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WO2010058640A1 - Dispositif de conversion photoélectrique - Google Patents

Dispositif de conversion photoélectrique Download PDF

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Publication number
WO2010058640A1
WO2010058640A1 PCT/JP2009/064570 JP2009064570W WO2010058640A1 WO 2010058640 A1 WO2010058640 A1 WO 2010058640A1 JP 2009064570 W JP2009064570 W JP 2009064570W WO 2010058640 A1 WO2010058640 A1 WO 2010058640A1
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Prior art keywords
layer
photoelectric conversion
film
intermediate contact
contact layer
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PCT/JP2009/064570
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English (en)
Japanese (ja)
Inventor
賢剛 山口
智嗣 坂井
薫典 鶴我
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三菱重工業株式会社
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Priority to CN2009801298886A priority Critical patent/CN102113127B/zh
Priority to EP09827421A priority patent/EP2348541A1/fr
Priority to US13/003,615 priority patent/US8598447B2/en
Publication of WO2010058640A1 publication Critical patent/WO2010058640A1/fr

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    • H—ELECTRICITY
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    • 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
    • C—CHEMISTRY; METALLURGY
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    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/08—Oxides
    • C23C14/086—Oxides of zinc, germanium, cadmium, indium, tin, thallium or bismuth
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    • B23K26/06—Shaping the laser beam, e.g. by masks or multi-focusing
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    • B23K26/00—Working by laser beam, e.g. welding, cutting or boring
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    • B23K26/00—Working by laser beam, e.g. welding, cutting or boring
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    • B23K26/00—Working by laser beam, e.g. welding, cutting or boring
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    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/3407—Cathode assembly for sputtering apparatus, e.g. Target
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    • H01L31/02—Details
    • H01L31/0224—Electrodes
    • H01L31/022466—Electrodes made of transparent conductive layers, e.g. TCO, ITO layers
    • H01L31/022483—Electrodes made of transparent conductive layers, e.g. TCO, ITO layers composed of zinc oxide [ZnO]
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    • H01L31/054—Optical elements directly associated or integrated with the PV cell, e.g. light-reflecting means or light-concentrating means
    • H01L31/0547—Optical elements directly associated or integrated with the PV cell, e.g. light-reflecting means or light-concentrating means comprising light concentrating means of the reflecting type, e.g. parabolic mirrors, concentrators using total internal reflection
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    • 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
    • H01L31/068—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 PN homojunction type, e.g. bulk silicon PN homojunction solar cells or thin film polycrystalline silicon PN homojunction solar cells
    • H01L31/0687—Multiple junction or tandem solar cells
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    • 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
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    • 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
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    • 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
    • H01L31/1884—Manufacture of transparent electrodes, e.g. TCO, ITO
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K2101/00—Articles made by soldering, welding or cutting
    • B23K2101/36—Electric or electronic devices
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    • B23K2103/00—Materials to be soldered, welded or cut
    • B23K2103/50—Inorganic material, e.g. metals, not provided for in B23K2103/02 – B23K2103/26
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    • 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
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    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/544—Solar cells from Group III-V 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
    • Y02E10/548—Amorphous silicon PV cells

Definitions

  • the present invention relates to a solar cell, and more particularly to a thin-film solar cell in which a power generation layer is formed by film formation.
  • Photoelectric conversion devices used in solar cells that convert solar energy into electrical energy include p-type silicon-based semiconductors (p-layers), i-type silicon-based semiconductors (i-layers), and n-type silicon-based semiconductors (n-layers).
  • p-layers p-type silicon-based semiconductors
  • i-layers i-type silicon-based semiconductors
  • n-layers n-type silicon-based semiconductors
  • the thin-film silicon solar cell includes that the area can be easily increased and that the film thickness is as thin as about 1/100 that of a crystalline solar cell, and that the material can be reduced. For this reason, the thin film silicon solar cell can be manufactured at a lower cost than the crystalline solar cell.
  • a disadvantage of the thin-film silicon solar cell is that the conversion efficiency is lower than that of the crystal system. In this technical field, improvement of conversion efficiency is an important issue, and a tandem solar cell having a photoelectric conversion layer in which two power generation cell layers are stacked has been proposed.
