技术领域technical field
本发明涉及光电转换材料领域，特别是涉及一种光伏器件以及含有该光伏器件的太阳能电池。The invention relates to the field of photoelectric conversion materials, in particular to a photovoltaic device and a solar cell containing the photovoltaic device.
背景技术Background technique
人类进入二十一世纪，环境污染和能源短缺已愈来愈制约着社会的可持续发展。太阳能等可再生能源技术代表了清洁能源的发展方向，作为最具可持续发展理想特征的太阳能光伏发电将进入人类能源结构并成为基础能源的重要组成部分。我国也已经将其作为构建和谐可持续发展的新型社会的重要基础条件列入国家中长期科技发展规划中。从广泛的意义讲，地球上的能源归根结底都来自于太阳。除核能和地热能等可以认为是在地球形成过程中储存下来的能量以外，其它所有能源都源于太阳发生的热核反应所释放的巨大能量，包括可再生能源和化石能源。太阳发射出的总辐射能量大约为3.75×1026W，考虑到地球大气层的反射和吸收之后，一年中地球表面所接受的太阳能高达1.05×1018KWh，大约是本世纪初全球初级能源消耗总量的一万倍。太阳给人类带来了光明，也给人类带来了取之不尽、用之不竭的自然能源，使我们看到未来的希望。As mankind enters the 21st century, environmental pollution and energy shortages have increasingly restricted the sustainable development of society. Renewable energy technologies such as solar energy represent the development direction of clean energy. As the most ideal feature of sustainable development, solar photovoltaic power generation will enter the human energy structure and become an important part of basic energy. my country has also listed it as an important basic condition for building a harmonious and sustainable new society in the national medium and long-term scientific and technological development plan. In a broad sense, the energy on the earth comes from the sun in the final analysis. Except for nuclear energy and geothermal energy, which can be considered as energy stored during the formation of the earth, all other energy sources come from the huge energy released by the thermonuclear reaction in the sun, including renewable energy and fossil energy. The total radiant energy emitted by the sun is about 3.75×1026 W. After considering the reflection and absorption of the earth’s atmosphere, the solar energy received by the earth’s surface in a year is as high as 1.05×1018 KWh, which is about the global primary energy consumption at the beginning of this century. 10,000 times the total amount. The sun has brought light to mankind, and also brought inexhaustible and inexhaustible natural energy to mankind, so that we can see the hope of the future.
提高太阳能电池的效率，必须从以下四个方面寻求突破：1)实现太阳能电池对太阳光全光谱的吸收，即陷光效应；2)增强光子转换成电子的效率，即光电效应；3)改善光生载流子的运输和提高电极采集的能力，即光伏效应；4)增加光伏电压，亦即光伏效应。目前的研究中，低维材料复合界面结构在太阳能电池中的应用及对光吸收的影响方面开始受到关注，主要研究在以下几方面：To improve the efficiency of solar cells, we must seek breakthroughs from the following four aspects: 1) to realize the absorption of the full spectrum of sunlight by solar cells, that is, the light trapping effect; 2) to enhance the efficiency of converting photons into electrons, that is, the photoelectric effect; 3) to improve The transportation of photogenerated carriers and the ability to improve electrode collection, that is, the photovoltaic effect; 4) increase the photovoltaic voltage, that is, the photovoltaic effect. In the current research, the application of low-dimensional material composite interface structure in solar cells and its influence on light absorption have begun to attract attention. The main research is in the following aspects:
(1)本发明的发明人之一制备了非金属纳米线(硅纳米线)，应用于硅基薄膜电池获得陷光效果[1]；(1) One of the inventors of the present invention has prepared non-metallic nanowires (silicon nanowires), which are applied to silicon-based thin film batteries to obtain light trapping effects[1] ;
(2)Vassilios利用金属纳米球构成陷光结构[2]；(2) Vassilios uses metal nanospheres to form a light-trapping structure[2] ;
(3)Daniel Inns利用非金属微球(硅纳微球)作为电池光反射结构实现陷光结构[3]；(3) Daniel Inns uses non-metallic microspheres (silicon nanospheres) as the light reflection structure of the battery to realize the light trapping structure[3] ;
(4)HarryA.Atwater通过模拟计算金属纳米球与太阳电池的接触，可以实现三重效果，a)在电池表面构成陷光结构；b)在半导体层与透明电极界面构成陷光结构；c)在吸光区与背电极界面构成表面等离子激元结构实现陷光功能[4]；(4) HarryA.Atwater can achieve triple effects by simulating the contact between metal nanospheres and solar cells, a) forming a light trapping structure on the surface of the cell; b) forming a light trapping structure at the interface between the semiconductor layer and the transparent electrode; The interface between the light-absorbing region and the back electrode constitutes a surface plasmon structure to realize the light-trapping function[4] ;
(5)本发明的发明人之一在电池背面通过铜纳米线与碲化镉电池背接触，通过退火重掺，获得隧道结结构，提高了电池性能[5]。(5) One of the inventors of the present invention contacts the back of the cadmium telluride battery through copper nanowires on the back of the battery, and re-doped through annealing to obtain a tunnel junction structure, which improves the performance of the battery [5].
但是，通过可控的低维材料与电池的复合界面工程，系统突破如上所述的陷光效应、光电效应和光伏效应在太阳能电池中的应用及对光吸收的影响尚未有相关的研究报道。However, through the controllable composite interface engineering of low-dimensional materials and batteries, there are no relevant research reports on the application of the above-mentioned light trapping effect, photoelectric effect and photovoltaic effect in solar cells and their impact on light absorption.
参考文献references
[1]Hang Zhou，Alan Colli，Arman Ahnood，Yang Yang，Nalin Rupesinghe，TimButler，Ibraheem Haneef，Pritesh Hiralal，Arokia Nathan，Gehan A.J.Amaratunga，Arrays of Parallel Connected CoaxialMultiwall-Carbon-Nanotube-Amorphous-Silicon Solar Cells，Adv.Mater.，21，3919-3923，2009.[1] Hang Zhou, Alan Colli, Arman Ahnood, Yang Yang, Nalin Rupesinghe, Tim Butler, Ibraheem Haneef, Pritesh Hiralal, Arokia Nathan, Gehan A.J. Amaratunga, Arrays of Parallel Connected CoaxialMultiwall-Carbon-Nanotube-Amorphous-SiliconsAdvanced Cells . Mater., 21, 3919-3923, 2009.
[2]Vassilios Yannopapas，Nikolay V.Vitanov，Ultra-subwavelength focusing oflight by a monolayer of metallic nanoshells with an adsorbed defect，phys.stat.sol.(RRL)2，287-289，2008.[2] Vassilios Yannopapas, Nikolay V.Vitanov, Ultra-subwavelength focusing oflight by a monolayer of metallic nanoshells with an absorbed defect, phys.stat.sol.(RRL)2, 287-289, 2008.
[3]Daniel Inns，Lei Shi，Armin G.Aberle，Silica Nanospheres as Back SurfaceReflectors for Crystalline Silicon Thin-film Solar Cells，Prog.Photovolt：Res.Appl.，16，187-194，2008.[3]Daniel Inns, Lei Shi, Armin G.Aberle, Silica Nanospheres as Back SurfaceReflectors for Crystalline Silicon Thin-film Solar Cells, Prog.Photovolt: Res.Appl., 16, 187-194, 2008.
[4]Harry A.Atwater，Albert Polman，“Plasmonics for improved photovoltaicdevices”Nature Material，9，205-213，2010.[4] Harry A. Atwater, Albert Polman, "Plasmonics for improved photovoltaic devices" Nature Material, 9, 205-213, 2010.
[5]Jun Liang，Hui Bi，Dongyun Wan，Fuqiang Huang，Novel CuNanowires/Graphene as Back Contact for CdTe Solar Cells，Adv.Func.Mater.，22，1267-1271，2012.[5] Jun Liang, Hui Bi, Dongyun Wan, Fuqiang Huang, Novel CuNanowires/Graphene as Back Contact for CdTe Solar Cells, Adv.Func.Mater., 22, 1267-1271, 2012.
发明内容Contents of the invention
本申请的目的是提供一种光伏器件，以及含有该光伏器件的太阳能电池。The purpose of the present application is to provide a photovoltaic device and a solar cell containing the photovoltaic device.
为了实现上述目的，本申请采用了以下技术方案：In order to achieve the above object, the application adopts the following technical solutions:
本申请公开了一种光伏器件，包括透明电极区、窗口区、吸收区，在透明电极区、窗口区、吸收区的至少一个区的入光面具有与纳米线和/或纳微球点接触形成的低维复合界面结构。The application discloses a photovoltaic device, including a transparent electrode region, a window region, and an absorption region, and the light incident surface of at least one of the transparent electrode region, the window region, and the absorption region has a point contact with a nanowire and/or a nanosphere The formed low-dimensional composite interface structure.
进一步的，本申请的光伏器件中，在其吸收区的背面具有与纳米线和/或纳微球点接触形成的低维复合界面结构。Furthermore, in the photovoltaic device of the present application, there is a low-dimensional composite interface structure formed by point contact with nanowires and/or nanospheres on the back of the absorption region.
本申请的实施方式中，纳米线、纳微球的材料为金属材料、或非金属材料、或金属与非金属的复合材料；其中金属材料选自铜，镍，锌，锡，镁，铝，锰，铬，镉，碲，铟，锑，钛，金，铂，钼，银中的一种或者几种；非金属材料选自硅、锗、硒、碳、氮化硼、硫化镉、硫化锌、二氧化钛、二氧化硅、氧化锌、硫化铜、氧化钒、锂化合物及它们的合金，和聚苯乙烯，聚噻吩，富勒烯及它们的衍生物中的一种或者几种，所述碳包括石墨烯、纳米碳管和不定性碳中的至少一种；金属与非金属的复合材料包括金属材料包裹非金属材料而成的复合材料，或非金属材料包裹金属材料而成的复合材料。In the embodiment of the present application, the materials of nanowires and nanospheres are metal materials, or non-metal materials, or composite materials of metal and non-metal; wherein the metal materials are selected from copper, nickel, zinc, tin, magnesium, aluminum, One or more of manganese, chromium, cadmium, tellurium, indium, antimony, titanium, gold, platinum, molybdenum, silver; non-metallic materials selected from silicon, germanium, selenium, carbon, boron nitride, cadmium sulfide, sulfide Zinc, titanium dioxide, silicon dioxide, zinc oxide, copper sulfide, vanadium oxide, lithium compounds and their alloys, and one or more of polystyrene, polythiophene, fullerene and their derivatives, said Carbon includes at least one of graphene, carbon nanotubes and indeterminate carbon; composite materials of metal and nonmetal include composite materials formed by wrapping metal materials with nonmetal materials, or composite materials formed by wrapping metal materials with nonmetal materials .
进一步的，纳米线的直径为5nm-500nm，纳米线的长度为50nm-5mm，纳米线之间的间距为10nm-100μm。Further, the diameter of the nanowires is 5nm-500nm, the length of the nanowires is 50nm-5mm, and the distance between the nanowires is 10nm-100μm.
进一步的，纳微球的直径为50nm-500μm，纳微球之间的间距为0-100μm。Further, the diameter of the nanospheres is 50 nm-500 μm, and the distance between the nanospheres is 0-100 μm.
本申请的实施方式中，点接触包括纳米线或纳微球与基面形成合金的点接触、纳米线或纳微球与基面不形成合金的点接触中的至少一种；其中，纳米线或纳微球与基面形成合金的点接触中，合金的直径或深度是纳米线直径的0.1-10倍，或者是纳微球直径的0.01-10倍。In the embodiment of the present application, the point contact includes at least one of the point contact between the nanowire or nanosphere and the base surface to form an alloy, and the point contact between the nanowire or nanosphere and the base surface without forming an alloy; wherein, the nanowire Or in the point contact of the alloy formed between the nanosphere and the base surface, the diameter or depth of the alloy is 0.1-10 times the diameter of the nanowire, or 0.01-10 times the diameter of the nanosphere.
本申请的光伏器件中，吸收区的材料选自二六族化合物、三五族化合物、硅材料、有机光电材料、染料敏化材料中的至少一种。In the photovoltaic device of the present application, the material of the absorption region is selected from at least one of group II-VI compounds, III-V compounds, silicon materials, organic photoelectric materials, and dye-sensitized materials.
进一步的，二六族化合物选自CdTe材料、CuInSe材料、CuInGaSe材料、CuZnSeS材料中的至少一种；三五族化合物选自GaAs材料、InP材料、InGaP材料中的至少一种；硅材料是单晶硅、多晶硅、硅薄膜、纳米硅晶颗粒中的一种；有机光电材料选自酞青锌、甲基叶林、蒽、联苯、半菁类及衍生物和聚噻吩中的至少一种；染料敏化材料包括TiO2和染色剂，所述染色剂包括无机材料或有机材料，所述无机材料包括钌染料，所述有机材料选自吲哚啉类染料、香豆素类染料、三苯胺类染料、菁类染料、方酸类染料、二烷基苯胺类染料、咔唑类染料、芴类染料、二萘嵌苯类染料、四氢喹啉类染料、卟啉类染料、酞菁类染料中的至少一种。Further, the group II compound is selected from at least one of CdTe materials, CuInSe materials, CuInGaSe materials, and CuZnSeS materials; the III and V group compounds are selected from at least one of GaAs materials, InP materials, and InGaP materials; the silicon material is a single One of crystalline silicon, polycrystalline silicon, silicon film, and nano-silicon crystal particles; the organic photoelectric material is selected from at least one of zinc phthalocyanine, methyl phyllin, anthracene, biphenyl, semicyanines and their derivatives, and polythiophene The dye-sensitized material includes TiO2 and a dyeing agent, the dyeing agent includes an inorganic material or an organic material, the inorganic material includes a ruthenium dye, and the organic material is selected from the group consisting of indoline dyes, coumarin dyes, three Aniline dyes, cyanine dyes, squarylium dyes, dialkylaniline dyes, carbazole dyes, fluorene dyes, perylene dyes, tetrahydroquinoline dyes, porphyrin dyes, phthalocyanines At least one of the class dyes.
