New! View global litigation for patent families

US20060084281A1 - Novel deposition of high-k MSiON dielectric films - Google Patents

Novel deposition of high-k MSiON dielectric films Download PDF

Info

Publication number
US20060084281A1
US20060084281A1 US11288699 US28869905A US2006084281A1 US 20060084281 A1 US20060084281 A1 US 20060084281A1 US 11288699 US11288699 US 11288699 US 28869905 A US28869905 A US 28869905A US 2006084281 A1 US2006084281 A1 US 2006084281A1
Authority
US
Grant status
Application
Patent type
Prior art keywords
source
dielectric
silicon
film
metal
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Abandoned
Application number
US11288699
Inventor
Ashutosh Misra
Matthew Fisher
Benjamin Jurcik
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Misra Ashutosh
Original Assignee
Ashutosh Misra
Matthew Fisher
Benjamin Jurcik
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date

Links

Images

Classifications

    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C16/00Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22Chemical 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
    • C23C16/30Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/308Oxynitrides
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C16/00Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22Chemical 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
    • C23C16/30Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/34Nitrides
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C16/00Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22Chemical 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
    • C23C16/30Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/40Oxides
    • C23C16/401Oxides containing silicon
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C16/00Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44Chemical 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
    • C23C16/448Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for generating reactive gas streams, e.g. by evaporation or sublimation of precursor materials
    • C23C16/4481Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for generating reactive gas streams, e.g. by evaporation or sublimation of precursor materials by evaporation using carrier gas in contact with the source material
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C16/00Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44Chemical 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
    • C23C16/455Chemical 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
    • C23C16/45523Pulsed gas flow or change of composition over time
    • C23C16/45525Atomic layer deposition [ALD]
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C16/00Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44Chemical 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
    • C23C16/455Chemical 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
    • C23C16/45523Pulsed gas flow or change of composition over time
    • C23C16/45525Atomic layer deposition [ALD]
    • C23C16/45527Atomic 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
    • C23C16/45531Atomic 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
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104Forming layers
    • H01L21/02107Forming insulating materials on a substrate
    • H01L21/02109Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02112Forming 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
    • H01L21/02172Forming 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
    • H01L21/02175Forming 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
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104Forming layers
    • H01L21/02107Forming insulating materials on a substrate
    • H01L21/02109Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02112Forming 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
    • H01L21/02172Forming 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
    • H01L21/02175Forming 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
    • H01L21/02181Forming 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 hafnium, e.g. HfO2
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104Forming layers
    • H01L21/02107Forming insulating materials on a substrate
    • H01L21/02109Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02112Forming 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
    • H01L21/02172Forming 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
    • H01L21/02175Forming 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
    • H01L21/02189Forming 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 zirconium, e.g. ZrO2
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104Forming layers
    • H01L21/02107Forming insulating materials on a substrate
    • H01L21/02225Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
    • H01L21/0226Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
    • H01L21/02263Forming 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
    • H01L21/02271Forming 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
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer, carrier concentration layer
    • H01L21/18Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer, carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/28Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in H01L21/20 - H01L21/268
    • H01L21/283Deposition of conductive or insulating materials for electrodes conducting electric current
    • H01L21/285Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation
    • H01L21/28506Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers
    • H01L21/28512Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers on semiconductor bodies comprising elements of Group IV of the Periodic System
    • H01L21/28556Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers on semiconductor bodies comprising elements of Group IV of the Periodic System by chemical means, e.g. CVD, LPCVD, PECVD, laser CVD
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer, carrier concentration layer
    • H01L21/18Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer, carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers
    • H01L21/314Inorganic layers
    • H01L21/3143Inorganic layers composed of alternated layers or of mixtures of nitrides and oxides or of oxinitrides, e.g. formation of oxinitride by oxidation of nitride layers
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer, carrier concentration layer
    • H01L21/18Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer, carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers
    • H01L21/314Inorganic layers
    • H01L21/3143Inorganic layers composed of alternated layers or of mixtures of nitrides and oxides or of oxinitrides, e.g. formation of oxinitride by oxidation of nitride layers
    • H01L21/3144Inorganic layers composed of alternated layers or of mixtures of nitrides and oxides or of oxinitrides, e.g. formation of oxinitride by oxidation of nitride layers on silicon
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer, carrier concentration layer
    • H01L21/18Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer, carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers
    • H01L21/314Inorganic layers
    • H01L21/3143Inorganic layers composed of alternated layers or of mixtures of nitrides and oxides or of oxinitrides, e.g. formation of oxinitride by oxidation of nitride layers
    • H01L21/3145Inorganic layers composed of alternated layers or of mixtures of nitrides and oxides or of oxinitrides, e.g. formation of oxinitride by oxidation of nitride layers formed by deposition from a gas or vapour
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer, carrier concentration layer
    • H01L21/18Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer, carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers
    • H01L21/314Inorganic layers
    • H01L21/316Inorganic layers composed of oxides or glassy oxides or oxide based glass
    • H01L21/31604Deposition from a gas or vapour
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer, carrier concentration layer
    • H01L21/18Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer, carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers
    • H01L21/314Inorganic layers
    • H01L21/316Inorganic layers composed of oxides or glassy oxides or oxide based glass
    • H01L21/31604Deposition from a gas or vapour
    • H01L21/31641Deposition of Zirconium oxides, e.g. ZrO2
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer, carrier concentration layer
    • H01L21/18Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer, carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers
    • H01L21/314Inorganic layers
    • H01L21/316Inorganic layers composed of oxides or glassy oxides or oxide based glass
    • H01L21/31604Deposition from a gas or vapour
    • H01L21/31645Deposition of Hafnium oxides, e.g. HfO2
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/70Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
    • H01L21/71Manufacture of specific parts of devices defined in group H01L21/70
    • H01L21/768Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
    • H01L21/76838Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the conductors
    • H01L21/76841Barrier, adhesion or liner layers
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S438/00Semiconductor device manufacturing: process
    • Y10S438/907Continuous processing

