WO2015050082A1 - Élément photovoltaïque et procédé de production de ce dernier - Google Patents

Élément photovoltaïque et procédé de production de ce dernier Download PDF

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WO2015050082A1
WO2015050082A1 PCT/JP2014/075880 JP2014075880W WO2015050082A1 WO 2015050082 A1 WO2015050082 A1 WO 2015050082A1 JP 2014075880 W JP2014075880 W JP 2014075880W WO 2015050082 A1 WO2015050082 A1 WO 2015050082A1
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transparent conductive
conductive film
photovoltaic device
thin film
semiconductor substrate
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PCT/JP2014/075880
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English (en)
Japanese (ja)
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小林　英治
宣孝 中村
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長州産業株式会社
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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
    • H01L31/072—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
    • 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
    • H01L31/022466—Electrodes made of transparent conductive layers, e.g. TCO, ITO layers
    • H01L31/022475—Electrodes made of transparent conductive layers, e.g. TCO, ITO layers composed of indium tin oxide [ITO]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
    • H01L31/1884—Manufacture of transparent electrodes, e.g. TCO, ITO
    • 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 photovoltaic device (solar cell) having a heterojunction and a method for manufacturing the photovoltaic device.
  • Photovoltaic elements are attracting attention as clean power generation means that does not generate greenhouse gases such as CO 2 and as power generation means with high operational safety in place of nuclear power generation.
  • photovoltaic elements there is a photovoltaic element having a heterojunction with high power generation efficiency (heterojunction photovoltaic element).
  • an n-type amorphous semiconductor thin film and a first transparent conductive film are laminated in this order on the light incident surface side of the n-type crystal semiconductor substrate, and the n-type crystal semiconductor substrate
  • a rear emitter type structure in which a p-type amorphous semiconductor thin film and a second transparent conductive film are laminated in this order on the side opposite to the light incident surface has been developed (see Patent Document 1).
  • each transparent conductive film is generally formed by sputtering.
  • the sputtering method tends to cause deterioration of the layer on the side to be laminated (usually an amorphous semiconductor layer). Therefore, it has been studied to form a transparent conductive film by an ion plating method that can suppress the occurrence of deterioration.
  • the ion plating method has a disadvantage that the cost is increased as compared with the sputtering method.
  • a widely used transparent conductive film made of ITO (Indium Tin Oxide) or the like is formed at a relatively high temperature (for example, 200 ° C. or higher) in order to crystallize and lower the resistance, or a post-deposition heat treatment. It is necessary to do.
  • a transparent conductive film is laminated or processed at a high temperature of 200 ° C. or higher, performance tends to deteriorate due to crystallization of an amorphous semiconductor or hydrogen diffusion. .
  • the present invention has been made in view of such circumstances, and provides a heterojunction photovoltaic device having high power generation efficiency even when a transparent conductive film is formed by sputtering, and a method for manufacturing such a photovoltaic device.
  • the purpose is to do.
  • the photovoltaic device according to the first invention that meets the above object includes an n-type crystal semiconductor substrate, an n-type amorphous semiconductor thin film stacked in this order on one side of the n-type crystal semiconductor substrate, and a first transparent element.
  • a photovoltaic device comprising a conductive film, a p-type amorphous semiconductor thin film and a second transparent conductive film stacked in this order on the other side of the n-type crystal semiconductor substrate, and one side used as a light incident surface
  • Either one or both of the first and second transparent conductive films is a transparent conductive film ( ⁇ ) formed of indium oxide doped with at least tantalum.
  • the power generation efficiency can be increased by forming the transparent conductive film ( ⁇ ) from indium oxide doped with at least tantalum. Specifically, the transparent conductive film ( ⁇ ) is crystallized at a relatively low temperature, and low resistance is obtained. For this reason, the transparent conductive film ( ⁇ ) having excellent low resistance can be obtained without high temperature treatment by sputtering, and a heterojunction photovoltaic device having high power generation efficiency can be obtained.
