CN101299446A - Selenide forerunner thin film and method for producing film cell through rapid selenium vulcanizing thermal treatment - Google Patents

Abstract

The invention relates to a method of a low cost selenide van thin film and the fast selenium sulfuration heat treatment to prepare the solar cell, which can be used in the nm selenide paint roll coating or the electrodeposit method to prepare the selenide van film, through the vacuum flash selenium sulfuration heat treatment, the high efficiency cadmium-free thin film solar cell or the photovoltaic integrated module. The thin film cell adsorption layer band gap is in the v-shaped distribution, and the flash selenium sulfuration heat treatment causes the CuSe in the porous loose thin film fusing, soaking, liquid phase serving the reaction growth of the CIGS film crystal and the self densification of the film with the In4Se3, reactive sputtering In2Se3 or In2S3 to neutralize the excessive CuxSe adsorbed by the film surface layer, going on splashing the micro excessive In2S3 to generate n-high-ohmic resistor Cu(In<1-y>Gay)<3>(SxSe<1-x>)<5> thin film cell shallow burying, then reacting the splashing deposit n-type In(OH,S)/ZnS(O,OH)/Zno(S) buffer layer with the i-layer, linking the slashing transparent conductive film/and laserprocessing collecting ellectrode to complete the preparation of the thin film cell.

Description

Selenide Precursor Thin Film and Rapid Selenium Sulfurization Heat Treatment to Prepare Thin Film Battery Method

technical field

The present invention relates to the preparation of compound semiconductor thin film devices, more specifically, to the preparation of copper indium gallium selenide sulfur [Cu(In _0.7 , Ga _0.3 )Se _2-x S _X abbreviated as CIGS] thin film solar cells by a non-vacuum low-cost method A method for preparing a thin-film solar cell or a photovoltaic integrated module directly and continuously after a selenide precursor thin film is subjected to vacuum rapid selenium sulfidation heat treatment.

Background technique

Solar cell power generation is a renewable energy technology that has the least impact on the environment in the process of generating electricity. For solar power technology to be commercially successful, solar cells must be more efficient, lower cost, better weather-resistant, and not add to other environmental concerns. The development of traditional crystalline silicon solar cell technology benefits from the continuous technological progress of electronic silicon semiconductor materials. To manufacture it requires polycrystalline silicon materials in the upstream materials of monocrystalline silicon. The economic added value of crystalline silicon solar cells is not high. It is a long-term The large-scale use of products that have accumulated income has diverted the material sources of the silicon semiconductor industry, which will inevitably further aggravate the global resource shortage and make its price more expensive; on the other hand, today's crystalline silicon solar Battery products and technologies still occupy a dominant position. It can basically meet the multiple requirements mentioned in the above-mentioned solar cell technology, but it cannot produce solar cells at low cost. The waste of silicon materials in the production process is as high as 70%, and It also needs to consume a large amount of primary energy, which will inevitably have an adverse impact on the environment; relatively speaking, the energy consumption of producing crystalline silicon solar cells requires more than three years of power generation to recover, even if the cheapest crystalline silicon solar cells output 1 watt of energy output The manufacturing cost is also 3 US dollars. The biggest bottleneck restricting the development of solar cells at this stage is the high raw material cost and production cost.

Solar cells based on thin-film technology are a technology that is in the development stage, and they offer a technical possibility for a substantial reduction in the cost of solar cells. The raw materials for manufacturing silicon thin-film solar cells are the same as those used in the manufacturing process of electronic monocrystalline silicon semiconductor devices. Thin-film solar cells have low photoelectric conversion efficiency and poor durability (performance degradation during use). Although this defect has been alleviated through technological progress, it cannot be completely cured. Based on the compound semiconductor Cu(In,Ga)Se ₂ thin film solar cell is a very promising solar cell technology, the bandgap width of CIGS thin film can be changed in the range of 1.04-1.68eV according to the Ga content; the absorption coefficient of visible light is as high as 10 ⁵ /cm, 1-2μm thick film can absorb most of the sunlight, which is suitable as the absorbing layer of cheap solar cells. CIGS thin-film solar cells have the characteristics of no fading, anti-radiation, and long life. The highest efficiency has reached 19.9%, which is close to the highest photoelectric conversion efficiency of polycrystalline silicon solar cells of 20.3%, and is the highest among all thin-film solar cells. And it can be deposited on a large area of cheap substrates - glass, stainless steel, titanium foil or PI plastic film and other base materials. Compared with crystalline silicon solar cells, it reduces the production process, so it has unique advantages in reducing costs. If The technical route of vacuum co-evaporation and sputtering metal pre-layer meets the production design requirements, and its cost is only 1/3 to 1/2 of that of crystalline silicon cells. After more than 20 years of research and development, CIGS thin film solar cells have basically achieved industrialization.

Although CIGS thin-film solar cells have low-cost potential, the development technology of high-efficiency CIGS thin-film solar cells for more than 20 years is based on vacuum equipment, and the selenization technology after vacuum sputtering metal pre-layer is only to reduce the control of co-evaporation Difficulty, suitable for the uniformity of large-scale preparation of thin-film batteries and the ease of industrialized continuous production and successful development, the relative utilization rate of raw materials is lower, and more vacuum manufacturing equipment is required. Since the evaporation method and the selenization method after sputtering are mainly based on vacuum equipment, the equipment is huge and expensive, and the initial investment in establishing a thin film battery production line is large. Moreover, the utilization rate of raw materials for depositing thin films is only 30-60%, and the cost of thin film preparation and target materials accounts for 45.3% of the total cost. Offset CIGS thin-film solar cells can be prepared as a low-cost thin film advantage, but also the current cost of CIGS thin-film solar cells is not as low as people expected the main reason.

The main purpose of low-cost preparation of CIGS thin-film batteries is to reduce the use of expensive vacuum equipment, reduce primary energy consumption in the manufacturing process and improve the utilization of raw materials. At present, there are two main ways to prepare CIGS thin films by non-vacuum method. One is to prepare Cu-In-Ga-Se raw materials into nano-coatings, and then wet-coat them on a suitable substrate to dry to form a film, and then carry out Heat treatment; the other is heat treatment after preparing CIGS thin film by water bath electrodeposition. These two technical approaches have common characteristics, all are to obtain the preset layer of CIGS film from water-soluble raw materials, and then carry out post-heating treatment; common advantages are: (1) simple equipment, small investment, low cost; (2) ), the utilization rate of raw materials is as high as 95% or more; (3) the thin film precursor can be deposited in a large area, continuous and low temperature method. This method has already made great breakthroughs, and many foreign companies have begun the process of industrialization. However, this method also has phenomena such as porous film quality, inclusions, and cracks after heating and selenization treatment.

The coating method is to mix Cu-In-Ga-Se in a certain proportion to form nanoparticle coatings with different compositions, and then use different coating techniques to dry on the substrate to form a precursor film. VKKapur et al. of ISET Company in the United States dissolved the Cu, In, and Ga elements required for the final film according to the Cu/(In+Ga) ratio mixture of the CuIn _0.7 Ga _0.3 Se ₂ stoichiometric formula in an acidic solution, and added an alkaline solution to neutralize the reaction. Form metal hydroxide, then rinse with water to remove by-products, dry to make metal oxide nanoparticles, mix with water and dispersant to form nano-coatings, and coat Mo/glass substrates with film-forming and Drying, and then reducing reaction in a mixed atmosphere of _H2 and _N2 at 500-550°C to obtain a dense Cu-In-Ga alloy film, and then selenized in a mixed atmosphere of _H2Se and _N2 at 420-450°C A CIGS thin film is formed. The thickness of the coated wet film is about 12 μm, and the film structure formed after drying is loose and porous, with a thickness of about 6 μm, and a thickness of about 2 μm after hydrogen reduction and selenization treatment. The highest efficiency of the CIGS thin film battery prepared by this method is 13.6% (0.08cm ² ) on the glass substrate, 13.0% on the flexible substrate Mo foil ^[1] , and the efficiency of the battery module with an area of 65cm ² is 8% ^{[2, 3]} . Its US invention patent is US5985691.

American Nanosolar company was established in 2002, and in 2003 decided to mainly research and develop CIGS thin film technology by non-vacuum method. They used different chemical reactions to prepare various non-oxide nanoparticles, such as CuInSe ₂ , CuGaSe, CuSe, In ₂ Se ₃ , by controlling the conditions of the reaction process to control the size of the nanoparticles. CuSe and In ₂ Se ₃ were used as the core to wrap pure selenium to make selenide nanoparticles, and formulated with water-soluble solvent to form a liquid coating, which was wet-coated (screen printing or roll printing method) on the sputtered surface. The film is dried on the aluminum foil deposited by spraying Mo film, and the organic solvent is volatilized by heating. The precursor selenide film is subjected to rapid thermal treatment (RTP) to prepare a PV (photovoltaic) grade film material, which utilizes the 180% of pure Se in the precursor selenide film. ℃ low-temperature melting point and 523 ℃ medium-temperature melting point of Cu _x Se, the liquid phase characteristics, carried out the physical and chemical processes of rapid heating densification of porous loose selenide precursor film, binary selenide synthesis reaction and liquid phase assisted growth of crystal, etc., prepared A columnar dense large-grain CIS thin-film solar cell absorber layer is produced, and the highest efficiency of a single (0.470cm ² ) CIGS thin-film solar cell on a glass substrate reaches 14.5% ^[4] . Nanosolar has applied for more than 50 U.S. patents, and the patent related to the above is US20070092648 (technical description: CuSe represents selenium-rich nanocrystalline particles, CuxSe represents the general name of various copper selenide components in the film, and Cu ₂ Se represents the real chemical composition).

In Japan, T.Wada et al. used ball milling method to grind the powder mixture of elemental Cu, In, Ga and Se. During the grinding process, they reacted to form nano Cu(In, Ga)Se ₂ powder, which was then mixed with organic solvent to form nano Particle coating, which is coated on Mo/glass substrate film, and the organic solvent is removed by heating; heat treatment in an inert _N2 gas environment under normal atmospheric pressure, so that the selenide film on the glass substrate is heated to 550-570 °C , the porous pre-layer selenide film was sintered into a dense polycrystalline film, and the conversion efficiency of the prepared battery was 2.7% ^[5,6] .

The research team led by K. Yoon ^[7] of the National Energy Research Institute of South Korea dissolved CuI, InI ₃ and GaI ₃ in pyrimidine, Na ₂ Se in methanol, and mixed reaction under the protection of low-temperature nitrogen to form CIGS of about 15nm Nanoparticles. An organic solvent is used to make a coating, and the coating is coated on the Mo substrate of the substrate, and two-stage heating and selenization are carried out in a rapid heat treatment furnace, and the efficiency of the prepared thin film battery is 1.11%.

The process of preparing CIGS precursor selenide film by electrodeposition method is to directly electrodeposit various CIGS selenide precursor films in acidic aqueous solution with Mo substrate as cathode. Bhattacharya et al. of the National Renewable Energy Laboratory (NREL) obtained a Cu-rich selenide precursor film by direct electrodeposition of CIGS elements in a chloride solution system, and heat-treated it in a vacuum selenium atmosphere. , while evaporating and depositing In and Ga, which account for about 50% of the total film, to adjust the chemical composition ratio of the film, so that the final film composition meets the requirements for preparing semiconductor devices, and the efficiency of the prepared thin film battery reaches 15.4% ^[8] . However, this electrodeposition solution is not stable, and a large amount of solute precipitates out after one day; in addition, the Ga content in the electrodeposited selenide precursor film is very low, and the ratio of Ga/(In+Ga) is only 0.1. After adding sulfamic acid and potassium hydrogen phthalate pH buffer solution, the stability of the electrodeposition solution was effectively improved, and a breakthrough was made in terms of process practicability ^[9] , the ratio of Ga/(In+Ga) in the film It can reach 0.3-0.7. The selenide precursor film is heat-treated in a vacuum selenium atmosphere, and at the same time, evaporates and deposits In and Ga, which account for 5-10% of the total film, to adjust the film composition to be close to the stoichiometric ratio. The efficiency of preparing a thin-film battery reaches 9.4 %. If the electro-deposited CIGS precursor selenide film is only heat-treated in H ₂ Se atmosphere, and then KCN solution is used to dissolve Cu ₂ Se in the Cu-rich phase of the film, the efficiency of the thin-film solar cell that does not need vacuum supplementary evaporation of In, Ga and Se components reaches 6.2% ^[10] . Bhattacharya and others have applied for and obtained a number of invention patents in the United States. Among them, the invention patent number obtained in China is: 96199008.2; Bhattacharya is now a Solopower company in the United States specializing in the production technology of electrodeposition selenide precursor film and heat treatment to prepare CIGS thin film cell photovoltaic modules. For research and development, Solopower received a venture capital of 30 million US dollars and established a 20MW pilot production line for electrodeposited CIGS thin film batteries.

