WO2018181128A1 - Procédé de production d'un élément de conversion photoélectrique - Google Patents

Procédé de production d'un élément de conversion photoélectrique Download PDF

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Publication number
WO2018181128A1
WO2018181128A1 PCT/JP2018/012036 JP2018012036W WO2018181128A1 WO 2018181128 A1 WO2018181128 A1 WO 2018181128A1 JP 2018012036 W JP2018012036 W JP 2018012036W WO 2018181128 A1 WO2018181128 A1 WO 2018181128A1
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Prior art keywords
electrode
photoelectric conversion
insulating film
surface side
main surface
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PCT/JP2018/012036
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English (en)
Japanese (ja)
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和田　英敏
末崎　恭
将典 福田
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株式会社カネカ
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Priority to JP2019509771A priority Critical patent/JP6780095B2/ja
Publication of WO2018181128A1 publication Critical patent/WO2018181128A1/fr

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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
    • H01L31/02—Details
    • H01L31/0224—Electrodes
    • 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
    • H01L31/072—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 heterojunction type
    • H01L31/0745—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 heterojunction type comprising a AIVBIV heterojunction, e.g. Si/Ge, SiGe/Si or Si/SiC solar cells
    • H01L31/0747—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 heterojunction type comprising a AIVBIV heterojunction, e.g. Si/Ge, SiGe/Si or Si/SiC solar cells comprising a heterojunction of crystalline and amorphous materials, e.g. heterojunction with intrinsic thin layer
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/24—Reinforcing the conductive pattern
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/30—Assembling printed circuits with electric components, e.g. with resistor
    • H05K3/32—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits
    • H05K3/34—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by soldering
    • 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

Definitions

  • the present invention relates to a method for manufacturing a photoelectric conversion element.
  • Patent Document 1 a conductive paste in which a conductive substance is dispersed in a resin is applied and dried on an n-type semiconductor region and a p-type semiconductor region in an environment of atmospheric pressure and normal temperature, A method for manufacturing a solar cell for forming an electrode layer is disclosed.
  • the solvent in the conductive paste is not sufficiently removed in the drying process under atmospheric pressure, and the solvent is released into the film forming apparatus in the upper film forming process. Therefore, there is a possibility of affecting the film forming quality of the upper layer.
  • the present disclosure has been made in view of the above problems, and an object thereof is to obtain the upper layer of the first electrode having better quality.
  • At least the first main surface side in the photoelectric conversion unit is formed with the first electrode using a conductive paste containing conductive particles, a thermosetting resin, and a solvent.
  • the air drying step may be a method of heating to a boiling point or higher of the solvent.
  • the vacuum drying step may be a method of heating to a boiling point or higher of the solvent.
  • thermosetting resin is thermoset and the first electrode is contracted to form the insulating film.
  • the photoelectric conversion element in the insulating film formation step, is formed from the non-formation region of the first electrode on the first main surface side of the photoelectric conversion unit.
  • the insulating film may be formed up to the first main surface side of the first electrode.
  • the photoelectric conversion unit includes a transparent electrode layer, and in the second electrode formation step, the insulating film starts from the transparent electrode layer. It is good also as a method of suppressing an output.
  • the film thickness of the insulating film on the first main surface side of the first electrode A method of forming the insulating film thinner than the thickness of the insulating film in the first electrode non-formation region on the first main surface side of the conversion unit may be employed.
  • silver is used as the conductive particles in the first electrode forming step, and the first electrode is used in the second electrode forming step. It is good also as a method of depositing copper as a starting point.
  • the second main surface of the photoelectric conversion unit opposite to the first main surface side Alternatively, the first electrode may be formed on the side.
  • the insulating film is formed on the first main surface side of the first electrode formed on the first main surface side in the insulating film forming step.
  • the insulating film may be formed on the second main surface side of the first electrode formed on the second main surface side.
  • FIG. 1 is a plan view showing the surface side (incident surface side) of the photoelectric conversion element according to this embodiment.
  • FIG. 2 is a plan view showing the back side of the photoelectric conversion element according to this embodiment.
  • FIG. 3 is a sectional view showing a section taken along line III-III in FIG.
  • FIG. 4 is a cross-sectional view showing a method for manufacturing a photoelectric conversion element according to this embodiment.
