EP2840165A1 - Verfahren zur Ablagerung von Metall auf einem Substrat, insbesondere für Metallisierung von Solarzellen und -modulen - Google Patents

Verfahren zur Ablagerung von Metall auf einem Substrat, insbesondere für Metallisierung von Solarzellen und -modulen Download PDF

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Publication number
EP2840165A1
EP2840165A1 EP13290195.0A EP13290195A EP2840165A1 EP 2840165 A1 EP2840165 A1 EP 2840165A1 EP 13290195 A EP13290195 A EP 13290195A EP 2840165 A1 EP2840165 A1 EP 2840165A1
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EP
European Patent Office
Prior art keywords
metal
substrate
laser
sensitizer
based molecules
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP13290195.0A
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English (en)
French (fr)
Inventor
Michel Ngamo
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
TotalEnergies Marketing Services SA
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Total Marketing Services SA
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Publication date
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Priority to EP13290195.0A priority Critical patent/EP2840165A1/de
Priority to PCT/EP2014/066847 priority patent/WO2015024775A1/en
Publication of EP2840165A1 publication Critical patent/EP2840165A1/de
Withdrawn legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/06—Coating on selected surface areas, e.g. using masks
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/28—Sensitising or activating
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals

Definitions

  • the present invention relates to a method for depositing metal on a substrate, in particular for metallization of solar cells and modules.
  • a photovoltaic module comprises a plurality of photovoltaic cells (or solar cells) connected in series and/or in parallel.
  • a photovoltaic cell is a semiconductor diode designed to absorb light energy and convert it into electrical energy.
  • This semiconductor diode comprises a p-n junction between two layers of respectively p-doped and n-doped silicon. During the formation of the junction, a potential difference (and therefore a local electric field) appears, due to the excess of free electrons in the n layer and due to the shortage of free electrons in the p layer.
  • Solar cells based on monocrystalline or polycrystalline silicon are conventionally developed by putting the positive and negative contacts on each of the faces of the cell.
  • the back face is generally completely covered with metal since only the conductivity counts (no light having to pass through the back face), whereas the front face, that is to say the one which is illuminated, is contacted by a metal grid which allows most of the incident light to pass through.
  • one known method comprises screen printing at module level, in particular with mini-modules of only several PV cells.
  • One problem of this known process is that the paste deposition is not homogenous enough and that cracks appear after a firing step on the wafer. The consequence of this is that the performance of the PV-cell and/ or module reduces because of a non-uniform topography of the metallic contacts and interconnections.
  • Another known method comprises Cu plating.
  • a seed layer is deposited by a vapour deposition (PVD) or a sputtering process (TiCu). Then a plating resist layer is deposed and patterned. After then, a seed layer is etched and the plating resist layer is removed before the final Cu plating.
  • PVD vapour deposition
  • TiCu sputtering process
  • the thickness of solar cells tends to be reduced for cost reduction of the wafer.
  • wafer of thickness of only about 100 ⁇ m are not easy to be handled mechanically without a growing risk of breach.
  • Conventional methods of metallization like screen printing methods show an important mechanical impact on the wafers that are no more acceptable with very thin wafers.
  • sensitizers For depositing metal on a substrate, it is well known to deposit a sensitizer on a substrate to catalyze the surface of the substrate, thus allowing subsequent deposition of metal on the catalyzed surface.
  • the sensitizers are deposited on the substrate in ionized form (for example in an aqueous solution) and they catalyze the surface of the substrate when deposited thereon.
  • Those sensitizing solutions are for example described in the handbook « Modern Electroplating » edited by Mordechay Schlesinger and Milan Paunovic, The Electrochemical Series (ECS), 5th Edition, 2010, in particular pages 447 to 459 .
  • An object of the invention is to provide a method for depositing metal on a substrate with an improved preciseness on the locations where the metal is deposited, thereby allowing precise formation of conductive tracks and / or electrical contacts.
  • US 4 440 801 describes a method for selective electro-less deposition of a metal on a polyester substrate.
  • the polyester substrate is submitted to UV radiation that may be emitted by a laser.
  • the process costs are increased because of a step of the mask mounting on the module prior to the illumination.
  • the mask will be in contact with the solar cells, thin cells may not be compatible because of the mechanical impact induced by this mask and, a mask may be not compatible with surfaces with different structures and height (e.g. space between cells in the module).
  • the effect of UV exposure of the polyester causes the polyester surface to become acidic and then strongly hydrophilic.
  • a pre-plating treatment bath has to be applied, like a dilute ammonia bath.
  • a pre-plating treatment bath has to be applied, like a dilute ammonia bath.
  • the method described in this document needs use of a mask, the polyester is directly exposed to UV light, and a pre-treatment bath is necessary to get electro-less plating only in the areas exposed to UV light.
  • US 4 268 536 describes also a method for depositing a metal on a surface.
  • the substrate is first etched and then immersed in a sensitizer solution. After then, the sensitizer solution was removed and the substrate dried and stored.
  • the dried substrate was exposed to UV-light through an imaging mask.
  • EP 1 367 872 describes a laser activated dielectrical material and method for using the same in an electro-less deposition process.
  • a dielectric coating containing a latent inert additive like inorganic fillers as for example titanium dioxide (TiO2), aluminium nitride (AlN) or Zirconium dioxide (ZiO2), that becomes catalytic to electro-less deposition after exposure to a laser beam is applied to a substrate.
  • a latent inert additive like inorganic fillers as for example titanium dioxide (TiO2), aluminium nitride (AlN) or Zirconium dioxide (ZiO2), that becomes catalytic to electro-less deposition after exposure to a laser beam is applied to a substrate.
