[go: up one dir, main page]

CN101529565A - Method for forming high dielectric film and method for manufacturing semiconductor device - Google Patents

Method for forming high dielectric film and method for manufacturing semiconductor device Download PDF

Info

Publication number
CN101529565A
CN101529565A CNA200780040077XA CN200780040077A CN101529565A CN 101529565 A CN101529565 A CN 101529565A CN A200780040077X A CNA200780040077X A CN A200780040077XA CN 200780040077 A CN200780040077 A CN 200780040077A CN 101529565 A CN101529565 A CN 101529565A
Authority
CN
China
Prior art keywords
high dielectric
dielectric film
semiconductor device
film
manufacture method
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.)
Pending
Application number
CNA200780040077XA
Other languages
Chinese (zh)
Inventor
内田博章
高桥毅
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.)
Tokyo Electron Ltd
Original Assignee
Tokyo Electron Ltd
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
Application filed by Tokyo Electron Ltd filed Critical Tokyo Electron Ltd
Publication of CN101529565A publication Critical patent/CN101529565A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • 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
    • H01L21/02318—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer post-treatment
    • H01L21/02345—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer post-treatment treatment by exposure to radiation, e.g. visible light
    • H01L21/02348—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer post-treatment treatment by exposure to radiation, e.g. visible light treatment by exposure to UV light
    • 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
    • H01L21/02148—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 the material containing hafnium, e.g. HfSiOx or HfSiON
    • 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
    • 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
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/42—Silicides
    • 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
    • H01L21/02142—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
    • H01L21/02159—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 the material containing zirconium, e.g. ZrSiOx
    • 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
    • H01L21/02181—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 hafnium, e.g. HfO2
    • 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
    • H01L21/02189—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 zirconium, e.g. ZrO2
    • 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
    • H01L21/02227—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a process other than a deposition process
    • H01L21/02255—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a process other than a deposition process formation by thermal 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
    • H01L21/02225—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
    • 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
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/22—Diffusion of impurity materials, e.g. doping materials, electrode materials, into or out of a semiconductor body, or between semiconductor regions; Interactions between two or more impurities; Redistribution of impurities
    • H01L21/225—Diffusion of impurity materials, e.g. doping materials, electrode materials, into or out of a semiconductor body, or between semiconductor regions; Interactions between two or more impurities; Redistribution of impurities using diffusion into or out of a solid from or into a solid phase, e.g. a doped oxide layer
    • H01L21/2251—Diffusion into or out of group IV semiconductors
    • H01L21/2254—Diffusion into or out of group IV semiconductors from or through or into an applied layer, e.g. photoresist, nitrides
    • H01L21/2255—Diffusion into or out of group IV semiconductors from or through or into an applied layer, e.g. photoresist, nitrides the applied layer comprising oxides only, e.g. P2O5, PSG, H3BO3, doped oxides
    • 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
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/26—Bombardment with radiation
    • H01L21/263—Bombardment with radiation with high-energy radiation
    • H01L21/268—Bombardment with radiation with high-energy radiation using electromagnetic radiation, e.g. laser radiation
    • H01L21/2686—Bombardment with radiation with high-energy radiation using electromagnetic radiation, e.g. laser radiation using incoherent radiation
    • 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
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
    • H01L21/28008—Making conductor-insulator-semiconductor electrodes
    • H01L21/28017—Making conductor-insulator-semiconductor electrodes the insulator being formed after the semiconductor body, the semiconductor being silicon
    • H01L21/28158—Making the insulator
    • H01L21/28167—Making the insulator on single crystalline silicon, e.g. using a liquid, i.e. chemical oxidation
    • H01L21/28194—Making the insulator on single crystalline silicon, e.g. using a liquid, i.e. chemical oxidation by deposition, e.g. evaporation, ALD, CVD, sputtering, laser deposition
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10D—INORGANIC ELECTRIC SEMICONDUCTOR DEVICES
    • H10D64/00—Electrodes of devices having potential barriers
    • H10D64/20—Electrodes characterised by their shapes, relative sizes or dispositions 
    • H10D64/27—Electrodes not carrying the current to be rectified, amplified, oscillated or switched, e.g. gates
    • H10D64/311—Gate electrodes for field-effect devices
    • H10D64/411—Gate electrodes for field-effect devices for FETs
    • H10D64/511—Gate electrodes for field-effect devices for FETs for IGFETs
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10D—INORGANIC ELECTRIC SEMICONDUCTOR DEVICES
    • H10D64/00—Electrodes of devices having potential barriers
    • H10D64/60—Electrodes characterised by their materials
    • H10D64/66—Electrodes having a conductor capacitively coupled to a semiconductor by an insulator, e.g. MIS electrodes
    • H10D64/68—Electrodes having a conductor capacitively coupled to a semiconductor by an insulator, e.g. MIS electrodes characterised by the insulator, e.g. by the gate insulator
    • H10D64/691—Electrodes having a conductor capacitively coupled to a semiconductor by an insulator, e.g. MIS electrodes characterised by the insulator, e.g. by the gate insulator comprising metallic compounds, e.g. metal oxides or metal silicates 
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/621—Aromatic anhydride or imide compounds, e.g. perylene tetra-carboxylic dianhydride or perylene tetracarboxylic di-imide
    • 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
    • H01L21/02178—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 aluminium, e.g. Al2O3
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10B—ELECTRONIC MEMORY DEVICES
    • H10B12/00—Dynamic random access memory [DRAM] devices
    • H10B12/01—Manufacture or treatment
    • H10B12/02—Manufacture or treatment for one transistor one-capacitor [1T-1C] memory cells
    • H10B12/03—Making the capacitor or connections thereto
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10B—ELECTRONIC MEMORY DEVICES
    • H10B12/00—Dynamic random access memory [DRAM] devices
    • H10B12/01—Manufacture or treatment
    • H10B12/02—Manufacture or treatment for one transistor one-capacitor [1T-1C] memory cells
    • H10B12/05—Making the transistor
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10D—INORGANIC ELECTRIC SEMICONDUCTOR DEVICES
    • H10D1/00—Resistors, capacitors or inductors
    • H10D1/60—Capacitors
    • H10D1/68—Capacitors having no potential barriers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10D—INORGANIC ELECTRIC SEMICONDUCTOR DEVICES
    • H10D30/00—Field-effect transistors [FET]
    • H10D30/60—Insulated-gate field-effect transistors [IGFET]

