EP2351090A2 - Procédé, dispositif et substance d'impression pour la fabrication d'une structure de contacts métallique - Google Patents

Procédé, dispositif et substance d'impression pour la fabrication d'une structure de contacts métallique

Info

Publication number
EP2351090A2
EP2351090A2 EP09736393A EP09736393A EP2351090A2 EP 2351090 A2 EP2351090 A2 EP 2351090A2 EP 09736393 A EP09736393 A EP 09736393A EP 09736393 A EP09736393 A EP 09736393A EP 2351090 A2 EP2351090 A2 EP 2351090A2
Authority
EP
European Patent Office
Prior art keywords
particles
printing
contact
layer
opening
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Withdrawn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
EP09736393A
Other languages
German (de)
English (en)
Inventor
Frank Machalett
Martin Dupke
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.)
Robert Bosch GmbH
Original Assignee
Robert Bosch GmbH
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Robert Bosch GmbH filed Critical Robert Bosch GmbH
Publication of EP2351090A2 publication Critical patent/EP2351090A2/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F77/00—Constructional details of devices covered by this subclass
    • H10F77/20—Electrodes
    • H10F77/206—Electrodes for devices having potential barriers
    • H10F77/211—Electrodes for devices having potential barriers for photovoltaic cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F71/00—Manufacture or treatment of devices covered by this subclass
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F71/00—Manufacture or treatment of devices covered by this subclass
    • H10F71/129—Passivating
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F71/00—Manufacture or treatment of devices covered by this subclass
    • H10F71/134—Irradiation with electromagnetic or particle radiation
    • 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 invention relates to a method for producing a metallic contact structure, in which an electrically to be contacted, provided with a thin layer of low conductivity surface of a substrate is to be contacted. Such a method is used in particular in the production of solar cells, but is also applicable in the manufacture of other electronic components or components of electrical equipment. Furthermore, the invention relates to a device and a printing substance for carrying out this method.
  • a., 16 th EC PVSEC, 2000 describes the contact formation by etching the glass in Si by a redox reaction: The electrical contact is made by a tunneling process over a chemically modified glass layer (T. Nakajima et al., Int Microelect., 6, 1983).
  • the contact resistance between solar cell and solar cell electrodes is determined by the size of the contact surface and the quality of the contact in screen printing with metal-containing printing pastes.
  • the printing pastes essentially contain silver particles (70-80% by weight) and organic components / solvents (15-30% by weight).
  • EP 1 801 891 A1 describes an electrically conductive paste which contains silver powder, glass frit, a binder and a sintering inhibitor and is used to produce solar cell electrodes.
  • the glass frit any glass can be used which can be used for application in an electrically conductive paste.
  • the glass point (softening point according to ASTM C338-57) should be between 450 ° C and 550 ° C, since the sintering process according to the EP 1 801 891 A1, for example, between 600 0 C and 800 0 C expires.
  • the chemical composition of the glass frit is classified as not important in the said patent. Possible glasses, such as lead borosilicate glass, zinc borosilicate glass or lead-free glasses are mentioned.
  • EP 1 801 890 Al a paste is called, which consists of two Silver powders of different grain size greater or smaller than 58nm, a glass frit and a binder.
  • Pigment glass frit for paints, paints, plastics, paper and the like. described. It gives particle sizes between l ⁇ m and 60 ⁇ m for glass frits with finely dispersed embedded TiO 2 or ZrO 2 -Kritalliten called.
  • the pigment frits are transparent systems with approximately 1 ⁇ m to 15 ⁇ m and a titanium oxide crystallite size of 0.01 ⁇ m to 1 ⁇ m.
  • US 4,375,007 discloses pastes with a small proportion of glass frit, the z.
  • EP 0 630 525 Bl is a "manufacturing method of a solar cell with combined metallization", which comprises a two-stage process for the production of the front side contact, and trench structures provides, in which a first existing palladium seed layer is produced, which then by galvanic or electroless Separation is strengthened.
  • DE 4 311 173 A1 describes a "method for the electroless deposition of a metal over a semiconductor surface.”
  • the local removal of a passivation layer takes place here by masking and structuring with photolithography and etching with hydrofluoric acid.
  • DE 10 2006 030 822 A1 also describes a method for producing a metallic contact structure of a solar cell.
  • This method comprises two process steps, applying a metallic contact structure to a surface of the solar cell and reinforcing the metallic structure in an electrolytic bath.
