EP2938761A1 - Substances de dopage destinées au dopage local de tranches de silicium - Google Patents

Substances de dopage destinées au dopage local de tranches de silicium

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Publication number
EP2938761A1
EP2938761A1 EP13817883.5A EP13817883A EP2938761A1 EP 2938761 A1 EP2938761 A1 EP 2938761A1 EP 13817883 A EP13817883 A EP 13817883A EP 2938761 A1 EP2938761 A1 EP 2938761A1
Authority
EP
European Patent Office
Prior art keywords
doping
acid
oxide
media
printed
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Withdrawn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
EP13817883.5A
Other languages
German (de)
English (en)
Inventor
Ingo Koehler
Oliver Doll
Sebastian Barth
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.)
Merck Patent GmbH
Original Assignee
Merck Patent 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 Merck Patent GmbH filed Critical Merck Patent GmbH
Priority to EP13817883.5A priority Critical patent/EP2938761A1/fr
Publication of EP2938761A1 publication Critical patent/EP2938761A1/fr
Withdrawn legal-status Critical Current

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
    • H01L31/186—Particular post-treatment for the devices, e.g. annealing, impurity gettering, short-circuit elimination, recrystallisation
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
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    • 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
    • C23C18/12—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 characterised by the deposition of inorganic material other than metallic material
    • C23C18/1204—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 characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
    • C23C18/1208—Oxides, e.g. ceramics
    • C23C18/1216—Metal oxides
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    • C23C18/1204—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 characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
    • C23C18/122—Inorganic polymers, e.g. silanes, polysilazanes, polysiloxanes
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    • C23C18/1229—Composition of the substrate
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    • 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
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    • C23C18/12—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 characterised by the deposition of inorganic material other than metallic material
    • C23C18/125—Process of deposition of the inorganic material
    • C23C18/1254—Sol or sol-gel processing
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    • 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
    • C23C18/14—Decomposition by irradiation, e.g. photolysis, particle radiation or by mixed irradiation sources
    • C23C18/143—Radiation by light, e.g. photolysis or pyrolysis
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/02—Elements
    • C30B29/06—Silicon
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B31/00—Diffusion or doping processes for single crystals or homogeneous polycrystalline material with defined structure; Apparatus therefor
    • C30B31/04—Diffusion or doping processes for single crystals or homogeneous polycrystalline material with defined structure; Apparatus therefor by contacting with diffusion materials in the liquid state
    • H—ELECTRICITY
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    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
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    • H01L21/02107—Forming insulating materials on a substrate
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    • H01L21/02126—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon the material containing Si, O, and at least one of H, N, C, F, or other non-metal elements, e.g. SiOC, SiOC:H or SiONC
    • H01L21/02129—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon the material containing Si, O, and at least one of H, N, C, F, or other non-metal elements, e.g. SiOC, SiOC:H or SiONC the material being boron or phosphorus doped silicon oxides, e.g. BPSG, BSG or PSG
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    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
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    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/22—Diffusion of impurity materials, e.g. doping materials, electrode materials, into or out of a semiconductor body, or between semiconductor regions; Interactions between two or more impurities; Redistribution of impurities
    • H01L21/225—Diffusion of impurity materials, e.g. doping materials, electrode materials, into or out of a semiconductor body, or between semiconductor regions; Interactions between two or more impurities; Redistribution of impurities using diffusion into or out of a solid from or into a solid phase, e.g. a doped oxide layer
    • H01L21/2251—Diffusion into or out of group IV semiconductors
    • H01L21/2254—Diffusion into or out of group IV semiconductors from or through or into an applied layer, e.g. photoresist, nitrides
    • H01L21/2255—Diffusion into or out of group IV semiconductors from or through or into an applied layer, e.g. photoresist, nitrides the applied layer comprising oxides only, e.g. P2O5, PSG, H3BO3, doped oxides
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    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/48—Manufacture or treatment of parts, e.g. containers, prior to assembly of the devices, using processes not provided for in a single one of the subgroups H01L21/06 - H01L21/326
    • H01L21/4814—Conductive parts
    • H01L21/4846—Leads on or in insulating or insulated substrates, e.g. metallisation
    • H01L21/4867—Applying pastes or inks, e.g. screen printing
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    • H01L31/02—Details
    • H01L31/0216—Coatings
    • H01L31/02161—Coatings for devices characterised by at least one potential jump barrier or surface barrier
    • H01L31/02167—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells
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    • H01L31/0216—Coatings
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    • H01L31/02168—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells the coatings being antireflective or having enhancing optical properties for the solar cells
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    • 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
    • H01L31/0256—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 the material
    • H01L31/0264—Inorganic materials
    • H01L31/028—Inorganic materials including, apart from doping material or other impurities, only elements of Group IV of the Periodic Table
    • H01L31/0288—Inorganic materials including, apart from doping material or other impurities, only elements of Group IV of the Periodic Table characterised by the doping material
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    • H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
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    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
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    • 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
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    • C23C18/10—Deposition of aluminium only
    • 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
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    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/547—Monocrystalline silicon 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
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Definitions

  • the present invention relates to a novel process for the preparation of printable, high viscosity oxide media and their use in solar cell manufacture, as well as the improved lifetime products produced using these novel media.
  • a silicon wafer (monocrystalline, multicrystalline or quasi-monocrystalline, p- or n-type base doping) is freed of adherent saw damage by means of an etching process and "simultaneously", usually in the same etching bath, texturized in this case, the creation of a preferred Surface (texture) as a result of the etching step or simply to understand the targeted, but not particularly oriented roughening of the wafer surface
  • the aforementioned etching solutions for treating the silicon wafers typically consist of dilute potassium hydroxide solution to which isopropyl alcohol has been added as solvent. Instead, other alcohols having a higher vapor pressure or higher boiling point than isopropyl alcohol may be added, provided that the desired etching result can be achieved thereby.
  • the desired etch result is a morphology that is randomly-etched, or rather etched out of the original surface.
  • Pyramids is characterized by square base.
  • density the density
  • the height and thus base area of the pyramids can be influenced by a suitable choice of the above-mentioned constituents of the etching solution, the etching temperature and the residence time of the wafers in the etching basin.
  • Temperature range of 70 - ⁇ 90 ° C performed, with ⁇ tzabträge of up to 10 pm per wafer side can be achieved.
  • the etching solution may consist of potassium hydroxide solution with an average concentration (10-15%).
  • this etching technique is hardly used in industrial practice. More often becomes one
  • Etching solution consisting of nitric acid, hydrofluoric acid and water used.
  • This etching solution can be modified by various additives such as sulfuric acid, phosphoric acid, acetic acid, N-methylpyrrolidone and also surfactants, which u. a.
  • Wetting properties of the etching solution and their etch rate can be specifically influenced.
  • These acid etch mixtures produce a morphology of interstitially arranged etch pits on the surface.
  • the etching is typically carried out at temperatures in the range between 4 ° C to ⁇ 10 ° C and the ⁇ tzabtrag here is usually 4 pm to 6 pm.
  • the wafers are placed in a tube furnace in a controlled atmosphere quartz glass tube consisting of dried nitrogen, dried oxygen and phosphoryl chloride, exposed.
  • the wafers are introduced at temperatures between 600 and 700 ° C in the quartz glass tube.
