WO2014057771A1 - Substrat métallique - Google Patents

Substrat métallique Download PDF

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Publication number
WO2014057771A1
WO2014057771A1 PCT/JP2013/074973 JP2013074973W WO2014057771A1 WO 2014057771 A1 WO2014057771 A1 WO 2014057771A1 JP 2013074973 W JP2013074973 W JP 2013074973W WO 2014057771 A1 WO2014057771 A1 WO 2014057771A1
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Prior art keywords
layer
metal substrate
reaction suppression
base material
aluminum
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PCT/JP2013/074973
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English (en)
Japanese (ja)
Inventor
晋司 山本
井上　良二
啓太 渡辺
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株式会社Ｎｅｏｍａｘマテリアル
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Priority to JP2014534838A priority Critical patent/JPWO2014057771A1/ja
Publication of WO2014057771A1 publication Critical patent/WO2014057771A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21B—ROLLING OF METAL
    • B21B3/00—Rolling materials of special alloys so far as the composition of the alloy requires or permits special rolling methods or sequences ; Rolling of aluminium, copper, zinc or other non-ferrous metals
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C21/00—Alloys based on aluminium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
    • B32B15/012—Layered products comprising a layer of metal all layers being exclusively metallic one layer being formed of an iron alloy or steel, another layer being formed of aluminium or an aluminium alloy
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/12—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of paper or cardboard
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/18—Layered products comprising a layer of metal comprising iron or steel
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/283—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C21/00—Alloys based on aluminium
    • C22C21/02—Alloys based on aluminium with silicon as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/001—Ferrous alloys, e.g. steel alloys containing N
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • 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
    • H01L31/0248—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 characterised by their semiconductor bodies
    • H01L31/036—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 characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes
    • H01L31/0392—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 characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate
    • H01L31/03926—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 characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate comprising a flexible substrate
    • 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
    • H01L31/0248—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 characterised by their semiconductor bodies
    • H01L31/036—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 characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes
    • H01L31/0392—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 characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate
    • H01L31/03926—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 characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate comprising a flexible substrate
    • H01L31/03928—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 characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate comprising a flexible substrate including AIBIIICVI compound, e.g. CIS, CIGS deposited on metal or polymer foils
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/206—Insulating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/12—Mountings, e.g. non-detachable insulating substrates
    • H01L23/14—Mountings, e.g. non-detachable insulating substrates characterised by the material or its electrical properties
    • H01L23/142—Metallic substrates having insulating layers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/0001—Technical content checked by a classifier
    • H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/541—CuInSe2 material PV cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a metal substrate suitable as a substrate of an electronic device using a semiconductor such as a solar cell.
  • thin-film solar cells in which a semiconductor film as a photoelectric conversion element is stacked on a glass substrate have been used from silicon-based solar cells using a silicon substrate.
  • silicon-based semiconductors have been mainly used as semiconductor film materials, but recently, compound-based semiconductors such as CIS, CIGS, CZTS, and CdTe, and organic semiconductors have been used. It has become.
  • Compound-based semiconductor films have high light absorptance, and heat treatment is performed at a high temperature of about 500 ° C. during film formation or after film formation to improve crystallinity of the semiconductor film and reduce defects. Can be realized and show high conversion efficiency.
  • Patent Document 1 proposes a metal substrate including a metal base material, an aluminum layer formed thereon, and an insulating layer formed of an anodized film integrally formed on the outer surface of the aluminum layer.
  • the anodized film is formed by anodizing the surface layer portion of the initial aluminum layer that is the base of the aluminum layer.
  • By forming the insulating layer a large number of semiconductor elements can be formed thereon.
  • a metal substrate can be reduced in weight as compared with a glass substrate, and has an advantage of excellent flexibility.
  • the metal substrate is not limited to a substrate for a thin film solar cell, but is also used as a substrate for an electronic device using a semiconductor such as a thin film transistor, LED, or organic EL.
