Classifications

• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
  • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
  • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
  • C23C16/45523—Pulsed gas flow or change of composition over time
  • C23C16/45525—Atomic layer deposition [ALD]
  • C23C16/45553—Atomic layer deposition [ALD] characterized by the use of precursors specially adapted for ALD
• • 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
  • 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
  • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
  • C07F7/1804—Compounds having Si-O-C linkages
  • C07F7/1872—Preparation; Treatments not provided for in C07F7/20
  • C07F7/188—Preparation; Treatments not provided for in C07F7/20 by reactions involving the formation of Si-O 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
  • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
  • C07F7/1804—Compounds having Si-O-C linkages
  • C07F7/1872—Preparation; Treatments not provided for in C07F7/20
  • C07F7/1892—Preparation; Treatments not provided for in C07F7/20 by reactions not provided for in C07F7/1876 - C07F7/1888
• • 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
  • C23C16/02—Pretreatment of the material to be coated
  • C23C16/0272—Deposition of sub-layers, e.g. to promote the adhesion of the main coating
• • 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
• • 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
  • C23C16/08—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 metal halides
  • C23C16/14—Deposition of only one other metal element
• • 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
• • 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
  • C23C16/308—Oxynitrides
• • 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
  • C23C16/34—Nitrides
• • 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
  • C23C16/34—Nitrides
  • C23C16/345—Silicon nitride
• • 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
  • C23C16/40—Oxides
  • C23C16/401—Oxides containing silicon
• • 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
  • C23C16/40—Oxides
  • C23C16/401—Oxides containing silicon
  • C23C16/402—Silicon dioxide
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
  • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
  • C23C16/4401—Means for minimising impurities, e.g. dust, moisture or residual gas, in the reaction chamber
  • C23C16/4408—Means for minimising impurities, e.g. dust, moisture or residual gas, in the reaction chamber by purging residual gases from the reaction chamber or gas lines
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
  • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
  • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
  • C23C16/45523—Pulsed gas flow or change of composition over time
  • C23C16/45525—Atomic layer deposition [ALD]
  • C23C16/45527—Atomic layer deposition [ALD] characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations
  • C23C16/45534—Use of auxiliary reactants other than used for contributing to the composition of the main film, e.g. catalysts, activators or scavengers
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
  • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
  • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
  • C23C16/45523—Pulsed gas flow or change of composition over time
  • C23C16/45525—Atomic layer deposition [ALD]
  • C23C16/45527—Atomic layer deposition [ALD] characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations
  • C23C16/45536—Use of plasma, radiation or electromagnetic fields
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  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
  • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
  • C23C16/48—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating by irradiation, e.g. photolysis, radiolysis, particle radiation
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  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
  • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
  • C23C16/50—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
  • H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
  • H10P14/20—Formation of materials, e.g. in the shape of layers or pillars of semiconductor materials
  • H10P14/24—Formation of materials, e.g. in the shape of layers or pillars of semiconductor materials using chemical vapour deposition [CVD]
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
  • H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
  • H10P14/20—Formation of materials, e.g. in the shape of layers or pillars of semiconductor materials
  • H10P14/32—Formation of materials, e.g. in the shape of layers or pillars of semiconductor materials characterised by intermediate layers between substrates and deposited layers
  • H10P14/3202—Materials thereof
  • H10P14/3204—Materials thereof being Group IVA semiconducting materials
  • H10P14/3211—Silicon, silicon germanium or germanium
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
  • H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
  • H10P14/20—Formation of materials, e.g. in the shape of layers or pillars of semiconductor materials
  • H10P14/34—Deposited materials, e.g. layers
  • H10P14/3402—Deposited materials, e.g. layers characterised by the chemical composition
  • H10P14/3404—Deposited materials, e.g. layers characterised by the chemical composition being Group IVA materials
  • H10P14/3411—Silicon, silicon germanium or germanium

Definitions

• the invention relates to organosilicon compounds that can be used to deposit silicon-containing films and generate vinyl-functionalized surfaces suitable for producing germanium seed layers that are advantageous for growing high quality reduced or metallic germanium films on solid substrate surfaces.
• the invention also relates to methods for using the compounds.
• Described herein are novel organoamino-vinylsilane and organoamino- allylsilane precursor compounds and compositions and methods comprising the same to deposit a silicon-containing film such as, without limitation, silicon oxide, silicon oxynitride, silicon oxycarbonitride, or carbon-doped silicon oxide via a thermal atomic layer deposition (ALD) or plasma enhanced atomic layer deposition (PEALD) process, or a combination thereof.
• ALD thermal atomic layer deposition
• PEALD plasma enhanced atomic layer deposition
• PECVD Plasma Enhanced Chemical Vapor Deposition
• CVD thermal Chemical Vapor Deposition
• EP1464724A2 discloses silicon- and germanium-containing precursors having the formula MX a H b (NR 1 R 2 ) c R 3 d R 4 e suitable for chemical vapor deposition of silicon and germanium films.
• Fama, S et al., Appl. Phys. Lett. 2002, 81, 586 describes the epitaxial growth of germanium on silicon by first depositing a thin Ge/Si buffer layer with GeH 4 by chemical vapor deposition at 350 °C followed by chemical vapor deposition of a thicker germanium film at 600 °C for the purpose of fabricating p-i-n photodetectors.
• Miao, Q. J.et al., Catal. Commun. 2003, 4, 637 describes the treatment of fumed silica with vinyltriethoxysilane in toluene under refluxing conditions for 48 hours followed by reaction with water for another 48 hours to functionalize the surface with vinyl groups.
• Zapilko, C. et al.. J. Am. Chem. Soc. 2006, 128, 16266 describes the functionalization of periodic mesoporous silica with chloropropyldimethylsilyl groups and vinyldimethylsilyl groups by treating it with a vinyl-substituted trisilylamine in toluene at 109 °C for 15 hours.
• US Patent No. 8,460,753 B2 describes precursors and methods to deposit silicon dioxide or silicon oxide films by ALD or CVD, wherein the precursors are aminovinylsilanes having the formula R 1 n R 2 m Si(NR 3 R 4 ) 4-n-m and cyclic silazanes having the formula (R 1 R 2 SiNR 3 ) p , wherein R 1 is an alkenyl or an aromatic, such as vinyl, allyl, and phenyl.
• US Pub. No. 20150275355 A1 describes compositions and methods for forming silicon oxide films using precursors having the formula R 1 n Si(NR 2 R 3 ) m H 4-m-n , more specifically using organoamino-methylsilane precursors.
• US Pub. No. 20090162973 A1 describes the deposition of germanium films or germanium antimony telluride films on a substrate using germanium containing precursors having the formula GeR x 1 (NR 2 R 3 ) ( 4- X) , wherein the method involves exposing the substrate to the germanium containing precursor alone or in conjunction with either an oxidizing gas or reducing gas.
• US Pub. No. 20110036289 A1 describes a method of depositing a germanium seed layer via CVD on a hydrogen-treated silicon substrate using GeH 4 precursor at low temperature, followed by subsequent growth of either an n-doped or p-doped germanium epitaxial film using GeH 4 precursor in the presence of either phosphine or diborane, respectively, at elevated temperatures.