Abstract

This disclosure discusses the forming of gate dielectrics in semi conductor devices, and more specifically to forming thin high-k dielectric films on silicon substrates typically using chemical vapor deposition or atomic layer deposition processes. The current invention forms a high-k dielectric film in a single film-forming step using a vapor phase silicon precursor in conjunction with a liquid phase metal precursor, a nitrogen source and an oxygen source for the deposition of a metal silicon oxy nitride (MSiON) film of desired stochiometry. The vapor phase silicon precursor is not coordinated to a metal allowing independent control over feeding of the metal source and the silicon source. Thus, the M/Si ratio can be easily varied over a wide range. Furthermore, the vapor phase silicon precursor, liquid phase metal precursor, nitrogen source and oxygen sources are chlorine free, eliminating the undesirable effects chlorine in the dielectric film and chloride by products in the reaction chamber and exhaust system. Furthermore, the vapor phase silicon precursor, nitrogen source and oxygen sources are carbon free, minimizing the incorporation of carbon in the dielectric film.

Description

    CROSS-REFERENCE
  • [0001]
    This application is related to and claims the benefit of U.S. Provisional Application No. 60/550,908, filed Mar. 5, 2004, entitled “Composition And Method For Deposition Of High-k Dielectric Films.”
  • BACKGROUND
  • [0002]
    Manufacturing of semiconductor devices employs a thin gate dielectric (typically silicon dioxide) between the underlying silicon substrate and the gate electrode. Depositing a thin dielectric film on a silicon substrate forms a gate dielectric. Typical processes for growth of dielectric films include oxidation, chemical vapor deposition and atomic layer deposition processes. As integrated circuit devices shrink, the thickness of the gate dielectric needs to shrink proportionally. However, semiconductor manufacturers have reached the limit to which the thickness of conventional gate dielectric materials can be decreased without compromising the electrical characteristics. Rather than degrading the dielectric properties by using a silicon dioxide dielectric that is only a few atomic layers thick, equivalent dielectric performance can be achieved by substituting the silicon dioxide for a thicker layer of a new material exhibiting a higher dielectric constant. Therefore, new compositions or methods to produce a dielectric film with a higher dielectric constant than silicon dioxide (referred to as “high-k dielectrics”) are required. These “high-k dielectrics” must have a low leakage current through the gate dielectric. Thus, it is desirable to develop new compositions and methods of depositing dielectric films with the required higher dielectric properties so that films with more than one or two layers of atoms can be deposited. Due to the requirements for thin dielectric films, having uniform coverage of material that is very high quality is critical to the performance of the gate dielectric.
  • [0003]
    Of particular interest is the formation of metal silicon oxynitride (“MSiON”) films. Forming a MSiON dielectric film typically involves feeding a metal source, a silicon source, an oxygen source and a nitrogen source (collectively referred to herein as the “dielectric precursors”) in the proper relative amounts to a deposition device wherein a silicon substrate is held at an elevated temperature. The dielectric precursors are fed to a deposition chamber through a “delivery system.” A “delivery system” is the system of measuring and controlling the amounts of the various dielectric precursors being fed to the deposition chamber. Various delivery systems are known to one skilled in the art. Once in the deposition chamber, the dielectric precursors react to deposit a dielectric film on the silicon substrate in a “forming” step. A “forming” step or steps, as used in this application, is the step or steps wherein materials are deposited on the silicon substrate or wherein the molecular composition or structure of the film on the silicon substrate is modified. The “desired final composition” of the dielectric film is the precise chemical composition and atomic structure of the gate dielectric after the last forming step is complete. Compounds of hafnium, such as hafnium oxides, hafnium silicates and hafnium silicon oxy nitrides are currently the most promising high-k gate dielectric choices. The metal source for the forming process is typically a liquid precursor solution containing the desired metal in a solvent. Similarly, the silicon sources available in the art prior to the current invention typically use a liquid precursor containing the desired silicon compound in a solvent.
  • [0004]
    U.S. Patent Publication No. U.S. 2003/0207549, PAJ Patent Application No. 2000272283, U.S. Pat. No. 06,399,208, and U.S. Patent Publication No. 2003/0207549 disclose information relevant to forming dielectric films. However, these references suffer from one or more of the disadvantages discussed below.
  • [0005]
    Some gate dielectric-forming processes require multiple forming steps. For instance, a dielectric film may be formed by depositing a metal and silicon on a substrate in a first step followed by a second “post deposition step” wherein the composition or structure of the deposited metal/silicon film is modified to achieve the desired final composition of a MSiON gate dielectric film. An example of a post deposition step is rapid thermal annealing in an environment that is filled of nitrogen or ammonia. Because control of the film composition is important in dielectric film deposition processes, the fewer the steps, the better the control of the process, and the higher the quality (reflected by dielectric constant, density, contamination, composition and other quality control properties) and conformality (the ability of the film to evenly deposit on all surfaces and shapes of substrate) of the dielectric film.
  • [0006]
    It is known in the art that any silicon sources that contain carbon in the ligands can lead to carbon in the film and result in degraded electrical properties. Furthermore, any chlorine incorporated in dielectric films is undesirable due to its harmful effect on the electrical properties of the film and the stability of the chlorine in the film (the stability makes it hard to remove chlorine from the dielectric film). Also, the presence of chlorine in the silicon or metal source results in the generation of chloride based particulates in the reaction chamber and deposits in the exhaust system. Thus, to achieve the ideal electrical properties and to minimize particulate generation and tool downtime due to exhaust system cleaning, it is desirable to deposit dielectric films from precursors free of carbon or chlorine in the atomic structure.
  • [0007]
    The physical properties of a MSiON dielectric film are affected by the metal (M) to silicon (Si) ratio, or M/Si. It is desirable to be able to control the M/Si ratio over a broad range. Thus, it is important to be able to vary the metal and silicon feed independently to achieve the broadest possible M/Si ratios. Some processes use a silicon source precursor that also contains some amount of the metal that is to be deposited. The problem encountered is that changes in the metal-containing silicon source precursor feed rate changes the total amount of the metal fed to the process (due to the metal contained in the silicon precursor). This limits the controllability of the deposition process because the silicon feed rate cannot be changed without also affecting the total amount of metal being fed to the deposition chamber. Furthermore, the ratio of M/Si that can be fed is limited by the composition of the metal in the silicon source precursor. Thus a change in desired M/Si ratio can require changing precursor solutions being fed to the process.
