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• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
  • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
  • C07F7/02—Silicon compounds
  • C07F7/025—Silicon compounds without C-silicon linkages
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
  • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
  • C07F7/02—Silicon compounds
  • C07F7/08—Compounds having one or more C—Si linkages
  • C07F7/10—Compounds having one or more C—Si linkages containing nitrogen having a Si-N linkage
• • 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
• • 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
  • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
  • C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material

Definitions

• the present invention relates generally to the formation of silicon-containing films in the manufacture of semiconductor devices, and more specifically to compositions and methods for forming such films, e.g., films comprising silicon, silicon nitride (Si 3 N 4 ), siliconoxynitride (SiO x N y ), silicon dioxide (Si0 2 ), etc., low dielectric constant (k) thin silicon-containing films, high k gate silicate films and low temperature silicon epitaxial films.
• Silicon nitride (Si 3 N ) thin films are widely employed in the microelectronic industry as diffusion barriers, etch-stop layers, sidewall spacers, etc.
• CVD precursors include bis(tert-butylamino)silane (BTBAS) or silane/ammonia, but such precursors usually require deposition temperature higher than 600°C for forming high quality Si 3 N 4 films, which is incompatible with the next generation IC device manufacturing, where deposition temperature of below 500°C, and preferably about 450°C, is desired. Therefore, development of low-temperature silicon-containing CVD precursors is particularly desired.
• BBAS bis(tert-butylamino)silane
• silane/ammonia silane/ammonia
• hexachlorodisilane Cl 3 Si-SiCl 3
• the drawbacks of using hexachlorodisilane in CVD processes include: (i) formation of large amount of NH 4 C1 during the process, which leads to the particle contamination and solid build-up in vacuum system and exhaust lines; (ii) possible chlorine incorporation in the chips, which could significantly reduce their life time and long-term performance; and (iii) the reaction by-products are known to be explosive. It is therefore desirable to develop new chlorine-free precursors that can be used for low- temperature CVD formation of silicon nitride thin films.
• the present invention relates generally to the formation of silicon-containing films, such as films comprising silicon, silicon nitride (Si 3 N ), siliconoxynitride (SiO x N y ), silicon dioxide (Si0 2 ), etc., silicon-containing low k films, high k gate silicates, and silicon epitaxial films, among which silicon nitride thin films are preferred, in the manufacture of semiconductor devices, and more specifically to compositions and methods for forming such silicon-containing films.
• silicon-containing films such as films comprising silicon, silicon nitride (Si 3 N ), siliconoxynitride (SiO x N y ), silicon dioxide (Si0 2 ), etc.
• silicon-containing low k films silicon oxide
• high k gate silicates silicon epitaxial films
• the present invention in one aspect relates to a group of halogen-free silane or disilane derivatives that are substituted with at least one alkylhydrazine functional groups and can be used as CVD precursors for deposition of silicon-containing thin films.
• silane derivatives of the present invention can be represented by the general formula of:
• Ri and R 2 may be the same as or different from each another and are independently selected from the group consisting of H, C ⁇ -C alkyl, aryl, and C 3 -C 6 cycloalkyl, or Ri and R 2 together may form C 3 -C ⁇ heterocyclic functional group with N, and wherein X, Y, and Z may be the same as or different from one another and are independently selected from the group consisting of H, C ⁇ -C 7 alkyl, alkylamino, dialkylamino, and alkylhydrazido (e.g., R 1 R 2 NNH-, wherein Ri and R 2 are same as described hereinabove).
• X, Y, and Z are all identical functional groups. More preferably, X, Y, and Z are all C ⁇ -C 7 alkyl, such as methyl or ethyl. Alternatively but also preferably, X, Y, and Z are all alkylhydrazido (e.g., R ⁇ R 2 NNH-, wherein Ri and R 2 are same as described hereinabove), such as N,N'-dimethylhydrazido or N.N'-diethylhydrazido.
• alkylhydrazido e.g., R ⁇ R 2 NNH-, wherein Ri and R 2 are same as described hereinabove
• the disilane derivatives of the present invention can be represented by the general formula of:
• R ⁇ ,R 2 , R , and R 4 may be the same as or different from each another and are independently selected from the group consisting of H, C1-C 7 alkyl, aryl, and C 3 -C 6 cycloalkyl, or Ri and R 2 together may form C 3 -C 6 heterocyclic functional group with N, or R 3 and R 4 together may form C 3 - C 6 heterocyclic functional group with N, and wherein X X 2 , Y l9 and Y 2 may be the same as or different from one another and are independently selected from the group consisting of H, C 1 -C 7 alkyl, alkylamino, dialkylamino, and alkylhydrazido (e.g., R ⁇ NNH-, wherein R ! and R 2 are same as described hereinabove).
