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WO2003083953A1 - Solar cell and method of manufacturing the same - Google Patents

Solar cell and method of manufacturing the same Download PDF

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Publication number
WO2003083953A1
WO2003083953A1 PCT/JP2003/002474 JP0302474W WO03083953A1 WO 2003083953 A1 WO2003083953 A1 WO 2003083953A1 JP 0302474 W JP0302474 W JP 0302474W WO 03083953 A1 WO03083953 A1 WO 03083953A1
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WIPO (PCT)
Prior art keywords
silicon layer
solar cell
containing carbon
silicon
monocrystalline
Prior art date
Application number
PCT/JP2003/002474
Other languages
French (fr)
Inventor
Takahiro Mishima
Naoki Ishikawa
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Ebara Corporation
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Publication date
Application filed by Ebara Corporation filed Critical Ebara Corporation
Priority to AU2003210011A priority Critical patent/AU2003210011A1/en
Publication of WO2003083953A1 publication Critical patent/WO2003083953A1/en

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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F71/00—Manufacture or treatment of devices covered by this subclass
    • H10F71/121—The active layers comprising only Group IV materials
    • H10F71/1215—The active layers comprising only Group IV materials comprising at least two Group IV elements, e.g. SiGe
    • H10F71/1218—The active layers comprising only Group IV materials comprising at least two Group IV elements, e.g. SiGe in microcrystalline form
    • 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
    • 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
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02367—Substrates
    • H01L21/0237—Materials
    • H01L21/02373—Group 14 semiconducting materials
    • H01L21/02381—Silicon, silicon germanium, germanium
    • 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
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02518—Deposited layers
    • H01L21/02521—Materials
    • H01L21/02524—Group 14 semiconducting materials
    • H01L21/02529—Silicon carbide
    • 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
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02518—Deposited layers
    • H01L21/02521—Materials
    • H01L21/02524—Group 14 semiconducting materials
    • H01L21/02532—Silicon, silicon germanium, germanium
    • 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
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02518—Deposited layers
    • H01L21/0257—Doping during depositing
    • H01L21/02573—Conductivity type
    • H01L21/02576—N-type
    • 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
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02518—Deposited layers
    • H01L21/0257—Doping during depositing
    • H01L21/02573—Conductivity type
    • H01L21/02579—P-type
    • 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
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02518—Deposited layers
    • H01L21/02587—Structure
    • 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
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02612—Formation types
    • H01L21/02617—Deposition types
    • H01L21/0262—Reduction or decomposition of gaseous compounds, e.g. CVD
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F10/00—Individual photovoltaic cells, e.g. solar cells
    • H10F10/10—Individual photovoltaic cells, e.g. solar cells having potential barriers
    • H10F10/16—Photovoltaic cells having only PN heterojunction potential barriers
    • H10F10/164—Photovoltaic cells having only PN heterojunction potential barriers comprising heterojunctions with Group IV materials, e.g. ITO/Si or GaAs/SiGe photovoltaic cells
    • H10F10/165—Photovoltaic cells having only PN heterojunction potential barriers comprising heterojunctions with Group IV materials, e.g. ITO/Si or GaAs/SiGe photovoltaic cells the heterojunctions being Group IV-IV heterojunctions, e.g. Si/Ge, SiGe/Si or Si/SiC photovoltaic 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
    • Y02E10/547—Monocrystalline silicon PV cells

Definitions

  • the present invention relates to a solar cell, and more particularly to a heterojunction solar cell including a junction of semiconductors having different band gaps .
  • the present invention also relates to a method of manufacturing such a solar cell.
  • a general solar cell has a structure in which a p-n junction is formed by doping amorphous silicon with impurities.
  • This type of solar cell i.e., an amorphous silicon solar cell, is suitable for mass production and can be manufactured at a relatively low cost.
  • the amorphous silicon solar cell has relatively low efficiency of generating electric power.
  • heterojunction solar cell in which semiconductors having different band gaps are jointed to each other.
  • the heterojunction solar cell has a junction formed by a combination of silicon and a semiconductor film such as SiC having a band gap wider than silicon.
  • Such a heterojunction solar cell is expected to have a higher efficiency of generating electric power .
  • a material having a different band gap is deposited on an amorphous silicon film by plasma CVD or electron cyclotron resonance (ECR) CVD.
  • ECR electron cyclotron resonance
  • the conventional manufacturing method of a heterojunction solar cell has been disadvantageous in view of productivity and manufacturing cost because of its low deposition rate and an extremely expensive apparatus being required.
  • a solar cell comprising a monocrystalline or polycrystalline silicon layer and a silicon layer containing carbon.
