CN102157595A - Silicon film/Cu(In, Ga)Se2 binode film battery process - Google Patents
Silicon film/Cu(In, Ga)Se2 binode film battery process Download PDFInfo
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- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 51
- 239000010703 silicon Substances 0.000 title claims abstract description 47
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 229910052733 gallium Inorganic materials 0.000 title claims abstract description 13
- 238000000034 method Methods 0.000 title claims abstract description 13
- 229910052738 indium Inorganic materials 0.000 title claims abstract description 10
- 239000010409 thin film Substances 0.000 claims abstract description 83
- KTSFMFGEAAANTF-UHFFFAOYSA-N [Cu].[Se].[Se].[In] Chemical compound [Cu].[Se].[Se].[In] KTSFMFGEAAANTF-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 239000010949 copper Substances 0.000 claims abstract description 12
- 239000000758 substrate Substances 0.000 claims abstract description 5
- 239000010408 film Substances 0.000 claims description 25
- 238000005516 engineering process Methods 0.000 claims description 19
- 238000000151 deposition Methods 0.000 claims description 18
- 230000008021 deposition Effects 0.000 claims description 13
- 238000002360 preparation method Methods 0.000 claims description 11
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 8
- 239000011521 glass Substances 0.000 claims description 7
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 claims description 6
- 238000005229 chemical vapour deposition Methods 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims 1
- 239000011248 coating agent Substances 0.000 claims 1
- 238000000576 coating method Methods 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 238000005457 optimization Methods 0.000 claims 1
- 150000003376 silicon Chemical class 0.000 claims 1
- 239000011669 selenium Substances 0.000 abstract description 11
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 229910021420 polycrystalline silicon Inorganic materials 0.000 abstract description 4
- HVMJUDPAXRRVQO-UHFFFAOYSA-N copper indium Chemical compound [Cu].[In] HVMJUDPAXRRVQO-UHFFFAOYSA-N 0.000 abstract description 3
- QNWMNMIVDYETIG-UHFFFAOYSA-N gallium(ii) selenide Chemical compound [Se]=[Ga] QNWMNMIVDYETIG-UHFFFAOYSA-N 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract 1
- 238000007736 thin film deposition technique Methods 0.000 abstract 1
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- 239000007789 gas Substances 0.000 description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 239000011701 zinc Substances 0.000 description 8
- 238000004544 sputter deposition Methods 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 5
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 4
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 4
- 238000010549 co-Evaporation Methods 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 230000008020 evaporation Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229910052711 selenium Inorganic materials 0.000 description 4
- 239000013077 target material Substances 0.000 description 4
- YNLHHZNOLUDEKQ-UHFFFAOYSA-N copper;selanylidenegallium Chemical compound [Cu].[Se]=[Ga] YNLHHZNOLUDEKQ-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910000838 Al alloy Inorganic materials 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910000085 borane Inorganic materials 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 229910021419 crystalline silicon Inorganic materials 0.000 description 2
- HQWPLXHWEZZGKY-UHFFFAOYSA-N diethylzinc Chemical group CC[Zn]CC HQWPLXHWEZZGKY-UHFFFAOYSA-N 0.000 description 2
- AXAZMDOAUQTMOW-UHFFFAOYSA-N dimethylzinc Chemical compound C[Zn]C AXAZMDOAUQTMOW-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910052774 Proactinium Inorganic materials 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 229920005591 polysilicon Polymers 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Physical Vapour Deposition (AREA)
- Photovoltaic Devices (AREA)
Abstract
本发明是以硅薄膜为衬底的铜铟镓硒(Cu(In，Ga)Se2简称CIGS)薄膜双结太阳电池，采用多种薄膜沉积技术制备出该双结太阳电池。该双结太阳电池分为上电池和下电池。巧妙的将下电池薄膜化，提高了下电池的性能。能够解决在多晶硅太阳电池生产过程中出现的工艺复杂，能耗高等问题，并且将铜铟镓硒薄膜上电池很好的和下电池结合，解决了CIGS薄膜太阳电池生产过程中出现的稳定性差等问题。最终提高叠层电池的各项性能。该双结薄膜电池具有较低的生产成本，较高的稳定性，很长的使用寿命，以及较高光电转换效率，因此该双结薄膜电池具有比较好的开发和应用价值。The invention uses a copper indium gallium selenide (Cu(In, Ga)Se 2 for short CIGS) thin film double-junction solar cell with a silicon thin film as the substrate, and adopts various thin film deposition techniques to prepare the double-junction solar cell. The double-junction solar cell is divided into an upper cell and a lower cell. Ingenious thinning of the lower battery improves the performance of the lower battery. It can solve the complex process and high energy consumption problems in the production process of polycrystalline silicon solar cells, and combine the copper indium gallium selenium thin film upper battery with the lower battery to solve the poor stability in the production process of CIGS thin film solar cells, etc. question. Finally, various performances of the laminated battery are improved. The double-junction thin-film battery has lower production cost, higher stability, long service life and higher photoelectric conversion efficiency, so the double-junction thin-film battery has better development and application value.
