WO2019174609A1 - 复合材料、化学水浴沉积方法和cigs光伏组件的制备方法 - Google Patents

复合材料、化学水浴沉积方法和cigs光伏组件的制备方法 Download PDF

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WO2019174609A1
WO2019174609A1 PCT/CN2019/078104 CN2019078104W WO2019174609A1 WO 2019174609 A1 WO2019174609 A1 WO 2019174609A1 CN 2019078104 W CN2019078104 W CN 2019078104W WO 2019174609 A1 WO2019174609 A1 WO 2019174609A1
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layer
substrate
composite material
material layer
water bath
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PCT/CN2019/078104
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French (fr)
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王磊
郭逦达
杨立红
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北京铂阳顶荣光伏科技有限公司
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Publication of WO2019174609A1 publication Critical patent/WO2019174609A1/zh

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    • H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
    • H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
    • H01L31/0264—Inorganic materials
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    • H01L31/0322—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 comprising only AIBIIICVI chalcopyrite compounds, e.g. Cu In Se2, Cu Ga Se2, Cu In Ga Se2
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    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
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    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/125—Process of deposition of the inorganic material
    • C23C18/1291—Process of deposition of the inorganic material by heating of the substrate
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    • H01L31/036—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes
    • H01L31/0392—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate
    • H01L31/03923—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate including AIBIIICVI compound materials, e.g. CIS, CIGS
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    • 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
    • H01L31/0749—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 including a AIBIIICVI compound, e.g. CdS/CulnSe2 [CIS] heterojunction solar cells
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    • 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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    • C08K2003/2275—Ferroso-ferric oxide (Fe3O4)
    • 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
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    • 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
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    • 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
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Definitions

  • the present disclosure relates to the field of thin film power generation technology, and more particularly to a chemical water bath deposition method and a method of preparing a CIGS photovoltaic module, and a composite material used in the two methods.
  • Chemical Bath Deposition has attracted great attention because of its low film forming temperature, suitable for preparing large-area films, easy to achieve continuous production, no pollution, and low material consumption.
  • CBD Chemical Bath Deposition
  • CIGS Cu, In, Ga, Se, copper indium gallium selenide
  • a cadmium sulfide (CdS) semiconductor thin film buffer layer is usually prepared by a chemical water bath deposition method.
  • a chemical water bath deposition method comprising the steps of: forming a first functional layer on one side of a substrate, and forming a composite material layer on another opposite side of the substrate, the composite material layer comprising a molecular hydrogel and magnetic nanoparticles mixed in the polymer hydrogel; the substrate on which the first functional layer and the composite material layer are formed are placed in a deposition solution, in the first Depositing on the functional layer forms a second functional layer; separating the composite layer from the substrate.
  • the first functional layer comprises a p-junction material layer.
  • the first functional layer further includes a light emitting layer, and the P-junction material layer and the light emitting layer are spaced apart to be insulated from each other.
  • the second functional layer comprises an n-junction material layer.
  • the mass percentage of the polymer hydrogel in the composite layer is 80% to 95%, and the mass percentage of the magnetic nanoparticles is 5% to 20%.
  • the polymeric hydrogel is selected from at least one of the group consisting of copolymerized crosslinkers of polyacrylic resins, polyvinyl alcohol, polyacrylamide, and silicon-based hydrogels.
  • the magnetic nanoparticles are selected from the group consisting of Fe 3 O 4 .
  • the substrate is inductively heated using an alternating magnetic field during deposition of the second functional layer.
  • the alternating magnetic field has a frequency of 450 kHz to 550 kHz.
  • the composite layer is dissolved with a solvent when the composite layer is separated from the substrate.
  • the solvent is selected from at least one of the group consisting of a dimethyl sulfoxide solvent and a dimethylformamide solvent.
  • the composite layer is formed on the other opposing side of the substrate by screen printing.
  • some embodiments of the present disclosure further provide a method of fabricating a CIGS photovoltaic module, the method comprising the steps of: forming a CIGS layer on one side of a substrate and forming a composite layer on another opposite side of the substrate
  • the composite material layer comprises a polymer hydrogel and magnetic nanoparticles mixed in the polymer hydrogel; and the substrate on which the CIGS layer and the composite material layer are formed is placed in a deposition solution Depositing a CdS layer on the CIGS layer; separating the composite material layer from the substrate.
  • the mass percentage of the polymer hydrogel in the composite layer is 80% to 95%, and the mass percentage of the magnetic nanoparticles is 5% to 20%.
  • the substrate is inductively heated using an alternating magnetic field during deposition of the CdS layer.
  • some embodiments of the present disclosure also provide a composite material comprising a polymer hydrogel and magnetic nanoparticles mixed in the polymer hydrogel.
  • the mass percentage of the polymer hydrogel is 80% to 95%, and the mass percentage of the magnetic nanoparticles is 5% to 20%.
  • the polymeric hydrogel is selected from at least one of the group consisting of copolymerized crosslinkers of polyacrylic resins, polyvinyl alcohol, polyacrylamide, and silicon-based hydrogels.
  • the magnetic nanoparticles are selected from the group consisting of Fe 3 O 4 .
  • FIG. 1 is a process flow diagram of a chemical water bath deposition method provided by some embodiments of the present disclosure
  • FIG. 2 is a schematic process diagram of a method for preparing a CIGS photovoltaic module according to some embodiments of the present disclosure
  • FIG. 3 is another schematic diagram of a process for preparing a CIGS photovoltaic module according to some embodiments of the present disclosure.
  • the chemical bath deposition (CBD) for producing a cadmium sulfide (CdS) semiconductor film mainly includes a rocking CBD process and a immersion CBD process.
  • the coating uniformity of the swing type CBD process is significantly higher than that of the immersion CBD process, which is mainly due to the higher temperature uniformity of the swing type CBD process.
  • the premixed liquid of the chemical reaction solution (the thiourea is not contained in the premixed solution) is first heated to the reaction temperature, and then the thiourea is added. After the premixed solution and the thiourea are uniformly stirred, The cold glass substrate enters the reaction chamber and begins CdS deposition. Therefore, the main problem of the immersion CBD process is that before the glass substrate enters, the formation of CdS particles has begun in the chemical reaction solution and is suspended in the chemical reaction solution, which has a negative influence on the coating process. The glass substrate which is not preheated is slowly heated by the chemical reaction liquid, and the deposition rate of CdS is lower at the initial stage, resulting in lower utilization rate of the chemical reaction liquid.
  • the front and back sides of the glass substrate are deposited by CdS, and finally only the front CdS film layer is the effective film layer of the module, and the CdS film layer on the back side will have to be cleaned, and the back side cleaning machine
  • the front CdS film layer is the effective film layer of the module, and the CdS film layer on the back side will have to be cleaned, and the back side cleaning machine
  • some embodiments of the present disclosure provide a chemical water bath deposition method, the method comprising the steps of:
  • the chemical water bath deposition method applies the composite material layer to form a protective layer on the other opposite side of the substrate such that the other opposite side of the substrate having the composite material layer is not associated with the deposition Contacting the solution while utilizing swelling of the polymeric hydrogel in the composite layer in the deposition solution to reduce the circulation rate of the deposition solution at the other opposite side of the substrate, avoiding Ineffective deposition of the second functional layer on the composite layer (because the deposition solution does not need to be deposited on the composite layer, even if deposited, it needs to be removed by subsequent processes). Therefore, not only the utilization rate of the deposition solution is improved, the material for reaction is saved, the cost is reduced, and the removal of the composite material layer is facilitated, and the cleaning difficulty is reduced.
  • the material of the substrate is not limited. For example, it may be a glass substrate or a metal substrate.