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Organic Chemistry (AREA)
  • Metallurgy (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • High Energy & Nuclear Physics (AREA)
  • Toxicology (AREA)
  • Electromagnetism (AREA)
  • Health & Medical Sciences (AREA)
  • Optics & Photonics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Formation Of Insulating Films (AREA)
  • Insulated Gate Type Field-Effect Transistor (AREA)
  • Chemical Vapour Deposition (AREA)

Abstract

本发明提供高电介质膜的形成方法和半导体装置的制造方法。该高电介质膜的形成方法包括：在基板上使用有机金属原料以350℃以下的温度通过ALD或CVD形成高电介质膜的工序；和在低压的含氧气氛中向高电介质膜照射紫外线，使膜中的氢脱离的工序。另外，半导体装置的制造方法包括：在半导体基板上使用有机金属原料以350℃以下的温度通过ALD或CVD形成高电介质膜作为栅极绝缘膜的工序；在低压的含氧气氛中向高电介质膜照射紫外线，使膜中的氢脱离的工序；和在高电介质膜之上形成栅极电极的工序。

Figure 200780040077

The present invention provides a method for forming a high dielectric film and a method for manufacturing a semiconductor device. The method for forming the high dielectric film comprises: using an organic metal raw material on a substrate to form a high dielectric film by ALD or CVD at a temperature below 350°C; The process in which hydrogen is detached. In addition, the manufacturing method of the semiconductor device includes: a process of forming a high dielectric film as a gate insulating film by ALD or CVD at a temperature below 350° C. on a semiconductor substrate; A step of irradiating ultraviolet rays to desorb hydrogen in the film; and a step of forming a gate electrode on the high dielectric film.

