WO2011149615A2 - Appareil et procédé hybride de dépôt chimique en phase vapeur à fil chaud et de dépôt chimique en phase vapeur activé par plasma - Google Patents

Appareil et procédé hybride de dépôt chimique en phase vapeur à fil chaud et de dépôt chimique en phase vapeur activé par plasma Download PDF

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Publication number
WO2011149615A2
WO2011149615A2 PCT/US2011/034091 US2011034091W WO2011149615A2 WO 2011149615 A2 WO2011149615 A2 WO 2011149615A2 US 2011034091 W US2011034091 W US 2011034091W WO 2011149615 A2 WO2011149615 A2 WO 2011149615A2
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WIPO (PCT)
Prior art keywords
reaction zone
substrate
showerhead
filaments
gas
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PCT/US2011/034091
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English (en)
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WO2011149615A3 (fr
Inventor
Annamalai Lakshmanan
Truc T. Tran
Nhon Ly
Izidor Voskoboynik
Dustin W. Ho
Tsutomu Tanaka
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Applied Materials, Inc.
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Publication of WO2011149615A2 publication Critical patent/WO2011149615A2/fr
Publication of WO2011149615A3 publication Critical patent/WO2011149615A3/fr

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    • 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
    • C23C16/24—Deposition of silicon only
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/453—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating passing the reaction gases through burners or torches, e.g. atmospheric pressure CVD
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45563—Gas nozzles
    • C23C16/45565—Shower nozzles
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45587—Mechanical means for changing the gas flow
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/50—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges
    • C23C16/505—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges using radio frequency discharges
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/06—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers
    • H01L31/075—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers the potential barriers being only of the PIN type, e.g. amorphous silicon PIN solar cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/06—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers
    • H01L31/075—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers the potential barriers being only of the PIN type, e.g. amorphous silicon PIN solar cells
    • H01L31/076—Multiple junction or tandem solar cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
    • H01L31/1804—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof comprising only elements of Group IV of the Periodic Table
    • Y—GENERAL 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/547—Monocrystalline silicon PV cells
    • Y—GENERAL 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/548—Amorphous silicon PV cells
    • Y—GENERAL 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • Embodiments of the invention relate to a method and apparatus for forming thin films on a substrate. More specifically, to a method and apparatus for forming thin films employed in photovoltaic devices or solar cells.
  • Photovoltaic (PV) devices or solar cells are devices which convert sunlight into direct current (DC) electrical power.
  • a thin film solar cell includes active regions, or photoelectric conversion units, and a transparent conductive oxide (TCO) film disposed as a front electrode and/or as a back electrode.
  • the photoelectric conversion unit includes a p-type silicon layer, an n- type silicon layer, and an intrinsic type (i-type) silicon layer sandwiched between the p-type and n-type silicon layers.
  • ⁇ -Si microcrystalline silicon film
  • a-Si amorphous silicon film
  • poly-Si polycrystalline silicon film
  • LID light induced degradation
  • a method and apparatus for producing thin films for photovoltaic (PV) devices is described.
  • the method and apparatus as described herein provide high deposition rates as well as provide films which are stable and less susceptible to light induced degradation effects.
  • an apparatus for depositing thin films on a substrate includes a chamber having a showerhead disposed in an opposing relationship to a substrate support, and at least a first gas source and a second gas source in fluid communication with a plurality of discrete reaction zones of the showerhead, the reaction zones comprising a first reaction zone contained in a space between a first side of the showerhead and the substrate support, the first reaction zone in electrical communication with a RF power supply, and a second reaction zone contained within an opposing second side of the showerhead, the second reaction zone being electrically isolated from the first reaction zone.
  • a method for forming a thin film on a substrate includes flowing a first precursor gas to a faceplate of a showerhead, biasing the faceplate to form a plasma in a first reaction zone that is in contact with a first side of the faceplate, wherein the formed plasma contains the first precursor gas, flowing a second precursor gas into a second reaction zone that is in contact with a second side of the showerhead, forming atomic radicals of the second precursor gas in the second reaction zone, and flowing the atomic radicals from the second side of the faceplate to the first side of the faceplate and into the plasma of the first precursor gas.
  • a solar cell is described.
  • the solar cell includes a substrate and a silicon layer covering the substrate, wherein the silicon layer is formed by the process comprising flowing a first precursor gas to a first reaction zone on a first side of a faceplate of a showerhead, forming a plasma of the first precursor gas in the first reaction zone, and flowing atomic radicals formed in a second reaction zone within the showerhead to the first side of the faceplate and into the plasma of the first precursor gas, the second reaction zone being on an opposing second side of the faceplate, wherein the silicon layer contains an SiH 2 content of about 1 % or less.