  • the tantalum content in the transparent conductive film ( ⁇ ) is preferably 0.1% by mass or more and 5% by mass or less in terms of oxide.
  • the indium oxide is further doped with at least one element (x) selected from the group consisting of titanium, vanadium and niobium.
  • element (x) selected from the group consisting of titanium, vanadium and niobium.
  • the contents of the tantalum and the element (x) in the transparent conductive film ( ⁇ ) are both 0.1% by mass or more in terms of oxides, and the tantalum and The total content of the element (x) is preferably 5% by mass or less in terms of oxide.
  • the second transparent conductive film is the transparent conductive film ( ⁇ ).
  • ⁇ transparent conductive film
  • the absorption loss of ITO increases, and as a result, the light transmittance (particularly, (Transmission of light having a wavelength of 900 to 1200 nm) is lowered, and output characteristics are lowered.
  • the 2nd transparent conductive film provided in the back side also has a high transmittance
  • the first transparent conductive film is also the transparent conductive film ( ⁇ ).
  • productivity and the like can be further increased in addition to power generation efficiency.
  • the n-type crystal semiconductor substrate has a surface having a texture structure.
  • a light confinement effect due to irregular reflection of light occurs, and the power generation efficiency and the like can be further increased.
  • the transparent conductive film ( ⁇ ) is preferably formed by a sputtering method having a formation temperature of less than 200 ° C.
  • a sputtering method having a formation temperature of less than 200 ° C.
  • a photovoltaic device manufacturing method includes an n-type crystal semiconductor substrate, an n-type amorphous semiconductor thin film stacked in this order on one side of the n-type crystal semiconductor substrate, Light having one transparent conductive film, a p-type amorphous semiconductor thin film and a second transparent conductive film stacked in this order on the other side of the n-type crystal semiconductor substrate, and one side used as a light incident surface.
  • the formation temperature in this step is less than 200 ° C.
  • the photovoltaic element manufacturing method it is possible to obtain a photovoltaic element having a low generation cost and high power generation efficiency.
  • amorphous means not only amorphous but also microcrystals.
  • Morocrystal means a crystal peak observed by Raman spectroscopy.
  • the “forming temperature” refers to a substrate temperature at the time of sputtering and a heat treatment temperature after film deposition by sputtering performed as necessary.
  • the photovoltaic device according to the first invention has high power generation efficiency.
  • the photovoltaic device has sufficient power generation efficiency and can be produced at low cost.
  • a photovoltaic device having high power generation efficiency can be manufactured at low cost.
  • the photovoltaic device 10 As shown in FIG. 1, the photovoltaic device 10 according to the first exemplary embodiment of the present invention is a plate-like multilayer structure.
  • the photovoltaic element 10 includes an n-type crystal semiconductor substrate 11, a first intrinsic amorphous semiconductor thin film 12 stacked in this order on one side (the upper side in FIG. 1) of the n-type crystal semiconductor substrate 11, an n-type A second intrinsic amorphous semiconductor thin film laminated in this order on the other side (lower side in FIG. 1) of the amorphous semiconductor thin film 13 and the first transparent conductive film 14 and the n-type crystal semiconductor substrate 11 15, a p-type amorphous semiconductor thin film 16 and a second transparent conductive film 17.
  • the photovoltaic element 10 is a collector electrode 18 disposed on the surface (one side) of the first transparent conductive film 14 and a collector electrode disposed on the surface (other side) of the second transparent conductive film 17.
  • the n-type crystal semiconductor substrate 11 is not particularly limited as long as it is a crystalline substrate having n-type semiconductor characteristics, and a known substrate can be used.
  • Examples of the crystal semiconductor constituting the n-type crystal semiconductor substrate 11 include SiC (SiGe), SiN, etc. in addition to silicon (Si), but silicon is preferable from the viewpoint of productivity.