Figure 200780040077

Description

The formation method of high dielectric film and the manufacture method of semiconductor device
Technical field
The present invention relates to be applicable to gate insulating film in the semiconductor device, capacitor films high dielectric film the formation method and use the manufacture method of the semiconductor device of this high dielectric film.
Background technology
In recent years, the requirement according to highly integrated, the high speed of LSI constitutes the continuous miniaturization of design rule of the semiconductor element of LSI, and thereupon, in cmos device, gate insulating film is required it is with SiO 2The following value of 1.5nm degree of the EOT of electric capacity conversion thickness (Equivalent Oxide Thickness, equivalent oxide thickness) expression.Realize the material of thin like this dielectric film as not increasing grid leakage current ground, high dielectric constant material, so-called High-k material receive publicity.
With high dielectric constant material as under the situation of gate insulating film, need its not with the counterdiffusion mutually of silicon substrate, stable aspect thermodynamics, from this viewpoint, the oxide of hafnium, zirconium or its metal silicate are considered to very promising.
As the film build method of such high dielectric film, known use organo metallic material carries out chemical vapor deposition (CVD) method of film forming, carries out the method (for example TOHKEMY 2004-079753 (patent documentation 1)) of film forming by atomic layer evaporation (ALD) method of alternative supply raw metal gas and oxidant as raw metal gas.And, after such film forming, carry out nitrogen according to demand and add operation, annealing operation etc., thereby can form the high dielectric gate insulating film.
But, forming according to these methods under the situation of high dielectric films, from doing one's utmost to avoid dysgenic viewpoint, trend towards under the condition of low temperature more, forming film to device.On the other hand, contain a large amount of hydrogen in the organic metal raw material, and, also use the gas that contains hydrogen as oxidant, in the process that makes the oxidation of organic metal raw material, generate hydrogeneous composition.If so hydrogeneous composition enters in the film, then under the condition of low temperature, be difficult to from film, discharge, remain in the film easily.If so hydrogeneous composition remains in the film, then when forming semiconductor device (transistor), can cause generation, the Vth skew of interfacial state (interface state), the reliability of infringement device.
Summary of the invention
Even the object of the present invention is to provide a kind of the use under the film formation at low temp condition of organo metallic material, also be difficult to the formation method of the high dielectric film of residual hydrogeneous composition in film.
Another object of the present invention is to provide a kind of manufacture method of semiconductor device of the manufacture method of using such high dielectric film.
Further, another object of the present invention is to provide a kind of storage medium that stores the program of the formation method that is used to carry out such high dielectric film.
According to first viewpoint of the present invention, a kind of formation method of high dielectric film is provided, it comprises: using the organic metal raw material to form the operation of high dielectric film by ALD or CVD with the temperature below 350 ℃ on the substrate; With the operation that in the oxygen-containing atmosphere of low pressure, the hydrogen in the film is broken away to above-mentioned high dielectric film irradiation ultraviolet radiation.
According to second viewpoint of the present invention, a kind of manufacture method of semiconductor device is provided, this semiconductor device has high dielectric film as gate insulating film or capacitor films, and above-mentioned high dielectric film forms by the method with following operation: using the organic metal raw material to form the operation of high dielectric film by ALD or CVD with the temperature below 350 ℃ on the substrate; With the operation that in the oxygen-containing atmosphere of low pressure, the hydrogen in the film is broken away to above-mentioned high dielectric film irradiation ultraviolet radiation.
According to the 3rd viewpoint of the present invention, a kind of manufacture method of semiconductor device is provided, it comprises: using the organic metal raw material to form operation as the high dielectric film of gate insulating film with the temperature below 350 ℃ by ALD or CVD on the semiconductor substrate; The operation that in the oxygen-containing atmosphere of low pressure, the hydrogen in the film is broken away to above-mentioned high dielectric film irradiation ultraviolet radiation; With the operation that on above-mentioned high dielectric film, forms gate electrode.
In above-mentioned first～the 3rd viewpoint,, can use oxide or the silicate of Hf or Zr as above-mentioned high dielectric film.In this case, can use the amide-type metallic compound as above-mentioned organic metal raw material.When forming high dielectric film, can use H 2O is as oxidant.
In addition, above-mentioned ultraviolet irradiation preferably carries out under the pressure of 0.665～665Pa.Above-mentioned ultraviolet irradiation preferably carries out under the state that substrate is heated to the temperature below 500 ℃.Above-mentioned ultraviolet irradiation can be at O 2Carry out in the gas atmosphere.Above-mentioned ultraviolet irradiation can use wavelength to carry out as the ultraviolet ray of 172nm.
According to the 4th viewpoint of the present invention, a kind of storage medium is provided, it stores in computer and carries out, the program of the formation device of control high dielectric film, said procedure is when carrying out, in the mode of the formation method of carrying out high dielectric film, make the formation device of the above-mentioned high dielectric film of computer control, the formation method of above-mentioned high dielectric film comprises: using the organic metal raw material to form the operation of high dielectric film by ALD or CVD with the temperature below 350 ℃ on the substrate; With the operation that in the oxygen-containing atmosphere of low pressure, the hydrogen in the film is broken away to above-mentioned high dielectric film irradiation ultraviolet radiation.
According to the present invention, after hydrogeneous composition remains in the film forming of high dielectric film in the film, that use organic metal raw material is undertaken by ALD or CVD with the condition below 350 ℃ easily, in the ultraviolet irradiation of carrying out under the low pressure condition in oxygen-containing gas atmosphere, thereby hydrogen is broken away from from high dielectric film, can prevent to remain in the reduction of the reliability of the device that causes in the film owing to hydrogeneous composition.