  • Figure 1 is a schematic cross-sectional view of one embodiment of a processing chamber.
  • Figure 2 is an enlarged view of a portion of the chamber body of the processing chamber of Figure 1.
  • Figure 3 is a plan view of the lid plate along line 3-3 of Figure 2.
  • Figure 4 is a schematic cross-sectional view of one embodiment of a bracket assembly that may be utilized in the processing chamber of Figure 1.
  • Figure 5 is a flowchart showing one embodiment of a thin film deposition method.
  • Figure 6 is a graph showing test results performed using embodiments of the processing chamber as described herein.
  • Figure 7 is a graph showing results of an a-Si deposition process using embodiments of the processing chamber as described herein.
  • Figures 8A-8C show Fourier transform infrared spectroscopy (FTIR) test results on a-Si films produced according to embodiments described herein.
  • FTIR Fourier transform infrared spectroscopy
  • Figure 9A is a schematic diagram of a single junction amorphous or micro-crystalline silicon solar cell that may be formed in the processing chamber of Figure 1.
  • Figure 9B is a schematic diagram of another embodiment of a solar cell that may be formed in the processing chamber of Figure 1.
  • the invention generally provides method and apparatus for forming thin films on a substrate utilizing using a catalytic chemical vapor deposition process combined with a plasma enhanced chemical vapor deposition process.
  • the method and apparatus is effectively utilized to deposit silicon films including microcrystalline silicon (Mc-Si) films, amorphous silicon (a-Si) films and polycrystalline silicon (poly-Si) films.
  • the silicon films may be utilized to form a solar cell or photovoltaic (PV) device for use in a solar module that is used to form a larger solar array for energy production.
  • CHAMBER DESIGN photovoltaic
  • FIG. 1 is a schematic cross-sectional view of one embodiment of a processing chamber 100 that may be utilized to practice embodiments described herein.
  • the processing chamber 100 includes a chamber body 102 comprising a lid assembly 104 disposed on a chamber base assembly 106.
  • the chamber base assembly 106 includes a susceptor or substrate support 108 disposed in an opposing relation to a showerhead assembly 1 10 disposed on the lid assembly 104.
  • the substrate support 108 may be coupled to an actuator 112 adapted to move the substrate support 108 linearly and/or rotationally relative to the showerhead assembly 110.
  • the chamber body 102 is coupled to a radio frequency (RF) power supply 114 to perform a plasma enhanced chemical vapor deposition (PECVD) process on a substrate 116 disposed on the substrate support 108.
  • the substrate support 108 includes a heating element (not shown), such as lamp or resistive heating device, to heat the substrate 116 to a desired temperature.
  • the substrate support 108 may also be coupled to a power supply, such as a direct current (DC) power supply (not shown) to provide electrostatic chucking of the substrate 116.
  • DC direct current
  • the substrate 116 may be a circular or rectangular and have a major side with a surface area available for deposition of about 700 centimeters 2 to about 1 meter 2 or greater, for example about 2 meters 2 to about 5.7 meters 2 , or greater.
  • the substrate 116 may be a silicon substrate, a glass substrate, a polymer substrate, a metal substrate, or other suitable substrate.
  • Chamber body 102 includes exhaust channel 115 at least partially surrounding substrate support 108. Exhaust channel 115 may be coupled to a vacuum pump to provide exhaust and/or negative pressure within the volume contained in the chamber body 102. Examples of a chamber body 102 that may be utilized include the PRODUCER ® chemical vapor deposition (CVD) system as well as the AKT ® PECVD systems available from Applied Materials, Inc., of Santa Clara, California.
  • CVD chemical vapor deposition
  • the processing chamber 100 includes a first gas supply 118A and a second gas supply 1 18B providing processing gases, carrier gases, purge gases, cleaning gases, and combinations thereof to lid assembly 104.
  • First gas supply 118A contains a first gas source 122A and a second gas source 120B that are in fluid communication with lid assembly 104 through a first conduit 121A.
  • Second gas supply 118B contains a third gas source 120A and a fourth gas source 122B that are in fluid communication with lid assembly 104 through a second conduit 121 B.
  • the gases from one or more of the gas sources 122A, 122B, 122A, 122B are delivered through the conduits to a processing zone 124 between the substrate 116 and showerhead assembly 10.