  • an intermediate contact layer made of a transparent conductive film is inserted for the purpose of suppressing dopant interdiffusion between the first power generation cell layer and the second power generation cell layer and adjusting the light quantity distribution. Is done.
  • the intermediate contact layer it is common to use Ga-doped ZnO (GZO).
  • GZO is a material having a refractive index of 2.0 and lower than Si, excellent plasma resistance, and excellent transparency.
  • GZO has a low resistivity
  • leakage current is caused in the cell connection portion, and the open circuit voltage and FF are reduced.
  • solutions such as adding a laser processing part to the structure of the connection part have been proposed.
  • the effective area is reduced and the cost is increased due to an increase in processes.
  • the conductivity of GZO can be controlled by reducing dopants or adjusting the amount of oxygen supplied during film formation to promote oxidation of GZO.
  • This invention is made
  • the electrical conductivity after hydrogen plasma exposure is set to the appropriate range, and the photoelectric conversion apparatus which the leakage current was suppressed and conversion efficiency improved is provided. .
  • the present invention provides a photoelectric conversion device including a photoelectric conversion layer including at least two power generation cell layers on a substrate, and an intermediate contact layer interposed between the adjacent power generation cell layers.
  • the intermediate contact layer mainly contains a compound represented by Zn 1-x Mg x O 2 (0.096 ⁇ x ⁇ 0.183).
  • an intermediate contact layer mainly composed of a compound obtained by adding MgO to ZnO By using an intermediate contact layer mainly composed of a compound obtained by adding MgO to ZnO, it is possible to prevent a decrease in resistance (that is, an increase in conductivity) after exposure to hydrogen plasma.
  • the conductivity of the intermediate contact layer after exposure to hydrogen plasma is determined as the contact resistance while suppressing the leakage current at the cell connection portion. It becomes controllable to the value by which a raise is suppressed. For this reason, it can be set as the photoelectric conversion apparatus which a form factor is improved and has high conversion efficiency.
  • the intermediate contact layer is made of a compound represented by Zn 1-x Mg x O 2 (0.096 ⁇ x ⁇ 0.183) to which Ga 2 O 3 is added. It may be included mainly.
  • the sheet resistance of the intermediate contact layer after exposure to hydrogen plasma is preferably 10 k ⁇ / ⁇ or more and 100 k ⁇ / ⁇ or less.
  • the sheet resistance of the intermediate contact layer after exposure to hydrogen plasma is desirably 10 k ⁇ / ⁇ or more.
  • the contact resistance (series resistance) in the stacking direction (direction perpendicular to the substrate film-forming surface) increases. Therefore, the sheet resistance of the intermediate contact layer after exposure to hydrogen plasma is preferably 100 k ⁇ / ⁇ or less.
  • An interface layer mainly including a compound represented by ZnO or Zn 1-x Mg x O 2 (0 ⁇ x ⁇ 0.096) is provided between the power generation cell layer on the substrate side and the intermediate contact layer. Also good.
  • ZnO or Zn 1-x Mg x O 2 having the above composition range whose Mg concentration is lower than that of the intermediate contact layer of the present invention is mainly formed on the power generation cell layer formed on the substrate side.
  • the interface layer is formed, the contact resistance in the film stacking direction can be further reduced. As a result, the form factor can be further improved, and a photoelectric conversion device having higher photoelectric conversion efficiency can be obtained.
  • the interface layer is represented by ZnO to which Ga 2 O 3 is added or Zn 1-x Mg x O 2 (0 ⁇ x ⁇ 0.096).
  • a compound may be mainly contained.
  • the thickness of the interface layer is preferably 5 nm or more and 10 nm or less.
  • the contact resistance can be improved.
  • the leakage resistance increases and the form factor decreases.
  • the thickness of the interface layer is not less than 5 nm and not more than 10 nm, it is possible to improve the contact resistance and suppress the leakage resistance and improve the photoelectric conversion efficiency.