The technology of irradiation ultraviolet radiation is disclosed in Japanese kokai publication hei 9-121035 communique when forming high dielectric film by the ALD method.But, in this communique, in the disclosed technology, hocket at O 3Ultraviolet irradiation (the UV-O that carries out in the atmosphere 3Annealing) and high dielectric film form, form the high dielectric film of specific thickness, thus oxygen disappearance that can repair membrane, thereby its with after the formation high dielectric film, carry out ultraviolet irradiation breaks away from hydrogen from film the present invention and have significantly different.Therefore, in the technology of Japanese kokai publication hei 9-121035 communique, in order to keep the O that is used to repair the oxygen disappearance 3Concentration need under high pressure carry out UV-O 3Annealing, and in the present invention, break away from the oxygen-containing gas atmosphere that forms low pressure in order to make hydrogen.
Though the mechanism that breaks away from about the hydrogen among the present invention is also not exclusively clear and definite, can infer that its reason is, the key by hydrogen atom such as ultraviolet irradiation cut-out C-H and other atoms utilizes oxygen-containing gas to repair this part.
Description of drawings
Fig. 1 is the flow chart of operation of an execution mode that is used to illustrate the formation method of high dielectric film of the present invention.
Fig. 2 A is the operation sectional view of operation of an execution mode that is used to illustrate the formation method of high dielectric film of the present invention.
Fig. 2 B is the operation sectional view of operation of an execution mode that is used to illustrate the formation method of high dielectric film of the present invention.
Fig. 3 is illustrated in residual after the film forming high dielectric film of state of hydrogen to be arranged as gate insulating film, and form gate electrode thereon, when carrying out necessary processing formation MOS type device thereafter, measure the result's who asks for Vfb skew gained figure by Vstress.
Fig. 4 is that the high dielectric film of the formation method of the expression high dielectric film that is used to implement present embodiment forms schematic representation of apparatus.
Fig. 5 A is the vertical cross-section diagram that is illustrated in the ultraviolet irradiation unit of carrying on the high dielectric membrane formation device of Fig. 4.
Fig. 5 B is the horizontal sectional view that is illustrated in the ultraviolet irradiation unit of carrying on the high dielectric membrane formation device of Fig. 4.
Fig. 6 A is the operation sectional view of Production Example of the mos semiconductor device of the expression method of using present embodiment.
Fig. 6 B is the operation sectional view of Production Example of the mos semiconductor device of the expression method of using present embodiment.
Fig. 6 C is the operation sectional view of Production Example of the mos semiconductor device of the expression method of using present embodiment.
Fig. 6 D is the operation sectional view of Production Example of the mos semiconductor device of the expression method of using present embodiment.
Fig. 6 E is the operation sectional view of Production Example of the mos semiconductor device of the expression method of using present embodiment.
Fig. 7 A is the figure that is illustrated in the result of the hydrogen concentration gained of measuring film under the situation of carrying out ultraviolet irradiation after the film forming of HfO film.
Fig. 7 B is the figure that is illustrated in the result of the hydrogen concentration gained of measuring film under the situation of not carrying out ultraviolet irradiation after the film forming of HfO film.
Embodiment
Below, with reference to accompanying drawing embodiments of the present invention are carried out specific description.
Fig. 1 is the flow chart of operation of an execution mode that is used to illustrate the formation method of high dielectric film of the present invention.Fig. 2 A, Fig. 2 B are the operation sectional views of this moment.
This method has: the operation (STEP1, Fig. 2 A) that forms high dielectric film 2 on substrate 1; With high dielectric film 2 is remained in the low pressure atmosphere and the operation (STEP2, Fig. 2 B) of irradiation ultraviolet radiation (UV) 3.
As by STEP1 by the material of the high dielectric film 2 of film forming, can exemplify various materials, above-mentioned hafnium, the oxide of zirconium or its metal silicate, i.e. HfO 2, ZrO 2, HfSiO xDeng certainly, can also enumerate SrTiO in addition x, La 2O 3, Y 2O 3
High dielectric film 2 carries out film forming by ALD or the CVD that uses the organic metal raw material with the temperature below 350 ℃.Use the organic metal raw material, utilize ALD or CVD, make temperature, thereby in device, use under the situation of the low material of thermal endurance such as NiSi, also can not be adversely affected below 350 ℃.Be preferably film temperature below 300 ℃.
Organic metal raw material as the film forming that is used to carry out above-mentioned material, can exemplify out TEMAH (テ ト ラ エ ト キ ス メ テ Le エ チ Le ア ミ De Ha Off ニ ウ system, four (ethyl dimethylamine base) hafnium), TDEAH (テ ト ラ ジ エ チ Le ア ミ De Ha Off ニ ウ system, four (diethylin) hafnium) and TEMAZ (テ ト ラ エ ト キ ス メ テ Le エ チ Le ア ミ De ジ Le コ ニ ウ system, four (ethyl dimethylamine base) zirconium) etc.
In addition, when these organic metal raw materials being carried out oxidation and form above-mentioned high dielectric film 2, can enumerate H as oxidant 2O, O 3, O 2, NO 2, N 2O, NO etc.Wherein, preferred H 2O is because it can and then reduce the residual carbon in the film.
When using these organic metal raw materials and oxidant and forming high dielectric film by ALD, on the pedestal of substrate-placing in being arranged on chamber, make and be specified vacuum atmosphere in the chamber, substrate is heated to the temperature of the regulation below 350 ℃, and, at first in chamber according to the rules flow supply with the organic metal raw material, make it to be adsorbed on the substrate, afterwards, flow is supplied with oxidant according to the rules, makes adsorbed organic metal raw material oxidation, forms the high dielectric film of 1～number molecular layer degree, alternate repetition carries out above-mentioned operation, forms the high-k films of desirable thickness.
In addition, using these organic metal raw materials and oxidant and forming by CVD under the situation of high dielectric film, on the pedestal of substrate-placing in being arranged on chamber, and substrate is heated to the temperature of the regulation below 350 ℃, and, supply with organic metal raw material and oxidant simultaneously, form the high-k films of desirable thickness.
Above-mentioned ALD utilizes oxidant to make it oxidation after the organic metal raw material film that is adsorbed with as thin as a wafer, so it is reactive high, compares with CVD, can carry out film forming at low temperatures.Therefore, in order to implement the more preferred ALD of film forming of low temperature.
