WO2011132775A1 - 薄膜太陽電池の製造方法 - Google Patents
薄膜太陽電池の製造方法 Download PDFInfo
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- WO2011132775A1 WO2011132775A1 PCT/JP2011/059959 JP2011059959W WO2011132775A1 WO 2011132775 A1 WO2011132775 A1 WO 2011132775A1 JP 2011059959 W JP2011059959 W JP 2011059959W WO 2011132775 A1 WO2011132775 A1 WO 2011132775A1
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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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/548—Amorphous silicon PV cells
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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 method for manufacturing a thin film solar cell in which a thin film is formed on a substrate.
- a film forming apparatus for forming thin film silicon or the like on a base material such as a glass substrate has, for example, a chamber, a gas introduction path for introducing a source gas into the chamber, and a pair of electrodes arranged in the chamber.
- a substrate for forming a deposited film is placed on one of the pair of electrodes, and a high frequency power source for applying high frequency power is connected to the other of the pair of electrodes.
- the plasma is generated in the space between the pair of electrodes by the high frequency power applied to the other of the pair of electrodes.
- the raw material gas is decomposed and excited to generate various active species.
- membrane is formed because a part of these active species deposits on a base material.
- the pressure in the chamber is set to 3 Torr (about 400 Pa) or more
- the source gas contains a silane-based gas and a hydrogen gas
- the flow rate of the hydrogen gas with respect to the silane-based gas is changed.
- a technique of 50 times or more has been proposed (see, for example, Patent Document 1 below).
- the upper limit of the film forming speed is usually less than 1.1 nm / second, and it is necessary to form a film at a high speed while maintaining a high quality film in order to increase productivity.
- an object of the present invention is to provide a method for manufacturing a thin-film solar cell capable of high-quality film formation even when film formation is performed at high speed.
- the manufacturing method of the thin film solar cell which concerns on this invention is a manufacturing method of the thin film solar cell which manufactures the thin film solar cell provided with the photoelectric converting layer containing the at least 1 layer of photoactive layer which has a crystalline silicon on a base material.
- a heated hydrogen gas having a flow rate ratio between the first electrode and the second electrode is supplied between the first electrode and the second electrode, and the application of the high-frequency power to the second electrode causes the first electrode and the second electrode to Even plasma generated between Te, characterized in that it comprises a photoactive layer formation step of forming the photoactive layer on the substrate.
- a thin film solar cell with high photoelectric conversion efficiency can be provided by forming a high quality thin film solar cell even when the film is formed at high speed.
- FIG. 1 It is a cross-sectional schematic diagram which shows an example of the thin film formation apparatus used for the manufacturing method of the thin film solar cell which concerns on this invention. It is a figure which shows typically the structural example of the heating body used for the manufacturing method of the thin film solar cell which concerns on this invention, (a) is a fragmentary perspective view which shows a mode that a part of heating body was cut
- FIG. 1 It is a sectional view (A), (b) is a top view which shows typically the structural example of the heating body used for the manufacturing method of the thin film solar cell which concerns on this invention, respectively. It is a figure which shows typically the structural example of the heating body used for the manufacturing method of the thin film solar cell which concerns on this invention, (a) is a top view, (b) was cut
- the thin film forming apparatus S includes a chamber 1, a first electrode 6 positioned in the chamber 1, and a first material 6 positioned in the chamber 1 and spaced apart from the first electrode 6.
- a second electrode 2 having a first supply part 4a capable of supplying a gas and a second supply part 4b capable of supplying a second source gas, and an introduction path connected to the first supply part 4a to introduce the first source gas And a heating means 11 arranged in the introduction path, a gas supply from the first supply part 4a, a gas supply from the second supply part 4b, and a control means for controlling the heating of the heating body 11 (not shown) And.
- the second electrode 2 functions as a shower electrode.
- a base material 10 on which a thin film is formed is disposed between the first electrode 6 and the second electrode 2 in the chamber 1.
- the base material 10 may be positioned between the first electrode 6 and the second electrode 2, and is not necessarily supported directly on the first electrode 6.
- the chamber 1 is a vacuum vessel having a reaction space that can be evacuated by at least an upper wall, a side wall, and a bottom wall.
- the inside of the chamber 1 is evacuated by the vacuum pump 7 and the internal pressure 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 6 has a function of an anode electrode and incorporates a heater for adjusting the temperature of the substrate 10.
- the first electrode 6 also functions as a temperature adjustment mechanism for the base material 10, whereby the base material 10 is adjusted to, for example, 100 to 400 ° C., more preferably 150 to 350 ° C.
- the first electrode 6 is made of a metal material such as stainless steel or aluminum.
- the base material 10 may be made of various materials that can withstand the above temperatures, such as a flat plate made of a glass substrate or the like, or a film made of a metal material or a resin.
- the high frequency power source 5 is connected to the second electrode 2, and high frequency power is applied to the second electrode 2.
- high frequency power from the high frequency power source 5 to the second electrode 2 plasma is formed in the space 8 located between the second electrode 2 and the substrate 10.
- the second electrode 2 is disposed to face the first electrode 6 and functions as a cathode electrode.
- the second electrode 2 has a plurality of supply parts 4 for supplying the gas introduced through the introduction path 3 into the chamber 1. These supply parts 4 are open toward the base material 10.
- a plurality of gas cylinders (not shown) that store different gases are connected to the first introduction path 3a and the second introduction path 3b.
- the gases introduced from the first introduction path 3a and the second introduction path 3b are not basically mixed until reaching the space 8 through the first supply part 4a and the second supply part 4b, respectively.
- the gas supplied to the plurality of supply parts 4 includes a first raw material gas supplied to the first supply part 4a and a second raw material having a higher decomposition probability than the first raw material gas supplied to the second supply part 4b. Including gas.
- the total gas decomposition rate is defined by the relational expression 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 material. Gas collision cross sections are shown respectively.
- exp ( ⁇ Ea / kTe) means a decomposition probability.