  • the gas mixture is transported through the quartz glass tube.
  • the phosphoryl chloride decomposes into a vapor consisting of phosphorus oxide (eg P2O5) and chlorine gas.
  • the vapor of phosphorus oxide is deposited among other things on the wafer surfaces (occupancy).
  • the silicon surface is oxidized at these temperatures to form a thin oxide layer. In this layer, the deposited phosphorus oxide is embedded, whereby a mixed oxide of silicon dioxide and phosphorus oxide formed on the wafer surface.
  • This mixed oxide is called phosphosilicate glass (PSG).
  • PSG phosphosilicate glass
  • the mixed oxide serves the silicon wafer as a diffusion source, wherein in the course of the diffusion, the phosphorus oxide diffuses in the direction of the interface between PSG glass and silicon wafer and is reduced there by reaction with the silicon on the wafer surface (silicothermally) to phosphorus.
  • the resulting phosphor has a solubility which is orders of magnitude greater in silicon than in the glass matrix from which it is formed, and thus dissolves preferentially in silicon due to the very high segregation coefficient.
  • the phosphorus in silicon diffuses along the concentration gradient into the volume of silicon. In this diffusion process, concentration gradients of the order of 105 between typical
  • a PSG layer is formed, which typically has a layer thickness of 40 to 60 nm. in the
  • the drive-in phase follows. This can be decoupled from the assignment phase, but is conveniently conveniently in time directly to the Occupancy coupled and therefore usually takes place at the same temperature.
  • the composition of the gas mixture is adjusted so that the further supply of phosphoryl chloride is suppressed.
  • the surface of the silicon is further oxidized by the oxygen contained in the gas mixture, whereby a phosphorus depleted silicon dioxide layer is also generated between the actual doping source, the phosphorus oxide highly enriched PSG glass and the silicon wafer
  • the tube furnace is automatically cooled and the wafers can be removed from the process tube at temperatures between 600 ° C to 700 ° C.
  • Composition of the gas atmosphere used for doping the formation of a so-called boron skin can be detected on the wafers.
  • This boron skin is dependent on various influencing factors: decisive for the doping atmosphere, the temperature, the doping time, the
  • Pretreatment were subjected (for example, their structuring with diffusion-inhibiting and / or -unterbindenden layers and
  • Doping sources for example, dilute solutions of phosphoric or boric acid, as well as sol-gel-based systems or solutions of polymeric Borazilitatien can be used.
  • Solvents from the aforementioned doping media is usually followed by a treatment at high temperature, while those unwanted and interfering, but the formulation-related, additives are either "burned" and / or pyrolyzed.The removal of solvents and the burn-out may, but need not, occur simultaneously.
  • the coated substrates usually pass through a continuous furnace at temperatures between 800 ° C and 1000 ° C, to shorten the cycle time, the temperatures in comparison to
  • Gas phase diffusion in the tube furnace can be slightly increased.
  • the prevailing in the continuous furnace gas atmosphere can according to the
  • Nitrogen dry air, a mixture of dry oxygen and dry nitrogen and / or, depending on the design of the furnace to be passed, zones of one and the other of the above
  • Driving the dopant can in principle be decoupled from each other.
  • the wafers present after the doping are coated on both sides with more or less glass on both sides of the surface. More or less in this case refers to modifications that can be applied in the context of the doping process: double-sided diffusion vs. quasi one-sided diffusion mediated by back-to-back arrangement of two wafers in a parking space of the process boats used.
  • the latter variant allows a predominantly one-sided doping, but does not completely prevent the diffusion on the back.
  • the wafers are on the one hand transhipped in batches in wet process boats and with their help in a solution of dilute hydrofluoric acid, typically 2% to 5%, immersed and left in this until either the surface is completely removed from the glasses, or Process cycle has expired, which is a sum parameter from the necessary ⁇ tzdauer and the automatic process automation represents.
  • the complete removal of the glasses can be determined, for example, by the complete dewetting of the silicon wafer surface by the dilute aqueous hydrofluoric acid solution.
  • the complete removal of a PSG glass is achieved under these process conditions, for example with 2% hydrofluoric acid solution within 210 seconds at room temperature.
  • the etching of corresponding BSG glasses is slower and requires longer process times and possibly also higher concentrations of the hydrofluoric acid used. After etching, the wafers are rinsed with water.
  • the etching of the glasses on the wafer surfaces can also be carried out in a horizontally operating method in which the wafers are introduced in a constant flow into an etching system in which the wafers pass through the corresponding process tanks horizontally (inline system).
  • the wafers are conveyed on rollers and rollers either through the process tanks and the etching solutions contained therein or the etching media are transported onto the wafer surfaces by means of roller application.
  • the typical residence time of the wafers in the case of etching the PSG glass is about 90 seconds, and the hydrofluoric acid used is somewhat more concentrated than in the batch process
  • the concentration of hydrofluoric acid is typically 5%.
  • the tank temperature compared to the
  • edge isolation is a process engineering imperative resulting from the intrinsic nature of double-sided diffusion, even with intentional unilateral back-to-back diffusion.
  • parasitic p-n transition On the (later) back side of the solar cell, there is a large-scale parasitic p-n transition, which, although due to process technology, is partly, but not completely, removed in the course of the later processing. As a result, the front and back of the solar cell are parasitic and parasitic
  • the wafers are unilaterally via an etching solution
  • etching solution consisting of nitric acid and hydrofluoric acid.
  • the etching solution may contain as minor constituents, for example, sulfuric acid or phosphoric acid.
  • the etching solution is imparted via rollers to the
  • etch removal typically achieved with these methods amounts to about 1 ⁇ m silicon at temperatures between 4 ° C. and 8 ° C. (including the surface to be treated
  • edge isolation can also be done with the help of
  • Plasma etching processes are performed. This plasma etching is then usually carried out before the glass etching. For this purpose, several wafers are stacked on each other and the outer edges become the plasma
  • the plasma is filled with fluorinated gases, for example
  • Tetrafluoromethane fed.
  • the glass etching is then generally carried out.
  • Solar cells with an anti-reflection coating which usually consists of amorphous and hydrogen-rich silicon nitride.
  • Antireflection coatings are conceivable. Possible coatings may include titanium dioxide, magnesium fluoride, tin dioxide and / or
  • the coating of the wafer surface with the silicon nitride mentioned above is fulfilled in essentially two functions: on the one hand, the layer generates an electric field due to the numerous incorporated positive charges that charge carriers in the silicon can keep away from the surface and the recombination of these charge carriers at the
  • this layer depending on its optical parameters, such as refractive index and layer thickness, this layer generates a reflection-reducing property which contributes to the fact that more light can be coupled into the later solar cell. Both effects can increase the conversion efficiency of the solar cell.
  • the antireflection reduction is most pronounced in the wavelength range of the light of 600 nm.
  • the directional and non-directional reflection shows a value of about 1% to 3% of the originally incident light (perpendicular incidence to the surface normal of the silicon wafer).
  • the above-mentioned silicon nitride films are currently deposited on the surface generally by direct PECVD method.
  • a gas atmosphere of argon is ignited a plasma, in which silane and ammonia are introduced.
  • the silane and the ammonia are converted in the plasma by ionic and radical reactions to silicon nitride and thereby deposited on the wafer surface.
