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]
  • C23C16/45527—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
  • C23C16/4554—Plasma being used non-continuously in between ALD reactions
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
  • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
  • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
  • H01L21/02104—Forming layers
  • H01L21/02107—Forming insulating materials on a substrate
  • H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
  • H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
  • H01L21/02263—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase
  • H01L21/02271—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition
  • H01L21/02274—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition in the presence of a plasma [PECVD]
• • 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
  • C23C16/04—Coating on selected surface areas, e.g. using masks
• • 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
  • C23C16/04—Coating on selected surface areas, e.g. using masks
  • C23C16/045—Coating cavities or hollow spaces, e.g. interior of tubes; Infiltration of porous substrates
• • 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
  • C23C16/40—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
  • C23C16/405—Oxides of refractory metals or yttrium
• • 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
  • C23C16/45531—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 specially adapted for making ternary or higher compositions
• • 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
  • C23C16/45542—Plasma being used non-continuously during the ALD reactions
• • 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
  • 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
• • 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
  • C23C16/56—After-treatment
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
  • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
  • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
  • H01L21/02104—Forming layers
  • H01L21/02107—Forming insulating materials on a substrate
  • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
  • H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
  • H01L21/02123—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon
  • H01L21/02126—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon the material containing Si, O, and at least one of H, N, C, F, or other non-metal elements, e.g. SiOC, SiOC:H or SiONC
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
  • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
  • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
  • H01L21/02104—Forming layers
  • H01L21/02107—Forming insulating materials on a substrate
  • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
  • H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
  • H01L21/02123—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon
  • H01L21/02126—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon the material containing Si, O, and at least one of H, N, C, F, or other non-metal elements, e.g. SiOC, SiOC:H or SiONC
  • H01L21/0214—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon the material containing Si, O, and at least one of H, N, C, F, or other non-metal elements, e.g. SiOC, SiOC:H or SiONC the material being a silicon oxynitride, e.g. SiON or SiON:H
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
  • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
  • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
  • H01L21/02104—Forming layers
  • H01L21/02107—Forming insulating materials on a substrate
  • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
  • H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
  • H01L21/02123—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon
  • H01L21/02142—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon the material containing silicon and at least one metal element, e.g. metal silicate based insulators or metal silicon oxynitrides
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
  • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
  • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
  • H01L21/02104—Forming layers
  • H01L21/02107—Forming insulating materials on a substrate
  • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
  • H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
  • H01L21/02123—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon
  • H01L21/02164—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon the material being a silicon oxide, e.g. SiO2
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
  • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
  • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
  • H01L21/02104—Forming layers
  • H01L21/02107—Forming insulating materials on a substrate
  • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
  • H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
  • H01L21/02172—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides
  • H01L21/02175—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides characterised by the metal
  • H01L21/02186—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides characterised by the metal the material containing titanium, e.g. TiO2
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
  • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
  • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
  • H01L21/02104—Forming layers
  • H01L21/02107—Forming insulating materials on a substrate
  • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
  • H01L21/02205—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition
  • H01L21/02208—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si
  • H01L21/02214—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si the compound comprising silicon and oxygen
  • H01L21/02216—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si the compound comprising silicon and oxygen the compound being a molecule comprising at least one silicon-oxygen bond and the compound having hydrogen or an organic group attached to the silicon or oxygen, e.g. a siloxane
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
  • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
  • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
  • H01L21/02104—Forming layers
  • H01L21/02107—Forming insulating materials on a substrate
  • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
  • H01L21/02205—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition
  • H01L21/02208—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si
  • H01L21/02219—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si the compound comprising silicon and nitrogen
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
  • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
  • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
  • H01L21/02104—Forming layers
  • H01L21/02107—Forming insulating materials on a substrate
  • H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
  • H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
  • H01L21/02263—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase
  • H01L21/02271—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition
  • H01L21/02277—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition the reactions being activated by other means than plasma or thermal, e.g. photo-CVD
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
  • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
  • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
  • H01L21/02104—Forming layers
  • H01L21/02107—Forming insulating materials on a substrate
  • H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
  • H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
  • H01L21/02263—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase
  • H01L21/02271—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition
  • H01L21/0228—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition deposition by cyclic CVD, e.g. ALD, ALE, pulsed CVD
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
  • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
  • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
  • H01L21/02104—Forming layers
  • H01L21/02107—Forming insulating materials on a substrate
  • H01L21/02296—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer
  • H01L21/02299—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer pre-treatment
  • H01L21/02304—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer pre-treatment formation of intermediate layers, e.g. buffer layers, layers to improve adhesion, lattice match or diffusion barriers