- exp ( ⁇ Ea / kTe) ⁇ ⁇ g is the collision cross-sectional area.
- the flow of the first source gas flowing through the first introduction path 3a may be divided and partly flow (mixed with the second source gas) into the second introduction path 3b.
- the first source gas and the second source gas are appropriately selected depending on the material of the thin 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 second source gas.
- H 2 (hydrogen) gas or the like is used as the non-Si-based gas.
- silicon-based gas examples include SiH 4 (silane), Si 2 H 6 (disilane), SiF 4 (silicon tetrafluoride), Si 2 F 6 (disilicon hexafluoride), and SiH 2 Cl 2 (dichlorosilane) gas.
- gases selected from the above are used.
- B 2 H 6 (diborane) gas or the like is used when forming a p-type Si-based thin film
- PH 3 (phosphine) gas or the like is used when forming an n-type Si-based thin film.
- the introduction path of the doping gas either the first introduction path 3a or the second introduction path 3b can be selected as necessary. However, as will be described later, when the heating body 11 connected to the heating power source 12 is provided in the first introduction path 3a, it is desirable to introduce the doping gas through the second introduction path 3b.
- the heating element 11 provided in the first introduction path 3a is a heated catalyst, a resistance heater, or the like.
- the heating catalyst body functions as an excitation activation (decomposition) of the contacting gas by passing an electric current through the medium and raising the temperature by heating.
- At least the surface of the heating catalyst body is made of a metal material.
- the metal material is preferably made of a metal material or an alloy material containing at least one of Ta, W, Re, Os, Ir, Nb, Mo, Ru, and Pt, which are refractory metal materials.
- a metal material as described above in a wire shape a plate shape or a mesh shape is used as the shape of the heating catalyst body. By setting the temperature of the heating catalyst body to 400 ° C. to 2000 ° C., the first source gas is heated and activated, and is also activated in the space 8.
- the heating element 11 may be composed of a heating element 21 that is a high-temperature element and a covering member 22 that covers the outer periphery of the heating element 21.
- the contact with the heat generating body 21 and 1st raw material gas is reduced.
- hydrogen absorption into the heating element 21 due to the first source gas and hydrogen embrittlement due to the hydrogenation reaction of the heating element material is reduced. Therefore, the life of the heating element 11 can be greatly extended. As a result, the frequency of maintenance that accompanies the stoppage of the apparatus is reduced, and productivity can be improved.
- the heating element 21 for example, a metal material such as an iron-chromium-aluminum alloy or nickel-chromium alloy having resistance heating, or a metal material such as platinum, molybdenum, tantalum, or tungsten, which is a refractory metal material, is used. Used.
- the covering member 22 may be a member having heat resistance.
- a metal member such as stainless steel, or ceramics such as alumina or silicon nitride can be used.
- coated member 22 can be aimed at by filling insulating materials, such as magnesium oxide, between the heat generating body 21 and a metal member.
- the covering member 22 may have a multilayer structure.
- coated member 22 is comprised with a member with high heat conductivity.
- a high-temperature fluid may be used as the heating element 21, and the high-temperature fluid is allowed to flow through the covering member serving as a pipe, thereby maintaining the high-speed film-forming effect of the high-quality film by heat activation of the first source gas.
- the life of 11 can be greatly extended.
- the flat plate shape provided with many through-holes 23 may be sufficient.
- the first source gas can be efficiently heated by increasing the surface area of the heating body 11.
- the first source gas passes through the through-hole 23, so that the first source gas is changed. While dispersing, the gas flow can be made uniform and the first source gas can be efficiently heated.
- the first source gas can be uniformly contacted with the heating body 11 and the first source gas can be efficiently heated. .
- the heating temperature of the heating body 11 may be 400 to 1000 ° C., and the first raw material gas is heated and activated, and further activated in the space 8. Further, by setting the heating temperature to a low temperature of 1000 ° C. or less, the warpage of the peripheral member constituting the chamber 1 or the second electrode 2 can be reduced, and the mechanical life of the peripheral member or the like can be improved.
- the higher-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 ... That is, a reaction in which a high molecular polymer is generated by SiH 2 insertion reaction.
- This SiH 2 is generated together with SiH 3 which is the main component of film formation when SiH 4 collides with electrons in the plasma.
- SiH 3 which is the main component of film formation when SiH 4 collides with electrons in the plasma.
- more high-order silane molecules are also generated.
- This higher-order silane production reaction is an exothermic reaction, and proceeds by discharging heat generated by the reaction into the space.
- the space from which reaction heat is to be discharged specifically, the space containing hydrogen gas as a main component
- the heating body 11 As described above, by using the heating body 11, a high-quality silicon film can be formed even under high-speed film forming conditions where the plasma excitation power is large.
- the heating element 11 is not particularly limited as long as it can heat the gas to a predetermined temperature.
- first supply unit 4a and the second supply unit 4b may be arranged in various patterns such as a dot-like lattice pattern or a staggered pattern arranged in an orderly manner.
- the number of the 1st supply part 4a and the 2nd supply part 4b may differ.
- the gas flow rate of the first raw material gas is different from the gas flow rate of the second raw material gas, for example, when the gas flow rate of the first raw material gas is higher than that of the second raw material gas, the first raw material gas is higher than the second supply unit 4b.
- first introduction path 3a and the second introduction path 3b may be connected to a gas adjustment unit that adjusts the flow rate, flow rate, temperature, and the like of the gas.
- the vacuum pump 7 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 preferably at least 1 ⁇ 10 ⁇ 3 Pa or less, preferably 1 ⁇ 10 ⁇ 4 Pa or less.
- the thin film forming apparatus S includes control means (not shown) for controlling the timing of gas supply from the first supply unit 4a, gas supply from the second supply unit 4b, and heating of the heating body 11.
- the heating body 11 is controlled to a predetermined temperature by controlling the power applied by the heating power source 12 to the heating body 11 by the control means.