  • the method is characterized in that the metallic contact structure is applied to the surface of the solar cell by using a metal-containing ink by means of at least one pressure nozzle.
  • the metal-containing ink is a diluted paste containing metal particles between 20 nm and 1000 nm in size. It is mentioned that before applying the metallic contact structure a dielectric layer on the solar cell is at least partially removed. This should be done, for example, by means of a laser.
  • An essential idea of the invention is the use of an admixture referred to herein as opening particles in a printing substance for producing a contact imparting layer of a contact structure in a precisely locally controllable printing process.
  • the opening particles open the thin film on the solar cell substrate locally and in a defined size, so that in a subsequent thermal process, such as a conventional sintering process, here referred to as contact particles electrically conductive particles through the opening created an electrical contact between a subsequently applied conductive layer and the substrate.
  • the opening particles are also referred to below as nanoparticles or nanoparticles, and for the contact particles, the terms metal particles or metal particles are used, although they are basically could consist of a non-metallic conductive material.
  • the defined application of the opening particles to the wafer surface has the following advantages: - There are many small openings in the thin film possible.
  • the number of openings can be controlled by the concentration of the nanoparticles in the paste or their distribution density at the surface.
  • the size of the opening can be influenced and optionally adjusted in a targeted manner. This can be ruled out that the opening is too large and the emitter is damaged.
  • the density of the lower layer can be kept low, since it is only to serve for the production of the contact.
  • the amount of metal available for alloying can be controlled. It can thus be avoided that too much metal penetrates into the Si and would damage the emitter.
  • the step of applying the contact-imparting layer comprises at least two partial steps using a first and second printing substance, wherein at least one of the printing substances contains opening particles, but no metal particles, and the other printing substance contains metal particles.
  • the printing substances contain opening particles and / or metal particles with different mean grain size.
  • the layer application in the sub-steps is in each case carried out in a precisely controlled manner so that a point of a second, metal particle-containing sub-layer is deposited on a point of an opening-particle-containing first sub-layer.
  • the grain size and / or the proportion of metal particles in a second printing substance at least equal to the grain size and / or the proportion of the opening particles in a first printing substance, in particular larger. This ensures that the openings formed by the penetration of the opening particles into the electrical layer on the substrate surface can be largely completely filled with the conductive material, whereby a particularly low contact resistance is achieved.
  • a printing fluid is used as the printing substance and applied to the surface to be contacted by means of an inkjet or aerosol printing process.
  • portions of conventional inkjet or aerosol printers and the extensive and sophisticated control software available to them can be used, as well as recourse to components or base compositions of known printing inks.
  • the pressurized liquid contains preferably silver or nickel particles as metal particles, and it is advisable to have a sufficiently low viscosity and, if appropriate, admixing of a surfactant fraction for the best possible wetting of the thin layer and for chemical compatibility with the material of the subsequently applied conductive layer respect, think highly of.
  • a printing powder is used as printing substance and this is applied to the surface to be contacted by means of a laser printing process.
  • This procedure is based on the well-known laser printing technology and may also use known hardware and software of that technology. As a result, short development and production times and low production costs of the corresponding manufacturing plants can be achieved.
  • Particles having a particle size between about 1 nm and 3 ⁇ m, in particular between 10 nm and 1 ⁇ m, are used as the opening particle component of a printing substance for carrying out the method according to the invention.
  • the particle size chosen for a specific method implementation depends on the thickness and possibly other parameters of the dielectric layer (thin layer) provided on the primary substrate surface, and may also deviate from the range specified here, if required, in terms of dimensions.
