WO2012057201A1 - Dispositif de conversion photoélectrique et procédé de fabrication d'un dispositif de conversion photoélectrique - Google Patents

Dispositif de conversion photoélectrique et procédé de fabrication d'un dispositif de conversion photoélectrique Download PDF

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WO2012057201A1
WO2012057201A1 PCT/JP2011/074665 JP2011074665W WO2012057201A1 WO 2012057201 A1 WO2012057201 A1 WO 2012057201A1 JP 2011074665 W JP2011074665 W JP 2011074665W WO 2012057201 A1 WO2012057201 A1 WO 2012057201A1
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photoelectric conversion
type semiconductor
semiconductor layer
layer
conversion unit
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Japanese (ja)
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祥二 佐見津
伸 浅利
征典 橋本
徹志 藤長
健一 今北
雅文 若井
一也 斎藤
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株式会社アルバック
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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
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/06—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers
    • H01L31/075—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers the potential barriers being only of the PIN type, e.g. amorphous silicon PIN solar cells
    • H01L31/076—Multiple junction or tandem solar cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/054—Optical elements directly associated or integrated with the PV cell, e.g. light-reflecting means or light-concentrating means
    • H01L31/056—Optical elements directly associated or integrated with the PV cell, e.g. light-reflecting means or light-concentrating means the light-reflecting means being of the back surface reflector [BSR] type
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/06—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers
    • H01L31/075—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers the potential barriers being only of the PIN type, e.g. amorphous silicon PIN solar cells
    • H01L31/077—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers the potential barriers being only of the PIN type, e.g. amorphous silicon PIN solar cells the devices comprising monocrystalline or polycrystalline materials
    • 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
    • Y02E10/52—PV systems with concentrators
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/547—Monocrystalline silicon PV cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/548—Amorphous silicon PV cells

Definitions

  • the present invention relates to a photoelectric conversion device and a method for manufacturing the photoelectric conversion device.
  • This application claims priority based on Japanese Patent Application No. 2010-242413 filed in Japan on October 28, 2010, the contents of which are incorporated herein by reference.
  • photoelectric conversion devices are generally used for solar cells, optical sensors, and the like, and in particular, solar cells have begun to spread widely from the viewpoint of efficient use of energy.
  • a photoelectric conversion device using single crystal silicon is excellent in energy conversion efficiency per unit area.
  • a photoelectric conversion device using single crystal silicon uses a silicon wafer obtained by slicing a single crystal silicon ingot, a large amount of energy is consumed for manufacturing the ingot, which increases the manufacturing cost. For example, when a large-area photoelectric conversion device installed outdoors as a solar cell is manufactured using single crystal silicon, the cost is considerably high at present.
  • amorphous (amorphous) silicon thin films (hereinafter also referred to as “a-Si thin films”) that can be manufactured at a lower cost can be manufactured at a lower cost, and thus have become widespread. ing.
  • the photoelectric conversion device using this amorphous (amorphous) silicon thin film has a lower conversion efficiency than a crystalline photoelectric conversion device using single crystal silicon, polycrystalline silicon, or the like. Therefore, as a method for improving the conversion efficiency of the photoelectric conversion device, a method of stacking two photoelectric conversion units into a tandem type has been proposed. For example, as shown in FIG. 6, an insulating transparent substrate 101 on which a transparent conductive film 102 is disposed is used, and a p-type semiconductor layer 131 and an i-type silicon layer (amorphous silicon layer) are formed on the transparent conductive film 102.
  • a stacked pin-type second photoelectric conversion unit 104 is sequentially stacked. Furthermore, a tandem photoelectric conversion device 100 in which a back electrode 105 is disposed on a second photoelectric conversion unit 104 is known (see, for example, Patent Document 1).
  • the back electrode 105 is formed of a conductive light reflecting film such as Ag (silver).
  • Ag silver
  • the back electrode 105 reflects the light transmitted through the first photoelectric conversion unit 103 and the second photoelectric conversion unit 104 and returns the light to the second photoelectric conversion unit 104 and the first photoelectric conversion unit 103 again.
  • a diffusion preventing layer made of GZO (TCO) or the like is inserted between the second photoelectric conversion unit 104 and the back electrode 105.
  • the light transmitted through the first photoelectric conversion unit 103 and the second photoelectric conversion unit 104 is absorbed by the diffusion prevention layer, and the effect of back surface reflection by Ag is impaired, and sunlight is efficiently converted into light. There was a problem that it could not be used.
  • a first object is to provide a photoelectric conversion device having a tandem structure.
  • a second object of the present invention is to provide a method for manufacturing a photoelectric conversion device capable of manufacturing a photoelectric conversion device having a tandem structure with improved photoelectric conversion efficiency by a simple method.
  • the present invention provides a photoelectric conversion device having a single structure including a pin-type photoelectric conversion unit made of a crystalline silicon-based thin film, avoiding light absorption at the back electrode, increasing light utilization efficiency, and photoelectric conversion.
  • a third object is to provide a photoelectric conversion device with improved efficiency.
  • a fourth object of the present invention is to provide a method for manufacturing a photoelectric conversion device capable of manufacturing a single-structure photoelectric conversion device with improved photoelectric conversion efficiency by a simple method.
  • the present invention employs the following means in order to solve the above problems and achieve the object. That is, (1) In a photoelectric conversion device according to one embodiment of the present invention, a transparent conductive film provided over a substrate; a p-type semiconductor layer, a substantially intrinsic i-type semiconductor layer, and an n-type semiconductor layer are stacked.
  • a pin-type first photoelectric conversion unit and a second photoelectric conversion unit; and the first photoelectric conversion unit, the second photoelectric conversion unit, and a back electrode are sequentially provided on the transparent conductive film;
  • the p-type semiconductor layer and the i-type semiconductor layer constituting the second photoelectric conversion unit are formed of a crystalline silicon-based thin film; the i-type semiconductor layer constituting the second photoelectric conversion unit; and the back electrode;
  • the n-type semiconductor layer constituting the second photoelectric conversion unit is formed from a microcrystalline silicon-based thin film containing oxygen; the n-type semiconductor layer constituting the second photoelectric conversion unit Thickness is 10 Greater than ⁇ 800 ⁇ is in the range of less.
  • an i-type semiconductor formed of an amorphous silicon-based thin film between the i-type semiconductor layer and the n-type semiconductor layer constituting the second photoelectric conversion unit.
  • the layer is preferably arranged as a barrier layer.
  • the photoelectric conversion device includes a microcrystalline silicon-based thin film between the n-type semiconductor layer and the back electrode constituting the second photoelectric conversion unit. It is preferable that a p-type semiconductor layer is further arranged.
  • a method for manufacturing a photoelectric conversion device includes a transparent conductive film provided over a substrate, a p-type semiconductor layer, a substantially intrinsic i-type semiconductor layer, and an n-type semiconductor layer.