  • an intermediate contact layer mainly containing a compound represented by Zn 1-x Mg x O 2 (0.096 ⁇ x ⁇ 0.183) between adjacent power generation cell layers leakage current in the cell connection portion And the contact resistance in the direction perpendicular to the film can be reduced. Therefore, the form factor is improved and a photoelectric conversion device having high photoelectric conversion efficiency can be obtained. Further, by forming an interface layer mainly composed of Zn 1 or Zn 1-x Mg x O 2 having a lower Mg concentration than the intermediate contact layer between the power generation cell layer on the substrate side and the intermediate contact layer, the contact layer Can be further reduced. As a result, the photoelectric conversion efficiency can be further improved.
  • FIG. 1 is a schematic diagram showing the configuration of the photoelectric conversion device of the present invention.
  • the photoelectric conversion device 100 is a tandem silicon solar cell, and includes a substrate 1, a transparent electrode layer 2, a first power generation cell layer 91 (amorphous silicon system) and a second power generation cell layer as the solar cell photoelectric conversion layer 3. 92 (crystalline silicon type), an intermediate contact layer 5, and a back electrode layer 4.
  • the silicon-based is a generic name including silicon (Si), silicon carbide (SiC), and silicon germanium (SiGe).
  • the crystalline silicon system means a silicon system other than the amorphous silicon system, and includes microcrystalline silicon and polycrystalline silicon.
  • a method for manufacturing a photoelectric conversion device according to the first embodiment will be described by taking a process for manufacturing a solar cell panel as an example.
  • 2 to 5 are schematic views showing a method for manufacturing the solar cell panel of the present embodiment.
  • FIG. 2 (a) A soda float glass substrate (substrate area is 1 m 2 or more, for example, 1.4 m ⁇ 1.1 m ⁇ plate thickness: 3.5 mm to 4.5 mm) is used as the substrate 1.
  • the end face of the substrate is preferably subjected to corner chamfering or R chamfering to prevent damage due to thermal stress or impact.
  • FIG. 2 (b) As the transparent conductive layer 2, a transparent conductive film having a thickness of about 500 nm to 800 nm and having tin oxide (SnO 2 ) as a main component is formed at about 500 ° C. with a thermal CVD apparatus. At this time, a texture with appropriate irregularities is formed on the surface of the transparent electrode film.
  • an alkali barrier film (not shown) may be formed between the substrate 1 and the transparent electrode film.
  • a silicon oxide film (SiO 2 ) is formed at a temperature of about 500 ° C. with a thermal CVD apparatus at 50 nm to 150 nm.
  • FIG. 2 (c) Thereafter, the substrate 1 is set on an XY table, and the first harmonic (1064 nm) of the YAG laser is irradiated from the film surface side of the transparent electrode film as indicated by an arrow in the figure.
  • the laser power is adjusted to be appropriate for the processing speed, and the transparent electrode film is moved relative to the direction perpendicular to the series connection direction of the power generation cells so that the substrate 1 and the laser light are moved relative to each other to form the groove 10.
  • FIG. 2 (d) As the first power generation cell layer 91, a p layer, an i layer, and an n layer made of an amorphous silicon thin film are formed by a plasma CVD apparatus. Using SiH 4 gas and H 2 gas as main raw materials, the amorphous silicon p layer 31 from the side on which sunlight is incident on the transparent electrode layer 2 at a reduced pressure atmosphere: 30 Pa to 1000 Pa and a substrate temperature: about 200 ° C. Then, an amorphous silicon i layer 32 and an amorphous silicon n layer 33 are formed in this order.
  • the amorphous silicon p layer 31 is mainly made of amorphous B-doped silicon and has a thickness of 10 nm to 30 nm.
  • the amorphous silicon i layer 32 has a thickness of 200 nm to 350 nm.
  • the amorphous silicon n layer 33 is mainly P-doped silicon containing microcrystalline silicon in amorphous silicon, and has a thickness of 30 nm to 50 nm.
  • a buffer layer may be provided between the amorphous silicon p layer 31 and the amorphous silicon i layer 32 in order to improve interface characteristics.
  • An intermediate contact layer 5 serving as a semi-reflective film is provided between the first power generation cell layer 91 and the second power generation cell layer 92 in order to improve contact and to obtain current matching.
  • target Ga 2 O 3 doped ZnO—MgO mixed target (MgO ratio: 5 to 10% by mass), RF power: 1.1 to 4.4 W / cm 2 , film forming pressure: 0.
