Classifications

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  • H10F77/30—Coatings
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  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
  • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
  • C23C18/12—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
  • C23C18/1295—Process of deposition of the inorganic material with after-treatment of the deposited inorganic material
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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
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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
  • C23C18/122—Inorganic polymers, e.g. silanes, polysilazanes, polysiloxanes
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  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
  • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
  • C23C18/12—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
  • C23C18/1229—Composition of the substrate
  • C23C18/1245—Inorganic substrates other than metallic
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
  • C23C18/14—Decomposition by irradiation, e.g. photolysis, particle radiation or by mixed irradiation sources
  • C23C18/143—Radiation by light, e.g. photolysis or pyrolysis
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  • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
  • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
  • H01L21/02104—Forming layers
  • H01L21/02365—Forming inorganic semiconducting materials on a substrate
  • H01L21/02367—Substrates
  • H01L21/0237—Materials
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  • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
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  • H01L21/02365—Forming inorganic semiconducting materials on a substrate
  • H01L21/02518—Deposited layers
  • H01L21/02521—Materials
  • H01L21/02524—Group 14 semiconducting materials
  • H01L21/02532—Silicon, silicon germanium, germanium
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  • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
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  • H01L21/02104—Forming layers
  • H01L21/02365—Forming inorganic semiconducting materials on a substrate
  • H01L21/02612—Formation types
  • H01L21/02617—Deposition types
  • H01L21/02623—Liquid deposition
  • H01L21/02628—Liquid deposition using solutions
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  • H10F71/00—Manufacture or treatment of devices covered by this subclass
  • H10F71/10—Manufacture or treatment of devices covered by this subclass the devices comprising amorphous semiconductor material
  • H10F71/103—Manufacture or treatment of devices covered by this subclass the devices comprising amorphous semiconductor material including only Group IV materials
  • H10F71/1035—Manufacture or treatment of devices covered by this subclass the devices comprising amorphous semiconductor material including only Group IV materials having multiple Group IV elements, e.g. SiGe or SiC
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  • H10F71/121—The active layers comprising only Group IV materials
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  • H10F71/00—Manufacture or treatment of devices covered by this subclass
  • H10F71/121—The active layers comprising only Group IV materials
  • H10F71/1215—The active layers comprising only Group IV materials comprising at least two Group IV elements, e.g. SiGe
  • H10F71/1218—The active layers comprising only Group IV materials comprising at least two Group IV elements, e.g. SiGe in microcrystalline form
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  • H10F71/128—Annealing
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  • H10F77/00—Constructional details of devices covered by this subclass
  • H10F77/10—Semiconductor bodies
  • H10F77/12—Active materials
  • H10F77/122—Active materials comprising only Group IV materials
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  • H10F77/10—Semiconductor bodies
  • H10F77/16—Material structures, e.g. crystalline structures, film structures or crystal plane orientations
  • H10F77/162—Non-monocrystalline materials, e.g. semiconductor particles embedded in insulating materials
  • H10F77/164—Polycrystalline semiconductors
  • H10F77/1642—Polycrystalline semiconductors including only Group IV materials
  • H10F77/1648—Polycrystalline semiconductors including only Group IV materials including microcrystalline Group IV-IV materials, e.g. microcrystalline SiGe
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  • H10F77/10—Semiconductor bodies
  • H10F77/16—Material structures, e.g. crystalline structures, film structures or crystal plane orientations
  • H10F77/169—Thin semiconductor films on metallic or insulating substrates
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E10/00—Energy generation through renewable energy sources
  • Y02E10/50—Photovoltaic [PV] energy
  • Y02E10/547—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
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E10/00—Energy generation through renewable energy sources
  • Y02E10/50—Photovoltaic [PV] energy
  • Y02E10/548—Amorphous 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
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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• • 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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  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31652—Of asbestos
  • Y10T428/31663—As siloxane, silicone or silane

Definitions

• the invention relates to a method for reducing or eliminating the bandgap shift in the manufacture of photovoltaic devices by coating a substrate with a formulation containing a silicon compound, e.g. In the manufacture of a solar cell, comprising a step of coating a substrate with a liquid silane formulation.