  • the n-type crystal semiconductor substrate 11 may be a single crystal or a polycrystal.
  • a texture structure is formed on one surface of the n-type crystal semiconductor substrate 11.
  • This texture structure may also be formed on the other surface.
  • This texture structure enables light confinement due to diffuse reflection of light.
  • a concavo-convex structure having a large number of pyramid shapes is irregularly arranged so as to cover substantially the entire upper and lower surfaces (one side and the other side) of the n-type crystal semiconductor substrate 11.
  • the height (size) of the concavo-convex structure (texture structure) may be uneven, and adjacent concavo-convex portions may overlap.
  • a vertex and a trough part may be roundish.
  • the height of the unevenness is about several ⁇ m to several tens of ⁇ m.
  • Such a texture structure can be obtained, for example, by immersing the substrate material in an etching solution containing about 1 to 5% by mass of sodium hydroxide and anisotropically etching the (100) plane of the substrate material.
  • the first intrinsic amorphous semiconductor thin film 12 is stacked on one side of the n-type crystal semiconductor substrate 11.
  • the semiconductor constituting the first intrinsic amorphous semiconductor thin film 12 include silicon (Si), SiC, SiGe, SiN, etc., but silicon is preferable from the viewpoint of productivity.
  • the thickness of the intrinsic amorphous semiconductor thin film 12 is not particularly limited, but can be, for example, 1 nm or more and 10 nm or less, and preferably 8 nm or less. When the film thickness is less than 1 nm, recombination of carriers is likely to occur due to defects easily occurring. Moreover, when this film thickness exceeds 10 nm, it becomes easy to produce the fall of a short circuit current and the increase in light absorption.
  • the n-type amorphous semiconductor thin film 13 is laminated on one side of the first intrinsic amorphous semiconductor thin film 12.
  • Examples of the semiconductor constituting the n-type amorphous semiconductor thin film 13 include n-type amorphous silicon, n-type amorphous SiC, SiGe, SiN, etc. From this point, n-type amorphous silicon is preferable.
  • the thickness of the n-type amorphous semiconductor thin film 13 is not particularly limited, but is preferably 1 nm to 15 nm, for example, and more preferably 2 nm to 10 nm. By setting the film thickness within such a range, occurrence of carrier recombination and series resistance can be reduced in a balanced manner.
  • the first transparent conductive film 14 (transparent conductive film ( ⁇ )) is stacked on one side of the n-type amorphous semiconductor thin film 13.
  • the material constituting the first transparent conductive film 14 is indium oxide doped with at least tantalum, and is further doped with at least one element (x) selected from the group consisting of titanium, vanadium and niobium. Is preferred. Of the elements (x), titanium is more preferable.
  • the first transparent conductive film 14 may further contain other elements (for example, tin and the like) as long as the effects of the present invention are not impaired.
  • the content of tantalum in the first transparent conductive film 14 is preferably 0.1% by mass or more and 5% by mass or less, more preferably 0.5% by mass or more and 3% by mass or less in terms of oxide (Ta 2 O 5 ). preferable. Further, the content of the element (x) in the first transparent conductive film 14 is preferably 0.1% by mass or more and 5% by mass or less in terms of oxides (TiO 2 , V 2 O 5 and Nb 2 O 5 ). 0.5 mass% or more and 3 mass% or less is more preferable. Furthermore, the total content of tantalum and element (x) is preferably 5% by mass or less, more preferably 3% by mass or less in terms of oxide.
  • each dopant tantalum and element (x)
  • the effect of adding each dopant is not sufficiently exhibited.
  • the content of each dopant exceeds the above upper limit, the absorption loss in the transparent conductive film increases as the carrier density increases, and sufficient translucency cannot be obtained.
  • content of indium oxide in the 1st transparent conductive film 14 90 mass% or more is preferable, 95 mass% or more is more preferable, 97 mass% or more and 99.9 mass% or less are further more preferable.