  • the first functional layer formed in the step a comprises a p-junction material layer.
  • the p-junction material layer is a light absorbing layer of a photovoltaic component, and the p-junction material layer includes, but not limited to, a CIGS layer (a copper indium gallium selenide layer), a single crystal silicon layer, a polysilicon layer, a gallium arsenide layer, And one or more of the organic dye layers.
  • the first functional layer further includes a light emitting layer, and the P-junction material layer and the light emitting layer are spaced apart to be insulated from each other.
  • the light emitting layer is a functional layer of an OLED (Organic Light-Emitting Diode), and the light emitting layer includes, but is not limited to, an organic light emitting semiconductor material layer.
  • the first mask may be used first, and the first mask is not used on the substrate.
  • Forming a P-junction material layer at the masked region, and then masking the already formed P-junction material layer with a second mask, and forming a region on the substrate that is not covered by the second mask Light-emitting layer.
  • the formed P-junction material layer and the light-emitting layer are spaced apart from each other to be insulated from each other.
  • the P-junction material layer and the light-emitting layer may be arranged at intervals, or may be adjacently arranged in regions.
  • the substrate can be used in both directions.
  • the substrate may absorb sunlight by the P-junction material layer to generate electricity and store electrical energy; at night, the substrate may use the stored electrical energy to cause the luminescent layer to emit light, thereby decorating and embellishing the building curtain wall .
  • the composite material layer is formed on the other opposite side of the substrate by screen printing.
  • the composite material layer comprises a polymer hydrogel and magnetic nanoparticles mixed in the polymer hydrogel, and thus has the characteristics of both materials, and is capable of induction heating, film forming property and swelling property.
  • the polymer hydrogel as a carrier can be screen printed.
  • a composite material comprising a polymer hydrogel and magnetic nanoparticles is coated on the other opposite side of the substrate by screen printing to facilitate uniformity of the composite layer.
  • the mass percentage of the polymer hydrogel in the composite layer is 80% to 95%, and the mass percentage of the magnetic nanoparticles is 5% to 20%.
  • the polymer hydrogel is selected from at least one of the following: a copolymerized crosslinked product of a polyacrylic resin, polyvinyl alcohol, polyacrylamide, and a silicon-based hydrogel.
  • the magnetic nanoparticles are selected from the group consisting of Fe 3 O 4 .
  • the strength, swelling, and the like of the composite layer can be adjusted by using different polymer hydrogel materials, which is not limited in the present application.
  • the copolymerized crosslinked product of the polyacrylic resin has good coating property, simple synthesis method, low cost, and good water swellability, the swelling ratio can be adjusted, and therefore, in some embodiments, the polymer hydrogel It is a copolymerized crosslinker of a polyacrylic resin.
  • the second functional layer in step b comprises an n-junction material layer.
  • the n-junction material layer is a buffer layer of the photovoltaic component, and is matched with the p-junction material layer to form a pn junction.
  • the sunlight is irradiated on the pn junction, the electrons and holes of the pn junction barrier region are opposite. The direction moves away from the barrier region, with the result that the p-region potential is raised and the n-region potential is lowered, so that voltage and current can be generated in the external circuit connected to the pn junction to convert the light energy into electrical energy.
  • a common n-junction material layer is a CdS layer
  • the second functional layer is a functional layer that can be used in conjunction with the first functional layer.
  • the substrate is inductively heated by an alternating magnetic field during deposition of the second functional layer, the alternating magnetic field having a frequency of 450 kHz to 550 kHz, and the heating temperature is according to the deposited
  • the second functional layer is determined.
  • the heating temperature is 60 ° C to 70 ° C;
  • the second functional layer deposited is a zinc sulfide (ZnS) layer, the heating temperature It is from 75 ° C to 80 ° C.
  • the substrate is inductively heated by an alternating magnetic field such that the substrate is first heated, and then the deposition solution is heated by the temperature of the substrate.
  • the alternating magnetic field is generated by an alternating magnetic field that matches an inductive heating function of the composite layer, the inductive heating function of the composite layer being related to the content of magnetic nanoparticles The higher the content of the magnetic nanoparticles, the better the induction heating function of the composite layer, so that the suitable induction heating function of the composite layer can be achieved by adjusting the mass percentage of the magnetic nanoparticles and the polymer hydrogel. .
  • the substrate is disposed in parallel with the sidewall of the container or the reaction tank containing the deposition solution, so as to arrange the circuit to make the alternating magnetic field
  • the substrate is substantially vertical (for example, as shown in FIG. 2, the alternating magnetic field 5 shown by the broken line is substantially perpendicular to the substrate 1), thereby enhancing the heating effect of the alternating magnetic field induction.
  • the principle of electromagnetic induction heating is to use magnetic field induction heating, for example, to make a high-speed varying high-frequency high-voltage current flow through the coil to generate a high-speed alternating magnetic field.
  • the alternating magnetic field 5 causes the magnetic nanoparticles in the composite layer to be rapidly heated.
  • the composite material layer when the composite material layer and the substrate are separated in the step c, the composite material layer is dissolved with a solvent.
  • the solvent includes, but is not limited to, at least one of a dimethyl sulfoxide (DMSO) solvent and a N-Dimethylformamide (DMF) solvent. Both the DMSO solvent and the DMF solvent can dissolve the polymer hydrogel.
  • DMSO dimethyl sulfoxide
  • DMF N-Dimethylformamide
  • Both the DMSO solvent and the DMF solvent can dissolve the polymer hydrogel.
  • the composite material layer is immersed in the solvent to be dissolved.
  • the magnetic nanoparticles in the composite layer also flow into the solvent to effectively separate the composite layer from the substrate.
  • the above-mentioned wet process for removing the composite material layer on the substrate not only has low technical cost, but also does not cause damage to the substrate, and at the same time, facilitates recycling and reuse of the magnetic nanoparticles.
  • the composite material layer as a protective layer on the other opposite side of the substrate such that the other opposite side of the substrate is not in contact with the deposition solution, avoiding the second Ineffective deposition of the functional layer on the other opposing side of the substrate;
  • the contactless induction heating of the magnetic nanoparticles in the composite layer is beneficial to ensure uniformity of heating of the substrate, and to ensure that the temperature of the substrate is higher than the temperature of the deposition solution, so that The deposition of the second functional layer is more likely to occur, increasing the deposition rate of the second functional layer on the first functional layer;
  • the polymer hydrogel in the composite material layer is an effective carrier of the magnetic nano particles, which not only ensures the uniform distribution of the magnetic nanoparticles, but also ensures that the magnetic nanoparticles are not lost from the composite material;
  • the polymer hydrogel swells in the deposition solution by immersing the molecules of the deposition solution, and thereafter the polymer hydrogel absorbs the molecules of the deposition solution at a reduced rate, thereby causing the other opposite side of the substrate
  • the cycle speed of the deposition solution is reduced, avoiding the ineffective deposition of the second functional layer on the composite layer, thereby facilitating the removal of the composite layer;
  • the synthesis process of the composite material in the composite material layer is mature, can be mass-produced, and the cost is low, and the incorporated magnetic nanoparticles can be reused;
  • the separation of the composite material layer from the substrate is not only low in technical cost, but also does not cause damage to the substrate;
  • magnetic nanoparticles can be recycled and reused.
  • the above chemical water bath deposition method can effectively improve the immersion CBD process, solve the problem of uniformity of substrate heating in the immersion CBD process, and improve the film formation efficiency and film formation uniformity of the immersion CBD process.
  • some embodiments of the present disclosure further provide a method for preparing a CIGS photovoltaic module, the method comprising the following steps:
  • the material layer 3 comprises a polymer hydrogel and magnetic nanoparticles mixed in the polymer hydrogel;
  • the substrate 1 formed with the CIGS layer 2 and the composite material layer 3 is placed in a deposition solution, deposited on the CIGS layer 2 to form a CdS layer 4;
  • the material of the substrate 1 is not limited, and the substrate of the conventional photovoltaic module can be used.
