CN113199683A - Micro-nano structure for improving solar cell surface light energy capture and preparation method thereof - Google Patents
Micro-nano structure for improving solar cell surface light energy capture and preparation method thereof Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
- B29C41/02—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of definite length, i.e. discrete articles
- B29C41/08—Coating a former, core or other substrate by spraying or fluidisation, e.g. spraying powder
- B29C41/10—Coating a former, core or other substrate by spraying or fluidisation, e.g. spraying powder by fluidisation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
- B29C41/34—Component parts, details or accessories; Auxiliary operations
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
- B29C41/34—Component parts, details or accessories; Auxiliary operations
- B29C41/50—Shaping under special conditions, e.g. vacuum
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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
- H01L31/02—Details
- H01L31/0236—Special surface textures
- H01L31/02366—Special surface textures of the substrate or of a layer on the substrate, e.g. textured ITO/glass substrate or superstrate, textured polymer layer on glass substrate
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2083/00—Use of polymers having silicon, with or without sulfur, nitrogen, oxygen, or carbon only, in the main chain, as moulding material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
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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
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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Abstract
The invention provides a micro-nano structure for improving the surface light energy capture of a solar cell and a preparation method thereof. The method is characterized in that: firstly, preparing a solar-grade glass substrate a into pit array structure glass b through a micromachining process, then pouring PDMS sol on the pit array structure to form a PDMS sol and structure glass mixture c, and finally performing die drawing on the cured PDMS film to prepare a PDMS film d with a surface micro-nano convex hull array structure. The invention is applied to the upper surface of the thin-film solar cell to form a surface light trapping structure, can effectively reduce light reflection, increase light absorption, prolong the optical path, strengthen the surface light energy capture capacity and finally improve the photoelectric conversion efficiency of the solar cell compared with a flat plate structure. The method can repeatedly prepare the surface micro-nano convex hull array structure by using the glass with the pit array structure, and has the advantages of simple process and cost reduction.
Description
(I) technical field
The invention relates to a micro-nano structure for improving the surface light energy capture of a solar cell and a preparation method thereof, belongs to the field of solar cells, and particularly relates to a micro-nano processing technology and an optoelectronic device.
(II) background of the invention
With the increasing population of the world and the gradual shortage of non-renewable resources, in the foreseeable future, the energy problem will become one of the main problems which plague the survival and development of human beings, and the energy contention will also become a strategic problem to be considered in all countries of the world. Solar energy, one of new energy sources, has the advantages of no pollution, renewability, large total amount, wide distribution and the like, and is increasingly paid more attention by people. The thin film solar cell is a main way for developing and utilizing solar energy resources in recent years, so how to improve the photoelectric conversion efficiency of the thin film solar cell has become a research focus of researchers engaged in the solar cell industry and the like.
The micro-nano light trapping structure has the characteristics of reducing light reflection, reducing light energy escape, increasing optical path length and the like, and can effectively improve the photoelectric conversion efficiency of the solar cell. The nano microsphere array structure has wide application in the field of solar cells due to the large surface area and good optical characteristics, so that how to prepare an ideal nano microsphere array structure is a very important research topic. A broadband return-reducing anti-reflection nano structure and a preparation method thereof (Chinese patent No. 202010571961.X) disclosed in 2011 of Huangfuqiang and Lidejian are mainly characterized in that a layer of nanosphere array structure is prepared on a nano film by adopting a sol-gel technology, or nanospheres are dispersed in a precursor solution to prepare a composite film; the preparation method of the ZnO spherical hollow-shell structure nanoparticle array (Chinese patent: 201310012724.3) disclosed by Lijing et al in 2013 mainly adopts a technical method of spin coating, reactive ion etching, deposition and annealing to prepare the ZnO spherical hollow-shell structure nanoparticle array on the surface of a solar cell; the preparation of a single-layer ordered silicon dioxide nanosphere array (Chinese patent: 201610565422.2) disclosed by Ringran et al in 2016 mainly adopts a drainage dispersion pulling method to prepare a single-layer ordered silicon dioxide nanosphere array at room temperature. The preparation methods all prepare the nano microsphere array structure, but the regularity and the single-layer order of the prepared nano microsphere array are difficult to ensure, the prepared nano microsphere array is used for preparing the array structure, and the technical methods are lack of independence.
The invention discloses a micro-nano structure for improving the surface light energy capture of a solar cell and a preparation method thereof. The method comprises the steps of preparing a pit array structure on the surface of a substrate by taking solar-grade glass as the substrate, then pouring a PDMS film on the pit array structure glass as a template, and transferring the pit structure on the structural glass to the PDMS film to prepare a micro-nano convex hull array structure (a nano microsphere array-like structure). Compared with the prior art, the method can prepare the micro-nano convex hull array structure which is orderly arranged and has a single layer, and the prepared glass with the pit array structure can be repeatedly used, so that the method has the advantages of simple process and cost reduction.
Disclosure of the invention
The invention aims to provide a micro-nano structure for improving the surface light energy capture of a solar cell and a preparation method thereof.
