WO2015115567A1 - Pile solaire, module de pile solaire, composant muni d'une électrode, dispositif à semi-conducteur et composant électronique - Google Patents

Pile solaire, module de pile solaire, composant muni d'une électrode, dispositif à semi-conducteur et composant électronique Download PDF

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Publication number
WO2015115567A1
WO2015115567A1 PCT/JP2015/052574 JP2015052574W WO2015115567A1 WO 2015115567 A1 WO2015115567 A1 WO 2015115567A1 JP 2015052574 W JP2015052574 W JP 2015052574W WO 2015115567 A1 WO2015115567 A1 WO 2015115567A1
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WIPO (PCT)
Prior art keywords
electrode
solar cell
mass
particles
phosphorus
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PCT/JP2015/052574
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English (en)
Japanese (ja)
Inventor
修一郎 足立
吉田　誠人
野尻　剛
倉田　靖
祥晃 栗原
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日立化成株式会社
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Publication of WO2015115567A1 publication Critical patent/WO2015115567A1/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
    • H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
    • H01L31/022425—Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/042—PV modules or arrays of single PV cells
    • H01L31/05—Electrical interconnection means between PV cells inside the PV module, e.g. series connection of PV cells
    • H01L31/0504—Electrical interconnection means between PV cells inside the PV module, e.g. series connection of PV cells specially adapted for series or parallel connection of solar cells in a module
    • H01L31/0512—Electrical interconnection means between PV cells inside the PV module, e.g. series connection of PV cells specially adapted for series or parallel connection of solar cells in a module made of a particular material or composition of 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

