WO2011062286A1 - 堆積膜形成装置 - Google Patents
堆積膜形成装置 Download PDFInfo
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- WO2011062286A1 WO2011062286A1 PCT/JP2010/070803 JP2010070803W WO2011062286A1 WO 2011062286 A1 WO2011062286 A1 WO 2011062286A1 JP 2010070803 W JP2010070803 W JP 2010070803W WO 2011062286 A1 WO2011062286 A1 WO 2011062286A1
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- 238000010438 heat treatment Methods 0.000 claims abstract description 147
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
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- MROCJMGDEKINLD-UHFFFAOYSA-N dichlorosilane Chemical compound Cl[SiH2]Cl MROCJMGDEKINLD-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
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- 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
- C23C16/45574—Nozzles for more than one gas
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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
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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
- C23C16/44—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
- C23C16/4401—Means for minimising impurities, e.g. dust, moisture or residual gas, in the reaction chamber
- C23C16/4405—Cleaning of reactor or parts inside the reactor by using reactive gases
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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
- C23C16/44—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
- C23C16/448—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 generating reactive gas streams, e.g. by evaporation or sublimation of precursor materials
- C23C16/452—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 generating reactive gas streams, e.g. by evaporation or sublimation of precursor materials by activating reactive gas streams before their introduction into the reaction chamber, e.g. by ionisation or addition of reactive species
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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
- C23C16/44—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
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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
- C23C16/44—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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
- H01J37/32—Gas-filled discharge tubes
- H01J37/32431—Constructional details of the reactor
- H01J37/3244—Gas supply means
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- 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
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- 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
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- 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
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- 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
- H01L31/182—Special manufacturing methods for polycrystalline Si, e.g. Si ribbon, poly Si ingots, thin films of polycrystalline Si
- H01L31/1824—Special manufacturing methods for microcrystalline Si, uc-Si
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- 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
- H01L31/20—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof such devices or parts thereof comprising amorphous semiconductor materials
- H01L31/202—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof such devices or parts thereof comprising amorphous semiconductor materials including only elements of Group IV of the Periodic Table
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- 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
- Y02E10/545—Microcrystalline silicon PV cells
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- 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
- the present invention relates to a deposited film forming apparatus for forming a deposited film such as a Si (silicon) film on a substrate.
- Methods of forming this Si-based thin film at a relatively low substrate temperature of 100 ° C. or higher and 400 ° C. or lower can be broadly divided into plasma CVD (Chemical Vapor Deposition) method and thermal catalytic CVD method (however, HW (Hot® Wire) ⁇ (Including methods of the same principle such as CVD method).
- the plasma CVD method uses plasma, the deposited film is damaged by charged particles such as ions and electrons. For this reason, there exists a possibility that the film quality of a deposited film may fall.
- the thermal catalytic CVD method since the thermal catalytic CVD method does not use plasma, the deposition film can be formed at high speed relatively easily without being damaged in principle by the charged particles.
- the heating catalyst body heated to a high temperature causes excessive decomposition of the raw material gas (for example, SiH 4 gas), and generation of SiH 2 , SiH, and Si that cause deterioration in film quality proceeds. For this reason, the film quality by the thermal catalytic CVD method is inferior to the film quality by the plasma CVD method.
- a low raw material gas decomposition probability such as H 2 gas through a gas supply path mechanism to enhance the decomposition probability typified are arranged in the heating catalyst body, decomposition activation of H 2 gas Can be introduced into the chamber.
- H 2 gas can be contributed to the formation of the microcrystalline silicon film without increasing the number of charged particles that cause a decrease in film quality, which is a problem in the plasma CVD method.
- a raw material gas having a high decomposition probability such as SiH 4 gas is introduced into the chamber through another gas supply path in which no heating catalyst body is provided.
- SiH 4 gas can be contributed to the formation of the deposited film while suppressing the generation of SiH 2 , SiH and Si that cause the film quality to deteriorate in the thermal catalytic CVD method.
- the gas-separated plasma CVD apparatus can form a high quality film at high speed.
- the gas separation type plasma CVD apparatus is characterized in that the source gas is separated and supplied according to the gas decomposition probability, so that the required flow rate is small under the deposited film forming conditions, and sufficient source gas cannot be supplied uniformly. is there.
- the flow rate of SiH 4 gas is as low as 1/10 or more and 1/200 or less than the flow rate of H 2 gas.
- the SiH 4 gas is difficult to be uniformly supplied from a plurality of gas supply units.
- deformation due to thermal expansion of the electrode plate tends to make the in-plane film thickness distribution of the deposited film non-uniform in a large deposited film forming apparatus having a deposition area exceeding 1 m 2 .
- An object of the present invention is to provide a deposited film forming apparatus capable of forming a deposited film having a uniform film thickness distribution, and in particular, a deposited film capable of suitably forming a Si-based thin film used for a thin-film Si-based solar cell.
- An object is to provide a forming apparatus.
- a deposited film forming apparatus comprises: A deposited film forming apparatus comprising a chamber, a first electrode located in the chamber, and a second electrode located in the chamber at a predetermined interval from the first electrode,
- the second electrode has an electrode base and a plurality of electrode plates disposed on the electrode base,
- the electrode plate includes: a first supply unit that supplies a first source gas to a space between the first electrode and the second electrode; a second supply unit that supplies a second source gas to the space; A first supply path that is connected to a first supply section and into which the first source gas is introduced; and a second supply path that is connected to the second supply section and into which the second source gas is introduced.
- the electrode substrate has a heating means for heating the first source gas, a first introduction path for introducing the first source gas into the first supply path, and the second source gas introduced into the second supply path. And a second introduction route to In the second supply path, the second raw material gas is introduced from the second introduction path, the main flow part not having the second supply part, and the second raw material gas is introduced from the main flow part, A plurality of tributaries having the second supply part; A connection portion between the second introduction path and the main flow portion is located in an adjacent portion of the electrode plates adjacent to each other.
- the above-described deposited film forming apparatus it is possible to uniformly supply a raw material gas having a low flow rate into each chamber from each supply unit while suppressing deformation due to thermal expansion of the electrode plate. As a result, an excellent deposited film having a uniform film thickness distribution can be formed on the substrate.
- FIG. 2 is a cross-sectional view taken along line AA in FIG. 1 and is a cross-sectional view schematically showing a structure of a second supply path.
- FIG. 3 is a perspective view partially seen through in order to explain a state in the vicinity of a connection portion between a second introduction path and a main flow portion in FIG. 2.
- It is a cross-sectional schematic diagram which shows one Embodiment of the heating catalyst body used for the deposited film formation apparatus which concerns on this invention.