  • the film is formed under conditions of 13 to 0.67 Pa and substrate temperature: 25 ° C. (near room temperature).
  • an intermediate contact layer mainly composed of Zn 1-x Mg x O 2 (0.096 ⁇ x ⁇ 0.183) having a film thickness of 20 nm to 100 nm is formed.
  • the sheet resistance of the intermediate contact layer 5 immediately after film formation is about 10 M ⁇ / ⁇ . Note that the intermediate contact layer may not contain Ga 2 O 3 .
  • the second power generation cell layer 92 is formed on the first power generation cell layer 91 using a plasma CVD apparatus at a reduced pressure atmosphere: 3000 Pa or less, a substrate temperature: about 200 ° C., and a plasma generation frequency: 40 MHz or more and 100 MHz or less.
  • a crystalline silicon p layer 41, a crystalline silicon i layer 42, and a crystalline silicon n layer 43 are sequentially formed.
  • the crystalline silicon p layer 41 is mainly made of B-doped microcrystalline silicon and has a thickness of 10 nm to 50 nm.
  • the crystalline silicon i layer 42 is mainly made of microcrystalline silicon and has a film thickness of 1.2 ⁇ m or more and 3.0 ⁇ m or less.
  • the crystalline silicon n layer 43 is mainly made of P-doped microcrystalline silicon and has a thickness of 20 nm to 50 nm.
  • an amorphous silicon n layer may be formed at the interface between the crystalline silicon i layer 42 and the crystalline silicon n layer 43.
  • the distance d between the plasma discharge electrode and the surface of the substrate 1 is preferably 3 mm or more and 10 mm or less. If it is smaller than 3 mm, it is difficult to keep the distance d constant from the accuracy of each component device in the film forming chamber corresponding to the large substrate, and there is a possibility that the discharge becomes unstable because it is too close. When it is larger than 10 mm, it is difficult to obtain a sufficient film forming speed (1 nm / s or more), and the uniformity of the plasma is lowered and the film quality is lowered by ion bombardment.
  • FIG. 6 shows the relationship between the MgO content in the ZnMgO-based compound and the sheet resistance of the ZnMgO-based film after the hydrogen plasma treatment.
  • the horizontal axis represents the MgO content
  • the vertical axis represents the sheet resistance.
  • a ZnMgO-based film is formed by using a target: ZnO sintered body (Ga 2 O 3 dopant) target or ZnO—MgO mixed target (Ga 2 O 3 dopant, MgO mass ratio: 5 to 12.5%), substrate temperature: The measurement was carried out under the conditions of 25 ° C., RF power: 4.4 W / cm 2 , target-substrate distance: 90 mm, film forming speed 0.17 nm / s, and film thickness: 70 nm. The hydrogen plasma treatment after film formation was performed under the conditions of H 2 gas flow rate: 0.1 slm, pressure: 133 Pa, applied power density: 0.5 W / cm 2 , treatment time: 5 minutes.
  • the leakage current can be reduced when the sheet resistance of the intermediate contact layer is 10 k ⁇ / ⁇ or more.
  • the sheet resistance of the intermediate contact layer is preferably 100 k ⁇ / ⁇ . From FIG. 6, it can be said that a ZnMgO-based film having a sheet resistance of 10 k ⁇ / ⁇ or more and 100 k ⁇ / ⁇ or less with an MgO mass of 5% (9.6 mol%) to 10% (18.3 mol%) is obtained.
  • FIG. 2 (e) The substrate 1 is placed on an XY table, and the second harmonic (532 nm) of the laser diode-pumped YAG laser is irradiated from the film surface side of the photoelectric conversion layer 3 as shown by the arrow in the figure.
  • Pulse oscillation 10 kHz to 20 kHz
  • laser power is adjusted so as to be suitable for the processing speed
  • laser etching is performed so that grooves 11 are formed on the lateral side of the laser etching line of the transparent electrode layer 2 from about 100 ⁇ m to 150 ⁇ m.
  • this laser may be irradiated from the substrate 1 side.