  • a pin-type first photoelectric conversion unit and a second photoelectric conversion unit that are stacked, and the first photoelectric conversion unit, the second photoelectric conversion unit, and a back electrode are sequentially provided on the transparent conductive film.
  • the p-type semiconductor layer and the i-type semiconductor layer constituting the second photoelectric conversion unit are formed from a crystalline silicon-based thin film, and the i-type semiconductor layer and the back surface constituting the second photoelectric conversion unit
  • the n-type semiconductor disposed between the electrode and the n-type semiconductor constituting the second photoelectric conversion unit is formed of a microcrystalline silicon-based thin film containing oxygen and constituting the second photoelectric conversion unit Layer thickness , A method of manufacturing a photoelectric conversion device that is in a range of greater than 100 ⁇ and less than or equal to 800 ⁇ , wherein the p-type semiconductor layer, the i-type semiconductor layer, the n-type semiconductor layer, and the second photoelectric conversion of the first photoelectric conversion unit
  • the p-type semiconductor layer, the i-type semiconductor layer, and the n-type semiconductor layer of the unit are formed at least in order, and an oxygen-containing gas is introduced when forming the n-type semiconductor layer of the second photoelectric conversion unit. To do.
  • a transparent conductive film provided over a substrate; a p-type semiconductor layer, a substantially intrinsic i-type semiconductor layer, and an n-type semiconductor layer are stacked.
  • a pin-type third photoelectric conversion unit; and the third photoelectric conversion unit and a back electrode are sequentially provided on the transparent conductive film; the p-type semiconductor layer and the i-type semiconductor layer are crystalline.
  • a silicon-based thin film; disposed between the i-type semiconductor layer and the back electrode; and the n-type semiconductor layer is formed from a microcrystalline silicon-based thin film containing oxygen; The thickness is in the range of more than 100 mm and not more than 800 mm.
  • a method for manufacturing a photoelectric conversion device includes a transparent conductive film provided over a substrate, a p-type semiconductor layer, a substantially intrinsic i-type semiconductor layer, and an n-type semiconductor layer.
  • a pin-type third photoelectric conversion unit wherein the third photoelectric conversion unit and a back electrode are provided in order on the transparent conductive film, and the front p-type semiconductor layer and the i-type semiconductor layer are The n-type semiconductor is formed from a crystalline silicon-based thin film, disposed between the i-type semiconductor layer and the back electrode, and the n-type semiconductor layer is formed from a microcrystalline silicon-based thin film containing oxygen.
  • a method for manufacturing a photoelectric conversion device wherein the thickness of the layer is in a range of greater than 100 mm and less than or equal to 800 mm, wherein the p-type semiconductor layer, the i-type semiconductor layer, and the n-type semiconductor layer are formed at least in order,
  • the n-type half of the photoelectric conversion unit In forming the body layer, introducing an oxygen-containing gas.
  • the n layer constituting the second photoelectric conversion unit is a microcrystalline silicon-based thin film containing oxygen, whereby i of the second photoelectric conversion unit is obtained.
  • the refractive index of the n-type semiconductor layer is lower than the refractive index of the n-type semiconductor layer.
  • the refractive index of the n-type semiconductor layer and the i-type semiconductor layer constituting the second photoelectric conversion unit can be transmitted through the i-type semiconductor layer of the first photoelectric conversion unit and the second photoelectric conversion unit. Due to the difference, the n-type semiconductor layer can reflect and return to each i-type semiconductor layer again.
  • the optical path length can be extended and the light utilization efficiency can be improved.
  • the n-type semiconductor layer which comprises a 2nd photoelectric conversion unit is arrange
  • the present photoelectric conversion device it is possible to provide a tandem photoelectric conversion device with improved photoelectric conversion efficiency.
  • a p-type semiconductor layer and an i-type semiconductor layer made of a crystalline silicon-based thin film are formed in this order.
  • the obtained photoelectric conversion device reflects the light transmitted through the i-type semiconductor layer by the n-type semiconductor layer constituting the second photoelectric conversion unit and returns it to each i-type semiconductor layer again, thereby reducing the optical path length.
  • the light utilization efficiency is improved.
  • the method for manufacturing a photoelectric conversion device it is possible to provide a method for manufacturing a photoelectric conversion device that can easily manufacture a tandem photoelectric conversion device with improved photoelectric conversion efficiency.
  • the n-type semiconductor layer constituting the third photoelectric conversion unit is a microcrystalline silicon-based thin film containing oxygen. Refractive index decreases.
  • the light that cannot be absorbed by the i-type semiconductor layer of the third photoelectric conversion unit and is transmitted through the n-layer is reflected by the difference in refractive index between the n-type semiconductor layer and the i-type semiconductor layer constituting the third photoelectric conversion unit. Then, it can be returned to the i layer again.
  • the optical path length can be extended and the light utilization efficiency can be improved.
  • the n-type semiconductor layer which comprises a 3rd photoelectric conversion unit is arrange
  • this photoelectric conversion device it is possible to provide a single-structure photoelectric conversion device with improved photoelectric conversion efficiency.
  • a p-type semiconductor layer and an i-type semiconductor layer made of a crystalline silicon-based thin film are sequentially formed.
  • the obtained photoelectric conversion device can extend the optical path length by reflecting the light transmitted through the i-type semiconductor layer by the n-type semiconductor layer and returning it to the i-layer again. improves.
  • the method for manufacturing a photoelectric conversion device it is possible to provide a method for manufacturing a photoelectric conversion device that can easily manufacture a tandem photoelectric conversion device with improved photoelectric conversion efficiency.
  • FIG. 1 is a structural cross-sectional view illustrating a layer configuration of a photoelectric conversion device.
  • a transparent conductive film 2 is provided on one surface 1a of the substrate 1, and the first photoelectric conversion unit 3 and the second photoelectric conversion unit 4 are provided on the transparent conductive film 2. They are stacked in this order.
  • Each of the first photoelectric conversion unit 3 and the second photoelectric conversion unit 4 includes a p-type semiconductor layer (p layer), a substantially intrinsic i-type semiconductor layer (i layer), and an n-type semiconductor layer (n layer). Are stacked to form a pin-type photoelectric conversion unit. Further, a back electrode 5 is provided on the second photoelectric conversion unit 4 so as to overlap therewith.
  • substantially intrinsic means that the Fermi level is in the middle of the forbidden band and functions as a pin-type i-type semiconductor layer even if a small amount of impurities is contained.
  • substrate 1 is formed from the durable insulating material which is excellent in the transmittance
  • a transparent conductive film 2 is provided on the substrate 1.
  • the transparent conductive film 2 is made of a light-transmitting metal oxide such as ITO (indium tin oxide), SnO 2 , or ZnO, and is formed by a vacuum deposition method or a sputtering method.