本申请的光伏器件中，吸收区的维度为纳米颗粒、块体、薄膜与薄膜叠层、薄膜与块体叠层中的一中。In the photovoltaic device of the present application, the dimension of the absorption region is one of nanoparticle, bulk, thin film and thin film stack, thin film and bulk stack.
本申请还公开了一种含有上述光伏器件的太阳能电池。The application also discloses a solar cell containing the above photovoltaic device.
由于采用以上技术方案，本发明的有益效果在于：Owing to adopting above technical scheme, the beneficial effect of the present invention is:
本申请的光伏器件和太阳能电池，借鉴飞蛾眼球表面的特殊结构，在光伏材料的界面上设计低维复合界面结构，增加了射入光伏材料的光通量，提高了光伏材料对阳光的采集，实现其光管理功能。同时，将纳米线和/或纳微球作为表面等离子激元(SPP)，进一步增强陷光效应，在不减弱电学性能的情况下增强陷光效果。此外，在形成低维复合界面结构时，对点接触进行控制，形成区域、深度和直径可控的掺杂，提供了一个既能减少空穴和电子复合机会，又利于传输空穴或电子的势场，从而提高了电子空穴的分离效率和运输能力，使得光生载流子(光子转换成电子/空穴)的寿命与电极采集的时间(速度)相匹配，产生的光电子能够同步地成为“伏打电子”，实现高效的光伏效应。并且通过点接触对掺杂界面的调控，调节能带工程，提高光伏电流和/或电压，提高了光伏转换能力。The photovoltaic device and solar cell of the present application draw on the special structure of the moth eyeball surface, and design a low-dimensional composite interface structure on the interface of the photovoltaic material, which increases the luminous flux injected into the photovoltaic material, improves the collection of sunlight by the photovoltaic material, and realizes Its light management function. At the same time, using nanowires and/or nano-microspheres as surface plasmon polaritons (SPPs) further enhances the light-trapping effect, and enhances the light-trapping effect without weakening the electrical performance. In addition, when forming a low-dimensional composite interface structure, the point contact is controlled, and the doping with controllable area, depth and diameter is formed, which provides a method that can not only reduce the recombination opportunities of holes and electrons, but also facilitate the transport of holes or electrons. Potential field, thereby improving the separation efficiency and transport capacity of electrons and holes, so that the lifetime of photogenerated carriers (photons converted into electrons/holes) matches the time (speed) of electrode collection, and the generated photoelectrons can become synchronously "Voltaic electronics" to achieve high-efficiency photovoltaic effect. Moreover, through the control of the doped interface through the point contact, the energy band engineering can be adjusted, the photovoltaic current and/or voltage can be increased, and the photovoltaic conversion ability can be improved.
附图说明Description of drawings
图1是本申请实施例中CdTe太阳电池结构示意图；Fig. 1 is the structural representation of CdTe solar cell in the embodiment of the present application;
图2是本申请实施例中CIGS太阳电池结构示意图；Fig. 2 is the structural representation of CIGS solar cell in the embodiment of the present application;
图3是本申请实施例中三五族GsAs太阳电池结构示意图；Fig. 3 is a schematic structural diagram of the III-V GsAs solar cell in the embodiment of the present application;
图4是本申请实施例中晶体硅太阳电池结构示意图；Fig. 4 is a schematic diagram of the structure of a crystalline silicon solar cell in an embodiment of the present application;
图5是本申请实施例中薄膜硅太阳电池结构示意图；Fig. 5 is a schematic diagram of the structure of a thin-film silicon solar cell in an embodiment of the present application;
图6是本申请实施例中染料敏化太阳电池结构示意图；6 is a schematic diagram of the structure of a dye-sensitized solar cell in an embodiment of the present application;
图7是本申请实施例中纳米线与光伏器件光伏材料的不同层点接触的结构示意图，71表示纳米线与透明电极区的入光面点接触，72表示纳米线与透明电极区的背面或窗口区的入光面点接触，73表示纳米线与窗口区的背面或吸收区的入光面点接触，74表示纳米线与吸收区的背面点接触；Figure 7 is a schematic structural view of the point contact between the nanowire and different layers of the photovoltaic material of the photovoltaic device in the embodiment of the present application, 71 indicates that the nanowire is in point contact with the light incident surface of the transparent electrode area, and 72 indicates that the nanowire is in contact with the back or the transparent electrode area The light incident surface of the window area is in point contact, 73 indicates that the nanowire is in point contact with the back of the window area or the light incident surface of the absorption area, and 74 indicates that the nanowire is in point contact with the back of the absorption area;
图8是本申请实施例中纳微球与光伏器件光伏材料的不同层点接触的结构示意图81表示纳微球与透明电极区的入光面点接触，82表示纳微球与透明电极区的背面或窗口区的入光面点接触，83表示纳微球与窗口区的背面或吸收区的入光面点接触，84表示纳微球与吸收区的背面点接触；Fig. 8 is a structural schematic diagram of point contact between nanospheres and different layers of photovoltaic materials in photovoltaic devices in the embodiment of the present application. The point contact of the light incident surface of the back or the window area, 83 indicates that the nano-microspheres are in point contact with the back of the window area or the light incident surface of the absorption area, and 84 indicates that the nano-microspheres are in point contact with the back of the absorption area;
图9是本申请实施例中纳米线和/或纳微球与光伏材料入光面和背面点接触的结构示意图，其中91表示纳米线与透明电极区入光面和吸收区的背面点接触，92表示纳微球与透明电极区入光面和吸收区的背面点接触，93表示纳米线与透明电极区入光面点接触，纳微球与吸收区背面点接触，94表示纳微球与透明电极区入光面点接触，纳米线与吸收区背面点接触；Fig. 9 is a schematic structural view of nanowires and/or nano-microspheres in point contact with the light incident surface and the back surface of the photovoltaic material in the embodiment of the present application, wherein 91 indicates that the nanowires are in point contact with the light incident surface of the transparent electrode area and the back surface of the absorption area, 92 represents the point contact between the nano-microsphere and the light incident surface of the transparent electrode area and the back side of the absorption area, 93 represents the point contact between the nanowire and the light incident surface of the transparent electrode area, and the point contact between the nano-microsphere and the back side of the absorption area, and 94 represents the point contact between the nano-microsphere and the The light-incident surface of the transparent electrode area is in point contact, and the nanowire is in point contact with the back of the absorption area;
图10是本申请实施例中纳米线穿过透明电极区与窗口区入光面点接触的结构示意图101，以及纳米线穿过透明电极区和窗口区与吸收区的入光面点接触的结构示意图102；Fig. 10 is a schematic diagram 101 of the structure of the nanowire passing through the transparent electrode region and the light incident surface of the window region in point contact with the light incident surface of the window region in the embodiment of the present application, and the structure of the nanowire passing through the transparent electrode region and the window region and the light incident surface of the absorption region in point contact schematic 102;
图11是本申请实施例中纳米线穿过光伏材料与其中一个区的入光面点接触，同时，纳米线与吸收区背面接触的结构示意图，111表示纳米线穿过透明电极区与窗口区的入光面点接触，同时纳米线与吸收区的背面点接触，112表示纳米线穿过透明电极区和窗口区与吸收区的入光面点接触，同时纳米线与吸收区的背面点接触；Figure 11 is a schematic diagram of the nanowire passing through the photovoltaic material to make point contact with the light-incident surface of one of the regions in the embodiment of the present application. At the same time, the nanowire is in contact with the back of the absorption region. 111 indicates that the nanowire passes through the transparent electrode region and the window region At the same time, the nanowire is in point contact with the back side of the absorption region, 112 indicates that the nanowire passes through the transparent electrode region and the window region and is in point contact with the light incident surface of the absorption region, and at the same time the nanowire is in point contact with the back side of the absorption region ;
图12是本申请实施例中纳米线穿过光伏材料与其中一个区的入光面点接触，同时，纳微球与吸收区背面接触的结构示意图，121表示纳米线穿过透明电极区与窗口区的入光面点接触，同时纳微球与吸收区的背面点接触，122表示纳米线穿过透明电极区和窗口区与吸收区的入光面点接触，同时纳微球与吸收区的背面点接触；Figure 12 is a schematic diagram of the nanowire passing through the photovoltaic material to make point contact with the light-incident surface of one of the regions in the embodiment of the present application, and at the same time, the nanosphere is in contact with the back of the absorption region, 121 indicates that the nanowire passes through the transparent electrode region and the window The light-incident surface of the absorption area is point-contacted, and the nano-microspheres are in point-contact with the back surface of the absorption area. Back point contact;
图13是本申请实施例中纳微球与光伏器件光伏材料的不同层点接触，同时，纳微球与吸收区的背面点接触的结构示意图，131表示纳微球与透明电极区背面或窗口区入光面点接触，同时纳微球与吸收区的背面点接触，132表示纳微球与窗口区背面或吸收区入光面点接触，同时纳微球与吸收区的背面点接触；Figure 13 is a schematic diagram of the point contact between nanospheres and different layers of the photovoltaic material of the photovoltaic device in the embodiment of the present application. The light-incident surface of the window area is point-contacted, and the nano-microspheres are in point-contact with the back of the absorption area, 132 indicates that the nano-microspheres are in point-contact with the back of the window area or the light-incident surface of the absorption area, and the nano-microspheres are in point contact with the back of the absorption area;
图14是本申请实施例中纳微球与光伏器件光伏材料的不同层点接触，同时，纳米线与吸收区的背面点接触的结构示意图，141表示纳微球与透明电极区背面或窗口区入光面点接触，同时纳米线与吸收区的背面点接触，142表示纳微球与窗口区背面或吸收区入光面点接触，同时纳米线与吸收区的背面点接触。Figure 14 is a schematic diagram of the point contact between nanospheres and different layers of the photovoltaic material of the photovoltaic device in the embodiment of the present application, and at the same time, the structure schematic diagram of point contact between nanowires and the back side of the absorption area, 141 represents the backside or window area of the nanospheres and the transparent electrode area The light incident surface is in point contact, and the nanowire is in point contact with the back of the absorption region. 142 indicates that the nanosphere is in point contact with the back of the window region or the light incident surface of the absorption region, and at the same time, the nanowire is in point contact with the back of the absorption region.
具体实施方式Detailed ways
本申请的一种实施方式中，在所述透明电极区、窗口区、吸收区的入光面和背面共计六个面中，至少一个面具有与纳米线和/或纳微球点接触形成的低维复合界面结构。其中“与纳米线和/或纳微球点接触形成低维复合界面结构”的实现方式是，11)在只有一个面具有低维复合界面结构时，采用纳米线或者纳微球与基面点接触；或者该面的部分采用纳米线点接触，其它部分采用纳微球点接触；12)在多个面具有低维复合界面结构时，其中一个或几个面采用纳米线点接触形成低维复合界面结构，其余面采用纳微球点接触形成低维复合界面结构。需要说明的是，在上述六个面中，在其中两个面相接触的情况下，在多个面上进行纳米线和/或纳微球点接触形成低维复合界面结构时，只选择两个接触面中的一个面与纳米线和/或纳微球点接触形成低维复合界面结构。In one embodiment of the present application, among the six surfaces of the transparent electrode region, the window region, and the light incident surface and the back surface of the absorption region, at least one surface has a point contact with the nanowire and/or the nanosphere. Low-dimensional composite interface structures. Among them, the realization method of "forming a low-dimensional composite interface structure in point contact with nanowires and/or nanospheres" is, 11) when only one surface has a low-dimensional composite interface structure, use nanowires or nanospheres and basal plane points contact; or part of the surface uses nanowire point contact, and other parts use nanosphere point contact; 12) When multiple surfaces have a low-dimensional composite interface structure, one or several surfaces use nanowire point contact to form a low-dimensional Composite interface structure, and the rest of the surface uses nano-microsphere point contact to form a low-dimensional composite interface structure. It should be noted that, among the above-mentioned six faces, in the case where two faces are in contact, when performing nanowire and/or nano-microsphere point contact on multiple faces to form a low-dimensional composite interface structure, only two One of the contact surfaces is in point contact with the nanowires and/or nanospheres to form a low-dimensional composite interface structure.
本申请的发明人在光伏器件的光伏材料(透明电极区、窗口区、吸收区)界面(入光面、背面)上设计低维复合界面结构，该低维复合界面结构表面的特殊结构设计，有利于增加射入光伏电池的光通量，提高了光伏器件对阳光的采集。同时，将纳米线和/或纳微球作为表面等离子激元(SPP)，进一步增强光伏器件的陷光效应，在不减弱电学性能的情况下增强陷光效果。此外，本申请的低维复合界面结构中纳米线和/或纳微球与界面进行可控的点接触，形成不同区域、深度和直径的掺杂，在电极与光伏材料的界面加入一个既能减少空穴和电子复合机会，又有利于传输空穴或者电子的势场，提高了电子空穴的分离效率和输运能力，使得光生载流子(光子转换成电子/空穴)的寿命与电极采集的时间(速度)相匹配，产生的光电子能够同步地成为“伏打电子”，实现高效的光伏效应。The inventor of the present application designed a low-dimensional composite interface structure on the interface (light-incident surface, back surface) of the photovoltaic material (transparent electrode region, window region, absorption region) of the photovoltaic device. The special structure design of the surface of the low-dimensional composite interface structure, It is beneficial to increase the luminous flux injected into the photovoltaic cell, and improves the collection of sunlight by the photovoltaic device. At the same time, nanowires and/or nanospheres are used as surface plasmon polaritons (SPPs) to further enhance the light trapping effect of photovoltaic devices, and enhance the light trapping effect without weakening the electrical performance. In addition, in the low-dimensional composite interface structure of the present application, nanowires and/or nanospheres make controllable point contact with the interface to form doping with different regions, depths and diameters. It reduces the chance of recombination of holes and electrons, and is conducive to the potential field of transporting holes or electrons, which improves the separation efficiency and transport capacity of electrons and holes, so that the lifetime of photogenerated carriers (photons converted into electrons/holes) is the same as that of The time (speed) of electrode collection is matched, and the generated photoelectrons can become "voltaic electrons" synchronously, realizing efficient photovoltaic effect.