  • the silicon layer containing carbon is formed on the monocrystalline or polycrystalline silicon layer by hot-wire CVD.
  • the silicon layer containing carbon should preferably have a fine crystalline silicon column therein.
  • the silicon layer containing carbon should preferably have a high conductivity.
  • the silicon layer containing carbon may comprise a p-type silicon layer having a conductivity ranging from about 5xl0 ⁇ 6 S/cm to about 5x10° S/cm.
  • the silicon layer containing carbon comprises an n-type silicon layer having a conductivity ranging from about 5xl0 "6 S/cm to about ⁇ xlO 1 S/cm.
  • the silicon layer containing carbon may comprise a high hydrogen concentration layer at an interface with the monocrystalline or polycrystalline silicon layer.
  • the hydrogen concentration layer should preferably have a hydrogen concentration ranging from 6 at % to 24 at %.
  • the silicon layer containing carbon is formed on the monocrystalline or polycrystalline silicon layer by hot-wire CVD.
  • the solar cell is formed as a heterojunction solar cell, it has good electric characteristics, e.g., a high open-circuit voltage, a high short-circuit current, and high conversion efficiency.
  • the silicon layer containing carbon is formed by hot-wire CVD , it is possible to manufacture a solar cell having a good-quality film with relatively high productivity.
  • FIG. 1 is a schematic view showing an arrangement of a solar cell according to a first embodiment of the present invention
  • FIG. 2 is a schematic view showing microcrystalline silicon columns in a silicon layer of the solar cell shown in
  • FIG. 1; FIG. 3A is a schematic view showing a hot-wire CVD apparatus according to an embodiment of the present invention
  • FIG . 3B is a schematic view showing a plasma CVD apparatus ; and FIG. 4 is a schematic view showing an arrangement of a solar cell according to a second embodiment of the present invention.
  • FIG. 1 shows a solar cell according to a first embodiment of the present invention.
  • the solar cell has a monocrystalline or polycrystalline silicon substrate 11 and a silicon layer 12 containing carbon therein.
  • the silicon layer 12 is formed by hot-wire CVD and adhered to an upper surface of the silicon substrate 11.
  • the solar cell according to the present embodiment comprises a heterojunction solar cell.
  • the monocrystalline or polycrystalline silicon substrate 11 should preferably be formed of a dendritic web (ribbon crystal) having a thickness of 150 ⁇ m or less , for example .
  • the monocrystalline or polycrystalline silicon substrate 11 can be produced as follows. A silicon material is melted in a crucible maintained at a predetermined temperature. A seed crystal is pulled up along a crystal axis of a predetermined orientation from the crucible to grow a thin ribbon-like
  • the silicon substrate 11 may comprise a monocrystalline silicon substrate having an orientation of ⁇ 100>.
  • the monocrystalline silicon substrate may be doped into an n-type semiconductor and have a resistivity of 2 ⁇ cm, for example.
  • the silicon layer 12 containing carbon is formed on the silicon substrate 11 by hot-wire CVD.
  • the silicon layer 12 is made of amorphous silicon carbide (a-SiC) containing microcrystalline silicon ( ⁇ c-Si) therein. Specifically, the silicon layer 12 is formed as a conductive film having a hetero-structure in which a-SiC and ⁇ c-Si are mixed with each other.
  • the silicon layer 12 containing carbon has a thickness ranging from about 1 nm to about 50 nm.
  • the silicon layer 12 is doped with impurities into an opposite type (e.g. , p-type) of the silicon substrate 11. Thus, a p-n junction is formed between the silicon substrate 11 and the silicon layer
  • the silicon layer 12 containing carbon has microcrystalline silicon columns 12b which are formed by columnar crystals of fine silicon.
  • the microcrystalline silicon columns 12b are present in the silicon layer (SiC layer) 12 containing amorphous carbon.
  • the microcrystalline silicon columns 12b are formed by columnar crystals perpendicular to a surface to be deposited.
  • Each of the microcrystalline silicon columns 12b has a diameter ranging from about 1 nm to 50 nm, typically from 10 nm to 20 nm.
  • the microcrystalline silicon columns 12b have a high conductivity as compared to the amorphous SiC layer present therearound.
  • the amount of the microcrystalline silicon columns 12b contained in the silicon layer 12 can be adjusted in a range of from about 0.1 volume % to about 80 volume % to adjust the conductivity of the silicon layer 12.
  • the amount of carbon in the silicon layer 12 can be adjusted in a wide range, for example, in a range of from about 0.1 volume % to about 70 volume %. The amount of carbon largely affects the conductivity of the silicon layer 12.