• US Pub. No. 20110084308 A1 discloses a method of selectively growing high quality strained or strain-relaxed Ge on patterned Si substrate, which involves the growth of a silicon-germanium buffer layer first via CVD with S ⁇ He and GeH 4 precursors at 350- 400 °C, followed by the growth of a Ge seed layer via CVD with GeH 4 precursor at 350- 400 °C, followed by the growth of Ge epitaxy film via CVD with GeH 4 precursor at 550- 600 °C.
• US Pub. Nos. 20130230975 A1 and 20140331928 A1 both describe the use of an aminogermane-based gas to form a germanium seed layer on a substrate followed by growth of a germanium thin film using a germane-based gas.
• the seed layer precursor in the invention disclosed herein utilizes silicon-amine functional groups as anchor groups to connect vinyl groups or allyl groups to the surface.
• This chemistry converts a hydroxyl rich surface into a vinyl or allyl rich surface.
• germane or digermane or another germanium precursor having at least one Ge-H bond will be introduced to the chamber and will react with the vinyl and/or allyl groups in a hydrogermylation reaction and form carbon bonded germyl or digermyl groups on the surface.
• the consequent germanium film deposited using a germanium precursor will grow instantly on this germyl rich surface without formation of islands.
• silicon precursors of the organoamino-vinylsilane and organoamino-allylsilane families comprising at least one vinyl or allyl group and at least one organoamino anchoring group compositions comprising the same, and methods using the same for depositing a silicon-containing film as well as forming a monolayer film comprising silicon and vinyl groups, which can facilitate the formation of a suitable seed layer for the deposition of metallic thin films, specifically germanium thin films.
• compositions comprising an organoamino-vinylsilane or an organoamino-allylsilane that is substantially free of at least one impurity species selected from organoamines, alcohols, halides, higher molecular weight species, and trace metals.
• the composition may further comprise a solvent.
• a film comprising silicon and vinyl groups is deposited onto a substrate using an organoamino-vinylsilane or an organoamino-allylsilane precursor in a deposition chamber under conditions for generating a vinyl-terminated layer suitable for growing a germanium seed layer and subsequently a high quality germanium film.
• a method for forming a germanium seed layer including the steps of: a. providing a substrate in a reactor; b. introducing into the reactor at least one precursor represented by Formula I and/or II; wherein R 1 is selected from the group consisting of a linear or branched Ci to Cio alkyl group, a linear or branched C 3 to C 10 alkenyl group, a linear or branched C 3 to C 10 alkynyl group, a C 3 to C 10 cyclic alkyl group, and a C 6 to C 10 aryl group; R 2 is selected from the group consisting of hydrogen, a linear or branched Ci to C 10 alkyl group, a linear or branched C 2 to C 6 alkenyl group, a linear or branched C 3 to C 6 alkynyl group, a C 3 to C 10 cyclic alkyl group, and a C 6 to Cioaryl group; R 3 and R
• purging the reactor with a purge gas d. introducing at least one germanium precursor comprising at least one Ge-H bond at a temperature such that the substrate is coated with at least one monolayer of germanium; e. purging the reactor with a purge gas; f. optionally introducing hydrogen or a hydrogen plasma source; g. optionally purging the reactor with a purge gas; h. introducing the same or a different germanium precursor as in step d at a temperature suitable to grow a film comprising germanium with a desired thickness.
• the germanium precursor having at least one Ge-H group includes, without limitation, one or more of trichlorogermane (C GeH), germane (GeH 4 ), digermane (Ge 2 H 6 ), tert-butylgermane ( l BuGeH 3 ), phenylgermane, sec-butylgemane, iso-butylgermane, and benzylgermane.
• a film comprising silicon and oxygen is deposited onto a substrate using the organoamino-vinylsilane precursor of Formula I and/or the organoamino-allylsilane precursor of Formula II and an oxygen- containing source under conditions for generating a silicon oxide or carbon doped silicon oxide film on the substrate.
• a film comprising silicon and nitrogen is deposited onto a substrate using the organoamino-vinylsilane precursor of Formula I and/or the organoamino-allylsilane precursor of Formula II and a nitrogen-containing source under conditions for generating a silicon nitride, carbon-doped silicon nitride, silicon oxynitride, or silicon oxycarbonitride film on the substrate.
• the organoamino-vinylsilane precursor according to Formula I and/or the organoamino-allylsilane precursor of Formula II are used as a dopant for metal containing films, such as but not limited to, metal oxide films or metal nitride films.
• steps d and h may be performed at the same temperature, or step d may be performed at a temperature lower than step h as to avoid or limit CVD of germanium film in step d until a sufficient Ge seed layer has been formed.
• step d is performed at a temperature higher than step h.
• the temperature is increased after step d in order for the at least one monolayer of germanium, known as the seed layer, to be annealed thermally or during the optional hydrogen or hydrogen plasma treatment prior to deposition of the subsequent germanium CVD film in step g.
• the at least one germanium precursor comprising at least one Ge-H bond is the same as the germanium CVD precursor.
• the at least one germanium precursor comprising at least one Ge-H bond is not the same as the germanium CVD precursor.
• a method of functionalizing the surface of a solid substrate such as, without limitation, silica, alumina, metal oxide, silicon wafer, dielectric thin film, or a metal surface with vinyl and/or allyl groups, the method comprising the steps of: a. providing a substrate in a reactor; b.
• At least one organoamino-vinylsilane precursor comprising at least one vinyl group and at least one organoamino anchoring group connected to at least one silicon atom represented by the following Formula I and/or at least one organoamino-allylsilane precursor comprising at least one allyl group and at least one organoamino anchoring group connected to at least one silicon atom represented by the following Formula II; and c. removing residual organoamino-vinylsilane or organoamino-allylsilane from the substrate with solvent and/or purge gas.
• the organoamino-vinylsilane and/or organoamino- allylsilane precursors disclosed herein may be introduced to the solid substrate as a neat liquid, as a solution in solvent, or in the vapor phase with or without a carrier gas at temperatures ranging from 0 °C to 500 °C.
• FIG. 1 is a flow diagram that depicts a general scheme in which the organoamino-vinylsilane precursors having Formula I (or alternatively Formula II) as disclosed herein are used to (a) functionalize a substrate surface with vinyl groups, making it suitable for (b) the formation of a germanium seed layer via hydrogermylation reaction with a germanium precursor comprising at least one Ge-H bond, allowing for (c) the subsequent growth of a smooth and uniform germanium film on top of that seed layer using at least one ALD or CVD Ge precursor.
• the organoamino-vinylsilane precursors having Formula I (or alternatively Formula II) as disclosed herein are used to (a) functionalize a substrate surface with vinyl groups, making it suitable for (b) the formation of a germanium seed layer via hydrogermylation reaction with a germanium precursor comprising at least one Ge-H bond, allowing for (c) the subsequent growth of a smooth and uniform germanium film on top of that seed layer using at least one ALD or CVD
• silicon precursor compounds and methods of using the same for the deposition of silicon containing films as well as the functionalization of substrate surfaces for subsequent processing including, but not limited to, the deposition of germanium films.