  • the in-plane long axis average crystal grain size of the crystalline indium oxide is preferably 10 nm or more and less than 300 nm, and more preferably 40 nm or more and 200 nm or less.
  • the in-plane long axis average crystal grain size is the measurement of the top 20 particles having the largest measured value by measuring the longest diameter of each crystal particle present in the plane in an image obtained from a scanning electron microscope (SEM). This is the number averaged value. Since the first transparent conductive film 14 is mainly composed of crystalline indium oxide having such a small particle diameter, even if the formation temperature is less than 200 ° C., the film has high crystallinity and high mobility. It becomes. In addition, it is thought that the crystal having such a small particle diameter is derived from doped tantalum.
  • the specific resistance value of the first transparent conductive film 14 is preferably 5 ⁇ 10 ⁇ 5 ⁇ ⁇ cm to 1 ⁇ 10 ⁇ 3 ⁇ ⁇ cm, and more preferably 5 ⁇ 10 ⁇ 4 ⁇ ⁇ cm.
  • the second intrinsic amorphous semiconductor thin film 15 is stacked on the other side of the n-type crystal semiconductor substrate 11.
  • the semiconductor constituting the second intrinsic amorphous semiconductor thin film 15 can be the same as the first intrinsic amorphous semiconductor thin film 12.
  • the film thickness of the second intrinsic amorphous semiconductor thin film 15 can be, for example, 1 nm or more and 10 nm or less.
  • the p-type amorphous semiconductor thin film 16 is laminated on the other side of the second intrinsic amorphous semiconductor thin film 15.
  • Examples of the semiconductor composing the p-type amorphous semiconductor thin film 16 include p-type amorphous silicon, p-type amorphous SiC, SiGe, SiN and the like. From this point, p-type amorphous silicon is preferable.
  • the thickness of the p-type amorphous semiconductor thin film 16 is not particularly limited, but is preferably 1 nm or more and less than 6 nm, for example, and more preferably 2 nm or more and 5 nm or less. By setting the film thickness within such a range, occurrence of carrier recombination and series resistance can be reduced in a balanced manner.
  • the second transparent conductive film 17 (transparent conductive film ( ⁇ )) is laminated on the other side of the p-type amorphous semiconductor thin film 16.
  • the material (composition), characteristics, preferable film thickness range, and the like for forming the second transparent conductive film 17 are the same as those of the first transparent conductive film 14.
  • the first transparent conductive film 14 and the second transparent conductive film 17 may be different in composition, film thickness, specific resistance, and the like.
  • the second transparent conductive layer laminated on the back side that is, on the p-type amorphous semiconductor thin film 16.
  • the second transparent conductive film 17 Since the current collecting property in the lateral direction (planar direction) of the film 17 becomes low, it is preferable that the second transparent conductive film 17 has a lower resistance than the first transparent conductive film 14. As the carrier density increases, the absorption in the near-infrared wavelength region of 900 nm or more in the transparent conductive film increases remarkably. However, when the n-type crystal semiconductor substrate 11 is silicon (Si), the wavelength is 900 nm to 1200 nm. Since the light absorptance is low, light with a wavelength of 900 nm to 1200 nm tends to reach the second transparent conductive film 17 laminated on the back side.
  • Si silicon
  • the upper limit of the carrier density in the second transparent conductive film 17 is 3 ⁇ 10 20 cm ⁇ 3 and the lower limit of the mobility is 40 cm 2 V ⁇ 1 s ⁇ 1 .
  • the collector electrodes 18 and 19 have a plurality of bus bar electrodes formed in parallel with each other at equal intervals, and a plurality of finger electrodes orthogonal to these bus bar electrodes and formed in parallel with each other at equal intervals.
  • the bus bar electrode and the finger electrode each have a linear shape or a strip shape, and are formed of a conductive material.
  • a conductive adhesive such as a silver paste or a metal conductive wire such as a copper wire can be used.