• the invention also relates to the production method of such a photovoltaic device.
• the conventional production of solar cells consists either in the counter doping of a doped semiconductor substrate by implantation or diffusion or deposition of a counter doped semiconductor layer on a doped semiconductor substrate by epitaxy or in the deposition of semiconductor layers of different doping from the gas phase in vacuum or variants of said methods.
• the disadvantage of all these methods is the economic and cost outlay that must be operated with it.
• a pn junction By depositing one or more layers of these silanes on a suitable substrate, a pn junction can be created which acts as a solar cell. The deposition takes place by means of a spin coater. The resulting layers are stabilized by a suitable temperature treatment, so that they typically assume a mixture of microcrystalline, nanocrystalline and amorphous (in short: polymorphic) structures. Unless explicitly stated, all microcrystalline, nanocrystalline and / or amorphous layers should be referred to as "polymorphic" in general, since a precise differentiation and definition is in most cases not well possible or is of secondary importance for the result obtained. How to produce silicon layers from silanes is known per se.
• GB 2077710 teaches the preparation of polysilanes of the general formula - (SiH 2 ) n - with n> 10 by simultaneous reduction and polymerization of SiH 2 Cl 2 with alkali metals.
• Such higher silanes are named as precursors for silicon layers, eg. B. for solar cells.
• JP 7267621 teaches the preparation of silicon layers from films of such silanes which are first UV-exposed in the cold and then heated to temperatures above 400 ° C
• These silanes are partially or completely oligomerized, z. B. by heating and / or UV irradiation.
• special phosphorus compounds or boron compounds are added in order to achieve an n- or p-type doping.
• the thin layers produced according to the prior art show an optical-electrical property, which is referred to as blue shift (blue shift) and is known from other examined objects.
• blue shift blue shift
• characteristic quantities-in the present case the diameter of the silicon particles-have values in the nanometer range the optical parameters shift into the blue.
• the absorption of photons by the resulting silicon layers begins only in the blue, while the absorption in the other spectral regions of the sun is considerably lower than for conventional monocrystalline silicon.
• solar cells have a maximum efficiency when the material used has a band gap of 1, 1 to 1, 5 eV. An increase in the band gap on z. B.
• the object of the present invention was to avoid the disadvantage of the relatively low energy yield of the incident sunlight in solar cells based on a sequence of thin polymorphic silicon layers, which were produced by spin-on deposition or a similar method, due to the large band gap shift. to cancel or compensate, without sacrificing the cost and procedural advantages that - in contrast to the solar cells based on single crystal - are connected to the alternatively produced solar cells based on thin polymorphic silicon layers.
• the cost and procedural advantages also exist in comparison with the thin-layer method in complex vacuum chambers, so-called.
• This object is achieved by a method for reducing or eliminating the band gap shift, which is observed in a solar cell or other photovoltaic device, wherein the manufacturing method of this solar cell or the photovoltaic device comprises a step in which a substrate having a formulation containing at least a silicon compound is coated, the process being characterized in that the formulation additionally contains at least one germanium compound.
• a photovoltaic device with improved energy efficiency of the irradiated sunlight can be produced.
• These include solar cells with only one diode sequence as well as tandem solar cells with more than one active diode.
• the energy yield can be improved because the large band gap shift ("blue shift"), which is observed when working with a formulation containing only silicon in the production of the photovoltaic device, is compensated for again by adding the germanium, so that the "bad" polymorphic silicon layer is “improved” again.
• the bandgap of typically over 1.9 eV can again be set to values of e.g. B. 1, 3 to 1, 5 eV are set. This again restores properties of polymorphic silicon with that for AM radiation, e.g. AM1 to AM1, 5 radiation, optimum band gap achieved, but with the significant advantage of thin film thickness and a favorable manufacturing process.