  • the properties of the layers can z. B. adjusted and controlled by the individual gas flows of the reactants.
  • the deposition of the above-mentioned silicon nitride layers can also be carried out using hydrogen as the carrier gas and / or the reactants alone. Typical deposition temperatures are in the range between 300 ° C to 400 ° C.
  • Alternative deposition methods may be, for example, LPCVD and / or sputtering.
  • Silicon nitride coated wafer surface the front electrode are defined.
  • the electrode has been established using the screen printing method using metallic
  • the sum of the residual constituents results from the necessary for the formulation of the paste theological aids, such as solvents, binders and thickeners.
  • the silver paste contains a special Glasfrit mixture, mostly oxides and mixed oxides based on
  • the glass frit fulfills essentially two functions: on the one hand it serves as a bonding agent between the wafer surface and the mass of the silver particles to be sintered, on the other hand it is responsible for the penetration of the silicon nitride covering layer in order to enable the direct ohmic contact to the underlying silicon.
  • the penetration of the silicon nitride takes place via an etching process with subsequent diffusion of silver present dissolved in the glass frit matrix into the silicon surface, whereby the ohmic contact formation is achieved.
  • the silver paste is deposited by screen printing on the wafer surface and then dried at temperatures of about 200 ° C to 300 ° C for a few minutes. For the sake of completeness, it should be mentioned that double-printing processes also find industrial application, which make it possible to print on an electrode grid generated during the first printing step, a congruent second.
  • Silver metallization increases, which can positively influence the conductivity in the electrode grid.
  • the solvents contained in the paste are expelled from the paste.
  • the printed wafer passes through a continuous furnace.
  • Such an oven generally has several heating zones, which can be independently controlled and tempered.
  • the wafers are heated to temperatures up to about 950 ° C. However, the single wafer is typically exposed to this peak temperature for only a few seconds. During the remaining run-up phase, the wafer has temperatures of 600 ° C to 800 ° C. In these Temperatures are contained in the silver paste contained organic impurities, such as binders, and the etching of the silver paste.
  • Silicon nitride layer is initiated. During the short time interval of the prevailing peak temperatures, contact formation occurs.
  • the front electrode grid consists of thin fingers
  • the rear bus buses are also usually by means of
  • the back electrode is defined following the pressure of the bus buses.
  • the electrode material is made of aluminum, which is why Definition of the electrode an aluminum-containing paste by screen printing on the remaining free area of the wafer back with a
  • Edge distance ⁇ 1 mm is printed.
  • the paste is ⁇ 80% aluminum.
  • the remaining components are those already mentioned under point 5 (such as solvents, binders, etc.).
  • the aluminum paste is bonded to the wafer during co-firing by causing the aluminum particles to start to melt during heating and remove silicon from the wafer in the wafer
  • the melt mixture acts as a dopant source and gives aluminum to the silicon (solubility limit: 0.016 atomic percent), whereby the silicon is p + doped as a result of this drive-in.
  • a eutectic mixture of aluminum and silicon which solidifies at 577 ° C. and has a composition with a mole fraction of 0.12 Si, is deposited on the wafer surface, inter alia.
  • This potential wall is generally referred to as the back surface field or back surface field.
  • edge isolation of the wafer has not already been carried out as described under point 3, this is typically carried out after co-firing with the aid of laser beam methods.
  • a laser beam is directed to the front of the solar cell and the front p-n junction is severed by means of the energy coupled in by this beam.
  • This trench with a depth of up to 15 pm as a result of
  • this laser trench is 30 pm to 60 pm wide and about 200 pm away from the edge of the solar cell.
  • solar cell architectures with both n-type and p-type base material. These solar cell types include u. a.
  • structured diffusion barriers may be deposited on the silicon wafers prior to depositing the glasses to define the regions to be doped.
  • a disadvantage of this method is that in each case only one polarity (n or p) of
  • Doping can be achieved. Somewhat simpler than the structuring of the doping sources or that of any diffusion barriers is the direct laser-beam driven driving-in of dopants from previously onto the
  • Wafer surfaces deposited dopant sources This method makes it possible to save costly structuring steps. However, it can not compensate for the disadvantage of a possible simultaneous simultaneous doping of two polarities on the same surface at the same time (co-diffusion), since this method is also based on a predeposition of a dopant source, which is activated only subsequently for the emission of the dopant. Disadvantage of this (post-) doping from such sources is the inevitable laser damage to the substrate: the laser beam must by absorbing the radiation into heat
  • Phosphoryl chloride and / or boron tribromide do not allow to selectively generate local dopants and / or locally different dopants on silicon wafers.
  • the creation of such structures is only possible by the use of known doping technologies by costly and expensive structuring of the substrates. When structuring different dopants and / or locally different dopants on silicon wafers.
  • the present invention provides a process for preparing corresponding oxide media in which the reaction is selected in the presence of boron-containing compounds selected from the group of boron oxide, boric acid and boric acid ester, and or of phosphorus-containing compounds from the group phosphorus (V) - oxide, phosphoric acid, polyphosphoric acid, phosphoric acid ester and phosphonic acid ester with alpha and beta-standing
  • Glyoxylic acid, tartaric acid, maleic acid, malonic acid, pyruvic acid, malic acid, 2-oxoglutaric acid can be used.
  • condensation in Presence of suitable organometallic compounds can be printable oxide media in the form of hybrid-sols and / or gels based dopants, using alcoholates / esters, hydroxides or oxides of aluminum, gallium, germanium, zinc, tin, titanium, zirconium, arsenic or lead , as well as mixtures thereof.
  • the oxide medium is dissolved to a high-viscosity, approximately glassy mass and the product obtained, either by addition of a suitable solvent selected from the group tetrahydrofuran, dioxane, diethyl ether, ethylene glycol dimethyl ether, N-methylpyrrolidone and dimethylformamide, pure or im Mixture is brought back into solution or retransformed by means of intensive shear mixing devices in a sol state and retransformed by repeated partial or complete structural recovery (gelling).
  • a suitable solvent selected from the group tetrahydrofuran, dioxane, diethyl ether, ethylene glycol dimethyl ether, N-methylpyrrolidone and dimethylformamide
  • the subject of the present invention is outside this production process
  • a paste is to be understood as meaning a composition which, due to the sol-gel-based synthesis, has a high viscosity of more than 500 mPas and is no longer flowable.
  • the prepared oxide media are dopant pastes prepared by an anhydrous sol-gel-based synthesis by condensation of 2- to 4-fold symmetrical and asymmetrically substituted alkoxysilanes and alkoxyalkylsilanes with a) symmetrical and asymmetric
  • Alkoxysilanes and alkoxyalkylsilanes single or various saturated, unsaturated branched, unbranched aliphatic, alicyclic and aromatic radicals, which in turn at any position of the Alkoxide radical can be functionalized by heteroatoms selected from the group O, N, S, Cl, Br.
  • boron-containing compounds used for carrying out the process are those which are selected from the group boron oxide, boric acid and boric acid esters.
  • oxide media are obtained with good properties when the phosphorus-containing compounds are selected from the group phosphorus (V) oxide, phosphoric acid, polyphosphoric acid,
  • Phosphoric acid esters and phosphonic acid esters with alpha and beta-siloxane functional groups Phosphoric acid esters and phosphonic acid esters with alpha and beta-siloxane functional groups.