- the deposited film forming apparatus S1 is located in the chamber 1, the first electrode 7 located in the chamber 1, and the first electrode 7 in the chamber 1 with a predetermined interval. And a second electrode 2 functioning as a shower electrode.
- the second electrode 2 is mainly composed of a plurality of electrode plates 2a and one or more electrode bases 2b on which these electrode plates 2a are arranged.
- the second electrode 2 has four electrode plates 2a arranged on one electrode base 2b.
- the base material 10 on which the deposited film is formed is disposed between the first electrode 7 and the second electrode 2. Note that the substrate 10 may be positioned between the first electrode 7 and the second electrode 2, and may not necessarily be held by the first electrode 7.
- the chamber 1 is a reaction vessel having a vacuum-tight reaction space constituted by at least an upper wall, a peripheral wall, and a bottom wall.
- the inside of the chamber 1 is evacuated by a vacuum pump 9 and the pressure in the chamber 1 is adjusted by a pressure regulator (not shown).
- the chamber 1 is made of a metal member such as stainless steel or aluminum.
- the first electrode 7 has a function of an anode electrode and incorporates a heater for adjusting the temperature of the substrate 10.
- the 1st electrode 7 functions also as a temperature adjustment mechanism of the base material 10, and the temperature of the base material 10 is adjusted to 100 degreeC or more and 400 degrees C or less, for example, More preferably, 150 degreeC or more and 350 degrees C or less.
- the first electrode 7 is made of a metal member such as stainless steel or aluminum.
- the substrate 10 may be a flat plate made of glass or the like, or a film made of a metal material or a resin.
- the high frequency power source 11 is connected to the second electrode 2 and a frequency of about 13.56 MHz to about 100 MHz is applied. When a film is formed in a large area of 1 m 2 or more, a frequency of about 60 MHz or less is preferably used. By applying electric power from the high frequency power supply 11 to the second electrode 2, plasma is formed in the space 8 between the second electrode 2 and the substrate 10.
- the second electrode 2 is arranged to face the first electrode 7 and functions as a cathode electrode.
- the electrode plate 2a constituting the second electrode 2 includes a first supply path 4 and a second supply path 5 connected to a plurality of introduction paths 3 (first introduction path 3a and second introduction path 3b), and these It has the 1st supply part 6a and the 2nd supply part 6b which are the supply parts 6 for supplying the gas introduce
- the 1st supply part 6a is a site
- the 2nd supply part 6b is 2nd. This is a part provided with a supply port for supplying the source gas to the space 8.
- the electrode plate 2a and the electrode base 2b are electrically connected, and the electrode plate 2a and the electrode base 2b are made of a metal member such as stainless steel, aluminum alloy or nickel base alloy.
- a plurality of gas cylinders (not shown) that store different gases are connected to the first supply path 4 and the second supply path 5 through the first introduction path 3a and the second introduction path 3b, which are a plurality of introduction paths.
- the gas introduced from the first introduction path 3a and the second introduction path 3b is not basically mixed until reaching the space 8 through the first supply section 6a and the second supply section 6b, respectively.
- the gas supplied to the plurality of supply units 6 includes a first source gas and a second source gas having a higher decomposition probability than the first source gas.
- the total gas decomposition rate is defined as exp ( ⁇ Ea / kTe) ⁇ Ng ⁇ Ne ⁇ ve ⁇ ⁇ g.
- ⁇ Ea is the excitation activation energy (dissociation energy) of the source gas
- k is the Boltzmann constant
- Te is the electron temperature
- Ng is the source gas concentration
- Ne is the electron concentration
- ve the electron velocity
- ⁇ g is the source gas collision cross section.
- exp ( ⁇ Ea / kTe) means a decomposition probability.
- exp ( ⁇ Ea / kTe) ⁇ ⁇ g may be the collision cross-sectional area, but the meaning is the same. Further, as will be described later, there is a case where the first source gas flowing through the first introduction path 3a is divided and partly flows into the second introduction path 3b (mixed with the second source gas).
- the first source gas and the second source gas are appropriately selected depending on the type of the deposited film.
- a Si-based thin film such as a-Si: H (hydrogenated amorphous silicon) or ⁇ c-Si: H (hydrogenated microcrystalline silicon)
- a non-Si based gas is used as the first source gas.
- Si-based gas can be used as the source gas.
- hydrogen (H 2 ) gas or the like is used as the non-Si gas.
- Si-based gas examples include SiH 4 (silane), Si 2 H 6 (disilane), SiF 4 (silicon tetrafluoride), Si 2 F 6 (silicon hexafluoride), or SiH 2 Cl 2 (dichlorosilane) gas. Used.
- the introduction path of the doping gas either the first introduction path 3a or the second introduction path 3b can be selected as necessary.
- heating means such as a heating catalyst body is provided in the first introduction path 3a.
- the heating catalyst body 12 is provided as the heating means as shown in the figure, the doping gas is introduced through the second introduction path 3b. It is desirable to do.
- a heating catalyst body 12 connected to a heating power source 13 can be provided as a heating means as shown in the figure. Accordingly, the first source gas is heated and activated by the heating catalyst body 12 heated to about 500 ° C. or more and 2000 ° C. or less, and is also activated in the space 8.
- the heated catalyst body 12 functions as a thermal catalyst body that excites and activates (decomposes) the gas in contact with the medium by passing an electric current through the medium and increasing the temperature by heating.
- At least the surface of the heating catalyst body 12 is made of a metal material.
- the metal material is preferably made of a pure metal or alloy material containing at least one of Ta, W, Re, Os, Ir, Nb, Mo, Ru, and Pt, which are high melting point metal materials.
- the shape of the heating catalyst body 12 is, for example, a metal material such as that described above formed into a wire shape, a plate shape, or a mesh shape.
- the heating means is not particularly limited as long as the gas can be heated to a predetermined temperature. In the following description, the heating catalyst body 12 will be described as an example.
- the heating catalyst body 12 is preheated for several minutes at a temperature higher than the heating temperature at the time of film formation before being used for film formation. Thereby, it can reduce that the impurity in the metal material of the heating catalyst body 12 is doped in the film at the time of film formation.
- the gas can be uniformly brought into contact with the thermal catalyst body 12, and the gas can be activated efficiently.
- decomposition of the first source gas can be promoted by heating the heating catalyst body 12. Furthermore, since the temperature of the first raw material gas that has not been decomposed or the first raw material gas that has been recombined after the decomposition is also rising, gas decomposition is further promoted in the space 8. In addition, since the second source gas is supplied from the second supply unit 6b without being brought into contact with the heating catalyst body 12 and excited and activated in the space 8, the second source gas is rapidly decomposed without being excessively decomposed. A high-quality thin film can be formed simultaneously with the film formation.