The purpose of the invention is realized as follows:
a micro-nano structure for improving the capture of solar cell surface light energy and a preparation method thereof are provided. The method is characterized in that: firstly, preparing a solar-grade glass substrate a into pit array structure glass b through a micromachining process, then pouring PDMS sol on the pit array structure to form a PDMS sol and structure glass mixture c, and finally, pulling out a cured PDMS film to prepare a PDMS film d with a surface micro-nano convex hull array structure. In the preparation process of the structure, a solar-grade glass substrate a needs to be thoroughly cleaned through an RCA (standard cleaning method) step, then a pit array structure is formed on the surface of the solar-grade glass substrate through micro-processing technologies such as photoetching, developing and ion beam etching and methods of HF etching and dry etching are combined to prepare a pit array structure glass b, then prepared PDMS sol is poured on the pit array structure glass for pouring and vacuum treatment, the PDMS sol is heated and cured for not less than 4 hours at the temperature of 70 ℃, and finally the cured micro-nano structure adhesive film is pulled out to prepare a PDMS adhesive film d with a surface micro-nano convex hull array structure.
The concrete preparation process of the pit array structure glass comprises the following steps: firstly, cleaning the solar grade glass by adopting an RCA cleaning method; secondly, sputtering a Cr layer and a Cu layer on the surface of the clean glass in sequence by adopting a magnetron sputtering method; thirdly, spin-coating photoresist on the Cr/Cu metal seed layer, and then performing drying treatment; fourthly, photoetching the sample by adopting ultraviolet light of 350-450 ℃ in photoetching equipment, developing in a developing solution, and finally baking the sample at the temperature of 70-90 ℃; fifthly, carrying out photoresist removing treatment on the baked sample by adopting an acetone solution; sixthly, etching the sample by adopting an HF solution; and finally, removing the metal seed layer of the etched sample by adopting ceric ammonium nitrate and high-chlorine etching liquid to prepare the glass with the pit array structure. If the aspect ratio of the pit array structure glass is less than 0.5, the glass can be etched by only adopting an HF etching method, and if the aspect ratio is more than 0.5, a method combining RIE etching and HF etching is needed. The period and the depth of the pit array structure glass are in the micro-nano level.
The specific preparation process of the surface micro-nano convex hull array structure comprises the following steps: firstly, uniformly mixing PDMS main body glue and a solid agent according to a mass ratio of 10: 1, and carrying out vacuum pumping treatment in a vacuum drying oven to remove residual air in PDMS mixed glue; secondly, pouring the PDMS mixed glue after air is removed on the prepared glass template with the pit array structure, and vacuumizing in a vacuum drying oven again to ensure that air in the glue and the structure pits is exhausted as much as possible. Thirdly, heating the mixture of the PDMS sol and the structural glass at 70 ℃ for not less than 4 hours to completely cure the PDMS sol; and fourthly, separating the PDMS adhesive film from the glass template with the pit array structure by adopting a demoulding process to prepare the PDMS adhesive film with the surface micro-nano convex hull array structure. The size and the period of the micro-nano convex hull array structure are in micro-nano level.
(IV) description of the drawings
FIG. 1 is a schematic view of the overall process for preparing a surface micro-nano convex hull array structure. In the figure, (a) is a solar grade glass substrate; (b) the glass is of a pit array structure; (c) is a mixture of PDMS sol and structural glass; (d) is a PDMS adhesive film with a surface micro-nano convex hull array structure.
Fig. 2 is a cross-sectional view of a PDMS adhesive film with a surface micro-nano convex hull array structure having an aspect ratio of about 0.4, where the aspect ratio is height/width.
Fig. 3 is a schematic cross-sectional view of a PDMS adhesive film with a surface micro-nano convex hull array structure having an aspect ratio of about 0.4 covering the upper surface of a thin-film solar cell. In the figure, 1 is a PDMS adhesive film with a micro-nano convex hull array structure; 2 is refractive index matching fluid; 3 is solar energy level plate glass; 4 is a battery front electrode layer; 5 is a p-i-n structural layer of the battery; 6 is a back electrode layer and a transition layer; and 7 is a back reflection layer.
Fig. 4 is a graph comparing external quantum efficiency of a flat PDMS solar cell and a surface micro-nano convex hull array structure PDMS solar cell.
FIG. 5 is an electron microscope image of PDMS (polydimethylsiloxane) adhesive film with a 500-fold magnification, wherein the aspect ratio of the surface micro-nano convex hull array structure is about 0.4.
(V) detailed description of the preferred embodiments
The invention is further illustrated below with reference to specific examples.
