケルシリサイド膜形成
　合成例８で得たＮｉ（ＣＯ）2（Ｐ（ＣＦ3）2ＣＦ2ＣＦ2Ｐ（ＣＦ3）2）を用い、原料容器の最初の保持温度を６０℃にした以外は、実施例１－１と同様にして成膜した。その結果、基板上に膜の堆積が確認され、Ｘ線光電子分析装置（ＸＰＳ）（ＫＲＡＴＯＳ製ＡＸＩＳ－ＮＯＶＡ）により膜の組成を調べたところ、ニッケルおよびケイ素の存在が確認された。また、炭素はほとんど確認されなかった。さらにＸ線回折装置（ＸＲＤ）（リガク製ＲＡＤ－γＸ）の分析から、この膜がニッケルシリサイド膜であることが確認された。また、ＣＶＤ装置からの排気ガスの分析でＨＦはほとんど確認されなかった。当該排気ガスの分析は、ＦＴ－ＩＲ（サーモエレクトロン製Ｎｉｃｏｌｅｔ３８０）で行った。 [Example 8-1]
Nickel silicide film formation using Ni (CO) 2 (P (CF 3 ) 2 CF 2 CF 2 P (CF 3 ) 2 ) Ni (CO) 2 (P (CF 3 ) 2 CF obtained in Synthesis Example 8 A film was formed in the same manner as in Example 1-1 except that 2 CF 2 P (CF 3 ) 2 ) was used and the initial holding temperature of the raw material container was changed to 60 ° C. As a result, deposition of the film was confirmed on the substrate, and when the composition of the film was examined by an X-ray photoelectron analyzer (XPS) (AXIS-NOVA manufactured by KRATOS), the presence of nickel and silicon was confirmed. Moreover, almost no carbon was confirmed. Further, analysis by an X-ray diffractometer (XRD) (RAD-γX manufactured by Rigaku) confirmed that this film was a nickel silicide film. Moreover, almost no HF was confirmed in the analysis of the exhaust gas from the CVD apparatus. The exhaust gas was analyzed by FT-IR (Nicolet 380 manufactured by Thermo Electron).

　［実施例８－２］
　・Ｎｉ（ＣＯ）2（Ｐ（ＣＦ3）2ＣＦ2ＣＦ2Ｐ（ＣＦ3）2）を用いたニッケル膜形成
　ＳｉＨ4とＨ2との混合ガスの代わりにＨ2ガスを用いた以外は実施例８－１と同様に成膜した。その結果、基板上に膜の堆積が確認され、Ｘ線光電子分析装置（ＸＰＳ）（ＫＲＡＴＯＳ製ＡＸＩＳ－ＮＯＶＡ）により膜の組成を調べたところ、ニッケルの存在が確認された。また、炭素はほとんど確認されなかった。さらにＸ線回折装置（ＸＲＤ）（リガク製ＲＡＤ－γＸ）の分析から、この膜がニッケル膜であることが確認された。また、ＣＶＤ装置からの排気ガスの分析でＨＦはほとんど確認されなかった。当該排気ガスの分析は、ＦＴ－ＩＲ（サーモエレクトロン製Ｎｉｃｏｌｅｔ３８０）で行った。 [Example 8-2]
Nickel film formation using Ni (CO) 2 (P (CF 3 ) 2 CF 2 CF 2 P (CF 3 ) 2 ) Except for using a H 2 gas instead of a mixed gas of SiH 4 and H 2 A film was formed in the same manner as in Example 8-1. As a result, deposition of the film was confirmed on the substrate, and when the composition of the film was examined with an X-ray photoelectron analyzer (XPS) (AXIS-NOVA manufactured by KRATOS), the presence of nickel was confirmed. Moreover, almost no carbon was confirmed. Further, the film was confirmed to be a nickel film by analysis with an X-ray diffractometer (XRD) (Rigaku RAD-γX). Moreover, almost no HF was confirmed in the analysis of the exhaust gas from the CVD apparatus. The exhaust gas was analyzed by FT-IR (Nicolet 380 manufactured by Thermo Electron).