Description
技术领域technical field
本发明是涉及多晶硅电池、硅薄膜电池和铜铟镓硒(Cu(In，Ga)Se2简称CIGS)薄膜太阳电池，通过多种技术工艺制备出硅薄膜/铜铟镓硒双结薄膜电池，其光电转换效率高于多晶硅太阳电池、硅薄膜太阳电池和铜铟镓硒薄膜太阳电池。涉及器件物理、薄膜技术和新型太阳能电池，属于新材料技术以及新能源技术领域。The invention relates to a polycrystalline silicon battery, a silicon thin film battery and a copper indium gallium selenide (Cu(In, Ga)Se 2 referred to as CIGS) thin film solar battery, and a silicon thin film/copper indium gallium selenide double-junction thin film battery is prepared through various technical processes. Its photoelectric conversion efficiency is higher than that of polycrystalline silicon solar cells, silicon thin film solar cells and copper indium gallium selenide thin film solar cells. It involves device physics, thin film technology and new solar cells, and belongs to the field of new material technology and new energy technology.
背景技术Background technique
在全球气候变暖、人类生态环境恶化、常规能源资源短缺并造成环境污染的形势下，太阳能光伏发电技术普遍得到各国政府的重视和支持。在技术进步的推动和逐步完善的法规政策的强力驱动下，光伏产业进入快速发展时期。In the context of global warming, deterioration of the human ecological environment, shortage of conventional energy resources and environmental pollution, solar photovoltaic power generation technology has generally received attention and support from governments around the world. Driven by technological progress and gradually improved regulations and policies, the photovoltaic industry has entered a period of rapid development.
薄膜太阳电池相较于晶体硅必须维持一定厚度而言，只需使用一层极薄光电材料，材料使用非常少；生产工序能够实现连续化，相对于晶体硅技术的间歇操作，效率大大提高且易于规模化；能够生产大尺寸电池，有助规模化生产。薄膜技术的优点能帮助大幅度降低生产成本，因而被认为有可能将太阳电池推向大众市场。特别是在多晶硅供应紧张，价格高的背景下，各国都加强了薄膜太阳电池的研究，以期能在下一代太阳电池技术的竞赛中抢得先机。Compared with crystalline silicon, thin-film solar cells must maintain a certain thickness, only need to use a very thin layer of photoelectric material, and use very little material; the production process can be continuous, and compared with the intermittent operation of crystalline silicon technology, the efficiency is greatly improved and Easy to scale; capable of producing large-size batteries, which facilitates large-scale production. The advantages of thin-film technology can help greatly reduce production costs, so it is considered possible to bring solar cells to the mass market. Especially under the background of tight supply and high price of polysilicon, all countries have strengthened the research of thin-film solar cells in order to seize the opportunity in the competition of next-generation solar cell technology.
本专利是结合硅薄膜和铜铟镓硒薄膜太阳电池的特点，制备高性能的新型硅薄膜/铜铟镓硒双结薄膜太阳电池，从而提高薄膜太阳电池光电转换效率。This patent is to combine the characteristics of silicon thin film and copper indium gallium selenide thin film solar cell to prepare a new type of silicon thin film/copper indium gallium selenide double junction thin film solar cell with high performance, so as to improve the photoelectric conversion efficiency of thin film solar cell.