  • the amounts of the microcrystalline silicon columns 12b and carbon are adjustable in the silicon layer 12. Further, the concentrations of doping materials are adjustable. Therefore, the conductivity of the silicon layer 12 and an effective band gap can be adjusted within wide ranges .
  • the conductivity can be adjusted in a range of from about 5xl0 -6 to about 5x10° (S/cm) , and an effective band gap can be adjusted in a range of from about 1.7 to about 2.6 eV.
  • the silicon layer 12 of the heterojunction solar cell can be formed so as to have a high conductivity, and it is possible to improve the efficiency of generating electric power and electric characteristics such as short-circuit currents and open-circuit voltages.
  • the hot-wire CVD apparatus has a gas supply device 21 for supplying gases, a high-temperature hot wire 22, and a substrate holder 24 for holding a substrate 23 to be processed. These components are housed in a vacuum chamber capable of being depressurized.
  • the high-temperature hot wire 22 is used to form a CVD film on a surface of the substrate 23 by heating and activating the gases supplied from the gas supply device 21.
  • the hot wire 22 comprises a wire made of tungsten, molybdenum, or the like, which is heated to a temperature ranging from 1500 to 2400 °C.
  • the hot-wire CVD apparatus has basically the same structure as a known catalytic CVD apparatus .
  • the term "hot wire" means a heated wire.
  • the hot wire may have a two- dimensional shape such as a sheet, or a three-dimensional shape.
  • a plasma CVD apparatus is shown in FIG. 3B.
  • the plasma CVD apparatus has electrodes 25 and 26 and a high frequency power supply 27 for applying a high frequency voltage between the electrodes 25 and 26.
  • gas molecules 28 to be deposited are formed into a plasma and vibrated in directions shown by arrows in FIG. 3B .
  • a CVD film is deposited on a surface of a substrate 23 to be processed.
  • the hot-wire CVD apparatus shown in FIG. 3A causes almost no damage to a substrate by a plasma, has a simpler and less expensive structure, and can easily be made larger in size as compared to the plasma CVD apparatus shown in FIG. 3B .
  • the hot-wire CVD apparatus can achieve a relatively high deposition rate of 5 to 10 nm/sec, for example, and produce a high-quality film of an amorphous silicon film or a microcrystalline silicon film in a relatively short time.
  • the silicon layer 12 includes a high hydrogen concentration p-type layer 12a disposed at a lower portion thereof, and a p-type layer 12c disposed at an upper portion thereof.
  • a high hydrogen concentration p-type layer is produced from gases mixed in the following ratio .
  • B 2 H 6 0.002
  • the hot wire 22 is adjusted at a temperature of 2100 °C
  • the substrate is adjusted at a temperature of 150 °C. Reaction occurs under a pressure of 10 Pa.
  • the substrate has a film thickness of 5 nm.
  • the concentration of hydrogen contained in the high hydrogen concentration p-type layer 12a is at least 6 at % (atomic %) .
  • the p-type layer 12c is formed on an upper surface of the high hydrogen concentration p-type layer 12a.
  • such a p-type layer is produced from gases mixed in the following ratio .
  • the hot wire 22 is adjusted at a temperature of 2100°C, and the substrate is adjusted at a temperature of 250°C. Reaction occurs under a pressure of 10 Pa.
  • the substrate has a film thickness of 15 nm.
  • a high hydrogen concentration silicon layer (N + layer) 11a is formed on a rear face of the silicon substrate 11 by hot-wire CVD.
  • a high hydrogen concentration silicon layer is produced from gases mixed in the following ratio .
  • the hot wire 22 is adjusted at a temperature of 1800 °C, and the substrate is adjusted at a temperature of 200 °C. Reaction occurs under a pressure of 10 Pa.
  • the substrate has a film thickness of 20 nm.
  • An antireflection film 15 is formed on an upper surface of the silicon layer 12 containing carbon.
  • the antireflection film 15 comprises an ITO film and has a thickness of about 0.05 ⁇ m.
  • Surface electrodes 16 of aluminum are deposited on the antireflection film 15.
  • the surface electrodes 16 have thicknesses of about 3 ⁇ m.
  • an electrode 13 of aluminum is deposited on a rear face of the silicon substrate 11.
  • the electrode 13 has a thickness of about 5 ⁇ m.
  • FIG. 4 shows a solar cell according to a second embodiment of the present invention.
  • the solar cell in the second embodiment has basically the same structure as the solar cell in the first embodiment.
  • the solar cell in the second embodiment differs from the solar cell in the first embodiment in that the solar cell in the second embodiment has a p-type monocrystalline or polycrystalline silicon substrate 11, and a silicon layer 12 containing carbon is doped into an n-type with impurities.