　［実施例９］
　・Ｎｉ（ＰＦ3）3（ＰＦ2ＮＨ（ＣＨ3））の成膜評価
　合成例９で得たＮｉ（ＰＦ3）3（ＰＦ2ＮＨ（ＣＨ3））について、示差熱熱重量同時測定装置（ＳＩＩ製ＴＧ／ＤＴＡ６２００）を用いて、５００℃まで加熱した時の揮発率を求めたところ、９９．０質量％であった。揮発残渣が非常に少なく、ニッケル含有膜形成材料として適していることがわかった。 [Example 9]
· Ni (PF 3) 3 ( PF 2 NH (CH 3)) Ni (PF 3) obtained in the film formation evaluation Synthesis Example 9 of 3 (PF 2 NH (CH 3 )), the differential thermogravimetric simultaneous analysis device It was 99.0 mass% when the volatilization rate when heating to 500 degreeC was calculated | required using (TG / DTA6200 made from SII). It has been found that there are very few volatile residues and it is suitable as a nickel-containing film-forming material.

　［実施例９－１］
　・Ｎｉ（ＰＦ3）3（ＰＦ2ＮＨ（ＣＨ3））を用いたニッケルシリサイド膜形成
　合成例９で得たＮｉ（ＰＦ3）3（ＰＦ2ＮＨ（ＣＨ3））を用い、原料容器の最初の保持温度を６０℃にした以外は、実施例１－１と同様にして成膜した。その結果、基板上に膜の堆積が確認され、Ｘ線光電子分析装置（ＸＰＳ）（ＫＲＡＴＯＳ製ＡＸＩＳ－ＮＯＶＡ）により膜の組成を調べたところ、ニッケルおよびケイ素の存在が確認された。また、炭素はほとんど確認されなかった。さらにＸ線回折装置（ＸＲＤ）（リガク製ＲＡＤ－γＸ）の分析から、この膜がニッケルシリサイド膜であることが確認された。また、ＣＶＤ装置からの排気ガスの分析でＨＦはほとんど確認されなかった。当該排気ガスの分析は、ＦＴ－ＩＲ（サーモエレクトロン製Ｎｉｃｏｌｅｔ３８０）で行った。 [Example 9-1]
· Ni (PF 3) 3 ( PF 2 NH (CH 3)) using a Ni obtained in the nickel silicide film formed in Synthesis Example 9 using (PF 3) 3 (PF 2 NH (CH 3)), the raw material container A film was formed in the same manner as in Example 1-1 except that the initial holding temperature was 60 ° C. As a result, deposition of the film was confirmed on the substrate, and when the composition of the film was examined by an X-ray photoelectron analyzer (XPS) (AXIS-NOVA manufactured by KRATOS), the presence of nickel and silicon was confirmed. Moreover, almost no carbon was confirmed. Further, analysis by an X-ray diffractometer (XRD) (RAD-γX manufactured by Rigaku) confirmed that this film was a nickel silicide film. Moreover, almost no HF was confirmed in the analysis of the exhaust gas from the CVD apparatus. The exhaust gas was analyzed by FT-IR (Nicolet 380 manufactured by Thermo Electron).

　［実施例９－２］
　・Ｎｉ（ＰＦ3）3（ＰＦ2ＮＨ（ＣＨ3））を用いたニッケル膜形成
　ＳｉＨ4とＨ2との混合ガスの代わりにＨ2ガスを用いた以外は実施例９－１と同様に成膜した。その結果、基板上に膜の堆積が確認され、Ｘ線光電子分析装置（ＸＰＳ）（ＫＲＡＴＯＳ製ＡＸＩＳ－ＮＯＶＡ）により膜の組成を調べたところ、ニッケルの存在が確認された。また、炭素はほとんど確認されなかった。さらにＸ線回折装置（ＸＲＤ）（リガク製ＲＡＤ－γＸ）の分析から、この膜がニッケル膜であることが確認された。また、ＣＶＤ装置からの排気ガスの分析でＨＦはほとんど確認されなかった。当該排気ガスの分析は、ＦＴ－ＩＲ（サーモエレクトロン製Ｎｉｃｏｌｅｔ３８０）で行った。 [Example 9-2]
Nickel film formation using Ni (PF 3 ) 3 (PF 2 NH (CH 3 )) Similar to Example 9-1 except that H 2 gas was used instead of the mixed gas of SiH 4 and H 2. A film was formed. As a result, deposition of the film was confirmed on the substrate, and when the composition of the film was examined with an X-ray photoelectron analyzer (XPS) (AXIS-NOVA manufactured by KRATOS), the presence of nickel was confirmed. Moreover, almost no carbon was confirmed. Further, the film was confirmed to be a nickel film by analysis with an X-ray diffractometer (XRD) (Rigaku RAD-γX). Moreover, almost no HF was confirmed in the analysis of the exhaust gas from the CVD apparatus. The exhaust gas was analyzed by FT-IR (Nicolet 380 manufactured by Thermo Electron).