  • a sensitizer solution is applied before copper deposition by electro-less plating.
  • a specific preparation step of the substrate is necessary before application of a sensitizer solution.
  • US 4 042 730 describes a classical process for electro-less plating that uses separate sensitization and activation process. However, this process is not selective enough and needs various mechanical manipulations that should be avoided because of the low thickness of the substrates in particular when used with solar modules and/or solar cells.
  • the invention proposes a method for depositing metal on a substrate comprising the following steps:
  • the laser activable metal based molecules of the sensitizer are deposited in a neutral state, they are inert and have no catalyzing properties in this state. This is quite different from the known solutions where a metal salt is contained in an aqueous solution and therefore already in an ionized, non-neutral state.
  • the present invention allows therefore to be more selective and precise thanks to the fact that the sensitizer is ionized (i.e. activated) only after it is exposed to the laser and only in the areas where it is exposed to such laser.
  • conductive patterns comprising for example conductive tracks and/or electrical contacts can be defined with a high resolution (for example with a width of 5-10 ⁇ m) and without submission of the wafers to mechanical stress. Furthermore, the patterns for metallization can be formed without the use of masks.
  • the whole method is a low temperature process, which does not impact the performance of the solar cells.
  • Said laser activable metal based molecules may comprise a metal salt or a metal oxide.
  • the sensitizer is a gel solution.
  • the sensitizer can be applied easily by spin coating as a thin film.
  • Such a gel can be dried and solidified which allows a more easy manipulation of the substrate.
  • the sensitizer comprises a support material for the metal based molecules conserving these metal based molecules in a neutral state.
  • Such a support material like a solvent or a polymer is non-aqueous and therefore may conserve the metal salts or metal oxide in a neutral state, meaning electrically non-charged or not ionized.
  • solvent toluene or a polymer may be used.
  • the metal atoms of said laser activable metal based molecules may be noble metal atoms, in particular palladium atoms or platinum atoms, or are metal atoms to be deposited on the substrate.
  • Salts or oxides with noble metal atoms show once laser activated a good performance to catalyze the substrate. Use of a metal atom that shall be deposited after then may be cheaper.
  • the chemical metal deposition step is realized by electro-less plating, which is quite cheap and simple to realize.
  • the deposited metal may have a thickness comprised between 0,1 - 10 ⁇ m. This range is quite a good compromise to create a first metal layer that has sufficient conductivity for subsequent electroplating.
  • the sensitizer is removed from the substrate after laser activation that may avoid any potential negative effect on the chemical metal deposition.
  • a step of deposition of a subsequent metal on the deposited metal through an electroplating process may be foreseen. This allows creating electrical contacts and / or conductor tracks which have an enough low resistivity.
  • the substrate is for example part of a solar cell or a solar module component.
  • the method according the invention allows creating conductive tracks and / or electrical contacts cheaper and easier.
  • two different substrates are placed adjacent to each other and where said metal deposition method is applied to form a conductor track on both substrates.
  • the method may be applied although the substrate underneath changes which is easier in a manufacturing process.
  • One of said two different substrates may belong to the module level components, in particular an insulator, an encapsulant, a plastic, or a glass and the other one of said two different substrates belongs to the solar cell level components, in particular an Si layer, a dielectrics layer, an oxide layer.
  • the invention also relates to a solar cell comprising electrical tracks and/ or electrical contacts realized by a method as defined above.
  • the invention also relates to a solar module comprising a plurality of solar cells as defined above.
  • FIG.1 schematically illustrates a substrate 1 to which a metal deposition method as described below shall be applied to form for example continuous conductor tracks or to form electrical contacts, in particular back contacts for a solar cell.
  • the substrate may be made of any non-conducting material, like an insulator, an encapsulant, a plastic, a glass, a dielectric layer, an oxide layer of a solar cell or a silicon based material.
  • the substrate 1 is conformed for example as a layer.
  • the substrate 1 may be the top or bottom layer of a stack of different layers of a PV module (photovoltaic module) or a solar cell.
  • the surface is plane, but might be also convex, concave or show some protrudes or relief / three dimensional shapes.
  • the substrate 1 belongs for instance to a solar / PV module and/or a solar cell where electrical tracks and/ or electrical contacts shall be realized by a method as described below. Concerning solar cells, the here described method may advantageously applied to solar cells with back contacts also known as rear contacted cells.
  • PCB printed circuit board
  • FIG 2 In a flowchart in figure 2 are represented different steps of an embodiment of a method for deposition of a metal on a substrate as shown for example in figure 1 .
  • a sensitizer 9 comprising laser activable metal based molecules in a neutral state, like for example a metal salt or a metal oxide, is disposed on the substrate 1.
  • the laser activable metal based molecules are in a neutral state when the sensitizer is deposited, they are inert and have no catalyzing properties in this state. As such, in a neutral state, they are inactive at a stable state and therefore do not have a catalytic effect on the substrate when simply deposed on the substrate.
  • the metal atom of the metal salt or oxide may be noble metal atom, in particular palladium atom (the metal salt would be PdCl 2 ) or platinum atom (the metal salt would be PtCl 2 ), or with metal atom to be deposited on the substrate (Cu chloride, Ni chloride or other salts). Also SnCl 2 can be envisaged.
  • salts and/or oxides with noble metal atoms show a good performance to catalyze the substrate.
  • the use of a metal atom that shall be deposited after then may be cheaper.