• the desired effect of "correcting" the band gap shift can be achieved whenever the germanium together with the silicon forms a polymorphic silicon germanium layer, on the one hand the proportion of germanium and on the other hand the degree and / or the nature of its distribution within the Silicon might affect the size of the bandgap. Therefore, in principle, all germanium compounds or germanium itself, if a corresponding distribution of the germanium in the silicon-germanium layer can be achieved by the coating method.
• germanium-hydrogen compounds ie, germanes and oligo- or polygermanes
• germanium-hydrogen compounds ie, germanes and oligo- or polygermanes
• germanium-hydrogen compounds ie, germanes and oligo- or polygermanes
• germanium-hydrogen compounds ie, germanes and oligo- or polygermanes
• germanium-hydrogen compounds ie, germanes and oligo- or polygermanes
• GeH 4 can be circulated under reduced pressure by a silent electric charge (see, for example, Hollemann-Wiberg, Lehrbuch der Anorganischen Chemie, 101st Edition, Verlag Walter de Gruyter, 1995, p 956, or E. Wiberg, E Amberger "Hydrides", Elsevier, Amsterdam 1971, pp. 639-718.)
• the germanium compounds can also be partially or completely oligomerized by irradiation or thermal treatment, with molar masses of from 500 g / mol 10000 g / mol, preferably 800 g / mol to 5000 g / mol, particularly preferably 1000 to 3000 g / mol can be set.
• the proportion of germanium in the silicon-containing formulation with which the substrate is coated is preferably 0.5 to 15.0 mol%, particularly preferably 3.0 to 12.0 mol%, very particularly preferably 4 , 0 to 10.0 mol .-%, based on the proportion of pure silicon and germanium. It is known from the literature that the band gap decreases approximately linearly from 1.8 eV to 1.35 eV with an addition of 18% GeH 4 , see FIG. 2 (D. Tahir, RACMM van Swaaij: High Quality Hydrogenated Amorphous Silicon -Germanium Alloys for Grading Purposes at the Inthnsic Layer Tandem Solar CeIIs, SAFE 2001: proceedings CD-ROM (pp. 191-194), Utrecht: STW technology foundation, TUD).
• the subject of the present invention also includes the above-mentioned production method itself, that is, the production method z.
• the method comprises a step in which a substrate is coated with a formulation containing at least one silicon compound, and the method is characterized in that the formulation additionally contains at least one germanium compound ,
• a general embodiment of the method according to the invention for producing a photovoltaic device comprising at least one layer consisting predominantly of silicon, preferably for producing a solar cell preferably comprises the steps: a) providing a substrate, b) providing a formulation containing at least one silicon compound, c ) Coating the substrate with the formulation, d) irradiating and / or thermally treating the coated substrate to form an at least partially polymorphic layer consisting predominantly of silicon, characterized in that the formulation additionally contains at least one germanium compound, so that the layer formed contains germanium in such a way that there is an at least partially polymorphic layer consisting predominantly of silicon germanium.
• n-Si and p-Si layer dopants are added, which are in the case of n-doping z. B. phosphorus compounds and in the case of p-doping z. B. boron compounds.
• z. B. additionally also an undoped i-Si layer can be arranged therebetween.
• the Proportion of pure silicon and germanium in the silicon-containing formulation used for coating and the proportion of germanium in the silicon-germanium layer is typically within these ranges. Since, depending on the coating and / or thermal treatment conditions and depending on the chemico-physical properties of the silicon and germanium compounds used different losses of silicon and germanium based on the amounts used in the coating and thermal treatment may be different Mol .-% - levels of germanium in the formulation used and the finished silicon germanium layer result.
• the bandgap shift may also be linked to the morphology, i. H.
• Various Si / Ge compositions can also affect the morphology, so that here too a deviation from the purely computational effect of the composition may result.
• the compounds mentioned can be partially or completely oligomerized, with molecular weights of from 500 g / mol to 10,000 g / mol, preferably from 1000 g / mol to 5000 g / mol.
• the silicon compounds, such as the above-described germanium compounds partially or entirely oligomerized by irradiation or thermal treatment, wherein molar masses of 500 g / mol to 10,000 g / mol, preferably 800 g / mol to 5000 g / mol, more preferably 1000 g / mol to 3000 g / mol can be adjusted.