Definitions

  • the electrode composition containing silver particles exhibits excellent characteristics as an electrode of a solar cell element.
  • silver is a precious metal and the bullion itself is expensive, and because of the problem of resources, a proposal for a material to replace silver is desired.
  • a promising material that can replace silver is copper that is applied to semiconductor wiring materials. Copper is abundant in terms of resources, and the cost of bullion is as low as about 1/100 of silver. However, copper is a material that is easily oxidized at a high temperature of 200 ° C. or higher in the atmosphere, and it is difficult to form an electrode in the above process.
  • solder is used to connect the electrode of the solar cell element and the wiring member (see, for example, Japanese Patent Application Laid-Open Nos. 2004-204256 and 2005-050780). Solder is widely used because it is excellent in connection reliability such as conductivity and fixing strength, is inexpensive and versatile. In recent years, lead-free solder has also become widespread as a solder used for connection between the electrode of the solar cell element and the wiring member from the environmental viewpoint.
  • the “wiring connection portion” means a portion in which a semiconductor substrate, a conductive layer, and a wiring member are laminated in this order in a solar cell.
  • the “conductive layer” means an electrode part including a metal part and a glass part, and a resin part, and a part located between the semiconductor substrate and the wiring member.
  • the “cross section parallel to the stacking direction of the conductive layers” means a surface obtained by cutting the solar cell perpendicular to the surface direction of the semiconductor substrate, and is also simply referred to as “cross section” below.
  • the “thickness” of the electrode portion means a distance between the line X1 and the line X2 calculated by a method described later.
  • the solar cell of the present invention can be obtained using, for example, an electrode composition to be described later, a connection material capable of forming a resin portion, and a wiring member.
  • a solar cell can be manufactured by a method including the following steps.
  • An electrode composition is applied onto the semiconductor substrate and heat-treated (fired) to form an electrode having voids therein.
  • a connecting material and a wiring member are arranged on the formed electrode and subjected to heat and pressure treatment, and at least a part of the connecting material enters at least a part of the gap of the electrode, and includes a metal part and a glass part.
  • a conductive layer including an electrode portion and a resin portion is formed, and the electrode and the wiring member are bonded.
  • connection between the electrode and the wiring member is made with solder or conductive paste
  • the adhesion between the electrode and the wiring member is inferior to the case where the connection material is used. This is presumably because even if there is a gap inside the electrode, solder or conductive paste does not enter the gap and the anchor effect cannot be obtained.
  • the electrode (electrode part) preferably contains copper, more preferably contains copper and tin, and further preferably contains copper, tin and nickel.
  • the metal part in the electrode (electrode part) preferably contains a Cu—Sn—Ni alloy phase, and the glass part preferably contains a Sn—PO glass phase, and at least a part of the Sn—PO glass phase. Is preferably disposed between the Cu—Sn—Ni alloy phase and the semiconductor substrate.
  • Electrode composition examples include an electrode composition containing metal-containing particles, glass particles, and a dispersion medium.
  • each component contained in the composition for electrodes used for manufacture of the solar cell of this invention is demonstrated in detail.
  • the composition for electrodes used for manufacturing the solar cell of the present invention contains metal-containing particles.
  • the type of metal-containing particles is not particularly limited, and can be selected from those that can form an electrode having voids inside by heat treatment (firing).
  • an electrode composition containing phosphorus-tin-containing copper alloy particles By using an electrode composition containing phosphorus-tin-containing copper alloy particles, oxidation of copper during firing in the atmosphere is suppressed, and an electrode having a low resistivity can be formed. Furthermore, formation of a reactant phase between copper and the semiconductor substrate is suppressed, and a good ohmic contact can be formed between the formed electrode and the semiconductor substrate. This can be considered as follows, for example.
  • the Sn—PO glass phase functions as a barrier layer for preventing mutual diffusion between copper and silicon, a good ohmic contact between the electrode formed by heat treatment (firing) and the silicon substrate can be obtained. It can be considered that it can be achieved. That is, the formation of a reactant phase (Cu 3 Si) formed when an electrode containing copper and silicon are directly contacted and heated is suppressed, and silicon performance (for example, pn junction characteristics) is not deteriorated. It is considered that good ohmic contact can be expressed while maintaining adhesiveness with the substrate. Conventionally, ohmic contact with a silicon substrate has been cited as a problem for applying copper to an electrode of a solar cell element.
  • the phosphorus content contained in the phosphorus-tin-containing copper alloy constituting the phosphorus-tin-containing copper alloy particles is not particularly limited. From the viewpoint of oxidation resistance and electrode resistivity, the phosphorus content is, for example, preferably 2% by mass to 15% by mass, more preferably 3% by mass to 12% by mass, and more preferably 4% by mass. It is more preferable that it is 10% by mass or more. When the phosphorus content in the phosphorus-tin-containing copper alloy is 15% by mass or less, a lower electrode resistivity can be achieved, and the productivity of the phosphorus-tin-containing copper alloy particles tends to be excellent. is there. Moreover, it exists in the tendency which can achieve the outstanding oxidation resistance because it is 2 mass% or more.
  • the phosphorus-tin-containing copper alloy may further contain other atoms inevitably mixed other than silver, manganese and cobalt.
  • Other atoms that are inevitably mixed include, for example, Sb, Si, K, Na, Li, Ba, Sr, Ca, Mg, Be, Zn, Pb, Cd, Tl, V, Al, Zr, W, and Mo.