Definitions

• the present disclosure relates generally to the field of semiconductor device manufacturing and, more particularly, to selective plasma enhanced atomic layer deposition (PEALD) of oxide films.
• PEALD plasma enhanced atomic layer deposition
• the present application relates to the selective deposition of an oxide on a substrate by plasma enhanced atomic layer deposition (PEALD).
• the oxide may comprise, for example, SiC3 ⁇ 4, SiOC, SiOCN or a metal oxide.
• the oxide comprises both metal and silicon.
• the oxide is selectively deposited on a dielectric surface of a substrate.
• the PEALD process does not utilize oxygen plasma or other reactive oxygen species.
• one of the reactants comprises reactive species from a plasma generated in a gas that does not comprise oxygen.
• a PEALD process for selectively depositing an oxide on a dielectric surface of a substrate comprises providing a substrate comprising a first dielectric surface and a second, different surface, such as a metal surface. At least one deposition cycle is carried out comprising alternately and sequentially contacting the substrate with a first precursor comprising oxygen and a component of the oxide, such as silicon or metal, and a second reactant.
• the second reactant comprises reactive species from a plasma generated in a gas that does not comprise oxygen.
• the second reactant may comprise hydrogen plasma.
• the hydrogen plasma may be generated in a gas comprising H 2 .
• the second reactant reacts with the first precursor adsorbed on the substrate surface to selectively form an oxide on the first dielectric surface relative to the second metal surface.
• the second reactant also reacts with the metal surface to reduce metal oxide that may be present on the metal surface.
• the second reactant may also remove OH groups that may be present on the metal surface.
• the deposition cycle may be repeated two or more times to form an oxide of the desired thickness on the dielectric surface.
• the second reactant is provided first, such that it reacts with the surface of the substrate, either with the dielectric surface where it can act to condition the surface for subsequent deposition, or with adsorbed first reactant from a prior deposition cycle.
• the dielectric surface comprises Si0 2 . In some embodiments the dielectric surface comprises a low-k material.
• the metal surface may comprise, for example,
• the oxide that is selectively deposited comprises S-O2, SiOC or SiOCN.
• the oxide is a metal oxide, such as titanium oxide.
• the oxide is any metal oxide that can be deposited from an oxygen containing precursor.
• the oxide that is selectively deposited comprises a mixture of two or more oxides.
• the oxide that is deposited comprises a mixture of two or more metal oxides.
• the oxide that is deposited comprises a mixture of silicon oxide and one or more metal oxides.
• an oxide is deposited that comprises metal and silicon, such as SiTiOx.
• a silicate is deposited.
• the first precursor is a silicon precursor, such as 3- methoxypropyltrimethoxysilane (MPTMS).
• the first precursor is MPTMS and the second reactant comprises hydrogen plasma.
• the first precursor is a metal precursor.
• the metal surface comprises a passivation layer, such as an organic material. An organic passivation layer may be selectively deposited on the metal surface relative to the dielectric surface prior to beginning the selective oxide deposition. In some embodiments a passivation layer on the metal surface is etched by the second reactant in the oxide deposition cycle.
• methods of selectively depositing a silicon oxide film on a dielectric surface of a substrate relative to a metal surface are provided.
• the methods may be PEALD methods, comprising a deposition cycle in which the substrate is alternately and sequentially contacted with a first reactant comprising silicon and oxygen and a second plasma reactant that does not comprise oxygen species.
• the second plasma reactant comprises plasma generated in a gas that does not comprise oxygen.
• the second plasma reactant comprises plasma generated in a gas comprising hydrogen and not oxygen.
• Species of the first reactant comprising silicon and oxygen adsorb on the dielectric surface and react with the second plasma reactant to form silicon oxide.
• the second plasma reactant comprises hydrogen plasma.
• FIG. 1 is a schematic of some embodiments, in which an oxide film is selectively deposited on SiC3 ⁇ 4 relative to a metal surface.
• the metal surface may be simultaneously reduced during deposition of SiOC on S1O2.
• SiOC may deposited by MPTMS and hydrogen plasma.
• Figures 2A and 2B illustrate the selectivity between W and Cu of an MPTMS process at 125 and 200°C.
• the Y axis is in at.%.
• Figure 3 3 illustrates selective deposition of SiOC on a low-k surface relative to a Cu surface by a PEALD process using H 2 plasma generated at a power of 67W.
• Figure 4 illustrates selective deposition of SiOC on a low-k surface relative to a Cu surface by a PEALD process using H 2 plasma generated at a power of 300W.
• Figure 5 A is a graph showing the refractive index (R.I.) of TiO(CN) films deposited using titanium isopropoxide (IV) using different plasma reactants.
• Figure 5B is a graph showing the growth rate per cycle of TiO(CN) films deposited using titanium isopropoxide (IV) using different plasma reactants.
• Oxide films such as silicon oxycarbide (SiOC) films, have a wide variety of applications, as will be apparent to the skilled artisan, for example in integrated circuit fabrication.
• various dielectric films particularly oxide films, precursors, and methods for depositing such films are provided.
• oxide thin films for example dielectric films such as S1O2, SiOC or other SiO-based dielectric films, or metal oxide films, are selectively deposited on a substrate by plasma-enhanced atomic layer deposition (PEALD) processes.
• PEALD plasma-enhanced atomic layer deposition
• an oxide film is selectively deposited on a first dielectric surface of a substrate relative to a second, different metal or metallic surface of the substrate by a PEALD process.
• S1O2 may be selectively deposited by PEALD on a S1O2 surface relative to a metal surface.
• Figure 1 shows a schematic of some embodiments, in which an oxide film is selectively deposited on S1O2 relative to a metal surface.
• the oxide film is selectively deposited using a PEALD process comprising contacting the substrate with a first precursor and a plasma reactant, such as a plasma generated in a gas comprising hydrogen.
• the PEALD process may comprise contacting the substrate with a first precursor comprising silicon and oxygen and a second precursor comprising plasma generated in a gas comprising Ar and H 2 (referred to herein as Ar/H 2 plasma) but not oxygen.
• the first precursor may contain both oxygen and one or more elements to be included in the oxide, such as a metal or silicon.
• the oxide film grows on a first surface, such as a dielectric surface. The growth is less or does not occur on a second surface, such as a metal or metallic surface.
• the plasma reactant in the PEALD process may serve two functions. First, it may serve as a reactant in the deposition process where it reacts with a previously adsorbed precursor on the dielectric surface to form the desired oxide on that surface. Second, the plasma acts on the metal surface to reduce or inhibit formation of oxide on that surface. Growth on the second metal surface may be inhibited, for example by reducing metal oxide on the metal surface, if any, and/or by removing oxygen from the metal surface, such as by removing OH groups and/or metal-oxygen bridges from the metal surface. The plasma does not remove oxygen (such as OH groups and/or metal-oxygen bridges) as easily from the first dielectric surface, such as a silicon oxide dielectric surface.
• the first precursor thus reacts and chemisorbs to the dielectric surface containing a greater concentration of OH-groups preferentially, relative to the reduced metal surface, having fewer OH-groups.
• the oxide is selectively deposited on the first dielectric surface relative to the second metal or metallic surface.
• a substrate comprising a first surface on which deposition of a dielectric material is desired, such as a dielectric surface, and second surface on which deposition is not desired, such as a metal surface, is alternately and sequentially contacted with a precursor comprising oxygen and one or more elements to be included in the deposited material and a plasma reactant.
• the plasma reactant comprises plasma generated in a gas that does not comprise oxygen.
• the plasma reactant does not comprise oxygen species.
• no reactants comprising oxygen species are used other than the first reactant.
• the plasma reactant comprises plasma generated in a gas comprising hydrogen.
• the precursor comprising oxygen and the plasma may be provided in pulses separated by a purge in which excess reactant and reaction byproducts, if any, are removed from the reaction space.
• the deposition process begins with a plasma pulse, and the reaction sequence, or deposition cycle, may be repeated a desired number of times (A):
• the deposition cycle begins with a precursor pulse, which is followed by a plasma pulse.
• a reducing plasma step may be provided before starting the deposition cycle.
• the reducing plasma step may be longer than the exposure to the plasma reactant in the deposition cycle.
• the reducing plasma a step is included in the deposition process at one or more intervals.
• the reducing plasma step is included before two or more deposition cycles.
• the reducing plasma step is included before each deposition cycle.
• the plasma in the longer reducing step may be the same as the plasma used in the deposition cycle, or may differ.
• This reducing plasma step may reduce substantially all metal oxide from the metal surface and ensure that substantially all OH groups or metal oxide bridges are removed from the metal surface:
• the reducing power can be tuned to such that the desired level of selectivity is obtained.
• the process conditions such as plasma power, can be tuned such mat growth does not proceed appreciably on the metal surface, or even at all.
• plasma power can also be used to tune the k value and wet etch resistance of the oxide film that is deposited.
• the plasma that is used in the deposition cycle and/or for the reducing plasma step is hydrogen based.
• the plasma may be generated in a gas comprising hydrogen, such as in H 2 gas, a mixture of H 2 and a noble gas, such as Ar, or in another gas comprising H 2 .
• the plasma is nitrogen based, or comprises nitrogen species.
• the plasma may be generated in a gas comprising nitrogen, such as a gas comprising N 2 , or a mixture of N 2 and a noble gas, such as Ar.