  • [0008]
    Vaporizing silicon precursor streams can also lead to problems with film composition control. Referring to FIG. 2, some processes in the art use a vaporizer to vaporize the liquid silicon source. The vaporized stream is then fed to the deposition chamber. When the metal source and the silicon source are supplied in liquid form, they must both be vaporized before being introduced into the deposition chamber. Vaporizing two different streams can lead to variable feed concentrations and formation of silicon or metal residues in the vaporizer that can adversely affect the conformality of the film composition. Differences in vaporization of the silicon and metal sources can also lead to compositional gradients in the dielectric.
  • [0009]
    Bubbling a carrier gas through a liquid precursor can also cause quality problems. In some processes, a silicon source is fed by bubbling a carrier gas through a liquid silicon source. A vaporizer is not used in these processes because the vapor pressure of the silicon source is high enough to be transported as a vapor in a mixture with the carrier gas. In these processes, the composition of the stream transporting the silicon source to the deposition chamber can vary with temperature and pressure in the bubbling system. This variability in stream composition leads to variability in the composition of the dielectric film, which is a significant quality control issue.
  • [0010]
    For the foregoing reasons, it is desirable to form a dielectric film of the final desired composition in a single forming step. Furthermore, the film should be free of any chlorine and contain as little carbon as possible in the molecular structure. It is also desirable to use a silicon source that is free of any deposition metals so the silicon source feed and the metal source feed may be independently controlled. Finally, it is desirable to have a silicon source that is in the vapor phase at process feed conditions to avoid the need to vaporize a liquid silicon source or bubble a carrier gas through a liquid source.
  • SUMMARY
  • [0011]
    The current invention is directed to methods and compositions that satisfy the need to form a thin MSiON dielectric film with high electrical qualities (large dielectric constant and low leakage current), and high conformality. The current invention avoids using multiple forming steps to assure uniform coverage and high conformality. Furthermore, the current invention provides a film that is free of chlorine and contains a minimum amount of carbon, both of which can degrade the electrical properties of the film. In addition, the current invention provides the ability to control the M/Si ratio in MSiON films over a broad range without changing precursor solutions. Finally, the current invention avoids the quality and conformality issues that can occur when vaporizing a liquid precursor solution containing multiple components or bubbling a carrier gas through a liquid silicon source.
  • [0012]
    The high-k MSiON dielectric film of the current invention is formed by vaporizing a metal source followed by feeding a plurality of dielectric precursors (dielectric precursors being the vaporized metal source, a silicon source, an oxygen source, and a nitrogen source) to a deposition device, and forming a dielectric film with the desired final composition in a single forming step. In other words, there is no need for a post deposition step to achieve the desired final composition the dielectric film. Feeding of a plurality of dielectric precursors to the deposition device is effectively concurrent. The high-k dielectric film forms on a silicon substrate in a single forming step without using a post deposition step to adjust the composition of the dielectric precursors in the dielectric film. The resulting high-k dielectric film has the desired MSiON composition, is absent chlorine, and the carbon incorporation is minimized to provide the highest quality dielectric properties.
  • [0013]
    The current invention uses a vapor phase silicon precursor in conjunction with a liquid phase metal precursor for the deposition of MSiON films of desired stochiometry. The vapor phase silicon precursor is sufficiently volatile at temperatures above 15° C. to supply the process as a vapor without bubbling a carrier gas through a liquid or heating in a vaporizer. This eliminates the control and quality problems associated with having to vaporize two precursors (a metal containing precursor and a silicon containing precursor) or bubble a carrier gas through a liquid to feed the silicon source. In addition, the vapor phase silicon precursor is not coordinated to a metal allowing independent control over feeding of the metal source and the silicon source. Thus, the M/Si ratio can be easily varied over a wide range without having to mix new precursor solutions and recalibrate the process to the new precursor mixture. Furthermore, the vapor phase silicon precursor is carbon and chlorine free, eliminating the undesirable effects of carbon and chlorine in the dielectric film. Finally, the current inventive method produces a dielectric film of the desired final composition is a single step.
  • [0014]
    The metal source in a MSiON film is typically a liquid precursor solution. The liquid phase precursor is injected into a system that vaporizes it into a gas phase. The vaporized precursor enters the deposition chamber where deposition occurs at an elevated temperature.
  • [0015]
    The silicon source of a MSiON film of the current invention is injected into the deposition chamber effectively concurrent with the vaporized metal precursor. The silicon source is in the vapor phase at process feed conditions. That is, the silicon source flows from the source container through the feed measurement and control system as a vapor without the need to be vaporized or without using a carrier gas. However, a gas phase inert may be used to dilute the silicon mixture if needed to obtain accurate flow measurements. Furthermore, the silicon source does not have any atoms of carbon, chlorine, or deposition metals in the molecular structure of the compound. Preferred silicon sources that are carbon and chlorine free are, but are not limited to, the following compounds or mixtures of the following compounds:
    Figure US20060084281A1-20060420-C00001
  • [0016]
    The oxygen and nitrogen sources are also injected into the deposition chamber concurrently with the vaporized metal source and the silicon source. Preferred oxygen and nitrogen sources are free of carbon and/or chlorine in their molecular structures.
  • [0017]
    The reaction of the dielectric precursors in the deposition chamber leads to the formation of a MSiON film on the silicon substrate. The composition of the dielectric film can be precisely controlled by precisely controlling the flow rates of each of the dielectric precursors independently. In a MSiON film, the feed rates of the silicon and metal sources are independently controllable, thus the M/Si ratio of the resulting dielectric film is controllable over a wide range without changing the composition of the metal source or the silicon source.
  • [0018]