  • PH 3 is used as a doping gas.
  • the conductivity of the silicon layer 12 can be adjusted in a range of from about 5 ⁇ l0 ⁇ 6 to about ⁇ xlO 1 (S/cm) .
  • an electrode 13 formed on a rear face of the silicon substrate 11 comprises a Ti/Pd/Ag layer.
  • SiH 4 , Si 2 H 6 , or the like is used as a silicon material gas
  • CH 4 , C 2 H 4 , C 2 H 2 , or the like is used as a carbon material gas.
  • PH 3 , B 2 H 6 , or the like is used as a doping gas for doping silicon with n-type or p-type impurities.
  • These material gases are activated by catalytic decomposing effect of a hot wire in a hot-wire CVD apparatus to form a conductive film having a columnar hetero-structure of a-SiC/ ⁇ c-Si on the silicon substrate 11.
  • the silicon layer 12 containing carbon has a wide band gap of about 2 eV.
  • the solar cell has a heterojunction between the silicon layer 12 and the silicon substrate 11.
  • a number of interface state levels have generally been formed near a surface of the silicon substrate.
  • hydrogen passivation can effectively be performed on a surface of the substrate 11 without any damage to the substrate 11, so that defective interface state levels can be reduced at bulk (interior of the substrate) and interface (surface of the substrate) .
  • the concentration of hydrogen should preferably be in a range of 6 to 24 at %, more preferably at least 8 at % .
  • SiH 4 is used as a material gas containing silicon, CH 4 as a material gas containing carbon, PH 3 or B 2 H 6 as a doping gas for impurities, and H 2 gas as a dilution gas.
  • a ratio of the carbon material gas to the material gases i.e., CH 4 / (SiH 4 +CH 4 )
  • a dilution ratio of the H 2 gas i.e., H 2 / (SiH 4 +CH 4 )
  • a ratio of a p-type doping gas to the material gases i.e.,
  • B 2 H 6 / (SiH 4 +CH 4 ) should preferably be in a range of about 0.001 % to about 1 % .
  • a ratio of an n-type doping gas to the material gases, i.e. , PH 3 / (SiH 4 +CH 4 ) should preferably be in a range of from about 0.001 % to about 1 %.
  • the hot-wire CVD apparatus described above was operated under the following conditions .
  • Temperature of hot wire (of tungsten or molybdenum) 1750 - 2400°C
  • the conductivity in a direction parallel to a deposition surface of a high hydrogen concentration p-type layer which had a hydrogen concentration more than 8 at % , was in a range of from 5 ⁇ l0 -6 to 5x10° (S/cm) .
  • the conductivity in a direction parallel to a deposition surface of a p-type layer was in a range of from 5 ⁇ l0 -6 to ⁇ xlO 1 (S/cm) .
  • the carbon concentration in the film was in a range of from 0.1 to 60 at % , and a microcrystalline silicon was deposited at a carbon concentration of 42 at % or less.
  • the deposited microcrystalline silicon had a diameter ranging from 1 to 50 nm.
  • a crystallization rate was in a range of from 60 to 90 % according to measurement with Raman spectroscopy .
  • a rate of hydrogen concentration in the film was in a range of from 2 to 24 at %.
  • An optically measured band gap was in a range of from 1.9 to 2.6 eV, which was measured for silicon layers 12 having carbon contents of about 30 to 40 volume %.
  • the solar cell in this example had a conversion efficiency of 12.2 % , which was improved from 10.8%, a short-circuit current density of 30.1 mA/cm 2 , which was improved from 27.8 mA/cm 2 , and an open-circuit voltage of 0.55 mV, which was improved from 0.54 mV.
  • a conductive film having a columnar hetero-structure of a-SiC/ ⁇ c-Si which is formed by hot-wire CVD may be applicable not only to a solar cell, but also to devices such as thin- film transistors (TFT) in display devices.
  • the present invention is suitable for use in a heterojunction solar cell including a junction of semiconductors having different band gaps .

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Abstract

A solar cell has a monocrystalline or polycrystalline silicon layer (11) and a silicon layer (12) containing carbon. The silicon layer (12) containing carbon is formed on the monocrystalline or polycrystalline silicon layer (11) by hot-wire CVD. The silicon layer (12) containing carbon has a fine crystalline silicon column (12b) therein. The silicon layer (12) containing carbon has a high conductivity. The silicon layer (12) containing carbon has a high hydrogen concentration layer (12a) at an interface with the monocrystalline or polycrystalline silicon layer (11).

Description

DESCRIPTION
SOLAR CELL AND METHOD OF MANUFACTURING THE SAME
Technical Field
The present invention relates to a solar cell, and more particularly to a heterojunction solar cell including a junction of semiconductors having different band gaps . The present invention also relates to a method of manufacturing such a solar cell.