• the disilane derivative compound of the present invention is characterized by functional groups that are symmetrically distributed in relation to the Si-Si bond.
• Preferred silane or disilane derivative compounds of the present invention include, but are not limited to, Me 3 Si(HNNMe 2 ), Si(HNNMe) 4 , Me 2 (HNNMe 2 )Si-Si(HNNMe 2 )Me 2 , and (HNBu (I NMe 2 )Si-Si(HNNMe 2 )(HNBu , ) 2 , wherein Bu and Me are consistently used as the respective abbreviations of butyl and methyl throughout the text hereinafter.
• Another aspect of the present invention relates to a method for forming a silicon- containing film on a substrate, comprising contacting a substrate under chemical vapor deposition conditions including a deposition temperature of below 550°C, preferably below 500°C, and more preferable below 450°C, with a vapor of a silane or disilane derivative compound that is substituted with at least one alkylhydrazine functional group.
• Still another aspect of the present invention relates to a method of making such silane or disilane derivative compounds, by reacting silane or disilane compounds comprising one or more halogen groups (i.e., halosilane or halodisilane) with alkylhydrazine in the presence of NEt 3 , to substitute the one or more halogen groups of such silane or disilane compounds with alkylhydrazine functional groups.
• halogen groups i.e., halosilane or halodisilane
• a still further aspect of the present invention relates to a method of making Me 3 Si(HNNMe 2 ), by reacting Me 3 SiCl with approximately one molar ratio of H 2 NNMe 2 in the presence of NEt 3 , according to the following reaction:
• a still further aspect of the present invention relates to a method of making
• Si(HNNMe 2 ) 4 by reacting SiCl 4 with approximately four molar ratio of H 2 NNMe 2 in the presence of NEt 3 , according to the following reaction:
• a still further aspect of the present invention relates to a method of making Me 2 (HNNMe 2 )Si-Si(HNNMe 2 )Me 2 , by reacting Me 2 (Cl)Si-Si(Cl)Me 2 with approximately two molar ratio of H 2 NNMe 2 in the presence of NEt 3 , according to the following reaction:
• a still further aspect of the present invention relates to a method of making, by reacting (HNBu t ) 2 (HNNMe 2 )Si-Si(HNNMe 2 )(HNBu , ) 2 , by reacting (HNBu t ) 2 (Cl)Si-Si(Cl)(HNBu t ) 2 with approximately two molar ratio of LiHNNMe 2 , according to the following reaction: NEt 3 (HNBu (Cl)Si-Si(Cl)(HNBu t ) 2 + 2LiHNNMe 2 * (Hr ⁇ u (HNNMe 2 )Si-
• Figure 1 is a STA plot for Si(HNNMe 2 ) 4 .
• Figure 2 is an X-ray crystal structure of the compound Si(HNNMe 2 ) .
• Figure 3 is a STA plot for Me 2 (HNNMe 2 )Si-Si(HNNMe 2 )Me 2 .
• Figure 4 is a STA plot for (HNBu t ) 2 (HNNMe 2 )Si-Si(HNNMe 2 )(HNBu t ) 2 .
• the present invention relates to silicon precursors for CVD formation of films on substrates, such as silicon precursors for forming low k dielectric films, high k gate silicates, low temperature silicon epitaxial films, and films comprising silicon, silicon oxide, silicon oxynitride, silicon nitride, etc., as well as to corresponding processes for forming such films with such precursors.
• Silane or disilane derivatives that contain one or more alkylhydrazine functional groups, free of any halogen substitutes, are found particularly suitable for low-temperature deposition of silicon nitride thin films, since the bond-strength of the nitrogen-nitrogen single bond in the hydrazine functional group relatively weak. Moreover, use of such halogen-free silicon precursors avoids the various problems involved in previous CVD processes using hexachlorodisilane.
• Preferred silane derivatives of the present invention can be represented by the general formula of: wherein Ri and R 2 may be the same as or different from each another and are independently selected from the group consisting of H, C ⁇ -C 7 alkyl, aryl, and C 3 -C 6 cycloalkyl, or Ri and R 2 together may form C 3 -C 6 heterocyclic functional group with N, and wherein X, Y, and Z may be the same as or different from one another and are independently selected from the group consisting of H, C1-C 7 alkyl, alkylamino, dialkylamino, and alkylhydrazido (e.g., R ⁇ R 2 NNH-, wherein Ri and R 2 are same as described hereinabove).