  • ITO indium tin oxide
  • SnO 2 Tin oxide
  • ZnO ZnO
  • the first photoelectric conversion unit 3 includes a p-type semiconductor layer (p layer) 31, a substantially intrinsic i-type semiconductor layer (i layer) 32, and an n-type semiconductor layer (n layer) 33. It has a pin structure. That is, a p-type semiconductor layer (p layer) 31, a substantially intrinsic i-type semiconductor layer (i-layer) 32, and an n-type semiconductor layer (n layer) 33 are stacked in this order, and the first photoelectric layer is stacked.
  • the conversion unit 3 is configured.
  • the first photoelectric conversion unit 3 is a photoelectric conversion unit formed of, for example, an amorphous (amorphous) silicon-based material.
  • the thickness of the p-type semiconductor layer (p layer) 31 of the first photoelectric conversion unit 3 is, for example, 80 mm
  • the thickness of the i-type semiconductor layer (i layer) 32 is, for example, 2000 mm
  • the thickness of (n layer) 33 is, for example, 200 mm.
  • the p layer 31, i layer 32, and n layer 33 of the first photoelectric conversion unit 3 are formed in separate plasma CVD reaction chambers.
  • the second photoelectric conversion unit 4 has a pin structure including a p-type semiconductor layer (p layer) 41, a substantially intrinsic i-type semiconductor layer (i layer) 42, and an n-type semiconductor layer (n layer) 43. have. That is, the p-type semiconductor layer (p-layer) 41, the substantially intrinsic i-type semiconductor layer (i-layer) 42, and the n-type semiconductor layer (n-layer) 43 are stacked in this order, so that the second photoelectric The conversion unit 4 is configured.
  • the second photoelectric conversion unit 4 is a photoelectric conversion unit made of a silicon-based material containing a crystalline material.
  • a p-type semiconductor layer (p layer) 41 constituting the second photoelectric conversion unit 4 and a substantially intrinsic i-type semiconductor layer (i layer) 42. are formed from a crystalline silicon-based thin film.
  • the n-type semiconductor layer (n layer) 43 constituting the second photoelectric conversion unit 4 is disposed between the i-type semiconductor layer (i layer) 42 constituting the second photoelectric conversion unit 4 and the back electrode 5. ing.
  • the n-type semiconductor layer (n layer) 43 is formed from a microcrystalline silicon-based thin film containing oxygen, and the thickness of the n-type semiconductor layer (n layer) 43 is in the range of 100 to 800 mm.
  • the n layer 43 constituting the second photoelectric conversion unit 4 is formed of a microcrystalline silicon-based thin film (for example, SiO) containing oxygen, the refractive index of the n layer 43 is the refractive index of the i layer 42. Falls below the rate.
  • the light that has been transmitted without being absorbed by each of the i layers 32 and 42 of the first photoelectric conversion unit 3 and the second photoelectric conversion unit 4 is reflected by the difference in refractive index between the n layer 43 and the i layer 42. And can be returned to the i layer 42 again.
  • the optical path length can be extended and the light use efficiency is improved.
  • the n layer 43 having a lower refractive index than the i layer 42 is disposed in front of the back electrode 5 in the light traveling direction, light absorption in the diffusion preventing layer of the back electrode 5 can be suppressed. .
  • photoelectric conversion device 10A (10) of a first embodiment it is possible to improve photoelectric conversion efficiency.
  • the thickness of the n layer 43 constituting the second photoelectric conversion unit 4 is greater than 100 mm and equal to or less than 800 mm.
  • the short circuit current (Jsc) increases as compared with the case where the thickness of the n layer, which is microcrystalline silicon containing no oxygen, is formed 300 mm.
  • the short-circuit current (Jsc) is reduced as compared with the case where the thickness of the n layer 43 which is microcrystalline silicon is 300 mm.
  • the thickness of the n layer 43 is 100 mm or less, the n layer 43 does not function and the conversion efficiency is lowered. Furthermore, in consideration of conversion efficiency, the thickness of the n layer 43 is preferably not less than 300 mm and not more than 700 mm. Since the open-circuit voltage (Voc) has a peak when the thickness of the n layer 43 is in the range of 300 to 700 mm, the conversion efficiency can be high within this range.
  • the intensity of the Raman scattered light attributed to the amorphous phase dispersed in the n layer 43 observed by a laser Raman microscope is denoted by Ia, and the Raman scattered light attributed to the microcrystalline phase dispersed in the n layer 43 is measured.
  • the crystallization ratio [value obtained by dividing Ic by Ia, hereinafter referred to as (Ic / Ia)] in the n layer 43 is 1.11.
  • (Ic / Ia) is 1.0 or more and it turns out that it is a microcrystal.
  • the (Ic / Ia) of the n layer 43 is preferably 1.0 or more.
  • the thickness of the p-type semiconductor layer (p layer) 41 of the second photoelectric conversion unit 4 is, for example, 150 mm
  • the thickness of the i-type semiconductor layer (i layer) 42 is, for example, 15000 mm
  • the thickness of (n layer) 43 is, for example, 300 mm.
  • an amorphous silicon-based thin film is interposed between the i-type semiconductor layer (i layer) 42 and the n-type semiconductor layer (n layer) 43.
  • the i-type semiconductor layer is preferably disposed as the barrier layer 45.
  • an i layer made of an amorphous silicon thin film is arranged as a barrier layer 45 between the i layer 42 made of a crystalline silicon thin film and the n layer 43. Holes that have flowed back to the n-layer side by the function of the layer are reflected to the p-layer side, and the short-circuit current (Jsc) can be improved.
  • the function of the barrier layer 45 can increase the band gap of the microcrystalline cell and improve the open circuit voltage (Voc).
  • Voc and Jsc can be improved by inserting the barrier layer 45, and the power generation efficiency of the second photoelectric conversion unit 4 can be improved. Can do. As a result, it is possible to improve the photoelectric conversion efficiency of the entire device.
  • the thickness of the barrier layer 45 is preferably in the range of 10 to 200 mm, for example. For example, it can be 50 mm.
  • the effect of increasing the photoelectric conversion efficiency is recognized when the thickness of the barrier layer 45 is in the range of 0 to 200 mm. In the range where the thickness of the barrier layer 45 is 50 mm or more, Jsc decreases. On the other hand, the increase in Voc and fill factor (FF) improves the photoelectric conversion efficiency as a whole.
  • the intensity of the Raman scattered light attributed to the amorphous phase dispersed in the barrier layer 45, observed with a laser Raman microscope, is Ia
  • the intensity of the Raman scattered light attributed to the microcrystalline phase dispersed in the barrier layer 45 is In the case of Ic, the crystallization ratio [value obtained by dividing Ic by Ia, hereinafter referred to as (Ic / Ia)] in the barrier layer 45 constituting the photoelectric conversion device 10A (10) is less than 1.0. .