  • photoelectric conversion is performed by using a high vapor pressure generated by energy absorbed by the amorphous silicon-based first power generation cell layer of the photoelectric conversion layer 3. Since the layer 3 can be etched, a more stable laser etching process can be performed. The position of the laser etching line is selected in consideration of positioning tolerances so as not to intersect with the etching line in the previous process.
  • FIG. 3 An Ag film / Ti film is formed as the back electrode layer 4 by a sputtering apparatus at a reduced pressure atmosphere and at a film forming temperature of 150 ° C. to 200 ° C.
  • an Ag film 150 nm or more and 500 nm or less
  • a Ti film having a high anticorrosion effect 10 nm or more and 20 nm or less are stacked in this order to protect them.
  • the back electrode layer 4 may have a laminated structure of an Ag film having a thickness of 25 nm to 100 nm and an Al film having a thickness of 15 nm to 500 nm.
  • a film thickness of 50 nm or more and 100 nm or less is formed between the photoelectric conversion layer 3 and the back electrode layer 4 by a sputtering apparatus.
  • a GZO (Ga-doped ZnO) film may be formed and provided.
  • FIG. 3 (b) The substrate 1 is placed on an XY table, and the second harmonic (532 nm) of the laser diode-pumped YAG laser is irradiated from the substrate 1 side as indicated by the arrow in the figure.
  • the laser light is absorbed by the photoelectric conversion layer 3, and the back electrode layer 4 is exploded and removed using the high gas vapor pressure generated at this time.
  • Pulse oscillation laser power is adjusted so as to be suitable for the processing speed from 1 kHz to 10 kHz, and laser etching is performed so that grooves 12 are formed on the lateral side of the laser etching line of the transparent electrode layer 2 from 250 ⁇ m to 400 ⁇ m. .
  • FIG. 3 (c) and FIG. 4 (a) The power generation region is divided to eliminate the influence that the serial connection portion due to laser etching is likely to be short-circuited at the film edge around the substrate edge.
  • the substrate 1 is set on an XY table, and the second harmonic (532 nm) of the laser diode pumped YAG laser is irradiated from the substrate 1 side.
  • the laser light is absorbed by the transparent electrode layer 2 and the photoelectric conversion layer 3, and the back electrode layer 4 explodes using the high gas vapor pressure generated at this time, and the back electrode layer 4 / photoelectric conversion layer 3 / transparent electrode layer 2 is removed.
  • Pulse oscillation 1 kHz or more and 10 kHz or less
  • the laser power is adjusted so as to be suitable for the processing speed, and the position of 5 mm to 20 mm from the end of the substrate 1 is placed in the X-direction insulating groove as shown in FIG.
  • Laser etching is performed to form 15.
  • FIG.3 (c) since it becomes X direction sectional drawing cut
  • the insulating groove formed to represent the Y-direction cross section at the position will be described as the X-direction insulating groove 15.
  • the Y-direction insulating groove does not need to be provided because the film surface polishing removal processing of the peripheral film removal region of the substrate 1 is performed in a later process.
  • the insulating groove 15 exhibits an effective effect in suppressing external moisture intrusion into the solar cell module 6 from the end portion of the solar cell panel by terminating the etching at a position of 5 mm to 15 mm from the end of the substrate 1. Therefore, it is preferable.
  • the laser beam in the above steps is a YAG laser
  • a YVO4 laser or a fiber laser there are some that can use a YVO4 laser or a fiber laser in the same manner.
  • FIG. 4 (a: view from the solar cell film side, b: view from the substrate side of the light receiving surface) Since the laminated film around the substrate 1 (peripheral film removal region 14) has a step and is easy to peel off in order to ensure a sound adhesion / seal surface with the back sheet 24 via EVA or the like in a later process, The film is removed to form a peripheral film removal region 14. When removing the film over the entire periphery of the substrate 1 at 5 to 20 mm from the end of the substrate 1, the X direction is closer to the substrate end than the insulating groove 15 provided in the step of FIG.
  • the back electrode layer 4 / photoelectric conversion layer 3 / transparent electrode layer 2 are removed by using grinding stone polishing, blast polishing, or the like on the substrate end side with respect to the groove 10 near the side portion. Polishing debris and abrasive grains were removed by cleaning the substrate 1.