  • Ti, Ni and Au can be mentioned.
  • the content of other unavoidably mixed atoms contained in the phosphorus-tin-containing copper alloy particles can be, for example, 3% by mass or less in the phosphorus-tin-containing copper alloy particles. From the viewpoint of the resistivity of the electrode, it is preferably 1% by mass or less.
  • the tin content to 3.0% by mass or more, the reactivity with copper and nickel and the reactivity with phosphorus are improved, and the Cu—Sn—Ni alloy phase and the Sn—PO glass phase respectively. Tends to be formed effectively.
  • the combination of phosphorus content, tin content, and nickel content contained in the phosphorus-tin-nickel-containing copper alloy constituting the phosphorus-tin-nickel-containing copper alloy particles includes oxidation resistance, electrode resistivity, copper
  • the phosphorus content is, for example, 2.0 mass% to 15.0 mass%.
  • the tin content is preferably 3.0% by mass to 30.0% by mass
  • the nickel content is preferably 3.0% by mass to 30.0% by mass, for example.
  • the shape of the phosphorus-tin-nickel-containing copper alloy particles is not particularly limited, and may be any of a substantially spherical shape, a flat shape, a block shape, a plate shape, a scale shape, and the like. From the viewpoint of oxidation resistance and reduction in the resistivity of the electrode, the shape of the phosphorus-tin-nickel-containing copper alloy particles is preferably substantially spherical, flat, or plate-shaped.
  • the nickel alloy particles are not limited as long as they are alloy particles containing nickel.
  • the nickel content is preferably, for example, nickel alloy particles having a content of 1% by mass or more, and the nickel content is 3% by mass. % Of nickel alloy particles, more preferably nickel alloy particles having a nickel content of 5% by mass or more, and nickel alloy particles having a nickel content of 10% by mass or more. It is particularly preferred. There is no particular limitation on the upper limit of the nickel content.
  • the particle diameter of the nickel-containing particles is not particularly limited, but as D50%, for example, it is preferably 0.5 ⁇ m to 20 ⁇ m, more preferably 1 ⁇ m to 15 ⁇ m, and even more preferably 3 ⁇ m to 15 ⁇ m. .
  • the particle diameter is preferably 0.5 ⁇ m to 20 ⁇ m, more preferably 1 ⁇ m to 15 ⁇ m, and even more preferably 3 ⁇ m to 15 ⁇ m. .
  • the contact area with the phosphorus-tin-containing copper alloy particles or the phosphorus-tin-nickel-containing copper alloy particles is increased by being 20 ⁇ m or less, and the phosphorus-tin-containing copper alloy particles or the phosphorus-tin-nickel-containing copper alloy particles The reaction tends to proceed effectively.
  • the glass particles are softened and melted at the electrode forming temperature to oxidize the silicon nitride contained in the contacted antireflection layer, thereby oxidizing silicon dioxide.
  • the antireflection layer can be removed by incorporating, glass particles that are usually used in the art can be used without particular limitation.
  • the particle diameter of the glass particles is not particularly limited.
  • the particle diameter (D50%) when the integrated volume is 50% is preferably 0.5 ⁇ m or more and 10 ⁇ m or less, and more preferably 0.8 ⁇ m or more and 8 ⁇ m or less.
  • the thickness is 0.5 ⁇ m or more, the workability during production of the electrode composition tends to be improved.
  • it is 10 ⁇ m or less, it can be uniformly dispersed in the electrode composition, fire-through can be efficiently generated in the heat treatment (firing) step, and the adhesion to the semiconductor substrate tends to be improved.
  • the method for measuring the particle size (D50%) of the glass particles is the same as the method for measuring the particle size of the phosphorus-tin-containing copper alloy particles.
  • the composition for electrodes used for manufacturing the solar cell of the present invention may contain a flux.
  • the flux By including the flux, the oxide film formed on the surface of the metal-containing particles can be removed, and the reduction reaction of the metal-containing particles during the heat treatment (firing) can be promoted. Furthermore, the effect that the adhesiveness of an electrode and a silicon substrate improves is also acquired.
  • the flux content when the electrode composition contains a flux the viewpoint of effectively expressing the oxidation resistance of the metal-containing particles and reducing the porosity of the portion where the flux is removed at the completion of the firing of the electrode From the total mass of the electrode composition, for example, it is preferably 0.1% by mass to 5% by mass, more preferably 0.3% by mass to 4% by mass, and 0.5% by mass. It is more preferably from 3.5% by weight, particularly preferably from 0.7% by weight to 3% by weight, and particularly preferably from 1% by weight to 2.5% by weight.
  • connection material used for manufacturing the solar cell of the present invention includes an adhesive.
  • the connection material includes an adhesive capable of connecting an electrode formed of the electrode composition and a wiring member described later in the manufacturing process of the solar cell, the shape, material, component content, and the like are particularly limited.
  • the state of the connecting material include a film form, a paste form, and a solution form.
  • the state of the connection material can be adjusted by the type and content of the components contained in the connection material. From the viewpoints of solar cell production efficiency, handleability, power generation performance stability, etc., the connecting material is preferably in the form of a film.
  • connection material When connecting the electrode of the solar cell element and the wiring member using a film-like connection material, since it is possible to connect in a low temperature region around 200 ° C., even when a thin solar cell element is used, the wiring Generation
  • a latent curing agent is preferred because the active point of reaction initiation by thermocompression bonding is relatively clear and suitable for a connection method involving a thermocompression bonding process.
  • the latent curing agent is a substance that exhibits a curing function under certain specific conditions (such as temperature).
  • specific conditions such as temperature
  • the latent curing agent include those obtained by protecting a normal curing agent with microcapsules and the like, and those having a structure in which a curing agent and various compounds form a salt. For example, when the latent curing agent exceeds a specific temperature, the curing agent is released from the microcapsules or the salt into the system, and exhibits a curing function.