  • carboxylic acids are acids from the group of formic acid, acetic acid, oxalic acid, trifluoroacetic acid, mono-, di- and
  • Trichloroacetic acid glyoxylic acid, tartaric acid, maleic acid, malonic acid, pyruvic acid, malic acid, 2-oxoglutaric particularly suitable for use in the inventive method.
  • the printable oxide media in the form of doping on the basis of hybrid sols and or gels using alcoholates / esters, hydroxides or oxides of aluminum, gallium, germanium, zinc, tin, titanium, zirconium, arsenic or lead, and mixtures thereof ("hybrid” sol or "hybrid” gel).
  • hybrid sols and gels can be sterically stabilized on the one hand by addition of suitable masking agents, complexing agents and chelating agents in a sub stoichiometric ratio, and on the other hand with regard to their condensation and
  • the oxide medium is dissolved to a high-viscosity, approximately glassy mass and the product obtained, either by addition of a suitable solvent or
  • Solvent mixture brought back into solution or retransformed by means of intensive shear mixing devices in a sol state and recover by repeated partial or complete structural recovery (gelation) to a homogeneous gel.
  • the process according to the invention has proven to be particularly advantageous in that the formulation of the highly viscous oxide medium takes place without the addition of thickening agents.
  • a stable mixture is prepared by the process according to the invention, which is storage stable for a period of at least three months. If, during manufacture, the oxide media is "capping agent",
  • produced oxide media are particularly well suited for use as a doping medium in the processing of silicon wafers for photovoltaic, microelectronic, micromechanical and micro-optical applications.
  • the oxide media produced according to the invention may vary depending on the consistency, i. H. depending on their theological properties, such as their viscosity, by spin or dip coating, drop casting, curtain or slot dye coating, screen or flexoprinting, gravure, ink jet or aerosol jet printing, offset printing, Micro Contact Printing, Electrohydrodynamic
  • Dispensing, roller or spray coating, ultrasonic spray coating, pipe jetting, laser transfer printing, ped printing or rotary screen printing Preferably, the high-viscosity, doping oxide media are processed by screen printing.
  • PERC PERL
  • PERT IBC solar cells
  • IBC solar cells BJBc or BCBJ
  • the solar cells further architectural features, such as MWT, EWT, selective emitter, Selective Front Surface Field, Selective Back Surface field and bifaciality.
  • Glass layers which act as a sodium and potassium diffusion barrier in the LCD technique as a result of a thermal treatment, in particular for producing thin, dense glass layers on the cover glass of a display consisting of doped SiO 2 , which the diffusion of ions from the cover glass into the viassigkristalline Prevent phase, find application.
  • the present invention accordingly also relates to the novel oxide media prepared according to the invention, which, prepared by the process described above, binary or ternary systems from the group S1O2-P2O5, S1O2-B2O3, S1O2-P2O5-B2O3 and S1O2-AI2O3-B2O3
  • Chelating agents are contained in the patent applications WO 2012/119686 A, WO2012 19685 A1 and WO2012 9684 A.
  • Process are carried out, wherein the surface-printed oxide medium, which is prepared by a method in the context of the invention, in a temperature range between 50 ° C and 750 ° C, preferably between 50 ° C and 500 ° C, more preferably between 50 ° C. and 400 ° C, using one or more, sequentially performed
  • Temper Colouren (tempering by means of a step function) and / or an annealing ramp, dried and compacted to the glazing , whereby a grip and abrasion resistant layer is formed with a thickness of up to 500 nm.
  • a heat treatment of the glazed on the surfaces layers at a temperature in the range between 750 ° C and 1100 ° C, preferably between 850 ° C and 1100 ° C. , more preferably between 850 ° C and 1000 ° C.
  • silicon-doping atoms such as boron and / or phosphorus are silicothermal
  • Treatment duration can be transported in depths of up to 1 ⁇ and electrical sheet resistances of less than 0 ⁇ / sqr can be achieved.
  • the surface concentration of the dopant can thereby / assume values greater than or equal 1 * 1 * 10 19 to 10 21 atoms cm 3 and is dependent on the type of dopant used in the printable Oxidmedium. It has proved to be particularly advantageous hereby that the surface concentration of the parasitic doping of not intentionally protected (masked) and not covered with the printable oxide media surface areas of the silicon substrate against those areas which have been specifically printed with the printable oxide media by at least two powers of ten differ from each other. In addition, this result can be achieved by the
  • Oxide medium can be printed as a doping medium on hydrophilic (provided with wet chemical and / or native oxide) and / or hydrophobic (with silane termination provided) silicon wafer surfaces.
  • hydrophilic provided with wet chemical and / or native oxide
  • hydrophobic with silane termination provided
  • Dopant such as phosphorus
  • this process for producing grip- and abrasion-resistant oxidic layers, which have a doping effect on silicon and silicon wafers can be characterized in that a) oxide media are used as n-type doping media for printing on silicon wafers and the printed doping media are dried, compacted and then one be subjected to subsequent gas phase diffusion with phosphoryl chloride, whereby high doping in the printed areas are obtained and lower
  • Dopings can be achieved in the areas that are exposed exclusively to the gas phase diffusion,
  • silicon wafers are printed with the oxide media as p-type oxide medium, in this case with boron-containing precursors, dried on the printed doping medium, compacted and then exposed to a subsequent gas phase diffusion with boron trichloride or boron tribromide, whereby high doping in the printed
  • Obtained areas and a lower doping is achieved in those areas that are exposed exclusively to the gas phase diffusion, or
  • the printed on Dotiermedien dried, compacted and then subjected to a subsequent gas phase diffusion with, for example, phosphoryl chloride in the case of a used n-type Dotiermediüms or with, for example, boron trichloride or boron tribromide in the case of a p-type doping medium used, whereby high doping in the non-printed areas and lower dopants in the printed areas can be obtained insofar as the source concentration of the oxidic doping media used is kept controlled controlled low controlled and the glasses obtained from the doping media a diffusion barrier against the gas phase transported to the wafer surface and deposited gas phase diffusants
  • Doping medium is dried and / or compressed and from the compacted doped oxide medium by means of
  • Doping medium is dried and compacted and from the
  • the silicon wafer is printed either over the entire area or locally with oxide media as doping media, which may be n- and p-doping acting media, optionally through
  • alternating structures which are dried and densified on printed structures and coated with suitable diffusion barrier materials, such as sol-gel based silica layers, sputtered or APCVD or PECVD based silicon dioxide, silicon nitride or silicon dioxide
  • Encapsulated Siliziumoxynitrid rappelen and the doping acting oxide media are brought due to suitable heat treatment for doping of the substrate,
  • the silicon wafer is printed either over the entire area or locally with oxide media as doping media, which may be n- and p-doping media, optionally through
  • the silicon wafer is printed either over the entire area or locally with oxide media as doping media, which may be n- and p-doping media, optionally in alternating sequence, such as printed n-doping oxide medium of any structure width, for example line width , adjacent to non-printed silicon surface also characterized by an arbitrary pattern width, the printed structures are dried and compacted, after which the wafer surface is subsequently covered with a full surface
  • Wafer surface can be provided, the latter doping media printable sol-gel-based oxidic
  • Doping materials other printable doping inks and / or pastes, doped with APCVD and / or PECVD glasses and dopants from conventional gas phase diffusion and doping may be, and the overlapping arranged and doping acting doping due to suitable
  • Heat treatment can be brought to the doping of the substrate and in this context, the respective bottom, printed, doping oxide medium due to suitable
  • Silicon nitride or silicon oxynitride may be covered, but not necessarily must be
  • the Sitiziumwafer either over the entire surface or locally with oxide media as doping, which may be n-doping and p-doping acting media is printed, optionally in an alternating structure sequence, such as printed n-doping oxide medium of any structure width, for example, line width, adjacent not printed silicon surface also characterized by any structure width, the printed structures are dried and compacted, after which the Waferoberf laugh over the entire surface with a
  • Wafer surface can be provided, wherein the latter doping media printable sol-gel-based oxidic
  • Doping materials other printable doping inks and / or pastes, doped with APCVD and / or PECVD glasses and dopants from conventional gas phase diffusion and doping may be, and the overlapping arranged and doping acting doping due to suitable
  • Heat treatment can be brought to the doping of the substrate and in this context the bottom of each printed printed doping oxide medium due to appropriate
  • the majority-carrier contrary polarity inducing doping medium must behave; furthermore, the other side of the wafer surface by means of a different and otherwise deposited dopant source (printable sol-gel-based oxide dopants, other printable dopant inks and / or pastes, doped APCVD and / or PECVD glasses and dopants from the conventional Gas phase diffusion) which may or may not necessarily be covered by the same or opposite doping as that which can induce from the bottom layer of the opposite wafer surface.