本申请进一步的改进实施方式中，在吸收区的背面设计与纳米线和/或纳微球点接触形成的低维复合界面结构；同时，透明电极区和窗口区的入光面和背面、吸收区的入光面共计五个面中，至少一个面具有纳米线和/或纳微球点接触形成的低维复合界面结构。需要说明的是，在上述五个面中，在其中两个面相接触的情况下，在多个面上进行纳米线和/或纳微球点接触形成低维复合界面结构时，只选择两个接触面中的一个面与纳米线和/或纳微球点接触形成低维复合界面结构。其中“与纳米线和/或纳微球点接触形成低维复合界面结构”的实现方式与前述相同。In a further improved embodiment of the present application, a low-dimensional composite interface structure formed by point contact with nanowires and/or nanospheres is designed on the back of the absorption region; Among the five light incident surfaces of the region, at least one surface has a low-dimensional composite interface structure formed by point contact of nanowires and/or nanospheres. It should be noted that, among the above-mentioned five faces, in the case where two faces are in contact, when performing nanowire and/or nano-microsphere point contact on multiple faces to form a low-dimensional composite interface structure, only two are selected. One of the contact surfaces is in point contact with the nanowires and/or nanospheres to form a low-dimensional composite interface structure. Wherein, the realization method of "forming a low-dimensional composite interface structure by point contact with nanowires and/or nanospheres" is the same as above.
本申请优选的实施方式中，具体包括，在吸收区的背面设计与纳米线和/或纳微球点接触形成的低维复合界面结构；同时，在透明电极区、窗口区、吸收区的其中一个区的入光面设计纳米线和/或纳微球点接触形成的低维复合界面结构。该优选的实施方式中又包括四种实现方式，21)背面和入光面的低维复合界面结构均采用纳米线；22)背面和入光面的低维复合界面结构均采用纳微球；23)背面的低维复合界面结构采用纳米线，入光面的低维复合界面结构采用纳微球；24)背面的低维复合界面结构采用纳微球，入光面的低维复合界面结构采用纳米线。需要说明的是，上述21)、22)、23)、24)中，背面是指吸收区的背面，入光面是指电极区、窗口区、吸收区的其中一个区的入光面。In the preferred embodiment of the present application, it specifically includes designing a low-dimensional composite interface structure formed by point contact with nanowires and/or nanospheres on the back of the absorption region; at the same time, in the transparent electrode region, window region, and absorption region. A low-dimensional composite interface structure formed by point contact of nanowires and/or nanospheres is designed on the light incident surface of one region. This preferred embodiment also includes four implementations, 21) nanowires are used for the low-dimensional composite interface structures on the back and light-incident surfaces; 22) nano-microspheres are used in the low-dimensional composite interface structures on the back and light-incident surfaces; 23) The low-dimensional composite interface structure on the back uses nanowires, and the low-dimensional composite interface structure on the light-incident surface uses nano-microspheres; 24) The low-dimensional composite interface structure on the back uses nano-microspheres, and the low-dimensional composite interface structure on the light-incident surface Using nanowires. It should be noted that, in the above 21), 22), 23), and 24), the back surface refers to the back surface of the absorption region, and the light incident surface refers to the light incident surface of one of the electrode region, window region, and absorption region.
前述本申请优选的实施方式中，采用两个低维复合界面结构分别实现增强陷光效应、提高光伏效应两个功能。在入光面利用仿生飞蛾眼球表面结构的低维复合界面结构提高阳光采集、增强陷光效果，飞蛾在漆黑的夜间仍能捕获微弱的光线，分辨障碍物；研究报道显示，这与飞蛾眼球表面的特殊结构相关，并认为飞蛾眼球表面的特殊结构能与空气形成一种折射率连续变化的高性能减反界面，该界面减反角度大，几乎能对各方向太阳光进行全光谱吸收。本申请的发明人借鉴飞蛾眼球表面的特殊结构，设计低维复合界面结构提高阳光采集、增强陷光效果；同时，在吸收区背面通过可控的点接触掺杂，低维复合界面结构提供了一个既能减少空穴和电子复合机会，又有利于传输空穴或电子的势场，提高了电荷的收集和转移能力，实现高效的光伏效应。需要说明的是，本申请中，增强陷光效应、提高光伏效应对低维复合界面结构本身来说并不是两个完全分离的效果。In the aforementioned preferred implementation mode of the present application, two low-dimensional composite interface structures are used to respectively realize two functions of enhancing the light trapping effect and improving the photovoltaic effect. On the light incident surface, the low-dimensional composite interface structure of the bionic moth eyeball surface structure is used to improve sunlight collection and enhance the light trapping effect. Moths can still capture weak light and distinguish obstacles in the dark night; research reports show that this is the same as that of flies It is related to the special structure of the surface of the moth eyeball, and it is believed that the special structure of the surface of the moth eyeball can form a high-performance anti-reflection interface with air with a continuously changing refractive index. spectral absorption. The inventors of this application drew on the special structure of the moth eyeball surface to design a low-dimensional composite interface structure to improve sunlight collection and enhance light trapping effects; at the same time, the low-dimensional composite interface structure provides A potential field that can not only reduce the recombination opportunities of holes and electrons, but also facilitate the transmission of holes or electrons, improves the collection and transfer capabilities of charges, and realizes efficient photovoltaic effects. It should be noted that in this application, enhancing the light trapping effect and improving the photovoltaic effect are not two completely separate effects for the low-dimensional composite interface structure itself.
需要说明的是，纳米线与窗口区的入光面点接触时，其实现方式包括两种：第一，纳米线在透明电极区和窗口区之间与窗口区入光面点接触，如图7的72；第二，纳米线穿过透明电极区与窗口区的入光面点接触，如图10的101、图11的111以及图12的121。纳米线与吸收区的入光面点接触时，其实现方式也包括两种：第一，纳米线在窗口区和吸收区之间与吸收区入光面点接触，如图7的73；第二，纳米线穿过透明电极区和窗口区与吸收区的入光面点接触，如图10的102、图11的112以及图12的122。It should be noted that when the nanowires are in point contact with the light-incident surface of the window area, there are two implementation methods: first, the nanowires are in point-contact with the light-incident surface of the window area between the transparent electrode area and the window area, as shown in Fig. 72 of 7; secondly, the nanowire passes through the transparent electrode region and makes point contact with the light-incident surface of the window region, such as 101 in FIG. 10 , 111 in FIG. 11 and 121 in FIG. 12 . When the nanowires are in point contact with the light-incident surface of the absorption region, there are two implementation methods: first, the nanowires are in point contact with the light-incident surface of the absorption region between the window region and the absorption region, as shown in Figure 7 73; Second, the nanowires pass through the transparent electrode region and the window region to make point contact with the light incident surface of the absorption region, such as 102 in FIG. 10 , 112 in FIG. 11 and 122 in FIG. 12 .
本申请所有实施方式中，纳米线、纳微球的材料包括金属材料、非金属材料、金属与非金属的复合材料；其中金属材料选自铜，镍，锌，锡，镁，铝，锰，铬，镉，碲，铟，锑，钛，金，铂，钼，银中的一种或者几种；非金属材料选自硅、锗、硒、碳、氮化硼、硫化镉、硫化锌、二氧化钛、二氧化硅、氧化锌、硫化铜、氧化钒、锂氧化物、锂酸化物及它们的合金，和聚苯乙烯，聚噻吩，富勒烯及它们的衍生物中的一种或者几种，所述碳包括石墨烯、纳米碳管和不定性碳中的至少一种；金属与非金属的复合材料包括金属材料包裹非金属材料而成的复合材料，非金属材料包裹金属材料而成的复合材料。纳米线的直径、长度和间距根据具体采用的材料的性质在直径5nm-500nm、长度50nm-5mm、间距10nm-100μm范围内调整；纳微球的粒径和间距同样根据具体采用的材料在粒径50nm-500μm、间距0-100μm范围内调整。In all embodiments of the present application, the materials of nanowires and nanospheres include metal materials, non-metal materials, and composite materials of metal and non-metal; wherein the metal materials are selected from copper, nickel, zinc, tin, magnesium, aluminum, manganese, One or more of chromium, cadmium, tellurium, indium, antimony, titanium, gold, platinum, molybdenum, silver; non-metallic materials selected from silicon, germanium, selenium, carbon, boron nitride, cadmium sulfide, zinc sulfide, Titanium dioxide, silicon dioxide, zinc oxide, copper sulfide, vanadium oxide, lithium oxide, lithium oxide and their alloys, and one or more of polystyrene, polythiophene, fullerene and their derivatives , the carbon includes at least one of graphene, carbon nanotubes and indeterminate carbon; composite materials of metal and nonmetal include composite materials formed by wrapping metal materials with nonmetal materials, and composite materials formed by wrapping metal materials with nonmetal materials composite material. The diameter, length and spacing of the nanowires are adjusted within the range of 5nm-500nm in diameter, 50nm-5mm in length, and 10nm-100μm in length according to the properties of the material used; The diameter is 50nm-500μm, and the pitch is adjusted within the range of 0-100μm.
本申请所有实施方式中，点接触分为两种，一种是纳米线或纳微球与基面形成合金的点接触，这种情况下，纳米线或纳微球与基面发生反应形成合金，合金的直径或深度根据具体选用的材料，在纳米线直径的0.1-10倍，或者纳微球直径的0.01-10倍范围之间；另一种是纳米线或纳微球与基面不形成合金的点接触，这种情况下，纳米线或纳微球与基面不会发生反应形成合金。需要说明的是，合金的深度是指纳米线或纳微球与基面形成合金，该合金陷入基面平面的深度；合金的直径是指合金在基面平面上的直径。其中合金的深度和直径通过控制纳米线或纳微球与基面点接触的温度和时间来控制，原则上温度越高、时间越长合金的直径越大、深度越深。In all embodiments of the present application, there are two types of point contact, one is the point contact of nanowires or nanospheres forming an alloy with the base surface, in this case, the nanowires or nanospheres react with the base surface to form an alloy , the diameter or depth of the alloy is in the range of 0.1-10 times the diameter of the nanowire or 0.01-10 times the diameter of the nanosphere according to the specific material selected; Point contacts that form alloys, in which case the nanowires or nanospheres do not react with the basal surface to form an alloy. It should be noted that the depth of the alloy refers to the depth at which the nanowires or nanospheres form an alloy with the basal plane, and the alloy sinks into the basal plane; the diameter of the alloy refers to the diameter of the alloy on the basal plane. The depth and diameter of the alloy are controlled by controlling the temperature and time of point contact between the nanowires or nanospheres and the basal surface. In principle, the higher the temperature and the longer the time, the larger the diameter and deeper the depth of the alloy.
本申请所有实施方式中，吸收区的材料选自二六族化合物、三五族化合物、硅材料中的至少一种；其中二六族化合物选自CdTe材料、CuInSe材料、CuInGaSe材料、CuZnSeS材料中的至少一种；三五族化合物选自GaAs材料、InP材料、InGaP材料中的至少一种；硅材料是单晶硅、多晶硅、硅薄膜、纳米硅晶颗粒中的一种；有机光电材料选自酞青锌、甲基叶林、蒽、联苯、半菁类及衍生物和聚噻吩中的至少一种；染料敏化材料包括TiO2和染色剂，所述染色剂包括无机材料或有机材料，所述无机材料包括钌染料，所述有机材料选自吲哚啉类染料、香豆素类染料、三苯胺类染料、菁类染料、方酸类染料、二烷基苯胺类染料、咔唑类染料、芴类染料、二萘嵌苯类染料、四氢喹啉类染料、卟啉类染料、酞菁类染料中的至少一种；吸收区为纳米颗粒或块体或薄膜与薄膜叠层或薄膜与块体叠层。本申请的实施方式中，窗口区的材料选自CdS、ZnS、AlInP2、GaAs、AlGaAs、硅中的至少一种。透明电极区为ZnO:Al(AZO)透明电极、In2O3:Sn(ITO)透明电极、SnO2:F(FTO)透明电极、TiO2:Nb(NTO)透明电极中的至少一种，透明电极的厚度50nm-1μm。In all embodiments of the present application, the material of the absorption region is selected from at least one of Group II compounds, Group III compounds, and silicon materials; wherein the Group II compounds are selected from CdTe materials, CuInSe materials, CuInGaSe materials, and CuZnSeS materials At least one of three and five group compounds selected from at least one of GaAs material, InP material, and InGaP material; the silicon material is one of single crystal silicon, polycrystalline silicon, silicon thin film, and nano-silicon crystal particles; the organic photoelectric material is selected from At least one of zinc phthalocyanine, methyl phyllin, anthracene, biphenyl, hemicyanines and derivatives, and polythiophene; dye-sensitized materials includeTiO and dyes, which include inorganic materials or organic material, the inorganic material includes ruthenium dye, and the organic material is selected from indoline dyes, coumarin dyes, triphenylamine dyes, cyanine dyes, squarylium dyes, dialkylaniline dyes, carba At least one of azole dyes, fluorene dyes, perylene dyes, tetrahydroquinoline dyes, porphyrin dyes, and phthalocyanine dyes; Lamination of layers or thin films with blocks. In an embodiment of the present application, the material of the window region is selected from at least one of CdS, ZnS, AlInP2 , GaAs, AlGaAs, and silicon. The transparent electrode area is at least one of ZnO:Al(AZO) transparent electrode, In2 O3 :Sn(ITO) transparent electrode, SnO2 :F(FTO) transparent electrode, TiO2 :Nb(NTO) transparent electrode, The thickness of the transparent electrode is 50nm-1μm.