Energy Development and Research Institute光伏能源开发研究所)作为法国CNRS(国家科学研究中心)、法国电力公司(EDF)和法国巴黎国立高等化学大学的联合研究单位(UnitéMixte de Recherche)成立于2005年。IRDEP-光伏能源开发研究所采取的主要工艺路线是电沉积CuInSe₂再对其表面进行硫化，形成CuIn(Se，S)₂的结构；近期目标为：(1)小面积电池的效率大于12％；(2)30×30cm²组件效率大于8％。主要措施是在CIS中加入Ga或S^[11，12]。他们采用硫酸盐体系进行电沉积富Cu相CuInSe₂薄膜的研究，再在S气氛中进行硫化热处理，获得大晶粒致密的柱状结构薄膜材料，然后用KCN溶液去除富Cu相。制备的电池最好效率为11.5％，衬底面积为30×30cm²时，电沉积的预置层的质量均匀，电池效率可达7％以上。存在问题是：沉积的薄膜一般是富Cu薄膜，经过热处理后需要在KCN溶液中刻蚀或溶解掉薄膜中富Cu相的Cu₂Se，它会影响薄膜表面的结构和电池pn结的质量。另外，热处理过程中Mo与Se反应易形成较厚的MoSe^[13]。IRDEP(

The Energy Development and Research Institute (Photovoltaic Energy Development Institute) was established in 2005 as a joint research unit (UnitéMixte de Recherche) of CNRS (National Center for Scientific Research), Electricity of France (EDF) and National Higher Chemistry University of Paris, France. The main process route adopted by IRDEP-Photovoltaic Energy Development Research Institute is to electrodeposit CuInSe ₂ and then sulfide its surface to form a CuIn(Se,S) ₂ structure; the short-term goal is: (1) The efficiency of small-area cells is greater than 12% ; (2) 30×30cm ² module efficiency is greater than 8%. The main measure is to add Ga or S to the CIS ^{[11, 12]} . They used the sulfate system for electrodeposition of Cu-rich phase CuInSe ₂ thin film research, and then carried out sulfidation heat treatment in S atmosphere to obtain a large-grain dense columnar structure thin film material, and then removed the Cu-rich phase with KCN solution. The best efficiency of the prepared battery is 11.5%. When the substrate area is 30×30cm ² , the quality of the electrodeposited preset layer is uniform, and the battery efficiency can reach more than 7%. The problem is that the deposited film is generally Cu-rich film. After heat treatment, Cu ₂ Se in the Cu-rich phase in the film needs to be etched or dissolved in KCN solution, which will affect the structure of the film surface and the quality of the pn junction of the battery. In addition, the reaction between Mo and Se during heat treatment tends to form thicker MoSe ^[13] .

Germany's A. Kampmann et al. used the sulfate system to conduct long-term research on electrochemical deposition, and established a roll-to-roll continuous electrodeposition pilot line at CISSolartechnik. The CIGS thin film is prepared on a thin metal tape with a bandwidth of 100mm. The process: Mo, Cu, steel, and stainless steel are used as the substrate of the thin film battery, and the barrier layer is deposited, the Mo layer is deposited by sputtering, and Cu-In is electrodeposited in sequence. After -Ga, Se is evaporated and deposited, and finally Na compounds are evaporated and deposited on the Se layer, and then a rapid heating and heat treatment is performed to form a CIGS film. The process is similar to the technology of selenization after vacuum sputtering. The efficiency of CIGS cells on thin stainless steel strips is 10.4% (with an area of 1.0cm ² ), and that with an area of 13.3cm ² is 6.6% ^[14] .

From the above documents and patent specifications, we know that the coating process of nano-coatings determines that various organic additives must be added so that the nanoparticles can be stably and uniformly dispersed in the solvent and prevent the flocculation of the nanoparticles. Impurity defects are formed in the semiconductor thin film, forming a porous and loose structure of the pre-set layer. After the paint is coated and dried to form a film, the nanoparticles are only in tangential point contact, and the contact area is relatively small. When heating to form a dense film with large grains, the reaction kinetics are hindered and the situation becomes very complicated. The reaction kinetics are thus in many ways related to the total amount of surface area in contact between the particles. Oxide nano-coatings require two heating steps, one is the reduction of loose structure oxides into dense metal alloys, and then heating for selenization or further selenization in H ₂ Se poisonous gas, the prepared light-absorbing layer has uniform composition, semiconductor The band gap is flat, and the sulfuration treatment can form a dual-performance p-type semiconductor film with a gradient band gap and a high surface resistance on the surface; however, its high-temperature hydrogen reduction time is long, energy consumption is large, and there is a danger of explosion. Its technical know-how is borrowed from vacuum sputtering The technology of preparing thin-film batteries by selenization after irradiating metal pre-layers; the preparation of selenide nanoparticles needs to be prepared by reaction in organic solvents, which consumes a large amount of organic solvents, which is easy to cause environmental pollution and relatively high cost; non-vacuum post-processing In the process of remelting and crystallization, the film densification mechanism depends on the liquid phase assisted recrystallization process of the low melting point components in the preset layer. Dense large-grain film; however, it is difficult to completely eliminate defects such as coating additives and inclusions left in the pores of the film, and the composition uniformity of the light-absorbing layer prepared by rapid heat treatment is poor, the crystallization quality of the film surface is not high, and impurities and grain boundaries are recombined More will affect the quality of the pn junction of the battery, making the open circuit voltage Voc of the thin film battery lower.

The characteristics of selenide film prepared by electrodeposition: it can self-purify the deposited material, use lower-purity raw materials, and change the composition of the pre-set film according to the deposition potential, which is convenient for forming a gradient band gap distribution. The coating method is denser than the pre-layer film. The existing problems are: the Mo substrate corrodes due to chemical replacement reaction at the initial stage of deposition, the solubility of solute in the solution is small, the current density of the electrodeposited semiconductor selenide film is relatively small, and the deposition rate of the film is slower than that of the electrodeposition method compared with the coating method. Low, the film contains a lot of oxygen, the stability of the solution still has problems, etc., only the treatment in _H2Se or _H2Se -like gas can effectively remove oxides, which adds difficulties to the elimination of toxic gases . On the other hand, it is inappropriate to excessively pursue the composition requirements of the electrodeposited selenide precursor film to meet the stoichiometric ratio of the thin film battery. The excessive high melting point selenide in the electrodeposited selenide precursor film will hinder the further densification of the film. Even if there is an excessive amount of CuSe (copper-rich structure), it cannot produce obvious liquid phase aggregation or agglomeration during the heating process, wrapping other particles to cause sliding, film deformation (densification) or precipitation on the film surface; if not deposited To neutralize excess Cu ₂ Se with In and Ga, KCN solution is required to dissolve Cu ₂ Se in the film through wetting.

Contents of the invention

The present invention is formed in view of the problems actually existing in the industrial production process of the above-mentioned technologies, and it provides a low-cost method for preparing selenide precursor films for CIGS thin-film cells and rapid selenium sulfidation heat treatment to directly prepare thin-film solar cells. It can be used for low-cost nano-coating printing roll coating method or water-bath electrodeposition precursor selenide thin film direct rapid selenium vulcanization treatment, and continuous production of thin-film battery follow-up process to prepare high-efficiency cadmium-free CIGS thin-film solar cell integrated photovoltaic modules. The light-absorbing layer of the thin-film solar cell is made of loose or porous microcrystalline precursor film melting, inter-particle infiltration, and liquid-phase assisted crystal synthesis reaction growth through rapid vacuum heat treatment, and metal target reactive sputtering of In ₂ Se ₃ and/or Or In ₂ S ₃ , so that the overall composition of the film changes from copper-rich to copper-poor structure, and a small amount of excess In ₂ S ₃ generates n-Cu with a high resistance OVC (ordered defect chalcopyrite) structure on the surface of the absorber layer of the thin film battery (In, Ga) ₃ (Se, S) ₅ constitutes the pn shallow buried junction and dual-performance light-absorbing layer for low-cost preparation of thin-film batteries; since the Ga and S elements in the selenide precursor film are respectively at the Mo back electrode and the film The surface layer has a relatively high content or the Ga in it has a V-shaped distribution. After rapid selenium sulfidation heat treatment, the semiconductor band gap of the film presents a V-shaped distribution in the depth direction of the film thickness, and the film surface has a pn shallow buried junction. As the temperature of the substrate decreases, the n-type high-resistance intrinsic i-In(OH,S)/ZnS(O,OH)/ZnO(S) transparent buffer layer and i-layer are deposited on the light absorbing layer by reactive sputtering. . Subsequent sputtering deposits a low-resistance transparent n-ZnO:Al thin film to form the n-type conductive layer of the battery, and this kind of low-cost selenide precursor film is completed to prepare a relatively complete pin structure for CIGS thin-film batteries, which has the highest efficiency with co-evaporation (19.9% ) CIGS thin film battery theoretical model and the actual structure showed a more obvious consistency.

Another object of the present invention is to provide a manufacturing process for CIGS thin-film solar cells, which can greatly reduce the investment in early stage manufacturing equipment and greatly improve the utilization of sparse precious metal raw materials in the thin-film solar cell manufacturing process compared with the vacuum method in the past The efficiency reduces the energy consumption in the manufacturing process, shortens and simplifies the manufacturing process, combines the technical advantages of co-evaporation and sputtering pre-layer selenization to prepare thin-film batteries, and improves the quality of thin-film batteries produced by low-cost preparation methods , thereby reducing the raw material and manufacturing costs of CIGS thin-film solar cells, and promoting the wider application of solar cells.

In order to solve the above-mentioned problems, the present invention provides the method for preparing thin-film solar cells by non-vacuum low-cost method for preparing the selenide precursor thin film of thin-film battery and rapid selenium sulfidation heat treatment, and its main features are: (1) molybdenum on rigid substrate substrate Sequential coating of nano-selenide coatings on the electrode film and drying to form a film, or sequential electroplating (or electrodeposition) of different components of nano-microcrystalline selenide precursor films, the composition and structure of the selenide precursor films are: (CuGaSe ₂ +CuSe ), (Ga ₂ Se ₃ +CuSe), In ₄ Se ₃ (or In ₂ Se ₃ +CuInSe ₂ ), CuSe [or (CuSe+Ga ₂ Se ₃ ), (CuSe+CuGaSe ₂ )] sequential combination ; (2) A stack of rigid substrates on which the selenide precursor film was prepared was placed in an airtight space in a vacuum chamber, heated in a high vacuum from room temperature to 290°C, injected with hydrogen, and then evacuated to a high vacuum and injected with hydrogen several times Operation and the first hydrogenation pretreatment process of injecting argon + hydrogen at last; (3) second selenization treatment, the stack of substrates is moved in parallel from top to bottom or bottom to top, and pushed into another stack of substrates one by one. In a relatively airtight space, start the heating of the bottom of the substrate first, and introduce H ₂ Se-like gas into the second airtight space, while maintaining sufficient selenium pressure (20-80kPa), move the substrate up and down Rapid heating or upper scanning heating and fixed heating and heating at the bottom moving with the substrate. The substrate itself is always kept at 350 ° C ~ 580 ° C. The surface layer of the substrate is heated by the mobile scanning of the high-power radiation heat source. It will quickly heat up to 350°C~1100°C, which will promote the rapid melting of the Cu _x Se/ and In ₄ Se ₃ phases in the selenide precursor film (liquefied at 523°C), assisting the liquid phase reaction growth of the CIGS film crystal and the densification of the film itself. After the large-grained and dense CIGS film is formed, a small amount of Cu _x Se in the surface layer will ooze out or absorb excess liquid phase; (4) the third selenium sulfidation treatment, when the substrate is at a suitable temperature of 520 ° C to 580 ° C, the The movement of the substrate is transferred to the sputtering position, and the pressure in the airtight space is adjusted to 0.3-25Pa. The excess liquid phase Cu _x Se on the surface of the substrate is neutralized and reacted by reactive sputtering of In ₂ Se ₃ or In ₂ S ₃ , and the substrate is strictly controlled. The sputtering amount of In ₂ Se ₃ or In ₂ S ₃ in the process of changing the composition of the CIGS film on the surface of the sheet from copper-rich to copper-poor structure; The amount of H ₂ Se gas is so that when the ambient selenium pressure reaches 20-80kPa, the high-power radiation heat source performs faster thermal scanning on the substrate; (6) the fifth high-temperature sulfurization treatment, after the H ₂ Se-like gas is evacuated, Re-inject the reactive sputtering gas H ₂ S+Ar, maintain the pressure at 0.3-25Pa, move the substrate to the sputtering position and perform reactive sputtering of In ₂ S ₃ , which generates n-type Cu (In _1-x Ga _x ) SSe or Cu(In _1-y Ga _y ) ₃ (Se _1-x S _x ) ₅ high-resistance layer; during the operation of the above-mentioned rapid selenium sulfidation heat treatment, the second airtight space is alternately filled with H ₂ Se-like gas or H ₂ S+Ar gas, high vacuum exhaust is carried out in the middle, and its pressure rises and falls; (7) the substrate after rapid selenium sulfide heat treatment is transferred to the third airtight cooling space; thus, the first Space The whole stack of substrates is put into the third cooling space after rapid selenium sulfidation heat treatment. This space is injected with Ar+H ₂ S mixed gas to ensure that the substrate substrate gradually drops from 580°C to 110°C. CIGS thin film material The internal selenium and sulfur elements are not lost; (8) the cooled substrates are pushed into the fourth airtight space respectively, and the high resistance intrinsic In(OH,S)/ZnS(O, OH)/ZnO(S) buffer layer and i layer, two or three pairs of pure metal sputtering target materials and reaction gases are: In/(Ar, H ₂ S and H ₂ O), Zn/(Ar, H ₂ S and H ₂ O) and Zn/(Ar, H ₂ S and O ₂ or CO ₂ ), the temperature of the substrate during the sputtering process is controlled at 110 ° C ~ 350 ° C; after the sputtering is completed, the airtight space After being pumped into a high vacuum state, a high-power radiation heat source is started to quickly scan the surface of the substrate; (9) the substrates deposited with a high-resistance buffer layer by reactive sputtering are respectively classified into the fifth cooling space; after the substrate is cooled, it can be transferred to The next laser processing or mechanical scribing of the electrode series connection process of the battery integrated assembly, or the process of depositing a low-resistance transparent conductive ZnO:Al film.