    The reaction of the dielectric precursors in the deposition chamber forms a dielectric film of the desired final composition in a single reaction step. There is no requirement for a post deposition step wherein the composition of the dielectric film is modified by a step after the dielectric precursors are deposited on the substrate.
  • [0019]
    Because the silicon, oxygen and nitrogen sources in this invention are all carbon and chlorine free, the resulting dielectric film has excellent properties, including a high dielectric constant when combined with a suitable metal in the proper ratio.
  • BRIEF DESCRIPTION OF THE DRAWINGS
  • [0020]
    FIG. 1 is a flow chart of the steps of the method for forming a MSiON dielectric film.
  • [0021]
    FIG. 2 is a flow chart of a Prior Art method for forming a MSiON dielectric film.
  • DESCRIPTION
  • [0022]
    The present invention is directed to a method of forming and composition of a high-k MSiON dielectric film on semiconductor pieces. The present invention is applicable to chemical vapor deposition and atomic layer deposition processes as well as others known to one skilled in the art.
  • [0023]
    Referring to the MSiON method of FIG. 1, the vaporizing step 1 comprises vaporizing a metal source to form a vaporized metal source. The metal source of one preferred embodiment is a precursor solution in liquid phase, preferably a dialkylamino, an alkoxy, or an inorganic compound of hafnium (Hf), zirconium (Zr), lanthanum (La), yitrium (Y), gadolinium (Gd), europium (Eu), or praseodymium (Pr). Preparing and vaporizing the liquid phase metal precursor solution is carried out in commercially available equipment under appropriate conditions known to one skilled in the art.
  • [0024]
    Referring again to the MSiON method of FIG. 1, during the feed step 2 a silicon source, an oxygen source, and a nitrogen source (collectively referred to as the dielectric precursors) are fed to a deposition chamber where a silicon substrate (on which deposition is needed) is placed at an elevated temperature. The deposition chamber is typically maintained between about 300 to about 900° C. Preferably the surface of the work piece in the deposition chamber will be between about 500 to about 600° C. The feeding of the dielectric precursors is effectively concurrent (atomic layer deposition involves high-speed sequential pulses of feed materials, which for the purposes of this invention is effectively concurrent).
  • [0025]
    Referring to the MSiON method of FIG. 1, during the feed step 2 of the MSiON method, the silicon source is controllably injected into the deposition chamber effectively concurrent with the vaporized metal source and the other dielectric precursors or silicon film components. In one preferred embodiment, a silicon source is in the vapor phase at process feed conditions. That is, the silicon source of one preferred embodiment has a vapor pressure of greater than approximately 50 torr at 20° C., sufficient to exist in the vapor phase in the feed control system without the need for vaporization or bubbler equipment in the delivery system. Trisilylamine, one preferred silicon source, may be stored as a liquid, but has sufficient vapor pressure (greater than 350 torr vapor pressure at 20° C.) to be in the vapor phase in the delivery system without the need to use a vaporizer or bubbler system. Because the silicon source is in the vapor phase, it can be accurately measured and controlled with conventional devices know in the art, and is not affected by deposits in a vaporizer or swings in feed conditions during vaporization of the silicon or metal source.
  • [0026]
    Still referring to the MSiON method of FIG. 1, preferred embodiments of the feed step 2 include, but are not limited to, the use a silicon source absent carbon or chlorine in the molecular structure. Thus, the dielectric film has a minimum amount of contained carbon and is free of chlorine, resulting in the optimum electrical properties.
  • [0027]
    Still referring to the MSiON method of FIG. 1, preferred embodiments of the feed step 2 include, but are not limited to, feeding the oxygen and nitrogen sources into the deposition chamber concurrently with the silicon source. Furthermore, the vaporized metal source is also fed concurrently in the feed step 2. Various preferred embodiments of the MSiON method use nitrogen sources that are free of carbon and/or chlorine in their molecular structures. It is not required that nitrogen be fed as a separate stream. The nitrogen source can be the same as the metal source, the silicon source, or the oxygen source. Preferred oxygen sources of the current invention are also free of carbon and/or chlorine in their molecular structures. Preferred embodiments include, but are not limited to oxygen, nitrous oxide, or ozone as the oxygen source. The nitrogen source of one preferred embodiment is ammonia. The oxygen and nitrogen sources are fed and controlled with devices known to one skilled in the art.
  • [0028]
    Referring again to the MSiON method of FIG. 1, the deposition and reaction of dielectric precursors in the deposition chamber leads to the formation of a MSiON film on the heated silicon substrate during the forming step 3. One preferred embodiment of a MSiON film is a hafnium silicon oxynitride film or a zirconium silicon oxynitride film formed by feeding a hafnium or zirconium metal using a mixture of a metal source (such as Hf(DEA)4 or Zr(DEA)4), trisilylamine, ammonia and nitrous oxide.
  • [0029]
    Referring again to the MSiON method of FIG. 1, the composition of the MSiON dielectric film can be controlled by varying the flow of each of the dielectric precursors independently during the feeding step 2. Particularly, the feed rate of the silicon source and the metal source are independently controllable because the silicon source does not contain any deposition metals. Thus, the silicon source feed rate can be varied independently of the metal source feed rate to affect the desired metal (M) to silicon (Si) ratio. Similarly, the metal source feed rate can be varied without affecting the silicon source feed rate, also changing the M/Si ratio. Because the feed rate of the silicon and metal sources are independently controllable, the M/Si ratio of the resulting dielectric film is controllable over a wide range without changing the composition of the metal source or the silicon source.
  • [0030]
    Referring to the MSiON method of FIG. 1, the feeding of the dielectric precursors to the deposition chamber results in the formation of a dielectric film of the desired final composition in a single forming step 3. There is no requirement for a post deposition step wherein the composition or structure of the dielectric film is modified after some or all of the dielectric precursors are deposited on the substrate to achieve the desired final composition.
  • [0031]
    Although the present invention has been described in considerable detail with reference to certain preferred versions thereof, other versions are possible. For example, the composition and method may be practiced in a process other then chemical vapor deposition or atomic layer deposition. In addition, the deposition of dielectric films can be accomplished at a variety of temperature and conditions. Furthermore, the invention may include a variety of metal, silicon, oxygen and nitrogen sources known in the art. Therefore, the spirit and scope of the appended claims should not be limited to the description of one of the preferred versions contained herein. The intention of the applicants is to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention as defined by the appended claims.

