Classifications

• • H—ELECTRICITY
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  • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
  • H10F77/00—Constructional details of devices covered by this subclass
  • H10F77/20—Electrodes
  • H10F77/206—Electrodes for devices having potential barriers
  • H10F77/211—Electrodes for devices having potential barriers for photovoltaic cells
  • H10F77/219—Arrangements for electrodes of back-contact photovoltaic cells
• • H—ELECTRICITY
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  • H10F10/00—Individual photovoltaic cells, e.g. solar cells
  • H10F10/10—Individual photovoltaic cells, e.g. solar cells having potential barriers
  • H10F10/16—Photovoltaic cells having only PN heterojunction potential barriers
  • H10F10/167—Photovoltaic cells having only PN heterojunction potential barriers comprising Group I-III-VI materials, e.g. CdS/CuInSe2 [CIS] heterojunction photovoltaic cells
• • H—ELECTRICITY
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  • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
  • H10F19/00—Integrated devices, or assemblies of multiple devices, comprising at least one photovoltaic cell covered by group H10F10/00, e.g. photovoltaic modules
  • H10F19/20—Integrated devices, or assemblies of multiple devices, comprising at least one photovoltaic cell covered by group H10F10/00, e.g. photovoltaic modules comprising photovoltaic cells in arrays in or on a single semiconductor substrate, the photovoltaic cells having planar junctions
• • H—ELECTRICITY
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  • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
  • H10F19/00—Integrated devices, or assemblies of multiple devices, comprising at least one photovoltaic cell covered by group H10F10/00, e.g. photovoltaic modules
  • H10F19/30—Integrated devices, or assemblies of multiple devices, comprising at least one photovoltaic cell covered by group H10F10/00, e.g. photovoltaic modules comprising thin-film photovoltaic cells
  • H10F19/31—Integrated devices, or assemblies of multiple devices, comprising at least one photovoltaic cell covered by group H10F10/00, e.g. photovoltaic modules comprising thin-film photovoltaic cells having multiple laterally adjacent thin-film photovoltaic cells deposited on the same substrate
  • H10F19/35—Structures for the connecting of adjacent photovoltaic cells, e.g. interconnections or insulating spacers
• • H—ELECTRICITY
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  • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
  • H10F19/00—Integrated devices, or assemblies of multiple devices, comprising at least one photovoltaic cell covered by group H10F10/00, e.g. photovoltaic modules
  • H10F19/90—Structures for connecting between photovoltaic cells, e.g. interconnections or insulating spacers
  • H10F19/902—Structures for connecting between photovoltaic cells, e.g. interconnections or insulating spacers for series or parallel connection of photovoltaic cells
  • H10F19/904—Structures for connecting between photovoltaic cells, e.g. interconnections or insulating spacers for series or parallel connection of photovoltaic cells characterised by the shapes of the structures
• • H—ELECTRICITY
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  • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
  • H10F71/00—Manufacture or treatment of devices covered by this subclass
  • H10F71/125—The active layers comprising only Group II-VI materials, e.g. CdS, ZnS or CdTe
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  • H10F77/00—Constructional details of devices covered by this subclass
  • H10F77/10—Semiconductor bodies
  • H10F77/12—Active materials
  • H10F77/126—Active materials comprising only Group I-III-VI chalcopyrite materials, e.g. CuInSe2, CuGaSe2 or CuInGaSe2 [CIGS]
  • H10F77/1265—Active materials comprising only Group I-III-VI chalcopyrite materials, e.g. CuInSe2, CuGaSe2 or CuInGaSe2 [CIGS] characterised by the dopants
• • H—ELECTRICITY
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  • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
  • H10F77/00—Constructional details of devices covered by this subclass
  • H10F77/10—Semiconductor bodies
  • H10F77/12—Active materials
  • H10F77/128—Active materials comprising only Group I-II-IV-VI kesterite materials, e.g. Cu2ZnSnSe4 or Cu2ZnSnS4
• • H—ELECTRICITY
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  • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
  • H10F77/00—Constructional details of devices covered by this subclass
  • H10F77/10—Semiconductor bodies
  • H10F77/12—Active materials
  • H10F77/128—Active materials comprising only Group I-II-IV-VI kesterite materials, e.g. Cu2ZnSnSe4 or Cu2ZnSnS4
  • H10F77/1285—Active materials comprising only Group I-II-IV-VI kesterite materials, e.g. Cu2ZnSnSe4 or Cu2ZnSnS4 characterised by the dopants
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
  • H10F77/00—Constructional details of devices covered by this subclass
  • H10F77/10—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
  • H10F77/1694—Thin semiconductor films on metallic or insulating substrates the films including Group I-III-VI materials, e.g. CIS or CIGS
• • H—ELECTRICITY
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  • H10F77/00—Constructional details of devices covered by this subclass
  • H10F77/20—Electrodes
  • H10F77/244—Electrodes made of transparent conductive layers, e.g. transparent conductive oxide [TCO] layers
  • H10F77/251—Electrodes made of transparent conductive layers, e.g. transparent conductive oxide [TCO] layers comprising zinc oxide [ZnO]
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E10/00—Energy generation through renewable energy sources
  • Y02E10/50—Photovoltaic [PV] energy
  • Y02E10/541—CuInSe2 material PV cells
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • 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
  • Y02E10/543—Solar cells from Group II-VI materials
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
  • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

• the present invention relates to photovoltaic thin-film solar modules and to a method for producing such thin-film solar modules.