  • FIG. 5 is a cross-sectional view showing a method for manufacturing a photoelectric conversion element according to this embodiment.
  • FIG. 6 is a cross-sectional view showing a method for manufacturing a photoelectric conversion element according to this embodiment.
  • FIG. 7 is a cross-sectional view showing a method for manufacturing a photoelectric conversion element according to this embodiment.
  • FIG. 1 is a plan view showing the surface side (incident surface side) of the photoelectric conversion element according to this embodiment.
  • FIG. 2 is a plan view showing the back side of the photoelectric conversion element according to this
  • FIG. 8 is a cross-sectional view showing a method for manufacturing a photoelectric conversion element according to this embodiment.
  • FIG. 9 is a cross-sectional view showing a method for manufacturing a photoelectric conversion element according to this embodiment.
  • FIG. 10 is a cross-sectional view illustrating a method for manufacturing a photoelectric conversion element according to this embodiment.
  • FIG. 1 is a plan view showing the surface side (incident surface side) of the photoelectric conversion element 100 according to this embodiment.
  • FIG. 2 is a plan view showing the back side of the photoelectric conversion element 100 according to this embodiment.
  • the photoelectric conversion element 100 of the present embodiment includes three wide electrodes (bus bar electrodes 80) substantially parallel to one side of a semiconductor substrate having a photoelectric conversion unit, and a bus bar.
  • a plurality of narrow finger electrodes 90 that are substantially perpendicular to the electrode 80 are formed.
  • the bus bar electrode 80 and the finger electrode 90 include a first electrode formed on the semiconductor substrate and a second electrode formed by a plating process starting from the first electrode.
  • An insulating film 70 is formed in a region where the bus bar electrode 80 and the finger electrode 90 are not formed on the front surface and the back surface of the photoelectric conversion element 100. Note that the bus bar electrode 80 and the finger electrode 90 may be formed only on the surface side, and in that case, the insulating film 70 may be formed only on the surface side.
  • FIG. 3 is a cross-sectional view showing a cross section taken along line III-III in FIG.
  • the photoelectric conversion unit 10 shown in FIG. 3 includes a semiconductor substrate such as single crystal silicon or polycrystalline silicon.
  • the photoelectric conversion unit 10 has an n-type semiconductor region and a p-type semiconductor region, and a PN junction is formed at the interface between them.
  • the n-type semiconductor region and the p-type semiconductor region may be configured using a crystalline semiconductor or an amorphous semiconductor.
  • an intrinsic semiconductor region may be provided between the crystalline silicon substrate and the amorphous silicon layer so that defects at the interface are reduced and characteristics of the bonding interface are improved. In that case, a PIN junction is formed between the n-type semiconductor region and the p-type semiconductor region.
  • the first main surface and the second main surface of the photoelectric conversion unit 10 are formed by printing a conductive paste containing conductive particles, a thermosetting resin, and a solvent.
  • One electrode 20 is provided.
  • the 1st electrode 20 functions as an electroconductive base layer at the time of forming the 2nd electrode 40 mentioned later by the plating method (electrolytic deposition method).
  • the volume resistivity is 10 ⁇ 2 ⁇ ⁇ cm or less, it is defined as being conductive. Further, if the volume resistivity is 10 2 ⁇ ⁇ cm or more, it is defined as insulating.
  • the conductive particles for example, silver, copper, aluminum, nickel, tin, bismuth, zinc, gallium, carbon, and a mixture thereof can be used.
  • thermosetting resin an epoxy resin, a phenol resin, an acrylic resin, or the like can be used.
  • An insulating film 70 is provided on the first main surface side of the first electrode 20 provided on the first main surface side of the photoelectric conversion unit 10.
  • the insulating film 70 is provided on both the photoelectric conversion unit 10 and the first main surface side and the second main surface side of the first electrode 20.
  • the insulating film 70 is provided on the first main surface side of the first electrode 20 at least in the region where the first electrode 20 is formed.
  • the insulating film 70 contributes to an improvement in adhesion between the first electrode 20 and a second electrode 40 described later.
  • the adhesion between silver and copper is small, but copper is formed on the insulating film 70 made of silicon oxide or the like.
  • the adhesion between the second electrode 40 and the insulating film 70 can be improved, and the reliability of the photoelectric conversion element 100 can be improved.
  • the insulating film 70 is formed not only on the formation region of the first electrode 20 but also on the entire surface on the first main surface side and the second main surface side of the photoelectric conversion unit 10. .