Background Art
A general solar cell has a structure in which a p-n junction is formed by doping amorphous silicon with impurities. This type of solar cell, i.e., an amorphous silicon solar cell, is suitable for mass production and can be manufactured at a relatively low cost. However, the amorphous silicon solar cell has relatively low efficiency of generating electric power.
There has been known another solar cell in which a p-n junction is formed by doping a monocrystalline or polycrystalline silicon substrate with impurities. While this solar cell has less productivity than the amorphous silicon solar cell because a monocrystalline or polycrystalline silicon substrate in the solar cell is thick, it has a higher efficiency of generating electric power than the amorphous silicon solar cell.
In recent years, there has also been developed a heterojunction solar cell in which semiconductors having different band gaps are jointed to each other. The heterojunction solar cell has a junction formed by a combination of silicon and a semiconductor film such as SiC having a band gap wider than silicon. Such a heterojunction solar cell is expected to have a higher efficiency of generating electric power . In a conventional manufacturing method of a heterojunction solar cell, a material having a different band gap is deposited on an amorphous silicon film by plasma CVD or electron cyclotron resonance (ECR) CVD. However, the conventional manufacturing method of a heterojunction solar cell has been disadvantageous in view of productivity and manufacturing cost because of its low deposition rate and an extremely expensive apparatus being required.
Disclosure of Invention The present invention has been made in view of the above drawbacks. It is, therefore, an object of the present invention to provide a solar cell having good electric characteristics such as efficiency of generating electric power and good productivity, and a method of manufacturing such a solar cell. According to a first aspect of the present invention, there is provided a solar cell comprising a monocrystalline or polycrystalline silicon layer and a silicon layer containing carbon. The silicon layer containing carbon is formed on the monocrystalline or polycrystalline silicon layer by hot-wire CVD.
The silicon layer containing carbon should preferably have a fine crystalline silicon column therein. The silicon layer containing carbon should preferably have a high conductivity. The silicon layer containing carbon may comprise a p-type silicon layer having a conductivity ranging from about 5xl0~6 S/cm to about 5x10° S/cm. Alternatively, the silicon layer containing carbon comprises an n-type silicon layer having a conductivity ranging from about 5xl0"6 S/cm to about δxlO1 S/cm. The silicon layer containing carbon may comprise a high hydrogen concentration layer at an interface with the monocrystalline or polycrystalline silicon layer. The hydrogen concentration layer should preferably have a hydrogen concentration ranging from 6 at % to 24 at %. According to a second aspect of the present invention, there is provided a method of manufacturing a solar cell . A monocrystalline or polycrystalline silicon layer is prepared, and then a silicon layer containing carbon is formed on the monocrystalline or polycrystalline silicon layer by hot-wire CVD.
According to the present invention, the silicon layer containing carbon is formed on the monocrystalline or polycrystalline silicon layer by hot-wire CVD. In this manner, it is easy to produce a heterojunction solar cell. Since the solar cell is formed as a heterojunction solar cell, it has good electric characteristics, e.g., a high open-circuit voltage, a high short-circuit current, and high conversion efficiency. Further, since the silicon layer containing carbon is formed by hot-wire CVD , it is possible to manufacture a solar cell having a good-quality film with relatively high productivity.
The above and other objects, features, and advantages of the present invention will be apparent from the following description when taken in conjunction with the accompanying drawings which illustrate preferred embodiments of the present invention by way of example.
Brief Description of Drawings
FIG. 1 is a schematic view showing an arrangement of a solar cell according to a first embodiment of the present invention;
FIG. 2 is a schematic view showing microcrystalline silicon columns in a silicon layer of the solar cell shown in
FIG. 1; FIG. 3A is a schematic view showing a hot-wire CVD apparatus according to an embodiment of the present invention;
FIG . 3B is a schematic view showing a plasma CVD apparatus ; and FIG. 4 is a schematic view showing an arrangement of a solar cell according to a second embodiment of the present invention.
Best Mode for Carrying Out the Invention
A solar cell according to embodiments of the present invention will be described below with reference to the accompanying drawings .