• Photovoltaic solar modules have long been known and commercially available. Suitable solar modules comprise on the one hand crystalline and amorphous silicon solar modules and on the other hand so-called thin-film solar modules. such
• thin film solar modules are based on the use of a so-called chalcopyrite semiconductor absorber layer, for example a Cu (In, Ga) (Se, S) system, and constitute a complex multilayer system.
• These thin film solar modules typically have a molybdenum back electrode layer on a glass substrate. This is provided in a process variant with a copper and indium and optionally gallium comprehensive precursor metal thin layer and then in the presence of hydrogen sulfide and / or hydrogen selenide at elevated
• Back electrode layer can be influenced on the efficiency of a thin-film solar cell.
• the back electrode layer has a high Have transverse conductivity in order to ensure a low-loss series connection.
• substances migrating from the substrate and / or the semiconductor absorber layer should have no influence on the quality and function of the back electrode layer or the semiconductor absorber layer.
• the material must be the
• Back electrode layer have a good adaptation to the thermal expansion behavior of the substrate and the overlying layers to avoid microcracks.
• the adhesion on the substrate surface should meet all common usage requirements. Although it is possible to achieve good efficiencies on the use of particularly pure back electrode material, but this is regularly accompanied disproportionately high production costs.
• the above-mentioned migration or, in particular, diffusion phenomena often lead to significant contamination of the back electrode material under the usual production conditions.
• Semiconductor absorber layer is introduced, diffuse by the aforementioned diffusion in the back electrode and thereby depleted in the semiconductor absorber layer. The consequence is significantly lower efficiencies of the finished solar module. Even with respect to all process and material optimizations, one is still very limited in the final design of the intended for distribution
• a solar cell with a morphologically well-formed absorber layer and good efficiencies should be obtained by treating the chalcopyrite semiconductor absorber layer with an element from the group of sodium, potassium and lithium in a dose of 10 14 to 10 16 atoms doped / cm 2 while providing a diffusion barrier between the substrate and the semiconductor absorber layer.
• an alkali-free substrate if it is desired to dispense with a diffusion barrier layer.
• the solar cell comprises a sodium glass substrate, a molybdenum back electrode layer, a CIGS layer, a buffer layer, a layer of intrinsic zinc oxide, and a layer of aluminum doped zinc oxide.
• a first separation trench extends over the molybdenum layer, the CIGS layer and the powder layer, a second separation trench begins above the molybdenum layer.
• An insulating material is deposited in the first separation trench, and a front electrode layer is obliquely deposited on the solar cell including the first separation trench. In this way, thin-film solar cells with improved light output should be obtained.
• a further object of the present invention was to make available thin-film solar modules which have a larger fill factor and a higher fill factor
• Embodiment of the thin-film solar module according to the invention comprising, in particular in this order,
• At least one substrate layer in particular a glass pane
• Back electrode layer in particular containing or substantially of molybdenum, at least one, in particular on the back electrode layer and / or on the
• Contact layer in particular ohmic contact layer, in particular containing or consisting essentially of molybdenum and / or molybdenum selenide and / or molybdenum sulfoselenide, at least one, in particular directly adjacent to the contact layer,
• Semiconductor absorber layer in particular chalcopyrite or kesterite semiconductor absorber layer
• first buffer layer in particular directly adjacent to the semiconductor absorber layer, comprising or consisting essentially of CdS or a CdS-free layer, in particular containing or consisting essentially of Zn (S, OH) or ln 2 S 3 , and / or
• At least one second buffer layer in particular directly on the semiconductor absorber layer or the first buffer layer, comprising and consisting essentially of intrinsic zinc oxide and / or high-resistance zinc oxide, and at least one, in particular on the semiconductor absorber layer, the first buffer layer and / or the second buffer layer immediate, transparent
• Front electrode layer in particular containing or consisting essentially of n-doped zinc oxide, characterized by
• spaced second structuring trenches filled or provided with at least one conductive material and extending to the contact layer or to the first
• spaced third patterning trenches extending to the contact layer or to the back electrode layer or to the barrier layer, in particular to the
• Barrier layer extend and each adjacent to a second
• the object underlying the invention is further achieved by a photovoltaic thin-film solar module (and second embodiment of a
• thin-film solar module comprising, in particular in this order,
• At least one substrate layer in particular a glass pane
• Back electrode layer in particular containing or made of molybdenum
• conductive barrier layer in particular bidirectional barrier layer
• Contact layer in particular ohmic contact layer, in particular containing or consisting of molybdenum and / or molybdenum selenide and / or molybdenum sulphoselenide,
• Semiconductor absorber layer in particular chalcopyrite or kesterite
• first buffer layer in particular directly adjacent to the semiconductor absorber layer, comprising or consisting essentially of CdS or a CdS-free layer, in particular containing or consisting essentially of Zn (S, OH) or ln 2 S 3 , and / or
• At least one second buffer layer in particular directly adjacent to the semiconductor absorber layer or the first buffer layer, containing and essentially formed from intrinsic zinc oxide and / or high-resistance zinc oxide, and at least one, in particular at the semiconductor absorber layer, the first
• Buffer layer and / or the second buffer layer directly adjacent, transparent front electrode layer in particular containing or substantially formed of n-doped zinc oxide, characterized by
• spaced fourth structuring trenches extending to the contact layer or to the back electrode layer or to the barrier layer, in particular to the Barrier layer, and each adjacent to a filled first structuring trench and present a first volume region extending from the barrier layer to the front electrode layer along the first
• a first conductive barrier layer may be present on the substrate layer in a first embodiment, followed by the back electrode layer, then the contact layer, then the semiconductor absorber layer, optionally the first or second buffer layer, and then the front electrode layer.