• a particular method for forming a germanium seed layer includes the steps of: a. providing a substrate in a reactor; b. introducing into the reactor at least one organoamino-vinylsilane precursor comprising at least one vinyl group and at least one organoamino anchoring group connected to at least one silicon atom represented by Formula I and/or at least one organoamino-allylsilane precursor comprising at least one allyl group and at least one organoamino anchoring group connected to at least one silicon atom represented by the following Formula II;
• R 1 is selected from the group consisting of a linear or branched Ci to Cio alkyl group, a linear or branched C 3 to C 10 alkenyl group, a linear or branched C 3 to C 10 alkynyl group, a C 3 to C 10 cyclic alkyl group, and a C6 to C 10 aryl group
• R 2 is selected from the group consisting of hydrogen, a linear or branched Ci to C 10 alkyl group, a linear or branched C 2 to C6 alkenyl group, a linear or branched C 3 to C6 alkynyl group, a C 3 to C 10 cyclic alkyl group, and a C6 to Cioaryl group
• R 3 and R 4 are each independently selected from the group consisting of hydrogen, a linear or branched Ci to C 10 alkyl group, a linear or branched C 2 to C6 alkenyl group, a linear or branched C 3 to C6 alkynyl group
• step d introducing at least one germanium precursor comprising at least one Ge-H bond at a temperature such that the substrate is coated with at least one monolayer of germanium; e. purging the reactor with a purge gas; f. optionally introducing hydrogen or a hydrogen plasma source; g. optionally purging the reactor with a purge gas; and h. introducing the same or a different germanium precursor as in step d at a temperature suitable to grow a film comprising germanium with a desired thickness.
• R 1 and R 2 are the same. In other embodiments, R 1 and R 2 are different. In some embodiments, R 3 and R 4 are the same. In other embodiments, R 3 and R 4 are different.
• R 3 and R 4 are independently selected from the group consisting of hydrogen, methyl, vinyl, and allyl.
• the organoamino-vinylsilane and organoamino-allylsilane precursors described herein are used to form monolayer films containing silicon plus vinyl and/or allyl groups as well as stoichiometric and non-stoichiometric silicon containing films such as, but not limited to, amorphous silicon, crystalline silicon, silicon oxide, carbon-doped silicon oxide, silicon oxycarbide, silicon nitride, silicon oxynitride, and silicon oxycarbonitride.
• organoamino-vinylsilane and organoamino-allylsilane precursors used in semi conductor processes are typically high purity volatile liquid chemicals that are vaporized and delivered to a deposition chamber or reactor as a gas to deposit a silicon containing film via CVD or ALD processes for semiconductor devices, however, they can also be introduced to substrates in the liquid phase (either neat or with a solvent).
• the selection of precursor materials for deposition depends upon the desired resultant silicon- containing material or film.
• a precursor material may be chosen for its content of chemical elements, its stoichiometric ratios of the chemical elements, and/or the resultant silicon containing film or coating that are formed under CVD.
• the precursor material may also be chosen for various other characteristics such as cost, relatively low toxicity, handling characteristics, ability to maintain liquid phase at room temperature, volatility, molecular weight, thermal stability, and/or other considerations.
• the precursors described herein can be delivered to the reactor system by any number of means, preferably using a pressurizable stainless steel vessel fitted with the proper valves and fittings, to allow the delivery of liquid or vapor phase precursor to the deposition chamber or reactor.
• Another particular method for forming a germanium seed layer includes the steps of: a. providing a substrate in a reactor; b. introducing into the reactor at least one organoamino-vinylsilane precursor comprising at least one vinyl group and at least one organoamino anchoring group connected to at least one silicon atom represented by Formula I and/or at least one organoamino-allylsilane precursor comprising at least one allyl group and at least one organoamino anchoring group connected to at least one silicon atom represented by the following Formula II;
• R 1 is selected from the group consisting of a linear or branched Ci to Cio alkyl group, a linear or branched C 3 to C 10 alkenyl group, a linear or branched C 3 to C 10 alkynyl group, a C 3 to C 10 cyclic alkyl group, and a C 6 to C 10 aryl group
• R 2 is selected from the group consisting of hydrogen, a linear or branched Ci to C 10 alkyl group, a linear or branched C 2 to C 6 alkenyl group, a linear or branched C 3 to C 6 alkynyl group, a C 3 to C 10 cyclic alkyl group, and a C 6 to Cioaryl group
• R 3 and R 4 are each independently selected from the group consisting of hydrogen, a linear or branched Ci to C 10 alkyl group, a linear or branched C 2 to C 6 alkenyl group, a linear or branched C 3 to C 6 alkynyl group
• purging the reactor with a purge gas d. introducing an oxygen-containing source; e. purging the reactor with a purge gas; f. reintroducing the organoamino-vinylsilane or organoamino-allylsilane precursor described above; g. purging the reactor with a purge gas; h. introducing at least one germanium precursor comprising at least one Ge-H bond at a temperature such that the substrate is coated with at least one monolayer of germanium; i. purging the reactor with a purge gas; j. optionally introducing hydrogen or a hydrogen plasma source; k. optionally purging the reactor with a purge gas; and I.
• step d introducing the same or a different germanium precursor as in step d at a temperature suitable to grow a film comprising germanium with a desired thickness; wherein steps b through e are repeated until a silicon-containing film of desired thickness is deposited prior to deposition of the germanium seed layer and subsequent germanium containing film.
• R 1 and R 2 are the same. In other embodiments, R 1 and R 2 are different. In some embodiments, R 3 and R 4 are the same. In other embodiments, R 3 and R 4 are different.
• R 3 and R 4 are independently selected from the group consisting of hydrogen, methyl, vinyl, and allyl.
• the silicon containing films deposited using the organoamino-vinylsilane and/or organoamino-allylsilane precursors described herein, whether a single monolayer or greater than a single monolayer, can serve as substrates suitable for reaction with germanium precursors comprising at least one Ge-H bond.
• germanium precursors comprising at least one Ge-H bond.
• These groups can each subsequently undergo a hydrogermylation reaction with a Ge-H bond of a germanium precursor molecule, thus anchoring a germanium atom or germyl group onto the surface wherever there is an available vinyl and/or allyl group.
• the vinyl and/or allyl group in this reaction is converted to an ethylene, ethylidene, propylene, or methylethylene linker between Si and Ge atoms.
• Exemplary germanium precursors comprising at least one Ge-H bond include, but are not limited to, one or more of trichlorogermane (ChGeH), germane (GeH4), digermane (Ge 2 H 6 ), tert-butylgermane (‘BuGeHs), phenylgermane, sec-butylgemane, iso- butylgermane, and benzylgermane [0037]
• Figure 1 depicts a general scheme in which the organoamino-vinylsilane precursors having Formula I as disclosed herein are used to (a) functionalize a substrate surface with vinyl groups, making it suitable for (b) the formation of a germanium seed layer via hydrogermylation reaction with a germanium precursor comprising at least one Ge-H bond, allowing for (c) the subsequent growth of a smooth and uniform germanium film on top of that seed layer using at least one ALD or CVD Ge precursor.
• the organoamino-vinylsilane and organoamino-allylsilane precursors described herein exhibit a balance of reactivity and stability that makes them ideally suitable as CVD or ALD precursors in microelectronic device manufacturing processes.
• the organoamino-vinylsilanes and/or organoamino-allylsilanes in this invention have at least one organoamino group (NR 1 R 2 ) which helps react the organoamino-vinylsilane and/or organoamino-allylsilane precursors with a hydroxyl surface during an ALD process.