• the plasma does not comprise oxygen species.
• the plasma is generated in a gas or gas mixture that does not comprise oxygen.
• the plasma may be generated in a gas comprising oxygen, or may otherwise comprise excited oxygen species.
• the plasma does not comprise nitrogen species.
• Plasma gases with more reducing power are preferable in some embodiments.
• noble gas alone can be used for generating the plasma.
• the plasma is generated in a noble gas, such as Ar gas without any other components.
• plasma for example hydrogen containing plasma may be generated by applying RF power of from about 5 W to about 5000 W, 10W to about 2000 W, from about 20 W to about 1000 W, from about 30W to 500W or from about 50 W to about 200 W.
• the RF power density may be from about 0.02 W/cm 2 to about 2.0 W/cm 2 , or from about 0.05 W/cm 2 to about 1.5 W/cm 2 .
• the RF power may be applied to second reactant that flows during the plasma contacting time, that flows continuously through the reaction chamber, and/or that flows through a remote plasma generator.
• the plasma is generated in situ, while in other embodiments the plasma is generated remotely.
• a showerhead reactor is utilized and plasma is generated between a susceptor (on top of which the substrate is located) and a showerhead plate.
• SiOC films are deposited.
• oxides other than SiOC are deposited.
• the oxides include oxophilic elements.
• oxides that can be deposited by the methods disclosed herein include and Again, in some embodiments the
• precursor utilized contains both oxygen and a second element desired in the oxides, such as metal or silicon.
• a surface may be a metal surface or a metallic surface.
• the metal or metallic surface may comprise metal, metal oxides, and/or mixtures thereof.
• the metal or metallic surface may comprise surface oxidation.
• the metal or metallic material of the metal or metallic surface is electrically conductive with or without surface oxidation.
• metal or a metallic surface comprises one or more transition metals.
• the metal or metallic surface comprises one or more of Al, Cu, Co, Ni, W, Nb, Fe.
• the metal or metallic surface comprises Cu.
• the metal or metallic surface comprises one or more noble metals, such as Ru.
• the metal or metallic surface comprises a conductive metal oxide, nitride, carbide, boride, or combination thereof.
• the metal or metallic surface may comprise one or more of RuOx, NbC x , NbB x ,
• the substrate may comprise a metal nitride
• the metal surface may comprise a metal carbide, including, but not limited to TiC and/or TaC.
• the metal surface may comprise a metal chalcogenide, including, but not limited to MoS 2 , Sb 2 Te3, and/or GeTe.
• the metal surface is a TiN surface. In some embodiments the metal surface is a W surface.
• the metal surface may comprise Zn, Fe, Mn, or Mo.
• the metal surface comprises Co, W, TiN, Ta or Cu.
• the dielectric surface may be, for example, a silicon oxide surface, such as a SiO 2 surface. In some embodiments the dielectric surface may be a low-k surface.
• a passivation layer such as an organic layer, may be present on the substrate prior to deposition, such as on the metal surface. In some embodiments a passivation layer is present on the metal surface but not on the dielectric surface.
• a passivation layer may be deposited on the metal surface prior to selective deposition of the oxide on the dielectric surface.
• a passivation layer may be selectively deposited on a metal layer. Selective deposition of a passivation layer may be carried out, for example, as described below, and as described in US Patent Application No. 15/170,769 or US Patent Application No. 15/486,124, each of which is incorporated by reference herein.
• a passivation layer may be present on both the metal surface and the dielectric surface prior to deposition. In some embodiments the passivation layer is thicker over the metal surface than over the dielectric surface.
• the plasma reactant used in the deposition process, or in the plasma treatment prior to the deposition process may etch the passivation layer, such that the passivation layer is etched fully away from the dielectric surface on which deposition is desired, while some passivation layer remains on the metal surface.
• the selectivity of the deposition process on the dielectric surface relative to the metal surface can thus be achieved or enhanced.
• etching of the passivation layer occurs during the selective deposition of the oxide, such as through the activity of the plasma reactant.
• the passivation layer over the metal surface may be replenished during the deposition process in order to achieve better selectivity when thicker films are deposited.
• the plasma may serve as described above to keep the metal as metallic, and remove OH-groups and/or metal oxide, such that the oxide is selectively deposited on the dielectric surface, such as an S1O2 or low-k surface, relative to the metal or metallic surface.
• the substrate may comprise an organic passivation layer.
• the reaction temperature of a PEALD process may be less than about 200 °C.
• the reaction temperature may be less than about ISO °C, less than about 100 °C, less than about 75 °C, or less man about 50 °C. Deposition temperatures in the absence of a passivation layer are described below.
• the substrate on which deposition is desired is loaded into a reaction space or reactor.
• the reactor may be part of a cluster tool in which a variety of different processes in the formation of an integrated circuit are carried out.
• a flow-type reactor is utilized.
• a shower head type of reactor is utilized.
• a space divided reactor is utilized.
• a high-volume manufacturing-capable single wafer ALD reactor is used.
• a batch reactor comprising multiple substrates is used.
• the number of substrates is in the range of 10 to 200, in the range of 50 to 150, or in the range of 100 to 130.
• reactors examples include commercially available equipment such as the F-120 ® reactor, F-450 ® reactor, Pulsar ® reactors - such as the Pulsar ® 2000 and the Pulsar ® 3000 - EmerALD ® reactor and Advance ® 400 Series reactors, available from ASM America, Inc of Phoenix, Arizona and ASM Europe B.V., Almere, Netherlands.
• Other commercially available reactors include those from ASM Japan K.K (Tokyo, Japan) under the tradename Eagle ® XP and XP8.
• the exposed surfaces of the workpiece can be pretreated to provide reactive sites to react with the first phase of the AID process. In some embodiments a separate pretreatment step is not required. In some embodiments the substrate is pretreated to provide a desired surface termination. In some embodiments the substrate is pretreated with plasma.
• Selectivity can be given as a percentage calculated by [(deposition on first surface)-(deposition on second surface)]/(deposition on the first surface).
• Deposition can be measured in any of a variety of ways. In some embodiments deposition may be given as the measured thickness of the deposited material. In some embodiments deposition may be given as the measured amount of material deposited.
• selectivity is greater than about 10%, greater than about 50%, greater than about 75%, greater than about 85%, greater than about 90%, greater than about 93%, greater than about 95%, greater than about 98%, greater than about 99% or even greater than about 99.5%.
• the selectivity can change over the duration or thickness of a deposition.
• deposition of the oxide only occurs on the first dielectric surface and does not occur on the second metal surface.
• deposition on the first surface of the substrate relative to the second surface of the substrate is at least about 80% selective, which may be selective enough for some particular applications.
• the deposition on the first surface of the substrate relative to the second surface of the substrate is at least about 50% selective, which may be selective enough for some particular applications.
• the deposition on the first surface of the substrate relative to the second surface of the substrate is at least about 10% selective, which may be selective enough for some particular applications.
• a passivation layer is selectively deposited on a first metal or metallic surface of a substrate relative to a second dielectric surface in order to facilitate or enhance subsequent selective deposition of an oxide on the dielectric surface relative to the metal surface, as described herein.
• a first organic reactant is vaporized to form a first reactant vapor.
• the reactant being vaporized may be liquid or solid under standard temperature and pressure conditions (room temperature and atmospheric pressure).
• the reactant being vaporized comprises an organic precursor, such as an amine, for example a diamine, such as 1,6-diamnohexane (DAH), or another organic precursor, such as a dianhydride, for example pyromellitic dianhydride (PMDA).
• an organic precursor such as an amine, for example a diamine, such as 1,6-diamnohexane (DAH), or another organic precursor, such as a dianhydride, for example pyromellitic dianhydride (PMDA).
• DABH 1,6-diamnohexane
• PMDA pyromellitic dianhydride
• the organic film comprises a polymer.
• the polymer deposited is a polyimide.
• the polymer deposited is a polyamide .
• Other examples of deposited polymers include dimers, trimers, polyurethanes, polythioureas, polyesters, polyimines, other polymeric forms or mixtures of the above materials.
• a substrate comprising a first conductive surface, for example a metal or metallic surface, and a second dielectric surface is provided and alternately and sequentially exposed to a first vapor phase reactant and a second vapor phase reactant in a deposition cycle.
• the first precursor exposure period is from about 0.01 seconds to about 60 seconds, about 0.0S seconds to about 30 seconds, about 0.1 seconds to about 10 seconds or about 0.2 seconds to about S seconds.
• the optimum exposure period can be readily determined by the skilled artisan based on the particular circumstances. In some embodiments where batch reactors may be used, exposure periods of greater than 60 seconds may be employed.
• the second precursor exposure period is from about 0.01 seconds to about 60 seconds, about 0.0S seconds to about 30 seconds, about 0.1 seconds to about 10 seconds or about 0.2 seconds to about S seconds. The optimum exposure period can be readily determined by the skilled artisan based on the particular circumstances. In some embodiments where batch reactors may be used, exposure periods of greater than 60 seconds may be employed.
• a deposition cycle may repeated until an organic film of a desired thickness is selectively deposited on the metal surface.