According to the present invention, the precursor selenide thin film is obtained by coating or rolling nano-selenide coating and drying film in a certain order, or sequential water-bath electrodeposition to prepare nano-microcrystalline selenide precursor film. These selenide precursor films The components are: the arrangement and combination of CuGaSe ₂ , Ga ₂ Se ₃ , CuInSe ₂ , CuSe, In ₄ Se ₃ or In ₂ Se ₃ , of which only selenium-rich CuSe and selenium-poor In ₄ Se ₃ have a low melting point (523°C) Selenides, which are indispensable or essential components in the selenide precursor film, determine whether the loose selenide film can be directly prepared with a large grain and dense absorbing layer film after rapid selenium sulfurization heat treatment. That is to say, it is necessary to carry out a synthesis reaction between a variety of binary (including a small amount of ternary) selenide microcrystalline particles, so that the precursor selenide film can finally generate a quaternary columnar, large-grain dense PV (photovoltaic) film. , in which the solid-liquid phase crystal reaction growth mechanism of the lower melting point binary selenide CuSe and/or In ₄ Se ₃ (523°C) should be used during the synthesis reaction, and the high melting point solid phase selenide in the precursor selenide film should not be allowed to (Ga ₂ Se ₃ , CuInSe ₂ , CuGaSe ₂ , In ₂ Se ₃ ) prevent the microscopic sliding and filling of microscopic holes caused by the melting and infiltration of low melting point selenide microcrystalline particles in the film, and the liquid phase wrapping high melting point particles Plastic deformation process and densification process of films such as blockage or blockage.

In the present invention, the precursor films coated with nano-selenide and roll-coated are inevitably mixed with polymeric organic matter, and the selenide film deposited by water bath electrodeposition contains more than 15% oxides. Vacuum heating, hydrogen injection, multiple operations of pumping to high vacuum and hydrogen injection, and finally the first hydrogenation pretreatment process of injecting argon + hydrogen; when the temperature of the selenide precursor film is below 290 ° C, the synthesis reaction inside it is relatively low. Small, it is beneficial for the surface and internal microcrystalline adsorption gas of the porous film to be desorbed, part of the oxides to be reduced, heating to volatilize or desorb the mixed organic matter and other technological measures are necessary. The selenide precursor film material is rapidly heated in the formal It is very beneficial for the subsequent recrystallization of thin films to prepare semiconductor devices after being modulated to an electronic-grade high-purity state. The second airtight space is evacuated to a high vacuum above 1×10 ^-3 Pa before introducing H ₂ Se-like gas. After the air pressure in the first airtight space is balanced, the gate valve between the two chambers is opened, and the first Push a piece of substrate in the room into the airtight space of the rapid selenium sulfidation heat treatment chamber and close the gate valve, continue to introduce H ₂ Se-like gas to a pressure _of 50-80kPa, and then proceed to the second selenium sulfide treatment process; The composition of Se gas components is: 30%-50% argon, 25%-35% hydrogen, 15%-45% H ₂ Se. On the premise of maintaining a sufficient selenium atmosphere, the moving substrate is first lowered and then upper or up and down at the same time. The substrate itself is kept at a temperature range of 350°C to 580°C, and the high-power radiation heat source makes the substrate The temperature of the precursor selenide film on the surface is rapidly raised to 350 ° C ~ 1100 ° C, which promotes the rapid melting of microcrystalline CuSe and/or In ₄ Se ₃ in the middle of the selenide precursor film (liquefied at 523 ° C) to assist the liquid phase reaction growth of CIGS thin film crystals, The film itself undergoes a densification process of remelting and recrystallization, and rapid heating promotes the chemical synthesis reaction in the precursor selenide film, and finally produces a CIGS film with a high melting point and large grain density. Since the composition of the selenide precursor film is strictly required to be a copper-rich structure, more microcrystalline CuSe is consciously arranged on the surface layer, and a small amount of liquid phase Cu _x Se will seep out of the surface layer after rapid heating. At this time, the substrate should be maintained at 520 ℃ ~ 580 ℃, the heater at the bottom of the substrate is in a constant power control state. When the entire substrate is completely formed with a CIGS large-grain dense film, excess liquid phase Cu ₂ Se will be adsorbed on its surface, the selenium pressure in the environment will be reduced to 0.3-15Pa, and the substrate will be transferred to the reactive sputtering area for reactive sputtering In ₂ Se ₃ or In ₂ S ₃ , strictly monitor the physical state of the substrate film surface under constant power heating conditions when the excess liquid phase Cu ₂ Se on the substrate surface is neutralized by reaction or when the copper content in the film is reduced to 24.5%. There will be a very obvious change, that is, the amount of sputtered In ₂ Se ₃ or In ₂ S ₃ needs to be accurately monitored during the transition of the composition of the CIGS film from copper-rich to copper-poor structure.

Since the selenide precursor film itself has a loose structure, its heat conduction performance is limited; in the present invention, it is preferable to heat and raise the temperature from the bottom first, and the CuGaSe ₂ +CuSe and Ga ₂ Se ₃ close to the molybdenum film in the selenide precursor film start at 380°C In the synthesis reaction, a small amount of CuGaSe ₂ in the film is used as the seed crystal of high melting point selenide, which induces Cu _x Se and Ga ₂ Se ₃ to react around it to form a wide-bandgap CuGaSe ₂ large-grain film, resulting in the molybdenum film on the substrate being covered by large grain CuGaSe ₂ is interconnected into sheets to cover each other; on the other hand, the trace amount of gallium and molybdenum in CuGaSe ₂ is easy to react to form a metal compound, which greatly improves the bonding force between the CIGS film and the molybdenum film of the back electrode, and prevents the molybdenum element of the back electrode from continuing to contact with excessive molybdenum. Selenium reacts to form MoSe. If the upper (or external) high-power radiation heat source quickly scans the selenide precursor film at this time, the surface will produce melting, intergranular infiltration, collapse or shrinkage, and the high melting point Cu(In, Ga)Se ₂ microcrystal It will induce the low melting point liquid phase Cu _x Se and In ₄ Se ₃ to react with Ga ₂ Se ₃ to grow into a CIGS large crystal film around it, the grain boundaries between the major grains are ablated, and the Ga and In elements at the bottom and surface of the precursor film Interdiffusion, naturally forming a smooth composition gradient distribution and semiconductor gradient band gap in the depth direction of the large-grained film. The excess or excess liquid phase Cu ₂ Se is adsorbed on the surface of the large-grained CIGS film, and is subsequently sputtered by In ₂ Se ₃ or In ₂ S ₃ to neutralize and react; increase the amount of injected H ₂ Se-like gas so that when the ambient pressure reaches 20-80kPa, start the high-power radiation heat source again to quickly scan the surface of the substrate, and the film on the surface of the substrate melts rapidly The grain boundaries between the large grains are cut off, Cu ₂ Se, In ₂ Se ₃ and other impurity phases in the grains are dissolved, and the low-lying places between the grain boundaries and the raised parts on the surface of the large grains are smoothed , so that the crystal of the CIGS film section is very complete, and the microscopic surface of the film is also very smooth, which reduces the effective grain boundary recombination in the film battery and increases the open circuit voltage Voc of the battery; after the H ₂ Se-like gas is evacuated, the H ₂ S gas is re-injected , the surface layer of the film after sputtering deposition of In ₂ S ₃ generates an n-type Cu(In _1-x Ga _x )SSe or Cu(In _1-y Ga _y ) ₃ (Se _1-X , S _X ) ₅ high resistance layer, Its thickness is about 20-40nm, forming a homogeneous shallow buried junction or dual-performance light-absorbing layer of thin-film batteries, improving the junction characteristics of thin-film batteries and suppressing leakage current, and improving the photoelectric conversion efficiency of thin-film batteries. Similarly, with the natural cooling of the CIGS film on the substrate, after the n-type intrinsically high resistance In(OH, S)/ZnS(O, OH)/ZnO(S) film of the sputtering battery buffer layer is started, the fourth gas After the dense space is evacuated to a high vacuum, a high-power radiation heat source is started to quickly scan the surface of the substrate to desorb the gas in the sputter-deposited buffer layer material, make the grains of the film more compact, and diffuse zinc and sulfur elements to the surface of the p-type CIGS film, improving The quality of the built-in electric field region of the pn junction of the thin film battery is guaranteed.

In the first hydrogenation pretreatment process of the present invention, it is also possible to add a vacuum exhaust process that cuts off the hydrogen supply and quickly opens the airtight space valve; through this vacuum exhaust process, the airtight space will temporarily become a high vacuum state, heating and The high vacuum makes the organic matter contained in the selenide precursor film volatilize or desorb again, and re-inject hydrogen to make the highly active hydrogen react with the oxides in the selenide precursor film, so that the selenide precursor film material can be reduced to electronic grade as much as possible High-purity state, completely remove the inclusion of organic matter in the film, and reduce the existence of oxides. Similarly, the vacuum chambers of the second, third, and fourth airtight spaces are also provided with a vacuum exhaust mechanism, which can perform vacuum exhaust operation procedures, and it is used to adjust certain states in the film.

Therefore, the CIGS thin-film solar cell prepared by rapid selenium sulfidation heat treatment through the low-cost selenide precursor film manufactured by the present invention can reliably obtain the characteristic photoelectric conversion efficiency of chalcopyrite-type thin-film solar cells. With the continuous improvement of technology, Its performance will reach the level of thin-film batteries prepared by vacuum co-evaporation.

The other objectives, advantages and novel features of the present invention will be stated in the following description, and this part will be easily understood by those skilled in the art through the study of the following descriptions of drawings, specific implementation methods and cases.

Description of drawings

Figure 1 is a schematic diagram of the structure of each layer of a general CIGS thin-film solar cell;

Fig. 2 is the thin-film solar cell structural diagram that the present invention's low-cost precursor selenide thin film and rapid selenium vulcanization treatment prepare;

Shown in Fig. 3 is that low-cost selenide precursor thin film of the present invention carries out fast selenium vulcanization heat treatment and prepares the schematic diagram of the principle of the light absorbing layer of CIGS thin film solar cell;

Fig. 4 is a schematic diagram of the main process of the production process of the CIGS thin film solar cell photovoltaic integrated module of the present invention. It is small, Figure 4(a) Reactive sputtering metal silicon, titanium target to prepare alkali barrier layers such as SiO, TN and SiN; Figure 4(b) Sputtering to prepare Mo electrode layer; Figure 4(c) Laser cutting molybdenum thin film The electrodes of each sub-battery were prepared in the back electric field; Fig. 4(d) nano-coating sequential roll coating or sequential electrodeposition to prepare selenide precursor film; Fig. 4(e) hydrogenation pretreatment of selenide precursor film; Fig. 4(f) selenide The precursor film is remelted and recrystallized in a selenium atmosphere; Fig. 4(g) liquid phase Cu ₂ Se is neutralized by reactive sputtering In ₂ Se ₃ or In ₂ S ₃ , and remelted and decrystallized after a high-power radiation heat source is quickly scanned Intergranular grain boundaries and smoothing the uneven surface of the film, and then sputtering In ₂ S ₃ to generate high-resistance n-type Cu(InGa) ₃ (SeS) ₅ ; Figure 4(h) Reactive sputtering indium zinc target to prepare In(OH , S)/ZnS(O, OH)/ZnO(S) thin-film battery buffer layer; Figure 4(i) laser irradiation treatment of contact electrodes; Figure 4(j) sputtered transparent conductive ZnO:Al layer; Figure 4(k ) laser irradiating anti-explosion punching to cut the transparent electrode layer; Figure 4 (l) CIGS thin-film cell photovoltaic integrated module electrode leads and packaging.