- the timing of the gas supply from the 1st supply part 4a and the gas supply from the 2nd supply part 4b is controlled by detecting the temperature of the heating body 11.
- this control means performs opening / closing control of a supply valve that supplies gas, heating control of the heating element 11 through a DC power source, and the like.
- the heating of the heating body 11 can promote the decomposition of the first source gas. Further, the first raw material gas that has not been decomposed or the first raw material gas that has been recombined after the decomposition has the gas temperature itself increased, so that the gas decomposition is further promoted in the space 8.
- the second source gas is supplied by the second supply unit 4b without being brought into contact with the heating body 11 and is 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.
- the thin film forming apparatus S has a configuration in which a plurality of film forming chambers are connected to a front chamber (not shown) having a mechanism for transporting the base material 10 via an on-off valve body that blocks the flow of the source gas. Also good.
- a device including a p-type film forming film forming chamber, an i-type film forming film forming chamber, and an n-type film forming film forming chamber is used.
- Two film forming chambers may have the above structure.
- productivity can be improved, for example, a thin film solar cell with high conversion efficiency can be formed. it can.
- the 1st electrode 6 In the chamber 1 provided with the 1st electrode 6 which functions as an anode, and the 2nd electrode 2 which is provided facing the 1st electrode 6 and functions as a cathode to which high frequency electric power is applied, the 1st electrode 6
- the base material preparation process which arrange
- the base material 10 may be arranged so that the distance between the surface of the base material 10 and the surface of the second electrode 2 opposed to the surface is 5 mm or more and 15 mm or less.
- a silicon-based gas containing silicon (second source gas) and a heated hydrogen gas (first source gas) having a flow rate ratio of 25 to 58 times that of the silicon-based gas The photoactive layer is formed on the substrate 10 by plasma generated between the first electrode 6 and the second electrode 2 by applying high-frequency power to the second electrode 2 while being supplied between the second electrode 2 and the second electrode 2.
- the photoactive layer formation process formed on this is required.
- a first source gas and a second source gas different from the first source gas are supplied onto the substrate 10 disposed in the chamber 1. Then, the plasma generated in the space 8 forms a film on the base material 10, but the heating step of heating the heating body 11 used for heating the first source gas, the first source gas and the second source material
- the photoactive layer may be formed by setting the gas pressure in the chamber 1 to 1000 Pa or more.
- a heating catalyst body or a resistance heater is disposed as the heating body 11 in the first source gas flow path, and the heating body 11 is heated to a temperature below its melting point.
- the first source gas may be heated by Further, in the photoactive layer forming step, the power density of the high-frequency power as 0.5 W / cm 2 or more 1.7 W / cm 2 or less or applying a high frequency power to the second electrode 2.
- the said photoactive layer formation process it is good to adjust a flow rate ratio in the middle of a process so that the flow ratio of the 1st source gas with respect to 2nd source gas may become small in the middle of a process rather than the time of a process start. Furthermore, it is good to heat the base material 10 at the temperature of 180 degreeC or more and 220 degrees C or less after the said photoactive layer formation process.
- a microcrystalline silicon film has a wavelength sensitivity up to a long wavelength region as compared to an amorphous silicon film. However, since the light absorption coefficient is small, it is necessary to form a thick film. A membrane is required.
- the pressure during film formation is set to 1000 Pa or more. This is because even when the film is formed at a high speed by increasing the power density of the high-frequency power, the ion temperature can be reduced and the film can be formed by reducing the electron temperature by using this high pressure condition. It is.
- the first source gas whose temperature has been increased by the heating body 11 is supplied to the space 8, the high-order silane generation reaction is reduced due to the gas heating effect, even in a high-pressure condition. This is because a quality film can be formed.
- the upper limit of pressure should just be about 2500 Pa from relations, such as abnormal discharge.
- productivity can be improved and manufacturing cost can be reduced.
- the flow rate ratio of the first source gas that is hydrogen gas to the second source gas that is silicon-based gas is preferably 25 times or more and 58 times or less (particularly 25 times or more and less than 50 times).
- the frequency of the high frequency power applied to the second electrode 2 is a frequency of about 13.56 MHz to 100 MHz.
- a frequency of about 60 MHz or less is used.
- the frequency is set to 40.68 MHz or less, the film unevenness of the film formed on the large area substrate can be further reduced.
- a frequency of 13.56 MHz or 27.12 MHz is used.
- manufacturing cost can be reduced, and the area can be easily increased, so that productivity can be improved.
- the power density of the high-frequency power is preferably 0.5 W / cm 2 or more and 2 W / cm 2 or less. In particular, it is preferable that the 0.5 W / cm 2 or more 1.7 W / cm 2 or less. If it is the said range, it can film-form at high-speed, reducing the ion damage to a film
- the Raman peak intensity ratio (crystalline phase peak intensity / amorphous phase peak intensity) in the Raman scattering spectrum is preferably 2.5 or more and 6 or less.
- the crystal phase peak intensity is defined as the peak intensity at 520 cm ⁇ 1
- the amorphous phase peak intensity is defined as the peak intensity at 480 cm ⁇ 1 .
- the Raman spectrum is measured using, for example, a Renishaw Ramanscope System 1000 using a He—Ne laser (wavelength 632.8 nm) as excitation light.
- the crystallization rate of the microcrystalline silicon film is 50% to 70% from the relationship between the Raman peak area ratio and the Raman peak intensity ratio.
- the heating temperature of the heating element 11 is lowered to 400 ° C. or more and 1000 ° C. or less, and the gas flow rate ratio of H 2 / SiH 4 is 50/1 or less and H 2 . Even if the flow rate is reduced, the crystallization rate can be reduced to about 50 to 70%.
- the thin film solar cell formed using the above-described manufacturing method is formed from a high-quality film at high speed, a thin film solar cell with high productivity and high conversion efficiency can be formed.
- a first conductive layer 31 made of a light-transmitting conductive material such as SnO 2 , ITO, or ZnO is formed on a light-transmitting base material 10 such as glass, plastic, or resin.