FIG. 1 shows a solar cell according to a first embodiment of the present invention. As shown in FIG. 1, the solar cell has a monocrystalline or polycrystalline silicon substrate 11 and a silicon layer 12 containing carbon therein. The silicon layer 12 is formed by hot-wire CVD and adhered to an upper surface of the silicon substrate 11. In this manner, the solar cell according to the present embodiment comprises a heterojunction solar cell. The monocrystalline or polycrystalline silicon substrate 11 should preferably be formed of a dendritic web (ribbon crystal) having a thickness of 150 μm or less , for example . The monocrystalline or polycrystalline silicon substrate 11 can be produced as follows. A silicon material is melted in a crucible maintained at a predetermined temperature. A seed crystal is pulled up along a crystal axis of a predetermined orientation from the crucible to grow a thin ribbon-like
(sheet-like) crystal. The thin crystal is clamped on an endless belt and continuously pulled up to form a long crystal. The produced long crystal is cut off into proper dimensions to produce a rectangular sheet-like monocrystalline or polycrystalline silicon substrate having a thickness of 150 im or less. Such a method of producing monocrystalline or polycrystalline silicon substrate is disclosed in Japanese patent publication No. 2002-087899 assigned to the assignee of this patent application, the disclosure of which is hereby incorporated by reference. The silicon substrate 11 may comprise a monocrystalline silicon substrate having an orientation of <100>. The monocrystalline silicon substrate may be doped into an n-type semiconductor and have a resistivity of 2 Ωcm, for example. As described above, the silicon layer 12 containing carbon is formed on the silicon substrate 11 by hot-wire CVD. The silicon layer 12 is made of amorphous silicon carbide (a-SiC) containing microcrystalline silicon (μc-Si) therein. Specifically, the silicon layer 12 is formed as a conductive film having a hetero-structure in which a-SiC and μc-Si are mixed with each other. The silicon layer 12 containing carbon has a thickness ranging from about 1 nm to about 50 nm. The silicon layer 12 is doped with impurities into an opposite type (e.g. , p-type) of the silicon substrate 11. Thus, a p-n junction is formed between the silicon substrate 11 and the silicon layer
12 so as to serve as a solar cell for generating electric power.
As shown in FIG. 2, the silicon layer 12 containing carbon has microcrystalline silicon columns 12b which are formed by columnar crystals of fine silicon. The microcrystalline silicon columns 12b are present in the silicon layer (SiC layer) 12 containing amorphous carbon. The microcrystalline silicon columns 12b are formed by columnar crystals perpendicular to a surface to be deposited. Each of the microcrystalline silicon columns 12b has a diameter ranging from about 1 nm to 50 nm, typically from 10 nm to 20 nm. The microcrystalline silicon columns 12b have a high conductivity as compared to the amorphous SiC layer present therearound. The amount of the microcrystalline silicon columns 12b contained in the silicon layer 12 can be adjusted in a range of from about 0.1 volume % to about 80 volume % to adjust the conductivity of the silicon layer 12. The amount of carbon in the silicon layer 12 can be adjusted in a wide range, for example, in a range of from about 0.1 volume % to about 70 volume %. The amount of carbon largely affects the conductivity of the silicon layer 12.
As described above, the amounts of the microcrystalline silicon columns 12b and carbon are adjustable in the silicon layer 12. Further, the concentrations of doping materials are adjustable. Therefore, the conductivity of the silicon layer 12 and an effective band gap can be adjusted within wide ranges . For example, in the case of a p-type silicon layer 12, the conductivity can be adjusted in a range of from about 5xl0-6 to about 5x10° (S/cm) , and an effective band gap can be adjusted in a range of from about 1.7 to about 2.6 eV. Thus, the silicon layer 12 of the heterojunction solar cell can be formed so as to have a high conductivity, and it is possible to improve the efficiency of generating electric power and electric characteristics such as short-circuit currents and open-circuit voltages.
A hot-wire CVD apparatus for forming the silicon layer 12 will be described below with reference to FIG. 3A. As shown in FIG. 3A, the hot-wire CVD apparatus has a gas supply device 21 for supplying gases, a high-temperature hot wire 22, and a substrate holder 24 for holding a substrate 23 to be processed. These components are housed in a vacuum chamber capable of being depressurized. The high-temperature hot wire 22 is used to form a CVD film on a surface of the substrate 23 by heating and activating the gases supplied from the gas supply device 21. The hot wire 22 comprises a wire made of tungsten, molybdenum, or the like, which is heated to a temperature ranging from 1500 to 2400 °C. The hot-wire CVD apparatus has basically the same structure as a known catalytic CVD apparatus . The term "hot wire" means a heated wire. The hot wire may have a two- dimensional shape such as a sheet, or a three-dimensional shape.