• hydroxyl surfaces are dielectric surfaces such as silicon oxide, silicon nitride, silicon (with native oxide), metal oxides, metal nitrides, or metal (with native oxide), other materials that may contain surface hydroxyl groups such as, for example, organic polymers, silicones, resins, plastics, beads, adsorbents, amorphous carbon, activated charcoal, minerals, organic matter, containers, and textiles are also expected to be reactive toward the at least one organoamino group on the organoamino-vinylsilane and/or the organoamino-allylsilane precursors described herein.
• dielectric surfaces such as silicon oxide, silicon nitride, silicon (with native oxide), metal oxides, metal nitrides, or metal (with native oxide)
• other materials that may contain surface hydroxyl groups such as, for example, organic polymers, silicones, resins, plastics, beads, adsorbents, amorphous carbon, activated charcoal, minerals, organic matter, containers, and textile
• organoamino anchoring group in the organoamino-vinylsilane and organoamino-allylsilane precursors described herein are expected to provide an advantage over chloro-vinylsilane, alkoxy-vinylsilane, vinyldisilazane, chloro-allylsilane, alkoxy-allylsilane, and allyl-disilazane precursors in regard to reaction with -OH terminated surfaces, especially at low temperatures and in the vapor phase.
• treating a substrate with triethoxyvinylsilane at a certain temperature may functionalize little to none of the substrate surface with vinyl groups, while treating the substrate with an organoamino-vinylsilane at the same temperature may provide a much higher level of functionalization.
• treating a substrate with triethoxyallylsilane at a certain temperature may functionalize little to none of the substrate surface with allyl groups, while treating the substrate with an organoamino-allylsilane at the same temperature may provide a much higher level of functionalization.
• Examples of current processes that can benefit from a high saturation of surface vinyl and/or allyl groups include, without limitation, (a) immobilizing species such as catalysts, ion exchange functional groups, adsorbents, or metal scavengers onto a solid support; (b) increasing the hydrophobicity of a substrate; (c) changing the optical properties or refractive index of a substrate for display applications; and/or (d) providing cross-linking sites for better adhesion after UV/thermal annealing of a subsequent coating.
• Certain precursors may have boiling points that are too high to be vaporized and delivered to the reactor to be deposited as a film on a substrate, so it is preferable to select smaller organoamino groups as well as smaller R-groups to provide precursors having boiling points of 250 °C or less, preferably boiling points of 200 °C or less. Having two or more organoamino groups can increase the boiling point significantly; precursors having higher relative boiling points require that the delivery container and lines need to be heated at or above the boiling point of the precursor under a given vacuum to prevent condensation or particles from forming in the container, lines, or both. With regard to stability, other precursors may form silane (SiH 4 ) or disilane (ShHe) as they degrade.
• Silane is pyrophoric at room temperature or it can spontaneously combust which presents safety and handling issues. Moreover, the formation of silane or disilane and other by-products decreases the purity level of the precursor, and changes as small as 1-2% in chemical purity may be considered unacceptable for reliable semiconductor manufacture.
• the organoamino-vinylsilane and/or organoamino- allylsilane precursors having Formula I and/or II described herein comprise 2% or less by weight, or 1% or less by weight, or 0.5% or less by weight of impurities (such as free organoamine, alcohol, chlorosilane, halide, or higher molecular weight disproportionation products) after being stored for a time period of 6 months or greater, or one year or greater which is indicative of being shelf stable.
• impurities such as free organoamine, alcohol, chlorosilane, halide, or higher molecular weight disproportionation products
• organoamino-vinylsilane and/or organoamino-allylsilane precursors having an Si-H group may be prone to degradation via polymerization thru intermolecular hydrosilylation reaction. That is, a reaction may occur between an Si-H group of one molecule and the vinyl and/or allyl group of another molecule if the size of the R 1 thru R 4 groups in Formula I and/or II do not provide enough steric protection.
• This hydrosilylation reaction may occur either slowly or spontaneously under storage conditions, or during purification (e.g. distillation), or during a deposition process and can be catalyzed by trace impurities.
• organoamino- vinylsilane precursor it is important to rid the organoamino- vinylsilane precursor of as many impurities as possible which may act as hydrosilylation/polymerization catalysts. Also, careful selection of the R 1 thru R 4 groups is required to allow facile reaction of the organoamino-vinylsilane and/or organoamino- allylsilane with the substrate surface under the desired conditions, while preserving innate stability of the precursor.
• R 3 and R 4 in Formula I and/or II are both organoamino groups. In other preferred embodiments, R 3 and R 4 in Formula I and/or II are both methyl groups. In other preferred embodiments, R 1-4 in Formula I and/or II are all methyl groups. In other preferred embodiments, R 3 and R 4 in Formula I and/or II are both vinyl groups. In other preferred embodiments, R 3 and R 4 in Formula I and/or II are both allyl groups. In other preferred embodiments, R 3 is an organoamino group, and R 4 is a vinyl group in Formula I. In other preferred embodiments, R 3 is an organoamino group, and R 4 is an allyl group in Formula II.
• R 3 is a methyl group and R 4 is a vinyl group in Formula I. In other preferred embodiments, R 3 is a methyl group and R 4 is an allyl group in Formula II.
• the organoamino-vinylsilane and organoamino-allylsilane precursors described herein are able to deposit high density materials at relatively low deposition temperatures, e.g., 1000 °C or less, 800 °C or less, 700°C or less, 500°C or less, or 400°C or less, 300°C or less, 200°C or less, 100°C or less, or 50°C or less.
• composition for forming a silicon- containing film comprising: an organoamino-vinylsilane having Formula I and/or an organoamino-allylsilane having Formula II described herein and a solvent(s).
• composition described herein may provide one or more advantages compared to existing silicon precursors such as TEOS, BDEAS, SiCI 4 .
• advantages include: better usage of the organoamino-vinylsilane and/or organoamino-allylsilane in semiconductor processes, better stability over long term storage, cleaner evaporation by flash vaporization, and/or overall more stable direct liquid injection (DLI) chemical vapor deposition process, allowing for deposition of higher quality silicon-containing films, furthermore allowing for more superior subsequent Ge film deposition.
• DLI direct liquid injection
• the weight percentage of the organoamino-vinylsilane and/or organoamino-allylsilane in the composition can range from 1 to 99% with the balance being solvent(s), wherein the solvent(s) does not react with the organoamino-vinylsilane and/or organoamino- allylsilane and has a boiling point similar to the organoamino-vinylsilane and/or organoamino-allylsilane.
• the difference between the boiling points of the organoamino-vinylsilane and/or organoamino-allylsilane and solvent(s) in the composition is 40 °C or less, more preferably 20 °C or less, or 10°C or less.
• organoamino-vinylsilane and/or organoamino-allylsilane precursors described in this invention to deposit a silicon- containing film such as, without limitation, silicon, silicon carbide, silicon nitride, carbon- doped silicon nitride, silicon oxide, silicon oxynitride, carbon-doped silicon oxynitride, and carbon-doped silicon oxide, providing that a metallic film such as a germanium film is to be subsequently deposited onto that silicon-containing film.