  • the width of each bus bar electrode is, for example, about 0.5 mm to 2 mm, and the width of each finger electrode is, for example, about 10 ⁇ m to 300 ⁇ m.
  • interval between each finger electrode it is about 0.5 mm or more and 4 mm or less, for example.
  • the collector electrode 19 on the other side may be a structure in which a conductive material is laminated on the entire surface, instead of a structure including a bus bar electrode and a finger electrode.
  • the collector electrode having such a structure can be formed by plating, metal foil lamination, or the like.
  • the photovoltaic elements 10 having such a structure are usually used by connecting a plurality of photovoltaic elements 10 in series. By using a plurality of photovoltaic power generation devices 10 connected in series, the generated voltage can be increased.
  • the light incident surface of the photovoltaic element 10 is on one side (the upper side in FIG. 1). That is, the photovoltaic device 10 has a rear emitter structure in which a p-type amorphous semiconductor thin film 16 is provided on the side opposite to the light incident surface with respect to the n-type crystal semiconductor substrate 11. According to the photovoltaic device 10, since the transparent conductive films 14 and 17 are formed of indium oxide doped with at least tantalum, the power generation efficiency is excellent. In particular, in the photovoltaic element 10, the second transparent conductive film 17 on the back side, which can reduce the lateral current collecting ability, is generally formed of indium oxide doped with at least tantalum.
  • the photovoltaic element 10 includes a step of laminating a first intrinsic amorphous semiconductor thin film 12 on one side of an n-type crystal semiconductor substrate 11, a step of laminating an n-type amorphous semiconductor thin film 13, and a first step.
  • a step of laminating the transparent conductive film 14 a step of laminating the second intrinsic amorphous semiconductor thin film 15 on the other side of the n-type crystal semiconductor substrate 11, and a step of laminating the p-type amorphous semiconductor thin film 16.
  • the order of each process will not be specifically limited as long as it is the order which can obtain the layer structure of the photovoltaic device 10.
  • a method of laminating the first and second intrinsic amorphous semiconductor thin films 12 and 15 for example, chemical vapor deposition (for example, plasma CVD method or catalytic CVD method (also called hot wire CVD method)) or the like is used.
  • chemical vapor deposition for example, plasma CVD method or catalytic CVD method (also called hot wire CVD method)
  • a well-known method is mentioned.
  • the plasma CVD method for example, a mixed gas of SiH 4 and H 2 can be used as the source gas.
  • a chemical vapor deposition method for example, a plasma CVD method or a catalytic CVD method (also called hot wire CVD method)
  • the film can be formed by a known method such as If by plasma CVD method, a mixed gas of SiH 4, H 2, and PH 3 for example in the n-type amorphous-based semiconductor thin film 13 as a source gas, the p-type amorphous-based semiconductor thin film 16 is, for example, SiH 4 And a mixed gas of H 2 and B 2 H 6 can be used.
  • Examples of the method of laminating the first and second transparent conductive films 14 and 17 include a sputtering method, a vacuum deposition method, an ion plating method (reactive plasma deposition method), and the like. Is preferred.
  • the sputtering method is excellent in film thickness controllability and the like, and can be performed at a lower cost than the ion plating method.
  • a sputtering target used for forming the first and second transparent conductive films 14 and 17 a sputtering target containing indium oxide as a main component and containing tantalum oxide and preferably an oxide of element (x) is used.
  • the component ratio of each component in the sputtering target can be appropriately adjusted according to the desired component ratio of the first and second transparent conductive films 14 and 17.
  • the sputtering target may further contain other components (for example, tin oxide).
  • content (content ratio) of the metal component in each transparent conductive films 14 and 17 is substantially the same as the used sputtering target. It is considered.