  • This barrier layer 45 can be controlled independently regardless of the crystallization rate (Ic / Ia) of the i-layer 42 of the microcrystalline cell. In other words, by adopting such a layer structure, the photoelectric conversion device 10 can improve Jsc. With such a layer structure, the power generation efficiency in the long wavelength region is improved, and the photoelectric conversion efficiency can be improved by about 1% in the microcrystalline tandem thin film solar cell.
  • the back electrode 5 should just be comprised by electroconductive light reflection films, such as Ag (silver) and Al (aluminum).
  • the back electrode 5 can be formed by sputtering or vapor deposition, for example.
  • the back electrode 5 is a laminate in which a layer made of a conductive oxide such as ITO, SnO 2 , or ZnO is formed between the n-type semiconductor layer (n layer) 43 of the second photoelectric conversion unit 4 and the back electrode 5. A structure is also possible.
  • the p layer 31, the i layer 32, and the n layer 33 of the first photoelectric conversion unit 3 are formed in order, and the second photoelectric conversion unit 4 is formed on the n layer 33 of the first photoelectric conversion unit 3.
  • the p layer 41 and the i layer 42 constituting the second photoelectric conversion unit 4 may be sequentially formed, and the n layer 43 constituting the second photoelectric conversion unit 4 may be formed on the i layer 42 constituting the second photoelectric conversion unit 4.
  • a p-layer 41 made of a crystalline silicon-based thin film and an i-layer 42 are sequentially formed, and an n-layer 43 made of a crystalline silicon-based thin film is formed on the i-layer 42. It is preferable. Thereby, since the n layer 43 can contain oxygen, the obtained photoelectric conversion device 10 reflects the light transmitted through the i layer 42 by the n layer 43 constituting the second photoelectric conversion unit 4. By returning to the i layer again, the optical path length can be extended, and the light utilization efficiency is improved. As described above, by including oxygen in the n layer 43 of the second photoelectric conversion unit 4, it is possible to easily manufacture the photoelectric conversion device 10 having a tandem structure with improved photoelectric conversion efficiency. A method for manufacturing a photoelectric conversion device according to the first embodiment of the present invention will be described below in the order of steps.
  • an insulating transparent substrate 1 on which a transparent conductive film 2 is formed is prepared.
  • the p-type semiconductor layer 31 and the i-type silicon layer (amorphous silicon layer) of the first photoelectric conversion unit 3 are formed on the transparent conductive film 2 formed on the insulating transparent substrate 1.
  • Layer) 32, the n-type semiconductor layer 33, and the p-type semiconductor layer 41 of the second photoelectric conversion unit 4 are formed in separate plasma CVD reaction chambers. That is, on the n-type semiconductor layer 33 of the first photoelectric conversion unit 3, the photoelectric conversion device first intermediate product 10a provided with the p-type semiconductor layer 41 constituting the second photoelectric conversion unit 4 is formed.
  • the p-type semiconductor layer 31 is, for example, a p-layer of amorphous silicon (a-Si) by plasma CVD in a separate reaction chamber.
  • the p-layer is composed of a substrate temperature of 170-200 ° C., an applied RF power of 40 W,
  • the pressure in the reaction chamber is 70 to 120 Pa, the reaction gas flow rate is 150 sccm for monosilane (SiH 4 ), 470 sccm for hydrogen (H 2 ), 45 sccm for diborane (B 2 H 6 / H 2 ) using hydrogen as a diluent gas, and methane (
  • the film is formed under the condition of CH 4 ) of 300 sccm.
  • the buffer layer is, for example, an i-layer of amorphous silicon (a-Si) by plasma CVD in an individual reaction chamber.
  • the i-layer is formed by a substrate temperature of 170-200 ° C., an applied RF power of 40 W, a pressure in the reaction chamber.
  • the film is formed under the conditions of 60 to 120 Pa, the reaction gas flow rate is 150 sccm for monosilane (SiH 4 ), 1500 sccm for hydrogen (H 2 ), and 200 sccm for methane (CH 4 ).
  • the i-type silicon layer (amorphous silicon layer) 32 is, for example, an i-layer of amorphous silicon (a-Si) by plasma CVD in an individual reaction chamber.
  • the film is formed under the conditions of 200 ° C., applied RF power of 40 W, reaction chamber pressure of 40 to 120 Pa, and the reaction gas flow rate of monosilane (SiH 4 ) of 300 sccm.
  • the n-type semiconductor layer 33 is, for example, an amorphous silicon (a-Si) n-layer formed by plasma CVD in a separate reaction chamber.
  • the n-type semiconductor layer 33 has a substrate temperature of 170-200 ° C. and an applied RF power. 100 to 1000 W, the pressure in the reaction chamber is 70 to 1000 Pa, the flow rate of the reaction gas is 20 to 150 sccm for monosilane (SiH 4 ), 550 to 2000 sccm for hydrogen (H 2 ), and phosphine (PH 3 / H with hydrogen as a diluent gas). 2 ) is formed under the condition of 15 to 60 sccm.
  • the p-type semiconductor layer 41 is, for example, a p-layer of microcrystalline silicon ( ⁇ c-Si) by a plasma CVD method in a separate reaction chamber.
  • the reaction chamber pressure is 500 to 1200 Pa
  • the reaction gas flow rate is 30 sccm for monosilane (SiH 4 ), 9000 sccm for hydrogen (H 2 ), and 12 sccm for diborane (B 2 H 6 / H 2 ) using hydrogen as a diluent gas.
  • the film is formed.
  • the same plasma CVD reaction chamber is formed on the p-type semiconductor layer 41 exposed to the atmosphere.
  • the i-type silicon layer (crystalline silicon layer) 42 constituting the second photoelectric conversion unit 4 is formed, the barrier layer 45 is formed, the n-type semiconductor layer 43 is formed, and the p-type semiconductor layer 46 is formed.
  • the photoelectric conversion device second intermediate product 10 b provided with the second photoelectric conversion unit 4 is formed on the first photoelectric conversion unit 3.
  • a photoelectric conversion device 10A (10) as shown in FIG. 1 is obtained.
  • the i-type silicon layer (crystalline silicon layer) 42 is, for example, an i-layer of microcrystalline silicon ( ⁇ c-Si) by plasma CVD in the same reaction chamber as the n-type semiconductor layer 43.
  • the film is formed under the conditions of a temperature of 170 to 200 ° C., an applied RF power of 550 W, a reaction chamber pressure of 500 to 1200 Pa, and a reaction gas flow rate of 38 cc for monosilane (SiH 4 ) and 2700 sccm for hydrogen (H 2 ).
  • the barrier layer 45 is an i layer of amorphous silicon (a-Si), for example, by plasma CVD in the same reaction chamber as the i-type semiconductor layer 42.
