CN108604502B - Method for forming CdTe thin film solar cells comprising a metal doping step and system for performing said metal doping step - Google Patents
Method for forming CdTe thin film solar cells comprising a metal doping step and system for performing said metal doping step Download PDFInfo
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- 239000010949 copper Substances 0.000 description 19
- 229910052802 copper Inorganic materials 0.000 description 17
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 16
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 11
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 11
- 238000009826 distribution Methods 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- 239000000463 material Substances 0.000 description 4
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- 239000010937 tungsten Substances 0.000 description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
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- 229910052721 tungsten Inorganic materials 0.000 description 3
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- 239000004020 conductor Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
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- 150000002739 metals Chemical class 0.000 description 2
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- 238000013508 migration Methods 0.000 description 2
- HBVFXTAPOLSOPB-UHFFFAOYSA-N nickel vanadium Chemical compound [V].[Ni] HBVFXTAPOLSOPB-UHFFFAOYSA-N 0.000 description 2
- 238000007761 roller coating Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 229910052715 tantalum Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910017009 AsCl3 Inorganic materials 0.000 description 1
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 1
- 229910018030 Cu2Te Inorganic materials 0.000 description 1
- 229910002531 CuTe Inorganic materials 0.000 description 1
- 229910001182 Mo alloy Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 229910001362 Ta alloys Inorganic materials 0.000 description 1
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- 229910001080 W alloy Inorganic materials 0.000 description 1
- 229910007709 ZnTe Inorganic materials 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- FAPDDOBMIUGHIN-UHFFFAOYSA-K antimony trichloride Chemical compound Cl[Sb](Cl)Cl FAPDDOBMIUGHIN-UHFFFAOYSA-K 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
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- 238000005229 chemical vapour deposition Methods 0.000 description 1
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- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- -1 copper salts Chemical class 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
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- 230000000694 effects Effects 0.000 description 1
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- 238000011010 flushing procedure Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
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- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 150000004772 tellurides Chemical class 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/1828—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof the active layers comprising only AIIBVI compounds, e.g. CdS, ZnS, CdTe
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/06—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers
- H01L31/072—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers the potential barriers being only of the PN heterojunction type
- H01L31/073—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers the potential barriers being only of the PN heterojunction type comprising only AIIBVI compound semiconductors, e.g. CdS/CdTe solar cells
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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
- 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
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Abstract
The present application relates to a method for producing a CdTe solar cell, starting with providing a semi-finished CdTe solar cell comprising a CdTe forming a first surface of the semi-finished CdTe solar cell. A metal layer is applied on a first surface of the semi-finished CdTe solar cell and an aqueous solution containing metal ions or containing metal-containing ions is applied on the back side of the semi-finished CdTe solar cell and is removed later. The application and removal of the aqueous solution may be performed before or after the application of the metal layer. Additionally, the semi-finished CdTe solar cell is additionally illuminated or external power is applied to the semi-finished CdTe solar cell for a first time period or a second time period, the first time period being a time period during which the aqueous solution is present on the backside of the semi-finished CdTe solar cell, the second time period being a time period before the metal layer is applied after the aqueous solution is removed.
Description
Technical Field
The present application relates to a method for producing CdTe solar cells comprising a metal doping step and a system for performing said metal doping step.
Background
In the prior art, CdTe solar cells have the following structure: a Transparent Conductive Oxide (TCO) is deposited on the glass substrate as a front contact. The TCO layer can include a high resistance buffer layer that helps minimize shunting effects in the solar cell. Over this, a cadmium sulfide (CdS) layer is deposited, followed by a cadmium telluride (CdTe) layer deposited on the cadmium sulfide layer. Finally, a metal layer, such as molybdenum, nickel vanadium, tantalum, titanium, tungsten, gold, or any composition or compound containing one of these elements, is applied to collect the charge carriers. This process is known as a superstrate configuration.
In order to achieve high efficiency of the solar cell, a good ohmic contact should be established between the CdTe layer and the metal layer. To this end, copper may be introduced into the CdTe layer at the interface with the metal layer. The copper can be provided to the CdTe layer as an elemental layer containing only copper or as a dopant contained in another material or as ions or as part of a chemical compound. The copper may be applied on the CdTe layer, for example, from a gas (e.g., by sputtering) or from an aqueous solution (e.g., of copper chloride or copper salts). The temperature treatment can be performed after the copper is applied on the CdTe layer. In the prior art, the process of incorporating copper into the CdTe layer is referred to as a copper doping step.