• a first conductive barrier layer may first be provided on the substrate layer, and then the first conductive barrier layer
• Thin-film solar modules in a third embodiment which is preferred, on the substrate layer, first the back electrode layer, then the conductive barrier layer, then the contact layer on the semiconductor absorber layer, then optionally the first or second buffer layer, and thereon the front electrode layer.
• Semiconductor absorber layer comprises a quaternary IB-IIIA-VIA Chalkopyrit harsh, in particular a Cu (In, Ga) Se 2 film, a penternäre IB-IIIA-VIA Chalkopyrit harsh, in particular a Cu (In, Ga) (sides x, S x) 2 layer, or a kesterite layer, in particular a
• Cu 2 ZnSn (Se x , Si x ) 4 layer for example, a Cu 2 ZnSn (Se) 4 - or a Cu 2 ZnSn (S) 4 layer, represents, or wherein x assumes any value from 0 to 1
• the substrate is preferably a plate or film.
• the substrate may, for example
• Glass substrate such as a glass pane, a flexible or non-flexible plastic layer, for example plastic films, or a metal plate, for example stainless steel layers or foils in particular, having a width greater than 0.5 m, in particular greater than 2.0 m, and a length greater than 1, 2 m, in particular greater than 3.0 m, represent.
• substrate formats in particular substrate glass formats, with a width of 3.2 m and a length of 6 m. From this can be, for example, 16
• Thin-film solar modules in module format 1.6 m x 0.7 m were obtained.
• the back electrode layer contains or is essentially formed from V, Mn, Cr, Mo, Ti, Co, Zr, Ta, Nb and / or W and / or contains or is essentially formed from an alloy containing V, Mn, Cr, Mo, Ti, Co, Fe, Ni, Al, Zr, Ta, Nb and / or W.
• the back electrode according to the present invention can also be used as a bulk back electrode and the system of bulk back electrode or Back electrode, barrier layer and contact layer are referred to as a multi-layer back electrode.
• the barrier layer forms a barrier for components migrating out of and / or over the back electrode layer, in particular diffusing or diffusing, in particular dopants, and / or for diffusing or diffusing out of and / or over the contact layer Diffusible, components, in particular dopants, in particular a bidirectional
• Barrier layer represents.
• the barrier layer prevents the depletion of the semiconductor layer on one of the dopant forming this layer, for. As sodium, whereby an unimpaired efficiency can be maintained.
• the barrier layer is expediently a barrier for alkali ions, in particular sodium ions, or compounds containing alkali metal ions, selenium or selenium compounds, sulfur or sulfur compounds and / or metals, in particular Cu, In, Ga, Fe, Ni, Ti, Zr, Hf, V, Nb , Ta, Al and / or W. It is preferably a bidirectional one
• the barrier layer prevents contamination of the semiconductor absorber layer with components of the substrate and / or the back electrode layer as well as contamination of the back electrode layer with components of the semiconductor layer such as Cu, In and Ga. In the latter case, the barrier layer prevents the depletion of
• the barrier layer of the back electrode according to the invention has barrier properties, in particular bidirectional barrier properties, to dopants, in particular to dopants for the semiconductor absorber layer and / or from the semiconductor absorber layer, to chalcogens such as selenium and / or sulfur and chalcogen compounds, compared to the metallic constituents of Semiconductor absorber layer such as Cu, In, Ga, Sn and / or Zn, against impurities such as iron and / or nickel from the
• the bidirectional barrier properties to dopants from the substrate are intended, on the one hand, to enrich for the interface of the back electrode or contact layer to the semiconductor absorber layer with alkali ions, e.g. out diffusing from a glass substrate, prevent. Such accumulations are known as a reason for semiconductor layer separations.
• the conductive barrier layer is said to help avoid adhesion problems.
• the barrier property for dopants is said to help avoid adhesion problems.
• the bidirectional conductive barrier layer is therefore intended to enable the conditions for a targeted metering of dopant into the semiconductor absorber layer in order to be able to achieve reproducibly high efficiencies of the solar cells and modules.
• the barrier property with respect to chalcogens should accordingly prevent them from reaching the back electrode and forming metal chalcogenide compounds there.
• these chalcogenide compounds e.g. MoSe
• Impurities of the back electrode material such as Fe and Ni provide so-called deep impurities for e.g. Chalcopyrite semiconductor (semiconductors) and are therefore to be kept over the barrier layer of the semiconductor absorber layer.
• the barrier layer usually has an average thickness of at least 10 nm, in particular at least 30 nm and preferably at most 250 nm or 150 nm. Due to the circumstance of the presence of a barrier layer, it is possible, for example, to significantly reduce the degree of purity of the back electrode material.
• the back electrode layer may be contaminated with at least one element selected from the group consisting of Fe, Ni, Al, Cr, Ti, Zr, Hf, V, Nb, Ta, W and / or Na and / or with compounds of said elements, without the efficiency of the back electrode according to the invention having
• Thin-film solar cell or des -moduls is permanently impaired.