  • the substrate 1 is a glass substrate, and the substrate of other common photovoltaic components can also be used according to specific working conditions.
  • the substrate 1 is inductively heated by an alternating magnetic field during deposition, and the temperature of the induction heating is 60 to 70 °C.
  • the deposition solution comprises a premixed solution of cadmium sulfate, ammonia water, pure water and a thiourea solution.
  • the substrate is first placed in a premixed solution, and the substrate is surface treated with ammonia water in the premixed solution, and the substrate is heated by induction to After the preset temperature, the thiourea solution was added, the reaction started, and CdS began to deposit.
  • the above method for preparing a CIGS photovoltaic module employs the above chemical water bath deposition method.
  • the composite material layer is used as a protective layer on one side of the substrate, so that the side surface of the substrate is not in contact with the deposition solution and the substrate is uniformly heated to make the CdS layer
  • the deposition is carried out on the CIGS layer, which avoids the ineffective deposition of the CdS layer and eliminates the trouble of subsequent chemical cleaning.
  • the CIGS photovoltaic module prepared above comprises a stacked substrate, a CIGS layer and a CdS layer, and the CdS layer uniformly and completely covers the surface of the CIGS layer to form a tight pn junction interface, ensuring exciton separation efficiency (exciton is electron not An electron-hole pair formed completely away from the nucleus is spatially coupled between electrons and holes in the electron-hole pair by coulomb interaction. The exciton separation will form free electrons and holes, and the separated electrons Both carriers and holes are carriers of current, and can be called carriers. The higher the exciton separation efficiency, the higher the photoelectric conversion efficiency, and the photoelectric conversion rate is ensured.
  • the CIGS photovoltaic module has the advantages of strong light absorption capability, good power generation stability, high conversion efficiency, long power generation time during the day, high power generation, low production cost and short energy recovery period. It can be applied not only to photovoltaic power plants, but also to photovoltaic building integration (BIPV, Building Integrated Photovoltaic) or photovoltaic roof power generation (photovoltaic attached buildings (not integrated with buildings), ie BAPV, Building Attached Photovoltaic) And other fields.
  • BIPV Photovoltaic building integration
  • photovoltaic roof power generation photovoltaic attached buildings (not integrated with buildings)
  • ie BAPV Building Attached Photovoltaic
  • flexible CIGS PV modules can also be used in portable power generation products such as power generation paper, power generation backpacks and the like.
  • the preparation method of the CIGS photovoltaic module will be further illustrated by some examples.
  • a glass substrate is selected as the substrate 1, and a CIGS layer 2 is plated on one side of the substrate 1.
  • a composite material layer 3 is coated on the other side of the substrate 1 by screen printing, and the composite material layer 3 comprises a copolymerized crosslinked product of a polyacrylic resin and Fe 3 mixed in a copolymerized crosslinked polyacrylic resin.
  • O 4 particles, the mass percentage of both are 90% and 10%, respectively.
  • the substrate 1 on which the CIGS layer 2 and the composite material layer 3 are formed is placed vertically, and immersed in a reaction tank containing a premixed solution of cadmium sulfate, ammonia water, and pure water. Thereafter, the alternating current loop is turned on so that the reaction tank is in an alternating magnetic field 5 having a frequency of 500 kHz generated by the alternating current, the alternating magnetic field 5 making a composite material containing Fe 3 O 4 magnetic particles A large amount of eddy current is generated in the layer 3, and the eddy current rapidly heats the composite material layer 3, thereby uniformly heating the substrate 1 to 65 °C. At this time, a thiourea solution was added to start CdS deposition on the surface of the CIGS layer 2.
  • the substrate 1 is turned upside down so that the side surface of the substrate containing the composite material layer 3 is immersed in the DMSO solution 6, and the copolymerized cross-linking material of the polyacrylic resin is dissolved, and the Fe 3 O 4 particles also flow in.
  • DMSO solution 6 the entire composite material layer 3 is separated from the substrate 1, and a CIGS photovoltaic module in which the substrate 1, the CIGS layer 2 and the CdS layer 4 are stacked is obtained, and the CdS layer 4 in the CIGS photovoltaic module is uniformly and completely covered on the surface of the CIGS layer 2. .
  • the light transmittance of the CdS layer 4 and the forbidden band width (Band gap, the bound electrons and holes must become free electrons or holes, and it is necessary to obtain sufficient energy to jump from the valence band to the conduction band.
  • the minimum value is the forbidden band width) is about 2.4eV, which is very suitable for the buffer layer of CIGS thin film solar cells.
  • a glass substrate is selected as the substrate 1, and a CIGS layer 2 is plated on one side of the substrate 1.
  • the composite material layer 3 is coated on the other side of the substrate 1 by screen printing, and the composite material layer 3 comprises polyvinyl alcohol and Fe 3 O 4 particles mixed in polyvinyl alcohol, and the mass percentages of the two are respectively 80% and 20%.
  • the substrate 1 on which the CIGS layer 2 and the composite material layer 3 are formed is placed vertically, and immersed in a reaction tank containing a premixed solution of cadmium sulfate, ammonia water, and pure water. Thereafter, the alternating current loop is turned on so that the reaction tank is in an alternating magnetic field 5 having a frequency of 550 kHz generated by the alternating current, the alternating magnetic field 5 making a composite material containing Fe 3 O 4 magnetic particles A large amount of eddy current is generated in the layer 3, and the eddy current rapidly heats the composite material layer 3, thereby uniformly heating the substrate 1 to 60 °C. At this time, a thiourea solution was added to start CdS deposition on the surface of the CIGS layer 2.
  • the substrate 1 is turned to the horizontal level so that the side surface of the substrate containing the composite material layer 3 is immersed in the DMF solution 6 to dissolve the polyvinyl alcohol material, and the Fe 3 O 4 particles also flow into the DMF solution 6, and the whole
  • the composite material layer 3 is separated from the substrate 1 to obtain a CIGS photovoltaic module in which the substrate 1, the CIGS layer 2 and the CdS layer 4 are laminated, and the CdS layer 4 in the CIGS photovoltaic module is uniformly and completely covered on the surface of the CIGS layer 2.
  • the light transmittance of the CdS layer 4 is increased and the forbidden band width is about 2.4 eV, which is very suitable for the buffer layer of the CIGS thin film solar cell.
  • a glass substrate is selected as the substrate 1, and a CIGS layer 2 is plated on one side of the substrate 1.
  • a composite material layer 3 is coated on the other side of the substrate 1 by screen printing, and the composite material layer 3 includes polyacrylamide and Fe 3 O 4 particles mixed in polyacrylamide, and the mass percentages of the two are respectively It is 85% and 15%.
  • the substrate 1 on which the CIGS layer 2 and the composite material layer 3 are formed is placed vertically, and immersed in a reaction tank containing a premixed solution of cadmium sulfate, ammonia water, and pure water. Thereafter, the alternating current loop is turned on so that the reaction tank is in an alternating magnetic field 5 having a frequency of 500 kHz generated by the alternating current, the alternating magnetic field 5 making a composite material containing Fe 3 O 4 magnetic particles A large amount of eddy current is generated in the layer 3, and the eddy current rapidly heats the composite material layer 3, thereby uniformly heating the substrate 1 to 68 °C. At this time, a thiourea solution was added to start CdS deposition on the surface of the CIGS layer 2.