As a comparative example, a plasma CVD apparatus is shown in FIG. 3B. The plasma CVD apparatus has electrodes 25 and 26 and a high frequency power supply 27 for applying a high frequency voltage between the electrodes 25 and 26. When a high frequency voltage is applied between the electrodes 25 and 26, gas molecules 28 to be deposited are formed into a plasma and vibrated in directions shown by arrows in FIG. 3B . In this manner, a CVD film is deposited on a surface of a substrate 23 to be processed. The hot-wire CVD apparatus shown in FIG. 3A causes almost no damage to a substrate by a plasma, has a simpler and less expensive structure, and can easily be made larger in size as compared to the plasma CVD apparatus shown in FIG. 3B . Particularly, the hot-wire CVD apparatus can achieve a relatively high deposition rate of 5 to 10 nm/sec, for example, and produce a high-quality film of an amorphous silicon film or a microcrystalline silicon film in a relatively short time.
In the present embodiment, as shown in FIG. 1, the silicon layer 12 includes a high hydrogen concentration p-type layer 12a disposed at a lower portion thereof, and a p-type layer 12c disposed at an upper portion thereof. For example, such a high hydrogen concentration p-type layer is produced from gases mixed in the following ratio . CH4: 0.9 SiH4: 0.1 H2: 9
B2H6: 0.002 For example, the hot wire 22 is adjusted at a temperature of 2100 °C, and the substrate is adjusted at a temperature of 150 °C. Reaction occurs under a pressure of 10 Pa. The substrate has a film thickness of 5 nm. The concentration of hydrogen contained in the high hydrogen concentration p-type layer 12a is at least 6 at % (atomic %) . The p-type layer 12c is formed on an upper surface of the high hydrogen concentration p-type layer 12a. For example, such a p-type layer is produced from gases mixed in the following ratio . CH4 : 0.1 SiH4: 0.1 H2: 1
B2H6: 0.005 For example, the hot wire 22 is adjusted at a temperature of 2100°C, and the substrate is adjusted at a temperature of 250°C. Reaction occurs under a pressure of 10 Pa. The substrate has a film thickness of 15 nm.
In the present embodiment, as shown in FIG. 1, a high hydrogen concentration silicon layer (N+ layer) 11a is formed on a rear face of the silicon substrate 11 by hot-wire CVD. For example, such a high hydrogen concentration silicon layer is produced from gases mixed in the following ratio . SiH„: 0.1 H2: 9
PH3: 0.005 For example, the hot wire 22 is adjusted at a temperature of 1800 °C, and the substrate is adjusted at a temperature of 200 °C. Reaction occurs under a pressure of 10 Pa. The substrate has a film thickness of 20 nm.
An antireflection film 15 is formed on an upper surface of the silicon layer 12 containing carbon. The antireflection film 15 comprises an ITO film and has a thickness of about 0.05 μm. Surface electrodes 16 of aluminum are deposited on the antireflection film 15. The surface electrodes 16 have thicknesses of about 3 μm. Similarly, an electrode 13 of aluminum is deposited on a rear face of the silicon substrate 11. The electrode 13 has a thickness of about 5 μm.
FIG. 4 shows a solar cell according to a second embodiment of the present invention. As shown in FIG. 4, the solar cell in the second embodiment has basically the same structure as the solar cell in the first embodiment. The solar cell in the second embodiment differs from the solar cell in the first embodiment in that the solar cell in the second embodiment has a p-type monocrystalline or polycrystalline silicon substrate 11, and a silicon layer 12 containing carbon is doped into an n-type with impurities. In order to form such an n-type silicon layer 12, PH3 is used as a doping gas. The conductivity of the silicon layer 12 can be adjusted in a range of from about 5χl0~6 to about δxlO1 (S/cm) . When the silicon substrate 11 comprises an n-type substrate, an electrode 13 formed on a rear face of the silicon substrate 11 comprises a Ti/Pd/Ag layer. In order to form an n-type or p-type silicon layer 12 containing carbon, SiH4, Si2H6, or the like is used as a silicon material gas, and CH4, C2H4, C2H2 , or the like is used as a carbon material gas. Further, PH3, B2H6, or the like is used as a doping gas for doping silicon with n-type or p-type impurities. These material gases are activated by catalytic decomposing effect of a hot wire in a hot-wire CVD apparatus to form a conductive film having a columnar hetero-structure of a-SiC/μc-Si on the silicon substrate 11. The silicon layer 12 containing carbon has a wide band gap of about 2 eV. Thus, the solar cell has a heterojunction between the silicon layer 12 and the silicon substrate 11.
For example, in a case where a monocrystalline or polycrystalline silicon substrate is used as a substrate on which a heterojunction is formed, a number of interface state levels have generally been formed near a surface of the silicon substrate. In a process of forming thin films by hot-wire CVD, when a thin film 12a of a high hydrogen concentration layer is first formed, hydrogen passivation can effectively be performed on a surface of the substrate 11 without any damage to the substrate 11, so that defective interface state levels can be reduced at bulk (interior of the substrate) and interface (surface of the substrate) . The concentration of hydrogen should preferably be in a range of 6 to 24 at %, more preferably at least 8 at % .