- the film thickness of the first conductive layer 21 is about 100 nm to 1 ⁇ m.
- the i-type semiconductor layer functions as a photoactive layer on the first conductive layer 31, and the photoactive layer is made of an amorphous semiconductor such as amorphous silicon and has a pin junction inside.
- an i-type semiconductor layer functions as a photoactive layer
- a second photoelectric conversion layer 33 made of a microcrystalline semiconductor such as microcrystalline silicon and having a pin junction therein is formed as the photoactive layer.
- the first p layer and the n layer of the first photoelectric conversion layer 32 are about 5 to 30 nm, respectively, and the thickness of the first i-type semiconductor layer is about 200 nm to 1 ⁇ m.
- the second p layer and the n layer of the second photoelectric conversion layer 33 are each about 5 to 30 nm, and the thickness of the second i-type semiconductor layer is about 1 to 5 ⁇ m.
- a second conductive layer 34 made of a light-transmitting conductive material such as SnO 2 , ITO, or ZnO is formed on the second photoelectric conversion layer 33.
- a third conductive layer 35 made of a material such as silver having a high reflectance with respect to light is formed on the second conductive layer 34.
- the thickness of the second conductive layer 34 is about 5 nm to 2 ⁇ m, and the thickness of the third conductive layer 35 is about 100 to 500 nm.
- One of the second conductive layer 34 and the third conductive layer 35 may be formed.
- the second conductive layer 34 may be formed of a metal material such as silver.
- the present embodiment not only the tandem structure as described above, but also a semiconductor made of an amorphous silicon film, a semiconductor made of an amorphous silicon germanium film and a semiconductor made of a microcrystalline silicon film, or a semiconductor made of an amorphous silicon film, a microcrystal
- the present invention can also be applied to a triple structure thin film solar cell in which a semiconductor made of a silicon film and a semiconductor made of a microcrystalline silicon germanium film are stacked.
- a microcrystalline silicon film that needs to be formed at least thickly is formed using the above manufacturing method, whereby a thin film solar cell with high productivity and high conversion efficiency can be manufactured.
- the film forming process may be divided into two, and the flow rate of the first raw material gas relative to the second raw material gas in the latter half of the film formation may be smaller than in the first half of the film formation.
- the film forming speed can be increased and the conversion efficiency can be increased. This is because the crystallization rate of the microcrystalline silicon film is not always constant and tends to be high in the latter half of the film formation under a constant dilution condition. It can be considered that the increase in the crystallization rate is reduced.
- the dilution rate at the end of film formation may be about 3 to 15% lower than the dilution rate at the start of film formation as compared to the time at the start of film formation.
- the substrate may be heated at 180 ° C. or higher and 220 ° C. or lower. That is, heat treatment is performed after the thin film solar cell is formed. By performing the heat treatment, the conversion efficiency can be further increased. This is because the open-circuit voltage is improved by increasing the conductivity of the p-type semiconductor layer and the n-type semiconductor layer of the photoelectric conversion layer and increasing the activation energy. Further, it is presumed that hydrogen-induced defects in the film including the i-type semiconductor layer are reduced by hydrogen in the film being transferred to a stable site by heat treatment.
- the heat treatment time may be about 15 to 90 minutes.
- the first source gas may be supplied before the second source gas.
- the base material 10 may be disposed in the chamber 1.
- the supply of the second source gas may be stopped before the supply of the first source gas is stopped.
- the base material 10 may be taken out of the chamber 1.
- the heating body 11 when the heating body 11 is composed of a heating catalyst body, the heating body 11 may be heated to 800 ° C. or higher.
- the heating body 11 In the exhaust process, when the heating body 11 is made of a heating catalyst body, the heating body 11 may be heated to 800 ° C. or higher.
- the following steps 1 and 2 are sequentially performed before generating plasma for forming a thin film between the first electrode 6 and the second electrode 2. Good.
- Process 1 (heating process): The heating body 11 made of a heating catalyst body is heated to 800 ° C. or higher in a state where the chamber 1 is evacuated (1 Pa or less, preferably 0.1 Pa or less).
- Step 2 gas supply step: a first source gas (hydrogen gas) is supplied from the first supply unit 4a and a second source gas (for example, silane) is supplied into the chamber 1 from the second supply unit 4b.
- the pressure is adjusted to a predetermined value. At this time, when the temperature of the heating body 11 does not reach a predetermined value necessary for forming a thin film, the heating body 11 is further heated.
- the first source gas is supplied into the chamber 1 before the second source gas in step 2, so that the second source gas is changed to the second source gas. Since it is possible to reduce the backflow to the first supply path 3a, it is possible to reduce the deterioration of the heating body 11 due to the contact with the second source gas.
- the source gas is excited and activated by plasma generated by applying high-frequency power to the second electrode 2 in a state where the inside of the chamber 1 is adjusted to a predetermined pressure, and a predetermined amount is applied to the substrate 10 placed on the first electrode 6.
- a thin film having a thickness of 5 mm is formed. Thereafter, the following steps 3 to 4 are sequentially performed.
- Step 3 exhaust step: With the heating element 11 made of the heating catalyst body heated to 800 ° C. or higher, the supply of the first source gas and the second source gas is stopped, and the source gas in the chamber 1 is sufficiently exhausted. To do.
- Process 4 (cooling process): The heating body 11 is cooled in a state where the inside of the chamber 1 is evacuated.
- the heating catalyst body When a heating catalyst body made of, for example, Ta (tantalum) or W (tungsten) is used as the heating body 11, the heating catalyst body absorbs hydrogen components such as hydrogen molecules and hydrogen atoms in the source gas, and the hydrogen Since the component forms a hydride at the crystal grain boundary, it is considered that a phenomenon that facilitates fracture at the crystal grain boundary, that is, hydrogen embrittlement occurs. According to the above steps 1 and 2, since the hydrogen gas of the first source gas is supplied into the chamber 1 in a state where the heating catalyst body is heated, hydrogen absorption into the heating catalyst body is reduced. In particular, when hydrogen gas is supplied in a state where the heating catalyst body is heated to 800 ° C.