  • the first gas source 122A includes a first precursor gas, such as methane (CH 4 ), trimethylboron (TMB), phosphine (PH 3 ) and silanes, for example monosilane (SiH 4 ) and the second gas source 120B includes a non- reactive gas, such as argon (Ar) or nitrogen (N 2 ).
  • gas from the first gas source 122A and/or second gas source 120B is provided to an intermediate zone 126 within showerhead assembly 1 10.
  • showerhead assembly 110 includes a dual zone faceplate 128 supplying gases from intermediate zone 126 to processing zone 124 while gases from third gas source 120A and/or fourth gas source 122B are provided separately to processing zone 124.
  • Third gas source 120A includes a second precursor gas, such as hydrogen (H 2 ) and the fourth gas source 122B includes a cleaning gas, such as fluorine containing gases, for example nitrogen trifluoride (NF 3 ). Gases from third gas source 120A and/or fourth gas source 122B are provided independently to processing zone 124 through faceplate 128.
  • a second precursor gas such as hydrogen (H 2 )
  • the fourth gas source 122B includes a cleaning gas, such as fluorine containing gases, for example nitrogen trifluoride (NF 3 ).
  • NF 3 nitrogen trifluoride
  • processing chamber 100 is utilized to form thin films on the substrate 116 using a chemical vapor deposition (CVD) process combined with a PECVD Process.
  • intermediate zone 126 is adapted for a catalytic CVD process while processing zone 124 is adapted to form a plasma processing zone in which a PECVD process can be performed.
  • faceplate 128 includes a first major side 129A and a second major side 129B opposing the first major side. The first major side opposes the substrate 116 and contains the processing zone 124 while the second major side contains the intermediate zone 126.
  • intermediate zone 126 of showerhead assembly 1 10 includes one or more filaments 134 coupled to a power supply 136 by connectors 138.
  • Power supply 136 may be an alternating current (AC) or DC power source.
  • power supply 136 is a DC power source, such as a 24 volt, 250 amp DC power source.
  • Radio frequency power supply 114 is coupled to showerhead assembly 110 to form a plasma containing the precursor gases delivered from third gas source 120A and/or fourth gas source 122B.
  • showerhead assembly 110 may be made of conductive materials, such as aluminum, stainless steel, nickel, alloys thereof and combinations thereof.
  • showerhead assembly 1 10 is electrically isolated from chamber body 102 by isolator 130 disposed between showerhead assembly 110 and a lid 132 of chamber body 102.
  • Isolator 130 may be made of quartz, ceramic or other dielectric materials.
  • a first cover 140 is disposed above and coupled to lid assembly 104.
  • the first cover 140 may be made of conductive materials, such as aluminum and is RF hot during operation.
  • a second cover 142 is coupled to lid 132 of chamber body 102 to house the first cover 140. Second cover 142 is grounded and/or at substantially the same electrical potential of the chamber body 102 due to the coupling with lid 132.
  • a RF insulator 144 is disposed between first cover 140 and second cover 142.
  • RF insulator 144 is utilized to isolate RF energy from conduits 121 A, 121 B as well as electrical cables 146A, 146B between connectors 138 and power supply 136.
  • RF insulator 144 comprises a plurality of toroids or rings 148 made of oxides of a metallic material, such as ferrite materials that are disposed around the tubular member 150.
  • the rings 148 function as an RF choke to prevent RF energy from reaching the electrical cables 146A, 146B and ensures the electrical cables 146A, 146B are not affected by RF energy during operation.
  • the rings 148 may also be used to prevent, or inhibit, the delivered RF energy from being transmitted to components external to, and other components within, the processing chamber 100.
  • a tubular member 150 containing electrical cables 146A, 146B and conduits 121 A, 12 B is disposed between first cover 140 and second cover 142. While the electrical cables 146A, 146B are insulated or clad with an insulative material, the RF insulator 144 provides electrical insulation for a majority of the length of the electrical cables 146A, 146B.
  • the tubular member 150 includes a length substantially equal to the distance between first cover 140 and second cover 142 such that about 10 rings 148 may be utilized to surround the tubular member 150 along the length of the tubular member 150. However, the actual number of rings 148 utilized may be based on dimensions (i.e. thickness) of the rings 148 and the length of the tubular member 50.
  • FIG. 2 is an enlarged view of a portion of the chamber body 102 of Figure 1.
  • showerhead assembly 110 includes a body 205 coupled to a lid plate 210.
  • Showerhead assembly 110 contains at least two discrete gas pathways adapted to deliver two separate gases to processing zone 124.