Claims (42)

  1. 1. A method for forming a MSiON dielectric film comprising the steps of:
    vaporizing a metal source to form a vaporized metal source;
    feeding a plurality of dielectric precursors to a deposition device, wherein said dielectric precursors comprise said vaporized metal source, a silicon source, an oxygen source, and a nitrogen source; and
    forming a dielectric film, wherein said dielectric film is formed with the desired final composition absent a post deposition step.
  2. 2. The method of claim 1, wherein said silicon source comprises a molecular structure absent carbon.
  3. 3. The method of claim 1, wherein said silicon source comprises a molecular structure absent chlorine.
  4. 4. The method of claim 1, wherein said silicon source is the vapor phase in the delivery system.
  5. 5. The method of claim 1, absent a step wherein said silicon source is vaporized.
  6. 6. The method of claim 1, absent a step wherein said silicon source is delivered by bubbling a gas through a liquid silicon source.
  7. 7. The method of claim 1, wherein said silicon source has a vapor pressure of at least about 50 torr at 20° C.
  8. 8. The method of claim 1, wherein said silicon source is selected from the group consisting of trisilylamine, disilylamine, silylamine, tridisilylamine, aminodisilylamine, tetrasilyldiamine, disilane, derivatives of disilane, and mixtures thereof.
  9. 9. The method of claim 1, wherein said silicon source is trisilylamine.
  10. 10. The method of claim 1, wherein said oxygen source comprises a molecular structure absent carbon.
  11. 11. The method of claim 1, wherein said oxygen source comprises a molecular structure absent chlorine.
  12. 12. The method of claim 1, wherein said oxygen source is selected from the group consisting of oxygen, nitrous oxide, ozone, and mixtures thereof.
  13. 13. The method of claim 1, wherein said nitrogen source comprises a molecular structure absent carbon.
  14. 14. The method of claim 1, wherein said nitrogen source comprises a molecular structure absent chlorine.
  15. 15. The method of claim 1, wherein said nitrogen source is the same as said metal source, said silicon source, or said oxygen source.
  16. 16. The method of claim 1, wherein said nitrogen source is ammonia.
  17. 17. The method of claim 1, wherein said metal source is selected from the group consisting of a dialkylamino, and alkoxy.
  18. 18. The method of claim 1, wherein said metal source is an inorganic compound selected from the group consisting of hafnium (Hf, zirconium (Zr), lanthanum (La), yitrium (Y), gadolinium (Gd), europium (Eu), praseodymium (Pr), and mixtures thereof.
  19. 19. The method of claim 1, wherein the amounts of said metal source and said silicon source in said desired final composition of said dielectric film are independently controllable.
  20. 20. The method of claim 1, wherein said forming a dielectric film step is completed using a chemical vapor deposition process.
  21. 21. The method of claim 1, wherein said forming a dielectric film step is completed using an atomic layer deposition process.
  22. 22. A MSiON dielectric film prepared by a process comprising the steps of:
    vaporizing a metal source to form a vaporized metal source;
    feeding a plurality of dielectric precursors to a deposition device, wherein said dielectric precursors comprise said vaporized metal source, a silicon source, an oxygen source, and a nitrogen source; and
    forming a dielectric film, wherein said dielectric film is formed with the desired final composition absent a post deposition step.
  23. 23. The dielectric film of claim 22, wherein said silicon source comprises a molecular structure absent carbon.
  24. 24. The dielectric film of claim 22, wherein said silicon source comprises a molecular structure absent chlorine.
  25. 25. The dielectric film of claim 22, wherein said silicon source is in the vapor phase in the delivery system.
  26. 26. The dielectric film of claim 22, absent a step wherein said silicon source is vaporized.
  27. 27. The dielectric film of claim 22, absent a step wherein said silicon source is delivered by bubbling a gas through a liquid silicon source.
  28. 28. The dielectric film of claim 22, wherein said silicon source has a vapor pressure of at least about 50 torr at 20° C.
  29. 29. The dielectric film of claim 22, wherein the source of said silicon is selected from the group consisting of trisilylamine, disilylamine, silylamine, tridisilylamine, aminodisilylamine, tetrasilyldiamine, disilane, derivatives of disilane, and mixtures thereof.
  30. 30. The dielectric film of claim 22, wherein the source of said silicon is trisilylamine.
  31. 31. The dielectric film of claim 30, wherein said metal source comprises hafnium.
  32. 32. The dielectric film of claim 31, wherein said oxygen source comprises nitrous oxide.
  33. 33. The dielectric film of claim 32, wherein said nitrogen source comprises ammonia.
  34. 34. The dielectric film of claim 22, wherein said oxygen source comprises a molecular structure absent carbon.
  35. 35. The dielectric film of claim 22, wherein said oxygen source comprises a molecular structure absent chlorine.
  36. 36. The dielectric film of claim 22, wherein said oxygen source is selected from the group consisting of oxygen, nitrous oxide, ozone, and mixtures thereof.
  37. 37. The dielectric film of claim 22, wherein said nitrogen source comprises a molecular structure absent carbon.
  38. 38. The dielectric film of claim 22, wherein said nitrogen source comprises a molecular structure absent chlorine.
  39. 39. The dielectric film of claim 22, wherein said nitrogen source is the same as said metals source or said silicon source, or said oxygen source.
  40. 40. The dielectric film of claim 22, wherein said nitrogen source is ammonia.
  41. 41. The dielectric film of claim 22, wherein said metal source is selected from the group consisting of a dialkylamino, and alkoxy.
  42. 42. The dielectric film of claim 22, wherein said metal source is an inorganic compound selected from the group consisting of hafnium (Hf), zirconium (Zr), lanthanum (La), yitrium (Y), gadolinium (Gd), europium (Eu), praseodymium (Pr), and mixtures thereof.
US11288699 2004-03-05 2005-11-28 Novel deposition of high-k MSiON dielectric films Abandoned US20060084281A1 (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
US55090804 true 2004-03-05 2004-03-05
US10939269 US7098150B2 (en) 2004-03-05 2004-09-10 Method for novel deposition of high-k MSiON dielectric films
US11288699 US20060084281A1 (en) 2004-03-05 2005-11-28 Novel deposition of high-k MSiON dielectric films