- the second source gas is changed to the second source gas by stopping the supply of the second source gas before the supply of the first source gas in Step 3. It is possible to reduce backflow to the one supply path 3a. Thereby, deterioration of the heating catalyst body accompanying the contact with the second source gas can be reduced.
- the thin film forming apparatus S includes a front chamber (not shown) connected to the chamber 1 so that the base material 10 can be carried in and out without the atmospheric pressure inside the chamber 1.
- a front chamber (not shown) connected to the chamber 1 so that the base material 10 can be carried in and out without the atmospheric pressure inside the chamber 1.
- the heating body 11 is heated so as to overlap in time with the operation in which the base material 10 is carried into the chamber 1. Further, in the step 4, it is preferable that the heating body 11 is cooled so that the operation of the substrate 10 being carried out of the chamber 1 overlaps in time. As a result, the process is shortened, and the productivity can be further improved.
- the processing time required for forming the thin film is increased by newly adding heating and cooling time for the heating element 11 in a vacuum state in the chamber 1.
- the loading / unloading operation of the base material 10 with the front chamber is performed.
- the heating / cooling step of the heating body 11 in a time-overlapping manner, the time required for forming a substantial thin film is shortened, and productivity can be maintained.
- the heating body 11 does not necessarily need to be heated and cooled, and may always be maintained at 800 ° C. or higher.
- 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 may be set to 50 to 700 Pa
- the gas flow ratio of H 2 / SiH 4 may be set to 2/1 to 40/1
- the high frequency power density may be set to 0.02 to 0.2 W / cm 2 .
- the first source gas whose temperature has been increased by the heating body 11 is supplied to the space 8. For this reason, 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 area A ⁇ b> 1 occupied by the heating body 11 may be wider than the thin film forming area A ⁇ b> 2 of the base material 10.
- the 1st source gas heated with the heating body 11 is uniformly supplied on the base material 10, maintaining the temperature.
- the space occupation density of the heating body 11 is small in the outer peripheral area of the heating body 11, so that efficient heating of the first source gas is difficult.
- the first source gas whose temperature has increased is in contact with the first source gas outside the region of the heating element 11 and the inner wall of the first introduction path 3a, the heat is removed and the temperature is lowered.
- the first source gas is kept on the base material 10 while maintaining a sufficiently high temperature. Since it is supplied uniformly, the quality of the thin film formed in the surface of the base material 10 becomes uniform, and a thin film solar cell having a uniform photoelectric conversion characteristic distribution can be formed.
- the area A3 occupied by the first supply unit 4a may be equal to or narrower than the area A1 occupied by the heating body 11, and may be wider than the thin film forming area A2 of the substrate 10.
- the first raw material gas can be uniformly brought into contact with the heating body 11, and the first raw material gas can be efficiently and uniformly heated.
- the first opening 13a for the first source gas to pass through is provided in the dispersion plate 13, and the heating element 11 occupies the area A4 occupied by the first opening 13a. It may be narrower than A1 and wider than the region A3 occupied by the first supply unit 4a.
- the radiation blocking member 14 it is preferable to provide the radiation blocking member 14 so as to cover the first supply unit 4a on the downstream side of the heating body 1 so that the radiant heat irradiated from the heating body 11 does not directly reach the base material 10. At this time, it is preferable that the radiation blocking member 14 has a function as a reflector that reflects the radiation irradiated from the heating body 11.
- the radiation blocking member 14 is provided with a second opening 14a through which the first source gas passes.
- the region A5 occupied by the second opening 14a may be equal to or narrower than the region A1 occupied by the heating body 11 and wider than the region A3 occupied by the first supply unit 4a.
- the above configuration also makes it difficult for the first source gas having a low temperature in the outer peripheral region of the heating body 11 and the vicinity thereof to be supplied to the space 8, and thus the quality of the thin film formed in the surface of the base material 10 becomes uniform, A thin film solar cell having a uniform photoelectric conversion characteristic distribution can be formed.
- a heat generating element such as a sheathed heater or a heat exchange pipe in which a high-temperature fluid such as gas or liquid is circulated may be used.
- a temperature of the edge part heating body 19 200 degreeC or more and 500 degrees C or less are preferable.
- the dispersion plate 13 and the radiation shielding member 14 have a plurality of support members 15 attached to the first introduction path 3a perpendicularly to the planar direction of each member. .
- the support member 15 in the central region of the dispersion plate 13 and the radiation blocking member 14, it is possible to reduce the warpage of the dispersion plate 13 and the radiation blocking member 14 due to the high temperature of the heating body 11.
- the gas flow passing through the radiation blocking member 14 can be maintained uniformly.
- the dispersion plate 13 and the radiation blocking member 14 may be subdivided into a plurality of pieces and fixed by the support member 15.
- the amount of warpage per sheet of the dispersion plate 13 and the radiation blocking member 14 accompanying the increase in the temperature of the heating element 11 can be reduced. 13 and the radiation flow through the radiation blocking member 14 can be maintained uniformly.
- the heating body 11 when the heating body 11 consists of a wire-shaped heating catalyst body as shown in FIG. 9, you may provide the auxiliary member 16 which supports the heating body 11 between the heating bodies 11 installed from one end to the other end. Absent.
- the auxiliary member 16 in the central portion of the heating body 11 installed from one end to the other end, the influence of heat with repeated use compared to the heating body 11 without the auxiliary member 16 shown in FIG. Since the possibility that the heated body 11 that has extended in contact with the first introduction path 3a or the adjacent heated bodies 11 come into contact with each other can be reduced, the replacement frequency of the heated body 11 can be reduced. And productivity can be improved. Further, when the heating body 11 extends and deforms, the distribution of the heating of the first source gas is generated, and the possibility that the quality of the thin film formed in the surface of the base material 10 becomes nonuniform can be reduced.