  • the i layer is formed by applying a substrate temperature of 170 to 200 ° C. and an applied RF The film is formed under the conditions that the power is 40 W, the pressure in the reaction chamber is 40 to 120 Pa, and the reaction gas flow rate is 300 sccm of monosilane (SiH 4 ).
  • the n-type semiconductor layer 43 is, for example, an n-layer of microcrystalline silicon ( ⁇ c-SiO) containing oxygen by plasma CVD in the same reaction chamber as the i-type silicon layer (crystalline silicon layer) 42.
  • the substrate temperature is 170 to 200 ° C.
  • the applied RF power is 1000 W
  • the pressure in the reaction chamber is 500 to 900 Pa
  • the reaction gas flow rate is 20 sccm for monosilane (SiH 4 ), 12000 sccm for hydrogen (H 2 ), and hydrogen as a diluent gas.
  • the film formation is performed under the condition that the phosphine (PH 3 / H 2 ) is 15 sccm and the carbon dioxide (CO 2 ) is 20 sccm.
  • the p-type semiconductor layer 46 is, for example, a p-layer of microcrystalline silicon oxide ( ⁇ c-Si) by plasma CVD in the same reaction chamber as the n-type silicon oxide layer (crystalline silicon oxide layer) 43.
  • the substrate temperature is 170-200 ° C.
  • the applied RF power is 750 W
  • the reaction chamber pressure is 500 to 1200 Pa
  • the reaction gas flow rate is 30 sccm for monosilane (SiH 4 ), 9000 sccm for hydrogen (H 2 )
  • hydrogen is the diluent gas.
  • Diborane (B 2 H 6 / H 2 ) is formed under the condition of 12 sccm.
  • the first film forming apparatus includes a p-type semiconductor layer 31, an i-type silicon layer (amorphous silicon layer) 32, an n-type semiconductor layer 33 in the first photoelectric conversion unit 3, and a p-type semiconductor in the second photoelectric conversion unit 4.
  • This is a so-called in-line type in which a plurality of film formation reaction chambers called chambers in which the layers 41 are separately formed are connected in a straight line.
  • the exposure device exposes the p layer of the second photoelectric conversion unit 4 to the atmosphere.
  • the second film formation apparatus includes the i-type silicon layer (crystalline silicon layer) 42, the barrier layer 45, the n-type semiconductor layer 43, and the p-type semiconductor layer 46 in the second photoelectric conversion unit 4 in the same film formation reaction chamber. This is a so-called batch type in which a plurality of substrates are processed at the same time.
  • a manufacturing system of the photoelectric conversion device 10 is shown in FIG. As shown in FIG. 3, the manufacturing system exposes the first film forming apparatus 60, the second film forming apparatus 70, and the substrate processed by the first film forming apparatus 60 to the atmosphere, and then the second film forming apparatus 70. And an exposure device 80 that moves to The first film forming apparatus 60 in the manufacturing system is provided with a charging (L) chamber 61 in which a substrate is first loaded and placed in a reduced pressure atmosphere. A heating chamber that heats the substrate temperature to a certain temperature may be provided in the subsequent stage of the L chamber 61 according to the process.
  • L charging
  • a p-layer film formation reaction chamber 62 for forming the p-type semiconductor layer 31 of the first photoelectric conversion unit 3 an i-layer film formation reaction chamber 63 for forming the i-type silicon layer (amorphous silicon layer) 32, and n
  • An n-layer film formation reaction chamber 64 for forming the p-type semiconductor layer 33 and a p-layer film formation reaction chamber 65 for forming the p-type semiconductor layer 41 of the second photoelectric conversion unit 4 are continuously arranged in a straight line.
  • an unload (UL) chamber 66 for returning the decompressed state to the atmospheric atmosphere and carrying out the substrate is arranged. At this time, as shown in FIG.
  • an insulating transparent substrate 1 having a transparent conductive film 2 formed thereon is prepared at a point A in FIG. Further, at point B in FIG. 3, as shown in FIG. 2B, the p-type semiconductor layer 31 of the first photoelectric conversion unit 3 and the i-type are formed on the transparent conductive film 2 formed on the insulating transparent substrate 1.
  • the photoelectric conversion device 10 first intermediate product 10 a provided with the silicon layer (amorphous silicon layer) 32, the n-type semiconductor layer 33, and the p-type semiconductor layer 41 of the second photoelectric conversion unit 4 is formed.
  • the second film forming apparatus 70 in the manufacturing system carries in the first intermediate product 10a of the photoelectric conversion device 10 first processed by the first film forming apparatus 60 and puts it in a reduced pressure atmosphere, or a substrate under reduced pressure.
  • a loading / unloading (L / UL) chamber 71 for unloading the substrate in an atmospheric atmosphere is disposed.
  • the i-type silicon layer (crystalline silicon layer) 42 of the second photoelectric conversion unit 4 is formed on the p-type semiconductor layer 41 of the second photoelectric conversion unit 4 through the preparation / removal (L / UL) chamber 71.
  • the barrier layer 45, the n-type semiconductor layer 43, and the p-type semiconductor layer 46 are sequentially formed in the same reaction chamber, and a pin layer film formation reaction chamber 72 capable of simultaneously processing a plurality of substrates is arranged. ing.
  • the photoelectric conversion device 10 in which the second photoelectric conversion unit 4 is provided is formed on the first photoelectric conversion unit 3 at a point C in FIG. 3.
  • the in-line type first film forming apparatus 60 is shown so that two substrates are processed simultaneously, and the i-layer film forming reaction chamber 63 is constituted by four reaction chambers 63a, 63b, 63c, and 63d. Shown configured. Also, in FIG. 3, the batch-type second film forming apparatus 70 is shown so that six substrates are processed simultaneously.
  • the photoelectric conversion device is a crystalline photoelectric conversion device on the p layer 31, the i layer 32, and the n layer 33 of the first photoelectric conversion unit 3 that is an amorphous photoelectric conversion device.
  • the second photoelectric conversion unit 4 is formed. Control of the crystallization rate distribution of the i layer 42 of the conversion unit 4 can be facilitated.
  • the barrier layer 45 in the same film formation chamber between the i layer 42 and the n layer 43 of the second photoelectric conversion unit 4, it is possible to obtain the photoelectric conversion device 10 having good characteristics. it can.
  • an i-type silicon layer (crystalline silicon layer) 42, a barrier layer 45, an n-type semiconductor layer 43, and a p layer 46 constituting the second photoelectric conversion unit 4 are formed on the p-type semiconductor layer 41 exposed to the atmosphere.
  • the i layer 42 it is desirable to subject the p layer 41 of the second photoelectric conversion unit 4 exposed to the atmosphere to OH radical-containing plasma treatment or hydrogen plasma treatment before forming the i layer 42.