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US11288699 US20060084281A1 (en) 2004-03-05 2005-11-28 Novel deposition of high-k MSiON dielectric films

Publications (1)

Publication Number Publication Date
US20060084281A1 true true US20060084281A1 (en) 2006-04-20

Family

ID=34915705

Family Applications (3)

Application Number Title Priority Date Filing Date
US10939269 Active US7098150B2 (en) 2004-03-05 2004-09-10 Method for novel deposition of high-k MSiON dielectric films
US10591629 Active US7482286B2 (en) 2004-03-05 2005-02-24 Method for forming dielectric or metallic films
US11288699 Abandoned US20060084281A1 (en) 2004-03-05 2005-11-28 Novel deposition of high-k MSiON dielectric films

Family Applications Before (2)

Application Number Title Priority Date Filing Date
US10939269 Active US7098150B2 (en) 2004-03-05 2004-09-10 Method for novel deposition of high-k MSiON dielectric films
US10591629 Active US7482286B2 (en) 2004-03-05 2005-02-24 Method for forming dielectric or metallic films

Country Status (3)

Country Link
US (3) US7098150B2 (en)
JP (1) JP5048476B2 (en)
WO (1) WO2005093126A1 (en)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050196977A1 (en) * 2004-03-02 2005-09-08 Semiconductor Leading Edge Technologies, Inc. Method of forming silicon nitride film and method of manufacturing semiconductor device
US20070010072A1 (en) * 2005-07-09 2007-01-11 Aviza Technology, Inc. Uniform batch film deposition process and films so produced
US20070031598A1 (en) * 2005-07-08 2007-02-08 Yoshikazu Okuyama Method for depositing silicon-containing films
US20080251836A1 (en) * 2007-04-16 2008-10-16 Hynix Semiconductor Inc. Non-volatile memory device and method for fabricating the same
US20110178322A1 (en) * 2010-01-15 2011-07-21 Yoshitaka Hamada Preparation process of trisilylamine
US9887080B2 (en) 2015-12-28 2018-02-06 Samsung Electronics Co., Ltd. Method of forming SiOCN material layer and method of fabricating semiconductor device