  • Seals 215, such as o-rings may be utilized at the interface between body 205 and lid plate 210 to facilitate the isolation of the intermediate zone 126.
  • a first gas pathway is contained in the lid plate 210 and a portion of the body 205 of showerhead assembly 110 while a second gas pathway is contained primarily in the body 205.
  • First gas pathway includes inlet 220 that provides a fluid path from first gas supply 118A through conduit 121A to a first channel 225A.
  • a perforated plate 228 is utilized as a blocker plate to evenly disperse gases from first channel 225 into intermediate zone 126.
  • Perforated plate 228 is fabricated from or contains a material that is adapted to withstand the elevated temperatures of the filaments 134.
  • perforated plate 228 is made of or contains a nickel containing material.
  • First gas pathway also includes intermediate zone 126 and openings 230 formed in body 205 between intermediate zone 126 and processing zone 124.
  • each opening 230 comprises a tube made of a ceramic material.
  • Second gas pathway includes inlet 235 that provides a fluid path from second gas supply 118B through conduit 121 B, conduit 240 formed in lid plate 210 and conduit 245 formed in body 205 to a second channel 225B formed in body 205.
  • Second channel 225B may be a single channel or multiple channels formed in a circular or linear manner within body 205.
  • Second channel 225B includes openings 250 that provide fluid communication from second channel 225B and processing zone 124.
  • showerhead assembly 110 also includes a cooling plate 255 disposed on lid plate 210.
  • Cooling plate 255 includes a fluid channel 260 in fluid communication with a fluid source 265.
  • Fluid source 265 is contains a fluid, such as deionized water that is circulated through fluid channel 260.
  • fluid source 265 is coupled to a heat exchanger 270 adapted to control the temperature of the fluid provided to fluid channel 260.
  • the temperature of fluid provided to fluid channel 260 is about 65°C to about 85°C, such as about 70°C to about 80°C.
  • FIG 3 is a plan view of the lid plate 210 along line 3-3 of Figure 2.
  • Perforated plate 228 is also shown disposed below filaments 134.
  • Perforated plate 228 includes a plurality of openings 300 adapted to disperse gases.
  • filaments 134 are coupled to the lid plate 210 by bracket assemblies 305.
  • Each bracket assembly 305 includes a clamp arm 310 that supports one or more of the filaments 134.
  • Each bracket assembly 305 is coupled to the lid plate 210 by a rod 315.
  • the rod 315 and clamp arm 310 are made of a conductive material.
  • the filaments 134 may be a wire or tube made of tungsten (W), molybdenum (Mo), tantalum (Ta), alloys thereof and combinations thereof.
  • the clamp arm 310 and rod 315 may be made of a stainless steel material to function as electrical connectors supplying electrical signals to the filaments 134.
  • FIG 4 is a schematic cross-sectional view of one embodiment of a bracket assembly 305, which may be part of the connector 138 ( Figures 1 and 2).
  • Connector 138 includes an insulative tube 400 coupled to a surface of lid plate 210.
  • Insulative tube 400 includes a bore 405 that is sized to receive rod 315.
  • Rod 315 extends through insulative tube 400 and through an opening 410 formed in lid plate 210.
  • Rod 315 is coupled to power supply 136 on one end and to clamp arm 310 on the other end.
  • insulative tube 400 is coupled to lid plate 210 by fasteners 415.
  • lid plate 210 is RF hot and rod 315 is electrically powered by power supply 136, which may be a DC or AC power supply.
  • Insulative tube 400 which may be made of a ceramic material, is utilized to maintain integrity of the RF and DC energy by preventing leakage of DC current and/or RF current.
  • opening 410 is sized to maintain an air gap between lid plate 210 and rod 315, which prevents arcing between surfaces of the showerhead assembly 1 10 and rod 315.
  • FIG. 5 is a flowchart showing one embodiment of a thin film deposition method 500 using the processing chamber 100 as described above.
  • a first precursor gas such as methane (CH 4 ), trimethylboron (TMB), phosphine (PH 3 ) and silanes, for example monosilane (SiH 4 ) is delivered to a faceplate 128 of the showerhead assembly 1 10.
  • the first precursor gas is delivered along a first flow path from the first gas source 122A to second channel 225B and through openings 250 to a first reaction zone (i.e., processing zone 124) on a first side 129A of the faceplate 128.
  • RF power is applied to the showerhead assembly 110 and a plasma of the first precursor gas is formed on the first side of the faceplate 128 above the substrate 116, as shown at 520.