- one heating element 11 is bent at the end portion so that the heating element 11 is arranged in a certain region.
- a plurality of heating elements 11 may be arranged on the other end.
- the heating element 11 extended from one end is bent toward the one end by bending the heating element 11 in the auxiliary member 16 provided in the center, and extended from the other end.
- the heating body 11 may be bent at the auxiliary member 16 provided in the center portion, and again toward the other end.
- auxiliary members 16 may be provided as shown in FIG.
- a heating mechanism 17 having a heating body 11 provided on a support frame 18 movable in the horizontal direction may be provided.
- the heating mechanism 17 may be moved from the side of the thin film forming apparatus S into and out of the apparatus. Thereby, the exchange operation
- power may be supplied to the heating body 11 by supplying power to the heating body 11 through the power line in the support frame 18.
- the coupling portion 18a is provided on the support frame 18 so that the heating body mechanisms 17 are coupled to each other so that the coupling portion 18a has an energization function. Electric power can be supplied from the heating body mechanism 17 connected to the power source 12 to another heating body mechanism 17.
- the heating body 11 located in the lower stage is replaced by using a heating body mechanism 17 that can move in the horizontal direction. Exchange work can be simplified and productivity can be improved.
- a first conductive layer made of an SnO 2 film having a thickness of 800 nm was formed on a glass substrate by a thermal CVD method. And the 1st photoelectric converting layer was formed on the 1st conductive layer using the thin film forming apparatus S shown in FIG.
- the first photoelectric conversion layer p-type, i-type and n-type amorphous silicon films were sequentially laminated, and an n-type microcrystalline silicon film was laminated thereon.
- the film thickness of the i-type amorphous silicon film was 250 nm.
- a second photoelectric conversion layer was formed on the first photoelectric conversion layer.
- the second photoelectric conversion layer p-type and i-type microcrystalline silicon films were sequentially laminated, and an n-type amorphous silicon film was laminated thereon.
- the film thickness of the i-type microcrystalline silicon film was 2.5 ⁇ m.
- Silane gas and hydrogen gas were used as source gases.
- B 2 H 6 (diborane) was used for the p-type semiconductor layer as a doping gas
- PH 3 (phosphine) was used for the n-type semiconductor layer.
- a second conductive layer made of a 10 nm thick ZnO film and a third conductive layer made of 300 nm thick silver were laminated on the second photoelectric conversion layer by sputtering.
- the heating catalyst body made of a tantalum wire is heated to 1500 ° C. to heat the hydrogen gas, and in other films, the heating catalyst body is heated. Did not do. No. of Table 1 which is a comparative example. In any of 14 to 21, heating element 11 was not heated.
- An i-type microcrystalline silicon film was formed according to the film forming conditions shown in Table 1.
- the temperature of the glass substrate was adjusted to 190 ° C.
- the distance between the glass substrate and the second electrode was 6 mm.
- the photoelectric conversion efficiency was measured in the thin film solar cell produced on each condition, and while showing the result in Table 1, No. 1 of Table 1 is shown. Nos. 1 to 13 and No. 1 as a comparative example.
- FIG. 16 shows the relationship between the film forming speed and the conversion efficiency for 14 to 21.
- the comparative example No Furthermore, by heating the source gas with the heating element 11, the comparative example No. It was confirmed that a thin film solar cell with high speed and high conversion efficiency was formed even when the dilution rate of silicon-based gas with hydrogen gas was lower than that of 14-21.
- the Raman peak intensity ratio was 2.85 or more and 5.32 or less and 2.5 or more and 6 or less.
- the film thickness up to 2 ⁇ m is No. in Table 1.
- Film formation was performed under the conditions of No. 5, and the remaining 0.5 ⁇ m was formed by changing the flow rate of hydrogen gas relative to the silane gas from 42 times to 40 times. As a result, the film forming speed was 1.6 nm / second, and the change efficiency was improved to 12.72%.
- a thin film forming apparatus S shown in FIG. 1 is used to supply hydrogen gas as a first source gas from the first supply unit 4a and supply silane gas as a second source gas into the chamber 1 from the second supply unit 4b. did. And the temperature of the heating body 11 which is a heating catalyst body at the time of thin film formation was fixed to 1500 degreeC, and the hydrogenated microcrystal silicon film
- the heating element 11 was a wire made of tantalum having a thickness of ⁇ 0.5 mm and formed into a zigzag shape.
- the temperature of the heating element 11 is 25 ° C. (temperature change E1: test 22 (comparative example)), 400 ° C. (temperature change E2: No) in a state where the evacuation is performed before supplying hydrogen gas to the space 8 in the chamber 1. .23), 600 ° C. (temperature change E3: No. 24), 800 ° C. (temperature change E4: No. 25), and 1500 ° C. (temperature change E5: No. 26) in advance, Hydrogen gas was supplied into the chamber 1 while maintaining the temperature.
- Hydrogen gas was introduced into the space 8 in the chamber 1 and the pressure in the chamber 1 was adjusted to 1300 Pa. For 22 to 25, the temperature of the heating element 11 was further heated to the heating temperature (1500 ° C.) at the time of forming the thin film.
- silane gas was supplied to the space 8 in the chamber 1, and high frequency power was applied to the second electrode 2 at 450 W to excite plasma. Then, a hydrogenated microcrystalline silicon film was formed on the substrate 10.
- FIG. 18 also shows the relationship between the supply and stop of the source gas accompanying the temperature change of the heating element 11.
- a series of steps of heating process ⁇ gas supply process ⁇ film forming process ⁇ evacuation process ⁇ cooling process is performed in 50 cycles, 100 cycles and 150 cycles. confirmed. This deterioration state was evaluated by the presence or absence of breakage when the heating element 11 after each cycle was simply bent by hand.
- Table 3 shows the results. In Table 3, “NG” means that the thermal catalyst 11 was broken when it was bent, and “G” means that it was not broken. “NA” means that the heating element 11 is not evaluated by bending.