- the hydrogen gas (first source gas) whose temperature has been raised by the heating catalyst body 12 is supplied to the space 8, the high-order silane formation reaction is suppressed in the space 8 due to the gas heating effect.
- the higher-order silane formation reaction is 1) SiH 4 + SiH 2 ⁇ Si 2 H 6 2) Si 2 H 6 + SiH 2 ⁇ Si 3 H 8 ... Similar SiH 2 insertion reaction continues ... This is a reaction in which a high molecular polymer is generated by the SiH 2 insertion reaction.
- SiH 2 is generated together with SiH 3 as a main component of film formation when SiH 4 collides with electrons in the plasma.
- more high-order silane molecules are also generated.
- first supply unit 6a and the second supply unit 6b may be arranged in various patterns such as a lattice pattern and a staggered pattern, respectively.
- the number of the 1st supply part 6a and the 2nd supply part 6b may differ.
- the first supply unit 6a is more than the second supply unit 6b.
- first introduction path 3a and the second introduction path 3b may be directly connected to each cylinder, or may be connected to a gas adjusting unit that adjusts the gas flow rate, flow velocity, temperature, and the like.
- the vacuum pump 9 it is desirable to use a dry vacuum pump such as a turbo molecular pump in order to suppress contamination of impurities into the film from the exhaust system.
- the ultimate vacuum is at least 1 ⁇ 10 ⁇ 3 Pa or less, preferably 1 ⁇ 10 ⁇ 4 Pa or less, and the pressure during film formation is 50 Pa or more and 7000 Pa or less, although it depends on the type of film to be formed.
- the second electrode 2 includes, for example, a plurality of electrode plates 2a that are rectangular and have the same shape in plan view (in this example, four substantially square electrode plates 2a are shown in plan view).
- the electrode base 2b and the electrode plate 2a are connected by bolts and nuts via a gasket (not shown), the maintenance can be easily performed. For this reason, productivity can be improved by shortening the maintenance time.
- Each electrode plate 2a serves as a second supply path 5 as a main flow portion 51 (a first main flow portion 51a extending in the vertical direction in the drawing and a second main flow portion extending in the horizontal direction in the drawing) provided around each electrode plate 2a. 52b) and a tributary portion 52 connected to the main flow portion 51 and extending in the vertical direction.
- the first supply path 4 and the first supply unit 6a are omitted.
- the main flow part 51 is not provided with the second supply part 6b, and the second supply part 6b is provided only in the tributary part 52. Further, the second supply path 5 is provided in the main stream portion 51 by providing a connection port 53 which is a connection portion with the second introduction path 3b formed in the electrode base 2b in the adjacent portion between the electrode plates 2a. It becomes possible to supply the second source gas directly to the main flow part 51 located in the vicinity.
- the second source gas is supplied equally from each second introduction path 3b. be able to.
- a flow rate control mechanism it is preferable to adjust the conductance of the introduction path 3, and the cross-sectional area of the introduction path 3 may be adjusted by a valve or a mass flow meter.
- the second introduction path 3b is also provided at both ends of the electrode plate, so that the second source gas can be supplied to the tributary section 52 almost evenly.
- first main flow portion 51a connected to the second introduction path 3b and the second main flow portion 51b connected to the tributary portion 52 intersect substantially perpendicularly, whereby the second source gas is supplied to the tributary portion 52 more evenly. be able to.
- FIG. 2 as shown in an enlarged view in FIG. 3, a plurality of connection ports 53 between the second introduction path 3 b and the first main flow portion 51 a are provided in adjacent portions between the electrode plates 2 a, and each first main flow is provided.
- the part 51a is connected to the second main flow part 51b provided in each electrode plate 2a, and the second source gas is supplied to the branch part 52 provided in each electrode plate 2a individually.
- the gas flow rate supplied to each electrode plate 2a can be individually controlled, so that it can be expected that the second source gas is supplied evenly.
- the first supply path 4 and the first supply unit 6a are omitted.
- route 3b and the 1st main flow part 51a should just be provided in the adjacent part of the electrode plate 2a adjacent to each other, for example, it connects only one place to the adjacent part of electrode plates 2a A mouth may be provided.
- the second electrode 2 has the electrode base 2b and the plurality of electrode plates 2a arranged on the electrode base 2b.
- the electrode plate 2 a includes a first supply unit 6 a that supplies the first source gas to the space 8 between the first electrode 7 and the second electrode 2, and a second supply that supplies the second source gas to the space 8.
- Section 6b a first supply path 4 connected to the first supply section 6a to introduce the first source gas, and a second supply path 5 connected to the second supply section 6b to introduce the second source gas. And have.
- the electrode base 2 b includes heating means (heating catalyst body 12) for heating the first source gas, a first introduction path 3 a for introducing the first source gas into the first supply path 4, and a second at the second supply path 5. And a second introduction path 3b for introducing the source gas.
- the second supply path 5 includes a main flow part 51 having no second supply part 6b into which the second raw material gas is introduced from the second introduction path 3b and a second raw material gas introduced from the main flow part 51. And a plurality of tributaries 52 having two supply sections 6b. And the connection part (connection port 53) of the 2nd introduction path
- a raw material gas having a small flow rate can be uniformly supplied into the chamber 1 from each supply unit while suppressing deformation due to thermal expansion of the electrode plate 2a.
- an excellent deposited film having a uniform film thickness distribution can be formed on the substrate 10.
- the installation area per unit (region) where the heating catalyst bodies 12 are provided can be reduced. For this reason, the elongation amount of the heating catalyst body 12 due to thermal expansion during heating can be reduced, and the problem that the heating catalyst body 12 contacts the side wall in the installation space of the heating catalyst body 12 can be reduced.
- the heating catalyst body 12 when the heating catalyst body 12 is provided so as to be paired with each electrode plate 2a, when the heating catalyst body 12 is maintained by removing the electrode plate 2a, the heating catalyst 12 Only the electrode plate 2a corresponding to the medium 12 may be removed. Thereby, the time required for maintenance can be shortened.
- the first introduction paths 3a By providing a plurality of first introduction paths 3a, it is possible to reduce variations in the supply amount of the first source gas supplied from each first supply unit 6a due to the increase in the area of the apparatus. Furthermore, the first source gas can be efficiently supplied to the heating catalyst bodies 12 provided in the first introduction paths 3a.