• the first precursor or reactant is an organic reactant such as a diamine, e.g., 1,6-diamnohexane (DAH), or any other monomer with two reactive groups.
• DAI 1,6-diamnohexane
• the second reactant or precursor is also an organic reactant capable of reacting with adsorbed species of the first reactant under the deposition conditions.
• the second reactant can be an anhydride, such as furan-2,S-dione (maleic acid anhydride), or more particularly a dianhydride, e.g., pyromellitic di anhydride (PMDA), or any other monomer with two reactive groups which will react with the first reactant.
• anhydride such as furan-2,S-dione (maleic acid anhydride)
• a dianhydride e.g., pyromellitic di anhydride (PMDA)
• the substrate is contacted with the first precursor prior to being contacted with the second precursor.
• the substrate is contacted with an amine, such as a diamine, for example 1,6-diamnohexane (DAH) prior to being contacted with another precursor.
• DAH 1,6-diamnohexane
• the substrate may be contacted with the second precursor prior to being contacted with the first precursor.
• the substrate is contacted with anhydride, such as furan-2,S-dione (maleic acid anhydride), or more particularly a dianhydride, e.g., pyromellitic dianhydride (PMDA) prior to being contacted with another precursor.
• anhydride such as furan-2,S-dione (maleic acid anhydride)
• a dianhydride e.g., pyromellitic dianhydride (PMDA)
• a process may begin with contacting the substrate with the second vapor phase precursor. It will be understood by the skilled artisan that contacted the substrate with the first precursor and second precursor are interchangeable in the processes described herein.
• different reactants can be used to tune the film properties. For example, a polyimide film could be deposited using 4,4'-oxydianiline or 1,4- diaminobenzene instead of 1,6-diaminohexane to get a more rigid structure with more aromaticity and increased dry etch resistance.
• the reactants do not contain metal atoms. In some embodiments the reactants do not contain semimetal atoms. In some embodiments one of the reactants comprises metal or semimetal atoms. In some embodiments the reactants contain carbon and hydrogen and one or more of the following elements: N, O, S, P or a halide, such as CI or F. In some embodiments the first reactant may comprise, for example, adipoyl chloride (AC).
• AC adipoyl chloride
• Deposition conditions for the passivation layer can differ depending upon the selected reactants and can be optimized upon selection.
• the reaction temperature can be selected from the range of about 80°C to about 2S0°C.
• the reaction temperature can be selected from the range of about 170°C to about 210°C.
• the reaction temperature can be selected from a range of about 80°C to about 1S0°C.
• the reaction temperature may be greater than about 160°C, 180°C, 190°C, 200°C, or 210°C.
• the selectively deposited organic film comprises polyamide the reaction temperature may be greater than about 80°C, 90°C, 100°C, 110°C, 120°C, 130°C, 140°C, or 150°C.
• the selectively deposited or formed organic film does not contain metal atoms. In some embodiments the selectively deposited or formed organic film does not contain semimetal atoms. In some embodiments the selectively deposited or formed organic film contains metal or semimetal atoms. In some embodiments the selectively deposited or formed organic film contains carbon and hydrogen and one or more of the following elements: N, O, S, or P.
• reactants for use in the selective deposition for forming an organic passivation layer may have the general formula: [0063]
• R I may be an aliphatic carbon chain comprising 1-5 carbon atoms, 2-5 carbon atoms, 2-4 carbon atoms, 5 or fewer carbon atoms, 4 or fewer carbon atoms, 3 or fewer carbon atoms, or 2 carbon atoms.
• the bonds between carbon atoms in the reactant or precursor may be single bonds, double bonds, triple bonds, or some combination thereof.
• a reactant may comprise two amino groups.
• the amino groups of a reactant may occupy one or both terminal positions on an aliphatic carbon chain. However, in some embodiments the amino groups of a reactant may not occupy either terminal position on an aliphatic carbon chain.
• a reactant may comprise a diamine.
• a reactant may comprise an organic precursor selected from the group of 1,2-diaminoethane (1), 1,3- diaminopropane (1) > l,4-diaminobutane(l), 1 ,5-diaminopentane (1), 1,2-diaminopropane (1), 2,3-butanediamine, 2,2-dimethyl- 1 ,3-propanediamine (1).
• reactants for use in the selective deposition processes for forming an organic passivation layer may have the general formula:
• R 2 may be an aliphatic carbon chain comprising 1-3 carbon atoms, 2-3 carbon atoms, or 3 or fewer carbon atoms.
• the bonds between carbon atoms in the reactant or precursor may be single bonds, double bonds, triple bonds, or some combination thereof.
• a reactant may comprise a chloride.
• a reactant may comprise a diacyl chloride.
• a reactant may comprise an organic precursor selected from the group of oxalyl chloride (I), malonyl chloride, and fumaryl chloride.
• a reactant comprises an organic precursor selected from the group of 1,4-diisocyanatobutane or 1,4-diisocyanatobenzene.
• a reactant comprises an organic precursor selected from the group of terephthaloyl dichloride, alkyldioyl dichlorides, such as hexanedioyl dichloride, octanedioyl dichloride, nonanedioyl dichloride, decanedioyl dichloride, or terephthaloyl dichloride.
• a reactant comprises an organic precursor selected from the group of 1,4- diisothiocyanatobenzene or terephthalaldehyde.
• a reactant being vaporized can be also a diamine, such as 1,4-diaminobenzene, decane- 1 , 10-diamine, 4- nitrobenzene- 1,3 -diamine, 4,4'-oxydianiline, or ethylene diamine.
• a reactant can be a terephthalic acid bis(2-hydroxyethyl) ester.
• a reactant can be a carboxylic acid, for example alkyl-, alkenyi-, alkadienyl-dicarboxylic or tricarboxylic acid, such as ethanedioic acid, propanedioic acid, butanedioic acid, pentanedioic acid or propane- 1 ,2,3-tricarboxylic acid.
• a reactant can be an aromatic carboxylic or dicarboxylic acid, such as benzoic acid, benzene- 1 ,2-dicarboxylic acid, benzene- 1,4-dicarboxylic acid or benzene- 1,3-dicarboxylic acid.
• a reactant may comprise one or more OH-groups bonded to a hydrocarbon.
• a reactant can be selected from the group of diols, triols, aminophenols such as 4-aminophenol, benzene- 1,4-diol or benzene- 1 ,3,5-triol.
• a reactant can be 8-quinolinol.
• the reactant can comprise alkenylchlorosilanes, like alkenyltrichlorosilanes, such as 7-octenyltrichlorosilane.
• an oxide may be selectively deposited on the dielectric surface relative to the metal surface, as described herein.
• SiOC is selectively deposited on a dielectric surface relative to a metal or metallic surface.
• the SiOC may be deposited, for example, as described herein or as described in US Patent Application No. 15/588,026, which is incorporated by reference herein.
• SiOCN is selectively deposited on a dielectric surface relative to a metal or metallic surface.
• the SiOCN may be deposited, for example, as described herein, or as described in US Patent Application No. 14/939,984 or 15/342,943, each of which is incorporated by reference herein.
• SiOSC is selectively deposited on a dielectric surface relative to a metal or metallic surface.
• the SiOSC may be deposited, for example, as described herein or as described in US Patent Application No. 62/502,118, which is incorporated by reference herein.
• SiOC silicon oxycarbide films
• SiOC is not intended to limit, restrict, or define the bonding or chemical state, for example the oxidation state of any of Si, O, C and/or any other element in the film.
• SiOC thin films may comprise one or more elements in addition to Si, O and C.
• SiOCN films may be deposited that comprise from about 0% to about 10% nitrogen on an atomic basis (at%).
• an SiOSC film may be deposited that comprises from about 0 to about 20% sulfur on an atomic basis.
• the SiOC may comprise from about 0% to about 30% carbon on an atomic basis. In some embodiments the SiOC films may comprise from about 0% to about 70% oxygen on an atomic basis. In some embodiments the SiOC films may comprise about 0% to about 50% silicon on an atomic basis.
• the deposited SiOC thin film may contain up to about 70% oxygen on an atomic basis (at%).
• a SiOC film may comprise oxygen from about 10% to about 70%, from about 15% to about 50%, or from about 20% to about 40% on an atomic basis.
• a SiOC film may comprise at least about 20%, about 40% or about 50% oxygen on an atomic basis.
• the deposited SiOC thin film may contain up to about 40% carbon on an atomic basis (at%).
• a SiOC film may comprise carbon from about 0.1% to about 40%, from about 0.5% to about 40%, from about 1% to about 30%, or from about 5% to about 20% on an atomic basis.
• a SiOC film may comprise at least about 1%, about 10% or about 20% carbon on an atomic basis.
• the deposited SiOC thin film may contain up to about 50% silicon on an atomic basis (at%).
• a SiOC film may comprise silicon from about 10% to about 50%, from about 15% to about 40%, or from about 20% to about 35% on an atomic basis.
• a SiOC film may comprise at least about 15%, about 20%, about 25 % or about 30% silicon on an atomic basis.
• the deposited SiOC thin film may contain up to about 40% sulphur on an atomic basis (at%).
• a SiOC film may comprise sulphur from about 0.01% to about 40%, from about 0.1% to about 40%, from about 0.5% to about 30%, or from about 1% to about 20% on an atomic basis.
• a SiOC film may comprise at least about 1%, about 10% or about 20% sulphur on an atomic basis.
• the deposited SiOC films do not comprise an appreciable amount of nitrogen. However, in some embodiments a SiOC film comprising nitrogen is deposited.
• the deposited SiOC films comprises less than about 30 at%, less than about 20 at%, less than about 15 at%, less than about 10 at%, less than about 5 at% of nitrogen, less than about 1 at% nitrogen, or less than about 0.1 at% nitrogen. In some embodiments the SiOC thin films do not comprise nitrogen.
• a SiOC film may comprise Si- C bonds and/or Si-0 bonds. In some embodiments a SiOC film may additionally comprise Si-N bonds. In some embodiments a SiOC film may additionally comprise Si-S bonds. In some embodiments a SiOC film may comprise Si-C bonds and Si-0 bonds and may not comprise Si-N bonds. In some embodiments a SiOC film may comprise Si-N bonds and Si-0 bonds and may not comprise Si-C bonds. In some embodiments a SiOC film may comprise Si-N bonds and Si-C bonds and may not comprise Si-0 bonds. In some embodiments a SiOC film may comprise Si-S bonds, Si-C bonds, and Si-0 bonds and may not comprise Si-N bonds.