• Ri and R 2 may be the same as or different from each another and are independently selected from the group consisting of H, C ⁇ -C 7 alkyl, aryl, and C 3 -C 6 cycloalkyl, or Ri and R 2 together may form C 3
• Preferred disilane derivatives of the present invention can be represented by the general formula of:
• R ⁇ ,R 2 , R 3 , and R 4 may be the same as or different from each another and are independently selected from the group consisting of H, -C7 alkyl, aryl, and C 3 -C 6 cycloalkyl, or R t and R 2 together may form C 3 -C ⁇ heterocyclic functional group with N, or R 3 and R 4 together may form C 3 - C ⁇ heterocyclic functional group with N, and wherein X X 2 , Y and Y 2 may be the same as or different from one another and are independently selected from the group consisting of H, C 1 -C 7 alkyl, alkylamino, dialkylamino, and alkylhydrazido (e.g., R ⁇ R 2 NNH-, wherein Ri and R 2 are same as described hereinabove).
• Disilane derivative compounds that are substantially symmetrical in structure in relation to the Si-Si bond, i.e., all functional groups of such compounds being symmetrically distributed in relation to the Si-Si bond, are particularly preferred for practicing of the present invention.
• such disilane derivative compounds may contain two identical alkylhydrazine functional groups and four identical C 1 -C5 alkyl functional groups that are symmetrically distributed in relation to the Si-Si bond, such as Me 2 (HNNMe)Si-Si(HNNMe)Me 2 .
• the silane or disilane derivative compounds as described hereinabove are advantageously characterized by a vaporization temperature of less than 300°C. Moreover, such compounds can be transported in vapor form at less than 300°C and under atmospheric pressure, with no or little ( -5%) residual material.
• the silicon-containing films that can be formed using such disilane precursor compounds include Si 3 N 4 thin films, high k gate silicates and silicon epitaxial films. In a particularly preferred embodiment of the invention, the films formed using such silane or disilane precursors comprise silicon nitride.
• Preferred silane or disilane compounds of the above-described formulas include, but are not limited to, Me 3 Si(HNNMe 2 ), Si(HNNMe 2 ) 4 , Me 2 (HNNMe 2 )Si-Si(HNNMe 2 )Me 2 , and
• Si(HNNMe 2 ) is a solid material having a melting temperature of approximately 73 °C.
• Figure 1 is a STA plot for Si(HNNMe 2 ) 4 , indicating that Si(HNNMe 2 ) 4 can be transported completely with very little ( ⁇ 2%) residual material at 500°C.
• Figure 2 shows the X-ray crystal structure of Si(HNNMe 2 ) .
• Example 3 Synthesis and characterization of Me7 HNNMe )Si-SifHNNMe 2 )Me [0037]
• a 3L flask was filled with a solution comprising 2.5L hexanes, 57 grams (561mmol) anhydrous NEt 3 , and 50 grams (267mmol) of Me 2 (Cl)Si-Si(Cl)Me 2 .
• 34 grams (561mmol) H 2 NNMe 2 was slowly added into the 3L flask at room temperature. White precipitate was observed during the addition of H 2 NNMe 2 .
• Figure 3 shows the STA plot for Me 4 Si 2 (HNNMe 2 ) 2 , which is a liquid at room temperature and can be transported in its vapor form completely with very little ( ⁇ 1%) residual material at about 350°C.
• the thermal stability of Me 4 Si 2 (HNNMe 2 ) 2 in solution at 100°C was monitored by proton NMR study for 7 days, and no significant decomposition was detected.
• Example 4 Synthesis and characterization of (HNBu t ) 2 ( ⁇ NNMe,)Si-Si(HNNMe ? )fHNBu t ) 2 [0039]
• 1.52 grams (25.3 mmol) of H 2 NNMe was slowly bubbled into the 250 mL flask at 0°C. Upon completion of the addition, the reaction flask was allowed to warm to room temperature and stirred for an additional hour.
• FIG. 1 shows the STA plot for (HNBu t ) 2 (HNNMe 2 )Si-Si(HNNMe 2 )(HNBu t ) 2 , which is a solid at room temperature and can be transported completely with very little ( ⁇ 0.03%) residual material at about 500°C.
• Such silane or disilane derivative compounds as described hereinabove can be used for low-pressure CVD deposition of various silicon-containing films, including silicon nitride thin films, consistent with the disclosure in U.S. Patent Application No.

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• 2003
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