However, copper readily migrates within CdTe, and thus can degrade the characteristics of CdTe solar cells over time. Therefore, it is very important to precisely control the amount and location of the copper introduced into the CdTe layer in order to achieve a good ohmic contact and at the same time reduce the risk of copper migration. This can be done by controlling, for example, the copper concentration in the aqueous solution or the time the aqueous solution is provided to the CdTe layer or the thermal budget of the temperature treatment step, which is defined by the temperature and duration of the temperature treatment step. Unfortunately, some of these parameters may not be precisely controlled as desired.
Disclosure of Invention
It is an object of the present invention to provide a method for forming CdTe thin film cells comprising a metal doping step, wherein the method provides improved control of the amount and location of metal ions introduced by the metal doping step within the CdTe layer. It is a further object to provide a system adapted to perform the method.
The method according to the application comprises the following steps: providing a semi-finished CdTe solar cell; applying an aqueous solution comprising metal ions or comprising metal-containing ions on the back side of the semi-finished CdTe solar cell, removing the aqueous solution from the back side of the semi-finished CdTe solar cell, and applying a metal layer on the first surface of the semi-finished CdTe solar cell for back contact. The semi-finished CdTe solar cell includes at least a transparent substrate, a front contact layer, a CdS layer, and a CdTe layer, wherein a surface of the CdTe layer opposite the transparent substrate forms a first surface of the semi-finished CdTe solar cell. The back side onto which the aqueous solution is applied is the first surface of the semi-finished CdTe solar cell or the first surface of the metal layer opposite the transparent substrate. The semi-finished CdTe solar cell may comprise further layers between said layers, and one or more layers (e.g. front contact layers) may also be formed as a layer sequence known in the art. The front contact layer is typically transparent and is typically realized by a Transparent Conductive Oxide (TCO). The CdS layer, CdTe layer and front contact layer or layer sequence are formed by methods known in the art.
The aqueous solution can be applied on the back side of the semi-finished CdTe solar cells by processes known in the art, such as but not limited to:
-immersion holding of the semi-finished CdTe solar cell (or the back of the semi-finished CdTe solar cell) in a receptacle
In the aqueous solution of (a) to (b),
-spraying the liquid,
-spin-coating,
sponge roll coating, etc.
The aqueous solution may be a metal salt, such as CuCl2、CuSO4、Cu(NO3)2、SbCl3、AsCl3AgCl or any other compound containing a metal-containing complex. In solution, the metal is present in the form of a metal ion or as a charged complex, i.e. bounded by metal-containing ions. The aqueous solution contains a metal in a concentration in the range between 0.05mmol/l and 10 mmol/l. As a result, metal ions, such As copper (Cu), antimony (Sb), silver (Ag) or arsenic (As), are introduced into the CdTe layer, or in other words: the CdTe layer is doped with metal ions.
The aqueous solution may be removed from the back side of the semi-finished CdTe solar cell by removing the semi-finished CdTe solar cell from the aqueous solution held in the container and/or by purging, rinsing with a cleaning solution, drying, or a combination thereof, or by other processes known in the art.
The step of applying a metal layer on the first surface of the semi-finished CdTe solar cell is known in the art and may comprise depositing molybdenum, nickel vanadium, gold, tantalum, tungsten, alloys of molybdenum, tantalum, titanium and tungsten, compounds containing molybdenum or tungsten or other materials, or using sputtering, evaporation/sublimationOr chemical vapor deposition or any other suitable deposition technique to deposit combinations or layer sequences of different ones of these materials. Furthermore, the step of applying a metal layer may also comprise forming an additional layer of another material, like ZnTe, Cu, between the first surface of the semi-finished CdTe solar cell and the metal layer2O、Cu2Te, CuTe or other metal telluride compounds, as are also known in the art.
According to the present application, the semi-finished CdTe solar cell is additionally illuminated and/or power is applied to the semi-finished CdTe solar cell by conductively connecting the semi-finished CdTe solar cell to a power source. As a result, an additional electric field is formed across the semi-finished CdTe solar cell. The step of additional lighting and/or application of power lasts for a first period of time, which is the period of time during which the aqueous solution is present on the back side of the semi-finished CdTe solar cell, and/or a second period of time, which is the period of time after the step of removing the aqueous solution from the back side of the semi-finished CdTe solar cell and before the step of applying the metal layer on the first surface is performed. The first period of time may be the whole time between the beginning of the step of applying the aqueous solution and the end of the step of removing the aqueous solution, i.e. the whole time during which the aqueous solution is at least partially present at the back side of the semi-finished CdTe solar cell, or only a fraction of this duration. The second period of time may be the entire time between the end of the step of removing the aqueous solution and the beginning of the step of applying the metal layer, i.e. the entire time between these two steps, or only a fraction of this duration.