  • the substrate 1 is turned to the horizontal level so that the side of the substrate containing the composite material layer 3 is immersed in the DMSO solution 6 to dissolve the polyacrylamide material, and the Fe 3 O 4 particles also flow into the DMSO solution 6, and the whole
  • the composite material layer 3 is separated from the substrate 1 to obtain a CIGS photovoltaic module in which the substrate 1, the CIGS layer 2 and the CdS layer 4 are laminated, and the CdS layer 4 in the CIGS photovoltaic module is uniformly and completely covered on the surface of the CIGS layer 2.
  • the light transmittance of the CdS layer 4 is increased and the forbidden band width is about 2.4 eV, which is very suitable for the buffer layer of the CIGS thin film solar cell.
  • a glass substrate is selected as the substrate 1, and a CIGS layer 2 is plated on one side of the substrate 1.
  • a composite material layer 3 is coated on the other side of the substrate 1 by screen printing, and the composite material layer 3 comprises a silicon-based hydrogel and Fe 3 O 4 particles mixed in the silicon-based hydrogel, both The mass percentages are 95% and 5%, respectively.
  • the substrate 1 on which the CIGS layer 2 and the composite material layer 3 are formed is placed vertically, and immersed in a reaction tank containing a premixed solution of cadmium sulfate, ammonia water, and pure water. Thereafter, the alternating current loop is turned on so that the reaction tank is in an alternating magnetic field 5 having a frequency of 450 kHz generated by the alternating current, the alternating magnetic field 5 making a composite material containing Fe 3 O 4 magnetic particles A large amount of eddy current is generated in the layer 3, and the eddy current rapidly heats the composite material layer 3, thereby uniformly heating the substrate 1 to 70 °C. At this time, a thiourea solution was added to start CdS deposition on the surface of the CIGS layer 2.
  • the substrate 1 is turned to the level so that the side of the substrate containing the composite layer 3 on the surface is immersed in the DMSO solution 6, the silicon-based hydrogel material is dissolved, and the Fe 3 O 4 particles are also flowed into the DMSO solution 6
  • the entire composite material layer 3 is separated from the substrate 1 to obtain a CIGS photovoltaic module in which the substrate 1, the CIGS layer 2 and the CdS layer 4 are stacked, and the CdS layer 4 in the CIGS photovoltaic module is uniformly and completely covered on the surface of the CIGS layer 2.
  • the light transmittance of the CdS layer 4 is increased and the forbidden band width is about 2.4 eV, which is very suitable for the buffer layer of the CIGS thin film solar cell.
  • a glass substrate is selected as the substrate 1, and a CIGS layer 2 and a light-emitting layer 2' are plated on one side of the substrate 1.
  • a composite material layer 3 is coated on the other side of the substrate 1 by screen printing, and the composite material layer 3 comprises a copolymerized crosslinked product of a polyacrylic resin and Fe 3 mixed in a copolymerized crosslinked polyacrylic resin.
  • O 4 particles, the mass percentage of both are 90% and 10%, respectively.
  • the substrate 1 on which the CIGS layer 2, the light-emitting layer 2', and the composite material layer 3 are formed is placed vertically, and immersed in a reaction tank containing a premixed solution of cadmium sulfate, ammonia water, and pure water.
  • the alternating current loop is turned on so that the reaction tank is in an alternating magnetic field 5 having a frequency of 500 kHz generated by the alternating current, the alternating magnetic field 5 making a composite material containing Fe 3 O 4 magnetic particles
  • a large amount of eddy current is generated in the layer 3, and the eddy current rapidly heats the composite material layer 3, thereby uniformly heating the substrate 1 to 65 °C.
  • a thiourea solution was added to start CdS deposition on the surface of the CIGS layer 2.
  • the substrate 1 was turned upside down so that the side of the substrate containing the composite layer 3 on the surface was immersed in the DMSO solution 6, the copolymerized cross-linking material of the polyacrylic resin was dissolved, and the Fe 3 O 4 particles also flowed in.
  • DMSO solution 6 the entire composite material layer 3 is separated from the substrate 1, and a CIGS photovoltaic module in which the substrate 1, the CIGS layer 2, the light-emitting layer 2' and the CdS layer 4 are stacked is obtained, and the CdS layer 4 in the CIGS photovoltaic module is uniformly and completely covered.
  • the CIGS layer 2 and the light-emitting layer 2' On the surface of the CIGS layer 2 and the light-emitting layer 2'.
  • the light transmittance of the CdS layer 4 and the forbidden band width (Band gap, the bound electrons and holes must become free electrons or holes, and it is necessary to obtain sufficient energy to jump from the valence band to the conduction band.
  • the minimum value is the forbidden band width) is about 2.4eV, which is very suitable for the buffer layer of CIGS thin film solar cells.
  • Some embodiments of the present disclosure also provide a composite material.
  • the composite material includes a polymer hydrogel and magnetic nanoparticles mixed in the polymer hydrogel.
  • the mass percentage of the polymer hydrogel is 80% to 95%, and the mass percentage of the magnetic nanoparticles is 5% to 20%.
  • the polymer hydrogel is selected from at least one of the following: a copolymerized crosslinked product of a polyacrylic resin, polyvinyl alcohol, polyacrylamide, and a silicon-based hydrogel.
  • the magnetic nanoparticles are selected from the group consisting of Fe 3 O 4 . Those skilled in the art can control the strength and swelling characteristics of the composite material by using different polymer hydrogel materials and magnetic nanoparticles according to specific working conditions, which is not limited in this application.
  • the composite material can be used as a film layer material.
  • the composite material is used to cover the surface of the substrate as a protective film to protect the surface of the related substrate from external chemical reactions and the like.
  • the composite material is used in a reaction including electromagnetic induction conditions, and after a current is supplied, a magnetic conductive substance such as Fe 3 O 4 magnetic particles inside the composite material can generate heat under the action of electromagnetic induction, thereby improving the The temperature of the composite.
  • the composite material can be dissolved in a dimethyl sulfoxide (DMSO) solvent, or a dimethylformamide (DMF) solvent, or the like.