发明内容Contents of the invention
本发明的目的在于提供一种具有高性能的硅薄膜/铜铟镓硒双结薄膜电池，电池分为上电池和下电池，上电池为铜铟镓硒薄膜电池，下电池为硅薄膜电池，结合了铜铟镓硒薄膜太阳电池和硅基太阳电池的优点，取长补短，提高电池的光电转换效率。The purpose of the present invention is to provide a high-performance silicon film/copper indium gallium selenide double-junction thin film battery, the battery is divided into an upper battery and a lower battery, the upper battery is a copper indium gallium selenide thin film battery, and the lower battery is a silicon thin film battery. Combining the advantages of copper indium gallium selenide thin-film solar cells and silicon-based solar cells, learning from each other to improve the photoelectric conversion efficiency of the cell.
本发明的技术方案是这样的：一、在导电玻璃上使用沉积技术沉积p-Si和n-Si薄膜，得到硅薄膜下电池。二、在硅薄膜下电池上，继续沉积n+-ZnO薄膜，然后使用共蒸发或溅射后硒化技术沉积p+-CuGaSe2和p-Cu(In，Ga)Se2薄膜，磁控溅射或化学气相沉积技术沉积i-ZnO、ZnO:Al，最后再蒸镀镍铝电极，得到硅薄膜/铜铟镓硒双结薄膜电池。三，通过上述方法，可以提高太阳电池的光电转化效率，电池具有较高的稳定性，低廉的制造成本等特点。The technical scheme of the present invention is as follows: 1. Deposit p-Si and n-Si thin films on conductive glass using deposition technology to obtain a battery under the silicon thin film. 2. On the battery under the silicon film, continue to deposit n + -ZnO film, and then use co-evaporation or post-sputtering selenization technology to deposit p + -CuGaSe 2 and p-Cu(In, Ga)Se 2 film, magnetron sputtering Deposit i-ZnO, ZnO:Al by radiation or chemical vapor deposition technology, and finally vapor-deposit nickel and aluminum electrodes to obtain silicon thin film/copper indium gallium selenium double junction thin film battery. Third, through the above method, the photoelectric conversion efficiency of the solar cell can be improved, and the cell has the characteristics of high stability, low manufacturing cost and the like.
所述制备的硅薄膜/铜铟镓硒双结薄膜电池的方法，通过如下步骤实现：The method for the prepared silicon thin film/copper indium gallium selenide double junction thin film battery is realized through the following steps:
一、硅薄膜下电池的制备。首先在沉积了ITO薄膜、FTO薄膜、ZnO:Al薄膜、金属钼薄膜的导电玻璃上，使用沉积技术沉积p-Si和n-Si薄膜，得到硅薄膜下电池。1. Preparation of battery under silicon thin film. Firstly, p-Si and n-Si films are deposited by deposition technology on conductive glass deposited with ITO film, FTO film, ZnO:Al film and metal molybdenum film to obtain a battery under the silicon film.
二、加热硅薄膜下电池，沉积n+-ZnO薄膜于硅薄膜下电池表面。2. Heating the battery under the silicon film, depositing n + -ZnO film on the surface of the battery under the silicon film.
三、铜镓硒和铜铟镓硒薄膜的生长采用多元共蒸发或溅射后硒化技术，先后分别沉积CuGaSe2、p-Cu(In，Ga)Se2薄膜。3. The growth of copper gallium selenide and copper indium gallium selenide thin films adopts multiple co-evaporation or selenization technology after sputtering, and deposits CuGaSe 2 and p-Cu(In, Ga)Se 2 thin films successively.
四、在p-Cu(In，Ga)Se2薄膜上沉积i-ZnO薄膜，得到高阻缓冲层。4. Depositing an i-ZnO thin film on the p-Cu(In, Ga)Se 2 thin film to obtain a high-resistance buffer layer.
五、磁控溅射ZnO:Al薄膜。5. Magnetron sputtering ZnO:Al film.