- No. in Table 3 is a comparative example. In No. 22, when 50 cycles of the series of steps had elapsed, the heating element 11 was already bent and easily broken. No. in Table 3 23 and no. In 24 (temperature changes E2 and E3), the fracture was confirmed when 100 cycles of the series of steps were performed. No. in Table 3 In 25 and 26 (temperature change E5 and temperature change E6), even after 150 cycles of the series of steps, the heating element 11 did not break and maintained ductility, and could be used further. From the above results, it was confirmed that the deterioration of the heating body 11 was reduced by setting the temperature of the heating body 11 to 800 ° C. or higher and supplying the hydrogen gas while maintaining the temperature.
- the thermal desorption analysis (TDS) method is used for hydrogen absorbed in the heated body 11 that has broken and in the heated body 11 that has not broken, or hydrogen that has been taken in as a hydride. ), A large amount of hydrogen was confirmed in the fractured heating element 11, but almost no hydrogen was identified in the heating element 11 that did not fracture. As described above, it was confirmed that the heating body 11 was also deteriorated by the hydrogen absorption by the preheating of the heating body 11 or the suppression of the hydride formation reaction by the TDS method.
- the heating catalyst body is preheated to 800 ° C. or higher, and then hydrogen gas is supplied, so that the heating catalyst body can be deteriorated without changing the film forming parameters or changing the material or structure of the heating catalyst body. It has been found that the productivity can be improved by extending the maintenance cycle without affecting the film quality and the film forming speed.
- Hydrogen gas which is the first source gas
- the silane gas which is 2nd raw material gas was supplied in the chamber 1 from the 2nd supply part 4b.
- the gas flow rate ratio of H 2 / SiH 4 was set to 45/1, and the high frequency power density (frequency: 27 MHz) was set to 0.96 W / cm 2 .
- the hydrogenated microcrystalline silicon film was formed on the white glass substrate 10 by changing the temperature of the heating element 11 when forming the thin film by dividing the gas pressure into 300 Pa or 1300 Pa.
- the crystal phase peak intensity was defined as the peak intensity at 520 cm ⁇ 1
- the amorphous phase peak intensity was defined as the peak intensity at 480 cm ⁇ 1 .
- the Raman spectrum was measured using a Renishaw Ramanscope System 1000 using a He—Ne laser (wavelength 632.8 nm) as excitation light. The results are shown in Table 4.
- the crystallization rate is 5% or less when the temperature of the heating element 11 is 1000 ° C. or less.
- the temperature of the heating body was 400 ° C. or lower, crystallization could not be confirmed.
- the crystallization rate is 53 % Or more and crystallization was confirmed.
- a thin film solar cell was formed using a thin film forming apparatus S as shown in FIG.
- a first conductive layer made of SnO 2 film having a thickness of 800nm on a substrate 10 of glass substrate by a thermal CVD method.
- a first photoelectric conversion layer was formed on the first conductive layer.
- an n-type microcrystalline silicon film was stacked on a layer in which p-type, i-type, and n-type amorphous silicon films were sequentially stacked.
- the film thickness of the i-type amorphous silicon film was 250 nm.
- the 2nd photoelectric converting layer was formed on the 1st photoelectric converting layer.
- an n-type amorphous silicon film was stacked on a layer in which p-type and i-type microcrystalline silicon films were sequentially stacked.
- the film thickness of the i-type microcrystalline silicon film was 2.5 ⁇ m.
- silane gas and hydrogen gas were used as the source gas
- B 2 H 6 was used as the p-type semiconductor layer as a doping gas
- PH 3 was used as the n-type semiconductor layer.
- a second conductive layer made of a ZnO film having a thickness of 10 nm and a third conductive layer made of silver having a thickness of 300 nm were formed on the second photoelectric conversion layer.
- the heating element 11 as the heating catalyst is heated to 1500 ° C. to heat the hydrogen gas, and in the other films, the thermal catalyst is used. No heating was performed.
- the heating element 11 was made of the same material and shape as in Example 1.
- the area A1 occupied by the heating element 11 is wider than the area A2 of the base material by 20 mm outside and 40 mm outside, respectively.
- 41 and 42 are areas where the area A1 occupied by the thermal catalyst is narrower 20 mm inside and 40 mm inside than the area A2 of the base material, respectively.
- the area A3 occupied by the first supply unit was an area wider by 30 mm than the area A2 of the base material.
- the dispersion plate 13 and the radiation preventing member 14 provided with a plurality of gas ejection holes of ⁇ 0.5 mm are widened upstream of the heating body 11 and downstream of the heating body 11 and 30 mm outside the area A2. installed.
- the conversion efficiency was measured in the thin film solar cell produced by each condition, and the difference of the average conversion efficiency in the center part of the base material 10 and the average conversion efficiency in the four corners of the base material 10 was compared. The results are shown in Table 5.
- the heating body was held only by the heating body support frame, and the heating body formed in a zigzag shape as in Example 2 was used.
- an auxiliary member made of quartz was attached to the support frame, and the heating body was held in the auxiliary member in addition to the support frame.
- Example 2 a first photoelectric conversion layer having an i-type amorphous silicon film and a second photoelectric conversion layer having an i-type microcrystalline silicon film were sequentially laminated to produce a thin film solar cell.
- the heating body was heated to a temperature of 1500 ° C. to form the film. And it repeated 100 times and produced the thin film solar cell.
- the thin film solar cell produced according to each condition was divided into 16 and the conversion efficiency was measured in each region. And the lowest conversion efficiency of the in-plane area
- Method 1 the thin-film solar cell produced for the 100th time had a photoelectric conversion efficiency of 22% lower than that of the thin-film solar cell produced for the first time, whereas in Method 2, the reduction was only 5%. .
- the high rate of decrease in photoelectric conversion efficiency in Method 1 is considered to be due to deformation of the heating element. In other words, it is considered that the characteristics deteriorated because the crystallization rate in the thin film solar cell produced by the adjacent heating bodies deformed and densely increased and exceeded the crystallization rate suitable for the photoelectric conversion efficiency.