  • the p layer, i layer, and n of the first photoelectric conversion unit 3 are formed on the transparent metal oxide electrode of the glass substrate 1 with the transparent metal oxide electrode (transparent conductive film 2) in a separate film formation chamber.
  • the i-type silicon layer (crystalline silicon layer) 42, the barrier layer 45, the n-type semiconductor layer 43, and the p-type semiconductor layer 46 constituting the second photoelectric conversion unit 4 may be formed in separate film formation chambers.
  • the i layer 42, the barrier layer 45, the n layer 43, and the p layer 46 of the second photoelectric conversion unit 4 may be stacked in succession with the OH radical-containing plasma processing in the same processing chamber.
  • the film formation chamber is provided for each treatment. Is treated with OH radical-containing plasma. This enables decomposition and removal of the residual impurity gas PH 3. Therefore, a good impurity profile can be obtained even when the film formation of the i layer 42, the barrier layer 45, the n layer 43, and the p layer 46 of the second photoelectric conversion unit 4 is repeated in the same processing chamber, and a laminated thin film having good power generation efficiency.
  • the photoelectric conversion device 10 can be obtained.
  • OH radical-containing plasma treatment applied to the p layer 41 of the second photoelectric conversion unit 4, it is desirable to use CO 2 , CH 2 O 2 or a mixed gas composed of H 2 O and H 2 as the process gas. . That is, for the generation of OH radical-containing plasma, (CO 2 + H 2 ), (CH 2 O 2 + H 2 ) or (H 2 O + H 2 ) is allowed to flow in the film formation chamber, for example, 13. It can be effectively generated by applying a high frequency such as 5 MHz, 27 MHz, or 40 MHz.
  • alcohols such as (HCOOCH 3 + H 2 ) and (CH 3 OH + H 2 ), and oxygen-containing hydrocarbons such as formate esters may be used.
  • oxygen-containing hydrocarbons such as formate esters
  • H 2 When CO 2 is used as the plasma generation gas in the generation of this OH radical-containing plasma, the presence of H 2 is necessary in the system, but in addition to (CH 2 O 2 + H 2 ) and (H 2 O + H 2 ) When oxygen-containing hydrocarbons such as alcohols such as (HCOOCH 3 + H 2 ) and (CH 3 OH + H 2 ) and formate esters are used, the presence of H 2 is not necessarily required in the system.
  • the reaction is gentle compared to O radicals, and the microcrystals formed on the p layer 31 and the i layer 32 of the first photoelectric conversion unit 3 without damaging the lower layer.
  • This is effective for the surface activity of the p layer 41 of the second photoelectric conversion unit 4 formed through the n layer 33 in which the phases are dispersed in the amorphous crystal phase. Therefore, the surface activation of the p layer 41 of the second photoelectric conversion unit 4 becomes possible, and it works effectively on the crystal formation of the i layer 42 of the second photoelectric conversion unit 4 laminated thereon, and is uniform even on a large-area substrate. It is possible to obtain a simple crystallization rate distribution. Even if the hydrogen plasma treatment is performed instead of the OH radical-containing plasma treatment, the same effect as the OH radical-containing plasma treatment can be obtained.
  • the crystalline n layer 33 and the p layer 41 of the second photoelectric conversion unit 4 formed on the amorphous p layer 31 and the i layer 32 of the first photoelectric conversion unit 3 in separate film formation chambers Even in a film in which microcrystalline silicon ( ⁇ c-Si) is dispersed in an amorphous silicon (a-Si) layer, microcrystalline silicon ( ⁇ c-Si) is dispersed in an amorphous silicon oxide (a-SiO) layer. A dispersed film may be used.
  • ⁇ c-Si microcrystalline silicon
  • a-SiO silicon
  • a film in which microcrystalline silicon ( ⁇ c-Si) is dispersed in an amorphous amorphous silicon oxide (a-SiO) layer can be adjusted to have a lower refractive index than an amorphous silicon (a-Si) semiconductor layer. Therefore, it is possible to improve the conversion efficiency by using a wavelength selective reflection film and confining short wavelength light on the top cell side. Regardless of the optical confinement effect, a film in which microcrystalline silicon ( ⁇ c-Si) is dispersed in an amorphous silicon oxide (a-SiO) layer is subjected to OH radical-containing plasma treatment to produce a second photoelectric layer. This effectively works to generate crystal growth nuclei of the i layer 42 and the n layer 43 of the conversion unit 4, and a uniform crystallization rate distribution can be obtained even on a large-area substrate.
  • the n layer 33 constituting the first photoelectric conversion unit 3 may be formed of a crystalline silicon thin film. That is, the crystalline n layer 33 and the p layer 41 of the crystalline second photoelectric conversion unit 4 are formed on the p layer 31 and the i layer 32 of the amorphous first photoelectric conversion unit 3. At this time, the p layer 31 of the amorphous first photoelectric conversion unit 3, the crystalline n layer 33 formed on the i layer 32, and the p layer 41 of the second photoelectric conversion unit 4 are formed in separate film formation chambers. After forming the p layer 31 and the i layer 32 of the first photoelectric conversion unit 3, it is desirable to form them continuously without opening to the atmosphere.
  • the atmosphere is released to the atmosphere, and the p layer 41, i layer 42, In the method of forming the n layer 43, the device performance is deteriorated due to the deterioration of the i layer 32 of the first photoelectric conversion unit 3 depending on the time, temperature, atmosphere, and the like of leaving the substrate open to the atmosphere. Therefore, after the p layer 31 and the i layer 32 of the first photoelectric conversion unit 3 are formed, the crystalline n layer 33 and the p layer 41 of the second photoelectric conversion unit 4 are continuously formed without opening to the atmosphere. .
  • the surface of the substrate on which the crystalline n layer 33 and the p layer 41 of the second photoelectric conversion unit 4 are formed is activated by OH radical-containing plasma treatment individually or in the same film formation chamber to generate crystal nuclei. And subsequently laminating the i-layer 42 of the crystalline second photoelectric conversion unit 4, the laminated thin-film photoelectric conversion device 10 A (10) having a uniform crystallization rate distribution over a large area and good power generation efficiency is obtained. Obtainable.
  • FIG. 4 is a structural cross-sectional view showing the layer configuration of the photoelectric conversion device 10B (10) according to the present embodiment.
  • the tandem structure photoelectric conversion device has been described.
  • the present invention is not limited to the tandem structure, and can also be applied to a single structure photoelectric conversion device.
  • this photoelectric conversion device 10B 10
  • a transparent conductive film 2 is provided on one surface 1a of the substrate 1, and a p-type semiconductor layer (p layer) 81 is substantially intrinsic on the transparent conductive film 2.
  • An i-type semiconductor layer (i layer) 82 and an n-type semiconductor layer (n layer) 83 are laminated in this order, and a pin-type third photoelectric conversion unit 8 is formed.