But, forming under the situation of high dielectric film by ALD or CVD like this, owing to contain a large amount of hydrogen in the organic metal raw material, so residual hydrogeneous composition in film easily, and, because film-forming temperature is below 350 ℃, be low temperature, so hydrogen is difficult to break away from from residual hydrogeneous composition.Therefore, if will in semiconductor device, use, then, cause generation, the Vth skew of interfacial state owing to remain in hydrogen in the film by the high dielectric film former state ground that such method is carried out the state after the film forming.For example, at the high dielectric film of the state that hydrogen is arranged with residual after the film forming as gate insulating film, and form gate electrode thereon, when carrying out necessary processing formation MOS type device thereafter, measure the result who asks for Vfb skew gained by Vstress, as shown in Figure 3, can confirm that Δ Vfb can reach 1.0V.
Therefore, in the present embodiment, after under the condition of easy residual hydrogeneous composition, forming high dielectric film as mentioned above, carry out the ultraviolet irradiation operation as STEP2.The ultraviolet irradiation operation of this STEP2 is carried out in the oxygen-containing atmosphere of low pressure condition.Like this, by the UV treatment with irradiation of low pressure, the hydrogen in the high dielectric film is broken away from.That is, can infer,, can cut off the hydrogen in the hydrogeneous composition and the key of other elements, thereby Hydrogen Energy break away from enough by the ultraviolet irradiation under the low pressure.Here, so-called low pressure is the enough low pressure of the degree that enough breaks away from of Hydrogen Energy.That is, the hydrogen in the high dielectric film under low pressure breaks away from when ultraviolet irradiation easily, therefore, carries out ultraviolet irradiation in low pressure atmosphere.Specifically, pressure is preferably below the 665Pa.In addition, the atmosphere during ultraviolet irradiation is oxygen-containing atmosphere, for example O 2Gas atmosphere.This be because, to O 2The gas irradiation ultraviolet radiation produces O 2Free radical also helps the disengaging of carbon when the hydrogen in helping film breaks away from.In addition, Ci Shi temperature is preferably below 500 ℃.This is in order to reduce the heat budget (thermal budget) to the device that forms on substrate.Be preferably below 450 ℃, further preferred below 400 ℃.As the ultraviolet ray of shining, wavelength is preferably about 150～250nm, for example can utilize ultra-violet lamp to shine.In ultraviolet irradiation, can use Xe lamp (wavelength 0.172 μ m).The ultraviolet irradiation time is preferably about tens of seconds degree to 1 minute.
The high dielectric film of Xing Chenging can reduce the residual harmful effect of hydrogen as mentioned above, so, can be applicable to the gate insulating film of mos semiconductor device, the capacitor films of in DRAM etc., using.
Then, the device to the formation method of the high dielectric film that is used to implement present embodiment describes.Fig. 4 is that the high dielectric film of the formation method of the expression high dielectric film that is used to implement present embodiment forms schematic representation of apparatus.
As shown in Figure 4, this high dielectric membrane formation device 10 comprises: the one-tenth film unit 11 that forms high dielectric film by CVD or ALD; To utilizing into film unit 11 by the ultraviolet irradiation unit 12 of the high dielectric film irradiation ultraviolet radiation (UV) of film forming; And can become between film unit 11 and the ultraviolet irradiation unit 12, do not destroy for example carrying room 13 of semiconductor wafer of vacuum ground conveyance substrate 1.Be provided with the transport mechanism 14 that is used for conveyance substrate 1 at carrying room 13.In addition, not shown load locking room is connected with carrying room 13, disposes the box that is equipped with a plurality of substrates in the outside of this load locking room.From box via load locking room with substrate 1 conveyance to carrying room, carry out predetermined process.
This high dielectric membrane formation device 10 has process controller 15, this process controller 15 is by each structural portion of control, the microprocessor (computer) of film unit 11, ultraviolet irradiation unit 12, carrying room 13 and transport mechanism 14 constitute, each structural portion is connected also Be Controlled with this process controller 15.In addition, on process controller 15, be connected with user interface 16, the keyboard of the input operation that this user interface 16 is instructed in order to manage high dielectric membrane formation device 10 by the process management person etc., can show visually that the display etc. of the running status of plasma processing apparatus constitutes.
In addition, be connected with the storage part 17 of the scheme of storing on process controller 15, this scheme is to be used for control program that control by process controller 15 is implemented in the various processing that high dielectric membrane formation device 10 carries out, to be used for carrying out the program of handling according to treatment conditions in each structural portion of high dielectric membrane formation device 10.Scheme is stored in the storage medium in the storage part 17.Storage medium both can be hard disk or semiconductor memory, also can be movably medium such as CDROM, DVD, flash memory.In addition, also can for example suitably transmit from other devices via special circuit.
As required, according to accessing scheme arbitrarily from storage part 17, process controller 15 is carried out, thereby under the control of process controller 15, in high dielectric membrane formation device 10, carried out desirable processing from the indication of user interface 16 etc.
Above-mentioned one-tenth film unit 11 has the common structure that uses in this kind film forming is handled, for example can use disclosed structure in TOHKEMY 2004-079753 communique.
In addition, as above-mentioned ultraviolet irradiation unit 12, can use the structure of in Fig. 5 A, Fig. 5 B, representing.Fig. 5 A is the vertical cross-section diagram of expression ultraviolet irradiation unit 12, and Fig. 5 B is a horizontal sectional view.
This ultraviolet irradiation unit 12 has the chamber 21 of rectangular shaped, in chamber 21 below, be provided with the workbench 22 of mounting substrate 1.The bottom of workbench 22 is more outstanding than the diapire of chamber 21, and workbench 22 can be by being provided with motor 23 rotations thereunder.Between the diapire of chamber 21 and workbench 22, be provided with the sealing mechanism 24 of fluid seal etc., when workbench 22 rotations, also can keep the air-tightness in the chamber 21.In workbench 22, be embedded with heater 25, to these heater 25 power supplies, can substrate 1 be heated to the temperature of regulation via workbench 22 by illustrated power supply never.