• a SiOC film may comprise Si-S bonds and Si-C bonds, and may not comprise Si-0 bonds. In some embodiments a SiOC film may comprise Si-S bonds, and Si-0 bonds and may not comprise Si-C bonds. In some embodiments the SiOC films may comprise more Si-0 bonds than Si-C bonds, for example a ratio of Si-0 bonds to Si-C bonds may be from about 1:1 to about 10:1. In some embodiments a deposited SiOC film may comprise one or more of SiN, SiO, SiC, SiCN, SiON, SiOSC, SiSC, SiOS, and/or SiOC.
• PEALD plasma enhanced ALD
• the PEALD processes do not comprise oxygen plasma or plasma comprising oxygen species.
• a substrate or workpiece is placed in a reaction chamber and subjected to alternately repeated surface reactions.
• thin SiOC films are formed by repetition of a self- limiting ALD cycle.
• each ALD cycle comprises at least two distinct phases. The contacting and removal of a reactant from the substrate may be considered a phase.
• a vapor phase first reactant comprising silicon contacts the substrate and forms no more than about one monolayer on the dielectric surface.
• This reactant is also referred to herein as "the silicon precursor,” “silicon-containing precursor,” or “silicon reactant” and may be, for example, (3-Ammopropyl)trimethoxysilane (APTMS), bis(triethoxysilyl)ethane (BTESE) or 3-memoxypropyltrimethoxysilane (MPTMS).
• the first reactant comprises both silicon and oxygen.
• a second reactant comprising a reactive species contacts the substrate and may convert adsorbed silicon to SiOC on the dielectric surface.
• the second reactant comprises a hydrogen plasma, such as a plasma, a nitrogen plasma, and/or a plasma generated in a noble gas.
• the second reactant comprises hydrogen radicals, hydrogen atoms and/or hydrogen plasma.
• the second reactant may comprise other species that are not hydrogen precursors.
• the second reactant may comprise a plasma of nitrogen, radicals of nitrogen, or atomic nitrogen in one form or another.
• the second reactant may comprise a species from a noble gas, such as He, Ne, Ar, Kr, or Xe, for example as radicals, in plasma form, or in elemental form. These reactive species from noble gases do not necessarily contribute material to the deposited film, but can in some circumstances contribute to film growth as well as help in the formation and ignition of plasma.
• a gas that is used to form a plasma may flow constantly throughout the deposition process but only be activated intermittently.
• a gas that is used to form a plasma does not comprise oxygen.
• the adsorbed silicon precursor is not contacted with a reactive species generated by a plasma from oxygen.
• a second reactant comprising reactive species is generated in a gas that does not comprise oxygen.
• a second reactant may comprise a plasma generated in a gas that does not comprise oxygen.
• the second reactant may be generated in a gas comprising less man about 1 atomic % (at%) oxygen, less than about 0.1 at% oxygen, less than about 0.01 at% oxygen, or less than about 0.001 at% oxygen.
• a gas that is used to form a plasma does not comprise nitrogen.
• the adsorbed silicon precursor is not contacted with a reactive species generated by a plasma from nitrogen.
• a second reactant comprising reactive species is generated in a gas that does not comprise nitrogen.
• a second reactant may comprise a plasma generated in a gas that does not comprise nitrogen.
• a gas that is used to form a plasma may comprise nitrogen.
• the second reactant may comprise nitrogen radicals, nitrogen atoms and/or nitrogen plasma.
• the second reactant may be generated in a gas comprising less than about 25 atomic % (at%) nitrogen, less than about 20 at% nitrogen, less than about IS at% nitrogen, less than about 10 at% nitrogen, less than about S at% nitrogen, less than about 1 at% nitrogen, less than about 0.1 at% nitrogen, less than about 0.01 at% nitrogen, or less than about 0.001 at% nitrogen.
• the second reactant may be generated in a gas comprising hydrogen and nitrogen, for example the second reactant may comprise H 2 and N 2 .
• the second reactant may be generated in a gas having a ratio of N 2 to H 2 (N2/H2) of less than about 20%, less than about 10%, or less than about 5%.
• a gas that is used to form a plasma does not comprise nitrogen or oxygen.
• the adsorbed silicon precursor is not contacted with a reactive species generated by a plasma from nitrogen or oxygen.
• a second reactant comprising reactive species is generated in a gas that does not comprise nitrogen or oxygen.
• a second reactant may comprise a plasma generated in a gas that does not comprise nitrogen or oxygen.
• Additional phases may be added and phases may be removed as desired to adjust the composition of the final film that is selectively deposited on the dielectric surface.
• one or more deposition cycles begin by contacting the substrate with the silicon precursor, followed by the second plasma reactant. In other embodiments deposition may begin by contacting the substrate with the second plasma reactant, followed by the silicon precursor.
• Excess reactant and reaction byproducts, if any, are removed from the vicinity of the substrate, and in particular from the substrate surface, between reactant contacting phases.
• excess reactant and reaction byproducts, if any, are removed from the substrate surface by, for example, purging the reaction chamber between reactant contacting phases, such as by purging with an inert gas.
• the flow rate and contacting time of each reactant is tunable, as is the removal step, allowing for control of the quality and various properties of the films.
• a gas is provided to the reaction chamber continuously during each deposition cycle, or during the entire PEALD process, and reactive species are provided by generating a plasma in the gas, either in the reaction chamber or upstream of the reaction chamber.
• the gas comprises hydrogen.
• the gas comprises nitrogen.
• the gas may comprise noble gas, such as helium or argon. The flowing gas may also serve as a purge gas for the first and/or second reactant (or reactive species).
• the deposition cycle is repeated until a SiOC film of the desired thickness is obtained on the dielectric surface.
• the deposition parameters such as the precursor flow rate, contacting time, removal time, and/or reactants themselves, may be varied in one or more deposition cycles during the PEALD process in order to obtain a film with the desired characteristics.
• the surface of the substrate is contacted with a reactant.
• a pulse of reactant is provided to a reaction space containing the substrate.
• the term “pulse” may be understood to comprise feeding reactant into the reaction chamber for a predetermined amount of time. The term “pulse” does not restrict the length or duration of the pulse and a pulse can be any length of time.
• the substrate is moved to a reaction space containing a reactant. In some embodiments the substrate is subsequently moved from a reaction space containing a first reactant to a second, different reaction space containing the second reactant.
• the substrate is contacted with the silicon reactant first. After an initial surface termination, if necessary or desired, the substrate is contacted with a first silicon reactant.
• the first reactant pulse comprises a carrier gas flow and a volatile silicon species, such as APTMS or MPTMS, that is reactive with the dielectric surface. Accordingly, silicon species adsorb upon the dielectric surface.
• the silicon reactant contacts the surface from about 0.05 seconds to about 5.0 seconds, about 0.1 seconds to about 3 seconds or about 0.2 seconds to about 1.0 seconds.
• the optimum contacting time can be readily determined by the skilled artisan based on the particular circumstances.
• excess first silicon reactant, and reaction byproducts, if any, are removed from the substrate surface.
• removing excess reactant and reaction byproducts, if any may comprise purging the reaction chamber.
• the reaction chamber may be purged by stopping the flow of the first reactant while continuing to flow a carrier gas or purge gas for a sufficient time to diffuse or purge excess reactants and reactant by-products, if any, from the reaction space.
• the excess first precursor is purged with the aid of inert gas, such as nitrogen or argon.
• the substrate may be moved from the reaction space containing the first reactant to a second, different reaction space.
• the first reactant is removed for about 0.1 seconds to about 10 seconds, about 0.3 seconds to about 5 seconds or about 0.3 seconds to about 1 second.
• Contacting and removal of the silicon reactant can be considered the first or silicon phase of the PEALD cycle.
• a second ieactant comprising a reactive species, such as hydrogen plasma is provided to the workpiece.
• Plasma may be generated in the reaction chamber or in a remote plasma generator and provided to the reaction chamber.
• hydrogen plasma may be formed by generating a plasma in hydrogen in the reaction chamber or upstream of the reaction chamber, for example by flowing the hydrogen (H 2 ) through a remote plasma generator.
• plasma is generated in flowing H 2 gas.
• H 2 flow may be from about 0.1 to about 0.4 slpm.
• a noble gas may also be included, such as Ar.
• the Ar co-flow may be, for example, about 2 slpm in some embodiments.
• H 2 is provided to the reaction chamber before the plasma is ignited or hydrogen atoms or radicals are formed. In some embodiments the H 2 is provided to the reaction chamber continuously and hydrogen containing plasma, atoms or radicals is created or supplied when needed.
• plasma is generated in flowing N 2 gas.
• N 2 flow may be from about 0.1 to about 0.4 slpm.
• a noble gas may also be included, such as Ar.
• the Ar co-flow may be, for example, about 2 slpm in some embodiments.
• N 2 is provided to the reaction chamber before the plasma is ignited or hydrogen atoms or radicals are formed. In some embodiments the N 2 is provided to the reaction chamber continuously and nitrogen containing plasma, atoms or radicals is created or supplied when needed.
• the second reactant for example comprising hydrogen plasma, contacts the substrate for about 0.1 seconds to about 10 seconds.
• the second reactant such as hydrogen containing plasma, contacts the substrate for about 0.1 seconds to about 10 seconds, 0.5 seconds to about S seconds or 0.S seconds to about 2.0 seconds.
• the second reactant contacting time may be even higher than about 10 seconds. In some embodiments, contacting times can be on the order of minutes. The optimum contacting time can be readily determined by the skilled artisan based on the particular circumstances.
• the second ieactant is provided in two or more distinct pulses, without introducing another reactant in between any of the two or more pulses.
• a plasma such as a hydrogen containing plasma