  • the thermal expansion coefficients of the aluminum layer and the anodic oxide film are greatly different, so that the anodic oxide film is cracked even at a temperature of about several hundred degrees Celsius. Insulation properties are likely to deteriorate, and sufficient heat resistance is not obtained. Therefore, as described in Patent Document 2, a metal substrate provided with a steel base material and a porous anodic oxide film thereon has been proposed. Since the porous anodic oxide film can relieve thermal stress acting on the porous anodic oxide film, the metal substrate can suppress the occurrence of cracks in the anodic oxide film at a temperature of about 500 ° C.
  • Patent Document 3 proposes a metal substrate in which an aluminum layer is formed on a steel base via a Ti layer. According to this metal substrate, the Ti layer suppresses the diffusion reaction between Al and Fe even at a high temperature of 550 ° C., so that the growth of intermetallic compounds is suppressed.
  • the growth of the intermetallic compound generated between the steel base and the aluminum layer is suppressed by the Ti layer, and the heat resistance of the metal substrate is improved. Since is an expensive material, an increase in material cost is inevitable. Although this problem can be alleviated to some extent by reducing the thickness of the Ti layer to about several ⁇ mTi, Ti is a material that has low extensibility and is easy to break. It is practically difficult to form a Ti layer. Therefore, it is difficult to realize it without using a physical vapor deposition method such as sputtering. Thus, an expensive vapor deposition apparatus is required to form a thin Ti layer, and the manufacturing cost of the metal substrate also increases.
  • the present invention has been made in view of such a problem, and is easy to manufacture, and even when subjected to heat treatment at a high temperature exceeding 500 ° C. without using an expensive material such as Ti, an aluminum layer or an insulating layer
  • An object of the present invention is to provide a metal substrate having excellent heat resistance that does not peel from the iron base material as a base.
  • the present inventor does not use an expensive material such as Ti, and various materials in which an intermetallic compound formed between an iron base and an aluminum layer hardly grows even when heated at a high temperature exceeding 500 ° C. As a result of the investigation, it was found that an Al—Si alloy material containing a specific amount of Si hardly grows an intermetallic compound even though the main component is Al, and the present invention has been completed.
  • the present invention relates to a metal substrate used in an electronic device using a semiconductor, and the metal substrate according to the first aspect of the present invention includes a base material layer and a reaction suppression layer, and is provided on one surface of the base material layer.
  • the reaction suppression layer is bonded, the base material layer is formed of an iron base material, and the reaction suppression layer is formed of an Al—Si alloy having a Si content of 0.2 mass% or more and 8.5 mass% or less. is there.
  • “mass%” is simply described as “%”.
  • the amount of Si in the Al—Si alloy is preferably 0.4% or more and 1.6% or less, more preferably 0.5% or more and 1.0% or less.
  • the reaction suppression layer is formed of an Al—Si alloy containing Si of 0.2% or more and 8.5% or less
  • the metal substrate is heat-treated at a high temperature exceeding 500 ° C.
  • Si inevitably diffuses and mixes into the Al—Fe-based intermetallic compound generated between the base material layer and the reaction suppression layer, so that the growth of the Al—Fe-based intermetallic compound is suppressed, As a result, peeling of the reaction suppression layer due to the growth of the intermetallic compound layer is prevented, and the heat resistance of the substrate is improved.
  • the base material layer and the reaction suppression layer can be easily bonded to each other by pressure welding, the metal substrate according to the present invention can be easily manufactured by a clad method without using an expensive vapor deposition apparatus. .
  • iron base material various alloy steels are used in addition to pure iron and carbon steel.
  • Stainless steel is preferable as the alloy steel.
  • ferritic stainless steel is more preferable than austenitic stainless steel in terms of thermal expansion coefficient and cost.
  • Stainless steel has excellent corrosion resistance, and Cr contained in the stainless steel inevitably diffuses and mixes with the intermetallic compound during the heat treatment, so that the growth of the intermetallic compound can be further suppressed. This advantage has been found in the process of the present invention.
  • the metal substrate of the second form according to the present invention is obtained by joining an aluminum layer to the outer surface of the reaction suppression layer, that is, the exposed surface, based on the metal substrate having the two-layer structure of the first form.
  • the aluminum layer is easily bonded to the reaction suppression layer by a cladding method.
  • the aluminum layer is preferably formed of pure Al. Since pure Al has few inclusions, the aluminum layer is excellent in surface smoothness as compared with the Al—Si alloy forming the reaction suppression layer. Furthermore, an aluminum anodic oxide film having a uniform thickness can be formed on the aluminum layer, and a semiconductor film having a uniform thickness can be formed thereon.