  • the p layer 81 and the i layer 82 constituting the third photoelectric conversion unit 8 are formed from a crystalline silicon-based thin film.
  • the n layer 83 which is disposed between the i layer 82 constituting the third photoelectric conversion unit and the back electrode 5 and which constitutes the third photoelectric conversion unit 8 is formed from a microcrystalline silicon thin film containing oxygen.
  • the thickness of the n layer 83 is in the range of 200 to 400 mm.
  • the refractive index of the n layer 83 is i. Lower than the refractive index of layer 82.
  • the light transmitted without being absorbed by the i layer 82 can be reflected by the n layer 83 due to the difference in refractive index between the n layer 83 and the i layer 82 and returned to the i layer 82 again.
  • the optical path length can be extended, and the light utilization efficiency is improved.
  • the n layer 83 having a lower refractive index than the i layer 82 is disposed in front of the back electrode 5 in the light traveling direction, light absorption in the diffusion preventing layer of the back electrode 5 can be suppressed. . As a result, the photoelectric conversion efficiency of the photoelectric conversion device 10B (10) is improved.
  • an amorphous silicon-based thin film is interposed between the i-type semiconductor layer (i layer) 82 and the n-type semiconductor layer (n layer) 83. It is preferable that the i layer made of is arranged as the barrier layer 85. Further, in the photoelectric conversion device 10B (10), a p-type semiconductor layer made of a microcrystalline silicon-based thin film is disposed between the n-type semiconductor layer (n layer) 83 and the back electrode 5 constituting the third photoelectric conversion unit 8. (P layer) 86 may be further arranged.
  • photoelectric conversion apparatus 10B which concerns on 2nd embodiment of this invention forms p layer 81 and i layer 82 which comprise the 3rd photoelectric conversion unit 8 in order, and the 3rd photoelectric conversion unit 8 An n layer 83 constituting the third photoelectric conversion unit 8 is formed on the i layer 82.
  • the p layer 81, i layer 82, and n layer 83 constituting the third photoelectric conversion unit 8 are all the p layer 41, i layer 42, and the second photoelectric conversion unit 4 in the first embodiment described above.
  • the n layer 43 can be formed in the same manner. In this way, by including oxygen in the n layer 43, the obtained photoelectric conversion device 10B (10) reflects the light transmitted through the i layer 82 by the n layer 83 and returns it to the i layer 82 again. As a result, the optical path length can be extended, and the light utilization efficiency is improved. As a result, according to the present invention, it is possible to provide a method for manufacturing a photoelectric conversion device that can easily manufacture a tandem photoelectric conversion device with improved photoelectric conversion efficiency.
  • the photoelectric conversion device manufactured by each example and comparative example and the manufacturing conditions are as follows.
  • a photoelectric conversion device having a tandem structure was fabricated and experimented.
  • the photoelectric conversion device was manufactured using a substrate having a size of 1100 mm ⁇ 1400 mm in any of the examples.
  • Example 1 is a p-layer, a buffer layer, and an amorphous amorphous silicon (a-Si) thin film formed from an amorphous amorphous silicon (a-Si) thin film as a first photoelectric conversion unit on a substrate.
  • An n layer containing microcrystalline silicon ( ⁇ c-Si) and a p layer containing microcrystalline silicon ( ⁇ c-Si) constituting the second photoelectric conversion unit are respectively formed on the i layer formed from Continuously formed in separate film forming chambers. Thereafter, the p layer of the second photoelectric conversion unit is exposed to the atmosphere, and the p layer of the second photoelectric conversion unit is subjected to hydrogen plasma treatment using hydrogen (H 2 ) as a process gas.
  • H 2 hydrogen
  • An n layer formed of oxygen-containing microcrystalline silicon ( ⁇ c-SiO) and a p layer formed of microcrystalline silicon ( ⁇ c-Si) are formed.
  • Example 1 the p layer, the i layer, the n layer of the first photoelectric conversion unit, and the p layer of the second photoelectric conversion unit are formed by plasma CVD in individual reaction chambers.
  • the p-type semiconductor layer 31 of the first photoelectric conversion unit has a substrate temperature of 170 ° C., an applied RF power of 40 W, a reaction chamber pressure of 80 Pa, a reaction gas flow rate of 150 sccm of monosilane (SiH 4 ), and hydrogen (H 2 ).
  • the film was formed to a thickness of 80 mm under conditions of 470 sccm, diborane (B 2 H 6 / H 2 ) using hydrogen as a diluent gas at 45 sccm, and methane (CH 4 ) at 300 sccm.
  • the film formation rate at this time was 132 liters / minute.
  • the buffer layer has a substrate temperature of 170 ° C., an applied RF power of 40 W, a reaction chamber pressure of 60 Pa, a reaction gas flow rate of 150 sccm for monosilane (SiH 4 ), 1500 sccm for hydrogen (H 2 ), and methane (CH 4 ).
  • the film formation rate at this time was 55 liters / minute.
  • the i layer of the first photoelectric conversion unit has a substrate temperature of 170 ° C., an applied RF power of 40 W, a reaction chamber pressure of 40 Pa, and a reaction gas flow rate of 2000 ⁇ with monosilane (SiH 4 ) of 300 sccm. A film was formed. The film formation rate at this time was 146 ⁇ / min. Furthermore, the n layer of the first photoelectric conversion unit has a substrate temperature of 170 ° C., an applied RF power of 100 W, a reaction chamber pressure of 80 Pa, and a reaction gas flow rate of 150 cc of monosilane (SiH 4 ) and hydrogen (H 2 ).
  • the film was formed to a thickness of 50 mm under conditions of 550 sccm and phosphine (PH 3 / H 2 ) using hydrogen as a diluent gas at 60 sccm. At this time, the film formation rate was 239 K / min. Further, the n layer has a substrate temperature of 170 ° C., an applied RF power of 1000 W, a reaction chamber pressure of 800 Pa, a reaction gas flow rate of 2000 sccm of hydrogen (H 2 ), and phosphine (PH 3 / H with hydrogen as a diluent gas). 2 ) was formed to a thickness of 150 mm under the condition of 15 sccm. At this time, the film formation rate was 191 ⁇ / min.
  • the substrate temperature is 170 ° C.
  • the applied RF power is 750 W
  • the reaction chamber pressure is 1200 Pa
  • the reaction gas flow rate is 30 sccm for monosilane (SiH 4 )
  • hydrogen H 2
  • a film was formed to a thickness of 150 mm under conditions of 9000 sccm and diborane (B 2 H 6 / H 2 ) using hydrogen as a diluent gas at 12 sccm. At this time, the film formation rate was 197 K / min.
  • the p layer of the second photoelectric conversion unit is exposed to the atmosphere, and the substrate temperature is 190 ° C., the power supply frequency is 13.56 MHz, the pressure in the reaction chamber is 700 Pa, and the process gas is H 2.