  • the photoelectric conversion unit 10 can be chemically and electrically protected from the plating solution when the second electrode 40 is formed. .
  • openings 72 as a plurality of deformed portions are provided.
  • the opening 72 when forming the second electrode 40 described later, a part of the surface of the first electrode 20 is exposed from the opening 72 and is exposed to the plating solution to be conductive. It becomes possible to deposit metal starting from the surface of the first electrode 20 exposed from the opening 72.
  • the second electrode 40 is formed on the insulating film 70 in the formation region of the first electrode 20 from the opening 72 provided in the insulating film 70.
  • the second electrode 40 is formed by depositing metal from the first electrode 20 through a plurality of openings 72 provided in the insulating film 70.
  • the metal to be deposited as the second electrode 40 for example, copper, nickel, tin, aluminum, chromium, silver, or the like can be used, and any material that can be formed by a plating method (electrolytic deposition) may be used.
  • the plurality of bus bar electrodes 80 and the plurality of finger electrodes 90 shown in FIGS. 1 and 2 are configured by the second electrode 40 and the first electrode 20.
  • the photoelectric conversion element 100 of the present disclosure is manufactured by a manufacturing method described later, the quality of the insulating film 70 formed after the formation of the first electrode 20 is good.
  • the first electrode 20 having a small resistivity and a low resistivity in the first electrode 20.
  • the photoelectric conversion element 100 itself is not exposed to high temperatures for a long time, the characteristics of the photoelectric conversion element 100 can be secured.
  • a photoelectric conversion unit 10 including a semiconductor substrate 11 made of crystalline silicon such as single crystal silicon or polycrystalline silicon and having a p-type semiconductor region 13A and an n-type semiconductor region 13B is prepared.
  • the semiconductor substrate 11 contains impurities for supplying electric charges to silicon in order to provide conductivity.
  • a single crystal silicon substrate contains an n-type containing an atom (for example, phosphorus) for introducing an electron into a silicon atom and an atom (for example, boron) for introducing a hole into a silicon atom.
  • an atom for example, phosphorus
  • an atom for example, boron
  • electrons having a smaller effective mass and scattering cross section generally have a higher mobility. From the above viewpoint, it is desirable to use an n-type single crystal silicon substrate as the semiconductor substrate 11.
  • a p-type semiconductor region 13A is formed on the first main surface side of the semiconductor substrate 11.
  • amorphous silicon including an amorphous component such as an amorphous silicon thin film, microcrystalline silicon (a thin film including amorphous silicon and crystalline silicon), or the like is used. It is desirable to include a layer.
  • B (boron) etc. can be used as a dopant impurity.
  • the method for forming the p-type semiconductor region 13A is not particularly limited, but, for example, a CVD method (Chemical Vapor Deposition) can be used.
  • a CVD method Chemical Vapor Deposition
  • SiH 4 gas is used, and hydrogen-diluted B 2 H 6 is preferably used as the dopant addition gas.
  • the addition amount of the dopant impurity for good in trace amounts it is preferable to use a mixed gas diluted beforehand with SiH 4 and H 2.
  • a gas containing a different element such as CH 4 , CO 2 , NH 3 , GeH 4 is added to alloy the silicon thin film, thereby reducing the energy gap of the silicon thin film. It can also be changed.
  • impurities such as oxygen and carbon may be added in a small amount in order to improve light transmittance. In that case, it can be formed by introducing a gas such as CO 2 or CH 4 during the CVD film formation.
  • the n-type semiconductor region 13B is formed on the second main surface side of the semiconductor substrate 11.
  • the material used for forming the n-type semiconductor region 13B desirably includes an amorphous silicon layer containing an amorphous component such as an amorphous silicon thin film or microcrystalline silicon.
  • P (phosphorus) etc. can be used as a dopant impurity.
  • the method for forming the n-type semiconductor region 13B is not particularly limited, but for example, a CVD method can be used.
  • SiH 4 gas is used, and hydrogen-diluted PH 3 is preferably used as the dopant addition gas.
  • the addition amount of the dopant impurity for good in trace amounts it is preferable to use a mixed gas diluted beforehand with SiH 4 and H 2.
  • a gas containing a different element such as CH 4 , CO 2 , NH 3 , GeH 4 is added to alloy the silicon thin film, thereby reducing the energy gap of the silicon thin film. It can also be changed.