本申请的实施方式中，透明电极区的制备方法包括：气相输运(HVPE)、Sputter、CVD、蒸镀法、电化学法中的至少一种；窗口区的制备方法包括：Sputter、蒸镀法、CVD、化学水浴沉积(CBD)、近真空升华(CSS)，电化学法中的至少一种；吸收区的制备方法包括：CSS、电化学沉积、Sputter、HVPE、CVD法中的至少一种。In the embodiment of the present application, the preparation method of the transparent electrode region includes: at least one of vapor phase transport (HVPE), Sputter, CVD, evaporation method, and electrochemical method; the preparation method of the window region includes: Sputter, evaporation method, CVD, chemical bath deposition (CBD), near vacuum sublimation (CSS), at least one of electrochemical methods; the preparation method of the absorption region includes: at least one of CSS, electrochemical deposition, Sputter, HVPE, CVD kind.
本申请中提到的基面，是指纳米线或纳微球与之结合的形成低维复合界面结构的面。The basal plane mentioned in this application refers to the plane to which the nanowires or nano-microspheres are combined to form a low-dimensional composite interface structure.
采用本申请提供的光伏器件制备的太阳能电池，由于光伏器件中具有低维复合界面结构，该低维复合界面结构仿生飞蛾眼球表面的特殊结构设计，有利于增加射入光伏电池的光通量，提高了光伏器件对阳光的采集。同时，将纳米线和/或纳微球作为表面等离子激元(SPP)，进一步增强光伏器件的陷光效应，在不减弱电学性能的情况下增强陷光效果，实现光管理功能。此外，本申请的低维复合界面结构中纳米线和/或纳微球与界面进行可控的点接触，在电极与光伏材料的界面加入一个既能减少空穴和电子复合机会，又有利于传输空穴或者电子的势场，提高了电子空穴的分离效率和输运能力，使得光生载流子(光子转换成电子/空穴)的寿命与电极采集的时间(速度)相匹配，产生的光电子能够同步地成为“伏打电子”，实现高效的光伏效应。并且，低维复合界面结构中，通过控制点接触对掺杂的调控，调节能带工程，提高电池光伏电流，提高了光伏转换能力，从而提高了太阳能电池的效率。The solar cell prepared by using the photovoltaic device provided by this application has a low-dimensional composite interface structure in the photovoltaic device, and the special structure design of the low-dimensional composite interface structure bionic moth eyeball surface is conducive to increasing the luminous flux injected into the photovoltaic cell and improving Photovoltaic devices harvest sunlight. At the same time, nanowires and/or nanospheres are used as surface plasmon polaritons (SPPs) to further enhance the light trapping effect of photovoltaic devices, enhance the light trapping effect without weakening the electrical performance, and realize the light management function. In addition, in the low-dimensional composite interface structure of the present application, the nanowires and/or nano-microspheres are in controllable point contact with the interface. Adding an interface between the electrode and the photovoltaic material can not only reduce the chance of hole and electron recombination, but also facilitate The potential field of transporting holes or electrons improves the separation efficiency and transport capacity of electrons and holes, so that the lifetime of photogenerated carriers (photons converted into electrons/holes) matches the time (speed) of electrode collection, resulting in The optoelectronics can become "voltaic electrons" synchronously to achieve high-efficiency photovoltaic effect. Moreover, in the low-dimensional composite interface structure, through the regulation of doping by controlling the point contact, the energy band engineering can be adjusted, the photovoltaic current of the battery can be improved, and the photovoltaic conversion ability can be improved, thereby improving the efficiency of the solar cell.
下面通过具体实施例结合附图对本申请作进一步详细说明。以下实施例仅对本申请进行进一步的说明，不应理解为对本申请的限制。以下实施例3-20描述顺序为实际操作过程中太阳能电池的制备顺序。The present application will be described in further detail below through specific embodiments in conjunction with the accompanying drawings. The following examples only further illustrate the present application, and should not be construed as limiting the present application. The sequence described in the following examples 3-20 is the preparation sequence of solar cells during actual operation.
实施例一纳微球的制备The preparation of embodiment one nanosphere
本申请使用的纳微球可以自己制备或直接购买商品化纳微球。The nano-microspheres used in this application can be prepared by oneself or directly purchased from commercialized nano-microspheres.
纳微球的制备方法包括：首先合成单分散性的聚合物种子，这些单分散聚合物种子可通过分散聚合和无皂乳液聚合法获得，分散聚合是把单体(如苯乙烯)，引发剂(AIBN)及稳定剂(PVA)等溶解在乙醇和水里。然后采用加热聚合法，通过搅拌速率、温度以及时间控制而制得粒径均一的纳微球(如聚苯乙烯微球)。The preparation method of nanosphere comprises: at first synthesizing the polymer seed of monodispersity, these monodisperse polymer seeds can be obtained by dispersion polymerization and soap-free emulsion polymerization, and dispersion polymerization is monomer (as styrene), initiator (AIBN) and stabilizer (PVA) are dissolved in ethanol and water. Then adopt heating polymerization method to prepare nano-microspheres (such as polystyrene microspheres) with uniform particle size by controlling stirring rate, temperature and time.
对于直接购买的纳微球，如聚苯乙烯纳微球(Sigma-Aldrich公司的产品53532-1G-F)、二氧化硅微球(龙口市瑞隆高科技有限公司的产品TOND-180)，将购买的纳微球与悬浮溶剂混匀，制备成纳微球悬浮液，控制纳微球用量以及悬浮溶剂的体积，使得悬浮液浓度控制在1mg/L-1g/L之间。其中悬浮溶剂为水或乙醇。混匀时磁搅拌器的搅拌速率为100-1000转每分钟。For directly purchased nano-microspheres, such as polystyrene nano-microspheres (product 53532-1G-F of Sigma-Aldrich Company), silica microspheres (product TOND-180 of Longkou Ruilong High-Tech Co., Ltd.), the The purchased nano-microspheres are mixed with the suspension solvent to prepare a nano-microsphere suspension, and the amount of nano-microspheres and the volume of the suspension solvent are controlled so that the concentration of the suspension is controlled between 1mg/L-1g/L. Wherein the suspending solvent is water or ethanol. When mixing, the stirring rate of the magnetic stirrer is 100-1000 revolutions per minute.
纳微球与基面点接触采用蒸发自组装法，即将上述纳微球悬浮液涂覆于光电材料的表面，在室温至60摄氏度之间的温度蒸发悬浮液的液体，纳微球在悬浮液的气-液相界面处进行高效组装形成紧挨致密的纳微球薄膜，沉积在基面上。The point contact between the nano-microsphere and the base surface adopts the evaporation self-assembly method, that is, the above-mentioned nano-microsphere suspension is coated on the surface of the photoelectric material, and the liquid of the suspension is evaporated at a temperature between room temperature and 60 degrees Celsius, and the nano-microsphere is in the suspension. High-efficiency assembly at the gas-liquid phase interface to form a dense nanosphere film that is deposited on the base surface.
纳微球在基面上的间距通过半导体微结构加工方式先在基面上做成具有特定间距微结构模板，使得纳微球只能占据一些特定的位置，从而控制纳微球沉积位置，可控地制备具有所需间距排列的纳微球薄膜。The spacing of the nanospheres on the basal surface is firstly made into a microstructure template with a specific spacing on the basal surface through semiconductor microstructure processing, so that the nanospheres can only occupy some specific positions, thereby controlling the deposition position of the nanospheres, which can Controlled preparation of nanosphere films with desired pitch arrangement.
纳微球与基面形成合金时，通过纳微球与基面的点接触的控制一定的温度和时间来控制组分元素互相之间的热扩散，形成所需深度和直径的合金区域。When the nano-microspheres form an alloy with the base surface, the thermal diffusion between the component elements is controlled by controlling the point contact between the nano-microspheres and the base surface for a certain temperature and time, and an alloy region with a required depth and diameter is formed.
实施例二纳米线的制备The preparation of embodiment two nanowires
纳米线与基面的点接触的实现方式是，直接在基面上生成纳米线，其间距通过半导体微结构加工方式先在基面上做成具有特定间距的微结构模板，使得生成的纳米线只能占据一些特定的位置，从而控制纳米线沉积位置，可控地制备具有所需间距排列的纳米线。The realization of the point contact between the nanowires and the basal surface is to directly generate the nanowires on the basal surface, and the spacing of the nanowires is first made into a microstructure template with a specific spacing on the basal surface through the semiconductor microstructure processing method, so that the generated nanowires Only some specific positions can be occupied, so as to control the deposition positions of the nanowires, and controllably prepare the nanowires with the desired pitch arrangement.
金属纳米线的制备方法以铜、银、镍等金属纳米线为例。模板为多孔氧化铝薄膜，由上海昊航化工有限公司提供(CAS number：Ultrathin Free-standingPorous Anodic Alumina)，以该模板为工作电极，金属片(铜、银、镍)为对电极，恒电位沉积法制备金属纳米线(铜、银、镍等)。沉积电位-0.4V至4V，沉积时间为10分钟至6分钟。沉积完毕后，用6mol/L的氢氧化钠溶液去除氧化铝模板，得到金属纳微线。通过所选取的多孔模板的孔洞间距来控制纳米线的间距。通过选取的多孔模板的空洞大小来控制纳米线的直径，通过沉积时间的长短来控制纳米线的长度。The preparation method of metal nanowires takes copper, silver, nickel and other metal nanowires as examples. The template is a porous alumina film provided by Shanghai Haohang Chemical Co., Ltd. (CAS number: Ultrathin Free-standing Porous Anodic Alumina). The template is used as the working electrode, and the metal sheet (copper, silver, nickel) is used as the counter electrode. Constant potential deposition Preparation of metal nanowires (copper, silver, nickel, etc.) Deposition potential -0.4V to 4V, deposition time 10 minutes to 6 minutes. After the deposition, the aluminum oxide template was removed with 6 mol/L sodium hydroxide solution to obtain metal nanowires. The spacing of the nanowires is controlled by the hole spacing of the selected porous template. The diameter of the nanowire is controlled by the hole size of the selected porous template, and the length of the nanowire is controlled by the length of the deposition time.
合金的形成可以是通过纳米线与基面的点接触的控制一定的温度和时间来控制组分元素互相之间的热扩散，形成所需深度和直径的合金区域。The alloy can be formed by controlling the thermal diffusion between component elements by controlling the point contact between the nanowire and the base surface for a certain temperature and time, and forming an alloy region with a required depth and diameter.
非金属纳米线的制备方法以ZnO为例，以ZnO纳米颗粒为种子层，通过半导体微加工方式控制颗粒间距，采用CVD方法，O2气氛下通入Zn蒸汽，通过温度与时间控制ZnO纳米线的直径与长度。The preparation method of non-metallic nanowires takes ZnO as an example, uses ZnO nanoparticles as the seed layer, controls the particle distance through semiconductor micromachining, adopts CVD method, passes Zn vapor underO2 atmosphere, and controls ZnO nanowires by temperature and time. diameter and length.
实施例三具有低维材料复合结构的CdTe太阳电池，透明电极区入光面纳微球Example 3 CdTe solar cell with low-dimensional material composite structure, nano-microspheres on the light-incident surface of the transparent electrode region
透明电极区入光面纳微球的制备：采用蒸发自组装法，将实施例一的纳微球的悬浮液涂覆于玻璃的表面，在室温至60摄氏度之间的温度蒸发悬浮液的液体，纳微球在悬浮液的气-液相界面处进行高效组装形成致密的纳微球薄膜，沉积在透明电极区的入光面上。纳微球在基面上的间距通过半导体微结构加工方式先在基面上做成具有特定间距微结构模板，使得纳微球只能占据一些特定的位置，从而控制纳微球沉积位置，可控地制备具有特定间距排列的纳微球薄膜。Preparation of nano-microspheres on the light-incident surface of the transparent electrode area: use the evaporation self-assembly method to coat the suspension of nano-microspheres in Example 1 on the surface of the glass, and evaporate the liquid in the suspension at a temperature between room temperature and 60 degrees Celsius , the nano-microspheres are efficiently assembled at the gas-liquid phase interface of the suspension to form a dense nano-microsphere film, which is deposited on the light incident surface of the transparent electrode region. The spacing of the nanospheres on the basal surface is firstly made into a microstructure template with a specific spacing on the basal surface through semiconductor microstructure processing, so that the nanospheres can only occupy some specific positions, thereby controlling the deposition position of the nanospheres, which can Controlled preparation of nano-microsphere thin films with specific pitch arrangement.
透明导电层制备：采用溅射法制备AZO导电玻璃，玻璃衬底温度为室温，载气为氩气或者氩氢混合气(其中氢气小于10％)，反应气压为0.1Pa，气体流量5sccm(standard cubic centimeter per minute，标准立方厘米/分钟)，功率为50W，靶距为5cm。沉积厚度约为600nm。得到导电玻璃，即透明电极区。Preparation of transparent conductive layer: AZO conductive glass is prepared by sputtering method, the temperature of the glass substrate is room temperature, the carrier gas is argon or argon-hydrogen mixed gas (wherein the hydrogen is less than 10%), the reaction pressure is 0.1Pa, and the gas flow rate is 5 sccm (standard Cubic centimeter per minute, standard cubic centimeter per minute), the power is 50W, and the target distance is 5cm. The deposition thickness is about 600nm. The conductive glass is obtained, that is, the transparent electrode area.
窗口层制备：采用溅射法制备CdS层，导电玻璃衬底温度为室温，反应气压为0.1Pa，功率为100W，靶材为CdS靶，其中N2作为载气，气体流量5sccm。沉积厚度约为100nm。Window layer preparation: The CdS layer was prepared by sputtering, the temperature of the conductive glass substrate was room temperature, the reaction pressure was 0.1Pa, the power was 100W, the target material was a CdS target, andN2 was used as the carrier gas, and the gas flow rate was 5 sccm. The deposition thickness is about 100 nm.