  • DMSO dimethyl sulfoxide
  • DMF dimethylformamide

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Abstract

一种化学水浴沉积方法，包括以下步骤：在基板（1）的一侧面形成第一功能层、在所述基板（1）的另一相对侧面上形成复合材料层（3），复合材料层（3）包括高分子水凝胶和混合于高分子水凝胶中的磁性纳米粒子；将形成有第一功能层和复合材料层（3）的基板（1）置于沉积溶液中，在第一功能层上沉积形成第二功能层；将复合材料层（3）和基板（1）分离。还包括一种复合材料。

Description

复合材料、化学水浴沉积方法和CIGS光伏组件的制备方法
相关申请的交叉引用
本申请要求于2018年3月14日提交中国专利局、申请号为201810209148.4、发明名称为“化学水浴沉积方法和CIGS光伏组件的制备方法”的中国专利申请的优先权和权益，其全部内容通过引用结合在本申请中。
技术领域
本公开涉及薄膜发电技术领域，特别是涉及化学水浴沉积方法及CIGS光伏组件的制备方法，以及两个所述方法中使用的复合材料。
背景技术
化学水浴沉积方法(Chemical Bath Deposition，CBD)，因其具有成膜温度低、适合于制备大面积薄膜、易于实现连续生产、无污染、材料消耗少等优越性，而受到人们极大的关注。如：在高转换效率的CIGS(Cu、In、Ga、Se，铜铟镓硒)薄膜太阳能电池的制备中，通常采用化学水浴沉积方法制备硫化镉(CdS)半导体薄膜缓冲层。
发明内容
一方面，提供一种化学水浴沉积方法，所述方法包括以下步骤：在基板的一侧面形成第一功能层、在所述基板的另一相对侧面形成复合材料层，所述复合材料层包括高分子水凝胶和混合于所述高分子水凝胶中的磁性纳米粒子；将形成有所述第一功能层和所述复合材料层的所述基板置于沉积溶液中，在所述第一功能层上沉积形成第二功能层；将所述复合材料 层和所述基板分离。
在本公开的一些实施例中，所述第一功能层包括p-结材料层。
在本公开的一些实施例中，所述第一功能层还包括发光层，所述P-结材料层和所述发光层间隔设置以彼此绝缘。
在本公开的一些实施例中，所述第二功能层包括n-结材料层。
在本公开的一些实施例中，所述复合材料层中所述高分子水凝胶的质量百分比为80％～95％，所述磁性纳米粒子的质量百分比为5％～20％。
在本公开的一些实施例中，所述高分子水凝胶选自以下至少一种：聚丙烯酸树脂的共聚交联物、聚乙烯醇、聚丙烯酰胺和硅基水凝胶。
在本公开的一些实施例中，所述磁性纳米粒子选自Fe 3O 4。
在本公开的一些实施例中，在所述第二功能层的沉积过程中利用交变磁场对所述基板进行感应加热。
在本公开的一些实施例中，所述交变磁场的频率为450kHz～550kHz。
在本公开的一些实施例中，将所述复合材料层和所述基板分离时，采用溶剂溶解所述复合材料层。
在本公开的一些实施例中，所述溶剂选自以下至少一种：二甲基亚砜溶剂和二甲基甲酰胺溶剂。在本公开的一些实施例中，所述复合材料层采用丝网印刷的方式形成于所述基板的所述另一相对侧面上。
另一方面，本公开一些实施例还提供一种CIGS光伏组件的制备方法，所述制备方法包括以下步骤：在基板的一侧面形成CIGS层、在所述基板的另一相对侧面形成复合材料层，所述复合材料层包括高分子水凝胶和混合于所述高分子水凝胶中的磁性纳米粒子；将形成有所述CIGS层和所述复合材料层的所述基板置于沉积溶液中，在所述CIGS层上沉积形成CdS层；将所述复合材料层和所述基板分离。
在本公开的一些实施例中，所述复合材料层中所述高分子水凝胶的质量百分比为80％～95％，所述磁性纳米粒子的质量百分比为5％～20％。
在本公开的一些实施例中，在所述CdS层的沉积过程中利用交变磁场对所述基板进行感应加热。
又一方面，本公开一些实施例还提供一种复合材料，所述复合材料包括高分子水凝胶和混合于所述高分子水凝胶中的磁性纳米粒子。
在本公开的一些实施例中，所述高分子水凝胶的质量百分比为80％～95％，所述磁性纳米粒子的质量百分比为5％～20％。
在本公开的一些实施例中，所述高分子水凝胶选自以下至少一种：聚丙烯酸树脂的共聚交联物、聚乙烯醇、聚丙烯酰胺和硅基水凝胶。
在本公开的一些实施例中，所述磁性纳米粒子选自Fe 3O 4。
附图说明
图1为本公开一些实施例提供的化学水浴沉积方法的工艺流程图；
图2为本公开一些实施例提供的CIGS光伏组件的制备方法的工艺示意图；
图3为本公开一些实施例提供的CIGS光伏组件的制备方法的另一工艺示意图。
具体实施方式
以下将结合实施例和附图对本公开提供的复合材料、化学水浴沉积硫化镉薄膜的方法作进一步说明。
制作硫化镉(CdS)半导体薄膜的化学水浴沉积法(CBD，Chemical Bath Deposition)主要包括摇摆式CBD工艺和浸泡式CBD工艺。其中，摇摆式CBD工艺的镀膜均匀性明显高于浸泡式CBD工艺的镀膜均匀性，这主要得益于摇摆式CBD工艺所具有的较高的温度均匀性。在摇摆式CBD工艺中沉积CdS时，玻璃基板被率先加热，而化学反应液则以常温 状态加入反应腔室。因此在摇摆式CBD工艺中，CdS会率先沉积在玻璃基板表面，这大大降低了化学反应液中形成的无规则CdS颗粒的浓度。
但是在浸泡式CBD工艺中，化学反应液的预混合液(预混合液中不含硫脲)会被率先加热至反应温度，之后再加入硫脲，待预混合液与硫脲搅拌均匀后，冷玻璃基板进入反应腔室，开始CdS沉积。因此浸泡式CBD工艺的主要问题在于，在玻璃基板进入之前，化学反应液中已经开始了CdS颗粒的生成并在该化学反应液中悬浮，这对镀膜工艺有负面影响。而未被预加热的玻璃基板则会缓慢地被化学反应液加热，CdS的沉积速率在初期较低，导致了较低的化学反应液利用率。另外，在浸泡式CBD工艺中，玻璃基板的正反面都会被CdS沉积，而最终只有正面的CdS膜层是组件的有效膜层，背面的CdS膜层将不得不被清洗干净，而背面清洗机的设计也存在很多技术挑战，成为了浸泡式CBD工艺产业化的瓶颈。
如图1所示，本公开的一些实施例提供一种化学水浴沉积方法，所述方法包括以下步骤：
a、在基板的一侧面形成第一功能层、在所述基板的另一相对侧面形成复合材料层，所述复合材料层包括高分子水凝胶和混合于所述高分子水凝胶中的磁性纳米粒子；
b、将形成有所述第一功能层和所述复合材料层的所述基板置于沉积溶液中，在所述第一功能层上沉积形成第二功能层；
c、将所述复合材料层和所述基板分离。
所述化学水浴沉积方法应用所述复合材料层在所述基板的所述另一相对侧面形成保护层，使具有所述复合材料层的所述基板的所述另一相对侧面不与所述沉积溶液接触，同时利用所述复合材料层中的高分子水凝胶在所述沉积溶液中的溶胀，使该基板的所述另一相对侧面处的所述沉积溶液的循环速度降低，避免了所述第二功能层在所述复合材料层的无效沉积(因为所述沉积溶液不需要在所述复合材料层上沉积，即便是沉积了，也 需要通过后续工艺去除)。因此不仅使所述沉积溶液的利用率得到提高，节约了反应用的物料，降低了成本；而且便于所述复合材料层的去除，降低了清洗难度。需要说明的是，在所述步骤a中，所述基板的材料不限。例如可以是玻璃基板、也可以是金属基板。