  • impurities such as oxygen and carbon may be added in a small amount in order to improve light transmittance. In that case, it can be formed by introducing a gas such as CO 2 or CH 4 during the CVD film formation.
  • a first intrinsic semiconductor region 12A is provided between the semiconductor substrate 11 and the p-type semiconductor region 13A
  • a second intrinsic semiconductor region is provided between the semiconductor substrate 11 and the n-type semiconductor region 13B.
  • 12B is provided.
  • i-type hydrogenated amorphous silicon composed of silicon and hydrogen
  • first intrinsic semiconductor region 12A and the second intrinsic semiconductor region 12B i-type hydrogenated amorphous silicon composed of silicon and hydrogen
  • i-type hydrogenated amorphous silicon is formed on the front and back surfaces of the semiconductor substrate 11 made of single crystal silicon by the CVD method, surface passivation can be effectively performed while suppressing impurity diffusion to the semiconductor substrate 11. .
  • a profile can be given to the energy gap by changing the amount of hydrogen in the film.
  • the first transparent electrode layer 14A is formed on the first main surface side of the p-type semiconductor region 13A
  • the second transparent electrode layer 14B is formed on the second main surface side of the n-type semiconductor region 13B.
  • the method for forming the first transparent electrode layer 14A and the second transparent electrode layer 14B is not particularly limited, but a physical vapor deposition method such as sputtering or a reaction between an organometallic compound and oxygen or water is used. A chemical vapor deposition (MOCVD) method or the like is preferable. In any film forming method, energy by heat or plasma discharge can be used.
  • a physical vapor deposition method such as sputtering or a reaction between an organometallic compound and oxygen or water is used.
  • a chemical vapor deposition (MOCVD) method or the like is preferable.
  • energy by heat or plasma discharge can be used.
  • transparent conductive metal oxides such as indium oxide, zinc oxide, tin oxide, titanium oxide, and composite oxides thereof are used. Further, a transparent conductive material made of a nonmetal such as graphene may be used.
  • indium-based composite oxides mainly composed of indium oxide are used as the first transparent electrode layer 14A and the second transparent electrode layer 14B. preferable.
  • a dopant to indium oxide. Examples of the impurity used as the dopant include Sn, W, Ce, Zn, As, Al, Si, S, and Ti.
  • the first electrode 20 ⁇ / b> A containing conductive particles, a thermosetting resin, and a solvent is formed on the first main surface side of the photoelectric conversion unit 10.
  • 20 A of 1st electrodes function as a conductive base layer at the time of forming the 2nd electrode 40 mentioned later by the plating method (electrolytic deposition method).
  • the first electrode 20 ⁇ / b> A is also formed on the second main surface side of the photoelectric conversion unit 10.
  • the first electrode 20A can be formed by, for example, an inkjet method, a screen printing method, a spray method, a roll coating method, or the like.
  • the first electrode 20A is preferably patterned in a predetermined shape such as a comb shape.
  • a screen printing method is suitable for forming the patterned first electrode 20A from the viewpoint of productivity.
  • a method of printing a printing paste containing conductive fine particles using a screen plate having an opening pattern corresponding to the pattern shape of the collector electrode is preferably used.
  • the first electrode 20A may be composed of a plurality of layers.
  • the first transparent electrode layer 14 ⁇ / b> A and the second transparent electrode layer 14 ⁇ / b> A are formed by including a lower layer having a low contact resistance with the first transparent electrode layer 14 ⁇ / b> A and the second transparent electrode layer 14 ⁇ / b> B on the surface of the photoelectric conversion unit 10.
  • An improvement in the fill factor of the solar cell can be expected with a decrease in contact resistance with the electrode layer 14B.
  • the conductive particles contained in the first electrode 20A for example, silver, copper, aluminum, nickel, tin, bismuth, zinc, gallium, carbon, and a mixture thereof can be used.
  • silver fine particles are used from the viewpoint of conductivity.
  • thermosetting resin included in the first electrode 20A an epoxy resin, a phenol resin, an acrylic resin, or the like can be used.
  • the first electrode 20 ⁇ / b> A can be cured in the thermosetting process described later.
  • an air drying process for drying the first electrode 20A under atmospheric pressure is performed.