• two or more sequential plasma pulses are generated by providing a plasma discharge for a first period of time, extinguishing the plasma discharge for a second period of time, for example from about 0.1 seconds to about 10 seconds, from about 0.S seconds to about S seconds or about 1.0 seconds to about 4.0 seconds, and exciting it again for a third period of time before introduction of another precursor or a removal step, such as before the Si-precursor or a purge step. Additional pulses of plasma can be introduced in the same way.
• a plasma is ignited for an equivalent period of time in each of the pulses.
• plasma for example hydrogen or nitrogen containing plasma
• a plasma power used for generating a nitrogen- containing plasma can be about 10W to about 5000W, about SOW to about 1,S00W, about 70W to about 1200W, about 80W to about 1,000W, about 10W to about 500W, or about 300 W to about 500W.
• the RF power density may be from about 0.02 W/cm 2 to about 2.0 W/cm 2 , or from about 0.05 W/cm 2 to about 1.5 W/cm 2 .
• the RF power may be applied to second reactant that flows during the plasma contacting time, that flows continuously through the reaction chamber, and/or that flows through a remote plasma generator.
• the plasma is generated in situ, while in other embodiments the plasma is generated remotely.
• a showerhead reactor is utilized and plasma is generated between a susceptor (on top of which the substrate is located) and a showerhead plate.
• the gap between the susceptor and showerhead plate is from about 0.1 cm to about 20 cm, from about 0.5 cm to about 5 cm, or from about 0.8 cm to about 3.0 cm.
• removing excess reactant and reaction byproducts, if any, may comprise purging the reaction chamber.
• the reaction chamber may be purged by stopping the flow of the second reactant while continuing to flow a carrier gas or purge gas for a sufficient time to diffuse or purge excess reactants and reactant by-products, if any, from the reaction space.
• the excess second precursor is purged with the aid of inert gas, such as nitrogen or argon, which is flowing throughout the PEALD cycle.
• the substrate may be moved from the reaction space containing the second reactant to a different reaction space.
• the removal may, in some embodiments, be from about 0.1 seconds to about 10 seconds, about 0.1 seconds to about 4 seconds or about 0.1 seconds to about 0.S seconds.
• the reactive species contacting and removal represent a second, reactive species phase in a SiOCN atomic layer deposition cycle.
• the two phases together represent one ALD cycle, which is repeated to form SiOC thin films of a desired thickness.
• the PEALD reactions may be performed at temperatures ranging from about 2S°C to about 700°C, from about 50°C to about 600°C, from about 20°C to about 200°C, from about 75°C to about 450°C, or from about 90°C to about 300°C.
• the deposition temperature is about 100°C to about 200°C.
• the optimum reactor temperature may be limited by the maximum allowed thermal budget. Therefore, in some embodiments the reaction temperature is from about 300 °C to about 400 °C. In some applications, the maximum temperature is around about 400 °C, and, therefore the PEALD process is run at that reaction temperature.
• the pressure of the reaction chamber during processing is maintained at from about 0.01 Torr to about SO Torr, or from about 0.1 Torr to about 10 Torr. In some embodiments the pressure of the reaction chamber is greater than about 6 Torr, or about 20 Torr. In some embodiments, a SiOCN deposition process can be performed at a pressure of about 1 Torr to about 500 Torr, about 1 Torr to about 20 Torr, about 2 Torr to about 10 Torr, about 20 Torr to about 50 Torr, or about 20 Torr to about 30 Torr.
• oxide deposition is performed at a pressure of about 0.1 Torr or greater, or 1 Torr or greater. In some embodiments the pressure may be up to about 760 Torr, up to about 500 Torr or up to about 50 Torr.
• a SiOC or SiOCN thin film is selectively deposited on a dielectric surface on a substrate in a reaction space by a PEALD deposition process comprising at least one cycle comprising:
• Si precursors can be used in the presently disclosed PEALD processes for forming SiOC and SiOCN.
• At least some Si precursors suitable for deposition of SiOCN by PEALD processes comprise nitrogen and have the following general formulas:
• R I may be an independently selected alkyl group
• R a may be an independently selected hydrocarbon group
• R III and R ⁇ may be independently selected alkyl groups and/or hydrogens.
• R I and R II are C1-C3 alkyl ligands, such as methyl, ethyl, n-propyl, or isopropyl.
• R I may be a Ci- C 4 alkyl ligand, such as methyl, ethyl, n-propyl, isopropyl, or tertbutyl.
• R II is not a C3 hydrocarbon.
• R II is a C 1 -C 2 hydrocarbon or a C 4 -C 6 hydrocarbon.
• R II may be an unsaturated hydrocarbon, such as a hydrocarbon containing one or more double bonds.
• R II may be an alkyl group where one of the hydrogens is removed.
• R III and R ⁇ are hydrogen.
• R I is methyl
• R II is n-propyl
• R ra is hydrogen
• RTM is hydrogen
• x l.
• some Si precursors may have the following general formula:
• R I and R II may be an independently selected alkyl group
• R II may be an independently selected hydrocarbon
• R III and R IV may be independently selected alkyl groups and/or hydrogens.
• R II may be an unsaturated hydrocarbon, such as a hydrocarbon containing one or more double bonds.
• R II may be an alkyl group where one of the hydrogens is removed.
• some Si precursors may have the following general formula:
• R II may be an independently selected hydrocarbon
• R III and R IV may be independently selected alkyl groups and/or hydrogens
• L is an independently selected alkyl group or halogen.
• R II may be an unsaturated hydrocarbon, such as a hydrocarbon containing one or more double bonds.
• R II may be an alkyl group where one of the hydrogens is removed.
• some Si precursors may have the following general formula:
• R II may be an independently selected hydrocarbon
• R III and RTM may be independently selected alkyl groups and/or hydrogens
• L is an independently selected alkyl group or halogen.
• R II may be an unsaturated hydrocarbon, such as a hydrocarbon containing one or more double bonds.
• R II may be an alkyl group where one of the hydrogens is removed.
• some Si precursors may have the following general formula:
• R I may be an independently selected alkyl group
• R II may be an independently selected hydrocarbon,.
• R I and R II are C1-C3 alkyl ligands, such as methyl, ethyl, n-propyl, or isopropyl.
• R I is methyl
• R II may be an unsaturated hydrocarbon, such as a hydrocarbon containing one or more double bonds.
• R II may be an alkyl group where one of the hydrogens is removed.
• some Si precursors may have the following general formula:
• R I may be an independently selected alkyl group
• R II may be an independently selected hydrocarbon
• R T and R II are C1-C3 alkyl ligands, such as methyl, ethyl, n-propyl, or isopropyl.
• R II may be an unsaturated hydrocarbon, such as a hydrocarbon containing one or more double bonds.
• R II may be an alkyl group where one of the hydrogens is removed.
• some Si precursors may have the following general formula:
• R I may be an independently selected alkyl group.
• R I is a C1-C4 alkyl ligand, such as methyl, ethyl, n-propyl, or isopropyl.
• the silicon precursor does not comprise a halogen. In some embodiments the silicon precursor may comprise at least one aminoalkyl ligand.
• a suitable silicon precursor may comprise at least one ligand which is bonded through carbon to silicon and contains at least one NH 2 -group attached to a carbon chain, for example an aminoalkyl ligand.
• a suitable silicon precursor may comprise at least one ligand which is bonded through carbon to silicon and contains an NH 2 -group attached to a carbon chain, for example an aminoalkyl ligand, and may also comprise at least one ligand which is bonded to silicon through an oxygen atom and in which an alkyl group is bonded to oxygen, for example an alkoxide ligand.
• a suitable silicon precursor may comprise at least one ligand which is bonded through carbon to silicon and contains at least one NR ⁇ R ⁇ -group, wherein R ra and RTM may be independently selected alkyl groups and/or hydrogens, attached to a carbon chain, for example an aminoalkyl ligand.
• a suitable silicon precursor may comprise at least one ligand which is bonded through carbon to silicon and in which ligand at least one nitrogen is bonded to carbon. Further the one ligand which is bonded through carbon to silicon and in which ligand at least one nitrogen is bonded to carbon may comprise hydrogen bonded to nitrogen.
• a suitable silicon precursor in addition to a ligand which is bonded to silicon through carbon, may comprise also an alkoxy ligand, such as methoxy, ethoxy, n-propoxy, i-propoxy or tertbutoxy ligand.
• a suitable silicon precursor comprises a carbon chain which is bonded to silicon through carbon, and in which there is an amino group, such as alkylamino or -NH 2 group, attached to the carbon chain and the carbon chain is a C1-C6 hydrocarbon, C2-C6 hydrocarbon or C2-C4 hydrocarbon, linear, branched or cyclic, containing only carbon and hydrogen.
• the carbon chain may be unsaturated and contain double carbon-carbon bonds.
• the carbon chain may contain other atoms than carbon and hydrogen.
• suitable Si precursors can be used in the presently disclosed PEALD processes for forming SiOC.
• the suitable Si precursors may not comprise nitrogen.
• a suitable Si precursor may comprise a silane.
• a suitable Si precursor for forming SiOC may comprise two Si atoms connected by, or bonded to, at least one hydrocarbon group. In some embodiments a suitable Si precursor may comprise two Si atoms connected by, or bonded to, at least one alkyl group. In some embodiments a suitable Si precursor may comprise two Si atoms connected by, or bonded to, at least one alkoxy group. In some embodiments a suitable Si precursor may comprise two Si atoms connected by, or bonded to, at least one silyl group. In some embodiments a suitable Si precursor may comprise two Si atoms connected by, or bonded to, at least one silyl ether group.
• a suitable Si precursor may comprise at least one -SH group, wherein the -SH may be bonded to an alkyl chain or a silicon atom. In some embodiments a suitable Si precursor may comprise at least one mercapto group. In some embodiments a suitable Si precursor may comprise at least one -FISH structure, wherein R may be a C 1 -C 5 alkyl group. In some embodiments a suitable Si precursor may comprise at least one -SH group on an alkyl chain and one or more alkoxy groups bonded to a silicon atom.