Thus, there are four possible process flows according to the present application, where the steps are performed in the order described, and only the steps of additional illumination and/or application of power may overlap with the steps of applying and removing the aqueous solution in the first part of the first, second and fourth process flows:
1. providing a semi-finished CdTe solar cell, applying an aqueous solution, additional lighting and/or applying power, removing the aqueous solution and applying a metal layer;
2. providing a semi-finished CdTe solar cell, applying a metal layer, applying an aqueous solution, additional lighting, and/or applying power and removing the aqueous solution;
3. providing a semi-finished CdTe solar cell, applying an aqueous solution, removing the aqueous solution, additional lighting and/or applying power and applying a metal layer;
4. providing a semi-finished CdTe solar cell, applying an aqueous solution, additional illumination and/or applying power, removing an aqueous solution, additional illumination and/or applying power and applying a metal layer.
The fourth case is a combination of the first case and the third case. In the first, third and fourth cases, the back of the semi-finished CdTe solar cell, on which the aqueous solution is applied, is formed by the surface of the CdTe layer as first surface of the semi-finished CdTe solar cell. In the second case, the back of the semi-finished CdTe solar cell, on which the aqueous solution is applied, is formed by the first surface of the metal layer.
The additional electric field across the semi-finished CdTe solar cell, formed by the additional illumination or by the supplied power, superimposes the intrinsic electric field formed by the pn-junction between the CdS layer and the CdTe layer. "superimposed" means that the additional electric field is enhanced or reversed from the intrinsic electric field. In case of additional illumination or contacting the front contact layer with the negative pole of the power supply, more metal ions or complexes of positively charged metals are migrated in the direction of the CdS layer within the CdTe layer than in case of no additional illumination or external power supply. In the case of contacting the front contact layer with the positive electrode of the power supply, the migration of metal ions or complexes of positively charged metals in the direction of the CdS layer within the CdTe layer is reduced compared to the case without an external power supply. Thus, the amount and location of the metal ions introduced into the CdTe layer by the metal doping step can be more precisely controlled as compared to prior art copper treatment steps which merely control the copper concentration in the aqueous solution or the duration of the copper treatment step.
Thus, according to the present application, the metal doping step comprises the following three substeps: applying an aqueous solution comprising metal ions or comprising metal-containing ions to the back side of the semi-finished CdTe solar cell, removing the aqueous solution from the back side of the semi-finished CdTe solar cell, and additionally illuminating and/or electrically connecting the semi-finished CdTe solar cell to a power source for a first time period or a second time period, wherein each sub-step is performed at a defined location, respectively, in the overall process flow.
By "additional illumination" is meant illumination that is greater than the illumination caused by light present during the copper processing step of the prior art. In the prior art, this step is not usually performed in a dark room, but under normal production conditions, including normal lighting conditions. The "extra illumination" is additionally provided by the special lighting unit to these illumination conditions and provides extra light with an illumination in the range of 5000 to 200000 lx. The wavelength of the light of the semi-finished CdTe solar cell which is additionally illuminated is in the absorption region of the CdTe solar cell and preferably in the range between 300 and 900 nm.
In this case, the semi-finished CdTe solar cell is conductively connected to a power source that provides an additional electric field across the semi-finished CdTe solar cell. In case the aqueous solution is not present on the back side of the semi-finished CdTe solar cell, an additional electric field may be provided between the aqueous solution and the front contact of the semi-finished CdTe solar cell or between the ground and the front contact. For example, the front contact layer of the semi-finished CdTe solar cell may be in electrically conductive connection with a first contact of a power source, and the aqueous solution may be in electrically conductive connection with a second contact of the power source. However, it is also possible to contact only the front contact layer, but leave the aqueous solution unconnected, i.e. floating, to the ground, or connect it to the ground. The additional electric field may cause a current to flow through the semi-finished CdTe solar cell, whose absolute value is greater than zero and less than or equal to twice the short circuit current of the CdTe solar cell. That is, the current may be positive or negative compared to the short circuit current.
Only one of the additional lighting and the power supply may serve as the sole measure, or both measures may be performed separately, sequentially or simultaneously in any order. If both measures are performed, the exposure amount of extra illumination and/or power, i.e., the amount of energy, can be reduced as compared to the case when only one measure is performed.