吸光层制备：采用溅射法制备CdTe层，上述衬底温度为300℃，反应气压为0.1Pa，功率为100W，氩气或者氩氧混合气作为载气，气体流量5sccm，靶材为CdTe靶，沉积厚度约为1～7μm。Preparation of light-absorbing layer: The CdTe layer is prepared by sputtering. The temperature of the above substrate is 300°C, the reaction pressure is 0.1Pa, the power is 100W, argon or argon-oxygen mixed gas is used as the carrier gas, the gas flow rate is 5 sccm, and the target material is CdTe target , the deposition thickness is about 1-7 μm.
背电极的制备：采用溅射法制备ZnTe/ZnTe:Cu/Cu复合层，上述衬底温度为300℃，反应气压为0.1Pa，功率为100W，氩气或者氩氧混合气作为载气，气体流量5sccm，靶材为ZnTe靶，ZnTe:Cu靶和Cu靶，沉积厚度分别为20nm，70nm，300nm。Preparation of back electrode: Prepare ZnTe/ZnTe:Cu/Cu composite layer by sputtering method, above substrate temperature is 300°C, reaction pressure is 0.1Pa, power is 100W, argon or argon-oxygen mixed gas is used as carrier gas, gas The flow rate is 5 sccm, the target materials are ZnTe target, ZnTe:Cu target and Cu target, and the deposition thicknesses are 20nm, 70nm and 300nm respectively.
本例分别采用了粒径为50nm、100nm、200nm、300nm、500nm的纳微球进行涂覆，纳微球紧挨致密排列，纳微球间的间距为零。In this example, nano-microspheres with particle sizes of 50nm, 100nm, 200nm, 300nm, and 500nm were used for coating respectively. The nano-microspheres are closely arranged and the distance between the nano-microspheres is zero.
实施例四具有低维材料复合结构的CdTe太阳电池，窗口区入光面纳微球Example 4 CdTe solar cell with low-dimensional material composite structure, nano-microspheres on the light-incident surface in the window area
透明导电层制备：采用LPCVD沉积FTO导电玻璃，衬底温度为400℃，反应气压为3kPa，反应前驱体为Tetramethyltin(TMT)，Bromotrifluoromethane(CBrF3)气体提供F源，同时通入O2和N2，其中N2作为载气。沉积厚度约为500nm。Preparation of transparent conductive layer: LPCVD is used to deposit FTO conductive glass, the substrate temperature is 400°C, the reaction pressure is 3kPa, the reaction precursor is Tetramethyltin (TMT), Bromotrifluoromethane (CBrF3 ) gas provides F source, and simultaneously feeds O2 and N2 , with N2 as the carrier gas. The deposition thickness is about 500nm.
纳微球的制备：将实施例一的纳微球的悬浮液通过旋涂机涂覆于上述透明导电层上，在室温至60摄氏度之间的温度蒸发悬浮液的液体，沉积在透明导电层上。需要指出的是，此处纳微球相当于是与透明电极区的背面点接触，但是，透明电极区紧接着就是窗口区，因此，也可以理解为纳微球是与窗口区的入光面点接触。Preparation of nanospheres: Coat the suspension of nanospheres in Example 1 on the above-mentioned transparent conductive layer by a spin coater, evaporate the suspension liquid at a temperature between room temperature and 60 degrees Celsius, and deposit it on the transparent conductive layer superior. It should be pointed out that here the nanospheres are equivalent to point contact with the back of the transparent electrode area, but the transparent electrode area is followed by the window area, therefore, it can also be understood that the nanospheres are the light incident surface point of the window area touch.
窗口层制备：采用溅射法制备，导电玻璃衬底温度为室温，反应气压为0.1Pa，功率为100W，靶材为CdS靶，其中N2作为载气，气体流量5sccm。沉积厚度约为100nm。Window layer preparation: Prepared by sputtering method, the temperature of the conductive glass substrate is room temperature, the reaction pressure is 0.1Pa, the power is 100W, the target material is CdS target, andN2 is used as the carrier gas, and the gas flow rate is 5 sccm. The deposition thickness is about 100 nm.
吸光层制备：采用溅射法制备，上述衬底温度为300℃，反应气压为0.1Pa，功率为100W，氩气或者氩氧混合气作为载气，气体流量5sccm，靶材为CdTe靶，沉积厚度约为1～7μm。Preparation of light-absorbing layer: prepared by sputtering method, the temperature of the above substrate is 300°C, the reaction pressure is 0.1Pa, the power is 100W, argon or argon-oxygen mixed gas is used as the carrier gas, the gas flow rate is 5 sccm, the target material is CdTe target, and the deposition The thickness is about 1 to 7 μm.
背电极的制备：采用溅射法制备ZnTe/ZnTe:Cu/Cu复合层，上述衬底温度为300℃，反应气压为0.1Pa，功率为100W，氩气或者氩氧混合气作为载气，气体流量5sccm，靶材为ZnTe靶，ZnTe:Cu靶和Cu靶，沉积厚度分别为20nm、70nm、300nm。Preparation of back electrode: Prepare ZnTe/ZnTe:Cu/Cu composite layer by sputtering method, above substrate temperature is 300°C, reaction pressure is 0.1Pa, power is 100W, argon or argon-oxygen mixed gas is used as carrier gas, gas The flow rate is 5 sccm, the target materials are ZnTe target, ZnTe:Cu target and Cu target, and the deposition thicknesses are 20nm, 70nm and 300nm respectively.
本例分别采用了粒径为5nm、10nm、20nm、30nm、50nm的纳微球进行涂覆，纳微球的间距在旋涂过程中随机分布，或者纳微球在基面上的间距通过半导体微结构加工方式先在基面上做成具有特定间距微结构模板，使得纳微球只能占据一些特定的位置，从而控制纳微球沉积位置，可控的制备具有特定间距排列的纳微球薄膜。In this example, nanospheres with a particle size of 5nm, 10nm, 20nm, 30nm, and 50nm were used for coating. The spacing of the nanospheres is randomly distributed during the spin coating process, or the spacing of the nanospheres on the base surface is passed through the semiconductor. The microstructure processing method first makes a microstructure template with a specific spacing on the base surface, so that the nanospheres can only occupy some specific positions, so as to control the deposition position of the nanospheres, and controllably prepare nanospheres with a specific spacing arrangement film.
实施例五具有低维材料复合结构的CdTe太阳电池，吸光层入光面纳微球Embodiment 5 CdTe solar cell with low-dimensional material composite structure, nano-microspheres on the light-incident surface of the light-absorbing layer
透明导电层制备：采用LPCVD沉积FTO导电玻璃，衬底温度为400℃，反应气压为3kPa，反应前驱体为Tetramethyltin(TMT)，Bromotrifluoromethane(CBrF3)气体提供F源，同时通入O2和N2，其中N2作为载气。沉积厚度约为500nm。Preparation of transparent conductive layer: LPCVD is used to deposit FTO conductive glass, the substrate temperature is 400°C, the reaction pressure is 3kPa, the reaction precursor is Tetramethyltin (TMT), Bromotrifluoromethane (CBrF3 ) gas provides F source, and simultaneously feeds O2 and N2 , with N2 as the carrier gas. The deposition thickness is about 500nm.
窗口层制备：采用化学水浴法制备CdS层，反应物为醋酸铵、醋酸镉、氨水以及硫脲。首先将密封容器中加入去离子水，加热至80℃，加入醋酸镉、醋酸铵、氨水，沉积厚度约为100nm。Preparation of the window layer: The CdS layer was prepared by the chemical water bath method, and the reactants were ammonium acetate, cadmium acetate, ammonia water and thiourea. First, add deionized water into a sealed container, heat it to 80°C, add cadmium acetate, ammonium acetate, and ammonia water, and deposit a thickness of about 100nm.
纳微球的制备：将实施例一的纳微球的悬浮液通过旋涂机涂覆于窗口区背面，在室温至60摄氏度之间的温度蒸发悬浮液的液体，沉积在窗口区上。需要指出的是，此处纳微球相当于是与窗口区的背面点接触，但是，窗口区紧接着就是吸收区，因此，也可以理解为纳微球是与吸收区的入光面点接触。Preparation of nanospheres: The suspension of nanospheres in Example 1 is coated on the back of the window area by a spin coater, and the liquid in the suspension is evaporated at a temperature between room temperature and 60 degrees Celsius, and deposited on the window area. It should be pointed out that here the nanospheres are in point contact with the back of the window area, but the window area is immediately followed by the absorption area, therefore, it can also be understood that the nanospheres are in point contact with the light incident surface of the absorption area.
吸光层制备：近真空升华法制备CdTe薄膜，衬底温度为500℃，氩气或者氩氧混合气作为载气，反应气压1kPa，蒸发源为CdTe，沉积厚度约为7μm。Preparation of light-absorbing layer: CdTe film was prepared by near-vacuum sublimation method, the substrate temperature was 500°C, argon or argon-oxygen mixed gas was used as carrier gas, the reaction pressure was 1kPa, the evaporation source was CdTe, and the deposition thickness was about 7μm.
背电极的制备：采用溅射法制备ZnTe/ZnTe:Cu/Cu复合层，上述衬底温度为300℃，反应气压为0.1Pa，功率为100W，氩气或者氩氧混合气作为载气，气体流量5sccm，靶材为ZnTe靶，ZnTe:Cu靶和Cu靶，沉积厚度分别为20nm、70nm、300nm。Preparation of back electrode: Prepare ZnTe/ZnTe:Cu/Cu composite layer by sputtering method, above substrate temperature is 300°C, reaction pressure is 0.1Pa, power is 100W, argon or argon-oxygen mixed gas is used as carrier gas, gas The flow rate is 5 sccm, the target materials are ZnTe target, ZnTe:Cu target and Cu target, and the deposition thicknesses are 20nm, 70nm and 300nm respectively.
本例分别采用了粒径为5nm、10nm、20nm、30nm、50nm的纳微球进行涂覆，纳微球的间距在旋涂过程随机分布，或者纳微球在基面上的间距通过半导体微结构加工方式先在基面上做成具有特定间距微结构模板，使得纳微球只能占据一些特定的位置，从而控制纳微球沉积位置，可控地制备具有特定间距排列的纳微球薄膜。In this example, nanospheres with particle sizes of 5nm, 10nm, 20nm, 30nm, and 50nm were used for coating, and the distance between nanospheres was randomly distributed during the spin coating process, or the distance between nanospheres on the base The structure processing method first makes a microstructure template with a specific spacing on the base surface, so that the nano-microspheres can only occupy some specific positions, thereby controlling the deposition position of the nano-microspheres, and controllably preparing a nano-microsphere film with a specific spacing arrangement .
实施例六具有低维材料复合结构的CdTe太阳电池，吸光层背面纳微球Example 6 CdTe solar cell with low-dimensional material composite structure, nano-microspheres on the back of the light-absorbing layer
透明导电层制备：采用LPCVD沉积FTO导电玻璃，衬底温度为400℃，反应气压为3kPa，反应前驱体为Tetramethyltin(TMT)，Bromotrifluoromethane(CBrF3)气体提供F源，同时通入O2和N2，其中N2作为载气。沉积厚度约为500nm。Preparation of transparent conductive layer: LPCVD is used to deposit FTO conductive glass, the substrate temperature is 400°C, the reaction pressure is 3kPa, the reaction precursor is Tetramethyltin (TMT), Bromotrifluoromethane (CBrF3 ) gas provides F source, and simultaneously feeds O2 and N2 , with N2 as the carrier gas. The deposition thickness is about 500nm.
窗口层制备：采用化学水浴法制备CdS层，反应物为醋酸铵、醋酸镉、氨水以及硫脲。首先将密封容器中加入去离子水，加热至80℃，加入醋酸镉、醋酸铵、氨水，沉积厚度约为100nm。Preparation of the window layer: The CdS layer was prepared by the chemical water bath method, and the reactants were ammonium acetate, cadmium acetate, ammonia water and thiourea. First, add deionized water into a sealed container, heat it to 80°C, add cadmium acetate, ammonium acetate, and ammonia water, and deposit a thickness of about 100nm.
吸光层制备：近真空升华法制备CdTe薄膜，衬底温度为500℃，氩气或者氩氧混合气作为载气，反应气压1kPa，蒸发源为CdTe，沉积厚度约为7μm。Preparation of light-absorbing layer: CdTe film was prepared by near-vacuum sublimation method, the substrate temperature was 500°C, argon or argon-oxygen mixed gas was used as carrier gas, the reaction pressure was 1kPa, the evaporation source was CdTe, and the deposition thickness was about 7μm.
吸光层背面纳微球的制备：采用蒸发自组装法，将实施例一的纳微球的悬浮液涂覆于吸光层上，在室温至60摄氏度之间的温度蒸发悬浮液的液体，纳微球在悬浮液的气-液相界面处进行高效组装形成致密的纳微球薄膜，沉积在吸光层上。Preparation of nano-microspheres on the back of the light-absorbing layer: use the evaporation self-assembly method to coat the suspension of nano-microspheres in Example 1 on the light-absorbing layer, evaporate the suspension liquid at a temperature between room temperature and 60 degrees Celsius, and the nano-microspheres The spheres are efficiently assembled at the gas-liquid phase interface of the suspension to form a dense nanosphere film, which is deposited on the light-absorbing layer.