  • the reaction suppression layer has a relatively smooth surface. In particular, when the Si content is as low as 1.6% or less, a smoother surface can be obtained. Therefore, even with a metal substrate that does not include the aluminum layer, a semiconductor film having a uniform thickness can be stacked above the reaction suppression layer.
  • the metal substrate of the third form according to the present invention is obtained by joining another reaction suppression layer to the other surface of the base material layer on the basis of the metal substrate having the two-layer structure of the first form.
  • the metal substrate of the 4th form by this invention is based on the metal substrate of the 3 layer structure of the said 2nd form, and another reaction suppression layer was joined to the other surface of the base material layer.
  • a metal substrate having a four-layer structure according to the fourth embodiment in which another aluminum layer is bonded to the outer surface of the other reaction suppression layer, that is, the exposed surface. It is.
  • the other reaction suppression layer is also formed of the Al—Si alloy in the same manner as the reaction suppression layer.
  • the said other aluminum layer is also formed with a pure aluminum like the said aluminum layer.
  • the other reaction suppressing layers and the other aluminum layers are also easily bonded to the adjacent layers by the cladding method.
  • the total thickness of the metal substrate in each form is 30 ⁇ m to 150 ⁇ m. By setting it to such a thickness, good flexibility can be imparted to the substrate.
  • an insulating layer may be formed on the outermost surface of the aluminum layer or the reaction suppression layer, that is, the exposed surface. That is, on the outer surface of the reaction suppression layer of the metal substrate of the first form, on the outer surface of the aluminum layer of the metal substrate of the second form, the reaction suppression layer and the other reaction suppression layer of the metal substrate of the third form
  • An insulating layer may be formed on any one or each of the outer surfaces, and on any one or each of the outer surfaces of the aluminum layer and the other reaction suppressing layer of the metal substrate of the fourth embodiment.
  • an insulating layer may be formed on the outer surface of either or each of the aluminum layer and the other aluminum layer of the metal substrate of the fifth embodiment.
  • the insulating layer for example, an anodic oxide film of aluminum can be used.
  • the insulating film By providing the insulating film, a semiconductor element composed of a number of semiconductor films electrically insulated from each other can be easily formed thereon.
  • the insulating layer also has an advantage of improving the corrosion resistance of the exposed surface of the reaction suppression layer or the aluminum layer.
  • a reaction suppression layer made of an Al—Si alloy containing a predetermined amount of Si is joined to a base material layer formed of an iron base material.
  • intermetallic compounds are difficult to grow. For this reason, even if it heat-processes at a high temperature over 500 degreeC to a metal substrate, peeling with a base material layer and a reaction suppression layer is suppressed, and the heat resistance excellent in the metal substrate can be provided.
  • the Al—Si alloy has a lower material cost than Ti and has good bondability by pressure welding, the metal substrate of the present invention is easy to manufacture and economical.
  • the present invention can provide a metal substrate suitable as a substrate for an electronic device using a semiconductor such as a solar cell.
  • FIG. 1 shows a metal substrate having a two-layer structure according to a first embodiment of the present invention.
  • the metal substrate is bonded to a base layer 1 formed of an iron base and the base layer 1.
  • the reaction suppression layer 2 is provided.
  • FIG. 2 shows a metal substrate having a three-layer structure according to the second embodiment of the present invention.
  • the metal substrate is composed of a base material layer 1 formed of an iron base material and an upper surface of the base material layer 1.
  • the reaction suppression layer 2 is bonded to the reaction suppression layer 2, and the aluminum layer 3 is further bonded to the reaction suppression layer 2.
  • adjacent layers may be joined only by pressure welding, but may be further diffusion joined.
  • FIG. 2 parts corresponding to the constituent parts of the metal substrate of the first embodiment are indicated by the same reference numerals. In other embodiments to be described later, corresponding parts are indicated by the same reference numerals.
  • an Fe-based alloy containing 50% or more of Fe is used.
  • pure iron, carbon steel, stainless steel, and iron-nickel alloy (Fe— (35% to 50%) Ni alloy) can be used.