• the final step of this Si-containing film deposition process is the organoamino-vinylsilane and/or organoamino-allylsilane precursor exposure, the resulting Si-containing film is much more susceptible to formation of a uniform Ge seed layer and thus smooth, conformal Ge film growth thereafter.
• the bulk composition, physical properties, and electrical properties of the Si-containing films described herein might also be achieved using various other silicon precursors and deposition methods known in the prior art.
• those films would still require functionalization with the organoamino- vinylsilane and/or organoamino-allylsilane precursors described herein prior to deposition of reduced or metallic germanium films in order for those germanium films to be of the same high quality. It is therefore clear how using a single silicon precursor such as an organoamino-vinylsilane or organoamino-allylsilane described herein to perform both the deposition of a silicon-containing film as well as the functionalization of that film with vinyl and/or allyl groups for subsequent Ge film growth would be much more favorable to using two different silicon precursors.
• organoamino-vinylsilane or organoamino-allylsilane described herein to perform both the deposition of a silicon-containing film as well as the functionalization of that film with vinyl and/or allyl groups for subsequent Ge film growth would be much more favorable to using two different silicon precursors.
• substituents R 1 and R 2 in Formula I and/or II can be linked together to form a ring structure.
• R 1 and R 2 are linked together to form a ring R 1 will include a bond for linking to R 2 and vice versa.
• the ring structure can be unsaturated such as a cyclic alkyl ring, or saturated such as an aryl ring.
• R 3 and R 4 in Formula I and/or II can be linked together to form a ring structure.
• the ring structure can also be substituted or unsubstituted.
• Exemplary cyclic ring groups include, but are not limited to, pyrrolidino, 2-methylpyrrolidino, 2,5,-dimethylpyrrolidino, piperidino, 2,6-dimethylpiperidino, pyrrolyl, and imidazolyl groups.
• substituents R 1 and R 2 are not linked.
• R 3 and R 4 are not linked.
• alkyl denotes a linear, or branched functional group having from 1 to 10 or 1 to 6 carbon atoms.
• exemplary alkyl groups include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, iso-pentyl, tert-pentyl, hexyl, iso-hexyl, and neo-hexyl.
• the alkyl group may have one or more functional groups such as, but not limited to, an alkoxy group, a dialkylamino group or combinations thereof, attached thereto. In other embodiments, the alkyl group does not have one or more functional groups attached thereto.
• cyclic alkyl denotes a cyclic functional group having from 3 to 10 or from 4 to 10 carbon atoms or from 5 to 10 carbon atoms.
• exemplary cyclic alkyl groups include, but are not limited to, cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl groups.
• aryl denotes an aromatic cyclic functional group having from 5 to 12 carbon atoms or from 6 to 10 carbon atoms.
• exemplary aryl groups include, but are not limited to, phenyl, benzyl, chlorobenzyl, tolyl, and o-xylyl.
• alkenyl group denotes a group which has one or more carbon-carbon double bonds and has from 3 to 10 or from 3 to 6 or from 3 to 4 carbon atoms.
• alkenyl groups include, but are not limited to, vinyl and allyl.
• alkynyl group denotes a group which has one or more carbon-carbon triple bonds and has from 3 to 10 or from 3 to 6 or from 3 to 4 carbon atoms.
• organoamino group denotes a group which has at least one alkyl or otherwise hydrocarbon group attached to a nitrogen atom and has from 1 to 10 or from 2 to 6 or from 2 to 4 carbon atoms.
• organoamino groups include, but not limited to, methylamino, ethylamino, normal-propylamine, iso-propylamino, normal-butylamino, iso-butylamino, sec- butylamino, tert-butylamino, cyclopentylamino, cyclohexylamino, phenylamino, dimethylamino, N-ethylmethylamino, diethylamino, di-iso-propylamino.
• dialkylamino group denotes a group which has two alkyl groups attached to a nitrogen atom, wherein each alkyl group has, for example, from 1 to 10, from 2 to 6, or from 2 to 4 carbon atoms.
• exemplary dialkylamino groups include, but limited to, dimethylamino, diethylamino, ethylmethylamino, di-normal-propylamine, di-iso-propylamino, di-normal-butylamino, di- iso-butylamino, di-sec-butylamino, di-tert-butylamino.
• one or more of the alkyl group, alkenyl group, alkynyl group, or aryl group in Formula I and II may be substituted or have one or more atoms or group of atoms substituted in place of, for example, a hydrogen atom.
• substituents include, but are not limited to, oxygen, sulfur, halogen atoms (e.g., F, Cl, I, or Br), nitrogen, and phosphorous.
• the at least one organoamino-vinylsilane precursor having Formula I and/or the at least one organoamino-allylsilane precursors having Formula II has one or more substituents comprising oxygen or nitrogen atoms.
• Table 1 lists examples of silicon precursors having at least one vinyl group and at least one organoamino anchoring group connected to at least one silicon atom according to Formula I.
• Table 2 lists examples of silicon precursors having at least one vinyl group and at least one organoamino anchoring group connected to at least one silicon atom according to Formula II. Table 2. Exemplary organoamino-allylsilane precursors.
• the organoamino-vinylsilane and/or organoamino-allylsilane precursors according to the present invention and compositions comprising the organoamino- vinylsilane and/or organoamino-allylsilane precursors according to the present invention are preferably substantially free of organoamines or halide ions.
• the term “substantially free” as it relates to halide ions (or halides) such as, for example, chlorides and fluorides, bromides, and iodides, means less than 5 ppm (by weight), preferably less than 3 ppm, and more preferably less than 1 ppm, and most preferably 0 ppm.
• the term “free of” as it relates to halide ions or other impurities means 0 ppm.
• Chlorides are known to act as decomposition catalysts for organoamino- vinylsilanes and organoamino-allylsilanes. Significant levels of chloride in the final product can cause the organoamino-vinylsilane and/or organoamino-allylsilane precursor to degrade. The gradual degradation of the organoamino-vinylsilane and/or organoamino-allylsilane may directly impact the film deposition process or surface functionalization process, making it difficult for the semiconductor manufacturer to meet film specifications.
• organoamines include, but not limited to, Ci to Cio organoamines, organodiamines.
• the silicon precursor compounds having Formulae I and II are preferably substantially free of metal ions such as, Li + , Na + , K + , Mg 2+ , Ca 2+ ,
• the term “substantially free” as it relates to Li, Na, K, Mg, Ca, Al, Fe, Ni, Cr, noble metal such as volatile Ru or Pt complexes from ruthenium or platinum catalysts used in the synthesis means less than 5 ppm (by weight), preferably less than 3 ppm, and more preferably less than 1 ppm, and most preferably 0.1 ppm as measured by ICP-MS or other analytical method for measuring trace metals.
• the method used to form the silicon-containing films or coatings are deposition processes.
• suitable deposition processes for the method disclosed herein include, but are not limited to, cyclic CVD (CCVD), MOCVD (Metal Organic CVD), thermal chemical vapor deposition, plasma enhanced chemical vapor deposition (“PECVD”), high density PECVD, photon assisted CVD, plasma-photon assisted (“PPECVD”), cryogenic chemical vapor deposition, chemical assisted vapor deposition, hot-filament chemical vapor deposition, CVD of a liquid polymer precursor, deposition from supercritical fluids, and low energy CVD (LECVD).