• silicon-hydrogen compounds ie silanes and oligo- or polysilanes
• these are accessible by chemical syntheses or catalytic annulation of SiH 4 , a high silicon content based on the molecular weight have the compounds and can be easily formulated with the preferred Germanic.
• Numerous examples of fundamentally suitable polysilanes can be found in WO 2007/044429 A2.
• the silicon and germanium containing formulation used in the methods of the invention is typically a liquid formulation. This consists of the aforementioned silicon and germanium compounds and optionally in admixture with solvents. Suitable solvents are, for. B. liquid at room temperature aliphatic or aromatic hydrocarbons and mixtures thereof. Examples are octane, nonane, decane, toluene, xylene, mesitylene, cyclooctane. The viscosity of the coating solution is typically 200 to 2000 mPas.
• oligomerization by means of UV irradiation or heat treatment higher silanes and germanes of the abovementioned formulas with n> 3 are used.
• a desired higher-viscosity liquid mixture containing oligo- / polygermanes, oligo- / polysilanes and / or corresponding copolymers / cooligomers can be prepared.
• solvent, dopants and / or other auxiliaries may be added. These further agents or substances can be added to the mixture independently of each other before the oligomerization and / or polymerization or only afterwards.
• the oligomerization and / or polymerization can be carried out partially or completely by irradiation or thermal treatment, wherein molar masses of 500 g / mol to 10000 g / mol, preferably 800 g / mol to 5000 g / mol, particularly preferably 1000 g / mol to 3000 g / mol, can be adjusted.
• WO 2007/044429 A2 can be found on page 13, line 14 to page 28, line 20, a large number of silicon and germanium-containing compounds, which can also be used in the process of the invention.
• the compounds and mixtures described therein may be part of the formulations described herein or used directly as these formulations.
• the solvent, dopants and / or other auxiliaries optionally additionally added to the silicon- and germanium-containing formulation may be added before, during and / or after the coating.
• the proportion of solvent based on the total formulation may be from 5 to 93% by weight, preferably from 15 to 60% by weight, particularly preferably from 25 to 45% by weight.
• the coating of the substrate with the silicon and germanium-containing formulation can be carried out in a known manner. Typical processes are: pouring, spin-on deposition, liquid phase sputtering, knife coating and rollcoating. In a preferred embodiment of the method according to the invention, the coating of the substrate takes place by means of spin-on deposition.
• the irradiation and / or thermal treatment of the coated substrate can also be carried out in a known manner.
• the substrate coated with the formulation is heated to temperatures of 300 to 1000 ° C., preferably 400 to 900 ° C., more preferably 500 to 800 ° C.
• an upstream curing by crosslinking can also be carried out with a UV lamp (eg wavelength 254 nm, power 15 watts or wavelength 180 nm).
• the coated substrate is supplied to a thermal treatment without irradiation. As heating units come z.
• the temperatures range from 300 0 C to 1000 0 C.
• the layers can also be post-treated by heating under Formiergas mixtures Hydrogen and nitrogen, or of hydrogen and argon (eg, H 2 / N 2 in volume ratio 5/95 to 10/90 or H 2 / Ar in volume ratio 5/95 to 10/90) at temperatures of 350 0 C to 800 0 C, preferably 400 0 C to 700 0 C.
• Suitable substrates are semiconductor wafers, metals, metal alloys, graphite or other conductive carbon substrates or other conductive formulations, eg. As metal flakes in a carbon matrix and coated with a conductive material insulators such as glass, ceramic or temperature-resistant plastics. In the case of coated insulators, care should be taken that the subsequent coverage of the substrate with silicon-germanium is not complete in terms of area, so that a conductive connection, eg. B. remains for power dissipation.
• Another object of the present invention is a photovoltaic device, in particular a solar cell or solar cell combinations, for. B. Tandem cells, which was prepared using the process of the invention described herein or can be prepared.