• barrier layers containing or essentially of at least one metal nitride, in particular TiN, MoN, TaN, ZrN and / or WN, at least one metal carbide, at least one metal boride and / or at least one metal silicon nitride, in particular TiSiN, TaSiN and / or WSiN.
• metal nitride in particular TiN, MoN, TaN, ZrN and / or WN
• metal carbide at least one metal boride and / or at least one metal silicon nitride, in particular TiSiN, TaSiN and / or WSiN.
• barrier layers for example TiN, which provide a surface reflecting the light. In this way, light that is the
• Semiconductor absorber layer has passed, be directed to increase the efficiency again by this.
• Such metal nitrides are preferred as barrier materials in the context of the present invention, for example TiN, in which the metal is deposited in terms of nitrogen stoichiometric or superstoichiometric, ie with excess nitrogen.
• the barrier layer in particular a metal nitride or
• Metallsiliziumnitridbarriere in this process stage, in particular in small quantities, metered.
• the barrier properties are to be increased without at the same time significantly lowering the conductivity of the barrier.
• the addition of oxygen in connection with the application of the barrier layer should cause the grain boundaries of the often polycrystalline thin-film barrier to be blocked with oxygen or oxygen compounds.
• barrier layer as part of a multi-layer back electrode system (of back electrode, barrier and contact layer) manifests itself when used in thin-film solar modules according to the invention in that the thickness of the semiconductor absorber layer, for example the chalcopyrite or kesterite layer, over conventional Systems can be significantly reduced.
• the barrier layer in particular if present in the form of metal nitrides, for example titanium nitride, or containing such metal or titanium nitrides present, which is the Reflecting solar radiation passing through the semiconductor absorber layer very effectively, so that a very good quantum efficiency can be achieved by way of the double passage through the semiconductor absorber layer. Due to the presence of said barrier layer in the back electrode according to the invention or in thin-film solar cells or modules containing this back electrode, the average thickness of the semiconductor absorber layer.
• the barrier layer is preferably present between the back electrode layer and the contact layer.
• the contact layer contains or is essentially formed from Mo, W, Ta, Nb, Zr and / or Co, in particular Mo and / or W, and / or contains or at least essentially forms a metal chalcogenide and / or at least one first layer, adjacent to the barrier layer, comprising or consisting essentially of Mo, W, Ta, Nb, Zr and / or Co, in particular Mo and / or W, and at least one second layer, not adjacent to the barrier layer, containing or essentially of at least one metal chalcogenide.
• the contact layer preferably directly adjoins the semiconductor absorber layer on the side facing the substrate directly on the barrier layer and / or on the side facing the front electrode.
• the contact layer contains at least one metal chalcogenide.
• the contact layer usually has an average thickness of
• the semiconductor absorber layer comprising at least one dopant, in particular at least one element selected from the group sodium, potassium and lithium and / or at least one compound of these elements, preferably with oxygen, selenium, sulfur, boron and / or halogens, eg Iodine,, or fluorine, and / or at least one alkali metal bronze, in particular sodium and / or potassium bronze, preferably with a metal selected from molybdenum, tungsten, tantalum and / or niobium.
• dopant in particular at least one element selected from the group sodium, potassium and lithium and / or at least one compound of these elements, preferably with oxygen, selenium, sulfur, boron and / or halogens, eg Iodine,, or fluorine, and / or at least one alkali metal bronze, in particular sodium and / or potassium bronze, preferably with a metal selected from molybdenum, tungsten, tantalum and / or niobium
• the dopant in particular sodium ions, is present in the contact layer and / or the semiconductor absorber layer advantageously in a dose in the range from 10 13 to 10 17 atoms / cm 2, in particular in the range from 10 14 to 10 16 atoms / cm 2 .
• the first buffer layer can be deposited both dry and wet-chemically.
• the first buffer layer may contain or be essentially formed from CdS or a CdS-free layer, in particular containing or consisting essentially of Zn (S, OH) or ln 2 S 3 .
• the second buffer layer preferably contains or is essentially formed from intrinsically conductive zinc oxide and / or high-resistance
• the material used for the front electrode is preferably transparent to electromagnetic radiation, in particular to radiation having a wavelength in the region of the absorption wavelength range of the semiconductor.
• Front electrode or is essentially formed from n-doped zinc oxide.
• Thin-film solar modules according to the invention are also distinguished, in particularly suitable embodiments, in that the average thickness of the Back electrode layer in the range of 50 nm to 500 nm, in particular in the range of 80 nm to 250 nm, and / or the barrier layer in the range of 10 nm to 250 nm, in particular in the range of 20 nm to 150 nm, and / or Contact layer in the range of 2 nm to 200 nm, in particular in the range of 5 nm to 100 nm, and / or the semiconductor absorber layer in the range of 400 nm to 2500 nm, in particular in the range of 500 nm to 2000 nm and preferably in the range of 800 nm to 1600 nm, and / or that of the first buffer layer in the range of 5 nm to 100 nm, in particular in the range of 10 nm to 70 nm, and / or that of the second buffer layer in the range of 10 nm to 150 nm, in
• microOhm * cm preferably 10 microOhm * cm. Under these conditions, ohmic losses in a series-connected module can be reduced even more efficiently.