• the metal containing films are deposited via atomic layer deposition (ALD), plasma enhanced ALD (PEALD) or plasma enhanced cyclic CVD (PECCVD) process.
• ALD atomic layer deposition
• PEALD plasma enhanced ALD
• PECCVD plasma enhanced cyclic CVD
• chemical vapor deposition processes refers to any process wherein a substrate is exposed to one or more volatile precursors, which react and/or decompose on the substrate surface to produce the desired deposition.
• atomic layer deposition process refers to a self-limiting (e.g., the amount of film material deposited in each reaction cycle is constant), sequential surface chemistry that deposits films of materials onto substrates of varying compositions.
• the precursors, reagents and sources used herein may be sometimes described as “gaseous”, it is understood that the precursors can be either liquid or solid which are transported with or without an inert gas into the reactor via direct vaporization, bubbling or sublimation.
• the vaporized precursors can pass through a plasma generator.
• the silicon-containing film is deposited using an ALD process.
• the silicon-containing film is deposited using a CCVD process.
• the silicon-containing film is deposited using a thermal CVD process.
• reactor as used herein, includes without limitation, reaction chamber or deposition chamber.
• the method disclosed herein avoids pre-reaction of the precursors by using ALD or CCVD methods that separate the precursors prior to and/or during the introduction to the reactor.
• deposition techniques such as ALD or CCVD processes are used to deposit the silicon-containing film.
• the film is deposited via an ALD process by exposing the substrate surface alternatively to the one or more the silicon-containing precursor, oxygen-containing source, nitrogen-containing source, or other precursor or reagent. Film growth proceeds by self-limiting control of surface reaction, the pulse length of each precursor or reagent, and the deposition temperature. However, once the surface of the substrate is saturated, the film growth ceases.
• the method described herein further comprises one or more additional silicon-containing precursors other than the organoamino-vinylsilane and/or organoamino-allylsilane precursors having the above Formula I and/or II.
• additional silicon-containing precursors include, but are not limited to, monoaminosilane (e.g., di-iso-propylaminosilane, di-sec-butylaminosilane, phenylmethylaminosilane; organo-silicon compounds such as trisilylamine (TSA); monoaminosilane (di-iso-propylaminosilane, di-sec-butylaminosilane, phenylmethylaminosilane); siloxanes (e.g., hexamethyl disiloxane (HMDSO) and dimethyl siloxane (DMSO), and hexachlorodisiloxane (HCDSO)); organosilanes (e.g., methylsilane, dimethylsilane, diethylsilane, vinyl trimethylsilane, trimethylsilane, tetramethylsilane, ethylsilane, disilylmethane, 2,4-disilapentan
• the one or more silicon-containing precursors may be introduced into the reactor at a predetermined molar volume, or from about 0.1 to about 1000 micromoles.
• the silicon-containing and/or organoamino-vinylsilane and/or organoamino-allylsilane precursor may be introduced into the reactor for a predetermined time period. In certain embodiments, the time period ranges from about 0.001 to about 500 seconds.
• the silicon-containing films deposited using the methods described herein are formed in the presence of oxygen using an oxygen- containing source, reagent or precursor comprising oxygen.
• An oxygen-containing source may be introduced into the reactor in the form of at least one oxygen-containing source and/or may be present incidentally in the other precursors used in the deposition process.
• Suitable oxygen-containing source gases may include, for example, water (H 2 0) (e.g., deionized water, purifier water, and/or distilled water), hydrogen peroxide (H 2 O 2 ), oxygen (O 2 ), oxygen plasma, ozone (O 3 ), NO, N 2 O, NO 2 , carbon monoxide (CO), carbon dioxide (CO 2 ) and combinations thereof.
• the oxygen- containing source comprises an oxygen-containing source gas that is introduced into the reactor at a flow rate ranging from about 1 to about 2000 square cubic centimeters (seem) or from about 1 to about 1000 seem.
• the oxygen-containing source can be introduced for a time that ranges from about 0.1 to about 100 seconds.
• the oxygen-containing source comprises water having a temperature of 10°C or greater.
• the precursor pulse can have a pulse duration that is greater than 0.01 seconds, and the oxygen-containing source can have a pulse duration that is less than 0.01 seconds, while the water pulse duration can have a pulse duration that is less than 0.01 seconds.
• the purge duration between the pulses that can be as low as 0 seconds or is continuously pulsed without a purge in-between.
• the oxygen-containing source or reagent is provided in a molecular amount less than a 1:1 ratio to the silicon precursor, so that at least some carbon is retained in the as deposited silicon-containing film.
• the silicon-containing films comprise silicon and nitrogen.
• the silicon-containing films deposited using the methods described herein are formed in the presence of nitrogen-containing source.
• a nitrogen-containing source may be introduced into the reactor in the form of at least one nitrogen-containing source and/or may be present incidentally in the other precursors used in the deposition process.
• Suitable nitrogen-containing source gases may include, for example, ammonia, hydrazine, monoalkylhydrazine, dialkylhydrazine, nitrogen, nitrogen/hydrogen, ammonia plasma, nitrogen plasma, nitrogen/hydrogen plasma, and mixture thereof.
• the nitrogen-containing source comprises an ammonia plasma or hydrogen/nitrogen plasma source gas that is introduced into the reactor at a flow rate ranging from about 1 to about 2000 square cubic centimeters (seem) or from about 1 to about 1000 seem.
• the nitrogen-containing source can be introduced for a time that ranges from about 0.1 to about 100 seconds.
• the precursor pulse can have a pulse duration that is greater than 0.01 seconds
• the nitrogen-containing source can have a pulse duration that is less than 0.01 seconds
• the water pulse duration can have a pulse duration that is less than 0.01 seconds.
• the purge duration between the pulses that can be as low as 0 seconds or is continuously pulsed without a purge in-between.
• the deposition methods disclosed herein may involve one or more purge gases.
• the purge gas which is used to purge away unconsumed reactants and/or reaction byproducts, is an inert gas that does not react with the precursors.
• Exemplary purge gases include, but are not limited to, argon (Ar), nitrogen (N2), helium (He), neon, hydrogen (H2), and mixtures thereof.
• a purge gas such as Ar is supplied into the reactor at a flow rate ranging from about 10 to about 2000 seem for about 0.1 to 1000 seconds, thereby purging the unreacted material and any byproduct that may remain in the reactor.
• the respective step of supplying the precursors, oxygen-containing source, the nitrogen-containing source, and/or other precursors, source gases, and/or reagents may be performed by changing the time for supplying them to change the stoichiometric composition of the resulting silicon-containing film.
• Energy is applied to the at least one of the precursor, oxygen-containing source, nitrogen-containing source, reducing agent, other precursors or combination thereof to induce reaction and to form the silicon-containing film or coating on the substrate.
• energy can be provided by, but not limited to, thermal, plasma, pulsed plasma, helicon plasma, high density plasma, inductively coupled plasma, X-ray, e-beam, photon, remote plasma methods, and combinations thereof.
• a secondary RF frequency source can be used to modify the plasma characteristics at the substrate surface.
• the plasma-generated process may comprise a direct plasma-generated process in which plasma is directly generated in the reactor, or alternatively a remote plasma-generated process in which plasma is generated outside of the reactor and supplied into the reactor.