- the number of first introduction paths 3a may be less than the number of electrode plates 2a, or may be the same as the number of electrode plates 2a. By doing in this way, it becomes easy to control the 1st source gas supplied from each electrode plate 2a. Further, by making the first introduction path 3a and the heating catalyst body 12 pair with each of the plurality of electrode plates 2a, the gas flow rate and the temperature of the heating catalyst body 12 are individually controlled by each electrode plate 2a. Therefore, a good film property distribution can be obtained.
- a rod-shaped reinforcing rib 15 supported by the second electrode 2 is provided at the center of the deposited film forming apparatus S2, and each electrode plate 2a is provided on the reinforcing rib 15. May be fixed.
- a plurality of electrode plates 2a can be attached to one first introduction path 3a.
- the second introduction path 3b may be provided inside the reinforcing rib 15.
- the second source gas can be supplied to the main flow part 51 from the vicinity of the center of the deposited film forming apparatus S2, and the second source gas can be supplied to the branch part 52 of each electrode plate 2a substantially evenly. .
- the first source gas can be efficiently brought into contact with the heating catalyst bodies 12.
- the heating temperature of each heating catalyst body 12 can be adjusted. Thereby, for example, the temperature of the heat catalyst body 12 provided in the outer peripheral portion is set to be higher because the temperature of the heat catalyst body is likely to be lowered at the outer peripheral portion of the first introduction path 3a due to heat exchange with the thermal catalyst space side wall. As a result, the temperature is equalized and the first source gas in the first introduction path can be heated uniformly.
- the heating catalyst body 12 is made of a wire-like metal wire
- the heating catalyst body 12 is seen in a plan view from the electrode plate 2a side and extends in a wave shape from one end of the electrode plate 2a toward the other end so as to overlap the electrode plate 2a.
- the density of the metal wires may be appropriately changed. For example, as shown in FIG.
- the metal wire is arranged on the electrode base 2b so that the area occupied by the metal wire in the electrode plate 2a is reduced at the central portion of the electrode plate 2a).
- the first source gas in 3a can be heated uniformly. Further, a plurality of linear metal wires may be arranged in parallel without making the metal wires corrugated.
- the reflective surface is mirror-finished or a deposited film forming process such as Ag, Al or Au is performed so that the reflectance is 80% or more, preferably 90% or more.
- each electrode plate 2a is electrically connected and electric power is applied from one high-frequency power source 11 to a plurality of electrode plates 2a.
- a high frequency power supply 11 may be provided corresponding to each second electrode 2 to insulate the second electrodes 2 from each other.
- this deposited film forming apparatus S3 it is possible to finely adjust the high frequency power and the phase applied to each second electrode 2 from each high frequency power supply 11. Thereby, a deposited film can be formed on the substrate 10 with uniform film quality and film thickness.
- the plurality of first introduction paths 3a may be combined into one space where the heating catalyst body 12 exists, and the plurality of electrode plates 2a may be attached. In this case, it is preferable to provide a plurality of heating catalyst bodies 12 to be paired with the electrode plate 2a. With this deposited film forming apparatus S4, it can be expected that the first source gas in the first introduction path 3a is heated uniformly.
- the electrode base 2b may have a cooling mechanism 16 for cooling the electrode base 2b and / or the electrode plate 2a.
- the cooling mechanism 16 may be provided with the cooling mechanism 16 for cooling the second electrode 2 in the vicinity of the first supply path 4 and the second supply path 5 in the electrode base 2b.
- a refrigerant path or a heat pipe through which a cooling medium flows can be used.
- the temperature increase of the second electrode 2 can be suppressed, an increase in the surface temperature of the substrate 10 is suppressed. As a result, a deposited film having good film quality can be formed.
- the in-plane temperature distribution of the electrode plate 2a can be made uniform, the in-plane temperature distribution of the substrate 10 is improved, and further, the in-plane temperature distribution of the source gas supplied from the electrode plate 2a is improved. Improved. For this reason, a deposited film having good film quality can be formed uniformly.
- the maintenance cycle of the apparatus can be lengthened and productivity can be improved.
- the temperature of the 2nd electrode 2 can be finely adjusted by providing the some cooling mechanism 16 so that it may become a pair with each 2nd electrode 2. FIG. Thereby, a deposited film can be formed on the substrate 10 with uniform film quality and film thickness.
- a cooling mechanism may be provided in a portion other than the second introduction path 3b between the plurality of first introduction paths 3a.
- a reflection plate 17 that reflects infrared radiation radiated from the heating catalyst 11 may be provided, and the cooling mechanism 16 may have a function as a reflection plate.
- the reflective surface is mirror-finished or a deposited film forming process such as Ag, Al or Au is performed so that the reflectance is 80% or more, preferably 90% or more.
- a plurality of reflecting plates 17 may be provided so as to be paired with each electrode plate 2a, and the maintainability can be improved.
- the outer peripheral portion of the deposited film forming apparatus has a communication portion 18 that can communicate with the outside, and in this communication portion 18, the heating catalyst body 12 in which the heating catalyst body 12 is disposed is replaced.
- the unit 19 may be attached so as to be fitted from the outside.
- the shape and size of the opening of the communication portion 18 are appropriately designed according to the size and shape of the heating catalyst body replacement unit 19 so that the vacuum in the film forming chamber can be maintained.
- the inner wall of the communication part 19 may have a tapered shape having an inclination angle of about 1 to 5 °.
- the heating catalyst body replacement unit 19 in which the heating catalyst body 12 is disposed is configured to be removable from the outside of the apparatus, it is possible to minimize the time required for replacing the heating catalyst body. And efficient production is possible. Furthermore, as compared with the conventional apparatus, the amount of moisture adhering to the atmosphere entering the thin film formation chamber is reduced, so that the vacuum baking time performed at the start of the film forming process performed after the heating catalyst body replacement can be shortened. Furthermore, since it is not necessary to remove the shower head (shower electrode) as compared with the conventional heating catalyst body replacement operation, variations in film quality due to the displacement of the shower head position after the heating catalyst body replacement is suppressed.
- the heating catalyst body exchanging unit 19 is configured for the purpose of arranging the heating catalyst body 12 so as to be electrically conductive, and for easily removing the heating catalyst body 12 provided inside the apparatus to the outside of the apparatus.
- the shape of the unit base 20 is not particularly limited as long as it is a shape that fits into the opening of the communication portion 18 formed in the apparatus.
- the planar shape may be a rectangular shape, a circular shape, an elliptical shape, or the like.
- the unit base 20 is made of a metal such as stainless steel. From the viewpoint of further strengthening the fitting with the opening of the communication portion 18, for example, an O-ring or the like is preferably disposed on the outer peripheral portion of the unit base 20, and the fitting portion of the outer peripheral portion has a step structure. It is preferable that In addition, since the unit base 20 is heated at the time of film formation, it is preferable to provide a cooling mechanism for the unit base 20 from the viewpoint of cooling at the time of removal.