Fig. 5 (a) shows that nano-coating printing roller coating method or water-bath electrodeposition method prepares the precursor selenide thin film rapid selenium vulcanization heat treatment and prepares the schematic structure diagram of thin-film battery light absorbing layer, buffer layer and i-layer device; Fig. 5 ( b) Schematic diagram of the principle of the in-line rapid selenium vulcanization heat treatment device for the selenide precursor thin film (made by the method of the present invention); Fig. 5 (c) The surface of the thin-film battery light-absorbing layer is continuously prepared with a high-resistance buffer layer and an intrinsic i layer ; Fig. 5 (b), Fig. 5 (c) are respectively enlarged views of two components of 32a and 34a in Fig. 5 (a) large system device.

Specific implementation method

The basic structure (shown in Figure 1) of the low-cost precursor selenide thin-film solar cell (shown in Figure 2) made by the present invention is the same as that of the traditional chalcopyrite-type CIGS thin-film solar cell, and only exists in the manufacturing route or method There are some differences. The selenide precursor thin film is first prepared by a non-vacuum low-cost method, and then the vacuum rapid selenium sulfide heat treatment is used to directly manufacture the p-type light absorbing layer of the thin-film battery (as shown in Figure 3), and the buffer layer of the p-n junction region of the thin-film battery. With the i layer, it can be transferred to the scribing process of the inline electrode series connection of the thin film solar cell integrated module (the bottom electrode of the battery is connected in series with the surface electrode), or continue to deposit the n-type low-resistance transparent window layer ZnO:Al, A single thin-film solar cell for routine laboratory testing was prepared.

When using ordinary soda-lime float glass with poor quality uniformity or glass with different batches and uneven quality, the alkali composition on the surface of the glass is seriously uneven, and there will be other impurities as the thin-film battery manufacturing process proceeds Diffusion into the light-absorbing layer 1d through the Mo thin-film electrode layer 1c affects the quality of the light-absorbing layer and the uniformity of large-area crystals; in addition, the implementation of the battery process will cause alkali explosion on the glass surface, making the Mo electrode layer thin film and light-absorbing The bonding force between the layers is weakened, which leads to the separation and detachment of the absorbing layer of the thin-film battery and the Mo thin film, which affects the photoelectric conversion efficiency and fill factor FF of the thin-film battery. In order to obtain homogeneous, excellent thin-film battery photovoltaic integrated components, the present invention preferably sequentially deposits an alkali barrier layer 1b and a Mo electrode film layer 1c on a soda-lime glass (also known as common soda-lime glass, English abbreviation SLG) substrate 1a, alkali The barrier layer is composed of SiO, TiN, SiN, etc. prepared by reactive sputtering metal silicon or metal titanium targets; another reason is that the selenide precursor film of the present invention contains the sodium salt required for the CIGS film optical absorption layer in the remelting and recrystallization process , it is not very necessary for the Na in the SLG substrate to diffuse through the Mo electrode film layer into the absorber layer.

Fig. 3 shows the structure of each layer of the preferred nano-coating sequential roll coating or electrochemical deposition of selenide precursor film layer by layer in the present invention, and during rapid selenium vulcanization heat treatment, the principle diagram of remelting recrystallization of the selenide precursor film, and Fig. 4 (f) Related.

Figure 5(a) shows a schematic diagram of the device principle for preparing the thin-film cell light absorption layer, buffer layer and i-layer after the SLG substrate is placed into the rapid selenium sulfide heat treatment device after the prefabricated selenide precursor thin film, and Figure 4(e) , Fig. 4(f), Fig. 4(g) and Fig. 4(h) show that the rapid selenium vulcanization heat treatment process of the precursor selenide thin film is corresponding, is to pass the gate valve 320, 321, 340, 341 to the hydrogenation pretreatment chamber 31a, the schematic schematic diagram of the in-line fast selenium sulfide heat treatment device connected respectively to the fast selenium sulfide heat treatment chamber 32a, the storage sheet cooling chamber 33a, the sputtering deposition chamber 34a, and the sheet taking chamber 35a, each chamber 31a, 32a, 33a, and 34a are respectively connected to vacuum exhaust mechanisms (not shown). If the vacuum equipment in Fig. 4(i), Fig. 4(j) and Fig. 4(k) is connected again, photovoltaic integrated modules of thin-film cells can be continuously prepared.

The device 31a in Fig. 5(a) corresponds to the hydrogenation pretreatment process of the precursor selenide thin film shown in Fig. 4(e), and a plurality of substrates 3a that can be accommodated in batches are mounted inside the hydrogenation pretreatment chamber 31a , the substrate 3a is placed on a support mechanism (not shown) that can be lifted up and down and is transported as a whole. The support frame is placed in the airtight space 312. There are a heater 311 and a heat radiation shielding plate 310 outside the airtight space, and the substrate The sheet pushing mechanism 313 also has a common introduction pipe for hydrogen and argon and a controllable exhaust valve (not shown) in the airtight space. A stack of substrates 3a stored in the hydrogenation pretreatment chamber has been subjected to sequential roll coating and drying of the nano-selenide precursor film on the Mo electrode film layer, or electrochemical sequential electrodeposition of the selenide precursor film, wherein the Mo bottom electrode film Have been laser cut into thin film monomers that are evenly divided; in the substrate 3a in batches, the substrate 3a that has been heated and hydrogenated is stored on a carrier that can be lifted and lowered and placed horizontally (not shown in the figure) Shown), it can push the substrates 3a one by one through the gate valve 320 to the dolly 323 of the rapid selenium sulfidation heat treatment chamber 32a by the cooperation of the substrate pushing mechanism 313 and the lifting support mechanism.

Fig. 5 (b) is the schematic diagram of the present invention's rapid selenium vulcanization heat treatment selenide precursor film to prepare the absorbing layer device of thin film battery, and it carries out the remelting and recrystallization process and the remelting recrystallization process of it and Fig. 4 (f) precursor selenide film in selenium atmosphere environment Figure 4(g) Reactive sputtering of In ₂ Se ₃ or In ₂ S ₃ neutralizes the adsorbed Cu _x Se on the surface of the remelted recrystallized absorber layer and sputters In ₂ S ₃ to form high resistance n-Cu (In _1-x The process corresponds to Ga _x )SSe or Cu(In _1-y Ga _y ) ₃ (Se _1-x S _x ) ₅ . In the rapid selenium vulcanization heat treatment chamber 32a, the substrate 3b is placed on the dolly 323 that can control the moving distance and speed, and many pairs of thermocouples that are in contact with the resistance heating device and the substrate 3b are evenly arranged under the substrate 3b, so that the substrate can be processed. Heating with temperature controllable or constant power at the back; high-power thermal radiation source 324 that can control moving distance, speed and power can quickly scan the surface of substrate 3b; ₂ Se or H ₂ Se-like gas inlet pipe, on the single side wall of the gas inlet pipe close to the trolley 323, a plurality of evenly arranged nozzle holes are arranged, and H ₂ Se or H ₂ Se-like gas flows from the nozzle holes to the moving substrate 3b surface (not shown); a pair of metal indium reactive sputtering target 325 is installed in the 32a chamber, and two sets of gas paths of argon and sputtering reaction gas introduction pipes are respectively installed on it; the above-mentioned devices are all arranged in In the airtight space 326, the airtight space 326 is equipped with a valve that can quickly open the exhaust or adjust the air pressure and a vacuum bare gauge (not shown) for detecting the gas pressure. The gate valve 321 is opened, and the substrate 3b is put into the substrate carrying mechanism 333 (not shown) which can be lifted horizontally by the taking-up mechanism 331 in the storage cooling chamber 33a.

In the storage cooling chamber 33a, the selenide precursor film on the substrate 3c has been successfully transformed into a copper-poor, large-grain and dense optical absorption layer after heating and sputtering In ₂ Se ₃ /In ₂ S ₃ . The temperature of 3c will gradually decrease from 540°C to 580°C at the time of transfer to 100°C, and the storage cooling chamber is always filled with 0.5 to 30Pa of H ₂ S + Ar gas to ensure that the optical absorption layer on the substrate 3c is in the process of temperature drop Selenium and sulfur elements will not volatilize or escape; as the substrate 3c gradually increases, when the gate valve 321 is closed, open the gate valve 340, and use the substrate pushing mechanism 332 to push the substrate 3c to the sputter deposition on the dolly 342 of the chamber 34a.

Fig. 5 (c) is the schematic diagram of the principle of the sputtering deposition buffer layer and the i-layer chamber 34a device, which is prepared from the direct reaction sputtering metal indium zinc target on the absorber layer of the CIGS thin film battery of Fig. 4 (h) (OH, S )/ZnS(O, OH)/ZnO(S) buffer layer corresponds to the i-layer process. In the sputtering deposition chamber 34a, the dolly 343 that can control the moving distance and speed has the same basic structure as the dolly 323 in the rapid selenium sulfidation heat treatment chamber, and a resistance heating device and two pairs of temperature-measuring thermocouples are evenly arranged under the substrate 3d. It is connected with the controller outside the vacuum chamber by a soft braided wire, and the substrate temperature is controlled at 80°C to 350°C, preferably 100°C to 180°C when sputtering the buffer layer and i-layer on the substrate surface; Two to three pairs of medium-frequency AC or DC pulse reactive sputtering metal targets 343, 345 and 346 are installed in room 34a, which are high-purity indium and zinc metal targets respectively, and two sets of gas pipelines are respectively installed on each pair of targets. Supply the sputtering and reaction gas required for the work. The sputtering deposition area is covered by a porous metal mesh and is connected to the ground wire alone instead of the casing. Its function is to shield the sputtering ions between the two targets and prevent charged ions Bombard the substrate 3d and destroy the structure of the pn junction of the thin film battery; similarly, a fixed high-power radiation heat source 344 is installed in the sputtering chamber 34a, and they are also placed in the airtight space 347, on which a movable Quickly open the controllable valve to exhaust or adjust the air pressure, and the vacuum bare gauge (not shown) to detect the gas pressure. After the sputtering of the buffer layer and the i-layer is completed, the substrate 3d after the rapid heat treatment of the high-vacuum surface layer is received into the substrate carrying mechanism (not shown) 352 by the taking-up mechanism 351 in the taking-up chamber 35a via the gate valve 341 On the support, a substrate-transferable supporting mechanism identical to the structure of the hydrogenation pretreatment chamber 31a is mounted in the taking-up chamber 35a, and a plurality of substrates 3e equivalent to batches can be stored on the horizontal shelf of the supporting mechanism. Above, open the gate of vacuum film taking room 35a, just can use forklift truck to directly transport the supporting mechanism of whole batch of substrate 3e out from vacuum film taking room, transfer to the next production process.

Example 1

When making CuInSe _2-x S _x thin-film solar cells with nano-selenide coatings, the surface of the SLG substrate is sputtered with an alkali barrier layer and a Mo back electrode film, and roll-coating CuSe and In ₄ selenide coatings on the surface of the substrate. Se ₃ (or In ₂ Se ₃ ) and CuSe each once, the present invention is preferably selenium-poor In ₄ Se ₃ (melting point 520°C) nano-coating; each time the coating is dried immediately after coating, the selenide precursor film presents CuSe/In ₄ Se ₃ (or In ₂ Se ₃ )/CuSe structure, total Cu/In film > 1.06, CuSe on the surface > CuSe on the bottom, the optimum ratio is 1.1-1.5, and the total thickness after drying is about 4-7 μm (requires final rapid selenium vulcanization The thickness of the absorbing layer prepared after heat treatment is about 0.9-1.8 μm), and the composition structure ratio of the three-layer selenide film is about 4:10:6.1. Before the precursor selenide film is dried for the last time, a certain amount of sodium salt needs to be evenly sprayed , it can assist the rapid selenium sulfidation heat treatment of selenide precursor film under lower conditions to obtain large-grain dense film. Put the dried precursor selenide film substrates 3a into the bracket of the horizontal carrying mechanism in the hydrogenation pretreatment chamber shown in Fig. 5(a) according to the specified number, and close the door of the vacuum chamber.