  • FIGS. 5 (a) and 5 (b) An attachment portion of the terminal box 23 is provided with an opening through window in the back sheet 24 to take out the current collector plate. Insulating materials are installed in a plurality of layers in the opening through window portion to suppress intrusion of moisture and the like from the outside. Processing so that power can be taken out from the terminal box 23 on the back side of the solar battery panel by collecting copper foil from one end of the photovoltaic power generation cells arranged in series and the other end of the solar power generation cell. To do. In order to prevent a short circuit with each part, the copper foil arranges an insulating sheet wider than the copper foil width.
  • an adhesive filler sheet made of EVA (ethylene vinyl acetate copolymer) or the like is disposed so as to cover the entire solar cell module 6 and not protrude from the substrate 1. .
  • a back sheet 24 having a high waterproof effect is installed on the EVA.
  • the back sheet 24 has a three-layer structure of PET sheet / Al foil / PET sheet so that the waterproof and moisture-proof effect is high.
  • the one with the back sheet 24 arranged in a predetermined position is deaerated inside in a reduced pressure atmosphere by a laminator and pressed at about 150 to 160 ° C., and EVA is crosslinked and brought into close contact.
  • FIG. 5 (a) The terminal box 23 is attached to the back side of the solar cell module 6 with an adhesive.
  • FIG. 5 (b) The copper foil and the output cable of the terminal box 23 are connected by solder or the like, and the inside of the terminal box 23 is filled with a sealing agent (potting agent) and sealed. Thus, the solar cell panel 50 is completed.
  • FIG. 5 (c) A power generation inspection and a predetermined performance test are performed on the solar cell panel 50 formed in the steps up to FIG. The power generation inspection is performed using a solar simulator of AM1.5 and solar radiation standard sunlight (1000 W / m 2 ).
  • FIG. 5 (d) Before and after the power generation inspection (FIG. 5C), a predetermined performance inspection is performed including an appearance inspection.
  • the resistivity of the intermediate contact layer 5 is controlled to be 10 k ⁇ / ⁇ or more and 100 k ⁇ / ⁇ or less, the leakage current at the cell connection portion is reduced and the contact resistance in the film stacking direction is reduced. Reduce. Therefore, the form factor increases and the photoelectric conversion efficiency is improved.
  • the photoelectric conversion device includes an interface layer between the first power generation cell layer 91 and the intermediate contact layer 5 in FIG.
  • the interface layer mainly contains a compound represented by ZnO or Zn 1-x Mg x O 2 (provided that 0 ⁇ x ⁇ 0.096 is satisfied). That is, the interface layer does not contain Mg or has a lower Mg content than the intermediate contact layer.
  • ZnO or Zn 1-x Mg x O 2 as the interface layer may contain Ga 2 O 3 as a dopant.
  • the film formation of the interface layer may be performed in a film formation chamber different from the intermediate contact layer or in the same film formation chamber.
  • the interfacial layer is formed by using an RF magnetron sputtering apparatus, target: Ga 2 O 3 doped ZnO sintered body or Ga 2 O 3 doped ZnO—MgO mixed target (MgO ratio: 0 to 5 mass%, 0 mass%)
  • RF power is 1.1 to 4.4 W / cm 2
  • film forming pressure is 0.13 to 0.67 Pa
  • substrate temperature is 25 ° C. (near room temperature).
  • an interface layer mainly composed of ZnO or Zn 1-x Mg x O 2 (0 ⁇ x ⁇ 0.096) is formed.
  • the film thickness of the interface layer is preferably 5 nm or more and 10 nm or less.
  • an intermediate contact layer having a higher MgO content than the interface layer is formed under the same conditions as in the first embodiment.
  • the total film thickness of the interface layer and the intermediate contact layer is 20 nm or more and 100 nm or less.
  • a Ga 2 O 3 doped ZnO sintered body or a Ga 2 O 3 doped ZnO—MgO mixed target (MgO ratio: 0 to 5 mass%, provided that 0
  • a substrate transport type RF magnetron sputtering apparatus in which a Ga 2 O 3 -doped ZnO—MgO mixed target (MgO ratio: 5 to 10 mass%) is arranged in parallel is used.