  • the iron-nickel alloy has a thermal expansion coefficient lower than that of carbon steel or stainless steel.
  • the thickness of the base material layer 1 can be variously selected depending on the use of the metal substrate, it is about 20 ⁇ m to 80 ⁇ m for the solar cell substrate.
  • the carbon steel is preferably a mild steel having a C content of 0.3% or less, more preferably a 0.2% or less extremely mild steel from the viewpoint of workability.
  • the carbon steel material SPCC, SPCD, or the like, which is a cold rolled steel sheet defined by JIS, can be used.
  • the stainless steel either austenitic stainless steel or ferritic stainless steel can be used. However, since ferritic stainless steel has a smaller coefficient of thermal expansion than austenitic stainless steel, the difference in thermal expansion from the semiconductor element can be reduced, and it is more preferable because it is economical.
  • the ferritic stainless steel include JIS-defined SUS405, 429, 430, and 434.
  • Si is essentially 0.2% or more and 8.5% or less, preferably 0.4% or more and 1.6% or less, more preferably 0.5% or more and 1.0%. %, And the balance is Al—Si alloy composed of Al and inevitable impurities.
  • Si is essentially 0.2% or more and 8.5% or less, preferably 0.4% or more and 1.6% or less, more preferably 0.5% or more and 1.0%. %
  • Al—Si alloy composed of Al and inevitable impurities.
  • the thickness of the reaction suppression layer 2 can be variously selected depending on the use of the metal substrate, but is about 0.1 ⁇ m to 30 ⁇ m for a solar cell substrate.
  • the metal substrate is held at 580 ° C. for 20 minutes by setting the Si content of the reaction suppression layer 2 to 0.4% to 1.6%, the bonding between the base material layer 1 and the reaction suppression layer 2 is performed. Is maintained well. However, if it exceeds 1.5%, it will melt at 580 ° C. due to a decrease in the melting point of the Al—Si alloy.
  • the Si amount from 0.5% to 1.0%, a sufficient bonding force can be ensured even when held at 600 ° C. for 10 minutes. However, if it exceeds 1.0%, it will melt at 600 ° C. due to a decrease in the melting point of the Al—Si alloy. Note that the heat treatment for crystallization and defect reduction of the compound semiconductor is more effective as it is heated at a higher temperature. In addition, the retention time can be shortened by processing at a high temperature.
  • the Al—Si alloy may essentially be a binary alloy of Al and Si, but various elements may be contained within a range not impairing the growth inhibiting action of the intermetallic compound. For example, Fe: 0.8% or less, Cu: 0.3% or less, Mn: 0.1% or less, Mg: 1.0% or less, Zn: 0.2% or less, other elements: 0.05 each % Or less and a total amount of 0.15% or less, various elements may be contained alone or in combination. For this reason, as the Al—Si alloy, Al—Si alloys such as 4043 (stretching material), 4004 (brazing material), 4045 (brazing material), and 4343 (brazing material) defined in JIS are used. be able to.
  • the aluminum layer 3 is preferably made of pure aluminum.
  • the purity of Al is preferably 99.0% or more, and more preferably 99.5% or more. The higher the purity of pure aluminum, the fewer the metal inclusions and non-metallic inclusions such as crystallization and precipitates, and a smooth surface can be easily obtained by rolling or chemical polishing.
  • Examples of the pure aluminum include 1N99, 1N90, 1080, 1070, 1060, 1050, and 1100 defined by JIS.
  • the thickness of the aluminum layer 3 is variously selected depending on the use of the metal substrate, but is about 5 ⁇ m to 40 ⁇ m for the solar cell substrate. Further, by setting the total thickness of the base material layer 1, the reaction suppression layer 2 and the aluminum layer 3 to about 30 ⁇ m to 150 ⁇ m, preferably about 50 to 120 ⁇ m, it is possible to impart good flexibility to the metal substrate. it can.
  • an iron base material base plate from which the base material layer 1 is based, an Al—Si alloy base plate from which the reaction suppression layer 2 is based, and a pure aluminum base plate from which the aluminum layer is based are prepared. These base plates are preferably softened and annealed in advance. Next, these base plates are superposed in the same order, the superposed material is cold-rolled, and the adjacent base plates are pressed against each other. At this time, it is preferable that the cold rolling is performed at a reduction rate of about 40% to 80% and only one reduction.