  • a different and otherwise deposited dopant source printable sol-gel-based oxide dopants, other printable dopant inks and / or pastes, doped APCVD and / or PECVD glasses and dopants from the conventional Gas phase diffusion
  • Oxide media their drying, and compression and / or doping by thermal treatment resulting glass layers with a
  • Acid mixture containing hydrofluoric acid and optionally phosphoric acid etched wherein the etching mixture used as etchant hydrofluoric acid in a concentration of 0.001 to 10 wt .-% or 0.001 to 10 wt .-%
  • the dried and compacted doping glasses can contain hydrofluoric acid and 0.001 to 10 wt .-% phosphoric acid in the mixture.
  • the dried and compacted doping glasses can the
  • Nitric acid such as the so-called p-etching, R-etching, S-etching or etch mixtures, etching mixtures consisting of flux and
  • In-line diffusion can achieve industrial throughput rates that are typically between 5 to 25% above the usual throughput rates of conventional
  • Dotierstoffquellen wet by means of suitable coating methods spraying, rolling, screen printing, etc.
  • suitable coating methods sprayying, rolling, screen printing, etc.
  • Typical and commonly used dopant sources include, but are not limited to, dilute alcoholic (in ethanol or isopropanol) or even aqueous solutions of phosphoric or boric acid. Optimally, these solutions should become a homogeneous film on the
  • Silicon surfaces lead, so that a uniform delivery of the
  • Phosphoric and boric acids have an increasing oxidic character upon drying of the solution and thermal transformation to polymeric species.
  • the oxides in question are volatile and therefore very easy to auto-doping
  • the structuring also relates to the creation of differently doped regions in a basically arbitrary, but often alternating, sequence in which either high and low-doped regions of a polarity (n- or p-type) or doped regions of alternating polarities (n - on p-type and vice versa) alternate.
  • n- or p-type polarity
  • n - on p-type and vice versa doped regions of alternating polarities
  • Wafer surface can be deposited
  • the printable dopant sources offer the potential to allow sufficient surface concentrations of dopants for the subsequent ohmic contacting of the doped regions
  • the printable dopant sources must be able to be driven into the treated silicon wafer in a co-diffusion step and thus simultaneously
  • the doping effect of these media remains, as described above, but generally not limited to these structured areas.
  • the doping can therefore not be limited specifically to the deposited areas.
  • Doping media is the occurrence of a significant collapse of the
  • Minority carrier lifetime is an essential basic parameter that decides on the conversion efficiency of a solar cell: low lifetime equal low efficiency and vice versa. Therefore, for the expert speaks against the use of the previously known printable doping media. The adverse effect on carrier lifetime is evident by the raw materials used to make the dopant media
  • auxiliaries necessary for the paste formulation, and in particular the polymeric binders are a source of contamination which is difficult to control and which has a negative effect on the electronic performance of the silicon.
  • These adjuvants may contain undesirable, harmful metals and metal ions, the concentration of which is typically only in the per thousand range.
  • silicon reacts very sensitively to metallic ones
  • Typical and especially harmful contaminants are, for example, iron, copper, titanium, nickel and other transition metals from this group of the Periodic Table of the Elements. These metals also belong to the medium-fast to very fast-diffusing dopants in silicon (the diffusion coefficients are usually five to six orders of magnitude larger than that of the deliberately polluted dopants themselves), so that they can penetrate much deeper into the volume during the exposure period of the doping as the desired dopants themselves, and thus can affect not only the surface silicon, but also its entire volume.
  • binders added in the formulation of pastes are generally very difficult to even chemically clean up or free of their cargo of metallic trace elements. The effort to clean them is high and is due to the high cost in any
  • Paste residue after the thermal treatment of the wafer is required. Both phenomena are known.
  • the persistence of, for example, partially burned-out paste remnants on the wafer surface also leads, among other problems, to a possible reduction in the effective carrier lifetime.
  • the carrier lifetime is determined by their time-dependent recombination of the minority carriers in the volume of silicon as well as due to the recombination on the surface of the wafer. Because contaminants typically limit carrier lifetime, those adhered to the wafer surface also result in their reduction by dramatically increasing the recombination rate at the wafer surface.
  • the present invention can be achieved by means of printable, viscous oxide media according to the invention which can be prepared by a sol-gel process.
  • these oxide media can be produced by suitable additives as printable doping media (doping pastes).
  • novel high-viscosity doping pastes can be synthesized on the basis of the sol-gel process and, if necessary, can be formulated further.
  • the synthesis of the sol and / or gel can be achieved by adding
  • Condensation initiators e.g. of a carboxylic acid anhydride and / or a strong carboxylic acid, to be controlled specifically in the absence of water. Therefore, the viscosity is controllable via the stoichiometry, for example by the addition of the acid anhydride.
  • the degree of crosslinking of the silica particles can be adjusted, whereby a highly swollen and printable network can arise in the form of a pasty gel, which by means of various printing processes on surfaces, preferably on
  • Silicon wafer surfaces can be printed.
  • the sol-gel reaction can be stopped by adding small amounts of a protic solvent, for example by adding branched and unbranched, aliphatic, cyclic, saturated and unsaturated and aromatic mono-, di-, tri- and polyols (alcohols), and glycols, their monoethers, monoacetates and the like, propylene glycols, their monoethers and monoacetates, and binary, tertiary, quaternary and higher mixtures of such solvents in any volume and / or
  • a protic solvent for example by adding branched and unbranched, aliphatic, cyclic, saturated and unsaturated and aromatic mono-, di-, tri- and polyols (alcohols), and glycols, their monoethers, monoacetates and the like, propylene glycols, their monoethers and monoacetates, and binary, tertiary, quaternary and higher mixtures of such solvents in any volume and / or
  • Solvents can be combined.