The standard process procedure of the rapid selenium vulcanization heat treatment of the precursor selenide film of the present invention is: open the valve of the vacuum exhaust device of the hydrogenation pretreatment chamber 31a and the inner airtight space 312, and simultaneously, the heater 311 raises the internal temperature of the airtight space from room temperature To 290°C, the preferred temperature ranges of nanometer precursor selenide or electrodeposition precursor selenide are: 30°C ~ 180°C and 30°C ~ 290°C, after pumping to a high vacuum of 1×10 ^-3 Pa, close the airtight space Valve, inject hydrogen to maintain the air pressure in the airtight space between 30-60kPa, keep it for 3-5 minutes, then evacuate it, pump it to a high vacuum and re-inject hydrogen, cycle 3-5 times, so that the organic additives in the nano-selenide coating Desorption and volatilization or hydrogenation decomposition (15% to 18% of the oxides in the electrodeposition precursor selenide film are partially reduced), the material in the selenide precursor film is pure electronic grade, and Ar+ is injected after the last evacuation H ₂ gas (respectively: 50～70% and 30～50%), lower the air pressure of the airtight space at the bottom to 0.3～20Pa, and open the gate valve 320 after the air pressure in the 32a chamber is balanced, and the substrate 3a is pushed to the On the dolly 323 of the rapid selenium sulfide heat treatment chamber 32a, close the gate valve 320.

After the hydrogenation pretreated substrate 3a is placed on the trolley 323, it is renamed as 3b, and the back heating device of the trolley substrate 3b is started, and the temperature is raised to 350-550°C (or 450-580°C is preferred for Ga selenide), and at the same time Open the valves of the gas passages on both sides of the trolley, inject H ₂ Se-like gas, and maintain the selenium atmosphere in the airtight space 326 at an air pressure of 30-80kPa. After the trolley moves, start a high-power radiation heat source to perform scanning-type rapid selenization on the substrate 3b Heat treatment, the temperature of the glass substrate is controlled at 530-580°C, the selenide on the surface of the substrate is rapidly heated to 550-1100°C, and the selenide precursor film is fully reacted to form a large-grain and dense CIS (or CIGS) film. Since the selenide precursor film itself has a copper-rich structure, excess liquid phase Cu ₂ Se will be adsorbed on the surface after rapid selenization heat treatment. Close the H ₂ Se-like gas pipeline valve and open the exhaust valve in the airtight space to reduce the environmental selenium concentration. When the air pressure reaches 0.5-25Pa, the trolley 323 moves to the position of the reactive sputtering target, and the heater at the bottom of the substrate 3b on the trolley 323 is in a state of constant power control. When reactive sputtering of In ₂ Se ₃ or In ₂ S ₃ is carried out on the substrate 3b to neutralize and react the liquid phase Cu ₂ Se, monitor the change of the difference between the pairs of thermocouples at the bottom of the substrate 3b on the trolley 323, which determines the reaction Sputtering In ₂ Se ₃ or In ₂ S ₃ per unit power or deposition amount per unit area, and precisely controlling the moving speed of the trolley 323; strictly controlling the selenide film on the surface of the substrate 3b due to reactive sputtering deposition of In ₂ Se ₃ or In ₂ S ₃ , the sudden change in the physical state (test temperature) of the film when the overall composition of the film changes from copper-rich to copper-poor structure, that is, the key change point when copper accounts for ≤24.5% of the film composition. The trolley substrate 3b always maintains an appropriate moving speed and a suitable deposition amount of In ₂ Se ₃ or In ₂ S ₃ by sputtering, and the entire surface of the substrate 3b is uniformly and completely transformed into the absorbing layer of the CIGS thin-film battery, and the sputtering is turned off. Radiation power source, sputtering argon and reaction gas H ₂ Se or H ₂ S, turn off the heater of the trolley 323, move it back to the high-power radiation heat source, open the valves of the gas circuits on both sides of the trolley, and inject H ₂ Se gas to 30 ~ 80kPa, restart the high-power radiation heat source to scan the surface of the substrate 3b more quickly, the trolley 323 and the high-power radiation heat source device 324 are in relative motion at the same time, the large grain CIS or CIGS on the surface of the substrate 3b The remelting of the grain boundary and the protrusion on the grain surface reduces the effective grain boundary recombination of the thin film battery and dissolves the impurity phase in the crystal, so as to achieve the purpose of increasing the open circuit voltage Voc of the thin film battery. Move the substrate to the vicinity of the sputtering position, reduce the air pressure in the airtight space to 0.5-25Pa, and replace the sputtering reaction gas with H ₂ S, start the heating power supply of the trolley, the moving mechanism and the reactive sputtering power supply, and reactively sputter In ₂ S _3. The surface layer of the substrate 3b is uniformly deposited, and a high-resistance n-CuInS ₂ or n-CuIn ₃ (Se _1-x , S _x ) ₅ is formed on the surface of the substrate 3b, with a thickness of about 20-40nm. At this time, the temperature of the substrate 3b It is about 480 ° C ~ 550 ° C. The gate valve 321 is opened, and the substrate 3b that has undergone selenium sulfidation treatment is sent to the supporting frame of the storage cooling chamber 33a, and naturally cooled under the protection of an Ar+H ₂ S atmosphere of 0.5-30Pa.

The substrate 3c cooled to below 100°C is transported to the trolley 342 of the sputtering deposition chamber 34a, the heater on the trolley 342 and the exhaust valve of the closed space 347 are opened, and the substrate 3c is heated to 80°C-350°C. Preferably at 100°C to 180°C, the airtight space is evacuated to a high vacuum of 1×10 ^-3 Pa or above, the valves of the reactive gas and sputtering argon on each reactive sputtering target are opened, and the airtight space is maintained at an air pressure of 0.2 to 25Pa , adjust the reaction and sputtering gas on each target to an appropriate ratio and flow rate, the target of the first sputtering target position is pure metal indium, the reaction gas is H ₂ S+H ₂ O, and the sputtering product is In(OH,S ), which contains a small amount of In ₂ O ₃ ; the materials of the second and third sputtering targets are metal pure zinc, and the reaction gases are H ₂ S+H ₂ O and H ₂ S+O ₂ or CO ₂ respectively. The sputtering products are ZnS(O, OH) and ZnO(S) respectively, the flow rate of the reaction gas H ₂ S on the second and third target positions is different, and the sputtering power is also different; the sputtering sequence of the buffer layer is: In( OH,S)/ZnS(O,OH)/ZnO(S), they cannot be reversed or produce other combinations. Turn on the sputtering power supply before the trolley substrate 3c approaches each sputtering target position, and sequentially sputter the buffer layer and the i-layer thin film of the thin-film battery. 130nm; after all layers of films are deposited on the surface of the substrate, turn off the heating power on the trolley 342, fully open the air pressure control valve on the airtight space ³⁴⁷ , and turn on the moving device and the The high-power radiant heat source 344 performs flash heat treatment on the CIS film, buffer layer and i-layer on the surface of the substrate, and the heat-affected area only accounts for 1-2 μm of the thickness of the film surface, which promotes the desorption of the adsorbed gas in the sputtered film, The grains are denser and the zinc and sulfur elements diffuse to the surface of the CIS film. Open the gate valve 341, the substrate 3c is received on the support of the substrate carrying mechanism 352 by the sheet taking mechanism 351 in the taking chamber 35a, until the number of substrates reaches a certain amount, the whole carrier is taken out of the vacuum chamber, and the substrate is rotated into the next operating procedure.

In Example 1, two types of thin film solar cells can be prepared, and the open circuit voltage Voc and photoelectric conversion efficiency of the CuInSeS thin film cell in which the liquid phase Cu _x Se is neutralized with In ₂ S ₃ are relatively high.

Example 2

When making CuIn _0.7 Ga _0.3 Se _2-x S _x thin film solar cells with nano-selenide coatings, four nano-selenide coatings are required, which are: (CuSe+CuGaSe ₂ ), Ga ₂ Se ₃ , In ₄ Se ₃ (or In ₂ Se ₃ +CuInSe ₂ ), CuSe, adjust them to the appropriate viscosity respectively, roll coating and drying on the substrate Mo thin film continuously, the four kinds of selenide coatings can be continuously filmed at one time, The structure of its precursor selenide film is: (CuSe+CuGaSe ₂ )/Ga ₂ Se ₃ /In ₄ Se ₃ (or In ₂ Se ₃ +CuInSe ₂ )/CuSe, the total Cu/(In+Ga) of the film>1.06, four The atomic structure ratio of the film composition of the layer is: (4+4):1:3.5:12.1, the thickness of the precursor selenide film is about 4-7 μm, and the ratio of the elements in the film is Ga/(In+Ga)≥0.3, Se/ M<I, surface CuSe>bottom CuSe. The feature of this CIGS thin film battery is that the gallium element in the selenide precursor film is concentrated on the bottom layer, the selenium-poor indium selenide compound phase is on the gallium selenide compound phase, and the rapid selenium sulfide heat treatment process is basically the same as that of embodiment 1; After heating, start the high-power radiation heat source. Due to the difference in the thermal conductivity of the selenide precursor film and the diffusion coefficient of the indium gallium element, the bottom layer preferentially generates a high-gallium CGS semiconductor film, and then inter-diffusion between the indium and gallium elements, and finally the CIGS film The indium gallium element in the medium is not uniformly distributed in the thickness direction, and the gradient distribution of the gallium element and the back electric field of the thin film battery are naturally formed. The formation of the back electric field improves the collection of carriers and the conversion efficiency of the thin film battery. With the shallow buried junction formed by the elements, the semiconductor band gap of the absorbing layer of the CIGS thin-film battery is distributed in a V shape. Compared with Example 1, the manufactured thin-film battery has greatly improved its cost performance.

Example 3

Preparation of CuInSe _2-x S _x thin film solar cells by electrochemical deposition of selenide precursor film. The ratio of the electrodeposition solution components is: 2.6mMol L ^-1 CuCl ₂ 2H ₂ O, 9.6mMol L ^-1 InCl ₃ and 5.5mM ol L ^-1 H ₂ SeO ₃ , LiCl0.236Mol L ^{- 1} ; and add the ph=3 buffering agent that potassium hydrogen phthalate and sulfamic acid are formed, record the pH～2.6 of electroplating solution, adopt the constant potential system of three electrodes, reference electrode is saturated calomel electrode (SCE) . Put the SLG substrate with the alkali barrier layer and the Mo back electrode film deposited by sputtering into the above-mentioned electroplating solution, pre-treat the Mo back electrode film of the substrate at -0.5V for 1 minute, and rinse the substrate with deionized water after taking it out. Blow dry with pure nitrogen, put it into the electroplating solution again after a certain period of time for electrodeposition, first deposit Cu _2-x Se at -0.2V for 5 to 8 minutes, deposit at -0.5V for 15 minutes, deposit at -0.6V for 45 Minutes, and then deposited at -0.2V for 5 to 8 minutes; the removed substrate was rinsed and dried with high-purity nitrogen, the surface of the selenide precursor film was silver gray, with a smooth and dense appearance, and the thickness was about 1.8 to 2.4 μm, the composition structure of the film is: Cu _2-x Se/CuInSe ₂ /Cu _2-x Se, Cu/In>1.06, the oxygen content in the film is about 15%, Cu _2-x Se on the surface>Cu _2-x Se on the bottom, Spray a certain amount of sodium salt before putting the substrate into the hydrogenation pretreatment chamber 31a of the rapid selenium sulfidation heat treatment device in Figure 5, and proceed according to the standard process procedure of Example 1, and the obtained substrate is connected in series through the electrodes of the integrated battery- Laser scribing heat treatment to prepare contact electrodes, sputtering ZnO:Al low-resistance transparent window layer, and laser anti-explosion stamping split surface electrodes and other processes can basically be calculated as integrated components of CIS thin-film batteries, cleaning the periphery and welding of large-area thin-film batteries Electrode leads can be used to test the photoelectric conversion efficiency of large-area modules and perform packaging process operations of photovoltaic modules.