  • the material used for the opening particles is glass, quartz or ceramic (such as corundum or other oxide or other ceramics, such as those used for hard coatings) into consideration. Depending on the particular application, in particular the properties of the thin film to be opened, a mixture of different materials can also be usefully used. Particularly suitable contact particles are silver and / or nickel particles, but in principle also carbon particles.
  • the opening particles are held on the dielectric layer by surface forces, and at the points of contact the dielectric layer is opened due to the temperature increase during the subsequent sintering process and the particles "sink" into it.
  • the application of the conductive layer is not necessarily carried out by a screen printing method, but may be configured as a deposition method. Incidentally, the state of the art is used for this stage of the method, so that no more detailed description is required in this regard.
  • the opening particles are surrounded by one or more protective layers, which protects them against the influence of external influences, in particular chemical and thermal.
  • This layer or layers extend the storage capacity of the printing substance and can be removed after applying the same to the thin layer of low conductivity in a subsequent process, in particular a thermal process.
  • the opening particles may contain in their interior a substance suitable for producing an electrical contact ("contact substance") Both in this embodiment and when opening particles and contact
  • contact substance a substance suitable for producing an electrical contact
  • the amount of material of both components is suitably matched to the thickness of the thin layer of low conductivity via the amount of orifice material in the outer layer of the pressure particles is adjusted to the size of the opening in the thin film and the amount of the contact material in the interior
  • the conductivity of the electrical contact between the conductive layer and the substrate can, independently of one another, be contacted via the size of the pressure particles and the proportions of opening and contact material of a single contact and the number of pressure particles per pressure surface can be set specifically.
  • FIGS. 2A and 2B are schematic representations for explaining the same step of a second embodiment of the method according to the invention.
  • FIG. 3 shows a schematic representation for explaining a third embodiment of the method according to the invention
  • 5A and 5B is a schematic cross-sectional view and plan view of a first configuration variant in the embodiment of the invention
  • FIGS. 5A and 6B show a schematic cross-sectional view and a top view, respectively, of a second configuration variant in the implementation of the invention, FIGS.
  • Fig. 8 is a plan view of a fourth configuration variant.
  • FIG. 1A is a cross-sectional view schematically showing a Si solar cell substrate 1 having an antireflective layer (dielectric layer) 3 of low conductivity applied on a main surface (front side) 1a in a first step of a method for producing a metallic contact structure.
  • an ink jet printing nozzle 5 connected to a printing liquid reservoir 7 applies a rapidly drying printing liquid 9 precisely locally controlled by a printing control unit 11 to the surface of the antireflection film 3 to form one according to the desired shape a later contact structure patterned contact-mediating layer 13 from.
  • the printing fluid 9 contains in addition to a binder composition, solvents and optionally additives to optimize the printing process glass nanoparticles and metal particles in dispersed form.
  • the representation is to be understood only as a schematic diagram; in a practical embodiment, a multi-printhead having a plurality of individual nozzles will be used, which in predetermined groups (as in a color ink jet printer) will be connected to different pressure fluid reservoirs and therefore pressure fluids having predeterminedly different glass frit and metal contents and contents possibly other parameters.
  • the properties of the contact-making layer formed can thereby be locally adjusted and optimized in a targeted manner.
  • FIG. 1B shows in a sketch-like manner a second step in the production of the mentioned contact structure, which follows the formation of the structured contact-mediating layer 13.
  • a printing screen 15 with open areas 15a and masking areas 15b is placed on the surface of the contact-mediating layer, the position of the latter corresponding to the position of the recesses in the contact-mediating layer 13.
  • a screen printing paste 19 is guided over the printing screen 15 with a predetermined surface pressure in the usual manner by screen printing method and pressed through the open areas 15a of the screen on the there pre-formed contact-mediating layer 13.
  • the process of producing the contact structure is then usually completed by a thermal treatment step (sintering step oe), in which at the same time the above-mentioned physico-chemical processes take place at the interface between the contact-mediating layer 13 and substrate surface Ia and to form an electrical contact between the Si substrate and the guide layer formed by the thermal treatment of the screen printing paste 19 lead the contact structure.