The first or second time period in which one or both of the measures are performed preferably lies in a range between 5s (seconds) and 30min (minutes). The duration of the first or second time period depends on the brightness and/or the power, respectively, the metal concentration in the aqueous solution and the desired distribution of the metal within the semi-finished CdTe solar cell.
Furthermore, during the first period of time, i.e. when one or both of the measures are carried out and the aqueous solution is present on the back side, the temperature of the semi-finished CdTe solar cell is controlled within the range between 25 ℃ and 80 ℃. In case the step of additional lighting and/or applying power is performed after the aqueous solution has been removed, during the second period of time, the temperature of the semi-finished CdTe solar cell is controlled within the range between 25 ℃ and 225 ℃. The temperature of the semi-finished CdTe solar cell is an additional parameter for controlling the distribution of the incoming metal within the semi-finished CdTe solar cell. To achieve the desired temperature, the semi-finished CdTe solar cell may be heated or cooled or heated and cooled sequentially in any order during the first or second time period.
As a result, the skilled person now has a large number of parameters that can be controlled in order to achieve the desired distribution of the metal within the semi-finished CdTe solar cell: brightness of the additional illumination, power supplied by the power source, duration of the first or second time period, temperature of the semi-finished CdTe solar cell during the first or second time period, and concentration of metal within the aqueous solution and time that the aqueous solution is present on the backside. Thus, the over-doping of the semi-finished CdTe solar cell with metal, i.e. the amount of metal introduced is higher than what is required for the formation of a good ohmic contact, can be reduced and the eventual degradation of the finished CdTe solar cell can be reduced while increasing the process window for the metal doping step.
The method according to the present application can comprise further steps like a temperature treatment step or conditioning step comprising illumination and/or providing power to CdTe solar cells, or a combination of these steps. However, these steps known in the prior art are performed at least after the step of applying a metal layer on the first surface of the semi-finished CdTe solar cell in order to form the back contact and in the absence of an aqueous solution.
According to the present application, the system for performing the metal doping step of a semi-finished CdTe solar cell comprises: a first unit for applying an aqueous solution comprising metal ions or comprising metal-containing ions to the back of a semi-finished CdTe solar cell; a second unit for removing the aqueous solution from the back side of the semi-finished CdTe solar cell, and a lighting unit. The semi-finished CdTe solar cell at least comprises a transparent substrate, a front contact layer, a CdS layer and a CdTe layer, wherein the back surface of the semi-finished CdTe solar cell is the surface of the semi-finished CdTe solar cell opposite to the transparent layer. In particular, the semi-finished CdTe solar cell may comprise a transparent substrate, a front contact layer, a CdS layer and a CdTe layer, wherein the back side is formed by a surface of the CdTe layer, or the semi-finished CdTe solar cell may comprise a transparent substrate, a front contact layer, a CdS layer, a CdTe layer and a metal layer, wherein the back side is formed by a surface of the metal layer. The illumination unit is adapted to additionally illuminate the semi-finished CdTe solar cell for a first period of time, which is a period of time during which the aqueous solution is present at the back side of the semi-finished CdTe solar cell.
The lighting units may be combined with the first unit and/or the second unit such that all combined units simultaneously perform their functions for at least a portion of their respective processing time. For example, if the first unit comprises a container holding the aqueous solution and means for immersing the semifinished CdTe solar cell in the aqueous solution, the illumination unit may be arranged such that the light generated by it illuminates at least a portion of the time during which the semifinished CdTe solar cell is immersed in the aqueous solution. However, the first unit and the lighting unit or the second unit and the lighting unit, although combined together, also perform their functions sequentially. By "combination of the first unit and/or the second unit with the lighting unit" is meant that the process range of the lighting unit at least partially overlaps with the first unit and/or with the second unit. By "process range" is meant the spatial range in which the light generated by the lighting unit affects the semi-finished CdTe solar cell. In one embodiment, the first unit and the lighting unit are arranged in one unit.