Example 4

Electrochemical deposition of selenide precursor film to prepare CuInGaSe _2-x S _x thin film solar cells, in which the precursor selenide film is only dependent on the deposition potential to control the composition of the film and the semiconductor band gap is V-shaped, and the film is a one-step method to obtain Cu-Se rich selenium compound precursor film. The composition ratio of the electrodeposition solution is: 2.0mMol·L ^-1 CuCl ₂ , 10.0mMol·L ^-1 InCl ₃ , 15.0mM ol·L ^-1 GaCl ₃ and 5.0mM ol·L ^-1 H ₂ SeO ₃ , 0.236Mol L ^-1 LiCl, adding potassium hydrogen phthalate and sulfamic acid ph = 3 buffer, the pH of the solution in the electrolytic cell was measured to be 2.6, using a three-electrode constant potential system, and the reference electrode was saturated glycerin Mercury electrode (SCE). The substrate is first immersed in the special pretreatment electrolytic bath, and the Mo film on the back electrode on the substrate is pretreated at -0.5V for 1 minute. The chemical replacement reaction between Mo and _Cux Se in the solution occurs, and a thin layer of _Cux Se is deposited. After taking it out, rinse it with deionized water and blow it dry with high-purity nitrogen gas. After standing for a certain period of time, put it into the _special electrolytic bath again for electrodeposition; ₂ ) Deposit at -0.75V potential for 25 minutes to obtain high gallium [Cu _2-x Se+Cu(In _0.5 , Ga _0.5 )Se ₂ ], deposit at -0.5V potential for 35 minutes, and then deposit 5 at -0.2V potential Minutes and -0.8V potential deposition for 3 minutes, the selenide precursor film has high gallium content on the bottom layer and the surface, because gallium selenide is a high melting point solid phase, the diffusion of Ga element in the film is relatively difficult, which determines its It plays a framework role in the remelting and recrystallization process of the selenide precursor film; the disposable electrodeposition substrate that controls the deposition potential is taken out, rinsed, blown dry with high-purity nitrogen and placed in an oven to dry, the surface of the electrodeposition film It presents a smooth and dense silver-gray appearance, with a thickness of about 1.8-2.4 μm. The layered structure distribution of the film composition is: (Cu _2-x Se+CuGaSe ₂ )/[Cu(In _0.5 , Ga _0.5 )Se ₂ ]/Cu (In _0.8 Ga _0.2 )Se ₂ /(Cu _2-x Se+CuGaSe ₂ )/CuIn _0.4 Ga _0.6 Se, Cu/(In+Ga)>1.06 in the film, Se/M<1, total composition CuSe+CuIn _0.7 Ga _0.3 Se ₂ , where surface layer CuSe>bottom CuSe, surface layer Ga element<bottom Ga element, the oxygen content in the film is about 15-17%; according to the standard process procedure of Example 1, dense large grains, banded High-quality CIGS thin-film solar cells with V-shaped gap distribution.

Example 5

Double-sided transparent CuInGaSe _2-x S _x thin film solar cells prepared by electrochemical deposition of selenide precursor film. A commercial ITO glass substrate was chosen for the electrodeposition of the selenide precursor thin film. Before deposition, the ITO glass was ultrasonically cleaned in isopropanol for 10 minutes and laser scribing was performed to divide the transparent conductive film. The sulfate electrochemical deposition system was selected, and the reference electrode was a saturated mercury sulfate electrode (the potential of MSE relative to the standard hydrogen electrode was + 650mV), constant potential electrodeposition of Ga ₂ Se ₃ and CuIn _0.7 Ga _0.3 Se ₂ in an aqueous solution of high-purity nitrogen deoxygenated at 80°C without stirring. Electrodeposit 0.2-0.3μm thick Ga ₂ Se ₃ on ITO first, the deposition potential is -1.1V (relative to saturated calomel electrode MSE), the solution composition is: 1mM SeO ₂ , 1mM Ga ₂ (SO ₄ ) ₃ and 0.3M K ₂ SO ₄ , the pH was adjusted to 2.4 with sulfuric acid. Re-deposition CIGS, deposition process: solution ratio: 0.3MK ₂ SO ₄ (pH2.4, adjusted by H ₂ SO ₄ ), 1.0mMCuSO ₄ , 3.0mMIn ₂ (SO ₄ ) ₃ , 3.0mMGa ₂ (SO ₄ ) ₃ and 1.7mMSeO ₂ ; deposition potential is -0.9V, film thickness is about 1.8-2.4, Cu/(In+Ga)>1.06 in the film, Se/M<1, Cu _2-x Se on the surface>Cu _2-x Se on the bottom, Surface layer Ga element < bottom Ga element. According to the standard rapid selenium sulfide heat treatment process procedure of Example 1, the obtained substrate undergoes the electrode connection operation of the integrated battery-laser scribing heat treatment to prepare contact electrodes, sputtering ZnO:Al low-resistance transparent window layer, laser detonation stamping split electrodes And electrode lead wire and encapsulation and other process operation procedures, the glass power generation curtain wall component of the special-purpose CIS thin film battery integrated module is obtained. The front side transmits sunlight to generate power, and the back side receives scattered infrared light, which can superimpose the light energy absorbed on both sides to generate power.

Example 6

This example is a preferred scheme for making CuIn _0.7 Ga _0.3 Se _2-x S _x thin film solar cells with nano-selenide coating. It is basically the same as the method of Example 2, and four kinds of nano-selenide coatings are also needed. Roll coating and drying are implemented on the substrate Mo electrode film, which can be film-formed step by step and continuously. The four kinds of selenide coatings are respectively It is: CuSe+CuGaSe ₂ , Ga ₂ Se ₃ , In ₄ Se ₃ (or In ₂ Se ₃ +CuInSe ₂ ), (CuSe+CuGaSe ₂ ); the precursor film structure is: (CuSe+CuGaSe ₂ )/Ga ₂ Se ₃ /In ₄ Se ₃ /(CuSe+CuGaSe ₂ ), the total Cu/(In+Ga) of the film>1.06, the atomic structure ratio in the four-layer film composition is: (4+3):1:3.5:(12.1+ 1), the thickness of the precursor selenide film is about 4-7 μm, in which the ratio of the main elements in the film is Ga/(In+Ga)≥0.3, Se/M<1, surface layer CuSe>bottom CuSe, surface layer Ga element<bottom Ga element . The rapid selenium sulfidation heat treatment process is the same as that of Example 2, the open circuit voltage Voc of the thin film battery is slightly higher than that of Example 2, and the semiconductor band gap of the thin film battery is in a V-shaped distribution.

Example 7

Three-step electrodeposition (Cu _2-x Se+CuGaSe ₂ )/In ₄ Se ₃ /Cu _2-x Se selenide precursor film to prepare CuInGaSe _2-x S _x thin film solar cell, electrodeposition adopts standard three-electrode system, anode Graphite fiber cloth is used for the electrode, and Ag/AgCl electrode is used for the reference electrode. The structure of the electrolytic cell can be circulated. The electrolyte is supplied by a circulation pump and forms a circulation. The solution ratio of the first step of deposition: 0.3MK ₂ SO ₄ , 1.0mMCuSO ₄ , 5.0mMGa ₂ (SO ₄ ) ₃ and 1.7mMSeO ₂ , H ₂ SO ₄ to adjust the pH=2.2±0.2; the deposition is controlled by the constant potential process, The deposition potential relative to the Ag/AgCl electrode is -0.75~-1.0V, and the ratio of [Cu]/[Ga] can be adjusted to be Cu-rich or Cu-poor; the solution ratio of the second deposition step: 1mM SeO ₂ , 1mM In ₂ (SO ₄ ) ₃ , 0.3MK ₂ SO ₄ and appropriate organic additives, the pH value is adjusted to 2.2 with sulfuric acid, and the deposition of selenium-poor In ₄ Se ₃ is controlled by the additive in the ppm amount in the solution; the third step is to replace Electrodeposition solution for electrodeposition of Cu _2-x Se. Selenide precursor thin film Cu/(In+Ga)>1.06, Se/M≤1, Ga/(Ga+In)=0.3～0.36, surface layer Cu _2-x Se>bottom Cu _2-x Se, surface layer Ga element< The Ga element at the bottom, the oxygen content in the film is about 15% or more. Carry out the rapid selenium sulfide heat treatment of the selenide precursor thin film according to the standard process procedure of embodiment 1, and then carry out follow-up other deposition processes and operations, just can obtain the CIGS thin film solar cell similar to embodiment 2, if the third step electrodeposition process adds Ga ₂ (SO ₄ ) ₃ , the thin film battery of Example 6 can be obtained.

Example 8

The battery substrates of the aforementioned precursor selenide thin films are all placed horizontally for rapid selenium sulfide heat treatment and sputtering deposition. According to the scope of the core technology of the present invention, it is also possible to design and manufacture equipment for vertical placement of substrates. The main flow of the photovoltaic module production process in Figure 4 and the upright operation of the substrate in the in-line rapid selenium vulcanization heat treatment device in Figure 5 are respectively adjusted, and other equipment is adjusted accordingly, which does not exceed the scope of the core technology of the present invention.

Like this, the substrates in the first hydrogenation pretreatment chamber are placed upright, and the hydrogenation pretreatment chamber can push two selenide precursor film substrates into the second fast selenium sulfide treatment chamber at a time, and the substrates on the trolley in the second chamber The film rack is also placed vertically, and a heater is placed in the middle of the substrate rack, which can bake the substrates on both sides of the outside, and arrange multiple pairs of thermocouples. At the same time, it can measure the temperature values of multiple points on the substrates on both sides. The work efficiency is higher and energy saving; two movable high-power radiation heat sources are symmetrically placed on both sides of the substrate rack trolley, and they can be turned on and moved at the same time; two symmetrically placed high-purity metal heat sources are placed next to the movable radiation heat source Indium reactive sputtering target device, they are vertically installed in a symmetrical position facing the trolley substrate rack; correspondingly, the gate valves of each chamber will open wider, and two substrates can enter and exit at the same time, taking and sending The chip mechanism is to operate the two substrates simultaneously. Similarly, the third substrate cooling chamber, the fourth sputtering chamber and the fifth taking-up chamber are all changed correspondingly to the first and second chambers, and the interior is changed from a horizontal working state to a vertical state; wherein, the fourth sputtering chamber Nearly double the device needs to be installed in the chamber, and there are four to six pairs of metal reactive sputtering targets, which are arranged symmetrically and vertically, and a pair of high-power radiation heat sources are also symmetrically and vertically positioned to scan the substrate in a lateral movement manner. Its operating procedures and processes are basically the same as the standard process for rapid selenium vulcanization heat treatment of selenide precursor films in Example 1, and its work efficiency is twice as high as that of the horizontally placed substrate device, and is more suitable for large substrates or super large substrate films Manufacture of cell photovoltaic modules.

Industrial availability

The invention is applicable to the preparation of selenide precursor films by rolling coating of nano-selenide coatings or water bath electrochemical deposition, and can directly and continuously prepare the optical absorption layer and buffer layer of CIGS thin film batteries through the rapid selenium vulcanization heat treatment of the selenide precursor films It can be used as a large-area photovoltaic module with high photoelectric conversion efficiency by connecting the subsequent single cell electrodes in series (inline integrated module), which is used for photovoltaic power plants or building integration. grid power generation.

Although the present invention has been described in detail with reference to the preferred embodiment and the accompanying drawings and examples, those skilled in the art can make various uses and modifications of the present invention without departing from the spirit and scope of the present invention. Accordingly, it should be considered that the detailed description and drawings herein are not limitations on the scope of the invention, which can be derived from the preceding claims, which are legally equivalent.