- a plurality of supports 21 are erected on the unit base 20, and the heating catalyst 12 is appropriately disposed between the supports 21.
- the heating catalyst body 12 is disposed so as to reciprocate between the supports 21 erected on the unit base body 20. It is preferable that a groove or the like is formed at the tip of the support 21 so that the heating catalyst 12 can be easily disposed.
- the arrangement method is not particularly limited, but in consideration of the thermal expansion of the heating catalyst body 12 during heating, for example, it is preferable to wind it around the groove at the tip of the support body 21 one or more times.
- the support body 21 located at the end has an energization section 22 for electrically connecting the heating catalyst body 12.
- the conductor is formed so as to penetrate through the support 21, and the screw structure of the conductor is exposed at the tip of the support 21.
- the heating catalyst body 12 is connected to this conductor.
- the energization part 22 it is preferable to use a metal material having a heat-resistant temperature of about 800 ° C. in a vacuum, and for example, a nickel base alloy or the like is used.
- the current-carrying unit 22 and the unit base 20 are not in electrical contact with each other.
- An insulating member 23 is disposed around the conductor and on the portion of the unit base 20 that can come into contact with the conductor.
- the insulating member 23 for example, alumina, quartz, or the like is used.
- the heating catalyst body replacement unit 19 is detachably fitted into the opening of the communication portion 18.
- the number of heating catalyst body replacement units 19 to be fitted is not particularly limited. Although it may be only one or plural, it is desirable that it can be individually controlled so as to be paired with the electrode plate 2a. Moreover, it attaches with an attachment screw etc. from a viewpoint of making fitting more firm.
- ⁇ Method for forming deposited film A method for forming a deposited film according to this embodiment will be described.
- the step of holding the substrate 10 on the first electrode 7, the step of applying high-frequency power to the second electrode 2, and the first source gas activated in the heated catalyst body 12 The second source gas is supplied from the first supply unit 6a to the base material 10 from the second supply unit 6b, and the second source gas is activated in the space 8 generated between the first electrode 7 and the second electrode 2. And a step of converting.
- the activated first source gas and second source gas are mixed in the space 8, and components in the source gas are deposited on the substrate 10, thereby forming a deposited film on the substrate 10. Is done.
- the base material 10 is transported by a base material transport mechanism or the like (not shown) and held on the first electrode 7. Then, it is fixed on the first electrode 7.
- the film thickness of the i-type amorphous silicon film may be 0.1 ⁇ m or more and 0.5 ⁇ m or less, preferably 0.15 ⁇ m or more and 0.3 ⁇ m or less.
- H 2 gas is supplied to the first introduction path 3 a and SiH 4 gas is supplied to the second supply path 5.
- the gas pressure is set to 100 Pa to 7000 Pa
- the gas flow ratio of H 2 / SiH 4 is set to 10/1 to 200/1
- the high frequency power density is set to 0.1 W / cm 2 to 1 W / cm 2. do it.
- the thickness of the i-type microcrystalline silicon film is 1 ⁇ m to 4 ⁇ m, preferably 1.5 ⁇ m to 3 ⁇ m, and the crystallization rate is about 70%. What is necessary is just to form.
- hydrogen gas first source gas
- first source gas hydrogen gas whose temperature has been increased by the heating catalyst body 12 is supplied to the space 8.
- the high-order silane formation reaction in the space 8 is suppressed by the gas heating effect, crystallization of the microcrystalline silicon film can be promoted, and the film can be formed at high speed.
- the formation of a hydrogenated microcrystalline silicon film has a much lower flow rate of SiH 4 gas than that of H 2 gas. For this reason, the gas pressure balance between the first and second supply units 6 is not achieved, and it becomes difficult to uniformly supply the SiH 4 gas from each of the second supply units 6b, and the film thickness distribution may be nonuniform.
- this possibility can be reduced by performing deposition using the deposited film forming apparatus.
- the gas pressure in the second supply path 5 is reduced by making the number of the second supply parts 6b smaller than that of the first supply parts 6a or by reducing the opening cross-sectional area of the second supply parts 6b.
- the SiH 4 gas can be uniformly ejected from the plurality of second supply parts 6b by increasing the size. Further, a part of the H 2 gas (first source gas) supplied to the first introduction path 3a is dividedly supplied to the second introduction path 3b, so that the total amount of gas supplied from the second supply unit 6b is increased. The flow rate can be increased. Accordingly, the gas pressure in the second supply passage 5 (total pressure) is increased, can be uniformly ejected SiH 4 gas from the plurality of the second supply unit 6b.
- step 1, step 2, and step 3 may be sequentially performed.
- Step 1 A carrier gas is supplied from the first supply unit 6a into the chamber 1, and a cleaning gas having a molecular formula containing fluorine and / or a molecular formula containing chlorine is supplied from the second supply unit 6b to the chamber 1.
- a cleaning gas having a molecular formula containing fluorine and / or a molecular formula containing chlorine is supplied from the second supply unit 6b to the chamber 1. The process of supplying inside.
- Step 2 A step of activating the cleaning gas by plasma generated between the first electrode 7 and the second electrode 2.
- Process 3 A process of stopping the supply of the cleaning gas and heating the heating means.
- At least one of the step of applying high-frequency power to the second electrode 2 and, for example, hydrogen gas or inert gas from the first supply unit 6a through the first introduction path 3a including the heating catalyst body 12 is used. Is supplied into the chamber 1, and cleaning is performed including at least one of a gas containing F (fluorine) in the molecular formula or a gas containing Cl (chlorine) in the molecular formula from the second supply unit 6b.
- a gas such as N 2 , Ar, or He can be used as an inert gas used for the carrier gas.
- a cleaning gas containing fluorine F 2 , CHF 3 , SF 6 , NF 3 , CF 4 , C 2 F 6 , C 3 F 8 , C 5 F 8 , ClF 3 , or C 2 ClF 5, etc.
- a gas such as Cl 2 , CCl 4 , ClF 3 , or C 2 ClF 5 can be used as a cleaning gas containing chlorine.
- the contact between the heating catalyst body 12 and the cleaning gas can be reduced.
- the chamber 1 can be cleaned while reducing the corrosion deterioration.
- the high-frequency power density applied to the second electrode 2 at the time of cleaning may be 0.1 W / cm 2 or more and 3 W / cm 2 or less.
- the heating means provided in the first introduction path 3a is heated.
- the temperature of the constituent members in the chamber 1 is increased.