在一些实施例中，所述步骤a中形成的所述第一功能层包括p-结材料层。所述p-结材料层是光伏组件的光吸收层，所述p-结材料层包括但不限于：CIGS层(铜铟镓硒层)、单晶硅层、多晶硅层、砷化镓层、和有机染料层中的任意一种或几种。在本公开一些实施例中，所述第一功能层还包括发光层，所述P-结材料层和所述发光层间隔设置以彼此绝缘。所述发光层是OLED(Organic Light-Emitting Diode，有机发光二极管)的功能层，所述发光层包括但不限于有机发光半导体材料层。
在所述步骤a中在所述基板上既形成P-结材料层、又形成发光层时，可以先使用第一个掩膜板，在所述基板上未被所述第一个掩膜板遮蔽的区域处形成P-结材料层，之后再使用第二个掩膜板遮蔽已经形成的P-结材料层，并在所述基板上未被所述第二个掩膜板遮蔽的区域形成发光层。所形成的P-结材料层和发光层相互间隔以彼此绝缘。所述P-结材料层和所述发光层可以相互间隔排列，也可以分区域相邻布置。在所述基板上既具有P-结材料层、又具有发光层的情况下，所述基板可以双向使用。白天，所述基板可以利用所述P-结材料层吸收太阳光以进行发电，并储存电能；晚上，所述基板可以利用储存的电能使所述发光层进行发光，从而装饰和点缀建筑物幕墙。
在所述步骤a中，所述复合材料层采用丝网印刷的方式形成于所述基板的所述另一相对侧面上。所述复合材料层包括高分子水凝胶和混合于所述高分子水凝胶中的磁性纳米粒子，因此具备这两种材料的特性，既能够感应加热，又具备成膜性和溶胀特性。其中，作为载体的高分子水凝胶可进行丝网印刷。通过丝网印刷的方式将包括高分子水凝胶和磁性纳米粒 子的复合材料涂覆在所述基板的所述另一相对侧面上，利于保证所述复合材料层的均匀性。
在所述步骤a中，所述复合材料层中的所述高分子水凝胶的质量百分比为80％～95％、所述磁性纳米粒子的质量百分比为5％～20％。所述高分子水凝胶选自以下至少一种：聚丙烯酸树脂的共聚交联物、聚乙烯醇、聚丙烯酰胺和硅基水凝胶。所述磁性纳米粒子选自Fe 3O 4。能够通过使用不同的高分子水凝胶材料，调整复合材料层的强度、溶胀等特性，本申请对此不做限制。考虑到聚丙烯酸树脂的共聚交联物具有好的涂膜性、合成方法简单、成本低，同时水溶胀性好，溶胀比例可调节，因此，在一些实施例中，所述高分子水凝胶为聚丙烯酸树脂的共聚交联物。
在一些实施例中，所述步骤b中的所述第二功能层包括n-结材料层。n-结材料层是光伏组件的缓冲层，与p-结材料层匹配形成p-n结，当太阳光照射在p-n结上时，p-n结势垒区(Barrier Region)的电子和空穴各自向相反的方向运动而离开势垒区，结果使p区电势升高、n区电势降低，从而可以在与p-n结连接的外电路中产生电压和电流，将光能转化成电能。常见的n-结材料层为CdS层，所述第二功能层为能够与所述第一功能层匹配使用的功能层。
在所述步骤b中，在所述第二功能层的沉积过程中利用交变磁场对所述基板进行感应加热，所述交变磁场的频率为450kHz～550kHz，所述加热温度根据沉积的所述第二功能层确定。例如，当所沉积的第二功能层为硫化镉(CdS)层时，所述加热温度为60℃～70℃；当所沉积的第二功能层为硫化锌(ZnS)层时，所述的加热温度为75℃～80℃。通过交变磁场对所述基板进行感应加热，使所述基板先被加热，然后所述沉积溶液再通过所述基板的温度而被加热。因此，保证了所述基板的温度高于所述沉积溶液的温度，使沉积更容易在所述基板上发生，避免了因所述沉积溶液的温度高于所述基板的温度而导致在所述沉积溶液中产生悬浮颗粒。在一些 实施例中，所述交变磁场由交变电流产生，所述交变磁场与所述复合材料层的感应加热功能匹配，所述复合材料层的感应加热功能与磁性纳米粒子的含量有关，磁性纳米粒子的含量越高，所述复合材料层的感应加热功能越好，因此能够通过调节磁性纳米粒子和高分子水凝胶的质量百分比来达到所述复合材料层的适合的感应加热功能。
在所述步骤b的所述第二功能层的沉积过程中，所述基板与盛放所述沉积溶液的容器或反应槽的侧壁呈平行设置，以便于布置电路，使交变磁场与所述基板基本垂直(例如，参见图2所示，虚线显示的交变磁场5与基板1基本垂直)，从而增强交变磁场感应的加热效果。电磁感应加热的原理是利用磁场感应加热，例如使高速变化的高频高压电流流过线圈以产生高速变化的交变磁场，当交变磁场内的磁力线通过导磁性金属材料时会在导磁性金属材料体内产生无数的小涡流，使导磁性金属材料本身自行高速发热。因此，在本公开的一些实施例中，交变磁场5使得所述复合材料层中的磁性纳米粒子被快速加热。
在一些实施例中，所述步骤c中将所述复合材料层和所述基板分离时，采用溶剂溶解所述复合材料层。所述溶剂包括但不限于二甲基亚砜(Dimethyl sulfoxide，DMSO)溶剂、N-二甲基甲酰胺(N-Dimethylformamide，DMF)溶剂中的至少一种。DMSO溶剂和DMF溶剂都可以溶解高分子水凝胶，要将所述复合材料层从所述基板分离时，将所述复合材料层浸泡于所述溶剂中进行溶解即可。所述溶剂将所述复合材料层中的高分子水凝胶溶解后，所述复合材料层中的磁性纳米粒子也随之流入溶剂中，使所述复合材料层与所述基板有效分离。上述去除所述基板上的所述复合材料层的湿法工艺，不仅技术成本低，而且不会对基板造成伤害，同时，还利于回收再利用磁性纳米粒子。
上述化学水浴沉积方法具有以下优点：
第一、在所述基板的所述另一相对侧面上形成所述复合材料层作为 保护层，使所述基板的所述另一相对侧面不与所述沉积溶液接触，避免了所述第二功能层在所述基板的所述另一相对侧面上的无效沉积；
第二、所述复合材料层中的磁性纳米粒子的无接触式感应加热既利于保证所述基板加热的均匀性，又利于保证所述基板的温度高于所述沉积溶液的温度，使所述第二功能层的沉积更容易发生，提高了所述第二功能层在所述第一功能层上的沉积速率；
第三、所述复合材料层中的高分子水凝胶作为磁性纳米粒子的有效载体，既利于保证磁性纳米粒子的均匀分布，又利于保证磁性纳米粒子不从复合材料中流失；
第四、高分子水凝胶在所述沉积溶液中由于浸入了沉积溶液分子而溶胀，此后高分子水凝胶吸收沉积溶液分子的速度降低，从而使该所述基板的所述另一相对侧面处的所述沉积溶液的循环速度降低，避免了所述第二功能层在所述复合材料层上的无效沉积，因此便于所述复合材料层的去除；
第五、所述复合材料层中的复合材料的合成工艺成熟，可大批量产、成本低廉，掺入的磁性纳米粒子能够重复利用；
第六、所述复合材料层从所述基板上的分离不仅技术成本低，而且不会对所述基板造成伤害；
第七、磁性纳米粒子能够回收再利用。
因此，上述化学水浴沉积方法能有效改善浸泡式CBD工艺，解决浸泡式CBD工艺中基板加热的均匀性问题，提高浸泡式CBD工艺的成膜效率和成膜均匀性。同时，能够保证第二功能层的沉积过程从基板的第一功能层面开始，减少沉积溶液中快速生成的悬浮颗粒。此外，还能够有效避免第二功能层在基板上的无效沉积，免去了后续针对无效沉积的第二功能层的化学清洗过程。如图2和图3所示，本公开的一些实施例还提供一种CIGS光伏组件的制备方法，所述方法包括以下步骤：