• the back electrode layer contains molybdenum and / or tungsten, in particular molybdenum, or is essentially formed from molybdenum and / or tungsten, in particular molybdenum, which contains conductive barrier layer TiN or Is formed essentially of TiN, and the contact layer MoSe 2 contains or is essentially formed of MoSe 2 .
• the first, second, third and / or fourth structuring trenches have expedient configurations of thin-film solar modules according to the invention
• Structuring trench preferably above 50 kOhm, in particular above 100 kOhm.
• thin-film solar modules there are regularly at least two, in particular a multiplicity of, monolithically integrated series-connected solar cells.
• Thin-film solar module comprising:
• At least one first structuring step comprising removing the layers applied to the substrate layer along spaced-apart lines by means of laser treatment (first laser treatment) to form the first
• Barrier layer up to and including the front electrode layer, along spaced apart lines to form second structuring trenches adjacent to or adjacent to first patterning trenches and in particular at least partially substantially parallel thereto, or
• Structuring trenches are adjacent or adjacent to these and in particular at least partially extend substantially parallel to these,
• At least one third structuring step comprising removing the layers extending from the contact layer or from the back electrode layer or from the barrier layer, in particular from the barrier layer, up to and including the barrier layer Front electrode layer extend, along spaced lines to form the third patterning trenches, which are second
• Structuring trenches are adjacent or adjacent to these and in particular run in sections substantially parallel to these,
• adjacent solar cell so that adjacent solar cells are electrically series-connected.
• Thin-film solar module comprising:
• At least one first structuring step comprising removing the layers applied to the substrate layer along spaced-apart lines by means of laser treatment (first laser treatment) to form first structuring trenches which separate adjacent solar cells,
• barrier layer up to and including the front electrode layer, along lines spaced apart to form fourth patterning trenches adjacent to or adjacent to first patterning trenches and in particular at least partially substantially parallel thereto,
• Structuring trenches adjacent trench wall extends with at least one conductive material, not filling / release of a thereto adjacent second volume region extending from the barrier layer to the front electrode layer along the separation trench wall, which does not extend to the first
• the sequence of steps i), jl), k), I) and m) is arbitrary as long as I), directly or indirectly, according to i) and m), directly or indirectly, according to jl) or that the order of steps i), j2), k) and I) is arbitrary, as long as I) , directly or indirectly, after i) comes.
• the chemical phase transformation in step j2) is preferably carried out by thermal decomposition of those layers which extend from the barrier layer up to and including the front electrode layer, in particular by means of laser treatment. This is done along with e.g. Laser light treated lines significantly increase the conductivity of said layers over the adjacent untreated layers. This allows these line-treated layers, similar to second structuring trenches filled with conductive material, to contact in the electrical
• Suitable pulse durations are e.g. above 1 nano-second.
• the thin-film solar module according to the invention makes it possible for the sequence of steps i), o), p) and q) to be arbitrary, as long as p), directly or indirectly, according to i) and q), directly or indirectly, comes to o), is preferred the sequence i), o), p), q) and r) or i), o), p) and t).
• steps i) and jl), i) and j2), i) and k), jl) and k), j2) and k), i), jl) and k) and / or i), j2) and k ) can be made simultaneously in a further development. Furthermore, steps i) and o) can also be carried out simultaneously.
• the substrate is at least partially permeable to electromagnetic radiation of the first laser treatment. Appropriately, this laser treatment of the first structuring step, in particular by laser ablation, take place from the side facing away from the coated side of the substrate.
• the second, third or fourth structuring trenches are produced by means of laser treatment (second, third or fourth laser treatment) and / or that in the second and / or third and / or fourth, in particular the third and / or fourth structuring step, the second, third or fourth structuring trenches are generated mechanically, in particular by means of needle scribing.
• Structuring trenches and / or the first line-shaped conductive areas at least partially, in particular completely, with an average width of not more than 50 ⁇ , in particular not more than 30 ⁇ and preferably not more than 15 ⁇ , produced.
• a further development of the inventive method also provides that, in particular adjacent, first and second and / or, in particular adjacent, first and third and / or, in particular adjacent, second and third structuring trenches, or, in particular adjacent, first, second and third structuring trenches or, in particular adjacent, first and fourth structuring trenches or
• first structuring trenches and first line-shaped conductive regions are guided at least in sections substantially parallel.
• such an embodiment is particularly suitable in which adjacent first, second and third or adjacent first and fourth structuring trenches or adjacent first structuring trenches and first linear conductive regions have a smaller average distance from one another than non-adjacent first, second and third or non-adjacent first and fourth
• third structuring trenches in particular all third ones, regularly become
• Structuring trenches or the first line-shaped conductive region of the respective adjacent first structuring trenches are separated.
• the first laser treatment, the second laser treatment and / or the third laser treatment are preferably carried out with laser light pulses having a pulse duration in the range from 1 pico-second to 1 nano-second.
• the method for the first and the second laser treatment for example
• Laser light pulses are used with a pulse duration of less than 10 pico-seconds.
• the line feed may e.g. Speeds of a few m / sec amount and is suitable for mass production.
• the first, second and third structuring step of the first embodiment of the method according to the invention or the first and fourth structuring step of the second embodiment of the method according to the invention regularly lead or regularly contribute to a monolithically integrated serial connection of the solar cells.
• These structuring steps are preferably designed as linear processing steps.