  • the sensitizer 9 composition comprises a support material for the metal based molecules that conserves these molecules in a neutral state as for example a solvent or a polymer.
  • the solvent is non-aqueous and therefore may conserve the metal salts and/or oxide in a neutral state, meaning electrically non-charged or not ionized.
  • solvent toluene or a polymer like PPSQ (PolyPhenylSilsesquioxane.) disolved in actone or toluene can be used.
  • the sensitizer 9 might be a gel based solution.
  • the sensitizer When deposited, the sensitizer is thus inert and inactive, which would mean that areas covered by the sensitizer, but that are not exposed to laser activation would not be catalyzed and thus would not be subject to chemical metal deposition.
  • the catalyzing process consist for the metal ion to interact with the atoms of the substrate surface by being reduced at the surface or by making this surface sensitive to further metal ions reduction during the metal chemical deposition.
  • these catalyzed areas may therefore contain then nuclei that act as centers for electro-less plating or show also at the surface of the substrate 1 open bindings where the metal atoms may be deposited via electro-less plating.
  • the deposition of the sensitizer is done by spin-coating or simple immersion.
  • the sensitizer can be applied easily by spin coating as a thin film or layer.
  • the sensitizer based material might solidified, for example during a curing step.
  • step 103 the sensitizer 9 is laser activated by a laser beam 10 so as to form catalyzed areas 11.
  • Arrows 13 illustrate the movement of the laser beam 10 that may scan all the surface coated with the sensitizer 9, but impact the surface only at predetermined locations so as to form the catalyzed areas 11.
  • the laser activates the sensitizer at the surface but also in the depth near the surface of the substrate.
  • the laser or laser head might move above the substrate 1.
  • the laser beam 10 moves across the substrate due to moving mirrors that deflect the outcoming laser beam to the areas to be activated.
  • the laser does not move and the substrate moves beneath the laser beam 10.
  • a combination where the substrate 1 moves as well as the laser beam 10 is also possible which enhances the throughput in the manufacturing process.
  • gaps 14 might be interesting for solar cell / modules manufacturing, in particular for example to implement later on other electrical / electronic components, like diodes, that may be used as by-pass diodes for avoiding shadowing effects.
  • the laser power may be adjusted in a way that the sensitizer 9 is solidified through the laser activation step.
  • the surface underneath of the substrate 1 is catalyzed.
  • the sensitizer is removed from the substrate 1 in step 105, for example in a cleaning step ( figure 5 ).
  • a platable metal 19 is disposed by chemical metal deposition, for example an electro-less plating process at said catalyzed areas 11 where the sensitizer has been activated by the laser.
  • the deposed metal defines for example electrical contacts 15 and/or conductor tracks 17.
  • the metal 19 that is deposited may be chosen to present a conductivity sufficient to allow an optional subsequent electro-plating process step and may be comprised in the group of a noble metal, Cu, Ti, W, Co, Ni, Zn, Sn, Ag. Among these metals, nickel is preferred for its price and good adherence and conduction properties.
  • the deposited metal 19 has a thickness comprised between 0,1 - 10 ⁇ m.
  • a second, subsequent metal may optionally be disposed through an electro-less or electroplating process on the first metal that has been deposited by electro-less plating before.
  • the second metal may be comprised in the group of a Cu, Ni, Zn, Sn, Ag.
  • copper is preferred because of its price and good adherence, in particular on nickel, and conduction properties.
  • the thickness of the second metal layer is comprised between 10 to 50-60 microns.
  • Ni is used as a first deposited metal 19 for a seed layer
  • Cu is used as the second subsequent metal for electroplating
  • first and second metal may be different or the same.
  • a protection layer in particular against corrosion, may be applied in a step 111.
  • OSP organic surface protection or Organic solderability preservatives
  • a protection layer of Sn or Ag is preferred.
  • the method of deposition includes electro-less, electroplating, metal immersion and others ways of coatings
  • an encapsulation step may be foreseen after step 111.
  • FIG.8 schematically illustrates two different substrates 1 and 3 to which a metal deposition method as described below shall be applied to form for example continuous conductor tracks at the interface of said two different a substrates 1 and 3 or to form electrical contacts, in particular back contacts.
  • both substrates 1 and 3 are placed adjacent to each other to form a surface 5.
  • both substrates 1 and 3 have a common interface 7, where they touch each other.
  • “Different” means here, that the nature of the materials are different, like for example an Si-layer on the one hand and plastic on the other hand (other examples are possible and detailed below).
  • substrates 1 and 3 are conformed for example as a layer.
  • these a substrates 1 and 3 are the top or bottom layer of a stack of different layers of a module or a solar cell, each stack may be different.
  • the method according the invention has the advantage that nearly no mechanical stress is applied to the wafer / cells, the conductive tracks and electrical contacts might be defined with high precision and the method allows a good cost compromise in using electro-less plating only for creating seed locations that are enforced then through conventional cheaper electroplating process. Therefore the overall cost of the metallization process can be optimized.
  • the above method is in particular well adapted for thin wafers (about 100 ⁇ m).
  • the above method is also a low temperature process which is suitable for module level processing with glass, encapsulants, backsheet and insulators. Thanks to laser activation, there is a great flexibility for the metal pattern definition.
EP13290195.0A 2013-08-19 2013-08-19 Verfahren zur Ablagerung von Metall auf einem Substrat, insbesondere für Metallisierung von Solarzellen und -modulen Withdrawn EP2840165A1 (de)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP13290195.0A EP2840165A1 (de) 2013-08-19 2013-08-19 Verfahren zur Ablagerung von Metall auf einem Substrat, insbesondere für Metallisierung von Solarzellen und -modulen
PCT/EP2014/066847 WO2015024775A1 (en) 2013-08-19 2014-08-05 Method for depositing metal on a substrate, in particular for metallization of solar cells and modules