  • the pressure welding material obtained as described above is subjected to diffusion annealing as necessary, and adjacent layers of the pressure welding material are diffusion bonded to each other.
  • Diffusion annealing is not indispensable, but this improves the bonding strength between the layers and improves the durability and handleability of the metal substrate.
  • an annealing temperature of about 350 to 450 ° C. and a holding time of about 1 to 10 minutes are sufficient.
  • the intermetallic compound layer formed between the base material layer and the reaction suppression layer is so thin that it cannot be observed with a microscope, and the bonding strength of these layers is considerably increased.
  • cold rolling may be performed as necessary.
  • a laminated material of an iron base material base plate, an Al—Si alloy base plate and a pure aluminum base plate was pressed by cold rolling to obtain a three-layer structure pressure contact material.
  • the present invention is not limited to this method.
  • an iron base material plate and an Al—Si alloy base plate are pressure-welded to produce a two-layered pressure-contact material, and this pressure-welding material and pure aluminum base plate are pressure-contacted.
  • a pressure contact material having a layer structure may be used.
  • a three-layer structure pressure contact material may be formed by pressure-contacting an iron base material base plate to a pressure-contact material having a two-layer structure obtained by pressure-contacting an Al—Si alloy base plate and a pure aluminum base plate.
  • the metal substrate according to the present invention is not limited to the metal substrate having the above-described two-layer structure and three-layer structure, and may have other laminated structures as described below. These laminated metal substrates can also be manufactured in the same manner as the three-layered metal substrate.
  • FIG. 3 shows the metal substrate according to the third embodiment, and the other surface of the base material layer 1 suppresses other reactions based on the metal substrate having the two-layer structure according to the first embodiment shown in FIG. Layer 2A is joined.
  • the thickness of the reaction suppression layer 2 bonded to one surface of the base material layer 1 and the other reaction suppression layer 2A bonded to the other surface the same or substantially the same, It is possible to prevent the warpage of the substrate that occurs when manufacturing by pressure welding.
  • FIG. 4 shows a metal substrate according to the fourth embodiment. Based on the metal substrate having a three-layer structure according to the second embodiment shown in FIG. Layer 2A is joined. In this case, by making the total thickness of the reaction suppression layer 2 and the aluminum layer 3 the same as or substantially the same as the thickness of the other reaction suppression layer 2A, it is possible to prevent the warpage of the substrate that occurs during the pressure contact. .
  • FIG. 5 shows a metal substrate according to the fifth embodiment. Based on the metal substrate having a four-layer structure according to the fourth embodiment shown in FIG. 4, another aluminum layer 3A is formed on the other reaction suppression layer 2A. Are joined. In this case, in order to prevent the metal substrate from warping, the total thickness of the reaction suppression layer 2 and the aluminum layer 3 and the total thickness of the other reaction suppression layer 2A and the other aluminum layer 3A should be the same or substantially the same. Is preferred.
  • the total thickness of all layers is preferably set to about 30 ⁇ m to 150 ⁇ m, and preferably about 50 ⁇ m to 120 ⁇ m. Thereby, favorable flexibility can be provided to the metal substrate.
  • the insulating layer 4 may be formed on the outer surface of the aluminum layer 3, that is, the exposed surface.
  • An anodic oxide film can be used as the insulating layer 4.
  • the anodic oxide film is integrally formed on the aluminum layer 3 by anodizing the surface layer of the initial aluminum layer bonded to the base material layer 1.
  • the initial aluminum layer is formed thicker than the thickness of the aluminum layer 3 by the thickness of the anodized film.
  • the insulating layer 4 has a thickness of about 1 ⁇ m to 15 ⁇ m.
  • the insulating layer 4 may be formed on the outer surface of the reaction suppression layer 2 for the metal substrate having the two-layer structure shown in FIG.
  • the method for forming the insulating layer 4 is not limited to anodizing.