S1、在基板1的一个侧面形成CIGS层2(或者形成CIGS层2和发光层3，所述发光层3见图3所示)、在基板1的另一相对侧面形成复合材料层3，复合材料层3包括高分子水凝胶和混合于所述高分子水凝胶中的磁性纳米粒子；
S2、将形成有CIGS层2和复合材料层3的基板1置于沉积溶液中，在CIGS层2上沉积形成CdS层4；
S3、将复合材料层3和基板1分离。
在S1中，所述基板1材料不限，常用的光伏组件的基板均可以，例如基板1为玻璃基板，也能够根据具体工况采用其他常用的光伏组件的基板。
在S3中，在沉积过程中利用交变磁场对所述基板1进行感应加热，所述感应加热的温度为60℃～70℃。所述沉积溶液包括硫酸镉、氨水、纯水的预混合溶液和硫脲溶液，所述基板先置于预混合溶液中，利用预混合溶液中的氨水对基板进行表面处理，基板经感应加热至预设温度以后，再加入硫脲溶液，反应开始，CdS开始沉积。
上述CIGS光伏组件的制备方法应用了上述化学水浴沉积方法，在制备过程中，以复合材料层作为基板一侧面的保护层，使基板该侧面不与沉积溶液接触并均匀加热基板，使CdS层的沉积在CIGS层上进行，避免了CdS层的无效沉积，免去了后续化学清洗的麻烦。
上述制备得到的CIGS光伏组件包括叠层设置的基板、CIGS层和CdS层，CdS层均匀、完整地覆盖在CIGS层表面以形成紧密的p-n结界面，确保激子分离效率(激子是电子未完全脱离原子核而形成的电子-空穴对，在电子-空穴对中电子和空穴之间通过库伦作用而在空间上耦合。激子分离将形成自由的电子和空穴，分离后的电子和空穴都是电流的载体，均可称为载流子。激子分离效率越高，光电转化效率也越高)，保证光电转化率。使CIGS光伏组件具有光吸收能力强，发电稳定性好、转化 效率高，白天发电时间长、发电量高，生产成本低以及能源回收周期短等优点。不仅可应用于光伏发电站，还可应用于光伏建筑一体化(即BIPV，Building Integrated Photovoltaic)或光伏屋顶发电(光伏附着建筑(并未与建筑形成一体化构造)，即BAPV，Building Attached Photovoltaic)等领域。此外，柔性的CIGS光伏组件也可使其应用于便携式发电产品，如发电纸，发电背包等。以下，将通过一些示例对所述CIGS光伏组件的制备方法做进一步的说明。
示例一：
参照图1和图2，选择玻璃基板作为基板1，并在基板1的一个侧面镀上CIGS层2。
然后，在基板1的另一侧面采用丝网印刷的方式涂上复合材料层3，复合材料层3包括聚丙烯酸树脂的共聚交联物和混合于聚丙烯酸树脂的共聚交联物中的Fe 3O 4颗粒，两者的质量百分比分别为90％和10％。
然后，将形成有CIGS层2和复合材料层3的基板1竖直放置，浸泡在盛有硫酸镉、氨水、纯水的预混合溶液的反应槽中。之后，接通交变电流回路，以使所述反应槽处于由所述交变电流产生的频率为500kHz的交变磁场5中，该交变磁场5使得含有Fe 3O 4磁性颗粒的复合材料层3中产生大量涡电流，涡电流快速加热该复合材料层3，进而使基板1均匀加热至65℃。此时加入硫脲溶液，开始在CIGS层2表面发生CdS沉积。
沉积结束后，将基板1翻转至水平，以使得表面含有复合材料层3的基底侧面浸泡在DMSO溶液6中，溶解聚丙烯酸树脂的共聚交联物材料，同时Fe 3O 4颗粒也随之流入DMSO溶液6，整个复合材料层3与基板1脱离，获得基板1、CIGS层2和CdS层4叠层设置的CIGS光伏组件，CIGS光伏组件中CdS层4均匀完整的覆盖在CIGS层2表面上。
经检验，CdS层4光透过率提高、禁带宽度(Band gap，被束缚的 电子和空穴要成为自由电子或者空穴，就必须获得足够能量从价带跃迁到导带，这个能量的最小值就是禁带宽度)约为2.4eV，非常适合做CIGS薄膜太阳能电池的缓冲层。
示例二：
参照图1和图2，选择玻璃基板作为基板1，并在基板1的一个侧面镀上CIGS层2。
然后，在基板1的另一侧面采用丝网印刷的方式涂上复合材料层3，复合材料层3包括聚乙烯醇和混合于聚乙烯醇中的Fe 3O 4颗粒，两者的质量百分比分别为80％和20％。
然后，将形成有CIGS层2和复合材料层3的基板1竖直放置，浸泡在盛有硫酸镉、氨水、纯水的预混合溶液的反应槽中。之后，接通交变电流回路，以使所述反应槽处于由所述交变电流产生的频率为550kHz的交变磁场5中，该交变磁场5使得含有Fe 3O 4磁性颗粒的复合材料层3中产生大量涡电流，涡电流快速加热该复合材料层3，进而使基板1均匀加热至60℃。此时加入硫脲溶液，开始在CIGS层2表面发生CdS沉积。
沉积结束后，将基板1翻转至水平，以使得表面含有复合材料层3的基底侧面浸泡在DMF溶液6中，溶解聚乙烯醇材料，同时Fe 3O 4颗粒也随之流入DMF溶液6，整个复合材料层3与基板1脱离，获得基板1、CIGS层2和CdS层4叠层设置的CIGS光伏组件，CIGS光伏组件中CdS层4均匀完整的覆盖在CIGS层2表面上。
经检验，CdS层4光透过率提高、禁带宽度约为2.4eV，非常适合做CIGS薄膜太阳能电池的缓冲层。
示例三：
参照图1和图2，选择玻璃基板作为基板1，并在基板1的一个侧面 镀上CIGS层2。
然后，在基板1的另一侧面采用丝网印刷的方式涂上复合材料层3，复合材料层3包括聚丙烯酰胺和混合于聚丙烯酰胺中的Fe 3O 4颗粒，两者的质量百分比分别为85％和15％。
然后，将形成有CIGS层2和复合材料层3的基板1竖直放置，浸泡在盛有硫酸镉、氨水、纯水的预混合溶液的反应槽中。之后，接通交变电流回路，以使所述反应槽处于由所述交变电流产生的频率为500kHz的交变磁场5中，该交变磁场5使得含有Fe 3O 4磁性颗粒的复合材料层3中产生大量涡电流，涡电流快速加热该复合材料层3，进而使基板1均匀加热至68℃。此时加入硫脲溶液，开始在CIGS层2表面发生CdS沉积。
沉积结束后，将基板1翻转至水平，以使得表面含有复合材料层3的基底侧面浸泡在DMSO溶液6中，溶解聚丙烯酰胺材料，同时Fe 3O 4颗粒也随之流入DMSO溶液6，整个复合材料层3与基板1脱离，获得基板1、CIGS层2和CdS层4叠层设置的CIGS光伏组件，CIGS光伏组件中CdS层4均匀完整的覆盖在CIGS层2表面上。
经检验，CdS层4光透过率提高、禁带宽度约为2.4eV，非常适合做CIGS薄膜太阳能电池的缓冲层。
示例四：
参照图1和图2，选择玻璃基板作为基板1，并在基板1的一个侧面镀上CIGS层2。
然后，在基板1的另一侧面采用丝网印刷的方式涂上复合材料层3，复合材料层3包括硅基水凝胶和混合于硅基水凝胶中的Fe 3O 4颗粒，两者的质量百分比分别为95％和5％。
然后，将形成有CIGS层2和复合材料层3的基板1竖直放置，浸泡在盛有硫酸镉、氨水、纯水的预混合溶液的反应槽中。之后，接通交变 电流回路，以使所述反应槽处于由所述交变电流产生的频率为450kHz的交变磁场5中，该交变磁场5使得含有Fe 3O 4磁性颗粒的复合材料层3中产生大量涡电流，涡电流快速加热该复合材料层3，进而使基板1均匀加热至70℃。此时加入硫脲溶液，开始在CIGS层2表面发生CdS沉积。