In the position relative of the roof of chamber 21, be provided with ultraviolet irradiation 26 with workbench 22.This ultraviolet irradiation 26 is provided with 2 ultra-violet lamps 27 that extend along the Width of chamber 21.Be provided with in the mode corresponding at the roof of chamber 21 with this ultra-violet lamp 27 fenestrate 28, from ultra-violet lamp 27 by window 28 to substrate 1 irradiation ultraviolet radiation.
Side at the relative minor face of the sidewall of chamber 21 is provided with 3 gases and imports parts 29.On these gases importing parts 29, be connected with and supply with for example O of oxygen-containing gas 2The gas supply system 30 of gas imports parts 29 from this gas supply system 30 by gas and supply with oxygen-containing gas in chamber 21, is retained as oxygen-containing atmosphere in the chamber 21.
The opposing party of the minor face of the sidewall of chamber 21, be provided with the exhaust outlet 31 of flat in the corresponding mode of allocation position that imports parts 29 with three gases.Be connected with blast pipe 32 at exhaust outlet 31, on this blast pipe 32, be connected with not shown exhaust apparatus with vacuum pump etc., thus, can be to carrying out vacuum exhaust in the chamber 21.
On the long limit of the sidewall of chamber 21, be provided with to be used to move into and take out of moving into of substrate 1 and take out of mouthfuls 33, this is moved into and takes out of mouthfuls 33 and can pass through gate valve 34 switches.
Utilize the high dielectric membrane formation device 10 that constitutes as mentioned above, in order to handle according to said sequence, at first, never illustrated box by load locking room to the carrying room 13 conveyance substrates 1 that remain vacuum.Then, substrate 1 is moved into into film unit 11 by the transport mechanisms 14 in the carrying room 13, then, ALD by using the organic metal raw material or CVD carry out high dielectric film on substrate 1 with the temperature below 350 ℃ film forming.
After film forming, by transport mechanism 14 with substrate 1 from becoming film unit 11 to ultraviolet irradiation unit 12 conveyances.Specifically, open gate valve 34, take out of mouthfuls 33 substrate 1 moved in the chamber 21 from moving into by transport mechanism 14, and be positioned on the workbench 22.Under this state, make to be the oxygen atmosphere of aforesaid low pressure condition in the chamber 21, make workbench 22 rotations by motor 23, and heat by 25 pairs of substrates 1 of heater.So, from the ultra-violet lamp 27 of ultraviolet irradiation 26 to irradiation ultraviolet radiation on the substrate 1 of workbench 22 rotations.Thus, carry out the disengaging of the hydrogen in the high dielectric film.
At this moment preferred condition is for as mentioned above, after the film forming of carrying out high dielectric film, by carrying out ultraviolet irradiation like this, can carry out the disengaging of the hydrogen in the high dielectric film, can prevent that the reliability that remains in the device that causes in the film owing to hydrogeneous composition from reducing.
Then, with reference to the operation sectional view of Fig. 6 A～Fig. 6 E, the example of the manufacturing of the mos semiconductor device of the method for using present embodiment is described.
At first, prepare to be formed with the Si substrate 100 (Fig. 6 A) of element separated region 101.At this moment, the transistor formation portion 102 of the interarea of Si substrate 100 is formed by Si, SiON, SiO etc.
Then, as mentioned above, use the organic metal raw material to form the gate insulating film 103 (Fig. 6 B) that constitutes by high dielectric film by ALD or CVD with the temperature below 350 ℃.Then, to gate insulating film 103 irradiation ultraviolet radiation in the oxygen-containing atmosphere of low pressure that constitutes by such high dielectric film that forms, make the hydrogen in the gate insulating film 103 break away from (Fig. 6 C).
Afterwards, according to method commonly used, on gate insulating film 103, form gate electrode 104 (Fig. 6 D).That is, for example on whole, form the film of gate electrode material such as polysilicon, carry out plasma etching by the resist film of photoetching technique after will be graphical as mask afterwards, thereby form gate electrode 104 by CVD.Afterwards, utilize the formation of side wall oxide film 105 and ion injection etc., form diffusion of impurities zone 106 (Fig. 6 E), obtain the mos semiconductor device.
Then, the experimental result that obtains being used to confirm effect of the present invention describes.
At first, on the Si substrate,, carry out the film forming of HfO film with the thickness of 10nm as high dielectric film.At this moment, use TEMAH, use H as oxidant as raw material 2O carries out film forming by ALD.Temperature during film forming is 250 ℃, and pressure is 60Pa.Then, the HfO film for such film forming gained carries out ultraviolet irradiation.At this moment, the O of 450 ℃ of formation temperatures, pressure 2.7Pa in chamber 2Gas atmosphere was by Xe lamp (wavelength 172nm) irradiation 1 minute.For the HfO film of such formation, measure remaining hydrogen concentration by SIMS.In order to compare, measure remaining hydrogen concentration too for the HfO film that does not carry out this processing.
This result of expression in Fig. 7 A, Fig. 7 B.Fig. 7 A is the situation of carrying out ultraviolet irradiation, the situation of Fig. 7 B for not carrying out ultraviolet irradiation.As shown in the drawing, can confirm that hydrogen concentration is 2.5 * 10 under the situation of not carrying out ultraviolet irradiation 21Atm/cm 3, become 7.0 * 10 by carrying out ultraviolet irradiation 20Atm/cm 3, be reduced to background level (background level).In addition, for irradiation ultraviolet radiation not and at 400 ℃ O 3The HfO film that has carried out under the atmosphere handling is measured hydrogen concentration similarly, and the result is the hydrogen concentration roughly the same with the situation that does not have ultraviolet irradiation, can confirm thus, and hydrogen breaks away from effect and produced by ultraviolet irradiation.
In addition, the present invention is not limited to above-mentioned execution mode, can carry out various distortion.For example, use ultraviolet radiator for ultraviolet irradiation in the above-mentioned execution mode, still be not limited thereto.In addition, though the example that the high dielectric film that will the method by present embodiment forms is applied to gate insulating film represent, also can be applied to capacitor films, and also can be applied to other purposes certainly.Further, represented to apply the present invention to the situation of semiconductor device in the above-described embodiment, but be not limited thereto, for example, also can be suitable for being that the flat-panel monitor (FPD) of representative forms under the situation of high dielectric film in other substrates such as substrates with liquid crystal watch showing device (LCD) with substrate.
Utilizability on the industry
The present invention is applicable to the gate insulating film of mos semiconductor device, the electric capacity of DRAM The formation of device film.