• the organoamino-vinylsilane and/or organoamino-allylsilane precursors, other silicon-containing precursors, and/or germanium precursors may be delivered to the reaction chamber such as a CVD or ALD reactor in a variety of ways.
• a liquid delivery system may be utilized.
• a combined liquid delivery and flash vaporization process unit may be employed, such as, for example, the turbo vaporizer manufactured by MSP Corporation of Shoreview, MN, to enable low volatility materials to be volumetrically delivered, which leads to reproducible transport and deposition without thermal decomposition of the precursor.
• the precursors described herein may be delivered in neat liquid form, or alternatively, may be employed in solvent formulations or compositions comprising same.
• the precursor formulations may include solvent component(s) of suitable character as may be desirable and advantageous in a given end use application to form a film on a substrate.
• the solvent or mixture thereof selected does not react with the organoamino-vinylsilane and/or organoamino-allylsilane.
• the amount of solvent by weight percentage in the composition ranges from 0.5% by weight to 99.5% or from 10% by weight to 75%.
• the solvent has a boiling point (b.p.) similar to the b.p. of the precursor having Formula I and/or II or the difference between the b.p. of the solvent and the b.p. of the precursor having Formula I or II is 40°C or less, 30°C or less, or 20°C or less, or 10°C.
• the difference between the boiling points ranges from any one or more of the following end-points: 0, 10, 20, 30, or 40°C. Examples of suitable ranges of b.p. difference include without limitation, 0 to 40°C, 20° to 30°C, or 10° to 30°C.
• suitable solvents in the compositions include, but are not limited to, an ether (such as 1,4-dioxane, dibutyl ether), a tertiary amine (such as pyridine, 1- methylpiperidine, 1-ethylpiperidine, N,N'-dimethylpiperazine, N,N,N',N'- tetramethylethylenediamine), a nitrile (such as benzonitrile), an alkyl hydrocarbon (such as octane, nonane, dodecane, ethylcyclohexane), an aromatic hydrocarbon (such as toluene, mesitylene), a tertiary aminoether (such as bis(2-dimethylaminoethyl) ether), or mixtures thereof.
• an ether such as 1,4-dioxane, dibutyl ether
• a tertiary amine such as pyridine, 1- methylpiperidine, 1-
• a vessel for depositing a silicon-containing film comprising one or more organoamino-vinylsilane and/or organoamino-allylsilane precursor(s) having Formula I or II is described herein.
• the vessel comprises at least one pressurizable vessel (preferably of stainless steel) fitted with the proper valves and fittings to allow the delivery of one or more precursors to the reactor for a CVD or an ALD process.
• the organoamino-vinylsilane and/or organoamino-allylsilane precursor having Formula I and/or II is provided in a pressurizable vessel comprised of stainless steel and the purity of the precursor is 98% by weight or greater or 99.5% or greater which is suitable for the majority of semiconductor applications.
• a pressurizable vessel comprised of stainless steel and the purity of the precursor is 98% by weight or greater or 99.5% or greater which is suitable for the majority of semiconductor applications.
• such vessels can also have means for mixing the precursors with one or more additional precursor if desired.
• the contents of the vessel(s) can be premixed with an additional precursor.
• the organoamino-vinylsilane and/or organoamino- allylsilane precursor and/or other precursor can be maintained in separate vessels or in a single vessel having separation means for maintaining the organoamino-vinylsilane and/or organoamino-allylsilane precursor and other precursor separate during storage.
• a cyclic deposition process such as CCVD, ALD, or PEALD may be employed, wherein at least one silicon- containing precursor selected from an organoamino-vinylsilane and/or organoamino- allylsilane precursor having the formulae described herein and optionally a nitrogen- containing source such as, for example, ammonia, hydrazine, monoalkylhydrazine, dialkylhydrazine, nitrogen, nitrogen/hydrogen, ammonia plasma, nitrogen plasma, nitrogen/hydrogen plasma are employed.
• a nitrogen- containing source such as, for example, ammonia, hydrazine, monoalkylhydrazine, dialkylhydrazine, nitrogen, nitrogen/hydrogen, ammonia plasma, nitrogen plasma, nitrogen/hydrogen plasma are employed.
• the gas lines connecting from the precursor canisters to the reaction chamber are heated to one or more temperatures depending upon the process requirements and the container of the organoamino-vinylsilane and/or organoamino-allylsilane precursor having the Formula I and/or II described herein is kept at one or more temperatures for bubbling.
• a solution comprising the at least one silicon-containing precursor having the formula described herein is injected into a vaporizer kept at one or more temperatures for direct liquid injection.
• a flow of argon and/or other gas may be employed as a carrier gas to help deliver the vapor of the at least one organoamino-vinylsilane and/or organoamino- allylsilane precursor to the reaction chamber during the precursor pulsing.
• the reaction chamber process pressure is about 10 Torr or less. In another embodiments, the reaction chamber process pressure is about 5 Torr or less.
• the silicon oxide or carbon doped silicon oxide film having carbon content ranging from zero at. % to 20 at. % is deposited using a thermal ALD process and a plasma comprising hydrogen to improve film properties.
• the method comprises: a. placing one or more substrates comprising a surface feature into a reactor and heating to reactor to one or more temperatures ranging from ambient temperature to about 550°C and optionally maintaining the reactor at a pressure of 100 torr or less; b.
• organoamino-vinylsilane and/or organoamino-allylsilane precursor comprising at least one vinyl and/or allyl group and at least one organoamino anchoring group connected to at least one silicon atom represented by the Formulae I and/or II; c. purging the reactor with an inert gas thereby removing unreacted silicon precursor and forming a composition comprising the purge gas and silicon precursor; d. providing an oxygen-containing source into the reactor to react with the surface to form a silicon and oxygen containing film; e. purging with inert gas to remove reaction by-products; f. repeating steps b to e to provide a desired thickness of either silicon oxide or carbon doped silicon oxide;
• the UV exposure step can be carried out either during film deposition, or once deposition has been completed.
• silicon and nitrogen containing film such as silicon nitride or silicon carbonitride can be deposited using the organoamino-vinylsilanes and/or organoamino-allysilanes as described herein with the same steps outlined above except that a nitrogen-containing source is used instead of an oxygen-containing source.
• the substrate includes at least one feature wherein the feature comprises a pattern trench with an aspect ratio of 1:9 or higher, and/or an opening of 180 nm or less.
• the plasma source is selected from the group consisting of hydrogen plasma, plasma comprising hydrogen and helium, and plasma comprising hydrogen and argon.
• Hydrogen plasma lowers film dielectric constant and boost the damage resistance to following plasma ashing process while still keeping the carbon content in the bulk almost unchanged.
• ALD or ALD-like refers to a process including, but not limited to, the following processes: a) each reactant including silicon precursor and reactive gas is introduced sequentially into a reactor such as a single wafer ALD reactor, semi-batch ALD reactor, or batch furnace ALD reactor; b) each reactant including silicon precursor and reactive gas is exposed to a substrate by moving or rotating the substrate to different sections of the reactor and each section is separated by inert gas curtain, i.e. spatial ALD reactor or roll to roll ALD reactor.