Explanation of reference signs

Code illustrate Code illustrate Code illustrate 1a Ordinary soda lime glass 2a CuGaSe ₂ +CuSe 20 vacuum chamber 1b Alkali barrier layer (SiO, SiN, TiN) 2b CuSe twenty one Alkali barrier sputtering target 1c Mo back electrode film 2c Ga ₂ Se ₃ twenty two Mo back electrode film sputtering target 1d Thin-film battery copper-poor absorber layer 2d In ₄ Se ₃ (or In ₂ Se ₃ ) twenty three Laser cutting Mo device 1e Thin film battery buffer layer 2e CuSe(+Ga ₂ Se ₃ ) twenty four Rapid selenium vulcanization heat treatment chamber 1f Transparent conductive window layer 2f Liquid phase Cu _X Se 25 High power radiant heat source 1g Copper-rich contact electrodes 2g Copper-rich absorber layer 26 Metal pure indium reactive sputtering target 3a Selenide Precursor Thin Film Substrate 31a Hydrogenation pretreatment vacuum chamber 27 Metal pure zinc reactive sputtering target

3b Selenium vulcanization treated substrate 32a Rapid selenium vulcanization heat treatment chamber 28 Metal pure zinc reactive sputtering target 3c CIGS absorbing layer substrate 33a Storage cooling room 29 Metal pure indium reactive sputtering target 3d sputtering buffer layer substrate 34a Buffer layer sputtering chamber 30 vacuum chamber 3e Substrates to be laser processed or scribed 35a Vacuum pick-up chamber 31 Laser preparation of copper-rich contact electrodes 310 Thermal Radiation Shield 311 heater 32 ZnO:Al conductive window sputtering target 312 Hydrogenation pretreatment airtight space 313 Substrate pushing mechanism 33 Laser anti-explosion split surface electrode 320 Gate valve 321 Gate valve 323   Controllable moving/heating trolley 324 Movable high-power thermal radiation source 325 Metal pure indium reactive sputtering target 326 Rapid selenium vulcanization treatment of airtight space 331 Pick-up mechanism 332 Substrate pushing mechanism 333 Substrate carrying mechanism 340 Gate valve 341 Gate valve 342   Controllable moving/heating trolley 343 Metal pure indium reactive sputtering target 344 Fixed high power thermal radiation source 345 Metal pure zinc reactive sputtering target 346 Metal pure zinc reactive sputtering target 347 Buffer layer sputtering airtight space 351 Pick-up mechanism 352 Substrate carrying mechanism

references

[1]M.Kaelin et al.Low cost processing of CIGS thin film solar cells.Solar Energy 77(2004)749-756

[2] V.K.Kapur, M.Fisher and R.Roe, "Nanoparticle Oxides Precursor Inks for Thin Film Copper Indium Gallium Selenide (CIGS) Solar Cells", Mat.Res.Soc.Proc.Vol.668, (2001)

[3]V.Kapur, A.Bansal, B.Gergen and P.Le.Commercialization of 'ink baesd'CIGS solar cells/modulesTechnical Digest of the International PVSEC-17, Fukuoka, Japan, 2007, 6O-A 11-05 ,462～463

[4] J.K.J.van Durcn, C.Leidholm, A.Pudov, M.R.Robinson, and Y.Roussillon. HIGH-PERFORMANCETHIN-FILM PHOTOVOLTAICS USING LOW-COST PROCESS TECHNOLOGY.Technical Digest of the International PVSEC-17, Fukuoka, Japan, 2007. PL5-3: 48～51

[5] T.Wada, Y.Matsuo, S.Nomura, Y.Nakamura, A.Miyamura, Y.Chiba, A.Yamada, and M.Konagai. Fabrication of Cu(In,Ga)Se ₂ thin films by a combination of mechanochemical and screen-printing/sintering processes.phys.stat.sol.(a) 203, No.11, 2593-2597(2006)

[6]Y.Chiba, A.Yamada, M.Konagai, Y.Matsuo, T.Wada Photoluminescence study of CIGS thin films grown by mechanochemical process.Technical Digest of the International PVSEC-17, Fukuoka, Japan, 2007, 5P-P3 -15.802～803

[7] SeJin Ahna, KiHyun Kimb, KyungHoon Yoon, Nanoparticle derived Cu(In, Ga)Se ₂ absorber layer for thinfilm solar cells.Colloids and Surfaces A: Physicochem.Eng.Aspects 313-314(2008)171-174

[8] RN Bhattacharya, JF Hiltner, W. Batchelor et al., 15.4% CuIn _1-x Ga _x Se ₂ -based photovoltaie cells from solution-based precursor films, Thin Solid Films, 361-362 (2000) 396

[9] Raghu N. Bhattacharya, Arturo M. Fernandez. CuIn1-xGaxSe2-based photovoltaic cells from electrode deposited precursor films. Solar Energy Materials & Solar Cells 76 (2003) 331-337

[10] Calixto ME, Dobson KD, McCandless BE, et al. Controlling growth chemistry and morphology of single-bath electrode deposited Cu(In, Ga)Se ₂ thin films for photovoltaic application. Journal of the Electrochemical Society 2006; 153(6): 521 -528.

[11] M. Alonso, M. Garriga, C. Durante Rincón, E. Hernández, M. León, Appli. Phys. A 74 (2002) 659;

[12] A.V.Mudryi, I.A.Victorov, V.F.Gremenok, A.I.Patuk, I.A.Shakin, M.V.Yakushev, Thin Solid Films431-432(2003)197

[13] O. Ramdani, E. Chassaing, B. Canava, P.-P. Grand, O. Roussel, M. Lamirand, E. Rzepka, A. Etcheberry, J.-F. Guillemoles, D. Lincot, O. .Kerrec.Electrochemical Cementation Phenomena on Polycrystalline MolybdenumThin Films from Cu(II)-In(III)-Se(IV)Acidic Solutions.Journal of The Electrochemical Society，154-8-D383-D393(2007)

[14] A.Kampmann, J.Rechid, S.Wulfi, M.Mihhailova, R.Thyen and A.Lossin.Low cost processing of CIGS solar cells on flexible metal substrates.19th European Photovoltaic Solar Energy Conference, 7-11June 2004, Paris, France.1806-1808

Claims (10)

1. an antivacuum low-cost legal system is equipped with the selenides precursor thin film and the rapid selenium sulfuration heat-treating methods of CIGS thin film solar cell, it is characterized in that, comprise: (1) is sequential applications nanometer selenides coating and drying and forming-film on the molybdenum electrode film of rigid substrate substrate, or order plating (or electro-deposition) different component nano microcrystalline selenides precursor thin film, this selenides precursor thin film composition with structure is respectively: (CuGaSe ₂+ CuSe), (Ga ₂Se ₃+ CuSe), In ₄Se ₃(or In ₂Se ₃+ CuInSe ₂), CuSe[or (CuSe+Ga ₂Se ₃), (CuSe+CuGaSe ₂)] order choice formula combination; (2) the one pile of rigid substrate that has prepared this selenides precursor thin film is placed in the airtight space in the vacuum chamber, by heating, inject hydrogen from room temperature to 290 ℃ high vacuum, be evacuated to high vacuum and the multi-pass operation of injecting hydrogen, the first hydrogenation preliminary treatment of the argon gas+hydrogen that reinjects at last again; (3) second selenizings are handled, and with this pile substrate from top to bottom or from bottom to top parallel moving, push another relative airtight space respectively blocks ofly, start the heating of substrate bottom earlier, and import class H to second airtight space ₂Se gas, keeping enough selenium air pressure (20～80kPa) time, substrate in moving carried out the fixed form heating of Fast Heating up and down or the heating of top scan-type and bottom moving with substrate and heat up, substrate itself remains at 350 ℃～580 ℃, the substrate top layer is because the movable type scanning heating of high power radiant heat source, forerunner's selenide thin film can be rapidly heated 350 ℃～1100 ℃, impels Cu in the selenides precursor thin film _xSe/ and In ₄Se ₃Be heated mutually and melt (523 ℃ of liquefaction) fast, the densification of auxiliary CIGS film crystal liquid phase reactor growth and film self, after the CIGS film of big crystal grain densification generated, its top layer can be oozed out trace or adsorb unnecessary liquid Cu _xSe; (4) the 3rd selenium vulcanizing treatment, base substrate are transferred to the sputter position with the substrate motion when 520 ℃～580 ℃ preference temperatures, regulate airtight space air pressure to 0.3～25Pa, by reactive sputtering In ₂Se ₃Or In ₂S ₃Neutralization reaction is fallen the unnecessary liquid Cu in substrate top layer _xSe, strict control substrate surface CIGS film composition is transformed in the poor steel structure process reactive sputtering In by rich copper ₂Se ₃Or In ₂S ₃Amount; (5) the 4th selenizings are handled, and reactive sputtering finishes the back and increases airtight space importing class H ₂The Se gas flow, when making its environment selenium air pressure reach 20～80kPa, the high power radiant heat source carries out the heat scan of faster speed to substrate; (6) the 5th high temperature vulcanized processing, emptying class H ₂Behind the Se gas, refill reactive sputtering gas H ₂S+Ar keeps air pressure at 0.3～25Pa, and substrate carries out reactive sputtering In after moving to the sputter position ₂S ₃, In ₂S ₃Generate n type Cu (In on the top layer of film _1-xGa _x) SSe or Cu (In _1-yGa _y) ₃(Se _1-xS _x) ₅Resistive formation; Vulcanize in the heat treated operating process at above-mentioned rapid selenium, second airtight space alternately charges into class H ₂Se gas or H ₂S+Ar gas carried out high vacuum exhaustion operation in the middle of it, and air pressure has to rise to have and falls; (7) will be transferred to the 3rd airtight cooling space through the substrate after the processing of rapid selenium heat of vulcanization; Like this, the whole pile of substrate in first space is included into the 3rd cooling space after through the rapid selenium vulcanizing treatment, and this space is injected with Ar+H ₂The S mist guarantees that base substrate drops in 110 ℃ of processes by 580 ℃ gradually, and the selenium element sulphur does not run off in the CIGS thin-film material; (8) substrate after the cooling is pushed into the 4th airtight space respectively, carry out the high resistant eigen I n (OH of metallic target reactive sputter-deposition hull cell, S)/and ZnS (O, OH)/ZnO (S) resilient coating and i layer, the target of two or three pairs of simple metal sputtering targets and the collocation of reacting gas foot: In/ (Ar, H ₂S and H ₂O), Zn/ (Ar, H ₂S and H ₂O) and Zn/ (Ar, H ₂S and O ₂Or CO ₂), the temperature of base substrate is controlled at 110 ℃～350 ℃ in the sputter procedure; Airtight space was pumped down to high vacuum state after sputter was finished, and started the quick scanning substrate of high power radiant heat source surface; (9) with reactive sputter-deposition the substrate behind high resistant resilient coating and the i layer be included into the 5th cooling space respectively; Operation that substrate cooling back just can change that next laser processing is handled or the electrode of the battery integrated package of machinery line is connected in series over to, or deposit the low-resistance transparent conducting ZnO: Al film operation.

2. the antivacuum low-cost legal system of narrating according to claim 1 is equipped with the method for the selenides precursor thin film and the rapid selenium heat of vulcanization Processing of Preparation thin film solar cell of CIGS thin film solar cell, the order that its selenides precursor thin film can adopt six kinds of nano microcrystalline selenides coating to make up is accepted or rejected and is constituted composition and each layer structure that applies selenides precursor thin film material, promptly sequential applications and drying are made the selenides precursor thin film on substrate Mo back electrode film, it is characterized in that, have the CuSe layer (phase) of rich selenium or/and the In of poor selenium in the selenides precursor thin film ₄Se ₃The layer (phase), this low melting point CuSe or/with In ₄Se ₃Nanometer selenide material shared volume ratio＞30% in the selenides precursor thin film; Cu/ in the selenides precursor film (In+Ga)=1.01～1.3, preferred Ga/ (Ga+In)=0.15～0.35, Se/M≤1; The CuSe of selenides precursor thin film mesexine＞bottom CuSe, best than 1.1～1.5, can not lack CuSe near molybdenum electrode film place; Bottom Ga element＞surface Ga element in the selenides precursor thin film, best than 9.0～10.0, or the Ga element only is distributed in the film place near molybdenum electrode.

3. the selenides precursor thin film of narrating according to claim 1 and the method for rapid selenium heat of vulcanization Processing of Preparation thin film solar cell, the structural feature of its electro-deposition selenides precursor thin film is: can adopt the step order electro-deposition of control sedimentation potential or the substep order electro-deposition of replacing different electrolytes composition to prepare the selenides precursor thin film, have independently Cu in the film _2-xThe Se phase allows directly to deposit in the electro-deposition selenides precursor thin film a certain amount of quaternary CuInGaSe ₂Microcrystal grain, Cu/ in the electrodeposited film (In+Ga)=1.01～1.3, preferred Ga/ (Ga+In)=0.15～0.35, Se/M≤1; Electro-deposition selenides precursor thin film mesexine Cu _2-xSe＞bottom Cu _2-xSe, best than 1.1～1.5, should not lack Cu near molybdenum electrode film place _2-xSe, low melting point Cu _2-xVolume ratio＞20% of the shared selenides precursor thin film of Se.

4. the antivacuum low-cost legal system of narrating according to claim 1 is equipped with the method for the selenides precursor thin film and the rapid selenium heat of vulcanization Processing of Preparation thin film solar cell of CIGS thin film solar cell, it is characterized in that, rapid selenium heat of vulcanization treatment process all carries out in the airtight space in vacuum chamber, and it is equipped with blocking class H ₂Se gas or Ar+H ₂The valve that S gas is supplied with, the operational sequence that can carry out vacuum exhaust in the airtight space.