• a suitable Si precursor may comprise at least one Si atom attached or bonded to one or more alkoxy groups. In some embodiments a suitable Si precursor may comprise at least one Si atom attached or bonded to one or more alkyl groups. In some embodiments a suitable Si precursor may comprise at least one Si atom attached or bonded to at least an alkyl group and an alkoxy group. [0146] In some embodiments, at least some Si precursors suitable for deposition of SiOC by PEALD processes may comprise bridged alkoxysilanes having the following general formula:
• each of R I and R II may be independently selected alkyl groups.
• each of R I and R II are independently selected C 1 -C 5 alkyl ligands, such as methyl, ethyl, n-propyl, isopropyi, tertbutyl, or pentyl.
• some Si precursors may comprise bridged alkoxyalkylsilanes having the following general formula:
• each of R I and R II are independently selected C 1 - C 5 alkyl ligands, such as methyl, ethyl, n-propyl, isopropyi, tertbutyl, or pentyl.
• R III may be an independently selected Ci-Ce alkyl ligand.
• some Si precursors may comprise cyclic alkoxysilanes having the following general formula:
• Formula (3) may alternately be represented by the structural formula:
• each of R I and R II may be independently selected alkyl groups.
• each of R I and R II are independently selected C 1 -C 5 alkyl ligands, such as methyl, ethyl, n-propyl, isopropyl, tertbutyl, or pentyl.
• some Si precursors may comprise cyclic alkoxyalkylsilanes having the following general formula:
• Formula (4) may alternately be represented by the structural formula:
• each of R I and R II are independently selected C 1 - C 5 alkyl ligands, such as methyl, ethyl, n-propyl, isopropyl, tertbutyl, or pentyl.
• R III may be an independently selected C 1 -C 8 alkyl ligand.
• some Si precursors may comprise linear alkoxysilanes having the following general formula:
• R I may be an independently selected alkyl group or hydrogen
• R II may be an independently selected alkyl group
• n 1-4.
• each of R I and R II are independently selected C 1 -C 5 alkyl ligands, such as methyl, ethyl, n-propyl, isopropyl, tertbutyl, or pentyl.
• R I may be hydrogen and R II may be an independently selected C 1 -C 5 alkyl ligand.
• some Si precursors may comprise linear alkoxysilanes having the following general formula:
• R I and R II are independently selected C 1 -C 5 alkyl ligands, such as methyl, ethyl, n-propyl, isopropyl, tertbutyl, or pentyl.
• R III may be an independently selected O-Ce alkyl ligand.
• some Si precursors may comprise alkoxysilanes having the following general formula:
• R I may be an independently selected alkyl group.
• R I may be an independently selected C 1 -C 5 alkyl ligand, such as methyl, ethyl, n-propyl, isopropyl, tertbutyl, or pentyl.
• some Si precursors may comprise alkoxyalkylsilanes having the following general formula:
• R I may be an independently selected C 1 -C 5 alkyl ligand, such as methyl, ethyl, n-propyl, isopropyl, tertbutyl, or pentyl.
• R II may be an independently selected Ci-Cs alkyl ligand.
• some Si precursors may comprise alkoxysilanes that do not comprise nitrogen and have the following general formula: [0173]
• R I may be an independently selected alkyl group
• R I may be an independently selected C 1 -C 5 alkyl ligand, such as methyl, ethyl, n-propyl, isopropyl, tertbutyl, or pentyl.
• R II may comprise, for example an alkenyl, alkynyl, phenyl, carbonyl, aldehyde, ester, ether, carboxyl, peroxy, hydroperoxy, thiol, acrylate, or methacrylate ligand.
• some Si precursors may the following general formula:
• R I may be an independently selected C1-C7 or C 1 -C 5 alkyl ligand
• R II may be an independently selected ligand consisting of carbon, and/or hydrogen, and/or oxygen.
• R II can be an alkoxyalkyl group.
• R II can be, for example, an alkenyl, alkynyl, phenyl, carbonyl, aldehyde, ester, ether, carboxyl, peroxy, or hydroperoxy group.
• R I is a methyl group
• R II is a 3-methoxypropyl ligand
• x is 1.
• some Si precursors may have the following general formula:
• each of R I and R II may be an independently selected C 1 - C 7 or C 1 -C 5 alkyl ligand
• R III may be an independently selected ligand consisting of carbon, and/or hydrogen, and/or oxygen.
• R III can be, for example, an alkenyl, alkynyl, phenyl, carbonyl, aldehyde, ester, ether, carboxyl, peroxy, or hydroperoxy group.
• R I , R II , and R III can each be a group independently selected from methyl, ethyl, i-propyl, n-propyl, n-butyl, i-butyl, and t-butyl.
• some Si precursors may have the following general formula:
• R I is an alkoxide ligand having from 1 to 5 carbon atoms, or a halide
• R II is any ligand comprising sulfur
• R III consists of one of a sulfhydryl, sulfide, disulfide, sulfinyl, sulfonyl, sulfino, sulfo, thiocyanate, isothiocyanate, or carbonothioyl functionality.
• R I , R II , and R III may each be independently selected.
• R I may comprise a methoxy ligand
• R II may comprise 3- mercaptopropyl
• x l
• y 0. That is, in some embodiments some an Si precursor may comprise In some embodiments a Si precursor may comprise
• the silicon precursor does not comprise a halogen. In some embodiments the silicon precursor does not comprise nitrogen. In some embodiments the carbon chain may be unsaturated and contain double carbon-carbon bonds. In some other embodiments the carbon chain may contain other atoms than carbon and hydrogen.
• the silicon precursor can comprise bis(triethoxysilyl)ethane (BTESE). In some embodiments the silicon precursor can comprise 3-methoxypropyltrimethoxysilane (MPTMS or In some embodiments the silicon precursor can comprise (3-mercaptopropyl)trimethoxysilane.
• BTESE bis(triethoxysilyl)ethane
• MTMS 3-methoxypropyltrimethoxysilane
• the silicon precursor can comprise (3-mercaptopropyl)trimethoxysilane.
• more than one silicon precursor may contact the substrate surface at the same time during an ALD phase.
• the silicon precursor may comprise more than one of the silicon precursors described herein.
• a first silicon precursor is used in a first ALD cycle and a second, different ALD precursor is used in a later ALD cycle.
• multiple silicon precursors may be used during a single ALD phase, for example in order to optimize certain properties of the deposited film.
• only one silicon precursor may contact the substrate during the deposition.
• the silicon precursor is not used as a silylating agent.
• the deposition temperature and/or the duration of the silicon precursor contacting step are selected such that the silicon precursor does not decompose.
• the silicon precursor may decompose during the silicon precursor contacting step.
• the silicon precursor does not comprise a halogen, such as chlorine or fluorine.
• the second reactant may comprise reactive species formed from compounds having both N and H, such as N3 ⁇ 4 and N2H4, a mixture of N2/H2 or other precursors having an N-H bond.
• the second reactant may be formed, at least in part, from N2.
• the second reactant may be formed, at least in part, from H 2 and N2, where the H2 and N2 are provided at a flow ratio (H2/N2), from about 100:1 to about 1 :100, from about 20:1 to about 1:20, from about 10:1 to about 1 :10, from about 5:1 to about 1:5 and/or from about 2:1 to about 4:1, and in some cases 1:1.
• a hydrogen-containing plasma for depositing SiOCN can be generated using both N2 and H2 at one or more ratios described herein.
• the second reactant may be generated from a gas containing less than about I atomic % (at%) nitrogen, less than about 0.1 at% nitrogen, less than about 0.01 at% nitrogen, or less than about 0.001 at% nitrogen. In some embodiments a second reactant does not comprise N2, NH3 or ⁇ 2 ⁇ 4.
• a metal oxide is selectively deposited on a dielectric surface relative to a metal or metallic surface.
• the metal oxide may be deposited, for example, as described herein or as described in US Patent Application No. 62/502,118, which is incorporated by reference herein.
• thin films comprising material other than SiOC may be selectively deposited by the processes as described herein.
• metal oxide films may be selectively deposited by PEALD processes that do not include oxygen plasma or excited oxygen species, essentially as described for SiOC and SiOCN above but using different first precursors. In these embodiments a different metal precursor is used in place of the silicon precursor in the processes as described herein.
• titanium oxide, niobium oxide, tantalum oxide, tungsten oxide, aluminum oxide or other metal oxide thin films may be selectively deposited by PEALD processes as described herein.
• a metal oxide film may comprise more than one metal oxide.
• the different metals may be provided by the same precursor, or by two or more different metal precursors that are be provided in one or more deposition cycles.
• oxide films comprising both silicon and metal may be selectively deposited as described herein by PEALD processes that do not include oxygen plasma or excited oxygen species.
• an oxide is selectively deposited that comprises both metal and silicon.
• an oxide film may comprise a mixture of a metal oxide and silicon oxide.
• an oxide film may comprise a metal silicate.
• a film may comprise silicon oxide and one or more of a transition metal oxide, such as ZrO 2 , HfO 2 , or TiCfe, AI2O3, lanthanide (+Sc+Y) oxides,
• a metal precursor is used, along with a silicon precursor in the processes as described herein.
• a deposition cycle for depositing a metal oxide and a deposition cycle for depositing a silicon oxide may be provided at a selected ratio in a deposition process in order to selectively deposit a film having a desired composition.
• a selective deposition process may comprise a single deposition cycle comprising alternately and sequentially contacting a substrate with a first metal precursor, a second silicon precursor and a third plasma reactant.
• the metal and silicon precursors and the third reactant can be as described herein for deposition of metal oxides and silicon oxides.
• the deposition cycle may begin with provision of the metal reactant, provision of the silicon reactant or provision of the third reactant.
• provision of each of the reactants may be separated by a purge step in which excess reactants and reaction byproducts are removed from the reaction space.
• the ratio of the metal precursor and the silicon precursor is selected and/or adjusted to provide a mixed metal oxide film with the desired composition.
• the metal precursors used to deposit oxide films comprising metal by the processes described herein may comprise volatile compounds comprising the desired metal and oxygen.
• a list of exemplary metal precursors that may be used to deposit metal oxide films by PEALD processes that do not include oxygen plasma or excited species of oxygen as described herein is provided in Table 1.