沉积结束后，将基板1翻转至水平，以使得表面含有复合材料层3的基底侧面浸泡在DMSO溶液6中，溶解硅基水凝胶材料，同时Fe 3O 4颗粒也随之流入DMSO溶液6，整个复合材料层3与基板1脱离，获得基板1、CIGS层2和CdS层4叠层设置的CIGS光伏组件，CIGS光伏组件中CdS层4均匀完整的覆盖在CIGS层2表面上。
经检验，CdS层4光透过率提高、禁带宽度约为2.4eV，非常适合做CIGS薄膜太阳能电池的缓冲层。
示例五
参照图1和图3，选择玻璃基板作为基板1，并在基板1的一个侧面镀上CIGS层2和发光层2’。
然后，在基板1的另一侧面采用丝网印刷的方式涂上复合材料层3，复合材料层3包括聚丙烯酸树脂的共聚交联物和混合于聚丙烯酸树脂的共聚交联物中的Fe 3O 4颗粒，两者的质量百分比分别为90％和10％。
然后，将形成有CIGS层2、发光层2’和复合材料层3的基板1竖直放置，浸泡在盛有硫酸镉、氨水、纯水的预混合溶液的反应槽中。之后，接通交变电流回路，以使所述反应槽处于由所述交变电流产生的频率为500kHz的交变磁场5中，该交变磁场5使得含有Fe 3O 4磁性颗粒的复合材料层3中产生大量涡电流，涡电流快速加热该复合材料层3，进而使基板1均匀加热至65℃。此时加入硫脲溶液，开始在CIGS层2表面发生CdS沉积。
沉积结束后，将基板1翻转至水平，以使得表面含有复合材料层3 的基底侧面浸泡在DMSO溶液6中，溶解聚丙烯酸树脂的共聚交联物材料，同时Fe 3O 4颗粒也随之流入DMSO溶液6，整个复合材料层3与基板1脱离，获得基板1、CIGS层2、发光层2’和CdS层4叠层设置的CIGS光伏组件，CIGS光伏组件中CdS层4均匀完整的覆盖在CIGS层2和发光层2’的表面上。
经检验，CdS层4光透过率提高、禁带宽度(Band gap，被束缚的电子和空穴要成为自由电子或者空穴，就必须获得足够能量从价带跃迁到导带，这个能量的最小值就是禁带宽度)约为2.4eV，非常适合做CIGS薄膜太阳能电池的缓冲层。
本公开的一些实施例还提供一种复合材料。所述复合材料包括高分子水凝胶和混合于所述高分子水凝胶中的磁性纳米粒子。
在本公开的一些实施例中，所述高分子水凝胶的质量百分比为80％～95％、所述磁性纳米粒子的质量百分比为5％～20％。所述高分子水凝胶选自以下至少一种：聚丙烯酸树脂的共聚交联物、聚乙烯醇、聚丙烯酰胺和硅基水凝胶。所述磁性纳米粒子选自Fe 3O 4。本领域技术人员能够根据具体工况，通过使用不同的高分子水凝胶材料和磁性纳米粒子，调控复合材料的强度、溶胀等特性，本申请对此不做限制。
在一些实施例中，所述复合材料能够用作膜层材料。例如，所述复合材料用于覆在基板表面作为保护膜，保护相关基板表面不受外界化学反应等影响。再例如，所述复合材料用于包括电磁感应条件的反应中，通入电流后，所述复合材料内部的导磁性物质如Fe 3O 4磁性颗粒可以在电磁感应的作用下发热，从而提升所述复合材料的温度。此外，所述复合材料能够溶解于二甲基亚砜(DMSO)溶剂、或者二甲基甲酰胺(DMF)溶剂、或者其他类似溶剂中。
以上所述实施例的各技术特征可以进行任意的组合，为使描述简洁， 未对上述实施例中的各个技术特征所有可能的组合都进行描述，然而，只要这些技术特征的组合不存在矛盾，都应当认为是本说明书记载的范围。
以上所述实施例仅表达了本公开的几种实施方式，其描述较为具体和详细，但并不能因此而理解为对本公开专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本公开构思的前提下，还可以做出若干变形和改进，这些都属于本公开的保护范围。因此，本公开专利的保护范围应以所附权利要求为准。

Claims (19)

  1. 一种化学水浴沉积方法，其中，所述方法包括以下步骤：
    在基板的一侧面形成第一功能层、在所述基板的另一相对侧面形成复合材料层，所述复合材料层包括高分子水凝胶和混合于所述高分子水凝胶中的磁性纳米粒子；
    将形成有所述第一功能层和所述复合材料层的所述基板置于沉积溶液中，在所述第一功能层上沉积形成第二功能层；
    将所述复合材料层和所述基板分离。
  2. 根据权利要求1所述的化学水浴沉积方法，其中，所述第一功能层包括p-结材料层。
  3. 根据权利要求2所述的化学水浴沉积方法，其中，所述第一功能层还包括发光层，所述P-结材料层和所述发光层间隔设置以彼此绝缘。
  4. 根据权利要求1所述的化学水浴沉积方法，其中，所述第二功能层包括n-结材料层。
  5. 根据权利要求1所述的化学水浴沉积方法，其中，所述复合材料层中所述高分子水凝胶的质量百分比为80％～95％，所述磁性纳米粒子的质量百分比为5％～20％。
  6. 根据权利要求1所述的化学水浴沉积方法，其中，所述高分子水凝胶选自以下至少一种：聚丙烯酸树脂的共聚交联物、聚乙烯醇、聚丙烯酰胺和硅基水凝胶。
  7. 根据权利要求1所述的化学水浴沉积方法，其中，所述磁性纳米粒子选自Fe 3O 4。
  8. 根据权利要求1所述的化学水浴沉积方法，其中，在所述第二功能层的沉积过程中利用交变磁场对所述基板进行感应加热。
  9. 根据权利要求8所述的化学水浴沉积方法，其中，所述交变磁场的频率为450kHz～550kHz。
  10. 根据权利要求1所述的化学水浴沉积方法，其中，所述将复合材料层和所述基板分离步骤包括：，采用溶剂溶解所述复合材料层。
  11. 根据权利要求10所述的化学水浴沉积方法，其中，所述溶剂选自以下至少一种：二甲基亚砜溶剂和二甲基甲酰胺溶剂。
  12. 根据权利要求1所述的化学水浴沉积方法，其中，在所述基板的另一相对侧面形成复合材料层步骤包括：
    所述复合材料层采用丝网印刷的方式形成于所述基板的所述另一相对侧面上。
  13. 一种CIGS光伏组件的制备方法，其中，所述制备方法包括以下步骤：
    在基板的一侧面形成CIGS层、在所述基板的另一相对侧面形成复合材料层，所述复合材料层包括高分子水凝胶和混合于所述高分子水凝胶中的磁性纳米粒子；
    将形成有所述CIGS层和所述复合材料层的所述基板置于沉积溶液 中，在所述CIGS层上沉积形成CdS层；
    将所述复合材料层和所述基板分离。
  14. 根据权利要求13所述的化学水浴沉积方法，其中，所述复合材料层中所述高分子水凝胶的质量百分比为80％～95％，所述磁性纳米粒子的质量百分比为5％～20％。
  15. 根据权利要求13所述的化学水浴沉积方法，其中，在所述CIGS层上沉积形成CdS层步骤包括：
    在所述CdS层的沉积过程中利用交变磁场对所述基板进行感应加热。
  16. 一种复合材料，包括高分子水凝胶和混合于所述高分子水凝胶中的磁性纳米粒子。
  17. 根据权利要求16所述的复合材料，其中，所述高分子水凝胶的质量百分比为80％～95％，所述磁性纳米粒子的质量百分比为5％～20％。
  18. 根据权利要求16所述的复合材料，其中，所述高分子水凝胶选自以下至少一种：聚丙烯酸树脂的共聚交联物、聚乙烯醇、聚丙烯酰胺和硅基水凝胶。
  19. 根据权利要求16任一项所述的复合材料，其中，所述磁性纳米粒子选自Fe 3O 4。
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