  • the substrate transport speed and the width of each target in the substrate transport direction are set so that the film thickness of the interface layer is 5 nm to 10 nm and the total film thickness of the interface layer and the intermediate contact layer is 20 nm to 100 nm.
  • film formation is performed while conveying the substrate from the ZnO sintered body or the low Mg content mixed target side to the high Mg content mixed target side, with the film formation conditions being substantially the same as those described above.
  • the boundary between the interface layer and the intermediate contact layer is not clear, unlike when each layer is formed in a different film forming chamber. It is considered that the Mg content continuously increases from the center toward the intermediate contact layer.
  • the contact resistance between the first power generation cell layer and the interface layer is lower than the contact resistance between the first power generation cell layer and the intermediate contact layer in the first embodiment.
  • the leakage current in the cell connection direction is further suppressed by setting the interface layer to a film thickness of 5 nm or more and 10 nm or less. For this reason, in the solar cell of 2nd Embodiment, a photoelectric conversion efficiency improves further.
  • Example 1 A tandem solar cell module having the structure shown in FIG. 1 was formed on a glass substrate (5 cm square). The film thickness of the i layer of the first power generation cell layer was 250 nm, and the film thickness of the i layer of the second power generation cell layer was 1.9 ⁇ m.
  • the intermediate contact layer is formed by using a target: ZnO sintered body target (Ga 2 O 3 dopant) or ZnO—MgO mixed target (Ga 2 O 3 dopant, MgO mass ratio: 5 to 12.5%), substrate temperature: The measurement was carried out under the conditions of 25 ° C., RF power: 4.4 W / cm 2 , target-substrate distance: 90 mm, film forming speed 0.17 nm / s, and film thickness: 70 nm.
  • a target ZnO sintered body target (Ga 2 O 3 dopant) or ZnO—MgO mixed target (Ga 2 O 3 dopant, MgO mass ratio: 5 to 12.5%
  • substrate temperature The measurement was carried out under the conditions of 25 ° C., RF power: 4.4 W / cm 2 , target-substrate distance: 90 mm, film forming speed 0.17 nm / s, and film thickness: 70 nm.
  • FIG. 7 shows the relationship between the MgO content of the intermediate contact layer and the module form factor.
  • the horizontal axis represents the MgO content
  • the vertical axis represents the module shape factor normalized by the value when the MgO content is 0%.
  • FIG. 8 shows the relationship between the MgO content of the intermediate contact layer and the photoelectric conversion efficiency of the module.
  • the horizontal axis represents the MgO content
  • the vertical axis represents the photoelectric conversion efficiency of the module normalized by the value when the MgO content is 0%.
  • the form factor and photoelectric conversion efficiency were improved by applying a ZnMgO-based material to the intermediate contact layer.
  • Example 2 A tandem solar cell module was formed on a glass substrate (5 cm square). The film thickness of the i layer of the first power generation cell layer was 250 nm, and the film thickness of the i layer of the second power generation cell layer was 1.9 ⁇ m. In the tandem solar cell module of Example 2, an interface layer was provided between the first power generation cell layer and the intermediate contact layer. The interface layer was formed using a ZnO sintered body target (Ga 2 O 3 dopant) under the same conditions as those for forming the intermediate contact layer of Example 1. The film thickness of the interface layer was 5 nm to 15 nm.
  • a ZnO sintered body target Ga 2 O 3 dopant
  • the intermediate contact layer was formed under the same conditions as in Example 1 using a ZnO—MgO mixed target (Ga 2 O 3 dopant, MgO mass ratio: 10%).
  • the film thickness of the intermediate contact layer was 70 nm.
  • the interface layer and the intermediate contact layer were formed in different film forming chambers.
  • FIG. 9 shows the relationship between the interface layer thickness and the module form factor.
  • the horizontal axis represents the interface layer thickness
  • the vertical axis represents the module shape factor normalized by the value when the interface layer thickness is 0 nm (only the intermediate contact layer).
  • FIG. 10 shows the relationship between the interface layer thickness and the module photoelectric conversion efficiency.
  • the horizontal axis represents the interface layer thickness
  • the vertical axis represents the module photoelectric conversion efficiency normalized by the value when no interface layer is provided.