  • the sputtering target includes, for example, a step (a) of preparing a solution containing an indium oxide precursor and a tantalum oxide precursor, adding an alkali compound to the solution, and depositing a metal hydroxide Step (b) to obtain a metal hydroxide, washing and drying the obtained metal hydroxide precipitate (c) to obtain a metal oxide powder, and sintering the obtained metal oxide powder after pulverization It can be obtained by a method including step (d).
  • the indium oxide precursor include indium nitrate and indium chloride
  • examples of the tantalum oxide precursor include tantalum chloride.
  • the pH of the solution obtained in step (a) is preferably 1 to 4.
  • the oxide of an element (x) or its precursor, a pH adjuster etc. is added to this solution.
  • the pH of the solution after adding the alkali compound in the step (b) is preferably 7 to 10.
  • the sintering temperature in step (d) can be about 1250 to 1600 ° C., and the sintering time can be about 10 to 20 hours.
  • the sputtering method can be performed using a known sputtering apparatus.
  • the initial degree of vacuum in the chamber of the sputtering apparatus can be about 1 ⁇ 10 ⁇ 7 to 1 ⁇ 10 ⁇ 5 Torr.
  • heat treatment can be performed as necessary.
  • this heat processing temperature 50 degreeC or more and less than 200 degreeC are preferable, and 180 degrees C or less is more preferable.
  • the formation temperature is less than 200 ° C. (more preferably, 150 ° C. or less.
  • the transparent conductive films 14 and 17 have the above-described composition, crystallization progresses even in the formation at such a relatively low temperature, and a low-resistance film can be obtained. it can. Further, when the formation temperature is less than 200 ° C., the influence on other amorphous semiconductor thin films and the like can be suppressed, and a heterojunction photovoltaic device having high power generation efficiency can be obtained.
  • the formation pressure can be about 7.5 ⁇ 10 ⁇ 4 to 7.5 ⁇ 10 ⁇ 3 Torr, and preferably 2 ⁇ 10 ⁇ 3 Torr to 7 ⁇ 10 ⁇ 3 Torr.
  • the collector electrodes 18 and 19 can be disposed by a known method.
  • a conductive adhesive is used as a material for the collector electrodes 18 and 19, it can be formed by a printing method such as screen printing or gravure offset printing.
  • a metal conducting wire for the collector electrodes 18 and 19 it can fix on the transparent conductive films 14 and 17 with a conductive adhesive or a low melting point metal (solder etc.).
  • the present invention is not limited to the above-described embodiments, and the configuration thereof can be changed without changing the gist of the present invention.
  • the first intrinsic amorphous semiconductor thin film 12 and the second intrinsic amorphous semiconductor thin film 15 included in the photovoltaic device 10 are not essential components.
  • the maximum output can be further increased in order to improve translucency by adopting a configuration in which the first intrinsic amorphous semiconductor thin film 12 on the light incident side is not laminated.
  • the first transparent conductive film 14 or the second transparent conductive film 17 may be formed of a transparent conductive material other than indium oxide doped with at least tantalum. Examples of the transparent conductive material include ITO, tungsten-doped indium oxide (Indium Tungsten Oxide: IWO), and cerium-doped indium oxide (Indium Ceriumu Oxide: ICO).
  • the first transparent conductive film 14 is a film formed by ion plating using, for example, IWO
  • the second transparent conductive film 17 is formed by sputtering using indium oxide doped with at least tantalum. Film.
  • a hydroxide precipitate was obtained by adding an alkali to an aqueous solution in which indium nitrate (In (NO 3 ) 3 ), tantalum chloride and tetraisopropyl orthotitanate were dissolved.
  • the hydroxide precipitate was dried and pulverized and then sintered to obtain a sintered body (sputtering target).
  • the amounts of tantalum chloride and tetraisopropyl orthotitanate were adjusted so that the contents of tantalum oxide and titanium oxide in the sputtering target were 0.5% by mass, respectively.