However, the lighting unit may also be spatially separated from the first unit and/or the second unit, such that the lighting unit is arranged in the flow order of the units after the first unit and before the second unit. The flow order of the units describes the order in which the units use them. The spatial arrangement of the units in the production plant may differ from the flow order of the units. When the semi-finished CdTe solar cell is within the process range of the lighting unit, the aqueous solution is at least partially present on the first surface of the semi-finished CdTe solar cell. For example, the first unit may comprise a container holding the aqueous solution and means for immersing the semi-finished CdTe solar cell in the aqueous solution, or may comprise a nozzle unit for spraying the aqueous solution onto the back side of the semi-finished CdTe solar cell, or may comprise a roller unit for roller-coating the aqueous solution onto the back side of the semi-finished CdTe solar cell. In all cases, the process range of the lighting unit is spatially separated from the first unit. Thus, the first unit ends its performance, i.e. by removing the semi-finished CdTe solar cells from the container holding the aqueous solution, or by stopping the spraying or rolling of the aqueous solution onto the back of the semi-finished CdTe solar cells, and then the semi-finished CdTe solar cells are transferred from the first unit to the process field of the lighting unit and illuminated there. In this case, the illumination unit is formed such that the aqueous solution remains on the back side of the semi-finished CdTe solar cell during illumination. For example, the lighting unit has a holder holding the semi-finished CdTe solar cell, so that the back face is held horizontally and the lateral distribution of the aqueous solution on the lateral extension of the back face is not altered compared to the lateral distribution produced by the first unit for applying the aqueous solution. Subsequently, the semi-finished CdTe solar cell is transferred from the lighting unit to a second unit, where the aqueous solution is removed from the back side of the semi-finished CdTe solar cell.
The illumination unit is adapted for illuminating the semi-finished CdTe solar cell with light having a wavelength in the absorption region of the CdTe solar cell, and preferably with light having a wavelength in the range of 300 to 900 nm. In a particular embodiment, the system additionally comprises a third unit for controlling the temperature of the semi-finished CdTe solar cell during the first period of time within a range between 25 ℃ and 80 ℃. Depending on the desired temperature of the semi-finished CdTe solar cell, the third unit may comprise a heating device or a cooling device or a combination thereof.
For example, the lighting unit and the third unit may be combined in a mild tunnel comprising one or more lamps generating light. The tunnel may be arranged in the flow order of the units after the first unit, where the aqueous solution is applied to the back side of the semi-finished CdTe solar cell, for example by spraying or roller coating, and before the second unit.
In addition to the lighting unit, the system may comprise a power source and a contact means for connecting the front contact layer of the semi-finished CdTe solar cell to the power source during the first period of time. When the power source is connected to the semi-finished CdTe solar cell, the power source is adapted to form an additional electric field across the semi-finished CdTe solar cell.
Drawings
Fig. 1A to 1C schematically show an exemplary process sequence of a method according to the present application.
Fig. 2 schematically shows a first embodiment of the system according to the application, wherein the first unit and the lighting unit are combined.
Fig. 3 schematically shows a second embodiment of the system according to the application, wherein the first unit and the lighting unit are separated from each other.
Detailed Description
The method and system according to the invention are explained in the following in exemplary embodiments, wherein the figures are not intended to limit the illustrated embodiments.
Fig. 1A shows a first exemplary process step of a method according to the present application. First, a semi-finished CdTe solar cell having a first surface as described above is provided in step S110. In a next step S120, an aqueous solution comprising metal ions as described above is applied on the first surface, i.e. on the surface of the CdTe layer. The aqueous solution is at least partially present on the first surface of the semi-finished CdTe solar cell until it is completely removed from the first surface in step S140, i.e., the aqueous solution is present for a period of time tAAnd (4) showing. From the beginningThe time from step S120 to the end of step S140 is from tDThe time of the metal doping step, which in the present example is equal to the time period t, is indicatedA. At time tADuring a first time period t1Additionally illuminating the semi-finished CdTe solar cell (step S131) and/or applying power to the semi-finished CdTe solar cell (step S132). That is, one or two steps S131 and S132 may be performed. If both steps are performed, steps S131 and S132 may be performed simultaneously in time or partially overlapping or completely separated. That is, the time period t for performing step S131 and step S132, respectively31And t32May be the same or different and they may overlap or be separated completely or partially on a time scale. However, the total period, i.e., the sum of all periods in which at least one of steps S131 and S132 is performed, is the first period t shown in fig. 1A1. Steps S131 and/or S132 may overlap with step S120 and/or with step S140. After step S140, a metal layer is applied on the first surface of the semi-finished CdTe solar cell (step S150). The combination or entirety of steps S120, S131, S132 and S140 is referred to as a metal doping step according to the present application.