  • it dries below the curing temperature of a thermosetting resin, heating the 1st electrode 20A.
  • it is preferable to dry at the boiling point of the solvent contained in the first electrode 20A.
  • under atmospheric pressure in the present disclosure includes not only 1013 mbar, but also includes a pressure fluctuation range due to normal climate change on the earth, including a pressure fluctuation range that occurs when operating with a heating device in that environment, for example, It is a sealed dryer that does not have a pressure adjustment mechanism, and includes pressure fluctuations caused by temperature rise and fall.
  • FIG. 8 is a schematic cross-sectional view showing a state of the first electrode 20A immediately after being formed on the first main surface side of the photoelectric conversion unit 10.
  • the first electrode 20A immediately after being formed is in a state in which a solvent 24 and a thermosetting resin 26 are mixed in conductive particles 22 such as silver.
  • the atmospheric pressure drying process is performed by passing the photoelectric conversion unit 10 formed with the first electrode 20A through a tunnel-shaped heating furnace adjusted to be equal to or lower than the curing temperature of the thermosetting resin 26.
  • FIG. 9 is a schematic cross-sectional view showing the state of the first electrode 20B after the air drying step.
  • the air drying process most of the solvent is evaporated because heat drying is performed. Due to air drying, bumping of the solvent can be suppressed, and as a result, generation of voids in the first electrode 20B can be suppressed. Note that at this stage, not all of the solvent 24 has been evaporated, and a slight amount of solvent 24 may remain in the deep portion of the first electrode 20B.
  • thermosetting resin 26 is not yet completely cured at this stage.
  • the deformed portion can be provided in the insulating film 70 by a thermosetting process performed after the insulating film 70 forming process described later.
  • thermosetting resin 26 is in an uncured state, and most of the solvent 24 is evaporated without causing a large gap in the first electrode 20B.
  • a vacuum drying process is performed in which the first electrode 20B after the air drying process is dried under vacuum.
  • it dries below the curing temperature of the thermosetting resin 26.
  • it is preferable to dry at the boiling point of the solvent contained in the first electrode 20B.
  • under the vacuum in this indication means the pressure conditions which are under the atmospheric pressure defined above.
  • the “boiling point of the solvent 24” in this vacuum drying process means not the boiling point of the solvent 24 under vacuum but the boiling point of the solvent 24 under atmospheric pressure.
  • the first electrode 20B after the air drying step is dried in a vacuum heating chamber adjusted to be equal to or lower than the curing temperature of the thermosetting resin 26.
  • FIG. 10 is a schematic cross-sectional view showing the state of the first electrode 20C after this vacuum drying step. Since the actual boiling point of the solvent 24 is reduced under vacuum, the solvent 24 remaining in the deep part of the first electrode 20C is also contained in the vacuum chamber adjusted to be equal to or higher than the boiling point of the solvent 24 under atmospheric pressure. It can be evaporated. In addition, since most of the solvent 24 has already been evaporated in the air drying process, which is the previous stage of this vacuum drying process, large bumping is unlikely to occur when the solvent 24 is evaporated in this vacuum drying process, resulting in a large amount. The generation of voids can be suppressed.
  • the solvent 24 can be evaporated without generating a large gap in the first electrode 20B, and the first low resistance.
  • the electrode 20B can be realized.
  • the remaining solvent 24 evaporates in the film forming apparatus in the insulating film 70 forming step described later, and the film forming component of the insulating film 70 is obtained. It can suppress that film forming quality is inhibited. Further, it is possible to reduce the risk that the film forming apparatus will fail.
  • this vacuum drying step is performed at a temperature lower than the curing temperature of the thermosetting resin 26. Therefore, the thermosetting resin 26 is in an uncured state even at this stage.
  • the deformed portion can be provided in the insulating film 70 by a thermosetting process performed after the insulating film 70 forming process described later.
  • thermosetting resin 26 by performing the vacuum drying step below the curing temperature of the thermosetting resin 26, it is possible to obtain an effect that the solvent 24 can be evaporated without exposing the photoelectric conversion element 100 to a high temperature for a long time. . That is, instead of evaporating the solvent 24 in the thermosetting process described later, the time of the thermosetting process can be minimized by evaporating the solvent 24 in the vacuum drying process which is the preceding process. . As a result, deterioration in characteristics of the photoelectric conversion element 100 can be suppressed.