- Chamber 2 2nd electrode 4: Supply part 4a: 1st supply part 4b: 2nd supply part 5: High frequency power supply 6: 1st electrode 10: Base material 11: Heating body 31: 1st conductive layer 32: 1st 1 photoelectric conversion layer 33: 2nd photoelectric conversion layer 34: 2nd conductive layer 35: 3rd conductive layer S: Thin film formation apparatus
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Abstract
Description
まず、本実施形態で使用する薄膜形成装置の基本構造について説明する。図1に示すように、薄膜形成装置S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6と、チャンバー1内に第1電極6と離間して位置して、第1原料ガスを供給できる第1供給部4aおよび第2原料ガスを供給できる第2供給部4bを備えた第2電極2と、第1供給部4aに接続されて第1原料ガスが導入される導入経路と、この導入経路内に配置されている加熱体11と、第1供給部4aからのガス供給、第2供給部4bからのガス供給および加熱体11の加熱を制御する制御手段(不図示)とを備えている。
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。
次に、薄膜太陽電池の製造方法の一例について説明する。基材10の上に、シリコン結晶相を有する少なくとも1層の光活性層を含む光電変換層を備えた薄膜太陽電池を製造するには、以下に示す工程が必要である。
次に、製造方法の変形例について説明する。図5に示すように、薄膜形成装置Sにおいて、加熱体11が占有する領域A1を基材10の薄膜形成領域A2よりも広くしてもよい。上記構成とすることによって、加熱体11で加熱された第1原料ガスがその温度を維持しつつ基材10上に均一に供給される。領域A1が領域A2より狭い場合、加熱体11の外周領域においては加熱体11の空間占有密度が小さいため、第1原料ガスの効率的な加熱が難しい。さらに、温度上昇した第1原料ガスが加熱体11の領域外にある第1原料ガスおよび第1導入経路3aの内壁に接触することよって熱を奪われ、温度が低下することから、十分なガスヒーティング効果が加熱体11の外周領域に近くなるほど得られにくい。
2 :第2電極
4 :供給部
4a :第1供給部
4b :第2供給部
5 :高周波電源
6 :第1電極
10 :基材
11 :加熱体
31 :第1導電層
32 :第1光電変換層
33 :第2光電変換層
34 :第2導電層
35 :第3導電層
S :薄膜形成装置
Claims (14)
- 基材の上に、結晶シリコンを有する少なくとも1層の光活性層を含む光電変換層を備えた薄膜太陽電池を製造する薄膜太陽電池の製造方法であって、
アノード用の第1電極と、該第1電極に対向して配置されて高周波電力が印加されるカソード用の第2電極とを備えているチャンバー内に、前記第1電極と前記第2電極との間に前記基材を配置する基材準備工程と、
前記チャンバー内のガス圧が1000Pa以上になるように、シリコンを含むシリコン系ガスと該シリコン系ガスの25倍以上58倍以下の流量比の加熱した水素ガスとを前記第1電極と前記第2電極との間に供給して、前記第2電極への前記高周波電力の印加によって前記第1電極と前記第2電極との間に発生させたプラズマでもって、前記光活性層を前記基材の上に形成する光活性層形成工程とを含むことを特徴とする薄膜太陽電池の製造方法。 - 前記シリコン系ガスとして、シラン、ジシラン、四フッ化珪素、六フッ化二珪素およびジクロロシランから選択される1種以上のガスを用いることを特徴とする請求項1に記載の薄膜太陽電池の製造方法。
- 前記基材準備工程において、前記基材の表面と該表面に対向させる前記第2電極の表面との距離が5mm以上15mm以下となるように前記基材を配置することを特徴とする請求項1または2に記載の薄膜太陽電池の製造方法。
- 前記光活性層形成工程において、前記水素ガスの流路に加熱体を配置して、該加熱体によって前記水素ガスを加熱することを特徴とする請求項1乃至3のいずれかに記載の薄膜太陽電池の製造方法。
- 前記加熱体として、加熱触媒体または抵抗加熱ヒーターを用いることを特徴とする請求項4に記載の薄膜太陽電池の製造方法。
- 前記加熱体を800℃以上に加熱することを特徴とする請求項4または5に記載の薄膜太陽電池の製造方法。
- 前記光活性層形成工程において、前記高周波電力のパワー密度を0.5W/cm2以上1.7W/cm2以下に設定す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薄膜太陽電池の製造方法。
- 前記光活性層形成工程において、前記高周波電力の周波数を13.56MHz以上40.68MHz以下に設定することを特徴とする請求項1乃至7のいずれかに記載の薄膜太陽電池の製造方法。
- 前記光活性層形成工程において、前記シリコン系ガスに対する前記水素ガスの流量比が工程開始時よりも工程途中で小さくなるように、工程途中で前記流量比を調整することを特徴とする請求項1乃至8のいずれかに記載の薄膜太陽電池の製造方法。
- 前記水素ガスを前記シリコン系ガスよりも先に前記第1電極と前記第2電極との間に供給す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薄膜太陽電池の製造方法。
- 前記光活性層形成工程の後に、前記基材を180℃以上220℃以下の温度で加熱することを特徴とする請求項1乃至10のいずれかに記載の薄膜太陽電池の製造方法。
- 前記光活性層形成工程の後に、前記水素ガスおよび前記シリコン系ガスの供給を停止して、前記チャンバー内を排気する排気工程と、前記加熱体を冷却する冷却工程とをさらに有することを特徴とする請求項4乃至11のいずれかに記載の薄膜太陽電池の製造方法。
- 前記排気工程において、前記シリコン系ガスの供給の停止を前記水素ガスの供給の停止よりも先に行なうことを特徴とする請求項12に記載の薄膜太陽電池の製造方法。
- 前記冷却工程において、前記基材を前記チャンバーの外に出すことを特徴とする請求項12または13に記載の薄膜太陽電池の製造方法。
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US9112088B2 (en) | 2015-08-18 |
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