In fig. 1B, a second exemplary process step of the method according to the present application is schematically illustrated. Step S210 corresponds to step S110 of fig. 1A. Then, in a next step S220, a metal layer is applied on the first surface of the semi-finished CdTe solar cell. As a result, the semi-finished CdTe solar cell has a back side formed by a metal layer. Subsequently, an aqueous solution containing metal ions as described above is applied on the back surface, i.e., on the surface of the metal layer (step S230). The aqueous solution is present at least partially on the back side of the semi-finished CdTe solar cell until it is completely removed from the back side in step S250, the aqueous solution being present for a time tAAnd (4) showing. The time from the start step S230 to the end step S250 is from tDThe time of the metal doping step is shown, which again equals the time period tA. At time tADuring a first time period t1In addition, the semi-finished CdTe solar cell is illuminated (step S241) and/or power is applied to the semi-finished productA CdTe solar cell (step S242). That is, one or two steps S241 and S242 may be performed. If both steps are performed, steps S241 and S242 may be performed simultaneously in time or partially overlapping or completely separated. That is, the time period t for performing the step S241 and the step S242, respectively41And t42May be the same or different and they may overlap or be separated completely or partially on a time scale. However, the total period of time, i.e., the sum of all periods of time in which at least one of steps S241 and S242 is performed, is the first period of time t shown in fig. 1B1. As described with reference to the first exemplary process sequence in fig. 1A, steps S241 and/or S242 may overlap with step S230 and/or with step S250. The combination or ensemble of steps S230, S241, S242 and S250 is referred to as a metal doping step according to the present application.
A third exemplary process step of the method according to the present application is explained with reference to fig. 1C. Step S310 corresponds to step S110 of fig. 1A and step S210 of fig. 1B. Then, an aqueous solution comprising metal ions as described above is applied on the first surface, i.e. on the surface of the CdTe layer (step S320). The aqueous solution is present at least partially on the first surface of the semi-finished CdTe solar cell until it is completely removed from the first surface in step S330, the aqueous solution being present for a period of time tAAnd (4) showing. After step S330, the semi-finished CdTe solar cell is additionally illuminated (step S341) and/or power is applied to the semi-finished CdTe solar cell (step S342) for an intermediate time period t between step S330 and step S350lDuring a second time period t2A metal layer is applied on the first surface in S350. That is, one or two steps S341 and S342 may be performed. If both steps are performed, steps S341 and S342 may be performed simultaneously in time or partially overlapping or completely separated. That is, the time period t for performing step S341 and step S342, respectively41And t42May be the same or different and they may overlap or be separated completely or partially on a time scale. However, the total period of time, i.e., the sum of all the periods of time in which at least one of steps S341 and S342 is performed, is the second time period shown in fig. 1CTime period t2. The combination or ensemble of steps S320, S330, S341 and S342 is referred to as a metal doping step according to the present application.
In fig. 2, a first embodiment (100) of the system according to the present application is schematically shown. The system (100) comprises a first unit (110), a second unit (120), a lighting unit (130) and a power supply (140). The first unit (110) is adapted to apply an aqueous solution (20) as described above on the back side (11) of the semi-finished CdTe solar cell (10). The back side can be the surface of the CdTe layer, or can be the surface of the metal layer used as the back contact layer. To this end, the first unit (110) comprises a container (111) holding an aqueous solution (20) and means (112) for immersing the semifinished CdTe solar cells (10) in the aqueous solution (20). The component (112) may be, for example, a holder with a clamp attached to the semi-finished CdTe solar cell (10). The aqueous solution (30) may be heated by the third unit (150) such that the aqueous solution (20) has a temperature between 25 ℃ and less than 100 ℃ (below the boiling point of the aqueous solution). As a result, if the semi-finished CdTe solar cell (10) is immersed in an aqueous solution (20), the semi-finished CdTe solar cell (10) preferably has a temperature between 25 ℃ and 80 ℃. Furthermore, an electrode (113) is provided which is likewise immersed in the aqueous solution (20). If one end of the power source (140) is electrically connected to the front contact layer of the semi-finished CdTe solar cell (10) and the other end is conductively connected to the electrode (113) by contact means comprising, for example, an electrical conductor (141), an electric field is formed between the first electrode (113) and the aqueous solution (20) on one side and the front contact layer of the semi-finished CdTe solar cell (10) on the other side. Thus, the movement of the metal ions or the ion-containing charged metal within the aqueous solution (20) and/or within the semi-finished CdTe solar cell (10) can be controlled. In addition, an illumination unit (130), for example a halogen lamp with an illuminance of 100000lx, is combined with the first unit (110) such that the illumination unit (130) illuminates the semi-finished CdTe solar cell (10) when the semi-finished CdTe solar cell (10) is immersed in the aqueous solution (20). After removing the semi-finished CdTe solar cells (10) from the aqueous solution (20), the semi-finished CdTe solar cells (20) are transferred to a second unit (120) (indicated by the arrow). The second unit (120) known in the art comprises, for example, a rinsing device (121) and a drying device (122), which removes the aqueous solution (20) or the remaining part thereof from the back side (11) of the semi-finished CdTe solar cell (10).