  • thermosetting resin 26 is in an uncured state, and the solvent 24 left in the deep portion of the first electrode 20C is also generated without causing a large gap in the first electrode 20C. It is important to evaporate.
  • the insulating film 70 is formed on at least the first main surface side of the first electrode 20 ⁇ / b> C provided on the first main surface side of the photoelectric conversion unit 10.
  • the insulating film 70 is also formed on the second main surface side of the first electrode 20 ⁇ / b> C provided on the second main surface side of the photoelectric conversion unit 10.
  • the insulating film 70 is also formed on the first main surface side and the second main surface side of the photoelectric conversion unit 10 in the region where the first electrode 20C is not formed.
  • this insulating film 70 contributes to an improvement in adhesion between the first electrode 20 and the second electrode 40 described later.
  • the adhesion between silver and copper is small, but copper is formed on the insulating film 70 made of silicon oxide or the like.
  • the adhesion between the second electrode 40 and the insulating film 70 can be improved, and the reliability of the photoelectric conversion element 100 can be improved. Therefore, even in the configuration in which the bus bar electrode 80 and the finger electrode 90 shown in FIGS. 1 and 2 are thinned, the adhesion between the first electrode 20 and the second electrode 40 can be ensured, and the yield can be reduced by suppressing peeling. It is possible to achieve both improvement and improvement in light collection efficiency by thinning the electrodes.
  • the insulating film 70 is formed not only on the formation region of the first electrode 20 but also on the entire surface on the first main surface side and the second main surface side of the photoelectric conversion unit 10. .
  • the insulating film 70 is formed also in the region where the first electrode 20 is not formed, it is possible to chemically and electrically protect the photoelectric conversion unit 10 from the plating solution in a second electrode forming step described later.
  • the photoelectric conversion unit 10 is configured to include the first transparent electrode layer 14A and the second transparent electrode layer 14B
  • the insulating film 70 is formed of the first transparent electrode layer 14A and the second transparent electrode layer 14B. By forming it on the entire exposed surface, it is possible to prevent metal from being deposited on the surfaces of the first transparent electrode layer 14A and the second transparent electrode layer 14B.
  • the insulating film 70 covers the first electrode 20C by forming the insulating film 70 on the entire surface of the photoelectric conversion unit 10 and the first main surface side and the second main surface side of the first electrode 20C.
  • the material constituting the insulating film 70 it is necessary to use an electrically insulating material, and it is desirable that the material has chemical stability against the plating solution.
  • the insulating film 70 is hardly dissolved in the second electrode forming step described later, and the first main surface and the second main surface of the photoelectric conversion unit 10 are not dissolved. It is possible to suppress the occurrence of damage.
  • the material constituting the insulating film 70 has high adhesion strength with the photoelectric conversion unit 10.
  • the material constituting the insulating film 70 is the first transparent electrode layer 14A. It is preferable to use a material having a high adhesion strength with the second transparent electrode layer 14B. By increasing the adhesion strength between the first transparent electrode layer 14A, the second transparent electrode layer 14B, and the insulating film 70, the insulating film 70 is less likely to be peeled off in the second electrode forming step described later. Metal deposition on the transparent electrode layer 14A and the second transparent electrode layer 14B can be prevented.
  • the insulating film 70 is preferably made of a material having a high light transmittance in a wavelength region that can be absorbed by the photoelectric conversion unit 10. Since the insulating film 70 is also formed on the light receiving surface side of the photoelectric conversion unit 10, more light can be taken into the photoelectric conversion unit 10 if light absorption by the insulating film 70 is small. For example, when the insulating film 70 has sufficient transparency with a transmittance of 90% or more, the optical loss due to light absorption in the insulating film 70 is small, and a step of removing the insulating film 70 after the second electrode forming step is necessary. Instead, it can be used as part of the photoelectric conversion element 100 as it is.
  • the manufacturing process of the photoelectric conversion element 100 can be simplified, and the productivity can be further improved.
  • the insulating film 70 when used as it is as a part of the photoelectric conversion element 100 without providing a process for removing the insulating film 70, the insulating film 70 has a high light transmittance in a wavelength region that can be absorbed by the photoelectric conversion unit 10. It is more desirable to use a material having sufficient weather resistance and stability against heat and humidity.
  • the material constituting the insulating film 70 may be an inorganic insulating material or an organic insulating material.