　［実施例１０］
　・Ｎｉ（ＰＦ3）3（ＰＦ2Ｎ（Ｃ2Ｈ5）2）の成膜評価
　合成例１０で得たＮｉ（ＰＦ3）3（ＰＦ2Ｎ（Ｃ2Ｈ5）2）について、示差熱熱重量同時測定装置（ＳＩＩ製ＴＧ／ＤＴＡ６２００）を用いて、５００℃まで加熱した時の揮発率を求めたところ、９９．１質量％であった。揮発残渣が非常に少なく、ニッケル含有膜形成材料として適していることがわかった。 [Example 10]
· For Ni (PF 3) 3 (PF 2 N (C 2 H 5) 2) Ni obtained by film formation evaluation Synthesis Example 10 (PF 3) 3 (PF 2 N (C 2 H 5) 2), a differential The volatilization rate when heated to 500 ° C. using a thermothermogravimetric simultaneous measurement apparatus (TG / DTA6200 manufactured by SII) was 99.1% by mass. It has been found that there are very few volatile residues and it is suitable as a nickel-containing film-forming material.

　［実施例１０－１］
　・Ｎｉ（ＰＦ3）3（ＰＦ2Ｎ（Ｃ2Ｈ5）2）を用いたニッケルシリサイド膜形成
　合成例１０で得たＮｉ（ＰＦ3）3（ＰＦ2Ｎ（Ｃ2Ｈ5）2）を用い、原料容器の最初の保持温度を６０℃にした以外は、実施例１－１と同様にして成膜した。その結果、基板上に膜の堆積が確認され、Ｘ線光電子分析装置（ＸＰＳ）（ＫＲＡＴＯＳ製ＡＸＩＳ－ＮＯＶＡ）により膜の組成を調べたところ、ニッケルおよびケイ素の存在が確認された。また、炭素はほとんど確認されなかった。さらにＸ線回折装置（ＸＲＤ）（リガク製ＲＡＤ－γＸ）の分析から、この膜がニッケルシリサイド膜であることが確認された。また、ＣＶＤ装置からの排気ガスの分析でＨＦはほとんど確認されなかった。当該排気ガスの分析は、ＦＴ－ＩＲ（サーモエレクトロン製Ｎｉｃｏｌｅｔ３８０）で行った。 [Example 10-1]
· Ni (PF 3) 3 ( PF 2 N (C 2 H 5) 2) was obtained with nickel silicide film formed Synthesis Example 10 using Ni (PF 3) 3 (PF 2 N (C 2 H 5) 2) A film was formed in the same manner as in Example 1-1 except that the initial holding temperature of the raw material container was changed to 60 ° C. As a result, deposition of the film was confirmed on the substrate, and when the composition of the film was examined by an X-ray photoelectron analyzer (XPS) (AXIS-NOVA manufactured by KRATOS), the presence of nickel and silicon was confirmed. Moreover, almost no carbon was confirmed. Further, analysis by an X-ray diffractometer (XRD) (RAD-γX manufactured by Rigaku) confirmed that this film was a nickel silicide film. Moreover, almost no HF was confirmed in the analysis of the exhaust gas from the CVD apparatus. The exhaust gas was analyzed by FT-IR (Nicolet 380 manufactured by Thermo Electron).