六、蒸镀镍铝电极，得到硅薄膜/铜铟镓硒双结薄膜电池。6. Evaporate nickel and aluminum electrodes to obtain silicon thin film/copper indium gallium selenium double junction thin film battery.
具体实施方式Detailed ways
实例1Example 1
硅薄膜/铜铟镓硒双结薄膜电池分为上电池和下电池，上电池为铜铟镓硒薄膜电池，下电池为硅薄膜电池。The silicon thin film/copper indium gallium selenide double junction thin film battery is divided into an upper battery and a lower battery, the upper battery is a copper indium gallium selenide thin film battery, and the lower battery is a silicon thin film battery.
一、硅薄膜下电池的制备。首先在导电玻璃上，使用磁控溅射沉积p-Si和n-Si薄膜，其中磁控溅射采用p型和n型硅靶材，得到硅薄膜下电池。具体实现步骤：在导电玻璃上，采用p型硅靶材，通入Ar气使工作气压为6Pa，两极电压为Vd＝240V，溅射时间为10min，得到p-Si薄膜；采用n型硅靶材，通入Ar气使工作气压为6Pa，两极电压为Vd＝240V，溅射时间为5min，得到n-Si薄膜，即得到了硅薄膜下电池。1. Preparation of battery under silicon thin film. Firstly, magnetron sputtering is used to deposit p-Si and n-Si thin films on conductive glass, wherein magnetron sputtering uses p-type and n-type silicon targets to obtain cells under silicon thin films. Specific implementation steps: on the conductive glass, use a p-type silicon target material, pass in Ar gas to make the working pressure 6Pa, the bipolar voltage is Vd = 240V, and the sputtering time is 10min to obtain a p-Si film; use n-type silicon The target material was fed with Ar gas so that the working pressure was 6Pa, the voltage between the poles was Vd = 240V, and the sputtering time was 5 minutes to obtain n-Si thin film, that is, the battery under the silicon thin film was obtained.
二、在硅薄膜下电池上，使用等离子体增强化学气相沉积技术沉积n+-ZnO薄膜，其中Zn源为二乙基锌或二甲基锌，氧源为H2和CO2混合气体。具体实现：待反应室抽真空至1×10-3Pa时，开始加热硅薄膜下电池，升高到沉积温度320℃，打开载气和反应源，通入氩气调节反应腔的真空度，使工作气压为10Pa，Zn源∶氧源＝1∶0.6-1∶0.9，与此同时打开等离子体，两极电压为Vd＝260V，沉积5min，保温5min。2. On the battery under the silicon thin film, use plasma enhanced chemical vapor deposition technology to deposit n + -ZnO thin film, wherein the Zn source is diethyl zinc or dimethyl zinc, and the oxygen source is a mixed gas of H 2 and CO 2 . Specific implementation: when the reaction chamber is evacuated to 1×10 -3 Pa, start heating the battery under the silicon thin film, raise it to a deposition temperature of 320°C, turn on the carrier gas and reaction source, and introduce argon gas to adjust the vacuum degree of the reaction chamber. The working pressure is 10 Pa, Zn source: oxygen source = 1:0.6-1:0.9, at the same time, the plasma is turned on, the voltage of the two poles is V d =260V, the deposition is 5 minutes, and the heat preservation is 5 minutes.
三、铜镓硒和铜铟镓硒薄膜的生长采用多元共蒸发技术，工艺如下：第一步首先蒸发99.9999％的金属Cu，Ga和Se，蒸发时间为5min，衬底温度为450℃，得到CuGaSe2；第二步开始蒸发In和Ga，Cu和Se，蒸发时间为25min，衬底温度为450℃，得到p-Cu(In，Ga)Se2薄膜。3. The growth of copper gallium selenide and copper indium gallium selenide film adopts multi-element co-evaporation technology. The process is as follows: the first step is to evaporate 99.9999% of metal Cu, Ga and Se, the evaporation time is 5min, and the substrate temperature is 450℃, and the obtained CuGaSe 2 ; In the second step, start to evaporate In and Ga, Cu and Se, the evaporation time is 25min, and the substrate temperature is 450°C to obtain a p-Cu(In,Ga)Se 2 film.