Families Citing this family (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4358492B2 (en) * 2002-09-25 2009-11-04 レール・リキード−ソシエテ・アノニム・プール・レテュード・エ・レクスプロワタシオン・デ・プロセデ・ジョルジュ・クロード Method for producing a thermochemical silicon nitride film by vapor deposition or a silicon oxynitride film
CN100431103C (en) * 2003-07-30 2008-11-05 因芬尼昂技术股份公司 High-K dielectric film, method for forming it, and related semiconductor device
US20050153571A1 (en) * 2003-11-17 2005-07-14 Yoshihide Senzaki Nitridation of high-k dielectric films
US7098150B2 (en) * 2004-03-05 2006-08-29 Air Liquide America L.P. Method for novel deposition of high-k MSiON dielectric films
US7605469B2 (en) * 2004-06-30 2009-10-20 Intel Corporation Atomic layer deposited tantalum containing adhesion layer
JP2006261434A (en) * 2005-03-17 2006-09-28 L'air Liquide Sa Pour L'etude & L'exploitation Des Procede S Georges Claude Method for forming silicon oxide film
US7875556B2 (en) * 2005-05-16 2011-01-25 Air Products And Chemicals, Inc. Precursors for CVD silicon carbo-nitride and silicon nitride films
JP4554446B2 (en) * 2005-06-21 2010-09-29 ルネサスエレクトロニクス株式会社 A method of manufacturing a semiconductor device
US7875312B2 (en) * 2006-05-23 2011-01-25 Air Products And Chemicals, Inc. Process for producing silicon oxide films for organoaminosilane precursors
US8530361B2 (en) 2006-05-23 2013-09-10 Air Products And Chemicals, Inc. Process for producing silicon and oxide films from organoaminosilane precursors
US7754510B2 (en) * 2007-04-02 2010-07-13 Xerox Corporation Phase-separated dielectric structure fabrication process
US7795614B2 (en) * 2007-04-02 2010-09-14 Xerox Corporation Device with phase-separated dielectric structure
JP5718808B2 (en) 2008-04-25 2015-05-13 エーエスエム インターナショナル エヌ.ヴェー.Asm International N.V. Synthesis and use of precursors for the ald of tellurium and selenium thin film
KR101829380B1 (en) * 2009-10-26 2018-02-19 에이에스엠 인터내셔널 엔.브이. Synthesis and use of precursors for ALD of group VA element containing thin films
CN102597066B (en) * 2009-10-28 2014-10-22 道康宁公司 Polysilanes - polysilazane copolymer, and preparation and use
JP2011243620A (en) * 2010-05-14 2011-12-01 Tokyo Electron Ltd Film formation method and film formation apparatus
US8912353B2 (en) 2010-06-02 2014-12-16 Air Products And Chemicals, Inc. Organoaminosilane precursors and methods for depositing films comprising same
US8771807B2 (en) 2011-05-24 2014-07-08 Air Products And Chemicals, Inc. Organoaminosilane precursors and methods for making and using same
US9337018B2 (en) * 2012-06-01 2016-05-10 Air Products And Chemicals, Inc. Methods for depositing films with organoaminodisilane precursors
US9064694B2 (en) 2012-07-12 2015-06-23 Tokyo Electron Limited Nitridation of atomic layer deposited high-k dielectrics using trisilylamine
KR20150036114A (en) 2012-07-20 2015-04-07 레르 리키드 쏘시에떼 아노님 뿌르 레뜌드 에렉스뿔라따시옹 데 프로세데 조르즈 클로드 Organosilane precursors for ald/cvd silicon-containing film applications
WO2015009997A1 (en) 2013-07-19 2015-01-22 L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Hexacoordinate silicon-containing precursors for ald/cvd silicon-containing film applications
US9382268B1 (en) 2013-07-19 2016-07-05 American Air Liquide, Inc. Sulfur containing organosilane precursors for ALD/CVD silicon-containing film applications
WO2016065219A1 (en) * 2014-10-24 2016-04-28 Air Products And Chemicals, Inc. Compositions and methods using same for deposition of silicon-containing film
WO2016094711A3 (en) * 2014-12-13 2016-10-13 L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Organosilane precursors for ald/cvd silicon-containing film applications and methods of using the same
US20180087150A1 (en) * 2015-03-30 2018-03-29 Air Liquide Advanced Materials, Llc Catalytic dehydrogenative coupling of carbosilanes with ammonia, amines and amidines

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5470398A (en) * 1990-09-25 1995-11-28 Matsushita Electric Industrial Co., Ltd. Dielectric thin film and method of manufacturing same
US6399208B1 (en) * 1999-10-07 2002-06-04 Advanced Technology Materials Inc. Source reagent composition and method for chemical vapor deposition formation or ZR/HF silicate gate dielectric thin films
US6544875B1 (en) * 1999-01-13 2003-04-08 Texas Instruments Incorporated Chemical vapor deposition of silicate high dielectric constant materials
US20030111678A1 (en) * 2001-12-14 2003-06-19 Luigi Colombo CVD deposition of M-SION gate dielectrics
US20030207549A1 (en) * 2002-05-02 2003-11-06 Jenq Jason Jyh-Shyang Method of forming a silicate dielectric layer
US20040040494A1 (en) * 2002-08-28 2004-03-04 Micron Technology, Inc. Systems and methods for forming strontium- and/or barium-containing layers
US20040198069A1 (en) * 2003-04-04 2004-10-07 Applied Materials, Inc. Method for hafnium nitride deposition
US6984591B1 (en) * 2000-04-20 2006-01-10 International Business Machines Corporation Precursor source mixtures
US20070190807A1 (en) * 2004-03-05 2007-08-16 Ashutosh Misra Method for forming dielectric or metallic films

Family Cites Families (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0521749A (en) * 1990-09-25 1993-01-29 Matsushita Electric Ind Co Ltd Dielectric thin film and manufacture thereof
JP3186872B2 (en) * 1992-11-19 2001-07-11 神港精機株式会社 Film deposition method of pulse plasma cvd
US6020243A (en) * 1997-07-24 2000-02-01 Texas Instruments Incorporated Zirconium and/or hafnium silicon-oxynitride gate dielectric
JP2000272283A (en) 1999-03-29 2000-10-03 Ap Faamu:Kk Paper file
US6780704B1 (en) * 1999-12-03 2004-08-24 Asm International Nv Conformal thin films over textured capacitor electrodes
JP2002053960A (en) * 2000-08-04 2002-02-19 Kojundo Chem Lab Co Ltd Cvd raw material composition for depositing zirconium and hafnium silicate film, its production method and method for depositing silicate film using the same
US6613695B2 (en) * 2000-11-24 2003-09-02 Asm America, Inc. Surface preparation prior to deposition
WO2002080244A9 (en) * 2001-02-12 2004-04-22 Asm Inc Improved process for deposition of semiconductor films
US6797599B2 (en) * 2001-08-31 2004-09-28 Texas Instruments Incorporated Gate structure and method
US6806145B2 (en) * 2001-08-31 2004-10-19 Asm International, N.V. Low temperature method of forming a gate stack with a high k layer deposited over an interfacial oxide layer
US6960537B2 (en) * 2001-10-02 2005-11-01 Asm America, Inc. Incorporation of nitrogen into high k dielectric film
JP4054215B2 (en) * 2002-05-01 2008-02-27 田中貴金属工業株式会社 Chemical vapor deposition method of starting compounds and iridium or iridium compound thin film for Cvd
EP1523763A4 (en) * 2002-07-18 2008-12-24 Aviza Tech Inc Molecular layer deposition of thin films with mixed components
CN1643673A (en) * 2002-07-19 2005-07-20 阿维扎技术公司 Metal organic chemical vapor deposition and atomic layer deposition
US6921702B2 (en) * 2002-07-30 2005-07-26 Micron Technology Inc. Atomic layer deposited nanolaminates of HfO2/ZrO2 films as gate dielectrics