• the metal precursor used to deposit metal oxide films by the processes described herein may comprise volatile compounds of formula:
• R I may be an independently selected hydrocarbon group and wherein M is a metal or Ge, for example a transition metal or Ge, Al, Ga, In, Sn, Pb, Bi, Sb, wherein x+y is equal to the oxidation state, or number of bonds of the metal atom, for example 3, 4, S, or 6.
• M is a metal or Ge, for example a transition metal or Ge, Al, Ga, In, Sn, Pb, Bi, Sb, wherein x+y is equal to the oxidation state, or number of bonds of the metal atom, for example 3, 4, S, or 6.
• each double or triple bond may be counted two or three times when determining the value of x+y.
• R II may be any ligand comprising carbon, hydrogen, nitrogen, halogen and/or oxygen.
• M is a transition metal selected from the group: Ti, V, Cr, M R , Z r , Nb, Mo, Ru, Rh, Pd, Ag, Au, Hf, Ta, W, Re, Os, Ir and Pt.
• M is a transition metal selected from the group: Cu, Fe, Co, Ni. In some embodiments M is a transition metal selected from the group: Au, Pt, Ir, Pd, Os, Ag, Re, Rh, and Ru.
• R I may be an independently selected Cl-CS alkyl ligand, such as a methyl, ethyl, n-propyl, isopropyl, tertbutyl, or pentyl ligand.
• R I can comprise oxygen or nitrogen or another heteroatom.
• R II may comprise, for example an alkenyl, alkynyl, cyclic hydrocarbons, amine, alky amine, phenyl, carbonyl, aldehyde, ester, ether, carboxyl, peroxy, hydroperoxy, thiol, acrylate, or methacrylate ligand.
• At least one of the ligands of the above formula above comprises oxygen.
• M can be also be a group 1 or 2 metal element.
• the metal precursor used to deposit metal oxide films by the processes described herein may comprise volatile compounds of formula:
• R T may be an independently selected alkyl group and wherein M is metal or Ge, for example transition metal or Ge, Al, Ga, In, Sn, Pb, Bi, Sb and wherein x is equal to the oxidation state, or number of bonds of the metal atom, for example 3, 4, S, or 6.
• each double or triple bond may be counted two or three times when determining the value of x.
• R I may be an independently selected Cl-CS alkyl ligand, such as methyl, ethyl, n-propyl, isopropyl, tertbutyl, or pentyl ligand.
• M is a transition metal selected from the group: Ti, V, Cr, Mn, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Au, Hf, Ta, W, Re, Os, Ir and Pt.
• M is a transition metal selected from the group: Cu, Fe, Co, Ni.
• M is a transition metal selected from the group: Au, Pt, Ir, Pd, Os, Ag, Re, Rh, and Ru.
• M may be a rare earth element, for example Sc, Y, La, Ce, or Nd.
• the metal precursor used to deposit metal oxide films by the processes described herein may comprise at least one multidentate ligand, such as a bidentate ligand, for example a betadiketonate ligand (acac, thd) or another multidentate/bidentate ligand which is bonded to the metal atom through at least one oxygen.
• the metal precursor used to deposit metal oxide films by the processes described herein may comprise a cyclic ligand, such as cyclopentadienyl ligand.
• the metal precursor used to deposit metal oxide films by the processes described herein may comprise an alkoxide precursor or alkoxide ligand. In some embodiments the metal precursor used to deposit metal oxide films by the processes described herein comprises at least one metal-oxygen bond. In some embodiments the metal precursor used to deposit metal oxide films by the processes described herein does not comprise a metal-oxygen bond, but comprises oxygen in the ligand. In some embodiments the metal precursor comprises metal or Ge, for example transition metal or Ge, Al, Ga, In, Sn, Pb, Bi, Sb. In some embodiments the metal precursor comprises group 1 or 2 metal element. In some embodiments M may be a rare earth element, for example Sc, Y, La, Ce, orNd.
• a metal oxide films may be deposited on a substrate comprising a photoresist or other organic material according to the processes described herein.
• a metal oxide film may be deposited on a substrate that may otherwise be destroyed by a PEALD process which includes oxygen plasma.
• a metal oxide film is selectively deposited on a first surface relative to a second surface comprising a passivation layer, such as an organic passivation layer.
• the metal oxide deposition may also serve to remove some or all of the passivation layer.
• a metal oxide film may be selectively deposited on a first dielectric surface relative to a metal or metallic surface, where the metal or metallic surface may comprise a passivation layer, such as an organic passivation layer.
• the metal oxide films deposited according to the PEALD processes as described herein may have wet etch resistances that are higher than the wet etch resistance of similar metal oxide films deposited by PEALD processes that include oxygen plasma or excited oxygen species.
• the formation of metal oxide films may be controlled by selecting a plasma power from a range, for example a range as described herein with respect to the deposition of SiOC, in a PEALD process in order to achieve a desired step coverage and/or WERR. That is, in some embodiments the process conditions used to control the formation of SiOC films as described herein can be used to control the formation of metal oxide films.
• the second reactants used in the PEALD processes for depositing metal oxide thin films are the same as the second reactants described herein with respect to the deposition of SiOC.
• the second reactant comprises a plasma generated in a gas comprising a noble gas, such as Ar.
• the second reactant is a plasma generated in a gas that does not comprise oxygen.
• the second reactant comprises plasma generated in Ar, plasma generated in Ar and N 2 or plasma generated in Ar and H 2 .
• the second reactant can be selected to control the amount of particular components of the metal oxide film, such as carbon and/or nitrogen.
• the plasma power may be controlled to adjust the composition of the film.
• a metal oxide comprising titanium is deposited by a PEALD process that does not use an oxygen plasma or other oxygen reactant.
• a titanium oxide film may be deposited by a PEALD process using titanium isopropoxide (IV) (TOP) in combination with a non-oxygen plasma.
• TOP titanium isopropoxide
• TTIP is utilized in a PEALD process in combination with a plasma generated in Ar, a plasma generated in a gas comprising Ar and nitrogen, or a plasma generated in a gas comprising Ar and hydrogen.
• a titanium oxide film comprising carbon is deposited by a PEALD process in which a titanium reactant such as TTIP is utilized in combination with a plasma generated in a noble gas, such as in pure Ar gas.
• the amount of carbon may be tuned by varying the plasma power.
• a titanium oxide film comprising carbon and nitrogen TiO(CN) is deposited by a PEALD process using a titanium reactant such as TOP in combination with a plasma generated in a gas comprising nitrogen, such as in a gas comprising Ar and N 2 .
• SiOC was also deposited on a substrate comprising a polyimide passivation layer on a substrate comprising Cu and low k surfaces.
• SiOC was deposited from MPTMS and H2 plasma and a SiOC film having a carbon concentration of less than 10 at.% was formed.
• Plasma was provided for 0.5s at power of 67 or 300 Watts. A pressure of 4.7 Torr was utilized. SiOC growth was observed on the low k surfaces but not on the Cu surfaces, at both power settings, as shown in Figures 3 and 4.
• SiOC was deposited by PEALD from MPTMS and H2/Ar plasma at a deposition temperature of 200°C to 300°C, with a H 2 flow of 0.1 to 0.4 slpm (over 2 slpm Ar co-flow) and a plasma power of 30 to 100W.
• SiOC films were deposited on silicon substrates comprising chemical oxide, as well as TiN and W surfaces.
• the process conditions could be tuned to produce SiOC films having very low k values ( ⁇ 3.5) and very low wet etch rate ( ⁇ 1 nm/min in dHF 0.7%). Minimal k values and wet etch rates were observed at about 300°C with 0.2 slpm H2 flow and 70W of power.
• the deposited SiOC layer was found to have a k value of about 4 and a wet etch rate of 1 nm/min.
• the deposition of SiOC was also observed to be selective toward a number of materials, including W and TiN.
• the process produce a film of less than lnm on W but about 10.S ran on S1O2 after 500 cycles.
• Titanium oxide thin films were deposited in a direct plasma PEALD reactor by an oxygen-free PEALD process using titanium isopropoxide (IV) (TTTP) as the titanium precursor.
• ⁇ was provided from a source bottle heated at 70°C.
• the ⁇ reactant was provided alternately and sequentially with three different plasma reactants.
• a plasma was generated in Ar, Ar and N 2 , and Ar and H 2 . Experiments were carried out at a deposition temperature of 200°C.
• Figure 5 A shows the refractive index of the resulting films. In the case of H 2 -containing plasma, the refractive index is very close to that of T1O2. However, the N 2 -containing plasma and pure Ar plasma showed different refractive indices, indicating variable film composition.
• Figure 5B shows the growth rate of the titanium oxide films using the three different plasma reactants.
• Table 3 shows composition data derived from RBS and XPS. Both XPS and RBS indicate that T1O2 films are deposited by H 2 -containing plasma. No crystalline structure was seen by XRD measurement. Indicating that amorphous T1O2 was deposited.
• WERR wet etch rate ratio
• TOX thermal silicon oxide
• the resultant film was a carbon rich TiOC film.
• the carbon content may be modified by tuning plasma power.
• N2 containing plasma introduced nitrogen into the films, resulting in a TiOCN film.

Landscapes

• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Physics & Mathematics (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Power Engineering (AREA)
• Condensed Matter Physics & Semiconductors (AREA)
• Microelectronics & Electronic Packaging (AREA)
• Computer Hardware Design (AREA)
• Manufacturing & Machinery (AREA)
• General Physics & Mathematics (AREA)
• General Chemical & Material Sciences (AREA)
• Materials Engineering (AREA)
• Organic Chemistry (AREA)
• Metallurgy (AREA)
• Mechanical Engineering (AREA)
• Plasma & Fusion (AREA)
• Inorganic Chemistry (AREA)
• Electromagnetism (AREA)
• Spectroscopy & Molecular Physics (AREA)
• Chemical Vapour Deposition (AREA)
• Formation Of Insulating Films (AREA)
• Electrodes Of Semiconductors (AREA)
• Crystals, And After-Treatments Of Crystals (AREA)

Priority Applications (8)

Applications Claiming Priority (2)

Related Child Applications (2)

Publications (1)

Family

ID=64274551

Family Applications (1)

Country Status (6)

Cited By (38)

Families Citing this family (248)

Citations (8)

Family Cites Families (311)