Claims (25)

1. the formation method of a high dielectric film is characterized in that, comprising:
Using the organic metal raw material to form the operation of high dielectric film by ALD or CVD with the temperature below 350 ℃ on the substrate; With
In the oxygen-containing atmosphere of low pressure,, make the operation of the hydrogen disengaging in the film to described high dielectric film irradiation ultraviolet radiation.
2. the formation method of high dielectric film according to claim 1 is characterized in that:
Described high dielectric film is oxide or the silicate of Hf or Zr.
3. the formation method of high dielectric film according to claim 2 is characterized in that:
Described organic metal raw material is the amide-type metallic compound.
4. the formation method of high dielectric film according to claim 1 is characterized in that:
When forming high dielectric film, use H 2O is as oxidant.
5. the formation method of high dielectric film according to claim 1 is characterized in that:
Described ultraviolet irradiation carries out under the pressure of 0.665～665Pa.
6. the formation method of a high dielectric film is characterized in that:
Described ultraviolet irradiation carries out under the state that substrate is heated to the temperature below 500 ℃.
7. the formation method of high dielectric film according to claim 1 is characterized in that:
Described ultraviolet irradiation is at O 2Carry out in the gas atmosphere.
8. the formation method of high dielectric film according to claim 1 is characterized in that:
Described ultraviolet irradiation uses wavelength to carry out as the ultraviolet ray of 172nm.
9. the manufacture method of a semiconductor device, this semiconductor device has high dielectric film as gate insulating film or capacitor films, and the manufacture method of this semiconductor device is characterised in that:
Described high dielectric film forms by the method that comprises following operation:
Using the organic metal raw material to form the operation of high dielectric film by ALD or CVD with the temperature below 350 ℃ on the substrate; With
In the oxygen-containing atmosphere of low pressure,, make the operation of the hydrogen disengaging in the film to described high dielectric film irradiation ultraviolet radiation.
10. the manufacture method of semiconductor device according to claim 9 is characterized in that:
Described high dielectric film is oxide or the silicate of Hf or Zr.
11. the manufacture method of semiconductor device according to claim 10 is characterized in that:
Described organic metal raw material is the amide-type metallic compound.
12. the manufacture method of semiconductor device according to claim 9 is characterized in that:
When forming described high dielectric film, use H 2O is as oxidant.
13. the manufacture method of semiconductor device according to claim 9 is characterized in that:
Described ultraviolet irradiation carries out under the pressure of 0.665～665Pa.
14. the manufacture method of semiconductor device according to claim 9 is characterized in that:
Described ultraviolet irradiation carries out under the state that substrate is heated to the temperature below 500 ℃.
15. the manufacture method of semiconductor device according to claim 9 is characterized in that:
Described ultraviolet irradiation is at O 2Carry out in the gas atmosphere.
16. the manufacture method of semiconductor device according to claim 9 is characterized in that:
Described ultraviolet irradiation uses wavelength to carry out as the ultraviolet ray of 172nm.
17. the manufacture method of a semiconductor device is characterized in that, comprising:
Using the organic metal raw material to form the operation of high dielectric film by ALD or CVD on the semiconductor substrate as gate insulating film with the temperature below 350 ℃;
In the oxygen-containing atmosphere of low pressure,, make the operation of the hydrogen disengaging in the film to described high dielectric film irradiation ultraviolet radiation; With
On described high dielectric film, form the operation of gate electrode.
18. the manufacture method of semiconductor device according to claim 17 is characterized in that:
Described high dielectric film is oxide or the silicate of Hf or Zr.
19. the manufacture method of semiconductor device according to claim 18 is characterized in that:
Described organic metal raw material is the amide-type metallic compound.
20. the manufacture method of semiconductor device according to claim 17 is characterized in that:
When forming described high dielectric film, use H 2O is as oxidant.
21. the manufacture method of semiconductor device according to claim 17 is characterized in that:
Described ultraviolet irradiation carries out under the pressure of 0.665～665Pa.
22. the manufacture method of semiconductor device according to claim 17 is characterized in that:
Described ultraviolet irradiation carries out under the state that substrate is heated to the temperature below 500 ℃.
23. the manufacture method of semiconductor device according to claim 17 is characterized in that:
Described ultraviolet irradiation is at O 2Carry out in the gas atmosphere.
24. the manufacture method of semiconductor device according to claim 17 is characterized in that:
Described ultraviolet irradiation uses wavelength to carry out as the ultraviolet ray of 172nm.
25. a storage medium, it stores in computer and carries out, the program of the formation device of control high dielectric film, it is characterized in that:
Described program in the mode of the formation method of carrying out high dielectric film, makes the formation device of the described high dielectric film of computer control when carrying out, the formation method of described high dielectric film comprises:
Using the organic metal raw material to form the operation of high dielectric film by ALD or CVD with the temperature below 350 ℃ on the substrate; With
The operation that in the oxygen-containing atmosphere of low pressure, the hydrogen in the film is broken away to described high dielectric film irradiation ultraviolet radiation.
CNA200780040077XA 2006-10-27 2007-10-22 Method for forming high dielectric film and method for manufacturing semiconductor device Pending CN101529565A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2006293304A JP2008112762A (en) 2006-10-27 2006-10-27 Method for forming high dielectric film and method for manufacturing semiconductor device
JP293304/2006 2006-10-27