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP13290195.0A EP2840165A1 (de) 2013-08-19 2013-08-19 Verfahren zur Ablagerung von Metall auf einem Substrat, insbesondere für Metallisierung von Solarzellen und -modulen

Publications (1)

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EP2840165A1 true EP2840165A1 (de) 2015-02-25

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EP13290195.0A Withdrawn EP2840165A1 (de) 2013-08-19 2013-08-19 Verfahren zur Ablagerung von Metall auf einem Substrat, insbesondere für Metallisierung von Solarzellen und -modulen

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WO (1) WO2015024775A1 (de)

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Publication number Priority date Publication date Assignee Title
DE102019220458A1 (de) * 2019-12-20 2021-06-24 Vitesco Technologies Germany Gmbh Verfahren zur Herstellung einer Leiterplatte und Leiterplatte
CN114786342B (zh) * 2022-04-27 2024-02-27 四川大学 一种基于激光技术的柔性可弯折金属图案及其制备方法和用途

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1367872A2 (de) * 2002-05-31 2003-12-03 Shipley Co. L.L.C. Laseraktiviertes dielektrisches Material und Methode zu dessen Anwendung in einem stromlosen Abscheidungsverfahren
WO2008087172A1 (de) * 2007-01-19 2008-07-24 Basf Se Verfahren zur herstellung strukturierter, elektrisch leitfähiger oberflächen
WO2011072506A1 (en) * 2009-12-17 2011-06-23 Byd Company Limited Surface metallizing method, method for preparing plastic article and plastic article made therefrom

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1367872A2 (de) * 2002-05-31 2003-12-03 Shipley Co. L.L.C. Laseraktiviertes dielektrisches Material und Methode zu dessen Anwendung in einem stromlosen Abscheidungsverfahren
WO2008087172A1 (de) * 2007-01-19 2008-07-24 Basf Se Verfahren zur herstellung strukturierter, elektrisch leitfähiger oberflächen
WO2011072506A1 (en) * 2009-12-17 2011-06-23 Byd Company Limited Surface metallizing method, method for preparing plastic article and plastic article made therefrom

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