Fig. 3 schematically shows a second embodiment (200) of the system according to the present application. The system (200) comprises a first unit (210), a second unit (220) and a lighting unit (230). The first unit (210) comprises a nozzle array or nozzle arrangement (211) connected by a fluid line (213) to a container (212) holding an aqueous solution (20) as described above. The aqueous solution (20) is sprayed by means of a nozzle device (211) on the back side (11) of the semi-finished CdTe solar cell (10) (as indicated by the dashed arrow). The back side can be the surface of the CdTe layer, or can be the surface of the metal layer used as the back contact layer. The semi-finished CdTe solar cell (10) is held on a holder (214), the holder (214) being rotatable. After applying the aqueous solution (20) to the back side (11) of the semi-finished CdTe solar cell (10), the semi-finished CdTe solar cell (10) with the aqueous solution present on its back side (11) is conveyed to a mild tunnel (240) in which a lighting unit (230) is installed. The illumination unit (230) is a lamp array providing light with a wavelength of 300 to 800nm and an illuminance of 30000 to 200000 lx. The illumination unit (230) illuminates the semi-finished CdTe solar cell (10) for a first period of time while the semi-finished CdTe solar cell (10) is held on a mild holder (241) within a mild tunnel (240). Thus, in the second embodiment (200) of the system shown, the first unit (210) and the lighting unit (230) are separate from each other. In order to keep the semi-finished CdTe solar cell (10) at the desired temperature during illumination, a third unit (250), for example a cooling device, is installed inside a mild tunnel (240). After illuminating the semi-finished CdTe solar cell (10), the semi-finished CdTe solar cell (10) is transferred from the mild tunnel (250) to the second unit (220), which second unit (220) may comprise the same or other devices as described with reference to fig. 2.
In the example shown in fig. 2 and 3, the illumination unit (130, 230) is arranged such that the light emitted by the illumination unit (130, 230) impinges on the back side (11) of the semi-finished CdTe solar cell (10). However, this is only one exemplary arrangement of a lighting unit, which may be used if the backside of the semi-finished CdTe solar cell is the first surface of the semi-finished CdTe solar cell, i.e. the surface of the CdTe layer. In case a metal layer has been applied on the CdTe layer such that the back of the semi-finished CdTe layer is the surface of the metal layer, the lighting unit should be arranged within the system for performing the metal doping step such that the light emitted by the lighting unit impinges on the sunlight side of the semi-finished CdTe solar cell, i.e. the transparent substrate. In any case, however, the semi-finished CdTe solar cell can be illuminated on the sunlight side.
The embodiments of the present invention described in the foregoing description are examples given by way of illustration, and the present invention is not limited thereto at present. Any modifications, variations and equivalent arrangements, as well as combinations of the embodiments, should be considered to be included within the scope of the present invention.
Reference numerals
10 semi-finished CdTe solar cell
11 back of semi-finished CdTe solar cell
20 aqueous solution
100. 200 system for performing a metal doping step
110. 210 first unit
111. 212 container
112 parts for impregnation
113 electrode
120. 220 second unit
121 flushing device
122 drying device
130. 230 lighting unit
140 power supply
141 electric conductor
211 nozzle arrangement
213 fluid line
214 holder
240 mild tunnel
241 mild holder
150. 250 third unit
t1First timeSegment of
t2A second period of time
tATime period of aqueous solution existence
tDTime period of the metal doping step
tlIntermediate time period
t31、t41Time period of additional illumination
t32、t42Time period of applying power
Claims (15)
1. A method for producing CdTe solar cells, comprising the steps of:
a) providing a semi-finished CdTe solar cell comprising at least a transparent substrate, a front contact layer, a CdS layer and a CdTe layer, wherein a surface of the CdTe layer opposite the transparent substrate forms a first surface of the semi-finished CdTe solar cell,
b) applying an aqueous solution comprising metal ions or comprising metal-containing ions on the back side of the semi-finished CdTe solar cell,
c) removing the aqueous solution from the back side of the semi-finished CdTe solar cell,
d) applying a metal layer on the first surface of the semi-finished CdTe solar cell, and
e) additionally illuminating the semi-finished CdTe solar cell and/or applying power to the semi-finished CdTe solar cell by electrically connecting the semi-finished CdTe solar cell to a power source,
wherein the back side of the semi-finished CdTe solar cell is the first surface of the semi-finished CdTe solar cell or a first surface of the metal layer opposite the transparent substrate,
characterized in that step e) lasts for a first period of time, which is the period of time during which the aqueous solution is present on the back side of the semi-finished CdTe solar cell, and/or a second period of time, which is the period of time after step c) and before step d).