  • a second precursor gas such as hydrogen (H 2 ) is delivered to the faceplate 128 of the showerhead assembly 1 10.
  • the second precursor gas is delivered along a second flow path from the third gas source 120A to first channel
  • the filaments 134 are powered up prior to flowing the first or second precursor gases. In one aspect, the filament temperature is ramped up sequentially in about 100°C increments.
  • power supply 136 voltages were between about 15V to about 26V to provide a temperature of the filaments 134 between about 1500°C to about 2200°C.
  • the second precursor gas ⁇ e.g., H 2
  • the heat exchanger 270 provides fluid to the cooling plate 255 at a temperature of about 70°C to about 78°C to cool the lid plate 210.
  • the lid plate 210 temperature may be maintained between about 70°C to about 78°C during processing.
  • the substrate support 108 is heated to a temperature of about 200°C to about 380°C. Pressures within the chamber body 102 may be maintained between about 266 milliTorr to about 4 Torr. .
  • a cleaning gas such as fluorine containing gases, for example nitrogen trifluoride (NF 3 ) is delivered to the faceplate 128 of the showerhead assembly 110.
  • the cleaning gas is flowed along the first flow path from the fourth gas source 122B to second channel 225B and through openings 250 to a first reaction zone ⁇ i.e., processing zone 124) on a first side of the faceplate 128.
  • RF power is applied to the showerhead assembly 110 and a plasma of the cleaning gas is formed on the first side 129A of the faceplate 128 above the substrate 116.
  • a second gas such as argon (Ar) is flowed to the faceplate 128 of the showerhead assembly 110.
  • the second gas is flowed along the second flow path from the second gas source 120B to first channel 225A, through perforated plate 228 to intermediate zone 126 on the second side 129B of the faceplate 28.
  • the power supply 136 is not utilized to heat the filaments 134.
  • a plasma containing the cleaning gas e.g., NF 3
  • the second gas ⁇ e.g., Ar
  • the chamber 00 is evacuated between cleaning and processing, which prevents reactions in the first conduit 121 A and second conduit 121 B, as well as other portions of the first flow path and the second flow path.
  • FIG. 6 is a graph 600 showing test results performed using the processing chamber 100 as described herein.
  • An etch process on an amorphous carbon containing material was performed on four substrates to determine the concentration of atomic radicals reaching the substrate surface.
  • the etch process was performed in a time period of 5 minutes for each of the four substrates.
  • the process conditions included heating the substrate support to about 350°C and providing a spacing between the substrate support and a lower surface of the faceplate of about 210 mils (5.3 mm).
  • two sets of four filaments (8 filaments 134) were used and heated to about 1800°C using the DC power source 136.
  • hydrogen gas was flowed at a rate of about 1500 standard cubic centimeters per minute (seem). During the test, no other precursor gas was provided other than hydrogen and the RF power source was not used.
  • Line 605 indicates a control substrate where the DC power source 136 was powered off and the filaments were cold as hydrogen flowed past them. After testing the control substrate, the filaments were heated to about 1800°C for the remaining three substrates.
  • Line 610 indicates an etch rate at a pressure of about 4 Torr.
  • Line 615 indicates an etch rate at a pressure of about 2 Torr.
  • Line 620 indicates an etch rate at a pressure of about 266 milliTorr.
  • Line 615 (2 Torr) indicates the highest etch rate, thus illustrating the effectiveness of using the heated filaments to improve the reactivity of the flowing processing gases, which in this case was hydrogen.
  • FIG. 7 is a graph 700 showing results of an a-Si deposition process on six substrates 705-730 with varied temperatures of the filaments 134.
  • Process conditions included heating the substrate support to about 210°C and providing a spacing between the substrate support and a lower surface of the faceplate 128 of about 640 mils (16.3 mm).
  • the interior of the chamber body 102 was maintained at a pressure of about 2.5 Torr.
  • hydrogen gas was flowed at a rate of about 1250 seem while SiH 4 was flowed at about 60 seem.
  • RF energy was provided at about 50 Watts from a 13.56 MHz RF power supply 114 while the power from power supply 136 was varied to change the temperature of the filaments 134.
  • the temperature of the filaments 134 is shown on the X axis of the graph.
  • Substrate 705 shows a deposition rate of about 258 A/min when the filaments 134 were not powered and the lid assembly 104 was maintained at a temperature of about 75°C.
  • Substrate 710 shows a slightly higher deposition rate as the temperature of the filaments 134 was increased to about 1500°C.
  • Substrates 715-725 show further increases in film thickness as the temperature of the filaments was increased.