  • the plasma treatment was performed under the condition of 1000 sccm.
  • the i layer of the second photoelectric conversion unit has a substrate temperature of 170 ° C., an applied RF power of 550 W, a reaction chamber pressure of 1200 Pa, and a reaction gas flow rate of 38 sccm for monosilane (SiH 4 ) and 2700 sccm for hydrogen (H 2 ).
  • a film having a thickness of 15000 mm was formed. At this time, the film formation rate was 247 K / min.
  • the barrier layer was formed to a thickness of 100 mm under the conditions of a substrate temperature of 170 ° C., an applied RF power of 40 W, a reaction chamber pressure of 40 Pa, and a reactive gas flow rate of monosilane (SiH 4 ) of 300 sccm.
  • the film formation rate at this time was 115 ⁇ / min.
  • the n layer of the second photoelectric conversion unit has a substrate temperature of 170 ° C., an applied RF power of 1000 W, a pressure in the reaction chamber of 800 Pa, and a reaction gas flow rate of 20 sccm for monosilane (SiH 4 ) and 12000 sccm for hydrogen (H 2 ).
  • a film having a thickness of 300 mm was formed under conditions of phosphine (PH 3 / H 2 ) using hydrogen as a diluent gas and 150 sccm of carbon dioxide (CO 2 ). At this time, the film formation rate was 94 cm / min.
  • the p layer has a substrate temperature of 170 ° C., an applied RF power of 750 W, a reaction chamber pressure of 1200 Pa, a reactive gas flow rate of 30 sccm for monosilane (SiH 4 ), 9000 sccm for hydrogen (H 2 ), and hydrogen as a diluent gas.
  • the formed diborane (B 2 H 6 / H 2 ) was formed to a thickness of 50 mm under the condition of 12 sccm. At this time, the film formation rate was 197 K / min.
  • n layer of the second photoelectric conversion unit has a substrate temperature of 170 ° C., an applied RF power of 1000 W, a reaction chamber pressure of 800 Pa, and a reaction gas flow rate of 20 sccm for monosilane (SiH 4 ) and 12000 sccm for hydrogen (H 2 ).
  • a phosphine (PH 3 / H 2 ) using hydrogen as a diluent gas was formed to a thickness of 300 mm under a condition of 15 sccm. At this time, the film formation rate was 174 K / min.
  • Table 1 shows the experimental results regarding the tandem photoelectric conversion device.
  • the photoelectric conversion devices of Example 1 and Comparative Example 1 were irradiated with AM 1.5 light at a light amount of 100 mW / cm 2 , and the short circuit current (Jsc) and the open circuit voltage (Voc) were measured as output characteristics at 25 ° C. .
  • the results are shown in Table 1.
  • the relationship between a wavelength and power generation efficiency is shown in FIG.
  • the n layer of the second photoelectric conversion unit is composed of microcrystalline silicon containing oxygen ( ⁇ c-SiO)
  • the n layer is made of microcrystalline silicon containing oxygen ( ⁇ c-SiO), so that the first photoelectric conversion unit, the second photoelectric conversion unit, and the like can be obtained by the light reflection effect. It can be seen that the photoelectric conversion efficiency is improved in both of the conversion units.
  • the short circuit current (Jsc) could be improved in both the first photoelectric conversion unit and the second photoelectric conversion unit.
  • the photoelectric conversion device and the method for manufacturing the photoelectric conversion device according to one embodiment of the present invention have been described.
  • the present invention is not limited to this, and changes may be made as appropriate without departing from the spirit of the invention. Is possible.
  • the present invention is widely applicable to photoelectric conversion devices and methods for manufacturing photoelectric conversion devices.
  • Photoelectric conversion device 31 p-type semiconductor layer 32 i-type silicon layer (amorphous silicon layer) 33 n-type semiconductor layer 41 p-type semiconductor layer 42 i-type silicon layer (crystalline silicon layer) 43 n-type semiconductor layer 45 barrier layer 46 p-type semiconductor layer 8 first photoelectric conversion unit 81 p-type semiconductor layer 82 i-type silicon layer (crystalline silicon layer) 83 n-type semiconductor layer 85 barrier layer 60 first film forming apparatus 61 preparation chamber 62 p layer film forming reaction chamber 63 (63a, 63b, 63c, 63d) i layer film forming reaction chamber 64 n layer film forming reaction chamber 65 p layer Film formation reaction chamber 66 Extraction chamber 70 Second film formation apparatus 71 Preparation / extraction chamber 72 Pin layer film formation reaction chamber 80 Exposure apparatus

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Abstract

Le dispositif de conversion photoélectrique selon l'invention comporte : une pellicule conductrice transparente ; une première unité de conversion photoélectrique ; et une seconde unité de conversion photoélectrique. La première unité de conversion photoélectrique, la seconde unité de conversion photoélectrique et une électrode de face arrière sont séquentiellement disposées sur la pellicule conductrice transparente. Une couche semi-conductrice de type p et une couche semi-conductrice de type i de la seconde unité de conversion photoélectrique sont respectivement formées de pellicules minces de silicium cristallin. Une couche semi-conductrice de type n de la seconde unité de conversion photoélectrique agencée entre la couche semi-conductrice de type i de la seconde unité de conversion photoélectrique et l'électrode de face arrière est formée d'une pellicule mince de silicium microcristallin qui contient de l'oxygène. L'épaisseur de la couche semi-conductrice de type n de la seconde unité de conversion photoélectrique est comprise entre 100 Å et 800 Å.
PCT/JP2011/074665 2010-10-28 2011-10-26 Dispositif de conversion photoélectrique et procédé de fabrication d'un dispositif de conversion photoélectrique WO2012057201A1 (fr)

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JP2003051604A (ja) * 2001-08-03 2003-02-21 Sanyo Electric Co Ltd 光起電力素子
JP2009141059A (ja) * 2007-12-05 2009-06-25 Kaneka Corp 薄膜光電変換装置
JP2009290115A (ja) * 2008-05-30 2009-12-10 Kaneka Corp シリコン系薄膜太陽電池
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JP2003051604A (ja) * 2001-08-03 2003-02-21 Sanyo Electric Co Ltd 光起電力素子
JP2009141059A (ja) * 2007-12-05 2009-06-25 Kaneka Corp 薄膜光電変換装置
JP2009290115A (ja) * 2008-05-30 2009-12-10 Kaneka Corp シリコン系薄膜太陽電池
WO2010087198A1 (fr) * 2009-01-30 2010-08-05 株式会社アルバック Procédé de fabrication d'un dispositif de conversion photoélectrique, dispositif de conversion photoélectrique, système de fabrication d'un dispositif de conversion photoélectrique et procédé d'utilisation d'un système de fabrication d'un dispositif de conversion photoélectrique
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