FIG. 2 shows an example of preparing a PDMS (polydimethylsiloxane) adhesive film with a surface micro-nano convex hull array structure having an aspect ratio of about 0.4. The specific implementation steps are as follows: firstly, preparing a hemispherical pit array structure with the period of about 20 mu m and the depth-to-width ratio of about 0.4 on solar-grade glass by photoetching, developing, etching and other processes; secondly, uniformly mixing the PDMS main body glue and a solid agent according to the mass ratio of (10: 1), and vacuumizing; then pouring the mixed glue with air removed on the prepared array structure to the thickness of 1mm, and carrying out vacuum-pumping treatment again; then heating the mixture of the PDMS sol and the structural glass at 70 ℃ for not less than 4 hours to completely cure the PDMS sol; and finally, separating the PDMS adhesive film from the glass template with the pit array structure by adopting a demoulding process to prepare the PDMS adhesive film with the surface micro-nano convex hull array structure with the height-to-width ratio of about 0.4. Observing the PDMS film with the prepared surface micro-nano convex hull array structure having the height-to-width ratio of about 0.3 under an electron microscope with the magnification of 500 times, wherein the observation condition is shown in FIG. 5.
Fig. 3 shows an example of the application of the surface micro-nano convex hull array structure in a solar cell. The specific implementation steps are as follows: firstly, taking 10-micron solar-grade flat glass 3 as a substrate, and depositing 0.3-micron TCO on the substrate to be used as a front electrode 4; secondly, depositing 0.3 mu m a-Si on the TCO to be used as a p-i-n structural layer 5 of the cell; then 0.1 μm AZO is deposited on the a-Si as a back electrode and a transition layer 6; then 0.3 mu m Ag is deposited on the AZO to be used as a back reflecting layer 7, and the preparation of the silicon thin film solar cell is completed; finally, the PDMS film 1 with the surface micro-nano convex hull array structure aspect ratio of about 0.4 prepared in the embodiment is covered on the upper surface of the silicon thin film solar cell, and ethanol C is filled in the middle2H5OH, liquid paraffin and bromonaphthalene C10H7And the refractive index matching fluid 2 prepared by Br according to the proportion of 1:1:1 is used for eliminating the influence of an air layer, and finally, the preparation of the solar cell with the surface micro-nano convex hull array structure is completed. Fig. 4 is a graph showing comparison of external quantum efficiency between a flat-plate PDMS solar cell and a surface micro-nano convex hull array structure PDMS solar cell, and it can be known from the graph that an external quantum curve of the surface micro-nano convex hull array structure PDMS solar cell is obviously improved compared with that of the flat-plate PDMS solar cell, which indicates that the micro-nano convex hull array structure has the advantages of reducing light reflection, increasing light absorption, prolonging light path, enhancing surface light energy capture capacity, and improving photoelectric conversion efficiency of the solar cell.
The specific implementation of the present invention is described in detail above, but it should be reiterated that the core content of the present invention is to pour PDMS sol on the glass with pit array structure, and prepare the micro-nano convex hull array structure with orderly arrangement and single-layer order by the method of pattern replication and transfer.
Claims (3)
1. A micro-nano structure for improving the capture of solar cell surface light energy and a preparation method thereof are provided. The method is characterized in that: firstly, preparing a solar-grade glass substrate a into pit array structure glass b through a micromachining process, then pouring PDMS sol on the pit array structure to form a PDMS sol and structure glass mixture c, and finally performing die drawing on the cured PDMS film to prepare a PDMS film d with a surface micro-nano convex hull array structure. In the preparation method of the structure, a solar-grade glass substrate a needs to be thoroughly cleaned through an RCA (standard cleaning method) step, then a pit array structure is formed on the surface of the solar-grade glass substrate through micro-processing technologies such as photoetching, developing and ion beam etching and a method of HF etching and dry etching, a pit array structure glass b is prepared, then prepared PDMS sol is poured on the surface of the pit array structure glass structure and is subjected to vacuum treatment, heating and curing are carried out on the PDMS sol for not less than 4 hours at the temperature of 70 ℃, finally the cured adhesive film is pulled out, and a PDMS adhesive film d with a surface micro-nano convex hull array structure is prepared.
2. The micro-nano convex hull array structure in the PDMS adhesive film with the surface micro-nano convex hull array structure and the preparation method of the micro-nano convex hull array structure according to claim 1 are characterized in that: taking the prepared pit array structure glass b as a template, then pouring PDMS (polydimethylsiloxane) glue on the template, copying and transferring the pit array structure on the structure glass to the PDMS glue film, and forming a micro-nano convex hull array structure on the surface of the structure glass; the micro-nano convex hull array structure is a geometric figure with periodic arrangement, the height-width ratio of the micro-nano convex hull array structure is 0.1-0.8, and the period and the size are both in micro-nano level; the geometric figures in the periodic arrangement are a hemispherical convex hull structure, an ellipsoidal convex hull structure and the like.
3. The PDMS adhesive film in the PDMS adhesive film with the surface micro-nano convex hull array structure as set forth in claim 1, wherein: the adopted material is PDMS (Polydimethylsiloxane), which is a high molecular organosilicon compound molecule; when the PDMS is used, PDMS main body glue and solid glue are uniformly mixed according to the mass ratio of (10: 1), and vacuum-pumping treatment is carried out to remove air in the mixed liquid; when the PDMS mixed liquid is poured on the structural glass, vacuumizing is carried out again, heating and curing are carried out at the temperature of 70 ℃ for 4 hours, and then demoulding is carried out, so that the PDMS adhesive film with the surface micro-nano convex hull array structure is prepared.
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