背电极的制备：采用溅射法制备ZnTe/ZnTe:Cu复合层，上述衬底温度为300℃，反应气压为0.1Pa，功率为100W，氩气或者氩氧混合气作为载气，气体流量5sccm，靶材为ZnTe靶，ZnTe:Cu靶，沉积厚度分别为20nm和70nm。采用印刷法在背面印刷石墨浆，200℃空气中退火30分钟，厚度约为10μmPreparation of the back electrode: Prepare the ZnTe/ZnTe:Cu composite layer by sputtering, the temperature of the above substrate is 300°C, the reaction pressure is 0.1Pa, the power is 100W, argon or argon-oxygen mixed gas is used as the carrier gas, and the gas flow rate is 5 sccm , the target material is ZnTe target, ZnTe: Cu target, the deposition thickness is 20nm and 70nm respectively. Graphite paste is printed on the back by printing method, annealed in air at 200°C for 30 minutes, and the thickness is about 10 μm
本例分别采用了纳微球粒径为50nm、100nm、200nm、300nm、500nm的纳微球进行涂覆，纳微球紧挨致密排列，纳微球间的间距可以为零，也可以随机分布，也可以纳微球在基面上的间距可以通过半导体微结构加工方式先在基面上做成具有特定间距微结构模板，使得纳微球只能占据一些特定的位置，从而控制纳微球沉积位置，可控地制备具有特定间距排列的纳微球薄膜。In this example, nanospheres with diameters of 50nm, 100nm, 200nm, 300nm, and 500nm were used for coating. The nanospheres are closely arranged, and the distance between the nanospheres can be zero or randomly distributed. , it is also possible that the spacing of the nanospheres on the basal surface can be made into a microstructure template with a specific spacing on the basal surface through semiconductor microstructure processing, so that the nanospheres can only occupy some specific positions, thereby controlling the size of the nanospheres. Deposition position, controllable preparation of nano-microsphere films with specific pitch arrangement.
实施例七具有低维材料复合结构的CdTe太阳电池，透明电极入光面纳微球，吸光层背面纳米线Example 7 CdTe solar cell with low-dimensional material composite structure, nanospheres on the light-incident surface of the transparent electrode, and nanowires on the back of the light-absorbing layer
透明导电层制备：采用Sputter沉积NTO导电玻璃，衬底温度为200℃，载气为氩气或者氩氢混合气(其中氢气小于10％)，反应气压为0.1Pa，气体流量5sccm，功率为50W，靶距为5cm。沉积厚度约为600nm。得到导电玻璃。Preparation of transparent conductive layer: use Sputter to deposit NTO conductive glass, the substrate temperature is 200°C, the carrier gas is argon or argon-hydrogen mixed gas (where the hydrogen is less than 10%), the reaction pressure is 0.1Pa, the gas flow rate is 5 sccm, and the power is 50W , the target distance is 5cm. The deposition thickness is about 600nm. Get conductive glass.
透明电极区入光面纳微球的制备：采用蒸发自组装法，将实施例一的纳微球的悬浮液涂覆于透明电极区的入光面，在室温至60摄氏度之间的温度蒸发悬浮液的液体，纳微球在悬浮液的气-液相界面处进行高效组装形成致密的纳微球薄膜，沉积在透明电极区入光面上。Preparation of nano-microspheres on the light-incident surface of the transparent electrode area: using the evaporation self-assembly method, coating the suspension of nano-microspheres in Example 1 on the light-incident surface of the transparent electrode area, and evaporating at a temperature between room temperature and 60 degrees Celsius The liquid in the suspension, the nano-microspheres are efficiently assembled at the gas-liquid phase interface of the suspension to form a dense nano-microsphere film, which is deposited on the light incident surface of the transparent electrode area.
窗口层制备：采用化学水浴法制备CdS层，反应物为醋酸铵、醋酸镉、氨水以及硫脲。首先将密封容器中加入去离子水，加热至80℃，加入醋酸镉、醋酸铵、氨水，沉积厚度约为100nm。Preparation of the window layer: The CdS layer was prepared by the chemical water bath method, and the reactants were ammonium acetate, cadmium acetate, ammonia water and thiourea. First, add deionized water into a sealed container, heat it to 80°C, add cadmium acetate, ammonium acetate, and ammonia water, and deposit a thickness of about 100nm.
吸光层制备：近真空升华法制备CdTe薄膜，衬底温度为500℃，氩气或者氩氧混合气作为载气，反应气压1kPa，蒸发源为CdTe，沉积厚度约为7μm。Preparation of light-absorbing layer: CdTe film was prepared by near-vacuum sublimation method, the substrate temperature was 500°C, argon or argon-oxygen mixed gas was used as carrier gas, the reaction pressure was 1kPa, the evaporation source was CdTe, and the deposition thickness was about 7μm.
吸光区背面纳米线的制备：在基面上的间距通过半导体微结构加工方式先在基面上做成具有特定间距微结构模板，使得引导纳米线合成和生长只能占据一些特定的位置，从而控制纳米线沉积位置，可控地制备具有特定间距排列的纳米线。具体的，采用模板法电化学沉积铜，银，镍等金属纳米线。上述模板为多孔氧化铝，以该模板为工作电极，金属片(铜、银、镍)为对电极，恒电位沉积法制备金属纳米线(铜、银、镍等)。沉积电位-0.4V至4V，沉积时间为10分钟至6分钟。沉积完毕后，用6mol/L的氢氧化钠溶液去除氧化铝模板，得到金属纳米线。Preparation of nanowires on the back of the light-absorbing region: the spacing on the basal surface is firstly made into a microstructure template with a specific spacing on the basal surface through semiconductor microstructure processing, so that the guided nanowire synthesis and growth can only occupy some specific positions, so that By controlling the deposition position of the nanowires, the nanowires with a specific pitch arrangement can be controllably prepared. Specifically, copper, silver, nickel and other metal nanowires are electrochemically deposited using a template method. The template above is porous alumina, the template is used as the working electrode, and the metal sheet (copper, silver, nickel) is used as the counter electrode, and the metal nanowire (copper, silver, nickel, etc.) is prepared by the constant potential deposition method. Deposition potential -0.4V to 4V, deposition time 10 minutes to 6 minutes. After the deposition, the aluminum oxide template was removed with 6 mol/L sodium hydroxide solution to obtain metal nanowires.
背电极的制备：采用溅射法制备ZnTe/ZnTe:Cu/Cu复合层，上述衬底温度为300℃，反应气压为0.1Pa，功率为100W，氩气或者氩氧混合气作为载气，气体流量5sccm，靶材为ZnTe靶，ZnTe:Cu靶和Cu靶，沉积厚度分别为20nm、70nm、300nm。Preparation of back electrode: Prepare ZnTe/ZnTe:Cu/Cu composite layer by sputtering method, above substrate temperature is 300°C, reaction pressure is 0.1Pa, power is 100W, argon or argon-oxygen mixed gas is used as carrier gas, gas The flow rate is 5 sccm, the target materials are ZnTe target, ZnTe:Cu target and Cu target, and the deposition thicknesses are 20nm, 70nm and 300nm respectively.
本例分别采用了纳微球粒径为50nm、100nm、200nm、300nm、500nm的纳微球进行涂覆，纳微球紧挨致密排列，纳微球间的间距可以为零，也可以随机分布，也可以纳微球在基面上的间距可以通过半导体微结构加工方式先在基面上做成具有特定间距微结构模板，使得纳微球只能占据一些特定的位置，从而控制纳微球沉积位置，可控地制备具有特定间距排列的纳微球薄膜。吸光区背面纳米线的直径为5nm-500nm，长度为50nm-5mm，纳米线之间的间距为10nm-100μm。In this example, nanospheres with diameters of 50nm, 100nm, 200nm, 300nm, and 500nm were used for coating. The nanospheres are closely arranged, and the distance between the nanospheres can be zero or randomly distributed. , it is also possible that the spacing of the nanospheres on the basal surface can be made into a microstructure template with a specific spacing on the basal surface through semiconductor microstructure processing, so that the nanospheres can only occupy some specific positions, thereby controlling the size of the nanospheres. Deposition position, controllable preparation of nano-microsphere films with specific pitch arrangement. The diameter of the nanowires on the back of the light absorption area is 5nm-500nm, the length is 50nm-5mm, and the distance between the nanowires is 10nm-100μm.
实施例八具有低维材料复合结构的CdTe太阳电池，窗口区入光面纳微球，吸光区背面纳米线Example 8: A CdTe solar cell with a low-dimensional material composite structure, nanospheres on the light-incident side of the window area, and nanowires on the back of the light-absorbing area
透明导电层制备：采用LPCVD在聚酰亚胺(PI)衬底上沉积FTO导电玻璃，衬底温度为400℃，反应气压为3kPa，反应前驱体为Tetramethyltin(TMT)，Bromotrifluoromethane(CBrF3)气体提供F源，同时通入O2和N2，其中N2作为载气。沉积厚度约为500nm。Preparation of transparent conductive layer: Deposit FTO conductive glass on polyimide (PI) substrate by LPCVD, the substrate temperature is 400°C, the reaction pressure is 3kPa, the reaction precursor is Tetramethyltin (TMT), Bromotrifluoromethane (CBrF3 ) gas F source is provided, and O2 and N2 are introduced at the same time, wherein N2 is used as the carrier gas. The deposition thickness is about 500nm.
纳微球的制备：将实施例一的纳微球的悬浮液通过旋涂机涂覆于透明电极区的背面，在室温至60摄氏度之间的温度蒸发悬浮液的液体，沉积在透明电极区上。需要指出的是，此处纳微球相当于是与透明电极区的背面点接触，但是，透明电极区紧接着就是窗口区，因此，也可以理解为纳微球是与窗口区的入光面点接触。Preparation of nanospheres: Coat the suspension of nanospheres in Example 1 on the back of the transparent electrode area by a spin coater, evaporate the liquid in the suspension at a temperature between room temperature and 60 degrees Celsius, and deposit it on the transparent electrode area superior. It should be pointed out that here the nanospheres are equivalent to point contact with the back of the transparent electrode area, but the transparent electrode area is followed by the window area, therefore, it can also be understood that the nanospheres are the light incident surface point of the window area touch.
窗口层制备：采用化学水浴法制备CdS层，反应物为醋酸铵、醋酸镉、氨水以及硫脲。首先将密封容器中加入去离子水，加热至80℃，加入醋酸镉、醋酸铵、氨水，沉积厚度约为100nm。Preparation of the window layer: The CdS layer was prepared by the chemical water bath method, and the reactants were ammonium acetate, cadmium acetate, ammonia water and thiourea. First, add deionized water into a sealed container, heat it to 80°C, add cadmium acetate, ammonium acetate, and ammonia water, and deposit a thickness of about 100nm.
吸光层制备：近真空升华法制备CdTe薄膜，衬底温度为500℃，氩气或者氩氧混合气作为载气，反应气压1kPa，蒸发源为CdTe，沉积厚度约为7μm。Preparation of light-absorbing layer: CdTe film was prepared by near-vacuum sublimation method, the substrate temperature was 500°C, argon or argon-oxygen mixed gas was used as carrier gas, the reaction pressure was 1kPa, the evaporation source was CdTe, and the deposition thickness was about 7μm.
吸光区背面纳微线的制备：采用模板法电化学沉积铜，银，镍等金属纳米线。上述模板为多孔氧化铝，以该模板为工作电极，金属片(铜、银、镍)为对电极，恒电位沉积法制备金属纳米线(铜、银、镍等)。沉积电位-0.4V至4V，沉积时间为10分钟至6分钟。沉积完毕后，用6mol/L的氢氧化钠溶液去除氧化铝模板，得到金属纳米线。Preparation of nanowires on the back of the light-absorbing region: use template method to electrochemically deposit copper, silver, nickel and other metal nanowires. The template above is porous alumina, the template is used as the working electrode, and the metal sheet (copper, silver, nickel) is used as the counter electrode, and the metal nanowire (copper, silver, nickel, etc.) is prepared by the constant potential deposition method. Deposition potential -0.4V to 4V, deposition time 10 minutes to 6 minutes. After the deposition, the aluminum oxide template was removed with 6 mol/L sodium hydroxide solution to obtain metal nanowires.
背电极的制备：采用溅射法制备ZnTe/ZnTe:Cu/Cu复合层，上述衬底温度为300℃，反应气压为0.1Pa，功率为100W，氩气或者氩氧混合气作为载气，气体流量5sccm，靶材为ZnTe靶，ZnTe:Cu靶和Cu靶，沉积厚度分别为20nm，70nm，300nm。Preparation of back electrode: Prepare ZnTe/ZnTe:Cu/Cu composite layer by sputtering method, above substrate temperature is 300°C, reaction pressure is 0.1Pa, power is 100W, argon or argon-oxygen mixed gas is used as carrier gas, gas The flow rate is 5 sccm, the target materials are ZnTe target, ZnTe:Cu target and Cu target, and the deposition thicknesses are 20nm, 70nm and 300nm respectively.
窗口区入光面纳微球的采用了粒径为5nm、10nm、20nm、30nm、50nm的纳微球进行涂覆，在基面上的间距可以通过半导体微结构加工方式先在基面上做成具有特定间距微结构模板，使得引导纳微球合成和生长只能占据一些特定的位置，从而控制纳微球沉积位置，可控地制备具有特定间距排列的纳微球。纳微球的间距在旋涂过程中随机分布可以为零，也可以随机分布，也可以纳微球在基面上的间距可以通过半导体微结构加工方式先在基面上做成具有特定间距微结构模板，使得纳微球只能占据一些特定的位置，从而控制纳微球沉积位置，可控地制备具有特定间距排列的纳微球薄膜。吸光区背面纳米线的直径为5nm-500nm，长度为50nm-5mm，纳米线之间的间距为10nm-100μm。The nano-microspheres on the light-incident surface of the window area are coated with nano-microspheres with particle sizes of 5nm, 10nm, 20nm, 30nm, and 50nm. The spacing on the base surface can be made on the base surface by semiconductor microstructure processing. A microstructure template with a specific pitch is formed, so that the synthesis and growth of the guided nano-microspheres can only occupy some specific positions, thereby controlling the deposition position of the nano-microspheres, and controllably preparing nano-microspheres with a specific pitch arrangement. The spacing of the nano-microspheres can be randomly distributed during the spin coating process. It can also be randomly distributed, or the spacing of the nano-microspheres on the basal surface can be made on the basal surface by semiconductor microstructure processing. The structural template allows the nanospheres to occupy only some specific positions, thereby controlling the deposition position of the nanospheres, and controllably preparing a nanosphere film with a specific pitch arrangement. The diameter of the nanowires on the back of the light absorption area is 5nm-500nm, the length is 50nm-5mm, and the distance between the nanowires is 10nm-100μm.