  • the inorganic insulating material for example, materials such as silicon oxide, silicon nitride, titanium oxide, aluminum oxide, and magnesium oxide can be used.
  • the organic insulating material for example, materials such as polyester, ethylene vinyl acetate copolymer, acrylic, epoxy, and polyurethane can be used.
  • silicon oxide, silicon nitride, silicon oxynitride, aluminum oxide, sialon (SiAlON), yttrium oxide, magnesium oxide, barium titanate, samarium oxide, Barium tantalate, tantalum oxide, magnesium fluoride, titanium oxide, strontium titanate and the like are preferably used.
  • silicon oxide, silicon nitride, silicon oxynitride, aluminum oxide, sialon (SiAlON), yttrium oxide, magnesium oxide, barium titanate, samarium oxide, Barium tantalate, tantalum oxide, magnesium fluoride, and the like are preferable, and silicon oxide, silicon nitride, and the like are particularly preferably used from the viewpoint that the refractive index can be appropriately adjusted.
  • these inorganic materials are not limited to those having a stoichiometric composition, and may include oxygen deficiency or the like.
  • the refractive index of the insulating film 70 is preferably lower than the refractive index of the surface of the photoelectric conversion unit 10.
  • the film thickness is preferably set to 20 nm or more, and more preferably set to 50 nm or more.
  • the film thickness of the insulating film 70 on the formation region of the first electrode 20C may be different from the film thickness of the insulation film 70 on the non-formation region of the first electrode 20C.
  • an appropriate film thickness is set for forming the opening 72 of the insulating film 70, and in the non-formation region of the first electrode 20C, an optical film having appropriate antireflection characteristics.
  • the film thickness may be set to be thick. That is, the insulating film 70 in the region where the first electrode 20C is formed may be formed thinner than the insulating film 70 in the region where the first electrode 20C is not formed.
  • the opening 72 in the insulating film 70 in the thermosetting process described later it is desirable to use an inorganic material having a small elongation at break as the material constituting the insulating film 70.
  • an inorganic insulating material such as silicon oxide or silicon nitride
  • a dry method such as a plasma CVD method or a sputtering method is preferably used as a method for forming the insulating film 70.
  • a wet method such as a spin coating method or a screen printing method is preferably used as a method for forming the insulating film 70. According to these methods, it is possible to form a dense film with few defects such as pinholes.
  • the temperature at which the insulating film 70 is formed is not particularly limited, but it is preferable to form the film while heating from the viewpoint of improving the uniformity of the film thickness. Moreover, it is preferable to form at a temperature lower than the heat-resistant temperature of the photoelectric conversion part 10, for example, when the photoelectric conversion part 10 contains an amorphous silicon material or a transparent electrode layer, it is preferable to form at 250 degrees C or less. .
  • the insulating film 70 is formed by a plasma CVD method from the viewpoint of forming a film having a denser structure.
  • a plasma CVD method from the viewpoint of forming a film having a denser structure.
  • the solvent 24 left in the deep part of the first electrode 20B is evaporated, even when the insulating film 70 is formed in the CVD apparatus, it remains in the CVD apparatus.
  • the solvent 24 evaporates in the CVD apparatus and does not coexist with the film forming component of the insulating film 70, so that the film forming quality can be improved.
  • the risk of failure of the CVD apparatus can be reduced.
  • thermosetting resin 26 included in the first electrode 20C is in an uncured state.
  • thermosetting process Next, a thermosetting process is performed in which the first electrode 20C is thermoset at a temperature equal to or higher than the curing temperature of the thermosetting resin.
  • thermosetting resin 26 in the first electrode 20C is cured, and the conductive particles 22 made of silver or the like are fused.
  • thermosetting process the conductivity of the first electrode 20 shown in FIG. 7 is ensured.
  • the first electrode 20 contracts with the curing of the thermosetting resin 26 and the fusion of the conductive particles 22, and as a result, the insulating film 70 has a plurality of deformed portions.
  • An opening 72 can be formed.
  • thermosetting resin 26 is cured and the conductive particles 22 are fused in this thermosetting process. As a result, the deterioration of the characteristics of the photoelectric conversion element 100 can be suppressed.