四、i-ZnO薄膜制备：使用等离子体增强化学气相沉积技术沉积i-ZnO薄膜，通入氩气调节反应腔的真空度，使工作气压为6Pa，主要调节Zn源和氧源的比例，Zn源∶氧源＝1∶1.0-1∶1.4，两极电压为Vd＝240V，沉积10min。4. Preparation of i-ZnO thin film: Deposit i-ZnO thin film using plasma enhanced chemical vapor deposition technology, and adjust the vacuum degree of the reaction chamber by introducing argon gas, so that the working pressure is 6Pa, mainly adjust the ratio of Zn source and oxygen source, Zn Source: Oxygen source=1:1.0-1:1.4, bipolar voltage V d =240V, deposition for 10 min.
五、ZnO∶Al薄膜制备：采用磁控溅射方法，采用ZnO∶Al靶材，通入Ar气使工作气压为6Pa，两极电压为Vd＝240V，沉积10min。溅射时间为10min。5. Preparation of ZnO:Al thin film: Magnetron sputtering method is adopted, ZnO:Al target material is adopted, Ar gas is introduced to make the working pressure 6 Pa, the voltage between two poles is V d =240V, and the deposition takes 10 min. The sputtering time was 10 min.
六、镍铝电极的制备：采用镍铝合金制作双结薄膜电池的电极，为了防止Al扩散到电池内部，常蒸发Al之前先蒸发一层Ni层。工艺条件为真空1×10-4Pa，先蒸发Ni，缓慢将电压升高，开挡板，蒸镀10s，然后再升高电压，蒸镀2min。6. Preparation of nickel-aluminum electrodes: Nickel-aluminum alloys are used to make electrodes for double-junction thin-film batteries. In order to prevent Al from diffusing into the battery, a layer of Ni is usually evaporated before Al is evaporated. The process condition is a vacuum of 1×10 -4 Pa, evaporate Ni first, slowly increase the voltage, open the baffle, and evaporate for 10 seconds, then increase the voltage again, and evaporate for 2 minutes.
实例2Example 2
硅薄膜/铜铟镓硒双结薄膜电池分为上电池和下电池，上电池为铜铟镓硒薄膜电池，下电池为硅薄膜电池。The silicon thin film/copper indium gallium selenide double junction thin film battery is divided into an upper battery and a lower battery, the upper battery is a copper indium gallium selenide thin film battery, and the lower battery is a silicon thin film battery.
一、硅薄膜下电池的制备。首先在导电玻璃上，使用等离子体增强化学气相沉积技术沉积p-Si和n-Si薄膜，等离子体增强化学气相沉积采用有机硅烷，掺杂用硼烷和磷烷，制备p-Si和n-Si，得到硅薄膜下电池。具体实现：反应室抽真空至1×10-3Pa时，开始加热玻璃基板，升高到沉积温度450℃，通入氩气、高纯硅烷和掺杂硼烷，调节反应腔的真空度，使工作气压为10-100Pa，打开等离子体，沉积时间为20min，得到p-Si薄膜，关闭掺杂硼烷，通入磷烷，继续沉积薄膜，沉积时间为5min，得到n-Si薄膜，即得到硅薄膜下电池。1. Preparation of battery under silicon thin film. First, p-Si and n-Si thin films are deposited on conductive glass using plasma-enhanced chemical vapor deposition. Si, to obtain a battery under the silicon thin film. Specific implementation: when the reaction chamber is evacuated to 1×10 -3 Pa, start heating the glass substrate, raise it to a deposition temperature of 450°C, pass in argon, high-purity silane and doped borane, and adjust the vacuum degree of the reaction chamber. The working pressure is 10-100Pa, the plasma is turned on, and the deposition time is 20 minutes to obtain a p-Si film, and the doping of borane is turned off, and phosphine is introduced to continue to deposit the film. The deposition time is 5 minutes to obtain an n-Si film, that is A battery under the silicon thin film is obtained.