• the present invention also includes in particular the use of a germanium compound in a production method for a photovoltaic device, if the method comprises a step in which a substrate is coated with a formulation comprising at least one silicon compound and the formulation additionally comprises at least one such germanium compound. Contains connection.
• FIG. 1 shows a Tauc plot for determining the bandgap of amorphous, multicrystalline or polymorphic semiconductors. Plotted is the square root of the product of the absorption coefficient (in cm “1 ) and photon energy (in eV) versus the photon energy, the quadrilaterals are the measured values and the regression lines are laid in. The intersection of the lines with the abscissa provides the bandgap (ropes, Grigorovici, Vancu (1966), Phys. Stat., Sol. 15, 627) The "higher silane silicon" curve was obtained from Comparative Example 1.
• FIG. 2 shows the optical band gap as a function of the Ge addition in mol%.
• the squares are values according to Tahir and van Swaaij (High Quality Hydrogenated Amorphous Silicon-Germanium Alloys for Grading Purposes at the Intrinsic Layer Tandem Solar Cell, SAFE 2001: proeeedings CD-ROM (pp. 191-194), Utrecht: STW technology foundation, TUD), the circles are values from the claims. As a reading aid, the values from the claims were connected by means of a compensation curve. Examples
• the mixture is diluted with 3 parts of toluene and applied by means of a spin coater to a pre-cleaned quartz plate (3 cm * 3 cm). Then the layer is heated to 500 ° C. with the aid of a hot plate. The result is a dark silicon layer. This layer is post-annealed in an oven under inert gas at 750 0 C for 30 min.
• the layer thickness as measured by a profilometer, KLA Tencor, type P15 (KLA-Tencor Corporation, Film and Surface Technology; 160 Rio Robles, San Jose, California, USA 95134), is 250 nm.
• the conductivity of the layer characterized as an ohmic resistance by measuring with a Hewlett Packard P 4156A Analyzer and converting to Ohm * cm is greater than 10 7 ohm * cm.
• the measured bandgap is 1.95 eV.
• the solution is again applied with the aid of a spin coater to a pre-cleaned quartz plate (3 cm * 3 cm) and heated with the aid of a hot plate, the layer to 500 0 C. It creates a dark n-doped silicon layer. This layer is post-annealed in an oven under inert gas at 750 0 C for 30 min.
• the layer thickness as measured by a profilometer, KLA Tencor, type P15 (KLA-Tencor Corporation, Film and Surface Technology; 160 Rio Robles, San Jose, California, USA 95134) is 210 nm.
• the conductivity of the layer, characterized as resistive ohmic resistance in Comparative Example 1 explained method is 40 ohms * cm.
• the bandgap measured by the method described in Comparative Example 1 is 1.90 eV.
• the solution is again applied with the aid of a spin coater to a pre-cleaned quartz plate (3 cm * 3 cm) and heated with the aid of a hot plate, the layer to 500 0 C.
• the result is a dark p-doped silicon layer. This layer is post-annealed in an oven under inert gas at 750 0C for 30 minutes.
• the film thickness measured with a profilometer, KLA Tencor, instrument type P15 (KLA-Tencor Corporation, Film and Surface Technology, 160 Rio Robles, San Jose, Calif., USA 95134) is 270 nm.
• the bandgap measured by the method described in Comparative Example 1 is 1.90 eV.
• the conductivity of the layer, characterized as an ohmic resistance according to the method explained in Comparative Example 1, is 15 ohm.cm.
• the high molecular weight fraction contains oligomers of cyclopentasilane in which partial germanium is incorporated via co-oligomerization.
• the mixture still contains residues of monomeric cyclopentasilane and unreacted PhH 2 GeSiH 3 .
• the mixture is diluted with 3 parts of toluene and applied by means of a spin coater to a pre-cleaned quartz plate (3 cm * 3 cm). Then the layer is heated to 500 ° C. with the aid of a hot plate. This layer is post-annealed in an oven under inert gas at 750 0 C for 30 min. The result is a dark silicon-germanium layer.