5. the antivacuum low-cost legal system of narrating according to claim 1 is equipped with the method for the selenides precursor thin film and the rapid selenium heat of vulcanization Processing of Preparation thin film solar cell of CIGS thin film solar cell, it is characterized in that the class H that selenizing heat treatment is used ₂Consisting of of Se gas ingredients: (30%～50%) Ar+ (25%～35%) H ₂+ (15%～45%) H ₂Se; Reactive sputtering In ₂Se ₃Sputter gas be argon gas, reacting gas is H ₂Se or class H ₂Se gas; Reactive sputtering In ₂S ₃Sputter gas be argon gas, reacting gas is H ₂S gas; The selenides precursor thin film and be transformed into fine and close big crystal grain fully, when poor slightly steel structure CIGS film begins flash heat treatment, selenium air pressure in its airtight space environment maintains 20～80kPa, but when the resilient coating of heat treatment CIGS hull cell and i layer, but be in the high vacuum environment and carry out.

6. the antivacuum low-cost legal system of narrating according to claim 1 is equipped with the method for the selenides precursor thin film and the rapid selenium heat of vulcanization Processing of Preparation thin film solar cell of CIGS thin film solar cell, the selenides precursor thin film is rich steel structure, the size of copper content all can not be accurately controlled in the film, need the rapid selenium heat of vulcanization to handle and accurately adjust copper content final in the film, make it be suitable for preparing the requirement of high efficiency CIGS hull cell semiconductor device, copper content should the strict scope of controlling be 20%～24.0% in its absorbed layer.It is characterized in that the selenides precursor thin film can ooze out or adsorb micro-liquid Cu through the top layer after the Fast Heating _xSe, the base substrate temperature maintenance is at 520 ℃～580 ℃, when the heating of bottom is in permanent power state of a control, by reactive sputter-deposition In ₂Se ₃Or In ₂S ₃With film top layer liquid Cu _xThe method of Se neutralization reaction is controlled the copper content in the film composition; Strict monitoring substrate membrane surface liquid Cu _xSe be neutralized react away or film composition in copper content descend when crossing the theoretical copper content 24.5% of CIGS semi-conducting material feature, bottom probe temperature value with permanent power heating condition subtegulum selenide thin film occurs significantly sporting sign, is accurately determining by heat treatment and sputtering sedimentation In ₂Se ₃Or In ₂S ₃Required In when making the selenides precursor thin film be transformed into the CIGS absorbed layer thin-film material of slightly poor steel structure fully ₂Se ₃Or In ₂S ₃Amount.

7. the antivacuum low-cost legal system of narrating according to claim 1 is equipped with the method for the selenides precursor thin film and the rapid selenium heat of vulcanization Processing of Preparation thin film solar cell of CIGS thin film solar cell, selenides precursor thin film on the back electrode molybdenum film is handled the place one's entire reliance upon heating in vacuum mode of uniqueness of the present invention of the fine and close PV of big crystal grain (photovoltaic) level film crystal that is transformed into by the rapid selenium heat of vulcanization, it is characterized in that, the substrate of selenides precursor thin film bottom adopts the mode of following the fixed heater that substrate moves all the time to heat, or does not follow substrate and move and but keep the lower heating amount even all the time, the mode of large tracts of land balanced heating heats; The top of selenides precursor thin film or the outside high power radiant heat source that adopts relative motion or pulse mode scan selenide thin film or the heating of dynamical fashion, the heating that the one dimension direction is arranged is uniform all the time, the heating of another dimension direction of motion is pulse or dynamic all the time, the heat that adds up of its large tracts of land heating should be uniform, when top or the heating of outside high power radiant heat source, selenide thin film is different with the residing temperature of substrate in most cases, exist evident difference, the pulse of top or outside or the heat that adds of scan mode only have very big influence to selenide thin film, and be less relatively to the influence of substrate; The bottom of substrate exists the point for measuring temperature more than three all the time, and the orientation of point for measuring temperature is consistent with the substrate direction of motion, and the temperature value that obtains is used to carry out the control of substrate bottom heated condition, or the control of other and this film related physical quantity.

8. the antivacuum low-cost legal system of narrating according to claim 1 is equipped with the method for the selenides precursor thin film and the rapid selenium heat of vulcanization Processing of Preparation thin film solar cell of CIGS thin film solar cell, the selenides precursor thin film in the atmosphere that high selenium is pressed by remelting crystallization again, top layer absorption or the liquid Cu of oozing out _xSe is by the In of reactive sputtering ₂Se ₃Or In ₂S ₃Neutralization reaction is fallen, and it is characterized in that the top layer liquid Cu _xSe is by the In of reactive sputtering ₂Se ₃Or In ₂S ₃When neutralization reaction is fallen, tangible flex point can appear in the temperature test curve of control substrate bottom heating power, illustrate that this selenide thin film is transformed into the semi-conducting material that meets stoichiometric proportion, is poor slightly steel structure fully, meet the essential condition of preparation hull cell absorbed layer fully; The In of sputtering sedimentation ₂Se ₃Make selenide thin film top layer semiconductor band gap smoothly descend the In of sputtering sedimentation ₂S ₃Selenide thin film top layer semiconductor band gap is smoothly risen, the about 40～60nm of its thickness; Subsequently, film surface continues reactive sputtering In ₂S ₃, will generate n type high resistant Cu (In on the top layer of selenide thin film _1-yGa _y) ₃(SxSe _1-x) ₅Thin-film material, form the homogeneity shallow embedding will prepare hull cell and tie the about 20～40nm of its thickness.

9. the antivacuum low-cost legal system of narrating according to claim 1 is equipped with the method for the selenides precursor thin film and the rapid selenium heat of vulcanization Processing of Preparation thin film solar cell of CIGS thin film solar cell, after handling through the rapid selenium heat of vulcanization, the selenides precursor thin film has been transformed into the PV level film crystal of big crystal grain densification, and then the resilient coating of deposit film battery and i layer continuously again, the pn knot that guarantees hull cell is not exposed to formation contaminating impurity and surface oxidation in the atmosphere, influence the device quality of hull cell, it is characterized in that, the absorbed layer surface of CIGS hull cell directly, reactive sputter-deposition In (OH continuously, S)/ZnS (O, OH)/thin-film material of three kinds of compositions of ZnO (S) constituted the resilient coating and the i layer of hull cell, its thickness is respectively: 15～25nm, 20～30nm and 50～75nm, add up to about 85～130nm, the sedimentary sequence of each thin-film material can not change, the boundary of material composition can be fuzzyyer, and wherein sulfur content reduces gradually, oxygen content increases gradually; Two or the three pairs of reactive sputterings are respectively pure indium of metal and pure zinc to the target of target, the reactive sputtering mode adopt the plane to target or bicylindrical shape rotating magnetron to target, shielding power supply adopts the power supply of DC pulse or midfrequent AC working method, the porous metals gauze screen covers this working region to the target sputtering sedimentation, and uncharged deposit passes thin thin wire netting and is deposited on formation resilient coating and i layer on the absorbed layer.

10. the antivacuum low-cost legal system of narrating according to claim 1 is equipped with the method for the selenides precursor thin film and the rapid selenium heat of vulcanization Processing of Preparation thin film solar cell of CIGS thin film solar cell, can set up the substrate that deposits the selenides precursor thin film through the continuous processing in the rapid selenium heat of vulcanization processing unit according to this method, directly prepare CIGS thin film solar cell optical absorbing layer, the first mode of manufacture line of resilient coating and i layer, and big substrate, behind roller coating of super large substrate or the electro-deposition selenides precursor thin film, enter rapid selenium heat of vulcanization processing unit in the upright mode of double-basis sheet, sputter prepares resilient coating and i layer and the integrated integrated apparatus that connects processing and sputter transparent conductive film of vacuum chamber inner laser electrode, a direct step is finished the second mode of manufacture line of CIGS thin-film cell photovoltaic integrated package all process steps, it is characterized in that (1) first kind of mode of manufacture line structure is: 1. hydrogenation pretreatment chamber, 2. rapid selenium heat of vulcanization process chamber, 3. store up the sheet cooling chamber, 4. sputter resilient coating and i floor chamber and 5. get five relatively independent working cells such as sheet chamber and be connected in series by slide valve and form; Wherein, but the supporting device of 1. settling oscilaltion, integral body to be handled upside down in the airtight space in the hydrogenation pretreatment chamber, and there are heater and heat radiation screening plate in the outside, but the mechanism of gas introduction tube, valve and vacuum exhaust; 2. the dolly of may command displacement and speed is installed in the airtight space of rapid selenium heat of vulcanization process chamber, place pending substrate on the dolly, it is many to thermocouple that dolly substrate bottom is arranging that equably resistive heating device contacts with substrate, the mode that can carry out substrate backside controllable temperature or firm power heats, dolly top is installed with may command displacement, the high power radiant heat source of speed and energy, it can carry out quick scan-type heating to substrate upper epidermis film, the dolly both sides are equipped with fixing gas introduction tube, ingress pipe offers the nozzle bore of a plurality of even layouts on the tube wall of dolly direction, gas flows to the substrate upper surface that moves from nozzle bore, and dolly top also is equipped with two circuits of a group reaction sputter target pair device and sputter and reacting gas; 4. be equipped with equally in the airtight space of sputter resilient coating and i floor chamber with rapid selenium heat of vulcanization process chamber in the dolly of same size, two circuits of two or three group reaction sputters to target and sputter and reacting gas are installed on dolly top in proper order, the material of sputtering target is respectively pure indium of metal and pure zinc, and sputter is installed with fixed high power radiant heat source to the centre of target is forward.(2) second kinds of mode of manufacture line structures are: 1. hydrogenation pretreatment chamber, 2. rapid selenium heat of vulcanization process chamber, 3. store up the sheet cooling chamber, 4. sputter resilient coating and i floor chamber, 5. the laser Integrated electrode connects processing and sputter transparent conductive film chamber and 6. gets six relatively independent working cells such as sheet chamber and is connected in series by slide valve and forms; Wherein, 1. the substrate in the hydrogenation pretreatment chamber all is vertical placement, but the supporting device that the vertical substrate of move left and right, integral body can be handled upside down is installed in its airtight space, and other parts are corresponding with being provided with of aforementioned hydrogenation pretreatment chamber; 2. the dolly of may command displacement and speed is installed in the airtight space in the rapid selenium heat of vulcanization process chamber, erect on the dolly and placing two pending back-to-back substrates, substrate presents the setting placement by frame on the dolly, substrate on end resistive heating device and the both sides substrate is contacted many to thermocouple by the frame intermediate arrangement, can carry out the heating of controllable temperature or firm power mode simultaneously to the back of both sides substrate, the moveable carriage both sides also respectively symmetry may command displacement is installed, two high power radiant heat source of speed and energy, can carry out vertically evenly the surface film of dolly substrate simultaneously by the substrate on the frame, the laterally heating of scan-type fast, the dolly both sides be separately installed with fixing gas introduction tube up and down, ingress pipe is near the nozzle bore that offers a plurality of even layouts on the tube wall of dolly substrate direction, gas flows to the surface of mobile substrate from nozzle bore, the nozzle pipeline of two road selenium gases is installed before and after the direction of motion of removable high power radiant heat source equally, guarantee the Fast Heating zone effectively, the supply of selenium element equably, dolly also is equipped with the reactive sputtering target pair device of two symmetrical high pure metal indium targets of placing and two circuits of sputter and reacting gas by the both sides of horse, and they are according to the installation of leaning on the vertical mode of symmetric position of frame substrate towards dolly; 4. the indoor dolly of sputter resilient coating and i layer equally also is that vertical is placed by frame, close with the dolly function of rapid selenium heat of vulcanization process chamber, dolly is installed four, six groups by the both sides of frame substrate in the setting mode and is faced substrate direction, the reactive sputtering target pair device of symmetry placement and two circuits of sputter and reacting gas, to middle forward two the high power radiant heat source fixtures that are installed with in vertical mode towards substrate that have of target; 5. the laser Integrated electrode connects that processing and sputter transparent conductive film are indoor dolly equally, what dolly was upright does not heat and temperature measuring equipment by having on the frame, but up and down two laser processing devices of fast moving and the accurate stepping of adaptive control are installed the bilateral symmetry of vacuum chamber, transparent window by vacuum chamber wall, laser can carry out the preliminary treatment of contact electrode and the processing of anti-quick-fried die-cut face electrode film to substrate surface, dolly is equipped with the vertical sputter of placing with symmetry of many groups to target by the substrate both sides of frame, can carry out the sputter of the transparent conductive film of ZnO:Al ceramic target; The many groups of manipulators that can carry out the propelling movement of two substrates or fetch, shift are simultaneously arranged in the middle of this mode of manufacture line.

Images