Next, preferable composition ratios of the material gases will be described below. In the following description, SiH4 is used as a material gas containing silicon, CH4 as a material gas containing carbon, PH3 or B2H6 as a doping gas for impurities, and H2 gas as a dilution gas. A ratio of the carbon material gas to the material gases, i.e., CH4/ (SiH4+CH4) , should preferably be in a range of from 0.01 % to 95 % . A dilution ratio of the H2 gas , i.e., H2/ (SiH4+CH4) , should preferably be in a range of from about 0 to about 50, i.e. , from about 0 % to about 5000 %.
A ratio of a p-type doping gas to the material gases, i.e.,
B2H6/ (SiH4+CH4) , should preferably be in a range of about 0.001 % to about 1 % . A ratio of an n-type doping gas to the material gases, i.e. , PH3/ (SiH4+CH4) , should preferably be in a range of from about 0.001 % to about 1 %.
In an example, the hot-wire CVD apparatus described above was operated under the following conditions . Deposition pressure: 10"1 - 102 Pa Temperature of hot wire (of tungsten or molybdenum) : 1750 - 2400°C
Temperature of substrate: 150 - 500 °C Distance between substrate and hot wire: 1 - 10 cm Deposition rate: 0.1 - 10 nm/sec Silicon layers formed by hot-wire CVD under the above conditions had the following characteristics.
The conductivity in a direction parallel to a deposition surface of a high hydrogen concentration p-type layer, which had a hydrogen concentration more than 8 at % , was in a range of from 5χl0-6 to 5x10° (S/cm) . The conductivity in a direction parallel to a deposition surface of a p-type layer was in a range of from 5χl0-6 to δxlO1 (S/cm) . The carbon concentration in the film was in a range of from 0.1 to 60 at % , and a microcrystalline silicon was deposited at a carbon concentration of 42 at % or less. The deposited microcrystalline silicon had a diameter ranging from 1 to 50 nm. A crystallization rate was in a range of from 60 to 90 % according to measurement with Raman spectroscopy . A rate of hydrogen concentration in the film was in a range of from 2 to 24 at %. An optically measured band gap was in a range of from 1.9 to 2.6 eV, which was measured for silicon layers 12 having carbon contents of about 30 to 40 volume %.
The solar cell in this example had a conversion efficiency of 12.2 % , which was improved from 10.8%, a short-circuit current density of 30.1 mA/cm2, which was improved from 27.8 mA/cm2, and an open-circuit voltage of 0.55 mV, which was improved from 0.54 mV.
In a heterojunction solar cell, the same conductive types of semiconductor layers may be joined to each other so as to have a junction (high-low junction) using their different band gaps . A conductive film having a columnar hetero-structure of a-SiC/μc-Si which is formed by hot-wire CVD may be applicable not only to a solar cell, but also to devices such as thin- film transistors (TFT) in display devices.
Although certain preferred embodiments of the present invention have been shown and described in detail, it should be understood that various changes and modifications may be made therein without departing from the scope of the appended claims .
Industrial Applicability
The present invention is suitable for use in a heterojunction solar cell including a junction of semiconductors having different band gaps .

Claims

1. A solar cell comprising: a monocrystalline or polycrystalline silicon layer; and a silicon layer containing carbon which is formed on said monocrystalline or polycrystalline silicon layer by hot-wire CVD.
2. A solar cell according to claim 1, wherein said silicon layer containing carbon has a fine crystalline silicon column therein.
3. A solar cell according to claim 1, wherein said silicon layer containing carbon has a high conductivity.
4. A solar cell according to claim 3, wherein said silicon layer containing carbon comprises a p-type silicon layer having a conductivity ranging from about 5xl0~6 S/cm to about 5x10° S/cm.
5. A solar cell according to claim 3, wherein said silicon layer containing carbon comprises an n-type silicon layer having a conductivity ranging from about 5χl0~6 S/cm to about δxlO1 S/cm.
6. A solar cell according to claim 1, wherein said silicon layer containing carbon comprises a high hydrogen concentration layer at an interface with said monocrystalline or polycrystalline silicon layer.
7. A solar cell according to claim 6 , wherein said hydrogen concentration layer has a hydrogen concentration ranging from 6 at % to 24 at %.
8. A method of manufacturing a solar cell, said method comprising: preparing a monocrystalline or polycrystalline silicon layer; and forming a silicon layer containing carbon on the monocrystalline or polycrystalline silicon layer by hot-wire CVD.
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