Publications (1)

Publication Number Publication Date
CN101529565A true CN101529565A (en) 2009-09-09

Family

ID=39324505

Family Applications (1)

Application Number Title Priority Date Filing Date
CNA200780040077XA Pending CN101529565A (en) 2006-10-27 2007-10-22 Method for forming high dielectric film and method for manufacturing semiconductor device

Country Status (5)

Country Link
JP (1) JP2008112762A (en)
KR (1) KR101078581B1 (en)
CN (1) CN101529565A (en)
TW (1) TW200832545A (en)
WO (1) WO2008050708A1 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109494302A (en) * 2017-09-12 2019-03-19 松下知识产权经营株式会社 The manufacturing method of capacity cell, imaging sensor and capacity cell
CN109494303A (en) * 2017-09-12 2019-03-19 松下知识产权经营株式会社 The manufacturing method of capacity cell, imaging sensor, the manufacturing method of capacity cell and imaging sensor

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8252653B2 (en) * 2008-10-21 2012-08-28 Applied Materials, Inc. Method of forming a non-volatile memory having a silicon nitride charge trap layer
JP5447632B2 (en) * 2012-11-29 2014-03-19 東京エレクトロン株式会社 Substrate processing equipment
KR102443695B1 (en) 2015-08-25 2022-09-15 삼성전자주식회사 Method of manufacturing semiconductor device

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3228245B2 (en) * 1998-11-13 2001-11-12 日本電気株式会社 Method for producing tantalum oxide film
KR100421219B1 (en) 2001-06-14 2004-03-02 삼성전자주식회사 Method for depositing atomic layer using organometallic complex having β-diketone ligand
KR100520633B1 (en) 2001-06-21 2005-10-11 마츠시타 덴끼 산교 가부시키가이샤 Semiconductor device and its manufacturing method
JP3742906B2 (en) * 2003-05-08 2006-02-08 シャープ株式会社 Manufacturing method of semiconductor device
KR100728962B1 (en) * 2004-11-08 2007-06-15 주식회사 하이닉스반도체 Capacitor of semiconductor device with zrconium oxide and method of manufacturing the same

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109494302A (en) * 2017-09-12 2019-03-19 松下知识产权经营株式会社 The manufacturing method of capacity cell, imaging sensor and capacity cell
CN109494303A (en) * 2017-09-12 2019-03-19 松下知识产权经营株式会社 The manufacturing method of capacity cell, imaging sensor, the manufacturing method of capacity cell and imaging sensor
CN109494303B (en) * 2017-09-12 2024-01-19 松下知识产权经营株式会社 Capacitive element, image sensor, method for manufacturing capacitive element, and method for manufacturing image sensor
CN109494302B (en) * 2017-09-12 2024-04-05 松下知识产权经营株式会社 Capacitive element, image sensor, and method for manufacturing capacitive element

Also Published As

Publication number Publication date
KR101078581B1 (en) 2011-11-01
JP2008112762A (en) 2008-05-15
WO2008050708A1 (en) 2008-05-02
TW200832545A (en) 2008-08-01
KR20090074218A (en) 2009-07-06

Similar Documents

Publication Publication Date Title
US7462571B2 (en) Film formation method and apparatus for semiconductor process for forming a silicon nitride film
JP5626925B2 (en) Method of forming a high dielectric constant gate stack having reduced equivalent oxide thickness
US10707074B2 (en) Method for manufacturing semiconductor device, non-transitory computer-readable recording medium, and substrate processing apparatus
JP6124477B2 (en) Semiconductor device manufacturing method, substrate processing apparatus, and recording medium
US20100062592A1 (en) Method for forming gate spacers for semiconductor devices
US20150162184A1 (en) Method of Manufacturing Semiconductor Device
US20090173979A1 (en) ALD OF AMORPHOUS LANTHANIDE DOPED TiOX FILMS
WO2013035561A1 (en) Semiconductor device manufacturing method and substrate treatment system
CN1672244A (en) Hafnium Aluminum Oxide Dielectric Thin Film
CN107863289B (en) Method for manufacturing semiconductor device, substrate processing apparatus, and storage medium
US8735305B2 (en) Methods of forming fluorinated hafnium oxide gate dielectrics by atomic layer deposition
TW201349343A (en) Semiconductor component manufacturing method and substrate processing system
CN101529565A (en) Method for forming high dielectric film and method for manufacturing semiconductor device
US20130316546A1 (en) Methods of atomic layer deposition of hafnium oxide as gate dielectrics
JP4090346B2 (en) Semiconductor device manufacturing method and substrate processing apparatus
JP6146874B2 (en) Semiconductor device manufacturing method, substrate processing method, substrate processing apparatus, and program
JP3578155B2 (en) Oxidation method of the object
JP2009132961A (en) Film-forming method, film-forming apparatus and storage medium
TWI354711B (en)
US20090233429A1 (en) Semiconductor device manufacturing method and substrate processing apparatus
US7427572B2 (en) Method and apparatus for forming silicon nitride film
JP3639812B2 (en) Etching method and etching apparatus
JP2005159316A (en) Manufacturing method for semiconductor device, film-forming apparatus, and memory medium
JP2011066187A (en) Film formation method and processing system
JP2009088236A (en) Method for forming film, apparatus for forming film, and storage medium

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C12 Rejection of a patent application after its publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20090909