  • a thermal treatment step sining step oe
  • FIG. 2A and 2B again purely schematically, a modification of the method described above in both process steps is shown.
  • the illustrated elements correspond to those shown in FIGS. 1A and 1B, are correct, the same reference numerals as there are chosen, and these elements will not be described again.
  • the essential difference in the first method step is that it is divided into two sub-steps, in which using two mutually parallel pressure nozzles 5.1, 5.2 two recorded in separate pressure fluid containers 7.1, 7.2 pressure fluids 9.1, 9.2 directly successively and directly above each other such on the anti-reflection layer. 3 be discharged, that then forms a lower sub-layer 13.1 and an upper sub-layer 13.2 comprehensive contact-mediating layer 13.
  • the first printing liquid 9.1 contains substantially only glass nanoparticles (in addition to binders and solvents, etc.) as the active substance essential to the practice of the invention, while the second printing liquid 9.2 essentially contains only metal particles but no glass nanoparticles ,
  • the size of the respective particles in the two pressure fluids is adjusted in accordance with the thickness and the physical parameters of the antireflection layer and on other process parameters for realizing an optimized contact-mediating layer.
  • the substrate 1 with the contact-mediating layer 13 arranged thereon is subjected to a gas-phase or vacuum deposition of silver Ag (symbolized by wavy arrows), after the opening regions of the contact-mediating layer 13 have become in the usual way were masked by a photoresist 21 to prevent Ag deposition in these areas.
  • An Ag conductive layer 23 is formed, which is structured according to a conventional treatment according to the pattern of the contact mediating layer 13.
  • a thermal aftertreatment to form a contact alloy in the boundary layer region will join the Si substrate 1.
  • FIG. 3 shows in a sketch-like manner a further modification of the method, specifically the use of a laser printing method for the production of the contact broker.
  • a printing powder 10 accommodated in a cartridge 8 is supplied to a laser printing head 6 which, under the control of a printing control unit 12, generates the contact imparting layer 13 as a printing pattern by the usual steps of a laser printing method.
  • the printing powder contains, in addition to conventional binders, etc. a glass frit content with glass nanoparticles and metal particles in a uniform distribution, which act after the application and drying of the powder to the contact-mediating layer 13 in the same manner as in the embodiments described above.
  • FIGS. 4A to 4C again in the manner of schematic cross-sectional representations, the operation of the invention is illustrated.
  • Fig. 4A shows a state in which glass nanoparticles A originally lying on the antireflection layer 3 of the Si substrate 1 have already penetrated into the antireflection layer 3 and penetrated therethrough into the surface 1a of the substrate 1.
  • silver particles B still lie on the antireflection layer 3.
  • FIG. 4B symbolically shows a part of the silver particles B through the apertures created by the glass nanoparticles through the antireflection layer 3 and into the surface of the silicon 1.
  • FIG. 4C shows, in this way, the contact-mediating layer 13 with the antireflection layer 3 and the substrate surface Ia is "interlocked" by conductive bridges, whereby a low contact resistance can be realized between a conductive layer 19 'formed over the contact-mediating layer 13 and the solar cell substrate 1.
  • the concentration and grain size of the glass and metal particles can be the number (density) and size the breakthroughs and the amount of penetrating into the substrate surface metal can be controlled specifically according to the existing requirements.
  • FIGS. 5A and 5B schematically show a regular configuration of alternating rows of equal size glass nanoparticles A and silver particles B (FIG. 5A) and ink droplets 9A of equal size containing glass nanoparticles and droplets 9B containing metal particles (FIGS. Fig. 5B).
  • this distribution is modified such that the particle size of the metal particles B (FIG. 6A) or the droplet size of the metal-containing ink B (FIG. 6B) is selected to be larger, that is, more metal to pass through Glass nanoparticles created breakthroughs in the dielectric layer is provided.
  • the ink droplets of inks 9A and 9B are not applied alternately, ie adjacent to one another, but the larger droplets of ink 9B are deposited directly over the smaller droplets of ink 9A.
  • a larger amount of silver particles than the amount of glass nanoparticles is provided on the surface of the dielectric layer to provide an overall larger amount of metal.
  • the average grain size of the glass and metal particles is the same here (as in FIG. 5A).