  • Alkoxysilanes and / or alkoxyalkylsilanes in the presence or further organometallic compound, under partially acidic conditions are generally known to the person skilled in the art from the literature. To represent the
  • the invention can be found attached to examples that are executable in more or less modified form and lead to pastes according to the invention.
  • Suitable printing methods for the pastes according to the invention may be spin coating or dip coating, drop casting, curtain or slot dye coating, screen or flexo printing, gravure or ink jet or aerosol jet printing, offset printing, microcontact printing, electrohydrodynamic dispensing , Roller or Spray Coating, Ultrasonic Spray Coating, Pipe Jetting, Laser Transfer Printing, Päd Printing and Rotary Screen Printing.
  • the properties of the doping media according to the invention can be more selectively adjusted so that they are optimally suitable for special printing processes and for application to specific surfaces with which they can interact intensively. In this way you can target properties, such as
  • particulate additives eg aluminum hydroxides and
  • particulate additives eg aluminum hydroxides and
  • each printing and coating method has its own requirements for the paste to be printed.
  • parameters to be set individually for the respective printing method are those such as the surface tension, the
  • the printable media in addition to their use as Dotierquelie as scratch protection and corrosion protection layers, eg.
  • Dotierquelie as scratch protection and corrosion protection layers
  • photovoltaic components are in particular solar cells and modules.
  • applications in the electronics industry are characterized by the use of said pastes in the following exemplified but not exhaustively enumerated fields: fabrication of thin-film solar cells from thin-film solar modules, organic solar cell manufacturing, printed circuit and organic electronics manufacturing, manufacturing of
  • Display elements based on the technologies of thin-film transistors (TFT), liquid crystals (LCD), organic light-emitting diodes (OLED) and touch-sensitive capacitive and resistive sensors.
  • TFT thin-film transistors
  • LCD liquid crystals
  • OLED organic light-emitting diodes
  • the print layout corresponds to a typical front side metallization with two busbars and a typical number of collecting electrode fingers, for example 68.
  • the nominal opening width of the electrode fingers is 100 pm. The fingers settle already after a small number of prints during the printing with paste drying in the structures. Less than ten substrates can be printed error-free.
  • the print layout corresponds to a square with 4 cm edge length. After this Printing the wafers are dried on a hot plate at 300 ° C for 2 minutes and then immediately introduced into a heated to 900 ° C muffle furnace. Depending on the exposure time in the muffle furnace, the doping effect is assessed. After doping the wafers, they are etched with 5% hydrofluoric acid solution, then in one at 50 ° C.
  • Example 1 shows a photograph of a wafer, printed and dried with a doping paste according to Example 2.
  • Table 1 Cleaning result using textured monocrystalline wafers as a function of the doping time in a muffle furnace when using a doping paste according to Example 2.
  • Table 2 Doping power when using textured monocrystalline wafers as a function of the exposure time in a muffle furnace using a doping paste according to Example 2. When using unilaterally polished silicon wafers show identical dependencies of the same under the same treatment conditions
  • Figure 2 shows a photomicrograph of a single-sided polished wafer doped for 10 minutes while maintaining the parameters described above using a paste according to Example 2. The photograph shows the wafer surface after cleaning.
  • Fig. 3 shows a photomicrograph of a single-sided polished wafer doped for 20 minutes using the parameters described above using a paste according to Example 2. The photograph shows the wafer surface after cleaning.
  • Figure 4 shows a photomicrograph of a single-sided polished wafer doped for 30 minutes using the parameters described above using a paste according to Example 2. The photograph shows the wafer surface and the boundary between printed and non-printed area after cleaning.
  • Figure 5 shows a photomicrograph of a single-sided polished wafer doped for 10 minutes using the parameters described above using a paste according to Example 2. The photograph shows the wafer surface and the boundary between printed and unprinted area after cleaning.
  • Table 3 Doping performance when using single-sided polished monocrystalline wafers depending on the exposure time in a muffle furnace
  • the doping effect of the paste obviously depends on the particular surface morphology of the substrates used.
  • the factor between the real and the apparent area of the surface is 1.73; d. h., that an identical concentration of dopant in the paste and resulting therefrom, provided that the same amount at the same
  • the doping paste has a nominal mass content of 29.2% silicon dioxide and 70.2% phosphorus oxide (provided that the entire organic material is completely removed and assuming that, despite the relatively high vapor pressure of P4O10, this does not result in mass loss during burnout of volatilization).
  • the doping paste has after a storage period of a few days one cuboid and gelatinous consistency, which further compresses to a relative solid gel.
  • the doping paste has a nominal (after all the organics are completely removed) burnout, assuming that despite the relatively high vapor pressure of P4O10, this loses no bulk loss due to volatilization on burnout.) Mass content of 45.2% silica and 54 , 8% phosphorus oxide.
  • the paste is then printed on silicon wafer with a screen printer. A sieve with the following parameters is used: 280 mesh, 25 ⁇ m thread strength (stainless steel), covering angle 22.5 °, 8 - 2 ⁇ m
  • Emulsion thickness over tissue The jump is 1, 1 mm and the squeegee pressure 1 bar.
  • the print layout corresponds to a square with 4 cm edge length.
  • the wafers are dried on a hot plate at 300 ° C for 2 minutes and then immediately placed in a heated to 900 ° C muffle furnace. Depending on the exposure time in the muffle furnace, the doping effect is subsequently assessed. After doping the wafers, they are etched with 5% hydrofluoric acid solution, then treated in a heated to 50 ° C, coupled with ultrasound water bath for 5 minutes and finally re-etched with 5% hydrofluoric acid. The cleaning effect on the wafers is dependent on their exposure time in the muffle furnace.
  • Table 4 Doping performance when using single-sided polished monocrystalline wafers depending on the exposure time in a muffle furnace
  • Fig. 6 shows the doping profile (ECV profile) of a one-sided polished
  • the paste has a dynamic viscosity of 5.1 Pa * s, measured at a shear rate of 25 1 / s, and a cubed gelatinous consistency and compacts into a gel in a few days' storage time.
  • the doping paste has a nominal (after all the organics are completely removed) burnout, assuming that despite the relatively high vapor pressure of P4O10, this will not lose mass due to volatilization on burnout.) Mass content of 34.5% silica and 64 , 5% phosphorus oxide.
  • the paste is then printed on silicon wafer with a screen printer.
  • a sieve with the following parameters is used: 280 mesh, 25 ⁇ m thread strength (stainless steel), wrap angle 22.5 °, 8-12 ⁇ m emulsion thickness over fabric.
  • the jump is 1, 1 mm and the squeegee pressure 1 bar.
  • the print layout corresponds to a square with 4 cm Edge length. After printing, the wafers are dried on a hot plate at 300 ° C for 2 minutes and then immediately placed in a heated to 900 ° C muffle furnace. Depending on the exposure time in the muffle furnace, the doping effect is assessed.
  • the wafers After doping the wafers, they are etched with 5% hydrofluoric acid solution, then treated in a heated to 50 ° C, coupled with ultrasound water bath for 5 minutes and finally re-etched with 5% hydrofluoric acid.
  • the cleaning effect on the wafers is dependent on their exposure time in the muffle furnace.
  • Table 5 Doping performance using single-side polished monocrystalline wafers as a function of the exposure time in a muffle furnace using a doping paste according to Example 4.