• the inventive method preferably provide that the
• Semiconductor absorber layer comprises a quaternary IB-IIIA-VIA Chalkopyrit harsh, in particular a Cu (In, Ga) Se 2 film, a penternäre IB-IIIA-VIA Chalkopyrit harsh, in particular a Cu (In, Ga) (sides x, S x) 2 layer, or a kesterite layer, in particular a
• Cu 2 ZnSn (Se x , Si x ) 4 layer for example, a Cu 2 ZnSn (Se) 4 - or a Cu 2 ZnSn (S) 4 layer, represents, or wherein x assumes values of 0 to 1.
• the method according to the invention can be used e.g. be made such that the contact layer comprises a layer sequence of at least one metal layer and at least one Metallchalkogenid Anlagen, wherein the metal layer on the
• Back electrode layer or on the conductive barrier layer abuts or adjacent and wherein the metal chalcogenide layer is applied to the semiconductor absorber layer or
• the method according to the invention can also be configured, for example, such that at least one first metal layer of e.g. Molybdenum, tantalum, zirconium, cobalt, tungsten and / or niobium is applied and that this first metal layer of e.g. Molybdenum, tantalum, zirconium, cobalt, tungsten and / or niobium is applied and that this first metal layer of e.g. Molybdenum, tantalum, zirconium, cobalt, tungsten and / or niobium is applied and that this first metal layer of e.g. Molybdenum, tantalum, zirconium, cobalt, tungsten and / or niobium is applied and that this first metal layer of e.g. Molybdenum, tantalum, zirconium, cobalt, tungsten and / or niobium is applied and that this first metal layer of e.g. Mo
• Metal layer in the production of the semiconductor absorber layer in particular the kesterite or chalcopyrite semiconductor absorber layer, in selenium and / or sulfur-containing
• Metal chalcogenide is reacted.
• at least one first metal layer of molybdenum, tantalum, tungsten, cobalt, zirconium and / or niobium is applied to the barrier layer, and this first metal layer is used in the production of the
• Semiconductor absorber layer in particular the kesterite or chalcopyrite semiconductor absorber layer is reacted completely in selenium and / or sulfur-containing atmosphere to form the contact layer to a metal chalcogenide.
• Semiconductor absorber layer in particular the kesterite or chalcopyrite semiconductor absorber layer, in an expedient embodiment, accordingly, the deposition of, in particular all, metallic components of
• Semiconductor absorber layer in particular of copper, indium and optionally gallium for the chalcopyrite semiconductor absorber layer and copper, zinc and tin for the kesterite semiconductor absorber layer, on the contact layer to form a second
• reaction temperatures are often also in the range of 500 ° C to 600 ° C. At such temperatures migrate, in particular diffuse, dopants, in particular sodium ions or
• Back electrode layer does not take place. Due to the mentioned relatively high temperatures in the processing of the semiconductor, it is advantageous that the selected layers of the multilayer back electrode, in particular the back electrode and / or the conductive barrier layer are so composed that their linear thermal
• Expansion coefficient are adapted to those of the semiconductor absorber and / or the substrate. Therefore, especially the back electrode and / or the substrate.
• Barrier layer of the thin-film solar modules according to the invention preferably be composed so that a linear thermal expansion coefficient of 14 * 10 "f " K, preferably 9 * 10 "6" K is not exceeded.
• the conductive barrier layer the first metal layer, in particular containing Mo, the contact layer, the second metal layer, in particular containing Cu, In and Ga, the first buffer layer, the second buffer layer and / or the
• Front electrode layer can be obtained by means of physical vapor deposition, in particular comprising physical vapor deposition (PVD) coating, vapor deposition by means of an electron beam evaporator, vapor deposition by means of a
• Sputter coating in particular DC or RF magnetron sputtering, each preferably in a high vacuum, or by means of chemical
• Vapor deposition in particular comprising chemical vapor deposition (CVD), low pressure (CVD) and / or atmospheric pressure (CVD).
• Structuring trench can be done with the insulator material in a single plant.
• the structuring steps of the method according to the invention and the filling steps can, if they do not have to be carried out sequentially, take place or be carried out in parts or completely simultaneously.
• an ink preferably a hotmelt aerosol ink
• the laser and ink-jet or aerosol jet devices are at least partially heated or heated, preferably with the proviso that the ink used has a viscosity of ⁇ ⁇ 1 Pas at a temperature of at least 40 ° C.
• an ink for in particular the ink jet and / or the aerosol jet device (s) comprises metal particles, in particular metal particles selected from a group consisting of silver, tin, zinc, chromium, cobalt, tungsten, titanium and / or mixtures thereof.
• the ink may be the
• Metal oxides for example lead oxide, bismuth oxide, titanium oxide, aluminum oxide,
• Magnesium oxide and / or mixtures thereof Magnesium oxide and / or mixtures thereof.
• thermoplastic compounds selected from the group consisting of C i6 to C 2 o, C i4 preferably up to C i6 linear aliphatic alcohols and / or polyhydric alcohols such as hexane-l, 6-diol.
• the ink contained in the ink may also be preferred that the ink contained in the ink
• Solvent is selected from glycol ether, M-methylpyrolidone, 2- (2-butoxyethoxy) ethanol and / or mixtures thereof.
• the ink contains dispersants and / or defoamers as additives.