  • Substrate 730 shows about a 14 % increase in film thickness when the temperature of the filaments was increased to about 2 00°C, thus showing an improvement in the deposition rate of the process.
  • thin films utilized in PV devices are susceptible to light induced degradation (LID) which decreases the efficiency and/or carrier lifetime in the formed PV device.
  • LID light induced degradation
  • prolonged exposure of the PV device to sunlight and/or heat causes restructuring of the atoms in the film layers contained within the PV device.
  • the hydrogen bonds within the films may break down and create carrier traps, which decreases the efficiency of the PV device.
  • the reconfiguration of the hydrogen bonding in a formed thin film silicon device is believed to be one of the leading causes of LID in both single junction PV devices and tandem junction PV devices.
  • high order silanes include SiH 2 as well as polymerized silicon molecules that appear as H-Si-H bonds in the deposited film. It is believed that the high order silanes in the formed film layers cause the deposited film to be unstable, which can cause the film to degrade with exposure to sunlight.
  • silicon polymerization is suppressed by the gas phase reaction of hydrogen (H 2 ) with the filaments 134, and a SiH 4 gas disposed in a plasma formed in the processing zone 124.
  • FIG. 8A is a graph 800 showing Fourier transform infrared spectroscopy (FTIR) test results on a-Si films deposited on four substrates 805-820 utilizing different temperatures of the filaments 134.
  • the filaments 134 comprise a tungsten containing material.
  • silane (SiH ) was delivered to processing zone 124 at a flow rate of about 60 seem.
  • RF power was applied at about 50 Watts to form a plasma.
  • Hydrogen (H 2 ) gas was delivered to the intermediate zone 126 at a flow rate of about 1250 seem.
  • Pressure within the chamber body 102 was maintained at about 2.5 Torr and the substrate support 108 was heated to about 210°C.
  • the temperature of the lid assembly 104 was maintained at a temperature of about 75°C.
  • a film was deposited on substrate 805 while no power was delivered to the filaments 134. Thus, hydrogen gas was not catalyzed in the test of substrate 805. Films were deposited on substrates 810-820 as the temperature of the filaments 134 was increased while the temperature of the lid assembly 104 was maintained at about 75°C. Sampling included testing of the film on two regions of each substrate 805-820. A first region included a geometrical center of each substrate 805-820 while the second region included testing of the film at about 1 ⁇ 2 of the radius of each substrate 805-820.
  • Figure 8B is a graph 825 showing the intensity versus wavemember data for substrate 805 while Figure 8C is a graph 830 showing the intensity versus wavemember data for substrate 820.
  • the graphs 800, 825 and 830 show a decrease of high order silanes in the deposited film of about 66% when the temperature of the filaments 134 are increased. Further testing showed films having the lowest percentage SiH 2 were obtained when the temperature of the filaments 134 was about 1966°C, or greater. Additionally, photoresponse of the PV devices was shown to increase with the increase in the temperature of the filaments 134. [0046] Other tests were performed but are not shown for brevity. Substrates were tested in light soaking simulators to determine cell efficiency of single junction solar cells. The light soaking simulator included lighting devices adapted to simulate energy of 1 kilowatt/square meter (roughly equivalent to one (1) sun).
  • a first substrate included a single junction solar cell formed by a PECVD process with a SiH 4 to hydrogen ratio of 1 :20 while the filaments were "off such that hydrogen was not catalyzed.
  • a second substrate included a single junction solar cell formed by a SiH 4 to hydrogen ratio of 1 :20 with the temperature of the filaments maintained at about 1800°C.
  • the first substrate contained about a 3% content of high order silanes while the second substrate contained about a 1% content of high order silanes.
  • Each of the first substrate and second substrate was light soaked for about 1000 hours.
  • the second substrate showed an increase in solar cell efficiency of about 0.5% as compared to the first substrate. Further, tests were performed to correlate higher LID percentages with the percentage of high order silanes within the single junction devices.
  • the LID was shown to decrease by about 10% in the second substrate as compared to about 15% for the first substrate.
  • lowering high order silanes in the film leads to lower LID and the films deposited utilizing the filaments 134 and the power supply 136 show less degradation.
  • Figure 9A is a simplified schematic diagram of a single junction amorphous or micro-crystalline silicon solar cell 900 that may be formed in the processing chamber 100 of Figure 1.
  • the single junction amorphous or micro-crystalline silicon solar cell 900 is oriented toward a light source or solar radiation 901.