  • Table 6 Doping performance using single-side polished monocrystalline wafers as a function of the exposure time in a muffle furnace using a doping paste according to Example 5.
  • the paste shows after a storage period of several weeks, the formation of finely dispersed white crystals or agglomerates.
  • Example 6 33 g of ethylene glycol monophenyl ether, 33 g of Texanol, 50 g of dibenzyl ether, 50 g of butyl benzoate are placed in a beaker and 3.75 g of phosphorus pentoxide (P 4 Oi 0 ) are introduced with vigorous stirring. It is stirred until the Phosporpentoxid has completely dissolved. The result is a slightly yellowish solution. 7.15 g of tetraethylorthosilicate and 8 g of ethylcellulose are added to these solutions and the mixture is stirred until a pasty mass is formed.
  • the paste has a dynamic viscosity of 10 Pa * s, measured at a shear rate of 25 1 / s. The paste shows after a storage period of a few days, the formation of finely dispersed white crystals or agglomerates.
  • a sieve with the following parameters is used: 280 mesh, 25 ⁇ m thread thickness (Stainless steel), covering angle 22.5 °, 8-12 ⁇ emulsion thickness over fabric.
  • the jump is 1.1 mm and the squeegee pressure 1 bar.
  • the print layout corresponds to a square with 4 cm edge length. After printing, the wafers are dried on a hotplate at 300 ° C for 2 minutes and then immediately introduced into a muffle furnace heated to 900 ° C for 20 minutes. After doping the wafers, they are etched with 5% hydrofluoric acid solution for 2 minutes and then thoroughly rinsed with water. The determination of the sheet resistance in the area printed with the paste gives a value of 23 ⁇ / sqr. The
  • Tetraethylorthosilicate 19 g of DL-lactic acid and 4.8 g of water are added and the mixture is heated to 125 ° C with stirring for 30 h. It arises a supple, colorless, slightly cloudy gel mass. The gel is screen printed on textured monocrystalline wafers. The following sieving and printing parameters are used: 280 mesh, 25 ⁇
  • Thread thickness (stainless steel), covering angle 22.5 °, 8 - 12 pm
  • Emulsion thickness over tissue The jump is 1, 1 mm and the squeegee pressure 1 bar.
  • the print layout corresponds to a square with 2 cm edge length.
  • the wafers are dried on a hotplate at 300 ° C for 2 minutes and then immediately introduced into a muffle furnace heated to 900 ° C for 20 minutes. After doping the wafers, they are etched with 5% hydrofluoric acid solution for 2 minutes and then thoroughly rinsed with water.
  • the printed on the wafer figure has a white-grayish color.
  • the resulting layer can be easily removed after drying on the hot plate by intensive rubbing.
  • no sheet resistance can be determined by means of four-point measurement after the doping.
  • FIG. 10 shows a photograph of the region of a textured monocrystalline silicon wafer printed with doping paste by screen printing. The picture was taken after a two-minute annealing of the wafer on the hotplate. The whitish-gray layer is not grip and abrasion resistant.
  • Tetraethylorthosilicate and 19 g of lactic acid are added and the mixture is heated to 90 ° C with stirring for 70 h.
  • the result is a transparent gel with a smooth consistency.
  • the mixture is then treated at 75 ° C for one hour on a rotary evaporator at 60 mbar.
  • the determination of the mass difference of the gel before and after the treatment on a rotary evaporator gives a mass loss of 8 g.
  • the gel has a nominal content of 3.4% Si0 2 in the paste and a nominal content of 58.7% S1O2 and 41.3% phosphorus oxide in the glass matrix, assuming that the organic constituents of the paste are completely burned out and during burnout, no loss of the phosphorus oxide contained in the paste occurs.
  • the gel is
  • the print layout corresponds to a square with 2 cm edge length. After printing, the wafers are dried on a hot plate at 300 ° C for 2 minutes (gripping and abrasion resistant) and then immediately introduced into a heated to 900 ° C muffle furnace for 20 minutes. After doping the wafers, they are etched with 5% hydrofluoric acid solution for 2 minutes and then thoroughly rinsed with water. The determination of the sheet resistance
  • Fig. 11 shows a microscope photograph of a doping with means
  • Silicon wafer The recording is done after the two-minute annealing of the wafer on the hot plate.
  • FIG. 12 shows a photograph of a region of a textured monocrystalline silicon wafer printed by means of screen printing with doping paste.
  • FIG. The recording has taken place after the doping of the wafer in the muffle furnace.
  • the preparation of the paste can also with different content of
  • Paste blends found that contain 8.1 g and 9.7 g
  • a paste prepared using the latter amount of phosphoric acid has a dynamic viscosity of 5 Pa * s, measured at a shear rate of 25 l / s.
  • Paste according to the invention can be used successfully: formic acid, acetic acid, oxalic acid, trifluoroacetic acid, mono-, di- and
  • the reaction time depends on the
  • Reaction temperature is between 4 h and 400 h.
  • the pastes produced in this way are storage-stable and have no formation of agglomerations or break-ins in their doping effects which are dependent on the respective storage period. Furthermore, the pastes produced according to Example 10 can be modified by the targeted addition of monofunctional or monoreactive (capping agent) siloxanes, whereby the storage stability of the doping media can be specifically increased.
  • monofunctional siloxanes may be:
  • FIG. 13 shows a microscope image of the region of a single-sidedly polished monocrystalline region which is printed by means of screen printing with doping paste
  • Tetraethylorthosilicate and 19 g of oxalic acid are added and the mixture is heated to 140 ° C with stirring for 4 h.
  • the result is a transparent gel with a smooth consistency.
  • the mixture is then treated at 75 ° C for one hour on a rotary evaporator at 60 mbar.
  • the gel is then homogenized in a high shear mixing apparatus with the addition of 2 ml of ethoxytrimethylsilane, allowed to rest for one day and then printed on textured and one-side polished monocrystalline wafers using a screen printer.
  • the following screen and printing parameters are used for this: 280 mesh, 25 ⁇ m
  • Thread thickness (stainless steel), covering angle 22.5 °, 8 - 12 m
  • Emulsion thickness over tissue is 1, 1 mm and the squeegee pressure 1 bar.
  • the print layout corresponds to a square with 2 cm
  • the wafers are dried on a hot plate at 300 ° C for 2 minutes (gripping and abrasion resistant) and then immediately introduced into a heated to 900 ° C muffle furnace for 20 minutes. After doping the wafers, they are etched with 5% hydrofluoric acid solution for 2 minutes and then thoroughly rinsed with water.
  • the determination of the sheet resistance (multiple determination) in the area printed with the paste gives values of on average 32 Q / sq., The sheet resistance outside the printed figure is> 1000 ⁇ / sqr.
  • the wafers are dried on a hot plate at 300 ° C for 2 minutes (gripping and abrasion resistant) and then immediately introduced into a heated to 900 ° C muffle furnace for 20 minutes. After doping the wafers, they are etched with 5% hydrofluoric acid solution for 2 minutes and then thoroughly rinsed with water.
  • the determination of the sheet resistance (multiple determination) in the area printed with the paste gives values of on average 35 ⁇ / sqr.
  • the sheet resistance outside the printed figure is> 1000 ⁇ / sqr.