实施例九具有低维材料复合结构的CdTe太阳电池，吸光层入光面纳微球，背面纳米线Example 9 A CdTe solar cell with a low-dimensional material composite structure, nanospheres on the light-incident surface of the light-absorbing layer, and nanowires on the back
透明导电层制备：采用LPCVD沉积FTO导电玻璃，衬底温度为400℃，反应气压为3kPa，反应前驱体为Tetramethyltin(TMT)，Bromotrifluoromethane(CBrF3)气体提供F源，同时通入O2和N2，其中N2作为载气。沉积厚度约为500nm。Preparation of transparent conductive layer: LPCVD is used to deposit FTO conductive glass, the substrate temperature is 400°C, the reaction pressure is 3kPa, the reaction precursor is Tetramethyltin (TMT), Bromotrifluoromethane (CBrF3 ) gas provides F source, and simultaneously feeds O2 and N2 , with N2 as the carrier gas. The deposition thickness is about 500nm.
透明缓冲层的制备：采用溅射法制备SnO2层，玻璃衬底温度为室温，载气为氩气或者氩氢混合气(其中氢气小于10％)，反应气压为0.1Pa，气体流量5sccm，功率为50W，靶距为7cm。沉积厚度约为200nm。Preparation of transparent buffer layer:SnO2 layer is prepared by sputtering method, the glass substrate temperature is room temperature, the carrier gas is argon or argon-hydrogen mixed gas (wherein the hydrogen is less than 10%), the reaction pressure is 0.1Pa, the gas flow rate is 5sccm, The power is 50W, and the target distance is 7cm. The deposition thickness is about 200nm.
窗口层制备：采用溅射法制备CdS层，导电玻璃衬底温度为室温，反应气压为0.1Pa，功率为100W，靶材为CdS靶，其中N2作为载气，气体流量5sccm。沉积厚度约为70nm。Window layer preparation: The CdS layer was prepared by sputtering, the temperature of the conductive glass substrate was room temperature, the reaction pressure was 0.1Pa, the power was 100W, the target material was a CdS target, andN2 was used as the carrier gas, and the gas flow rate was 5 sccm. The deposition thickness is about 70nm.
纳微球的制备：将实施例一的纳微球的悬浮液通过旋涂机涂覆于窗口区背面，在室温至60摄氏度之间的温度蒸发悬浮液的液体，沉积在窗口区上。需要指出的是，此处纳微球相当于是与窗口区的背面点接触，但是，窗口区紧接着就是吸收区，因此，也可以理解为纳微球是与吸收区的入光面点接触。Preparation of nanospheres: The suspension of nanospheres in Example 1 is coated on the back of the window area by a spin coater, and the liquid in the suspension is evaporated at a temperature between room temperature and 60 degrees Celsius, and deposited on the window area. It should be pointed out that here the nanospheres are in point contact with the back of the window area, but the window area is immediately followed by the absorption area, therefore, it can also be understood that the nanospheres are in point contact with the light incident surface of the absorption area.
吸光层制备：采用溅射法制备，上述衬底温度为300℃，反应气压为0.1Pa，功率为100W，氩气或者氩氧混合气作为载气，气体流量5sccm，靶材为CdTe靶，沉积厚度约为5～7μm。Preparation of light-absorbing layer: prepared by sputtering method, the temperature of the above substrate is 300°C, the reaction pressure is 0.1Pa, the power is 100W, argon or argon-oxygen mixed gas is used as the carrier gas, the gas flow rate is 5 sccm, the target material is CdTe target, and the deposition The thickness is about 5-7 μm.
吸光区背面纳微线的制备：采用模板法电化学沉积铜，银，镍等金属纳米线。上述模板为多孔氧化铝，以该模板为工作电极，金属片(铜、银、镍)为对电极，恒电位沉积法制备金属纳微线(铜、银、镍等)。沉积电位-0.4V至4V，沉积时间为10分钟至6分钟。沉积完毕后，用6mol/L的氢氧化钠溶液去除氧化铝模板，得到金属纳微线。Preparation of nanowires on the back of the light-absorbing region: use template method to electrochemically deposit copper, silver, nickel and other metal nanowires. The above-mentioned template is porous alumina, and the template is used as a working electrode, and a metal sheet (copper, silver, nickel) is used as a counter electrode, and a metal nanowire (copper, silver, nickel, etc.) is prepared by a constant potential deposition method. Deposition potential -0.4V to 4V, deposition time 10 minutes to 6 minutes. After the deposition, the aluminum oxide template was removed with 6 mol/L sodium hydroxide solution to obtain metal nanowires.
背电极的制备：采用溅射法制备ZnTe/ZnTe:Cu/Cu复合层，上述衬底温度为300℃，反应气压为0.1Pa，功率为100W，氩气或者氩氧混合气作为载气，气体流量5sccm，靶材为ZnTe靶，ZnTe:Cu靶和Cu靶，沉积厚度分别为20nm、70nm、300nm。Preparation of back electrode: Prepare ZnTe/ZnTe:Cu/Cu composite layer by sputtering method, above substrate temperature is 300°C, reaction pressure is 0.1Pa, power is 100W, argon or argon-oxygen mixed gas is used as carrier gas, gas The flow rate is 5 sccm, the target materials are ZnTe target, ZnTe:Cu target and Cu target, and the deposition thicknesses are 20nm, 70nm and 300nm respectively.
窗口区入光面纳微球的采用了粒径为5nm、10nm、20nm、30nm、50nm的纳微球进行涂覆，纳微球的间距在旋涂过程中可以为零，也可以随机分布，也可以纳微球在基面上的间距可以通过半导体微结构加工方式先在基面上做成具有特定间距微结构模板，使得纳微球只能占据一些特定的位置，从而控制纳微球沉积位置，可控地制备具有特定间距排列的纳微球薄膜。吸光区背面纳米线的直径为5nm-500nm，长度为50nm-5mm，纳米线之间的间距为10nm-100μm。The nano-microspheres on the light-incident surface of the window area are coated with nano-microspheres with a particle size of 5nm, 10nm, 20nm, 30nm, and 50nm. The spacing of the nano-microspheres can be zero or randomly distributed during the spin coating process. It is also possible that the spacing of nanospheres on the basal surface can be made into a microstructure template with a specific spacing on the basal surface through semiconductor microstructure processing, so that the nanospheres can only occupy some specific positions, thereby controlling the deposition of nanospheres Position, controllable preparation of nano-microsphere films with specific pitch arrangement. The diameter of the nanowires on the back of the light absorption area is 5nm-500nm, the length is 50nm-5mm, and the distance between the nanowires is 10nm-100μm.
实施例十具有低维材料复合结构的CIGS太阳电池，透明电极入光面纳微球Example 10 A CIGS solar cell with a low-dimensional material composite structure, and nano-microspheres on the light-incident surface of the transparent electrode
导电层制备：采用溅射法在玻璃衬底上制备Mo层作为电极，玻璃衬底温度为室温，载气为氩气或者氩氢混合气(其中氢气小于10％)，反应气压为0.1Pa，气体流量5sccm，功率为100W，靶距为5cm。沉积厚度约为600nm。得到Mo电极。Conductive layer preparation: Sputtering is used to prepare a Mo layer on a glass substrate as an electrode. The temperature of the glass substrate is room temperature, the carrier gas is argon or argon-hydrogen mixed gas (wherein the hydrogen is less than 10%), and the reaction pressure is 0.1Pa. The gas flow rate is 5 sccm, the power is 100W, and the target distance is 5cm. The deposition thickness is about 600nm. Obtain Mo electrode.
吸光层制备：采用溅射法在衬底上制备CIGS层，衬底温度为200℃，载气为氩气或者氩氢混合气(其中氢气小于10％)，反应气压为0.1Pa，气体流量5sccm，功率为100W，靶距为5cm。沉积厚度约为1.5μm。得到CIGS吸光层。Preparation of light-absorbing layer: CIGS layer is prepared on the substrate by sputtering method, the substrate temperature is 200°C, the carrier gas is argon or argon-hydrogen mixed gas (where the hydrogen is less than 10%), the reaction pressure is 0.1Pa, and the gas flow rate is 5 sccm , the power is 100W, and the target distance is 5cm. The deposition thickness is about 1.5 μm. Obtain CIGS light absorbing layer.
硒化：惰性气体气氛下，以硒金属为硒源，500℃下退火30min。Selenization: Under an inert gas atmosphere, use selenium metal as the selenium source, and anneal at 500°C for 30min.
窗口层制备：采用化学水浴法制备CdS层，反应物为醋酸铵、醋酸镉、氨水以及硫脲。首先将密封容器中加入去离子水，加热至60℃，加入醋酸镉、醋酸铵、氨水，沉积厚度约为70nm。Preparation of the window layer: The CdS layer was prepared by the chemical water bath method, and the reactants were ammonium acetate, cadmium acetate, ammonia water and thiourea. First, add deionized water into a sealed container, heat it to 60°C, add cadmium acetate, ammonium acetate, and ammonia water, and deposit a thickness of about 70nm.
透明缓冲层的制备：采用溅射法制备ZnO层，玻璃衬底温度为室温，载气为氩气或者氩氢混合气(其中氢气小于10％)，反应气压为0.1Pa，气体流量5sccm，功率为50W，靶距为7cm。沉积厚度约为50nm。Preparation of the transparent buffer layer: the ZnO layer is prepared by sputtering, the temperature of the glass substrate is room temperature, the carrier gas is argon or argon-hydrogen mixed gas (wherein the hydrogen is less than 10%), the reaction pressure is 0.1Pa, the gas flow rate is 5 sccm, and the power It is 50W, and the target distance is 7cm. The deposition thickness is about 50nm.
透明电极的制备：采用溅射法制备AZO层，玻璃衬底温度为室温，载气为氩气或者氩氢混合气(其中氢气小于10％)，反应气压为0.1Pa，气体流量5sccm，功率为100W，靶距为5cm。沉积厚度约为500nm。Preparation of transparent electrode: AZO layer was prepared by sputtering method, the temperature of the glass substrate was room temperature, the carrier gas was argon or argon-hydrogen mixed gas (wherein the hydrogen was less than 10%), the reaction pressure was 0.1Pa, the gas flow rate was 5 sccm, and the power was 100W, the target distance is 5cm. The deposition thickness is about 500nm.
透明电极入光面纳微球的制备：采用蒸发自组装法，将实施例一的纳微球的悬浮液涂覆于透明电极区的入光面，在室温至60摄氏度之间的温度蒸发悬浮液的液体，纳微球在悬浮液的气-液相界面处进行高效组装形成致密的纳微球薄膜，沉积在透明电极区的入光面上。Preparation of nano-microspheres on the light-incident surface of the transparent electrode: apply the suspension of nano-microspheres in Example 1 on the light-incident surface of the transparent electrode area by evaporative self-assembly method, and evaporate and suspend at a temperature between room temperature and 60 degrees Celsius The nano-microspheres are efficiently assembled at the gas-liquid phase interface of the suspension to form a dense nano-microsphere film, which is deposited on the light incident surface of the transparent electrode area.
本例分别采用了粒径为50nm、100nm、200nm、300nm、500nm的纳微球进行涂覆，纳微球紧挨致密排列，纳微球间的间距可以为零，也可以随机分布，也可以纳微球在基面上的间距可以通过半导体微结构加工方式先在基面上做成具有特定间距微结构模板，使得纳微球只能占据一些特定的位置，从而控制纳微球沉积位置，可控地制备具有特定间距排列的纳微球薄膜。In this example, nanospheres with particle sizes of 50nm, 100nm, 200nm, 300nm, and 500nm were used for coating. The spacing of the nanospheres on the base surface can be made into a microstructure template with a specific spacing on the base surface through semiconductor microstructure processing, so that the nanospheres can only occupy some specific positions, thereby controlling the deposition position of the nanospheres. Controllable preparation of nano-microsphere films with specific pitch arrangement.
实施例十一具有低维材料复合结构的CIGS太阳电池，窗口区入光面纳微球Example 11 CIGS solar cell with low-dimensional material composite structure, nano-microspheres on the light-incident surface of the window area
导电层制备：采用溅射法在玻璃衬底上制备Mo层作为电极，玻璃衬底温度为室温，载气为氩气或者氩氢混合气(其中氢气小于10％)，反应气压为0.1Pa，气体流量5sccm，功率为100W，靶距为5cm。沉积厚度约为600nm。得到Mo电极。Conductive layer preparation: Sputtering is used to prepare a Mo layer on a glass substrate as an electrode. The temperature of the glass substrate is room temperature, the carrier gas is argon or argon-hydrogen mixed gas (wherein the hydrogen is less than 10%), and the reaction pressure is 0.1Pa. The gas flow rate is 5 sccm, the power is 100W, and the target distance is 5cm. The deposition thickness is about 600nm. Obtain Mo electrode.
吸光层制备：采用共蒸法在衬底上制备CIGS层，衬底温度为200℃，载气为氩气或者氩氢混合气(其中氢气小于10％)，反应气压为0.1Pa，气体流量5sccm，工作距离为5cm。沉积厚度约为1.5μm。得到CIGS吸光层。Preparation of light-absorbing layer: Co-evaporation method is used to prepare CIGS layer on the substrate, the substrate temperature is 200°C, the carrier gas is argon or argon-hydrogen mixed gas (where the hydrogen is less than 10%), the reaction pressure is 0.1Pa, and the gas flow rate is 5 sccm , the working distance is 5cm. The deposition thickness is about 1.5 μm. Obtain CIGS light absorbing layer.