  • the insulating film 70 in the formation region of the first electrode 20 is locally thin even if the opening 72 is not completely formed. If the thin film region, which is the film thickness region, is formed as the deformed portion, the second electrode 40 can be formed in the second electrode forming step described later. That is, when the thickness of the insulating film 70 is reduced, the withstand voltage is generally lowered. Therefore, even when the opening 72 is not formed in the insulating film 70 until immediately before energization in the second electrode forming process described later, voltage is applied to the insulating film 70 by energization in the second electrode forming process. As a result, the dielectric breakdown of the insulating film 70 selectively occurs from the thin film region provided in the insulating film 70, and the opening 72 is formed in the insulating film 70.
  • the opening 72 can be formed in the insulating film 70 more reliably.
  • the 2nd electrode 40 formation process which forms the 2nd electrode 40 from the 1st electrode 20 as a starting point is performed.
  • the first electrode 20 is provided on the first main surface side and the second main surface side of the photoelectric conversion unit 10
  • the first electrode 20 of the insulating film 70 in the formation region of the first electrode 20 is provided.
  • a second electrode 40 is formed on one main surface side and on the second main surface side.
  • the second electrode 40 is formed by depositing metal starting from a plurality of openings 72 provided in the insulating film 70, and is electrically connected to the first electrode 20 through the openings 72.
  • the metal to be deposited as the second electrode 40 for example, copper, nickel, tin, aluminum, chromium, silver, or the like can be used, and any material that can be formed by a plating method (electrolytic deposition) may be used.
  • the second electrode 40 can be formed by either an electroless plating method or an electrolytic plating method, but the electrolytic plating method is preferable from the viewpoint of productivity.
  • the deposition rate of the metal can be increased, so that the second electrode 40 can be formed in a short time.
  • the second electrode 40 may be composed of a plurality of layers. For example, after the first second electrode layer made of a material having high conductivity such as copper is formed on the first electrode 20 via the insulating film 70, the second second electrode layer having excellent chemical stability. By forming on the surface of the first second electrode layer, a collector electrode having low resistance and excellent chemical stability can be formed.

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Abstract

Un procédé de production d'un élément de conversion photoélectrique selon la présente invention comprend : une première étape de formation d'électrode dans laquelle une première électrode est formée sur au moins un premier côté de surface principale d'une unité de conversion photoélectrique avec l'utilisation d'une pâte conductrice qui contient des particules conductrices, une résine thermodurcissable et un solvant; une étape de séchage atmosphérique dans laquelle la première électrode est séchée en étant chauffée à la pression atmosphérique de façon à ne pas dépasser la température de durcissement de la résine thermodurcissable; une étape de séchage sous vide dans laquelle la première électrode est séchée sous vide en étant chauffée sous vide de manière à ne pas dépasser la température de durcissement de la résine thermodurcissable après l'étape de séchage atmosphérique; et une étape de formation de film isolant dans laquelle un film isolant est formé sur le premier côté de surface principale de la première électrode après l'étape de séchage sous vide.
PCT/JP2018/012036 2017-03-31 2018-03-26 Procédé de production d'un élément de conversion photoélectrique WO2018181128A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011084775A1 (fr) * 2009-12-21 2011-07-14 First Solar, Inc. Dispositif photovoltaïque doté d'une couche tampon
JP2012508812A (ja) * 2008-11-14 2012-04-12 アプライド・ナノテック・ホールディングス・インコーポレーテッド 太陽電池製造用インク及びペースト
JP2013247060A (ja) * 2012-05-29 2013-12-09 Harima Chemicals Group Inc 導電性金属厚膜形成用材料および導電性金属厚膜の形成方法
WO2014185537A1 (fr) * 2013-05-17 2014-11-20 株式会社カネカ Cellule solaire, procédé de production de cette dernière et module de cellule solaire

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012508812A (ja) * 2008-11-14 2012-04-12 アプライド・ナノテック・ホールディングス・インコーポレーテッド 太陽電池製造用インク及びペースト
WO2011084775A1 (fr) * 2009-12-21 2011-07-14 First Solar, Inc. Dispositif photovoltaïque doté d'une couche tampon
JP2013247060A (ja) * 2012-05-29 2013-12-09 Harima Chemicals Group Inc 導電性金属厚膜形成用材料および導電性金属厚膜の形成方法
WO2014185537A1 (fr) * 2013-05-17 2014-11-20 株式会社カネカ Cellule solaire, procédé de production de cette dernière et module de cellule solaire

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