- this heating means it may be provided separately in the chamber 1 or on the outer wall of the chamber 1, but by separately using the heating catalyst body 12 provided in the first introduction path 3 a for the thin film formation and the heating process, a separate heating means is not necessarily provided. There is no need to provide it. Therefore, suppression of deterioration in characteristics after cleaning by this method does not increase the cost of the apparatus.
- the heating means including the heating catalyst body 12 is used as the heating means will be described as an example.
- the heating of the constituent members in the chamber 1 by the heating catalyst body 12 is performed by heating the temperature of the heating catalyst body 12 to 300 ° C. or more and 2000 ° C. or less.
- the residual gas is exhausted from the chamber 1 by evacuating the chamber 1 during and after the heating.
- heating is performed while supplying any one of a hydrogen gas, an inert gas, or a thin film forming gas, or a mixed gas of these gases, so that the desorbed cleaning gas is again contained in the chamber 1. It can be pushed out of the chamber 1 before adhering to the components. For this reason, the residual ratio of the cleaning gas in the apparatus can be further reduced.
- the cleaning gas is introduced in the cleaning process, so that the residual amount of the cleaning gas is large.
- the effect of pushing out from the introduction path by the gas is added to the desorption of the cleaning gas residual component by heating, and the residual ratio of the cleaning gas in the second introduction path 3b is further increased.
- the pressure in the chamber and the gas flow rate are determined so that the gas residence time ⁇ (seconds) defined by the following relational expression is 30 seconds or less, preferably 15 seconds or less. Good.
- P the pressure in the chamber (Pa)
- V the space volume in the chamber (m 3 )
- Q the gas supply amount (Pa ⁇ m 3 / sec).
- the pressure in the chamber is about 50 Pa to 300 Pa.
- the heating process is performed while applying a high frequency power to the second electrode 2 and accompanied by glow discharge generated between the first electrode 7 and the second electrode 2.
- cleaning gas that has been easily desorbed from members of the apparatus reacts with activated hydrogen by hydrogen plasma by supplying hydrogen gas, and the cleaning gas can be removed from the apparatus more efficiently.
- desorption of the cleaning gas can be further promoted by the hydrogen gas whose temperature has increased.
- a vacuum pump By supplying a thin film forming gas and adding a preliminary film formation, such as supplying a first source gas from the first introduction path 3a and supplying a second source gas from the second introduction path 3b, a vacuum pump The component of the cleaning gas that cannot be removed from the chamber by exhausting by the air 9 is taken into the film formed on the constituent member in the chamber 1 by the preliminary film formation, and the influence of the cleaning gas component at the time of forming the solar cell element is reduced. Can do. Further, by setting a base material during preliminary film formation, a film in which a cleaning gas component is taken in is formed on the base material, and then the base material is taken out of the chamber 1 to remove the base material from the chamber 1. The residual ratio of the cleaning gas can be further reduced.
- the cleaning gas cannot be sufficiently removed only by the preliminary film formation. Therefore, after the heating process with hydrogen plasma is performed, the heating process with film formation is performed. By doing so, the cleaning gas can be more efficiently removed from the apparatus.
- the residual rate of the cleaning gas in the apparatus can be further reduced by performing the heating process a plurality of times. Further, the supply gas is stopped during a plurality of heating steps, and the inside of the chamber 1 is once evacuated by the vacuum pump 9 to reduce the desorbed cleaning gas from adhering to the components in the chamber again. Can do.
- the heating means is also heated in the cleaning process, so that the adhered film can be removed while reducing the adhesion of the cleaning gas to the constituent members in the chamber 1. Therefore, the residual ratio of the cleaning gas after the cleaning process Can be reduced, the time of the heating process performed next can be shortened, and productivity can be improved.
- the thin film forming apparatus was cleaned by supplying Ar gas (carrier gas) from the first supply unit and NF 3 gas (cleaning gas) from the second supply unit into the chamber. .
- Example 1 while heating the heating catalyst body to 1500 ° C. after the cleaning process, hydrogen gas is supplied into the chamber from the first supply unit and the second supply unit, and high frequency power is applied to the second electrode to generate hydrogen plasma. Treatment was carried out for 20 minutes.
- Example 2 as in Example 1, while heating the heating catalyst body to 1500 ° C., hydrogen gas is supplied into the chamber from the first supply unit and the second supply unit, and high-frequency power is supplied to the second electrode. Is applied and hydrogen plasma treatment is performed for 20 minutes, heating of the heating catalyst body is stopped, the inside of the apparatus is evacuated, a glass substrate is installed in the apparatus, and hydrogen gas is supplied from the first supply unit to the second supply unit. Silane gas was supplied to preliminarily form a microcrystalline silicon film having a thickness of 1 ⁇ m on a glass substrate.
- hydrogen gas treatment is performed for 20 minutes by supplying hydrogen gas from the first supply unit and the second supply unit into the chamber without heating the heating catalyst body, and applying high-frequency power to the second electrode.
- a glass substrate is set in the apparatus, hydrogen gas is supplied from the first supply part, and silane gas is supplied from the second supply part, and the microcrystalline silicon having a thickness of 1 ⁇ m on the glass substrate The membrane was pre-deposited.
- Example 2 a glass substrate having a transparent conductive film made of SnO 2 formed on the surface is placed in the apparatus.
- the pre-formed glass substrate is taken out, and the glass substrate on which the transparent conductive film is formed is installed.
- p-type hydrogenated amorphous silicon, i-type hydrogenated amorphous silicon, n-type hydrogenated amorphous silicon, p-type hydrogenated microcrystalline silicon, i-type hydrogenated microcrystalline silicon, n-type Hydrogenated amorphous silicon was deposited.
- the heating catalyst body was heated to 1500 ° C. only when the i-type hydrogenated microcrystalline silicon film was formed, and the heating catalyst body was not heated in the other films.
- a transparent conductive film made of ITO and a metal electrode made of silver were formed on the n-type hydrogenated amorphous silicon by sputtering to produce a solar cell element. And this solar cell element was produced twice more continuously.
- the output characteristics (conversion efficiency and fill factor) of the solar cell element produced after the cleaning method under each condition were measured with a simulator.
- the measurement conditions at this time were the surface temperature of the solar cell element: 25 ° C., the spectral distribution: AM1.5 global solar radiation standard sunlight, and the irradiance: 100 mW / cm 2 .
- the results in each example are shown in Table 1.
- Example 1 and Example 2 the conversion efficiency of the solar cell element produced for the first time was higher than that of the comparative example.