  • the method for measuring the particle size (D50%) of the conductive particles is the same as the method for measuring the particle size of the phosphorus-tin-containing copper alloy particles.
  • the content of the conductive particles in the connection material is preferably 1% by volume or more and 15% by volume or less, for example, from the viewpoint of conductivity, with the total volume of the connection material being 100% by volume. It is more preferably 12% by volume or less and further preferably 3% by volume or more and 10% by volume or less.
  • the connecting material can be produced, for example, by applying a coating solution obtained by dissolving or dispersing the above-described various materials in a solvent onto a release film such as a polyethylene terephthalate film and removing the solvent.
  • the wiring member used for manufacturing the solar cell of the present invention is not particularly limited.
  • a solder-coated copper wire (tab wire) for solar cells can be suitably used.
  • the solder composition include Sn—Pb, Sn—Pb—Ag, and Sn—Ag—Cu. Considering the influence on the environment, it is preferable to use Sn—Ag—Cu based solder which does not substantially contain lead.
  • heat treatment (firing) conditions for forming an electrode on a semiconductor substrate using the electrode composition commonly used heat treatment (firing) conditions can be applied.
  • the heat treatment (firing) temperature is 800 ° C. to 900 ° C., but when an electrode composition containing metal-containing particles containing at least phosphorus and copper is used, a general heat treatment is performed from a low temperature heat treatment (firing) condition. It can be applied to a wide range up to (firing) conditions.
  • a copper-containing electrode having good characteristics can be formed by heat treatment (firing) performed in a wide temperature range of 450 ° C. to 900 ° C.
  • the heat treatment (firing) time can be selected according to the heat treatment (firing) temperature and the like, and can be, for example, 1 second to 20 seconds.
  • the light receiving surface output extraction electrode 4 and the light receiving surface current collecting electrode 8 provided on the light receiving surface side schematically shown in FIG. 3, and the back surface collecting electrode 5 and back surface formed on the back surface schematically shown in FIG. A method for forming the output extraction electrode 6 will be described.
  • the light receiving surface output extraction electrode 4, the light receiving surface current collecting electrode 8 and the back surface output extraction electrode 6 are formed from an electrode composition.
  • the back current collecting electrode 5 is formed of an aluminum electrode composition containing glass powder.
  • an electrode composition and an aluminum electrode composition are screen printed. And a desired pattern, followed by drying, followed by heat treatment (firing) at about 750 ° C. to 900 ° C. in the air.
  • aluminum in the aluminum electrode composition that forms the back current collecting electrode 5 during heat treatment (firing) diffuses to the back surface of the semiconductor substrate 1 to form the p + -type diffusion layer 7.
  • an ohmic contact can be obtained between the semiconductor substrate 1 and the back surface collecting electrode 5 and the back surface output extraction electrode 6.
  • the aluminum electrode composition for forming the back surface collecting electrode 5 is first printed and dried. After heat treatment (baking) at about 750 ° C. to 900 ° C. in the atmosphere to form the back current collecting electrode 5, the electrode composition is applied to the light receiving surface side and the back surface side, and after drying, 450 ° C. to 650 in the air after drying.
  • a method of forming the light receiving surface output extraction electrode 4, the light receiving surface current collecting electrode 8, and the back surface output extraction electrode 6 by heat treatment (firing) at about 0 ° C. is exemplified.
  • connection material since the connection material is used, the object to which the wiring member is connected does not need solder wettability as described above.
  • the connection material by using the connection material, the antireflection layer 3 formed on the semiconductor substrate 1 and the wiring member can be firmly adhered.
  • the connection material since the connection material enters at least a part of the voids existing inside the electrode, the wiring member can be firmly adhered. Further, when the electrode portion and the wiring member are in contact with each other or the connecting material contains conductive particles, electrical connection between the light receiving surface current collecting electrode 8 and the wiring member is made. Will improve.
  • the present invention is not limited to this.
  • size of the member in each figure is notional, The relative relationship of the magnitude
  • a connection body 10 and a wiring member 9 are arranged in this order on the light receiving surface output extraction electrode 4 and the back surface output extraction electrode 6 to obtain a laminate (lamination process).
  • heat pressure treatment thermocompression treatment
  • the back surface output extraction electrode 6 and the wiring member 9 are pressure bonded to form a solar cell. Is done.
  • the solar cell module of the present invention includes the solar cell of the present invention, and a sealing material that seals the solar cell so that a part of the wiring member in the solar cell is located outside the sealing portion,
  • a sealing material that seals the solar cell so that a part of the wiring member in the solar cell is located outside the sealing portion.
  • the area of the portion located on the electrode part side was determined to be equal within the range obtained from the observation cross section.
  • the position in the height direction of the line X2 parallel to the width direction is set so that the area of the portion of the semiconductor substrate located on the electrode portion side of the line X2 and the portion other than the semiconductor substrate closer to the semiconductor substrate side of the line X2 It was determined that the area of the portion to be positioned was equal within the range obtained from the observation cross section.
  • a distance between the line X1 and the line X2, that is, a line that equally divides the thickness of the electrode was defined as a line X.