• the film thickness as measured by a profilometer, KLA Tencor, instrument type P15 (KLA-Tencor Corporation, Film and Surface Technology; 160 Rio Robles, San Jose, California, USA 95134) is 240 nm.
• the bandgap measured by the method described in Comparative Example 1 is 1, 85 eV.
• the conductivity of the layer, characterized as an ohmic resistance according to the method explained in Comparative Example 1, is greater than 10 7 ohm.cm.
• Example 1 is repeated except that tri (o-tolyl) phosphorus is added as a dopant in the step of diluting the mixture of oligomers of cyclopentasilane, with partial germanium incorporation via co-oligomerization and monomeric cyclopentasilane and unreacted PhH 2 GeSiH 3 .
• the solution is applied to a pre-cleaned quartz plate (3 cm * 3 cm). Then the layer is heated to 500 ° C. with the aid of a hot plate. The result is a dark silicon-germanium layer. This layer is post-annealed in an oven under inert gas at 750 0 C for 30 min.
• the layer thickness as measured by a profilometer, KLA Tencor, instrumentation P15 (KLA-Tencor Corporation, Film and Surface Technology, 160 Rio Robles, San Jose, California USA 95134) is 220 nm.
• the bandgap measured by the method described in Comparative Example 1 is 1.84 eV.
• the conductivity of the layer, characterized as an ohmic resistance according to the method explained in Comparative Example 1, is 36 ohm.cm.
• Example 1 is repeated except that decaborane-14 is added as a dopant in the step of diluting the mixture of oligomers of cyclopentasilane, with partial germanium incorporation via co-oligomerization and monomeric cyclopentasilane and unreacted PhH 2 GeSiH 3 .
• the solution is applied to a pre-cleaned quartz plate (3 cm * 3 cm). Then the layer is heated to 500 ° C. with the aid of a hot plate. This layer is post-annealed in an oven under inert gas at 750 0 C for 30 min. The result is a dark silicon-germanium layer.
• the film thickness as measured by a profilometer, KLA Tencor, Equipment Exp. P15 (KLA-Tencor Corporation, Film and Surface Technology; 160 Rio Robles, San Jose, Calif. USA 95134) is 270 nm.
• the bandgap measured by the method described in Comparative Example 1 is 1, 81 eV.
• the conductivity of the layer, characterized as an ohmic resistance according to the method explained in Comparative Example 1, is 17 ohm.cm.
• Example 1 is repeated, wherein 10.1 g of cyclopentasilane and 3.04 g of PhH 2 GeSiH 3 are subjected to UV oligomerization in the first step.
• the mixture is diluted with 3 parts of toluene and applied by means of a spin coater to a pre-cleaned quartz plate (3 cm * 3 cm).
• the layer is heated to 500 ° C. with the aid of a hot plate.
• the result is a dark silicon germanium layer.
• This layer is post-annealed in an oven under inert gas at 750 0 C for 30 min.
• the film thickness as measured by a profilometer, KLA Tencor, Equipment Exp P15 (KLA-Tencor Corporation, Film and Surface Technology; 160 Rio Robles, San Jose, Calif. USA 95134) is 250 nm.
• the bandgap measured by the method described in Comparative Example 1 is 1, 53 eV.
• the conductivity of the layer, characterized as an ohmic resistance according to the method explained in Comparative Example 1, is greater than 10 7 ohm.cm.
• Example 4 is repeated, again subjecting 10.1 g of cyclopentasilane and 3.04 g of PhH 2 GeSiH 3 to UV-oligomerization in the first step. But on dilution, Th (o-tolyl) phosphorus is added as a dopant along with the toluene. The mixture is applied to a pre-cleaned quartz plate (3 cm * 3 cm) using a spin coater. Then the layer is heated to 500 ° C. with the aid of a hot plate. The result is a dark silicon-germanium layer. This layer is post-annealed in an oven under inert gas at 750 0 C for 30 min.
• the film thickness as measured by a profilometer, KLA Tencor, instrument type P15 (KLA-Tencor Corporation, Film and Surface Technology; 160 Rio Robles, San Jose, Calif. USA 95134) is 230 nm.