  • the obtained sputtering target was attached to a DC magnetron sputter, an initial vacuum degree in the chamber was set to 1 ⁇ 10 ⁇ 6 Torr or less, and an In—Ta—Ti—O-based thin film was deposited on a glass substrate with a thickness of 100 nm at room temperature. It was. Thereafter, the In—Ta—Ti—O-based thin film was heat-treated at 150 ° C. for 2 hours in an air atmosphere to obtain a transparent conductive film. The surface of the obtained transparent conductive film was confirmed to have crystallinity by SEM observation, and the specific resistance was 3.78 ⁇ 10 ⁇ 4 ⁇ ⁇ cm.
  • the in-plane long axis average crystal grain size based on the SEM image was 100 nm. Moreover, as a result of measuring the resistance change after storing the obtained transparent conductive film at 80 ° C. under a room temperature of 85% for 5 days, the resistance change was within 3.2%.
  • a transparent conductive film was obtained in the same manner as in Production Example 1 using an indium tin oxide sputtering target having an indium oxide content of 90% by mass and a tin oxide content of 10% by mass.
  • the surface of the obtained transparent conductive film could not be confirmed by SEM observation, and the specific resistance was 7.19 ⁇ 10 ⁇ 4 ⁇ ⁇ cm.
  • the resistance change was within 12.9%.
  • n-type single crystal silicon substrate On one side of the n-type single crystal silicon substrate, a first intrinsic amorphous silicon thin film (film thickness 6 nm), an n-type amorphous silicon thin film (film thickness 8 nm), and a first transparent conductive film (film thickness) 65 nm) was laminated in this order.
  • the n-type single crystal silicon substrate used what formed the fine uneven structure (texture structure) which has innumerable pyramid shape on both surfaces. This concavo-convex structure was formed by immersing the substrate material in an etching solution containing about 3% by mass of sodium hydroxide and anisotropically etching the (100) plane of the substrate material.
  • a second intrinsic amorphous silicon thin film (film thickness 6 nm), a p-type amorphous silicon thin film (film thickness 4 nm), and a second transparent conductive film ( A film thickness of 65 nm) was laminated in this order.
  • Each silicon thin film was laminated by a plasma CVD method.
  • n-type amorphous silicon thin film (film thickness: 8 nm) and a first transparent conductive film (film thickness: 65 nm) were laminated in this order on one side of an n-type single crystal silicon substrate (first intrinsic amorphous system)
  • the experiment was performed in the same manner as in Experimental Example 1 except that no silicon thin film was stacked.
  • the first and second transparent conductive films in each experimental example and comparative example were laminated by the following materials and methods.
  • ion plating method experimental example 1 experimental example 2: In—Ta—Ti—O material (manufacturing) Sputtering target of Example 1), sputtering method (film formation conditions of Production Example 1)
  • the maximum output (Pmax) of each obtained photovoltaic device was measured. As measurement results, values based on Comparative Example 1 are shown in FIG. In addition, each was measured by using one side as a light incident surface, that is, a heterojunction structure (Rear emitter) in which the p layer was laminated on the opposite side to the light incident side.
  • a heterojunction structure Rear emitter
  • the photovoltaic elements of Experimental Examples 1 and 2 have a higher maximum output than Comparative Examples 1 and 2 in which a transparent conductive film is formed of ITO. Moreover, since a high-performance transparent conductive film is formed by a sputtering method, it can be efficiently produced at low cost.
  • the transparent conductive film is formed by sputtering, it has sufficient power generation efficiency, so that a photovoltaic device having low power generation efficiency and high power generation efficiency can be provided at low cost.