  • the insulating layer may be formed by performing heat treatment or plasma treatment on the surface layer of the initial aluminum layer or the initial reaction suppression layer. Moreover, after coating glass frit on the aluminum layer 3 or the reaction suppression layer 2, you may form by heating-melting the coating layer and cooling. Furthermore, it can also be directly formed on the aluminum layer 3 or the reaction suppression layer 2 by vapor deposition or the like. In this case, an insulating layer made of a compound such as alumina or silicon dioxide is formed on the aluminum layer 3 or the reaction suppression layer 2.
  • An insulating layer may be formed on the side surface.
  • the insulating layer 4 drawn by a two-dot chain line is shown on the outer surface of each of the reaction suppressing layer 2 and the other reaction suppressing layer 2 ⁇ / b> A, but the insulating layer is provided only on one of the outer surfaces. It may be formed.
  • the insulating layer 4 made of an anodized film can be simultaneously formed on the outer surface thereof.
  • an anodic oxide film can be formed only on the other outer surface by coating one of the outer surfaces with a resin, for example.
  • the insulating layer 4 may be formed in the metal substrate of the fourth embodiment shown in FIG. 4, one or each of the outer surface of the aluminum layer 3 as one outermost layer and the other reaction suppression layer 2A as the other outermost layer.
  • the insulating layer 4 may be formed in the metal substrate of the fifth embodiment shown in FIG. 5.
  • either one of the outermost aluminum layer 3 and the other outermost aluminum layer 3A or the other outer layer 3A are formed on the outer surface of each.
  • An insulating layer may be formed in FIG. 3 to FIG. 5, the insulating layer 4 drawn by a two-dot chain line is shown on the outer surface of one outermost layer and the other outermost layer, but the insulating layer is formed only on one outer surface. May be formed.
  • the metal substrate provided with the insulating layer by setting the total thickness of all layers including the insulating layer to about 30 to 150 ⁇ m, preferably about 50 to 120 ⁇ m, the metal substrate can be provided with good flexibility. it can.
  • the metal substrate of each sample shown in Table 1 was manufactured by the following method. First, for each sample, the base plate for base layer, the base plate for reaction suppression layer, and the base plate for aluminum layer shown in Table 1 are prepared, the base plates are overlapped, and the overlapping material is pressed. It was. Furthermore, the obtained pressure contact material was subjected to diffusion annealing, and a metal substrate as a sample was manufactured.
  • the base layer base plate is a cold-rolled steel plate (JIS-regulated SPCC) and a stainless steel plate (SUS 430) each having a thickness of 0.5 mm.
  • the Al-Si alloy plate (thickness 0.5 mm) with a Si amount of 5% was used, and the aluminum layer base plate was a pure aluminum plate (thickness 0.4 mm) with a purity of 99.8%.
  • Each base plate was an annealed material having a width of 20 mm and previously softened and annealed.
  • the chemical composition of SPCC of the cold-rolled steel sheet and SUS430 of stainless steel was as follows.
  • the superposed material was cold-rolled by passing it through a pair of rolls at a reduction rate of 70%, and the adjacent layers were pressed together.
  • the obtained pressure contact material had a thickness of 420 ⁇ m mm and a width of 20 mm.
  • the pressure contact material was subjected to diffusion annealing at an annealing temperature of 400 ° C. and an annealing time (holding time) of 3 minutes.
  • the metal substrate manufactured as described above may be further cold-rolled at an appropriate reduction rate so as to have a thickness of about 100 ⁇ m.
  • a test piece having a length of 30 mm and a width of 10 mm was taken from the metal substrate of each sample shown in Table 1 along the length direction of the substrate.
  • Each test piece was heated under the temperature and holding time shown in Table 2 under a hydrogen gas atmosphere.
  • the thickness of the intermetallic compound layer formed between the base material layer and the reaction suppression layer was measured by the following method. Five observation parts were set at equal intervals in the length direction of the test piece, the cross section of each observation part was observed with a microscope (magnification 400), the thickness of the intermetallic compound layer was measured, and the average of the measured thicknesses The value was calculated
  • a bending test was performed using each test piece after heating, and the peeled state of the base material layer and the reaction suppression layer was examined.
  • the bending test was performed by the following method. As shown in FIG. 7, the test piece was bent at a 90 ° angle with a radius of 2 mm with the base material layer 1 side as the inner side at the center in the length direction, and then returned to the original flat state. The peeling state in the bending part of the base material layer 1 and the reaction suppression layer 2 was observed. The observation results are shown in Table 3.