　［実施例１０－２］
　・Ｎｉ（ＰＦ3）3（ＰＦ2Ｎ（Ｃ2Ｈ5）2）を用いたニッケル膜形成
　ＳｉＨ4とＨ2との混合ガスの代わりにＨ2ガスを用いた以外は実施例１０－１と同様に成膜した。その結果、基板上に膜の堆積が確認され、Ｘ線光電子分析装置（ＸＰＳ）（ＫＲＡＴＯＳ製ＡＸＩＳ－ＮＯＶＡ）により膜の組成を調べたところ、ニッケルの存在が確認された。また、炭素はほとんど確認されなかった。さらにＸ線回折装置（ＸＲＤ）（リガク製ＲＡＤ－γＸ）の分析から、この膜がニッケル膜であることが確認された。また、ＣＶＤ装置からの排気ガスの分析でＨＦはほとんど確認されなかった。当該排気ガスの分析は、ＦＴ－ＩＲ（サーモエレクトロン製Ｎｉｃｏｌｅｔ３８０）で行った。 [Example 10-2]
Nickel film formation using Ni (PF 3 ) 3 (PF 2 N (C 2 H 5 ) 2 ) Example 10-1 except that H 2 gas was used instead of the mixed gas of SiH 4 and H 2 A film was formed in the same manner as described above. As a result, deposition of the film was confirmed on the substrate, and when the composition of the film was examined with an X-ray photoelectron analyzer (XPS) (AXIS-NOVA manufactured by KRATOS), the presence of nickel was confirmed. Moreover, almost no carbon was confirmed. Further, the film was confirmed to be a nickel film by analysis with an X-ray diffractometer (XRD) (Rigaku RAD-γX). Moreover, almost no HF was confirmed in the analysis of the exhaust gas from the CVD apparatus. The exhaust gas was analyzed by FT-IR (Nicolet 380 manufactured by Thermo Electron).

　［比較例１］
　・Ｎｉ（ＰＦ3）4の成膜評価
　［比較例１－１］
　・Ｎｉ（ＰＦ3）4を用いたニッケルシリサイド膜形成
　Ｎｉ（ＰＦ3）4を用い、原料容器の最初の保持温度を６０℃にした以外は、実施例１－１と同様にして成膜した。その結果、基板上に膜の堆積が確認され、Ｘ線光電子分析装置（ＸＰＳ）（ＫＲＡＴＯＳ製ＡＸＩＳ－ＮＯＶＡ）により膜の組成を調べたところ、ニッケルおよびケイ素の存在が確認された。また、炭素はほとんど確認されなかった。さらにＸ線回折装置（ＸＲＤ）（リガク製ＲＡＤ－γＸ）の分析から、この膜がニッケルシリサイド膜であることが確認された。しかしながら、ＣＶＤ装置からの排気ガスの分析でＨＦが副生していることを確認した。当該排気ガスの分析は、ＦＴ－ＩＲ（サーモエレクトロン製Ｎｉｃｏｌｅｔ３８０）で行った。 [Comparative Example 1]
-Ni (PF 3 ) 4 Film Formation Evaluation [Comparative Example 1-1]
Nickel silicide film formation using Ni (PF 3 ) 4 A film was formed in the same manner as in Example 1-1 except that Ni (PF 3 ) 4 was used and the initial holding temperature of the raw material container was changed to 60 ° C. . As a result, deposition of the film was confirmed on the substrate, and when the composition of the film was examined by an X-ray photoelectron analyzer (XPS) (AXIS-NOVA manufactured by KRATOS), the presence of nickel and silicon was confirmed. Moreover, almost no carbon was confirmed. Further, analysis by an X-ray diffractometer (XRD) (RAD-γX manufactured by Rigaku) confirmed that this film was a nickel silicide film. However, analysis of exhaust gas from the CVD apparatus confirmed that HF was by-produced. The exhaust gas was analyzed by FT-IR (Nicolet 380 manufactured by Thermo Electron).