- Example 2 in which preliminary film formation was performed, it was possible to sufficiently reduce the mixing of the cleaning gas component during the formation of the semiconductor film, compared with Example 1 in which only the heating process was performed, and thus higher conversion efficiency was obtained.
- Example 1 and Example 2 it can confirm that the solar cell element produced at the 1st time is substantially equivalent to the conversion efficiency of the solar cell element produced at the 2nd time and the 3rd time, and has a stable output characteristic. It was possible to produce a solar cell element having the same.
- the present invention is not limited to the above-described embodiments, and many modifications and changes can be made within the scope of the present invention.
- the second supply part 6b may be provided more on the center side than the end part side of the tributary part, or the opening cross-sectional area of the second supply part 6b may be increased toward the center of the tributary part. Gas can be supplied.
- the deposited film forming apparatus in which the electrodes and the base material are provided in the horizontal direction has been described as an example.
- a deposited film forming apparatus in which the electrodes and the base material are provided in the vertical direction may be used.
- a deposited film having a uniform film thickness distribution can be formed.
- the plurality of supply units may include a first supply unit 6a having a space for generating a hollow cathode (Hollow Cathode) discharge so as not to generate a hollow cathode discharge.
- the second supply unit 6b having a small degree of discharge may be provided. That is, as shown in FIG. 11, in the first supply unit 6a, the flow passage cross-sectional area is gradually increased toward the gas outlet on the gas outlet side of the first supply unit 6a so that the hollow cathode discharge 60 can be generated. You may make it become.
- the hollow cathode discharge is a kind of glow discharge, in which electrons reciprocate due to electrostatic confinement, and the energy of the electrons is used for plasma generation, and the plasma density becomes extremely high.
- the first supply portion 6a of the second electrode 2 has a cross-sectional area perpendicular to the axis in the depth direction as the depth increases, that is, as the distance from the first electrode 7 increases. For example, it is formed in a taper shape or a step shape so that the cross-sectional area becomes small. For this reason, a hollow cathode discharge is generated at a position at an arbitrary depth in the recess according to the atmospheric pressure in the discharge space. Further, the first source gas can further promote the decomposition of the first source gas by the high density plasma of the hollow cathode discharge in the first supply unit 6a.
- the above-described action further promotes activation of the first source gas and reduces excessive decomposition of the second source gas.
- the heating catalyst can be used even if there is little first source gas passing through the first introduction path 3a.
- the decomposition of the first source gas can be further promoted by the heating by the medium 12 and the high density plasma of the hollow cathode discharge. Therefore, a high-quality deposited film can be formed on the substrate 10 at a sufficiently high speed.
- a SiC-based wide gap film such as a-SiC (amorphous silicon carbide)
- the first supply unit having a space for generating a hollow cathode discharge.
- H 2 gas is supplied to the first introduction path 3a
- SiH 4 (silane) gas and CH 4 gas are supplied to the second supply path 5.
- the gas pressure may be set to 100 Pa or more and 700 Pa or less
- the high frequency power density may be 0.01 W / cm 2 or more and 0.1 W / cm 2 or less.
- the SiC-based wide gap film is used as a light incident side window layer of a solar cell.
- the thickness of the p-type amorphous silicon carbide film is 0.005 ⁇ m or more and 0.03 ⁇ m or less, preferably 0.01 ⁇ m or more and 0.02 ⁇ m or less. What is necessary is just to form.
- the SiC wide gap film can also be used as a photoactive layer (i-type layer).
- the first supply section 6a having a space for generating a hollow cathode discharge is provided.
- H 2 gas is supplied to the first introduction path 3a
- Ge-based gas such as SiH 4 (silane) gas or GeH 4 (german) gas is supplied to the second supply path 5.
- the gas pressure may be set to 100 Pa to 700 Pa and the high frequency power density may be set to 0.01 to 0.2 W / cm 2 .
- the SiGe narrow gap film is used to absorb light having a long wavelength that cannot be absorbed by the Si film.
- the film thickness of the i-type amorphous silicon germanium film is 0.1 ⁇ m to 0.5 ⁇ m, Preferably, it may be formed to be 0.15 ⁇ m or more and 0.3 ⁇ m or less.
- the film thickness of the i-type microcrystalline silicon germanium film is 1 ⁇ m or more and 4 ⁇ m or less, preferably What is necessary is just to form in 1.5 to 3 micrometer.
- the thin film solar cell formed using the above manufacturing method is formed from a high-quality film at a high speed, it is possible to produce a solar cell with high productivity and high conversion efficiency.
- a thin film solar cell for example, a tandem structure in which a semiconductor made of an amorphous silicon film and a semiconductor made of a microcrystalline silicon film are laminated from the light receiving surface side, a semiconductor made of an amorphous silicon film and an amorphous silicon germanium film are used. And a triple structure in which a semiconductor made of a microcrystalline silicon film, a semiconductor made of an amorphous silicon film, a semiconductor made of a microcrystalline silicon film, and a semiconductor made of a microcrystalline silicon germanium film are stacked. In addition, it is only necessary that at least one of the semiconductors can be formed by the above manufacturing method.