• the term “ashing” refers to a process to remove the photoresist or carbon hard mask in semiconductor manufacturing process using a plasma comprising oxygen source such as 0 2 /inert gas plasma, O 2 plasma, CO 2 plasma, CO plasma, H 2 /O 2 plasma or combination thereof.
• the term “damage resistance” refers to film properties after oxygen ashing process.
• Good or high damage resistance is defined as the following film properties after oxygen ashing: film dielectric constant lower than 4.5; carbon content in the bulk (at more than 50 A deep into film) is within 5 at. % as before ashing; Less than 50 A of the film is damaged, observed by differences in dilute HF etch rate between films near surface (less than 50 A deep) and bulk (more than 50 A deep).
• the organoamino-vinylsilane and/or organoamino- allylsilane precursors having Formulae I and/or II described herein can also be used as a dopant for metal containing films, such as but not limited to, metal oxide films or metal nitride films.
• the metal containing film is deposited using an ALD or CVD process such as those processes described herein using metal alkoxide, metal amide, or volatile organometallic precursors.
• suitable metal alkoxide precursors include, but are not limited to, group 3 to 6 metal alkoxide, group 3 to 6 metal complexes having both alkoxy and alkyl substituted cyclopentadienyl ligands, group 3 to 6 metal complexes having both alkoxy and alkyl substituted pyrrolyl ligands, group 3 to 6 metal complexes having both alkoxy and diketonate ligands; group 3 to 6 metal complexes having both alkoxy and ketoester ligands.
• suitable metal amide precursors include, but are not limited to, tetrakis(dimethylamino)zirconium (TDMAZ), tetrakis(diethylamino)zirconium (TDEAZ), tetrakis(ethylmethylamino)zirconium (TEMAZ), tetrakis(dimethylamino)hafnium (TDMAH), tetrakis(diethylamino)hafnium (TDEAH), and tetrakis(ethylmethylamino)hafnium (TEMAH), tetrakis(dimethylamino)titanium (TDMAT), tetrakis(diethylamino)titanium (TDEAT), tetrakis(ethylmethylamino)titanium (TEMAT), tert-butylimino tri(diethylamino)tanta
• organometallic precursors examples include, but are not limited to, group 3 metal cyclopentadienyls or alkyl cyclopentadienyls.
• exemplary Group 3 to 6 metal herein include, but not limited to, Y,
• the resultant silicon-containing films or coatings can be exposed to a post-deposition treatment such as, but not limited to, a plasma treatment, chemical treatment, ultraviolet light exposure, electron beam exposure, and/or other treatments to affect one or more properties of the film.
• a post-deposition treatment such as, but not limited to, a plasma treatment, chemical treatment, ultraviolet light exposure, electron beam exposure, and/or other treatments to affect one or more properties of the film.
• the silicon-containing films described herein have a dielectric constant of 6 or less.
• the films can a dielectric constant of about 5 or below, or about 4 or below, or about 3.5 or below.
• films having other dielectric constants e.g., higher or lower can be formed depending upon the desired end-use of the film.
• silicon carbonitride wherein the carbon content is from 1 at% to 80 at% measured by XPS.
• silicon containing film that is formed using the organoamino- vinylsilane and/or organoamino-allylsilane precursors and processes described herein is amorphous silicon wherein both sum of nitrogen and carbon contents is ⁇ 10 at%, preferably ⁇ 5 at%, most preferably ⁇ 1 at% measured by XPS.
• the method described herein may be used to deposit a silicon-containing film on at least a portion of a substrate.
• suitable substrates include but are not limited to, silicon, germanium doped silicon, germanium, S1O 2 , S1 3 N 4 , OSG, FSG, silicon carbide, hydrogenated silicon carbide, silicon nitride, hydrogenated silicon nitride, silicon carbonitride, hydrogenated silicon carbonitride, boronitride, antireflective coatings, photoresists, a flexible substrate, organic polymers, porous organic and inorganic materials, metals such as copper and aluminum, and diffusion barrier layers such as but not limited to TiN, Ti(C)N, TaN, Ta(C)N, Ta, W, or WN.
• the films are compatible with a variety of subsequent processing steps such as, for example, chemical mechanical planarization (CMP) and anisotropic etching processes.
• CMP chemical mechanical planarization
• the deposited films have applications, which include, but are not limited to, computer chips, optical devices, magnetic information storages, coatings on a supporting material or substrate, microelectromechanical systems (MEMS), nanoelectromechanical systems, thin film transistor (TFT), light emitting diodes (LED), organic light emitting diodes (OLED), IGZO, and liquid crystal displays (LCD).
• MEMS microelectromechanical systems
• TFT thin film transistor
• LED light emitting diodes
• OLED organic light emitting diodes
• IGZO liquid crystal displays
• the methods described herein provide a high quality film including germanium, silicon, silicon carbide, silicon nitride, carbon doped silicon nitride, silicon oxide, silicon oxynitride, carbon doped silicon oxynitride, carbon-doped silicon oxide.
• high quality means a film that exhibits one or more of the following characteristics: a density of about 2.1 g/cc or greater, 2.2 g/cc or greater, 2.25 g/cc or greater; a wet etch rate that is 2.5 A/s or less, 2.0 A/s or less, 1.5 A/s or less, 1.0 A/s or less, 0.5 A/s or less, 0.1 A/s or less, 0.05 A/s or less, 0.01 A/s or less as measured in a solution of 1:100 of HF to water dilute HF ( 0.5 wt% dHF) acid, an electrical leakage of about 1 or less e-8 A/cm 2 up to 6 MV/cm); a hydrogen impurity of about 5 e20 at/cc or less as measured by SIMS; very low non-uniformity, low levels of surface roughness, and combinations thereof.
• a thermally grown silicon oxide film has 0.5 A/s etch rate in 0.5 wt% HF.
• one or more silicon precursors having Formulae I and II described herein can be used to form silicon and oxygen containing films that are solid and are non-porous or are substantially free of pores.
• the following examples illustrate methods for preparing organoamino- vinylsilane and/or organoamino-allylsilane precursors, depositing silicon-containing films, generating vinyl-functionalized and/or allyl-functionalized surfaces, and producing germanium seed layers described herein and are not intended to limit it in any way.
• Example 2 Treatment of silica gel with tris(ethylamino)vinylsilane.
• silica gel (DavasilTM grade 645, 60-100 mesh, 150 A) was stirred in 5 mL of a 50 wt% solution of tris(ethylamino)vinylsilane in THF at 80 °C for 2 hours. The liquid phase was decanted, and the solids were rinsed several times with hot THF before being dried under vacuum. Both the untreated and treated silica gels were analyzed by FTIR spectroscopy as KBr pellets. The sharp peak at 3741 cm -1 in the FTIR spectrum of the untreated silica gel corresponding to the isolated surface Si-OH groups was not detected in the FTIR spectrum of the treated silica gel.
• the treated silica gel showed the following new peaks in the FTIR spectrum: 3418 (N-H), 3062 (vinyl C-H), 3021 (vinyl C-H), 2968 (vinyl C-H), 2935 (ethyl C-H), 2876 (ethyl C-H). This shows that the surface of the silica gel was functionalized with vinyl groups and ethylamino groups at a relatively low temperature and short amount of time after treatment with tris(ethylamino)vinylsilane.

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