　［比較例１－２］
　・Ｎｉ（ＰＦ3）4を用いたニッケル膜形成
　ＳｉＨ4とＨ2との混合ガスの代わりにＨ2ガスを用いた以外は比較例１－１と同様に成膜した。その結果、基板上に膜の堆積が確認され、Ｘ線光電子分析装置（ＸＰＳ）（ＫＲＡＴＯＳ製ＡＸＩＳ－ＮＯＶＡ）により膜の組成を調べたところ、ニッケルの存在が確認された。また、炭素はほとんど確認されなかった。さらにＸ線回折装置（ＸＲＤ）（リガク製ＲＡＤ－γＸ）の分析から、この膜がニッケル膜であることが確認された。しかしながら、ＣＶＤ装置からの排気ガスの分析でＨＦが副生していることを確認した。当該排気ガスの分析は、ＦＴ－ＩＲ（サーモエレクトロン製Ｎｉｃｏｌｅｔ３８０）で行った。 [Comparative Example 1-2]
Nickel film formation using Ni (PF 3 ) 4 A film was formed in the same manner as Comparative Example 1-1 except that H 2 gas was used instead of the mixed gas of SiH 4 and H 2 . As a result, deposition of the film was confirmed on the substrate, and when the composition of the film was examined with an X-ray photoelectron analyzer (XPS) (AXIS-NOVA manufactured by KRATOS), the presence of nickel was confirmed. Moreover, almost no carbon was confirmed. Further, the film was confirmed to be a nickel film by analysis with an X-ray diffractometer (XRD) (Rigaku RAD-γX). However, analysis of exhaust gas from the CVD apparatus confirmed that HF was by-produced. The exhaust gas was analyzed by FT-IR (Nicolet 380 manufactured by Thermo Electron).

Claims (15)