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5470398A (en) * 1990-09-25 1995-11-28 Matsushita Electric Industrial Co., Ltd. Dielectric thin film and method of manufacturing same
US6544875B1 (en) * 1999-01-13 2003-04-08 Texas Instruments Incorporated Chemical vapor deposition of silicate high dielectric constant materials
US6399208B1 (en) * 1999-10-07 2002-06-04 Advanced Technology Materials Inc. Source reagent composition and method for chemical vapor deposition formation or ZR/HF silicate gate dielectric thin films
US6984591B1 (en) * 2000-04-20 2006-01-10 International Business Machines Corporation Precursor source mixtures
US20030111678A1 (en) * 2001-12-14 2003-06-19 Luigi Colombo CVD deposition of M-SION gate dielectrics
US20030207549A1 (en) * 2002-05-02 2003-11-06 Jenq Jason Jyh-Shyang Method of forming a silicate dielectric layer
US20040040494A1 (en) * 2002-08-28 2004-03-04 Micron Technology, Inc. Systems and methods for forming strontium- and/or barium-containing layers
US20040198069A1 (en) * 2003-04-04 2004-10-07 Applied Materials, Inc. Method for hafnium nitride deposition
US20070190807A1 (en) * 2004-03-05 2007-08-16 Ashutosh Misra Method for forming dielectric or metallic films

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050196977A1 (en) * 2004-03-02 2005-09-08 Semiconductor Leading Edge Technologies, Inc. Method of forming silicon nitride film and method of manufacturing semiconductor device
US7510984B2 (en) * 2004-03-02 2009-03-31 Ulvac, Inc. Method of forming silicon nitride film and method of manufacturing semiconductor device
US20070031598A1 (en) * 2005-07-08 2007-02-08 Yoshikazu Okuyama Method for depositing silicon-containing films
US20070010072A1 (en) * 2005-07-09 2007-01-11 Aviza Technology, Inc. Uniform batch film deposition process and films so produced
US20080251836A1 (en) * 2007-04-16 2008-10-16 Hynix Semiconductor Inc. Non-volatile memory device and method for fabricating the same
US7851285B2 (en) * 2007-04-16 2010-12-14 Hynix Semiconductor Inc. Non-volatile memory device and method for fabricating the same
US20110178322A1 (en) * 2010-01-15 2011-07-21 Yoshitaka Hamada Preparation process of trisilylamine
US8461367B2 (en) 2010-01-15 2013-06-11 Shin-Etsu Chemical Co., Ltd. Preparation process of trisilylamine
US9887080B2 (en) 2015-12-28 2018-02-06 Samsung Electronics Co., Ltd. Method of forming SiOCN material layer and method of fabricating semiconductor device

Also Published As

Publication number Publication date Type
US20070190807A1 (en) 2007-08-16 application
JP2007526399A (en) 2007-09-13 application
JP5048476B2 (en) 2012-10-17 grant
US20050196970A1 (en) 2005-09-08 application
US7482286B2 (en) 2009-01-27 grant
WO2005093126A1 (en) 2005-10-06 application
US7098150B2 (en) 2006-08-29 grant

Similar Documents

Publication Publication Date Title
US5916359A (en) Alkane and polyamine solvent compositions for liquid delivery chemical vapor deposition
US5835677A (en) Liquid vaporizer system and method
US6074945A (en) Methods for preparing ruthenium metal films
US8668957B2 (en) Method of forming dielectric films, new precursors and their use in semiconductor manufacturing
US4845054A (en) Low temperature chemical vapor deposition of silicon dioxide films
US5908947A (en) Difunctional amino precursors for the deposition of films comprising metals
US20050020017A1 (en) Lanthanide oxide / hafnium oxide dielectric layers
US6818517B1 (en) Methods of depositing two or more layers on a substrate in situ
US6720259B2 (en) Passivation method for improved uniformity and repeatability for atomic layer deposition and chemical vapor deposition
US20080274302A1 (en) Film formation method and apparatus for semiconductor process
US6348412B1 (en) Organometallic compound mixtures in chemical vapor deposition
US20030235961A1 (en) Cyclical sequential deposition of multicomponent films
US7053009B2 (en) Nanolaminate film atomic layer deposition method
US20030040196A1 (en) Method of forming insulation layer in semiconductor devices for controlling the composition and the doping concentration
US7077902B2 (en) Atomic layer deposition methods
US5968611A (en) Silicon nitrogen-based films and method of making the same
US20020015790A1 (en) Source reagent compositions for CVD formation of high dielectric constant and ferroelectric metal oxide thin films and method of using same
US20020001974A1 (en) Method for manufacturing zirconium oxide film for use in semiconductor device
EP0212691A1 (en) Low temperature chemical vapor deposition of silicon dioxide films
US20080214003A1 (en) Methods for forming a ruthenium-based film on a substrate
US6110531A (en) Method and apparatus for preparing integrated circuit thin films by chemical vapor deposition
US20090035946A1 (en) In situ deposition of different metal-containing films using cyclopentadienyl metal precursors
US20110262642A1 (en) Process for Producing Silicon and Oxide Films from Organoaminosilane Precursors
EP0533129A2 (en) Deposition of silicon dioxide films at temperatures as low as 100 C by LPCVD using organodisilane sources
US20030017266A1 (en) Chemical vapor deposition methods of forming barium strontium titanate comprising dielectric layers, including such layers having a varied concentration of barium and strontium within the layer