• the structuring trenches may be e.g. over the length of a
• Thin-film solar module can be manufactured in one continuous operation.
• structuring trenches with a length of 1.6 m and more can be obtained in this way.
• a limitation on the length of the structuring trenches may e.g. be given by the length of the module or substrate or by equipment specifications, but not by the inventive method itself.
• the decay of the first structuring trench with the insulator material and / or the decay of the second structuring trench or of the first volume region of the fourth structuring trench with conductive material takes place in a preferred embodiment by the ink-jet or the aerosol-jet method.
• the insulator material as well as the conductive material can be very finely dosed, as it is e.g. Also known from the inkjet printer industry.
• droplets having a volume in the range from about 10 pico liters to less than one pico liter can be finely dosed and e.g. Precision xyz table adjusts precisely into the
• Structuring trench e.g. about drop size, drop rate and / or feed and / or by appropriate lateral adjustment.
• a fast-curing insulator ink or a UV-curable electrically-insulating varnish known from semiconductor technology can be used.
• the UV illumination preferably takes place immediately after the filling step.
• the present invention is based on the surprising finding that the sequence of structuring processes, in particular in combination with a multi-layer back electrode containing an especially bidirectional barrier layer, photovoltaic thin-film solar modules with monolithically integrated series-connected solar cells in mass production in high quality and with high efficiencies cost-effective and reproducible.
• the cell and module format design can also be varied in large areas in mass production and corresponding customer requirements can be taken into account and implemented on a large scale. This also applies to the customer's
• Thin-film solar module desired open circuit voltage and the short-circuit current to.
• the Strukturiergräben are prepared before the semiconductor formation process, which is why the Strukturiergräben under the action of the semiconductor used in the high temperatures and possibly also alkali diffusion in the range of 350 ° C to 600 ° C and under selenium or Sulfur then often corrode. This is accompanied by a layer undercrossing and the formation of microcracks by mechanical stress, caused by the volume expansion of the under selenium and / or sulfur corroded metals.
• Such a melt edge is generally particularly susceptible to reaction with selenium and / or sulfur among the
• the method according to the invention also makes it possible to circumvent the otherwise frequently occurring damage to the insulating barrier layer in the laser process. As a result, alkali ions can be prevented from being uncontrolled from the substrate glass into the semiconductor absorber layer. By avoiding the overdoping of the semiconductor absorber layer and by the decay of Strukturiergrabens with
• Figure 1 is a schematic cross-sectional view of a manufacturing stage of a first
• Embodiment of the thin-film solar module according to the invention obtained according to a first embodiment of the method according to the invention
• Figure 2 is a schematic cross-sectional view of a following
• FIG. 3 shows a schematic cross-sectional view of a further manufacturing stage of the thin-film solar module according to the invention obtained by the method according to the invention
• FIG. 4 shows a schematic cross-sectional view of a further manufacturing stage of the thin-film solar module according to the invention obtained by the method according to the invention
• FIG. 5 shows a schematic cross-sectional view of a further manufacturing stage of the thin-film solar module according to the invention obtained by the method according to the invention
• FIG. 6 shows a schematic cross-sectional view of a further manufacturing stage of the thin-film solar module according to the invention obtained by the method according to the invention
• Figure 7 is a schematic cross-sectional view of a manufacturing stage of a
• Thin-film solar module obtained according to an alternative embodiment of the method according to the invention.
• Figure 8 is a schematic cross-sectional view of another manufacturing stage of the alternative embodiment of the invention.
• Thin-film solar module based on the manufacturing stage according to FIG. 7;
• Figure 9 is a schematic cross-sectional view of a manufacturing stage of a
• Thin-film solar module obtained according to an alternative embodiment of the method according to the invention.
• Figure 10 is a schematic cross-sectional view of another manufacturing stage of the alternative embodiment of the invention.
• Thin-film solar module based on the manufacturing stage according to FIG. 9.
• FIG. 1 shows a schematic cross-sectional view of an intermediate fabrication stage 1a of a thin-film solar module 1 according to the invention.
• a bulk back electrode layer 4 is deposited on the glass substrate 2 by means of thin-film deposition. made of molybdenum. Adjacent thereto is a bidirectional reflective barrier layer 6 of e.g. TiN or ZrN, which can also be obtained by thin film deposition. On the barrier layer 6 lies in the illustrated
• Embodiment an ohmic contact layer 8 of a metal chalcogenide such as molybdenum selenide.
• This contact layer can be obtained in different ways, as already generally explained above.
• Molybdenum selenide sputtered from a Molybdänselenidtarget.
• a metal layer can be applied, which subsequently in front of and / or during the formation of the semiconductor absorber layer into the corresponding one
• the contact layer 8 may also be admixed with at least one dopant, for example sodium ions or a sodium compound, in particular sodium sulfite or sodium sulfide.
• the layer 10 represents the semiconductor absorber layer and can be present, for example, as a chalcopyrite or as a kesterite semiconductor absorber layer. Methods of applying these semiconductor absorber layers are known to those skilled in the art. If a dopant is present in the contact layer, it usually diffuses into the latter under the conditions of formation of the semiconductor absorber layer.
• first the first buffer layer 12 of, for example, CdS, Zn (S, OH) or ln 2 S 3 and the second buffer layer 14 of intrinsic zinc oxide have been applied to the semiconductor absorber layer 10, followed by the front electrode layer 22 of n-doped zinc oxide.