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Abstract
Description
チャンバーと、該チャンバー内に位置している第1電極と、前記チャンバー内に前記第1電極と所定間隔を隔てて位置している第2電極とを備えた堆積膜形成装置であって、
前記第2電極は、電極基体と、該電極基体の上に配置された複数の電極板とを有しており、
該電極板は、前記第1電極と前記第2電極との間の空間に第1原料ガスを供給する第1供給部と、前記空間に第2原料ガスを供給する第2供給部と、前記第1供給部に接続されて前記第1原料ガスが導入される第1供給経路と、前記第2供給部に接続されて前記第2原料ガスが導入される第2供給経路とを有しており、
前記電極基体は、前記第1原料ガスを加熱する加熱手段と、前記第1供給経路に前記第1原料ガスを導入する第1導入経路と、前記第2供給経路に前記第2原料ガスを導入する第2導入経路とを有しており、
前記第2供給経路は、前記第2導入経路から前記第2原料ガスが導入される、前記第2供給部を有さない本流部と、該本流部から前記第2原料ガスが導入される、前記第2供給部を有する複数の支流部とを有しており、
互いに隣り合う前記電極板の隣接部に、前記第2導入経路と前記本流部との接続部が位置していることを特徴とする。
図1に示すように、堆積膜形成装置S1は、チャンバー1と、チャンバー1内に位置している第1電極7と、チャンバー1内に第1電極7と所定間隔を隔てて位置しており、シャワー電極として機能する第2電極2とを有する。ここで、第2電極2は主に複数の電極板2aおよびこれらの電極板2aが配置されている1以上の電極基体2bで構成されている。堆積膜形成装置S1においては、第2電極2は1つの電極基体2bの上に4つの電極板2aが配置されている。また、堆積膜が形成される基材10が第1電極7と第2電極2との間に配置されている。なお、基材10は、第1電極7と第2電極2との間に位置させるようにすればよく、必ずしも第1電極7で保持しなくともよい。
1) SiH4+SiH2→Si2H6
2) Si2H6+SiH2→Si3H8
・・・ 以下、同様なSiH2挿入反応が続く・・・
といったSiH2挿入反応によって高分子重合体が生成していく反応である。
本実施形態の堆積膜の形成方法について説明する。堆積膜を形成するには、第1電極7に基材10を保持させる工程と、第2電極2に高周波電力を印加する工程と、第1原料ガスを加熱触媒体12により活性化した状態で第1供給部6aから、また、第2原料ガスを第2供給部6bから基材10に向かって供給し、第2原料ガスを第1電極7と第2電極2間に生じる空間8において活性化する工程と、を有する。これら工程によって、活性化された第1原料ガスと第2原料ガスとは、空間8で混ざり、原料ガス中の成分が基材10上に堆積することで、堆積膜が基材10上に形成される。
次に、上述した薄膜形成の前に行うクリーニング方法を含めた薄膜形成方法の例について、堆積膜形成装置S1を例にとり説明する。
ここで、Pはチャンバー内圧力(Pa)、Vはチャンバー内空間容積(m3)、Qはガス供給量(Pa・m3/sec)である。例えば、チャンバー内圧力としては、50Pa以上300Pa以下程度で行われる。
図1の堆積膜形成装置を用いてArガス(キャリアガス)を第1供給部、NF3ガス(クリーニングガス)を第2供給部からチャンバー内に供給して、薄膜形成装置のクリーニングを行った。
本発明は上述した実施形態に限定されるものではなく、本発明の範囲内で多くの修正および変更を加えることができる。例えば、第2供給部6bを支流部の端部側よりも中央側に多く設けたり、第2供給部6bの開口断面積が支流部の中央に向かうに従って大きくしてもよく、これにより均一にガスを供給することができる。
2 :第2電極
2a :電極板
2b :電極基体
3a :第1導入経路
3b :第2導入経路
4 :第1供給経路
5 :第2供給経路
51 :本流部
52 :支流部
53 :接続口(接続部)
6a :第1供給部
6b :第2供給部
7 :第1電極
8 :空間
10 :基材
12 :加熱触媒体(加熱手段)
16 :冷却機構
Claims (10)
- チャンバーと、該チャンバー内に位置している第1電極と、前記チャンバー内に前記第1電極と所定間隔を隔てて位置している第2電極とを備えた堆積膜形成装置であって、
前記第2電極は、電極基体と、該電極基体の上に配置された複数の電極板とを有しており、
該電極板は、前記第1電極と前記第2電極との間の空間に第1原料ガスを供給する第1供給部と、前記空間に第2原料ガスを供給する第2供給部と、前記第1供給部に接続されて前記第1原料ガスが導入される第1供給経路と、前記第2供給部に接続されて前記第2原料ガスが導入される第2供給経路とを有しており、
前記電極基体は、前記第1原料ガスを加熱する加熱手段と、前記第1供給経路に前記第1原料ガスを導入する第1導入経路と、前記第2供給経路に前記第2原料ガスを導入する第2導入経路とを有しており、
前記第2供給経路は、前記第2導入経路から前記第2原料ガスが導入される、前記第2供給部を有さない本流部と、該本流部から前記第2原料ガスが導入される、前記第2供給部を有する複数の支流部とを有しており、
互いに隣り合う前記電極板の隣接部に、前記第2導入経路と前記本流部との接続部が位置していることを特徴とする堆積膜形成装置。 - 複数の前記電極板のそれぞれに、前記第2導入経路と前記本流部との接続部が位置していることを特徴とする請求項1に記載の堆積膜形成装置。
- 複数の前記電極板のそれぞれは、前記第1導入経路を有していることを特徴とする請求項1または請求項2に記載の堆積膜形成装置。
- 前記電極基体は、該電極基体または前記電極板を冷却する冷却機構を有していることを特徴とする請求項3に記載の堆積膜形成装置。
- 前記電極基体は、前記加熱手段を複数有していることを特徴とする請求項1乃至4のいずれかに記載の堆積膜形成装置。
- 前記加熱手段の個数は、前記電極板の個数と同じであることを特徴とする請求項1乃至5のいずれかに記載の堆積膜形成装置。
- 前記電極基体は、補強リブを有しており、該補強リブに複数の前記電極板が固定されていることを特徴とする請求項1乃至6のいずれかに記載の堆積膜形成装置。
- 前記補強リブの内部に前記第2導入経路があることを特徴とする請求項7に記載の堆積膜形成装置。
- 前記加熱手段は、電流を流す金属線を有しており、前記電極板を平面透視した際に、該電極板における前記金属線の占有面積が前記電極板の中央部で小さくなるように、前記金属線が前記電極基体に配置されていることを特徴とする請求項1乃至9のいずれかに記載の堆積膜形成装置。
- 前記第1供給部は、ホローカソード放電が生じうるように、前記第1供給部の出口側において、流路断面積が出口に向かって次第に広くなっていることを特徴とする請求項1乃至9のいずれかに記載の堆積膜形成装置。
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US20190211450A1 (en) * | 2018-01-10 | 2019-07-11 | Asm Ip Holding B.V. | Shower plate structure for supplying carrier and dry gas |
US11149350B2 (en) * | 2018-01-10 | 2021-10-19 | Asm Ip Holding B.V. | Shower plate structure for supplying carrier and dry gas |
CN113130293A (zh) * | 2020-01-15 | 2021-07-16 | 株式会社国际电气 | 半导体装置的制造方法、基板处理装置和记录介质 |
JP2021111760A (ja) * | 2020-01-15 | 2021-08-02 | 株式会社Kokusai Electric | 半導体装置の製造方法、基板処理装置およびプログラム |
JP7118099B2 (ja) | 2020-01-15 | 2022-08-15 | 株式会社Kokusai Electric | 半導体装置の製造方法、基板処理装置およびプログラム |
CN113130293B (zh) * | 2020-01-15 | 2023-10-24 | 株式会社国际电气 | 半导体装置的制造方法、基板处理装置和记录介质 |
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JPWO2011062286A1 (ja) | 2013-04-11 |
US20120228129A1 (en) | 2012-09-13 |
US9206513B2 (en) | 2015-12-08 |
JP5570528B2 (ja) | 2014-08-13 |
CN102668032A (zh) | 2012-09-12 |
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