  • Dibenzylether added. To this solution is added 23 g of tetraethylorthosilicate and 19 g of formic acid, and the mixture is refluxed with stirring for 30 minutes. The result is a transparent gel with a smooth consistency. The mixture is then treated at 75 ° C for one hour on a rotary evaporator at 60 mbar. The gel is then homogenized in a mixer with high shear and addition of 2 ml of ethoxytrimethylsilane.
  • Butoxy) ethoxy) ethylene glycol acetate To this solution is added 23 g of tetraethyl orthosilicate and 19 g of glycolic acid, and the mixture is refluxed with stirring for 45 minutes. The result is a transparent gel with a smooth consistency. The mixture is then treated at 75 ° C for one hour on a rotary evaporator at 60 mbar. The gel is then homogenized in a blender with high shear and addition of 2 ml of ethoxytrimethylsilane.
  • the print layout corresponds to a square with 2 cm edge length.
  • the wafers are dried on a hot plate at 300 ° C for 2 minutes (grip and abrasion resistant) and then immediately heated to 900 ° C Muffle furnace introduced for 20 minutes. After doping the wafers, they are etched with 5% hydrofluoric acid solution for 2 minutes and then thoroughly rinsed with water. The determination of the sheet resistance (multiple determination) in which with the paste
  • Sheet resistance outside the printed figure is> 1000 ⁇ / sqr.
  • reaction mixture 1 tetrahydrofuran
  • reaction mixture 1 79 g of the reaction mixture consisting of tetrahydrofuran, acetic anhydride and the condensate of phosphoric acid and tetraethyl orthosilicate are introduced into the dropping funnel (reaction mixture 1). After reaching the aforementioned
  • the paste is supple and creamy and very easy to process by screen printing. For this purpose, a printing screen with a mesh count of 165 cm "1 , a thread thickness of 27 pm (polyester), a
  • the print layout corresponds to a square with 2 cm edge length.
  • the wet film mass applied during printing can be varied between 0.6 mg / cm 2 to 1.5 mg / cm 2 as a result of the targeted influencing of the printing parameters.
  • the wafers are dried on a hot plate at 300 ° C for 2 minutes (grip and abrasion resistant) and then immediately placed in a heated to 950 ° C muffle furnace for 15 minutes. After doping the wafers, they are etched with 5% hydrofluoric acid solution for 2 minutes and then thoroughly rinsed with water.
  • the determination of the sheet resistance (multiple determination) in the area printed with the paste gives values of on average 33 ⁇ / sqr.
  • Sheet resistance outside the printed figure was> 1000 ⁇ / sqr.
  • the heat source is removed and allowed to cool the gel in the apparatus.
  • the water separator collects a distillate mass of about 89 g.
  • the cooled paste is then attached to a
  • Ethoxytrimethylsilane can also be carried out at 60 ° C for 1 h when heated again.
  • the paste is supple and creamy and very good
  • the print layout corresponds to a square with 2 cm edge length.
  • the wet film mass applied during printing can be varied between 0.6 mg / cm 2 to 1.5 mg / cm 2 as a result of the targeted influencing of the printing parameters.
  • the wafers are dried on a hot plate at 300 ° C for 2 minutes (grip and abrasion resistant) and then immediately placed in a heated to 950 ° C muffle furnace for 15 minutes. After doping the wafers, they are etched with 5% hydrofluoric acid solution for 2 minutes and then thoroughly rinsed with water.
  • the determination of the sheet resistance (multiple determination) in the area printed with the paste gives values of on average 37 ⁇ / sqr.
  • Sheet resistance outside the printed figure is> 1000 ⁇ / sqr
  • the content of acetic anhydride in the reaction mixture 1 according to Example 18 can be varied. It has proved to be advantageous for this purpose to use masses between 50 g and 204 g of the reactant. If the amount of acetanhydride presented in the reaction mixture exceeds 100 g, the Tetraethylorthosilicat can also without the addition of
  • Tetrahydrofuran be dropped into the warm reaction mixture. Furthermore, the duration of refluxing may be complete after all additions have been made Reactants be between 30 minutes and 240 minutes.
  • Suitable inert solvents other than tetrahydrofuran are other sufficiently polar and non-protic solubilizers, such as 1,4-dioxane and dibenzyl ether, into account, although other comparable solvents can be used for this purpose.
  • the synthesis of the doping paste can also be carried out in modified form, including in a
  • Tetraethyl orthosilicate is then slowly and carefully added dropwise to a mixture of the appropriate amount of phosphoric acid dissolved in tetrahydrofuran and acetic anhydride.
  • the reaction starts immediately when added dropwise and is highly exothermic.
  • the temperature of the preheated tetraethylorthosilicate essentially determines the rate of dropping to be used, with the following rule being true: the warmer the slower the sequence of drops. It is especially at the point of drop to pay attention to spontaneously occurring precipitation, which should be avoided.
  • Temperature low-boiling components are expelled, which can be advantageously removed by means of a water separator from the reaction mixture.
  • the progress of the reaction can be monitored by increasing the viscosity.
  • Reaction mixture begins to assume a syrup-like character, this is by means of the second reaction mixture, consisting of a solution of those mentioned in the aforementioned examples
  • Reaction mass dissolves smoothly in the inflowing reaction mixture.
  • the formation of a glassy mass from the syrup-like reaction mixture should be avoided at all costs.
  • the reaction is continued after the overlay until gelation begins.
  • Fig. 1 Recording a wafer printed and dried with a
  • Fig. 2 Microscopic image of a wafer polished on one side, doped for 10 minutes with a paste according to Example 2. The photograph shows the wafer surface after cleaning.
  • Fig. 3 Microscopic image of a wafer polished on one side, doped for 20 minutes with a paste according to Example 2. The photograph shows the wafer surface after cleaning.
  • Fig. 4 Microscopic image of a wafer polished on one side, doped for 30 minutes with a paste according to Example 2. The image shows the wafer surface and the boundary between printed and non-printed area after cleaning.
  • Fig. 5 Microscopic image of a wafer polished on one side, doped for 10 minutes with a paste according to Example 2. The image shows the wafer surface and the boundary between printed and not
  • FIG. 8 Doping profile (ECV profile) of a single-side polished monocrystalline wafer after 20 minutes of treatment with the doping paste according to Example 8.
  • FIG. 10 shows a region of a textured monocrystalline silicon wafer printed with doping paste by screen printing.
  • FIG. after two minutes of tempering on the hot plate.
  • FIG. 12 Recording of a region of a textured monocrystalline silicon wafer printed with doping paste by screen printing after doping in the muffle furnace.
  • FIG. 13 Microscope image of the area of a monocrystalline polished on one side with doping paste by means of screen printing
  • FIG. 14 Doping profile (ECV measurement) of a silicon wafer polished on one side, printed with the doping paste according to the invention (sheet resistance on average 26 ⁇ / sqr).
  • FIG. 15 Recording of a region of a textured monocrystalline with screen printing printed with doping paste according to Example 17

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Abstract

La présente invention concerne un nouveau procédé de production de substances d'oxydes à haute viscosité, imprimables, et leur utilisation dans la production de cellules solaires.
EP13817883.5A 2012-12-28 2013-12-18 Substances de dopage destinées au dopage local de tranches de silicium Withdrawn EP2938761A1 (fr)

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