  • 10 photovoltaic device
  • 11 n-type crystal semiconductor substrate
  • 12 first intrinsic amorphous semiconductor thin film
  • 13 n-type amorphous semiconductor thin film
  • 14 first transparent conductive film
  • 15 first 2 intrinsic amorphous semiconductor thin film
  • 16 p-type amorphous semiconductor thin film
  • 17 second transparent conductive film
  • 18, 19 collector electrode

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  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Electromagnetism (AREA)
  • General Physics & Mathematics (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Sustainable Energy (AREA)
  • Manufacturing & Machinery (AREA)
  • Photovoltaic Devices (AREA)

Abstract

L'invention concerne un élément photovoltaïque (10) dont un côté est utilisé comme surface d'entrée de lumière, et qui comprend : un substrat semi-conducteur cristallin de type n (11) ; un mince film semi-conducteur amorphe de type n (13) et un premier film conducteur transparent (14) stratifiés selon la séquence donnée sur un côté du substrat semi-conducteur cristallin de type n (11) ; ainsi qu'un mince film semi-conducteur amorphe de type p (16) et un second film conducteur transparent (17) stratifiés selon la séquence donnée sur l'autre côté du substrat semi-conducteur cristallin de type n (11). Le premier et/ou le second film conducteur transparent (14, 17) sont composés d'oxyde d'indium qui a été dopé au moins au tantale.
PCT/JP2014/075880 2013-10-01 2014-09-29 Élément photovoltaïque et procédé de production de ce dernier WO2015050082A1 (fr)

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JP2013206499A JP2015072938A (ja) 2013-10-01 2013-10-01 光発電素子及びその製造方法
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10869435B2 (en) 2016-08-01 2020-12-22 Enplas Corporation Emitter and drip-irrigation tube

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018074077A (ja) * 2016-11-02 2018-05-10 ソニー株式会社 撮像素子、固体撮像装置及び電子デバイス
CN114342090A (zh) * 2019-08-30 2022-04-12 京浜乐梦金属科技株式会社 积层结构体及积层结构体的制造方法

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JPH02309511A (ja) * 1989-05-24 1990-12-25 Showa Denko Kk 透明導電膜
JPH09150477A (ja) * 1995-11-30 1997-06-10 Idemitsu Kosan Co Ltd 透明導電積層体
WO2006095733A1 (fr) * 2005-03-09 2006-09-14 Idemitsu Kosan Co., Ltd. Film conducteur transparent amorphe, cible et procédé de fabrication pour film conducteur amorphe
JP2008028133A (ja) * 2006-07-20 2008-02-07 Sanyo Electric Co Ltd 太陽電池モジュール
WO2009116580A1 (fr) * 2008-03-19 2009-09-24 三洋電機株式会社 Cellule solaire et son procédé de fabrication
JP2011006725A (ja) * 2009-06-24 2011-01-13 Sumitomo Metal Mining Co Ltd 酸化インジウム系スパッタリングターゲットおよびその製造方法
JP2011077240A (ja) * 2009-09-30 2011-04-14 Sanyo Electric Co Ltd 光起電力装置

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Publication number Priority date Publication date Assignee Title
JPH02309511A (ja) * 1989-05-24 1990-12-25 Showa Denko Kk 透明導電膜
JPH09150477A (ja) * 1995-11-30 1997-06-10 Idemitsu Kosan Co Ltd 透明導電積層体
WO2006095733A1 (fr) * 2005-03-09 2006-09-14 Idemitsu Kosan Co., Ltd. Film conducteur transparent amorphe, cible et procédé de fabrication pour film conducteur amorphe
JP2008028133A (ja) * 2006-07-20 2008-02-07 Sanyo Electric Co Ltd 太陽電池モジュール
WO2009116580A1 (fr) * 2008-03-19 2009-09-24 三洋電機株式会社 Cellule solaire et son procédé de fabrication
JP2011006725A (ja) * 2009-06-24 2011-01-13 Sumitomo Metal Mining Co Ltd 酸化インジウム系スパッタリングターゲットおよびその製造方法
JP2011077240A (ja) * 2009-09-30 2011-04-14 Sanyo Electric Co Ltd 光起電力装置

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10869435B2 (en) 2016-08-01 2020-12-22 Enplas Corporation Emitter and drip-irrigation tube

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