  • the solar cell 900 generally comprises a substrate 902, such as a glass substrate, polymer substrate, metal substrate, or other suitable substrate, with thin films formed thereover.
  • the substrate 902 is a glass substrate that is about 2200mm x 2600mm x 3mm in size.
  • the solar cell 900 further comprises a first transparent conducting oxide (TCO) layer 910 (e.g., zinc oxide (ZnO), tin oxide (SnO)) formed over the substrate 902, a first p-i-n junction 920 formed over the first TCO layer 910, a second TCO layer 940 formed over the first p-i-n junction 920, and a back contact layer 950 formed over the second TCO layer 940.
  • TCO transparent conducting oxide
  • ZnO zinc oxide
  • SnO tin oxide
  • the substrate and/or one or more of the thin films formed thereover may be optionally textured by wet, plasma, ion, and/or mechanical processes.
  • the first TCO layer 910 is textured, and the subsequent thin films deposited thereover generally follow the topography of the surface below it.
  • the first p-i-n junction 920 may comprise a p-type amorphous silicon layer 922, an intrinsic type amorphous silicon layer 924 formed over the p-type amorphous silicon layer 922, and an n-type amorphous silicon layer 926 formed over the intrinsic type amorphous silicon layer 924.
  • the p-type amorphous silicon layer 922 may be formed to a thickness between about 60A and about 300A
  • the intrinsic type amorphous silicon layer 924 may be formed to a thickness between about 1 ,500A and about 3.500A
  • the n-type amorphous semiconductor layer 926 may be formed to a thickness between about 100A and about 500A.
  • the back contact layer 950 may include, but is not limited to a material selected from the group consisting of Al, Ag, Ti, Cr, Au, Cu, Pt, alloys thereof, and combinations thereof.
  • FIG. 9B is a schematic diagram of an embodiment of a solar cell 900 that may be formed in the processing chamber 100 of Figure 1.
  • the solar cell 900 is a multi-junction solar cell that is oriented toward the light or solar radiation 901.
  • the solar cell 900 comprises a substrate 902, such as a glass substrate, polymer substrate, metal substrate, or other suitable substrate, with thin films formed thereover.
  • the solar cell 900 may further comprise a first transparent conducting oxide (TCO) layer 910 formed over the substrate 902, a first p-i-n junction 920 formed over the first TCO layer 910, a second p-i-n junction 930 formed over the first p-i-n junction 920, a second TCO layer 940 formed over the second p-i-n junction 930, and a back contact layer 950 formed over the second TCO layer 940.
  • TCO transparent conducting oxide
  • the first TCO layer 910 is textured, and the subsequent thin films deposited thereover generally follow the topography of the surface below it.
  • the first p-i-n junction 920 may comprise a p-type amorphous silicon layer 922, an intrinsic type amorphous silicon layer 924 formed over the p- type amorphous silicon layer 922, and an n-type microcrystalline silicon layer 926 formed over the intrinsic type amorphous silicon layer 924.
  • the p- type amorphous silicon layer 922 may be formed to a thickness between about 60A and about 300A
  • the intrinsic type amorphous silicon layer 924 may be formed to a thickness between about 1 ,500A and about 3,500A
  • the n-type microcrystalline semiconductor layer 926 may be formed to a thickness between about 100A and about 400A.
  • the second p-i-n junction 930 may comprise a p-type microcrystalline silicon layer 932, an intrinsic type microcrystalline silicon layer 934 formed over the p-type microcrystalline silicon layer 932, and an n-type amorphous silicon layer 936 formed over the intrinsic type microcrystalline silicon layer 934.
  • the p-type microcrystalline silicon layer 932 may be formed to a thickness between about 100A and about 400A
  • the intrinsic type microcrystalline silicon layer 934 may be formed to a thickness between about 10,000A and about 30,000A
  • the n- type amorphous silicon layer 936 may be formed to a thickness between about 100A and about 500A.
  • the back contact layer 950 may include, but is not limited to a material selected from the group consisting of Al, Ag, Ti, Cr, Au, Cu, Pt, alloys thereof, and combinations thereof.
  • one or more of the layers used to form one or more layers in a thin film, or crystalline, silicon solar cell device, such as solar cell 900A or 900B is formed by flowing a first processing gas (e.g. , H 2 ) across the heated filaments 134, which are disposed in the intermediate zone 126.
  • the first processing gas is catalyzed by interaction with the filaments 134 and atomic radicals of the first processing gas is delivered into the processing zone 124.
  • a RF plasma is formed over a substrate using the first processing gas and a second processing gas (e.g., silane).