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

Abstract

L'invention concerne une pile solaire et un module de pile solaire ayant une fiabilité de connexion supérieure et une adhérence supérieure entre une électrode et un élément de câblage. La pile solaire comporte une section de connexion de câblage dans laquelle sont stratifiés, dans cet ordre : un substrat à semi-conducteur ayant une jonction p-n ; une couche conductrice contenant une section en résine et une section d'électrode contenant une section en métal et une section en verre ; et un organe de câblage. Une section est contenue de sorte que lorsqu'on observe une région, dans laquelle la longueur dans une direction perpendiculaire à la direction de stratification dans une coupe transversale parallèle à la direction de stratification de la couche conductrice dans la section de connexion de câblage est de 100 µm, la proportion de la longueur totale de la section au niveau de laquelle la section d'électrode chevauche un câble (X) à la longueur totale du câble (X) divisant équitablement l'épaisseur de la section d'électrode n'est pas supérieure à 95 %.
PCT/JP2015/052574 2014-01-31 2015-01-29 Pile solaire, module de pile solaire, composant muni d'une électrode, dispositif à semi-conducteur et composant électronique WO2015115567A1 (fr)

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JP2014-017940 2014-01-31
JP2014017940 2014-01-31

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WO2015115567A1 true WO2015115567A1 (fr) 2015-08-06

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017033343A1 (fr) * 2015-08-27 2017-03-02 日立化成株式会社 Composition pour formation d'électrode, électrode, élément de batterie solaire, batterie solaire, et procédé de fabrication d'élément de batterie solaire

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6681607B2 (ja) * 2015-09-30 2020-04-15 パナソニックＩｐマネジメント株式会社 太陽電池セルおよび太陽電池セルの製造方法
JP6785057B2 (ja) * 2016-05-02 2020-11-18 ルネサスエレクトロニクス株式会社 半導体装置およびその製造方法
JP2022157011A (ja) * 2021-03-31 2022-10-14 東洋アルミニウム株式会社 ペースト組成物、及び、ゲルマニウム化合物層の形成方法

Citations (3)

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Publication number Priority date Publication date Assignee Title
JP2007158302A (ja) * 2005-11-10 2007-06-21 Hitachi Chem Co Ltd 接続構造及びその製造方法
JP2012227183A (ja) * 2011-04-14 2012-11-15 Hitachi Chem Co Ltd 電極用ペースト組成物及び太陽電池素子
WO2013073478A1 (fr) * 2011-11-14 2013-05-23 日立化成株式会社 Composition de pâte pour électrode, élément de cellule solaire, cellule solaire

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007158302A (ja) * 2005-11-10 2007-06-21 Hitachi Chem Co Ltd 接続構造及びその製造方法
JP2012227183A (ja) * 2011-04-14 2012-11-15 Hitachi Chem Co Ltd 電極用ペースト組成物及び太陽電池素子
WO2013073478A1 (fr) * 2011-11-14 2013-05-23 日立化成株式会社 Composition de pâte pour électrode, élément de cellule solaire, cellule solaire

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017033343A1 (fr) * 2015-08-27 2017-03-02 日立化成株式会社 Composition pour formation d'électrode, électrode, élément de batterie solaire, batterie solaire, et procédé de fabrication d'élément de batterie solaire

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