二、在硅薄膜下电池上，使用等离子体增强化学气相沉积技术沉积n+-ZnO薄膜，其中Zn源为二乙基锌或二甲基锌，氧源为H2和CO2混合气体。具体实现：待反应室抽真空至1×10-3Pa时，开始加热硅薄膜下电池，升高到沉积温度320℃，打开载气和反应源，通入氩气调节反应腔的真空度，使工作气压为10-100Pa，Zn源∶氧源＝1∶0.6-1∶0.9，与此同时打开等离子体，两极电压为Vd＝240V，沉积5min，保温5min。2. On the battery under the silicon thin film, use plasma enhanced chemical vapor deposition technology to deposit n + -ZnO thin film, wherein the Zn source is diethyl zinc or dimethyl zinc, and the oxygen source is a mixed gas of H 2 and CO 2 . Specific implementation: when the reaction chamber is evacuated to 1×10 -3 Pa, start heating the battery under the silicon thin film, raise it to a deposition temperature of 320°C, turn on the carrier gas and reaction source, and introduce argon gas to adjust the vacuum degree of the reaction chamber. The working pressure is 10-100Pa, Zn source: oxygen source = 1:0.6-1:0.9, at the same time, the plasma is turned on, the voltage of the two poles is V d =240V, the deposition is 5 minutes, and the heat preservation is 5 minutes.
三、铜镓硒和铜铟镓硒薄膜的生长采用多元共蒸发技术，工艺如下：第一步首先蒸发99.9999％的金属Cu，Ga和Se，蒸发时间为5min，温度为350℃，得到CuGaSe2；第二步开始蒸发In和Ga，Cu和Se，蒸发时间为25min，温度为450℃，得到p-Cu(In，Ga)Se2薄膜。3. The growth of copper gallium selenide and copper indium gallium selenide film adopts multi-element co-evaporation technology, the process is as follows: the first step is to evaporate 99.9999% of metal Cu, Ga and Se, the evaporation time is 5min, and the temperature is 350 ℃ to obtain CuGaSe 2 ; The second step begins to evaporate In and Ga, Cu and Se, the evaporation time is 25min, and the temperature is 450°C to obtain a p-Cu(In, Ga)Se 2 film.
四、i-ZnO薄膜制备：使用等离子体增强化学气相沉积技术沉积i-ZnO薄膜，通入氩气调节反应腔的真空度，使工作气压为10Pa，主要调节Zn源和氧源的比例，Zn源∶氧源＝1∶1.0-1∶1.4，两极电压为Vd＝240V，沉积5min。4. Preparation of i-ZnO thin film: Deposit i-ZnO thin film using plasma enhanced chemical vapor deposition technology, and adjust the vacuum degree of the reaction chamber by introducing argon gas, so that the working pressure is 10Pa, mainly adjust the ratio of Zn source and oxygen source, Zn Source: Oxygen source=1:1.0-1:1.4, bipolar voltage V d =240V, deposition for 5 minutes.
五、ZnO:Al薄膜制备：采用磁控溅射方法，采用ZnO:Al靶材，通入Ar气使工作气压为4.0-10Pa，两极电压为Vd＝240V，沉积10min。溅射时间为10min。5. Preparation of ZnO:Al thin film: adopt magnetron sputtering method, adopt ZnO:Al target material, feed Ar gas so that the working pressure is 4.0-10Pa, the two-pole voltage is V d =240V, and deposit for 10 minutes. The sputtering time was 10 min.
六、镍铝电极的制备：采用镍铝合金制作双结薄膜电池的电极，为了防止Al扩散到电池内部，常蒸发Al之前先蒸发一层Ni层。工艺条件为真空1×10-4Pa，先蒸发Ni，缓慢将电压升高，开挡板，蒸镀10S，然后再升高电压，蒸镀2min。6. Preparation of nickel-aluminum electrodes: Nickel-aluminum alloys are used to make electrodes for double-junction thin-film batteries. In order to prevent Al from diffusing into the battery, a layer of Ni is usually evaporated before Al is evaporated. The process condition is a vacuum of 1×10 -4 Pa, evaporate Ni first, slowly increase the voltage, open the baffle, and evaporate for 10 seconds, then increase the voltage again, and evaporate for 2 minutes.
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