　配位子を４個有するニッケル錯体を少なくとも１種含むニッケル含有膜形成材料であって、
　前記配位子の種類が、ＣＯ、ＰＦ3、ＰＦ2（ＣＦ3）、ＰＦ（ＣＦ3）2、Ｐ（ＣＦ3）3、ＰＦ2Ｒ1、ＰＦＲ2Ｒ3、ＰＦ2ＮＲ4Ｒ5、Ｐ（ＣＦ3）2ＣＨ2ＣＨ2Ｐ（ＣＦ3）2およびＰ（ＣＦ3）2ＣＦ2ＣＦ2Ｐ（ＣＦ3）2からなる群（ただし、Ｒ1～Ｒ5は各々独立に、Ｈ、炭素数１～６のアルキル基またはフェニル基であり、Ｐ（ＣＦ3）2ＣＨ2ＣＨ2Ｐ（ＣＦ3）2およびＰ（ＣＦ3）2ＣＦ2ＣＦ2Ｐ（ＣＦ3）2は配位子２個分に相当する。）より選ばれる２種以上であることを特徴とするニッケル含有膜形成材料。 A nickel-containing film-forming material comprising at least one nickel complex having four ligands,
The type of the ligand is CO, PF 3 , PF 2 (CF 3 ), PF (CF 3 ) 2 , P (CF 3 ) 3 , PF 2 R 1 , PFR 2 R 3 , PF 2 NR 4 R 5. , P (CF 3 ) 2 CH 2 CH 2 P (CF 3 ) 2 and P (CF 3 ) 2 CF 2 CF 2 P (CF 3 ) 2 (wherein R 1 to R 5 are each independently H, an alkyl group having 1 to 6 carbon atoms or a phenyl group, and P (CF 3 ) 2 CH 2 CH 2 P (CF 3 ) 2 and P (CF 3 ) 2 CF 2 CF 2 P (CF 3 ) 2 are A nickel-containing film-forming material characterized in that it corresponds to two ligands. 　前記配位子の種類が、ＣＯおよびＰＦ3の２種である請求項１に記載のニッケル含有膜形成材料。 The nickel-containing film-forming material according to claim 1, wherein the types of the ligand are two types, CO and PF 3 . 　前記配位子の種類が、ＣＯおよびＰＦ2（ＣＦ3）の２種である請求項１に記載のニッケル含有膜形成材料。 The nickel-containing film forming material according to claim 1, wherein the types of the ligand are two kinds of CO and PF 2 (CF 3 ). 　前記配位子の種類が、ＣＯおよびＰＦ（ＣＦ3）2の２種である請求項１に記載のニッケル含有膜形成材料。 The nickel-containing film-forming material according to claim 1, wherein the types of the ligand are two kinds of CO and PF (CF 3 ) 2 . 　前記配位子の種類が、ＣＯおよびＰ（ＣＦ3）3の２種である請求項１に記載のニッケル含有膜形成材料。 The nickel-containing film-forming material according to claim 1, wherein the ligands are two types, CO and P (CF 3 ) 3 . 　前記配位子の種類が、ＰＦ3およびＰＦ2（ＣＦ3）の２種である請求項１に記載のニッケル含有膜形成材料。 The nickel-containing film forming material according to claim 1, wherein the types of the ligand are two kinds of PF 3 and PF 2 (CF 3 ). 　前記配位子の種類が、ＰＦ3およびＰＦ2Ｒ1（ただし、Ｒ1は、Ｈ、炭素数１～６のアルキル基またはフェニル基である。）の２種である請求項１に記載のニッケル含有膜形成材料。 2. The ligand according to claim 1, wherein the type of the ligand is two types of PF 3 and PF 2 R 1 (wherein R 1 is H, an alkyl group having 1 to 6 carbon atoms, or a phenyl group). Nickel-containing film forming material. 　前記配位子の種類が、ＰＦ3およびＰＦ2ＮＲ4Ｒ5（ただし、Ｒ4およびＲ5は、各々独立にＨ、炭素数１～６のアルキル基またはフェニル基である。）の２種である請求項１に記載のニッケル含有膜形成材料。 The ligands are PF 3 and PF 2 NR 4 R 5 (wherein R 4 and R 5 are each independently H, an alkyl group having 1 to 6 carbon atoms, or a phenyl group). The nickel-containing film-forming material according to claim 1. 　前記ニッケル錯体が、Ｎｉ（ＣＯ）2（Ｐ（ＣＦ3）2ＣＨ2ＣＨ2Ｐ（ＣＦ3）2）である請求項１に記載のニッケル含有膜形成材料。 The nickel-containing film forming material according to claim 1, wherein the nickel complex is Ni (CO) 2 (P (CF 3 ) 2 CH 2 CH 2 P (CF 3 ) 2 ). 　前記ニッケル錯体が、Ｎｉ（ＣＯ）2（Ｐ（ＣＦ3）2ＣＦ2ＣＦ2Ｐ（ＣＦ3）2）である請求項１に記載のニッケル含有膜形成材料。 The nickel-containing film forming material according to claim 1, wherein the nickel complex is Ni (CO) 2 (P (CF 3 ) 2 CF 2 CF 2 P (CF 3 ) 2 ). 　化学気相成長法（ＣＶＤ）による膜形成に用いられる請求項１～１０のいずれかに記載のニッケル含有膜形成材料。 11. The nickel-containing film forming material according to claim 1, which is used for film formation by chemical vapor deposition (CVD). 　ニッケル含有膜が、ニッケル膜またはニッケルシリサイド膜である請求項１～１１のいずれかに記載のニッケル含有膜形成材料。 The nickel-containing film-forming material according to any one of claims 1 to 11, wherein the nickel-containing film is a nickel film or a nickel silicide film. 　前記ニッケルシリサイド膜のＳｉ源が、ＳｉaＨ2a+2（ただし、ａは１～３の整数である。）またはＲbＳｉＨ4-b（ただし、ｂは１～３の整数であり、Ｒは炭素数１～３のアルキル基を表す。）の構造式で示される少なくとも１種のケイ素化合物である請求項１２に記載のニッケル含有膜形成材料。 Si source of the nickel silicide film is Si a H 2a + 2 (where a is an integer of 1 to 3) or R b SiH 4-b (where b is an integer of 1 to 3; R 13. The nickel-containing film-forming material according to claim 12, which is at least one silicon compound represented by the structural formula: (C 1 represents an alkyl group having 1 to 3 carbon atoms). 　前記ケイ素化合物が、シラン、ジシラン、トリシラン、メチルシラン、ジメチルシラン、トリメチルシラン、エチルシラン、ジエチルシランまたはトリエチルシランである請求項１３に記載のニッケル含有膜形成材料。 The nickel-containing film forming material according to claim 13, wherein the silicon compound is silane, disilane, trisilane, methylsilane, dimethylsilane, trimethylsilane, ethylsilane, diethylsilane, or triethylsilane. 　請求項１～１４のいずれかに記載のニッケル含有膜形成材料を用いて、化学気相成長法（ＣＶＤ）によりニッケル含有膜を形成することを特徴とするニッケル含有膜の製造方法。 A method for producing a nickel-containing film, comprising forming a nickel-containing film by chemical vapor deposition (CVD) using the nickel-containing film forming material according to any one of claims 1 to 14.
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