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Abstract

La présente invention a trait à un substrat métallique exceptionnellement résistant à la chaleur qui est utilisé dans un dispositif électronique dans lequel un semi-conducteur est utilisé. Le substrat métallique est équipé d'une couche de matériau de base (1) et d'une couche de suppression de réaction (2) qui est jointe à la couche de matériau de base (1). La couche de matériau de base (1) est constituée d'un matériau de base de fer tel que du fer, de l'acier au carbone, de l'acier inoxydable ou un alliage de fer et de nickel. La couche de suppression de réaction (2) est constituée d'un alliage Al-Si qui est doté d'une teneur en Si de 0,2 à 8,5 pourcent en masse et, de préférence, de 0,4 à 1,6 pourcent en masse. Une couche d'aluminium peut être jointe à la surface extérieure de la couche de suppression de réaction (2).
PCT/JP2013/074973 2012-10-12 2013-09-17 Substrat métallique WO2014057771A1 (fr)

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BE1022819B1 (nl) * 2015-03-12 2016-09-13 Polyvision, Naamloze Vennootschap Fotovoltaïsche zonnecel en werkwijze om ze te vervaardigen
JP2021512493A (ja) * 2018-01-31 2021-05-13 ラム リサーチ コーポレーションＬａｍ Ｒｅｓｅａｒｃｈ Ｃｏｒｐｏｒａｔｉｏｎ 静電チャック（ｅｓｃ）ペデスタル電圧分離
US11817341B2 (en) 2017-06-02 2023-11-14 Lam Research Corporation Electrostatic chuck for use in semiconductor processing
US11835868B2 (en) 2018-03-20 2023-12-05 Lam Research Corporation Protective coating for electrostatic chucks

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JPH06330346A (ja) * 1993-05-24 1994-11-29 Nippon Steel Corp アルミメッキ鋼板
JP2010501732A (ja) * 2006-08-30 2010-01-21 ブルースコープ・スティール・リミテッド 金属被覆鉄ストリップ
JP2010229483A (ja) * 2009-03-26 2010-10-14 Nisshin Steel Co Ltd 耐食性に優れたＺｎ−Ａｌ系めっき鋼板およびその製造方法
JP2011124538A (ja) * 2009-11-11 2011-06-23 Fujifilm Corp 絶縁層付金属基板、それを用いた半導体装置および太陽電池の製造方法、並びに太陽電池

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JPH06330346A (ja) * 1993-05-24 1994-11-29 Nippon Steel Corp アルミメッキ鋼板
JP2010501732A (ja) * 2006-08-30 2010-01-21 ブルースコープ・スティール・リミテッド 金属被覆鉄ストリップ
JP2010229483A (ja) * 2009-03-26 2010-10-14 Nisshin Steel Co Ltd 耐食性に優れたＺｎ−Ａｌ系めっき鋼板およびその製造方法
JP2011124538A (ja) * 2009-11-11 2011-06-23 Fujifilm Corp 絶縁層付金属基板、それを用いた半導体装置および太陽電池の製造方法、並びに太陽電池

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE1022819B1 (nl) * 2015-03-12 2016-09-13 Polyvision, Naamloze Vennootschap Fotovoltaïsche zonnecel en werkwijze om ze te vervaardigen
US11817341B2 (en) 2017-06-02 2023-11-14 Lam Research Corporation Electrostatic chuck for use in semiconductor processing
JP2021512493A (ja) * 2018-01-31 2021-05-13 ラム リサーチ コーポレーションＬａｍ Ｒｅｓｅａｒｃｈ Ｃｏｒｐｏｒａｔｉｏｎ 静電チャック（ｅｓｃ）ペデスタル電圧分離
JP7374103B2 (ja) 2018-01-31 2023-11-06 ラム リサーチ コーポレーション 静電チャック（ｅｓｃ）ペデスタル電圧分離
US11990360B2 (en) 2018-01-31 2024-05-21 Lam Research Corporation Electrostatic chuck (ESC) pedestal voltage isolation
US11835868B2 (en) 2018-03-20 2023-12-05 Lam Research Corporation Protective coating for electrostatic chucks

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