Landscapes

  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Electrodes Of Semiconductors (AREA)
  • Photovoltaic Devices (AREA)

Abstract

L'invention concerne un procédé de fabrication d'une structure de contacts métallique, en particulier la structure de contacts d'une cellule solaire. Une substance d'impression est appliquée par un procédé d'impression sans impact, piloté localement, sur la surface d'un substrat dont les contacts électriques doivent être réalisés, qui a été dotée d'une couche mince de faible conductivité, en particulier une couche de passivation ou une couche antiréflexion de la cellule solaire. La substance d'impression contient des particules d'ouverture ayant une granulation moyenne qui est adaptée à l'épaisseur de la couche mince ainsi que des particules de contact et elle forme sur la surface une couche intermédiaire de contactage. Dans une étape suivante, une couche conductrice est produite sur la couche intermédiaire de contact. Les particules d'ouverture sont conçues pour, dans un processus aval, en particulier un processus thermique, ouvrir localement la couche mince de faible conductivité, dans des dimensions définies, si bien que, dans ce processus ou dans un processus d'aval, en particulier un processus thermique, les particules de contact établissent au travers des ouvertures un contact électrique entre la couche conductrice et le substrat.
EP09736393A 2008-10-31 2009-09-24 Procédé, dispositif et substance d'impression pour la fabrication d'une structure de contacts métallique Withdrawn EP2351090A2 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE102008054166 2008-10-31
DE102009009840A DE102009009840A1 (de) 2008-10-31 2009-02-20 Verfahren, Vorrichtung und Drucksubstanz zur Herstellung einer metallischen Kontaktstruktur
PCT/EP2009/062372 WO2010049223A2 (fr) 2008-10-31 2009-09-24 Procédé, dispositif et substance d'impression pour la fabrication d'une structure de contacts métallique

Publications (1)

Publication Number Publication Date
EP2351090A2 true EP2351090A2 (fr) 2011-08-03

Family

ID=42114730

Family Applications (1)

Application Number Title Priority Date Filing Date
EP09736393A Withdrawn EP2351090A2 (fr) 2008-10-31 2009-09-24 Procédé, dispositif et substance d'impression pour la fabrication d'une structure de contacts métallique

Country Status (3)

Country Link
EP (1) EP2351090A2 (fr)
DE (1) DE102009009840A1 (fr)
WO (1) WO2010049223A2 (fr)

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DE102010024307A1 (de) * 2010-06-18 2011-12-22 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Verfahren zur Herstellung einer metallischen Kontaktstruktur einer photovoltaischen Solarzelle
EP2583314B1 (fr) 2010-06-18 2016-12-07 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Procédé de fabrication d'une structure de contact métallique d'une cellule solaire photovoltaïque
DE102011016335B4 (de) * 2011-04-07 2013-10-02 Universität Konstanz Nickelhaltige und ätzende druckbare Paste sowie Verfahren zur Bildung von elektrischen Kontakten beim Herstellen einer Solarzelle
DE102013219846A1 (de) 2013-10-01 2015-04-02 Robert Bosch Gmbh Verfahren und Vorrichtung zum Kontaktieren einer Oberfläche einer Fotovoltaikzelle

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Also Published As

Publication number Publication date
WO2010049223A2 (fr) 2010-05-06
WO2010049223A3 (fr) 2011-09-09
DE102009009840A1 (de) 2010-05-27

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