• the layer sequence 2, 4, 6, and 8 of a thin-film solar module 1 according to the invention shown in FIG. 1 can be manufactured in a single system in a substantially coherent process. Throughout the process span can be processed in a single plant. Thus, not only costly process steps are avoided, but also reduces the risk of contamination of the product intermediates, for example, with oxygen.
• FIG. 2 shows the first made at the intermediate production stage 1a
• first isolation trenches 16 have been produced which ultimately define the widths of the solar cells of the monolithically integrated series connection.
• the solar cells 100 and 200 are separated from each other by the first separation trench 16. In this way, e.g. over an average ditch width of 15 ⁇ m along lines, all layers above the substrate have been removed, including the front electrode layer.
• a second structuring process has been carried out on the layer system by means of laser treatment, this time from the upper side, forming second separating trenches 20 spaced apart.
• second separating trenches 20 From the front electrode layer 22 via the buffer layers and the semiconductor absorber layer 10 up to and including the contact layer 8, all layers have been removed up to the barrier layer, preferably over an average width of 15 ⁇ m.
• These second separation trenches 20 can also be generated mechanically, eg by means of needle scribing. They are attached adjacent to the first separation trenches 16 and have, for example over an average distance less than 50 ⁇ , for example, of about 30 ⁇ .
• First and second separating trenches 16, 20 are preferably present here essentially in parallel.
• the first isolation trenches 16 e.g. by means of ink-jet or aerosol-jet process with a curable example with UV light
• Insulator material 18 are filled.
• the first separation trench should preferably be up to the front electrode layer 22, as shown in FIG. above the second
• Buffer layer 14 may be filled with the insulator material 18 in order to avoid later short circuits in the wall region of the structuring flank on the cell 200 side facing. You get the manufacturing level ld.
• the steps of the first and second laser structuring as well as the filling of the first separation trenches with insulator material may in this case preferably be carried out in one and the same installation. This eliminates a complex adjustment, but this must be done only once. Also, the first and second isolation trenches may be mounted closer together, thereby increasing the photovoltaic active area of the thin film solar module.
• third separating trenches 24 are produced, which, like the second separating trenches 20, extend to the barrier layer 6, manufacturing stage le (see FIG. 5). They are mounted adjacent to the second separation trenches 20 and have e.g. over an average distance less than 50 ⁇ , for example, of about 30 ⁇ . Second and third separating trenches 20, 24 are preferably present here essentially in parallel.
• the third separation trenches 24 may be laser or mechanically, e.g. by Nadelritzens be obtained.
• the first, second and third separation trenches 16, 20 and 24 of the solar cell 100 form mutually adjacent isolation trenches in the sense of
• the second separation trenches 20 are filled with a highly conductive material 26 in the illustrated embodiment and at the same time a conductive bridge 28 with this conductive material 26 along the surface of the front electrode layer 22 via the filled with insulator material 18 adjacent first separation trench 16 to the adjacent solar cell 200, for example, to the front electrode layer 22 of this solar cell 200 generated.
• a conductive bridge 28 with this conductive material 26 along the surface of the front electrode layer 22 via the filled with insulator material 18 adjacent first separation trench 16 to the adjacent solar cell 200, for example, to the front electrode layer 22 of this solar cell 200 generated.
• the application of the conductive material may e.g. done by Ink-Jet or Aerosoljet method.
• the target formats of the thin film solar modules can be obtained in an expedient embodiment by means of cutting from the original format of the substrate after the manufacturing stage lf.
• FIG. 7 shows an alternative to the previously described production stages 1c and 1f. Instead of first creating the second separation trench 20 to subsequently fill it with conductive material, one can by means of targeted
• Embodiment described second divisional trench a highly conductive region 30, preferably parallel to the first separation trench 16, which forms a conductive path from the back electrode 4 to the front electrode 22.
• the first separation trench 16 can then be filled with insulator material 18 and then the third separation trench 24 can be produced mechanically or by means of laser treatment, corresponding to the fabrication stages ld and le. This is followed, analogously to the manufacturing stage lf described above
• Fig. 9 shows a further alternative to the invention
• the procedure is similar to that of the above-described production stages la to le, ie first and second Dividing trenches 16 and 20 produced and the first separation trench is filled with an insulating material 18.
• the second separating trench 20 'of the embodiment according to FIG. 9 is made wider than the second separating trench 20 according to FIG. 5.
• the second separation trench 20 ' can not be wider in this embodiment, too
• a first volume region 32 of the second separation trench 20 ' is filled with a curable, conductive material 26 in a location-specific manner, with the omission / omission of the adjacent second volume region 34.
• Insulator material 18 filled first separation trench 16 generated across.
• the first volume region 32 extends from the first separation trench wall 36, adjacent to the adjacent first separation trench 16, into a wall region 40 of the conductive material 26
• the second volume region 34 accordingly extends from the second separation trench wall 38 to the wall region 40. Both begin at the barrier layer 6 and transversely align the thin film solar module 1 through to the front electrode 22. Contact of the first volume region 32 with the second separation trench wall 38 is to Avoid short circuits.
• Embodiments be essential.

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• 2012
  • 2012-04-12 DE DE102012205978A patent/DE102012205978A1/de not_active Withdrawn
• 2013
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  • 2013-03-28 US US14/391,646 patent/US20150068580A1/en not_active Abandoned
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