  • the interface layer thickness is 5 nm or more and 10 nm or less
  • the module shape factor and photoelectric conversion efficiency are improved as compared with the case where the interface layer is not provided.
  • the interface layer was 15 nm
  • the module shape factor and photoelectric conversion efficiency were reduced. This is considered to be because when the interface layer is thick, leakage current is generated in the interface layer and the contact property is deteriorated. Even when the MgO content of the intermediate contact layer was 5% by mass, the same effect was observed.
  • Example 3 A tandem solar cell module having the same configuration as that of Example 2 was formed.
  • the interface layer and the intermediate contact layer were formed in the same film forming chamber.
  • a substrate transport type film forming apparatus in which eight targets are arranged in parallel in the substrate transport direction was used.
  • One target on the substrate introduction side (upstream side) is a ZnO sintered body target (Ga 2 O 3 dopant), and the remaining target is a ZnO—MgO mixed target (Ga 2 O 3 dopant, MgO mass ratio: 10%). It was.
  • the film forming conditions were the same as in Example 1 and Example 2.
  • the intermediate contact layer was formed at a conveyance speed at which the total film thickness was 70 nm.
  • the form factor and photoelectric conversion efficiency of the tandem solar cell module of Example 3 were 1.03 and 1.05 times that of the tandem solar cell module that does not form the intermediate contact layer, respectively.
  • tandem solar cell has been described as a solar cell, but the present invention is not limited to this example.
  • the present invention can be similarly applied to a triple solar cell.

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Abstract

La présente invention concerne un dispositif de conversion photoélectrique qui possède une efficacité de conversion améliorée, le courant de fuite étant supprimé par le réglage de la conductivité électrique après exposition à un plasma d'hydrogène dans une plage appropriée. Plus spécifiquement, la présente invention porte sur un dispositif de conversion photoélectrique (100) qui comprend, sur un substrat (1), une couche de conversion photoélectrique (3) dotée d'au moins deux couches de cellules de production électrique (91, 92), et d'une couche de contact intermédiaire (5) interposée entre les couches de cellules de production électrique (91, 92). Ledit dispositif de conversion photoélectrique (100) se caractérise en ce que la couche de contact intermédiaire (5) contient un composé représenté par la formule suivante : Zn1-xMgxO2 (0,096 ≤ x ≤ 0,183) en tant que composant principal.
PCT/JP2009/064570 2008-11-19 2009-08-20 Dispositif de conversion photoélectrique WO2010058640A1 (fr)

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US13/003,615 US8598447B2 (en) 2008-11-19 2009-08-20 Photoelectric conversion device

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WO2012102449A1 (fr) * 2011-01-25 2012-08-02 Lg Innotek Co., Ltd. Cellule solaire, et procédé de fabrication associé

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WO2012040299A2 (fr) 2010-09-22 2012-03-29 First Solar, Inc Dispositif photovoltaïque à couche mince doté d'une couche fenêtre en oxyde de zinc et de magnésium
US20140246083A1 (en) 2013-03-01 2014-09-04 First Solar, Inc. Photovoltaic devices and method of making
WO2016056546A1 (fr) * 2014-10-06 2016-04-14 株式会社カネカ Cellule solaire, module de cellule solaire, procédé de fabrication de cellule solaire, et procédé de fabrication de module de cellule solaire
DE102019006095A1 (de) * 2019-08-29 2021-03-04 Azur Space Solar Power Gmbh Vereinzelungsverfahren zur Vereinzelung einer mehrere Solarzellenstapel umfasssenden Halbleiterscheibe

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CN1307707C (zh) * 2003-09-19 2007-03-28 中国科学院上海微系统与信息技术研究所 一种含镁锌氧的金属－绝缘层－半导体结构及制备工艺
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EP2472595A1 (fr) * 2009-08-26 2012-07-04 Sharp Kabushiki Kaisha Élément photovoltaïque empilé et procédé de fabrication d'élément photovoltaïque empilé
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WO2012102449A1 (fr) * 2011-01-25 2012-08-02 Lg Innotek Co., Ltd. Cellule solaire, et procédé de fabrication associé
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JP2010123737A (ja) 2010-06-03
US8598447B2 (en) 2013-12-03

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