• the bandgap measured by the method described in Comparative Example 1 is 1, 55 eV.
• the conductivity of the layer, characterized as an ohmic resistance according to the method explained in Comparative Example 1, is 42 ohm.cm.
• Example 4 is repeated, 10.1 g of cyclopentasilane and 6.08 g of PhH 2 GeSiH 3 again being subjected to UV oligomerization in the first step. But on dilution, decaborane-14 is added as a dopant along with the toluene. The mixture is applied to a pre-cleaned quartz plate (3 cm * 3 cm) using a spin coater. Then the layer is heated to 500 ° C. with the aid of a hot plate. The result is a dark silicon-germanium layer. This layer is post-annealed in an oven under inert gas at 750 0 C for 30 min.
• the film thickness measured with a profilometer, KLA Tencor, instrument type P15 (KLA-Tencor Corporation, Film and Surface Technology, 160 Rio Robles, San Jose, Calif., USA 95134) is 260 nm.
• the bandgap measured by the method described in Comparative Example 1 is 1, 53 eV.
• the conductivity of the layer, characterized as an ohmic resistance according to the method explained in Comparative Example 1, is 12 ohm.cm.
• Example 1 is repeated, wherein 10.1 g of cyclopentasilane and 6.08 g of PhH 2 GeSiH 3 are subjected to UV oligomerization in the first step.
• the mixture is diluted with 3 parts of toluene and applied by means of a spin coater to a pre-cleaned quartz plate (3 cm * 3 cm). Then the layer is heated to 500 ° C. with the aid of a hot plate. The result is a dark silicon germanium layer. This layer is post-annealed in an oven under inert gas at 750 0 C for 30 min.
• the film thickness as measured by a profilometer, KLA Tencor, instrument type P15 (KLA-Tencor Corporation, Film and Surface Technology; 160 Rio Robles, San Jose, California, USA 95134) is 250 nm.
• the bandgap measured by the method described in Comparative Example 1 is 1, 41 eV.
• the conductivity of the layer, characterized as an ohmic resistance according to the method explained in Comparative Example 1, is greater than 107 ohm.cm.
• Example 7 is repeated, again subjecting 10.1 g of cyclopentasilane and 6.08 g of PhH 2 GeSiH 3 to UV-oligomerization in the first step. But on dilution, Th (o-tolyl) phosphorus is added as a dopant along with the toluene. The mixture is applied by means of a spin coater to a pre-cleaned quartz plate (3 cm * 3 cm). Then with the help of a hot plate the Layer heated to 500 0 C. The result is a dark silicon-germanium layer. This layer is post-annealed in an oven under inert gas at 750 0 C for 30 min.
• the film thickness as measured by a profilometer, KLA Tencor, Equipment Exp. P15 (KLA-Tencor Corporation, Film and Surface Technology; 160 Rio Robles, San Jose, Calif. USA 95134) is 220 nm.
• the bandgap measured by the method described in Comparative Example 1 is 1, 39 eV.
• the conductivity of the layer, characterized as an ohmic resistance according to the method explained in Comparative Example 1, is 33 ohm.cm.
• Example 7 is repeated, again subjecting 10.1 g of cyclopentasilane and 6.08 g of PhH 2 GeSiH 3 to UV-oligomerization in the first step. But on dilution, it is added along with decaboran-14 as a dopant. The mixture is applied by means of a spin coater to a pre-cleaned quartz plate (3 cm * 3 cm). Then the layer is heated to 500 ° C. with the aid of a hot plate. The result is a dark silicon-germanium layer. This layer is post-annealed in an oven under inert gas at 750 0 C for 30 min.
• the film thickness as measured by a profilometer, KLA Tencor, Equipment Exp. P15 (KLA-Tencor Corporation, Film and Surface Technology; 160 Rio Robles, San Jose, Calif. USA 95134) is 280 nm.
• the bandgap measured by the method described in Comparative Example 1 is 1, 38 eV.
• the conductivity of the layer, characterized as an ohmic resistance according to the method explained in Comparative Example 1, is 14 ohm.cm.

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