2. The method according to claim 1, characterized in that steps b) and c) are performed before step d), the back side is the first surface of the semi-finished CdTe solar cell, and step e) is continued for the first period of time, which is the period of time during which the aqueous solution is present on the back side of the semi-finished CdTe solar cell.
3. The method according to claim 1, characterized in that steps b) and c) are performed after step d), the back side being the first surface of the metal layer, and step e) is continued for the first period of time, which is the period of time during which the aqueous solution is present on the back side of the semi-finished CdTe solar cell.
4. The method according to claim 1, characterized in that steps b) and c) are performed before step d), the back side is the first surface of the semi-finished CdTe solar cell, and step e) is continued for the second period of time, which is the period of time after step c) before step d).
5. The method according to claim 1, characterized in that the light additionally illuminating the semi-finished CdTe solar cell has a wavelength in the absorption region of the CdTe solar cell.
6. The method of claim 5, wherein the wavelength of the light is in a range of 300nm to 900 nm.
7. The method according to claim 1, characterized in that said power source provides an electric current flowing through said semi-finished CdTe solar cell having an absolute value greater than zero and less than or equal to twice the short circuit current of said CdTe solar cell.
8. The method of claim 1, wherein the first time period or the second time period is in a range between 5s and 30 min.
9. The method according to claim 2 or claim 3, characterized in that during said first period of time, the temperature of the semi-finished CdTe solar cell is controlled within a range between 25 ℃ and 80 ℃.
10. The method according to claim 4, characterized in that during said second period of time, the temperature of the semi-finished CdTe solar cell is controlled in the range between 25 ℃ and 225 ℃.
11. A system for performing the metal doping step of semi-finished CdTe solar cells, said system comprising:
a first unit for applying an aqueous solution comprising metal ions or comprising metal-containing ions to the back of a semi-finished CdTe solar cell comprising at least a transparent substrate, a front contact layer, a CdS layer and a CdTe layer, wherein the back of the semi-finished CdTe solar cell is the surface of the semi-finished CdTe solar cell opposite to the transparent substrate,
-a second unit for removing the aqueous solution from the back side of the semi-finished CdTe solar cell; and
-an illumination unit adapted to additionally illuminate the semi-finished CdTe solar cell for a first period of time, the first period of time being a period of time during which the aqueous solution applied by the first unit is present on the back side of the semi-finished CdTe solar cell.
12. The system according to claim 11, characterized in that said illumination unit is adapted to illuminate said semi-finished CdTe solar cell with light having a wavelength in the absorption area of said CdTe solar cell.
13. The system of claim 12, wherein the wavelength of the light is in a range of 300nm to 900 nm.
14. The system according to claim 11, further comprising a third unit for controlling the temperature of the semi-finished CdTe solar cell in the range between 25 ℃ and 80 ℃ for the first period of time.
15. The system of claim 11, further comprising a power source and a contact device for connecting the semi-finished CdTe solar cell to the power source, wherein the power source is adapted to form an additional electric field across the semi-finished CdTe solar cell during the first period of time when the power source is connected to the semi-finished CdTe solar cell.
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| PCT/CN2016/112433 WO2018119685A1 (en) | 2016-12-27 | 2016-12-27 | Method for forming a cdte thin film solar cell including a metal doping step and system for performing said metal doping step |
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| CN117080082A (en) * | 2022-05-10 | 2023-11-17 | 中国建材国际工程集团有限公司 | Method for manufacturing semi-finished CdTe-based thin film solar cell device |
| CN117080080A (en) * | 2022-05-10 | 2023-11-17 | 中国建材国际工程集团有限公司 | Method for manufacturing semi-finished CdTe-based thin film solar cell device |
| WO2023236106A1 (en) * | 2022-06-08 | 2023-12-14 | China Triumph International Engineering Co., Ltd. | Method for manufacturing cdte based thin film solar cell with graded refractive index profile within the cdte-based absorber layer and cdte based thin film solar cell with graded refractive index profile |
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| DE112016006558T5 (en) | 2018-11-29 |
| CN108604502A (en) | 2018-09-28 |
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