  • an intrinsic amorphous silicon layer (i-type a- Si layer) is formed by flowing hydrogen (H 2 ) across about 8 filaments 134 maintained at a temperature between about 1600 °C and about 2400 °C and into the processing zone 124 in which a plasma is formed by delivering between about 10 Watts and 1 ,000 Watts of RF energy at a frequency of 13.56 MHz.
  • silane (SiH 4 ) is delivered to processing zone 124 at a flow rate of about 10 seem to about 500 seem while hydrogen (H 2 ) is delivered to intermediate zone 126 at a flow rate of about 50 seem to about 3,000 seem.
  • the spacing between faceplate 128 and substrate support 108 is maintained at about 200 mils (5.08 mm) to about 1 ,600 mils (40.6 mm).
  • the pressure is maintained between about 1 Torr and about 15 Torr, and the temperature of the substrate support 108 was maintained between about 150 °C and about 300 °C to achieve a deposition rate between about 100 angstroms per minute (A/min) and about 1 ,200 A/min on a substrate having a surface area of about 70,650 square millimeters (mm 2 ).
  • a method and apparatus for producing thin films for solar cells or PV devices is described.
  • the method and apparatus as described herein provide high deposition rates as well as provide films which are stable and less susceptible to LID effects.
  • the apparatus includes a chamber having a dual channel faceplate containing two discrete gas paths and reaction zones.
  • the method includes catalytically reacting a first precursor to provide atomic radicals to a plasma of a second precursor in order to reduce the percentage of high order silanes in the deposited film.
  • the reduction of high order silanes has been shown to decrease LID effects, which increases the efficiency and lifetime of the PV devices.
  • the first reaction zone includes a hotwire CVD apparatus.
  • chamber surfaces may be cleaned utilizing fluorine containing compounds, which may not be possible in conventional hotwire CVD apparatus due to the reaction of cleaning gases with filament materials.
  • embodiments described herein produce films with an increased deposition rate and increased stability, which increases throughput and increases robustness of the PV devices.
  • Embodiments described herein may be utilized for oxide removal (e.g., copper oxide) prior to barrier layer deposition.
  • the hybrid hotwire PECVD system described herein may be utilized to enhance deposition rates and film quality in blanket film deposition for interlayer dielectrics as well as coatings formed by CVD and/or PECVD for a variety substrates, such as glass, silicon, metal, metal oxides, among others.

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Abstract

La présente invention concerne un procédé et un appareil permettant de fabriquer des films minces pour dispositifs photovoltaïques (PV). Dans un mode de réalisation, la présente invention concerne un appareil permettant de déposer des films minces sur un substrat. Ledit appareil comprend une enceinte comportant une douchette disposée à l'opposé d'un support de substrat et au moins une première source de gaz et une seconde source de gaz en communication fluidique avec une pluralité de zones réactionnelles discrètes de ladite douchette, lesdites zones réactionnelles correspondant à une première zone réactionnelle enfermée dans un espace situé entre un premier côté de la douchette et le support du substrat, ladite première zone réactionnelle étant en communication électrique avec une source d'alimentation en énergie radioélectrique, et à une seconde zone réactionnelle enfermée à l'intérieur d'un second côté opposé de la douchette, ladite seconde zone réactionnelle étant isolée d'un point de vue électrique de la première zone réactionnelle.
PCT/US2011/034091 2010-05-24 2011-04-27 Appareil et procédé hybride de dépôt chimique en phase vapeur à fil chaud et de dépôt chimique en phase vapeur activé par plasma WO2011149615A2 (fr)

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JPWO2017203751A1 (ja) * 2016-05-23 2019-03-22 株式会社カネカ 太陽電池及びその製造方法、並びに太陽電池パネル
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JP2019533085A (ja) * 2016-10-04 2019-11-14 コブス エスアエス 化学蒸着反応器の中にガスを搬送するための装置
WO2022087145A1 (fr) * 2020-10-23 2022-04-28 Applied Materials, Inc. Chambre de traitement de semi-conducteur destinée à recevoir une formation de plasma parasite
US11615973B2 (en) 2014-11-26 2023-03-28 Applied Materials, Inc. Substrate carrier using a proportional thermal fluid delivery system

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CN109004065B (zh) * 2018-07-27 2019-11-29 浙江晶科能源有限公司 一种提高n型双面电池效率的方法

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JPWO2017203751A1 (ja) * 2016-05-23 2019-03-22 株式会社カネカ 太陽電池及びその製造方法、並びに太陽電池パネル
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