窗口层制备：采用化学水浴法制备CdS层，反应物为醋酸铵、醋酸镉、氨水以及硫脲。首先将密封容器中加入去离子水，加热至60℃，加入醋酸镉、醋酸铵、氨水，沉积厚度约为70nm。Preparation of the window layer: The CdS layer was prepared by the chemical water bath method, and the reactants were ammonium acetate, cadmium acetate, ammonia water and thiourea. First, add deionized water into a sealed container, heat it to 60°C, add cadmium acetate, ammonium acetate, and ammonia water, and deposit a thickness of about 70nm.
窗口区入光面纳微球的制备：将实施例一的纳微球的悬浮液通过旋涂机涂覆于透明电极区的入光面，在室温至60摄氏度之间的温度蒸发悬浮液的液体，沉积在窗口区的入光面上。Preparation of nano-microspheres on the light-incident surface of the window area: the suspension of nano-microspheres in Example 1 is coated on the light-incident surface of the transparent electrode area by a spin coater, and the suspension is evaporated at a temperature between room temperature and 60 degrees Celsius. Liquid, deposited on the light incident surface of the window area.
本例分别采用了粒径为5nm、10nm、20nm、30nm、50nm的纳微球进行涂覆，纳微球的间距在旋涂过程中可以为零，也可以随机分布，也可以纳微球在基面上的间距可以通过半导体微结构加工方式先在基面上做成具有特定间距微结构模板，使得纳微球只能占据一些特定的位置，从而控制纳微球沉积位置，可控地制备具有特定间距排列的纳微球薄膜。In this example, nanospheres with particle sizes of 5nm, 10nm, 20nm, 30nm, and 50nm were used for coating. The distance between the nanospheres can be zero or randomly distributed during the spin coating process. The spacing on the basal surface can be made into a microstructure template with a specific spacing on the basal surface through semiconductor microstructure processing, so that the nanospheres can only occupy some specific positions, so as to control the deposition position of the nanospheres and controllable preparation Thin films of nanospheres arranged at specific pitches.
透明缓冲层的制备：采用溅射法制备ZnO层，玻璃衬底温度为室温，载气为氩气或者氩氢混合气(其中氢气小于10％)，反应气压为0.1Pa，气体流量5sccm，功率为50W，靶距为7cm。沉积厚度约为50nm。Preparation of the transparent buffer layer: the ZnO layer is prepared by sputtering, the temperature of the glass substrate is room temperature, the carrier gas is argon or argon-hydrogen mixed gas (wherein the hydrogen is less than 10%), the reaction pressure is 0.1Pa, the gas flow rate is 5 sccm, and the power It is 50W, and the target distance is 7cm. The deposition thickness is about 50nm.
透明电极的制备：采用溅射法制备AZO层，玻璃衬底温度为室温，载气为氩气或者氩氢混合气(其中氢气小于10％)，反应气压为0.1Pa，气体流量5sccm，功率为100W，靶距为5cm。沉积厚度约为500nm。Preparation of transparent electrode: AZO layer is prepared by sputtering method, the temperature of the glass substrate is room temperature, the carrier gas is argon or argon-hydrogen mixed gas (wherein the hydrogen is less than 10%), the reaction pressure is 0.1Pa, the gas flow rate is 5 sccm, and the power is 100W, the target distance is 5cm. The deposition thickness is about 500nm.
实施例十二具有低维材料复合结构的CIGS太阳电池，吸光层入光面纳微球Example 12 CIGS solar cell with low-dimensional material composite structure, nano-microspheres on the light-incident surface of the light-absorbing layer
导电层制备：采用溅射法在玻璃衬底上制备Mo层作为电极，玻璃衬底温度为室温，载气为氩气或者氩氢混合气(其中氢气小于10％)，反应气压为0.1Pa，气体流量5sccm，功率为100W，靶距为5cm。沉积厚度约为600nm。得到Mo电极。Conductive layer preparation: Sputtering is used to prepare a Mo layer on a glass substrate as an electrode. The temperature of the glass substrate is room temperature, the carrier gas is argon or argon-hydrogen mixed gas (wherein the hydrogen is less than 10%), and the reaction pressure is 0.1Pa. The gas flow rate is 5 sccm, the power is 100W, and the target distance is 5cm. The deposition thickness is about 600nm. Obtain Mo electrode.
吸光层制备：采用共蒸法在衬底上制备CIGS层，衬底温度为200℃，载气为氩气或者氩氢混合气(其中氢气小于10％)，反应气压为0.1Pa，气体流量5sccm，工作距离为5cm。沉积厚度约为1.5μm。得到CIGS吸光层。Preparation of light-absorbing layer: Co-evaporation method is used to prepare CIGS layer on the substrate, the substrate temperature is 200°C, the carrier gas is argon or argon-hydrogen mixed gas (where the hydrogen is less than 10%), the reaction pressure is 0.1Pa, and the gas flow rate is 5 sccm , the working distance is 5cm. The deposition thickness is about 1.5 μm. Obtain CIGS light absorbing layer.
硒化：惰性气体气氛下，以硒金属为硒源，500℃下退火30min。Selenization: Under an inert gas atmosphere, use selenium metal as the selenium source, and anneal at 500°C for 30min.
吸光层入光面纳微球的制备：将实施例一的纳微球的悬浮液通过旋涂机涂覆于透明电极区的入光面，在室温至60摄氏度之间的温度蒸发悬浮液的液体，沉积在窗口区的入光面上。Preparation of nano-microspheres on the light-incident surface of the light-absorbing layer: the suspension of nano-microspheres in Example 1 is coated on the light-incident surface of the transparent electrode area by a spin coater, and the suspension is evaporated at a temperature between room temperature and 60 degrees Celsius. Liquid, deposited on the light incident surface of the window area.
本例分别采用了粒径为5nm、10nm、20nm、30nm、50nm的纳微球进行涂覆，纳微球的间距在旋涂过程中可以为零，也可以随机分布，也可以纳微球在基面上的间距可以通过半导体微结构加工方式先在基面上做成具有特定间距微结构模板，使得纳微球只能占据一些特定的位置，从而控制纳微球沉积位置，可控地制备具有特定间距排列的纳微球薄膜。In this example, nanospheres with particle sizes of 5nm, 10nm, 20nm, 30nm, and 50nm were used for coating. The distance between the nanospheres can be zero or randomly distributed during the spin coating process. The spacing on the basal surface can be made into a microstructure template with a specific spacing on the basal surface through semiconductor microstructure processing, so that the nanospheres can only occupy some specific positions, so as to control the deposition position of the nanospheres and controllable preparation Thin films of nanospheres arranged at specific pitches.
窗口层制备：采用化学水浴法制备CdS层，反应物为醋酸铵、醋酸镉、氨水以及硫脲。首先将密封容器中加入去离子水，加热至60℃，加入醋酸镉、醋酸铵、氨水，沉积厚度约为70nm。Preparation of the window layer: The CdS layer was prepared by the chemical water bath method, and the reactants were ammonium acetate, cadmium acetate, ammonia water and thiourea. First, add deionized water into a sealed container, heat it to 60°C, add cadmium acetate, ammonium acetate, and ammonia water, and deposit a thickness of about 70nm.
透明缓冲层的制备：采用溅射法制备ZnO层，玻璃衬底温度为室温，载气为氩气或者氩氢混合气(其中氢气小于10％)，反应气压为0.1Pa，气体流量5sccm，功率为50W，靶距为7cm。沉积厚度约为50nm。Preparation of the transparent buffer layer: the ZnO layer is prepared by sputtering, the temperature of the glass substrate is room temperature, the carrier gas is argon or argon-hydrogen mixed gas (wherein the hydrogen is less than 10%), the reaction pressure is 0.1Pa, the gas flow rate is 5 sccm, and the power It is 50W, and the target distance is 7cm. The deposition thickness is about 50nm.
透明电极的制备：采用溅射法制备AZO层，玻璃衬底温度为室温，载气为氩气或者氩氢混合气(其中氢气小于10％)，反应气压为0.1Pa，气体流量5sccm，功率为100W，靶距为5cm。沉积厚度约为500nm。Preparation of transparent electrode: AZO layer is prepared by sputtering method, the temperature of the glass substrate is room temperature, the carrier gas is argon or argon-hydrogen mixed gas (wherein the hydrogen is less than 10%), the reaction pressure is 0.1Pa, the gas flow rate is 5 sccm, and the power is 100W, the target distance is 5cm. The deposition thickness is about 500nm.
实施例十三具有低维材料复合结构的CIGS太阳电池，吸光层背面纳微球Example 13 CIGS solar cell with low-dimensional material composite structure, nano-microspheres on the back of the light-absorbing layer
导电层制备：采用溅射法在玻璃衬底上制备Mo层作为电极，玻璃衬底温度为室温，载气为氩气或者氩氢混合气(其中氢气小于10％)，反应气压为0.1Pa，气体流量5sccm，功率为100W，靶距为5cm。沉积厚度约为600nm。得到Mo电极。Conductive layer preparation: Sputtering is used to prepare a Mo layer on a glass substrate as an electrode. The temperature of the glass substrate is room temperature, the carrier gas is argon or argon-hydrogen mixed gas (wherein the hydrogen is less than 10%), and the reaction pressure is 0.1Pa. The gas flow rate is 5 sccm, the power is 100W, and the target distance is 5cm. The deposition thickness is about 600nm. Obtain Mo electrode.
吸光层背面纳微球的制备：采用蒸发自组装法，将实施例一的纳微球的悬浮液涂覆于导电层上，在室温至60摄氏度之间的温度蒸发悬浮液的液体，纳微球在悬浮液的气-液相界面处进行高效组装形成致密的纳微球薄膜，沉积在导电层上。需要说明的是，由于导电层紧邻吸光层，并且阳光是从吸光层经过在到导电层的，因此，沉积在导电层上的纳微球也可以理解为是与吸光层背面点接触。Preparation of nano-microspheres on the back of the light-absorbing layer: use the evaporation self-assembly method to coat the suspension of nano-microspheres in Example 1 on the conductive layer, evaporate the suspension liquid at a temperature between room temperature and 60 degrees Celsius, and the nano-microspheres The spheres are efficiently assembled at the gas-liquid phase interface of the suspension to form a dense nanosphere film, which is deposited on the conductive layer. It should be noted that since the conductive layer is adjacent to the light-absorbing layer, and sunlight passes through the light-absorbing layer to the conductive layer, the nanospheres deposited on the conductive layer can also be understood as being in point contact with the back of the light-absorbing layer.
本例分别采用了纳微球粒径为50nm、100nm、200nm、300nm、500nm的纳微球进行涂覆，纳微球紧挨致密排列，纳微球间的间距可以为零，也可以随机分布，也可以纳微球在基面上的间距可以通过半导体微结构加工方式先在基面上做成具有特定间距微结构模板，使得纳微球只能占据一些特定的位置，从而控制纳微球沉积位置，可控地制备具有特定间距排列的纳微球薄膜。In this example, nanospheres with diameters of 50nm, 100nm, 200nm, 300nm, and 500nm were used for coating. The nanospheres are closely arranged, and the distance between the nanospheres can be zero or randomly distributed. , it is also possible that the spacing of the nanospheres on the basal surface can be made into a microstructure template with a specific spacing on the basal surface through semiconductor microstructure processing, so that the nanospheres can only occupy some specific positions, thereby controlling the size of the nanospheres. Deposition position, controllable preparation of nano-microsphere films with specific pitch arrangement.
吸光层制备：采用溅射法在衬底上制备CIGS层，衬底温度为200℃，载气为氩气或者氩氢混合气(其中氢气小于10％)，反应气压为0.1Pa，气体流量5sccm，功率为100W，靶距为5cm。沉积厚度约为1.5μm。得到CIGS吸光层。Preparation of light-absorbing layer: CIGS layer is prepared on the substrate by sputtering method, the substrate temperature is 200°C, the carrier gas is argon or argon-hydrogen mixed gas (where the hydrogen is less than 10%), the reaction pressure is 0.1Pa, and the gas flow rate is 5 sccm , the power is 100W, and the target distance is 5cm. The deposition thickness is about 1.5 μm. Obtain CIGS light absorbing layer.
窗口层制备：采用Sputter法制备ZnS层，衬底温度为室温，载气为氩气或者氩氢混合气(其中氢气小于10％)，反应气压为0.1Pa，气体流量5sccm，功率为50W，靶距为7cm。沉积厚度约为70nm。Window layer preparation: The ZnS layer was prepared by the Sputter method, the substrate temperature was room temperature, the carrier gas was argon or argon-hydrogen mixed gas (wherein the hydrogen gas was less than 10%), the reaction pressure was 0.1Pa, the gas flow rate was 5 sccm, and the power was 50W. The distance is 7cm. The deposition thickness is about 70nm.
透明电极的制备：采用溅射法制备AZO层，玻璃衬底温度为室温，载气为氩气或者氩氢混合气(其中氢气小于10％)，反应气压为0.1Pa，气体流量5sccm，功率为100W，靶距为5cm，其中N2作为载气。沉积厚度约为500nm。Preparation of transparent electrode: AZO layer is prepared by sputtering method, the temperature of the glass substrate is room temperature, the carrier gas is argon or argon-hydrogen mixed gas (wherein the hydrogen is less than 10%), the reaction pressure is 0.1Pa, the gas flow rate is 5 sccm, and the power is 100W, the target distance is 5cm, and N2 is used as the carrier gas. The deposition thickness is about 500nm.
实施例十四具有低维材料复合结构的CIGS太阳电池，透明电极区入光面纳微球，吸光区背面纳米线Example 14 CIGS solar cell with low-dimensional material composite structure, nano-microspheres on the light-incident side of the transparent electrode region, and nanowires on the back of the light-absorbing region
导电层制备：采用溅射法在PI衬底上制备Mo层作为电极，玻璃衬底温度为室温，载气为氩气或者氩氢混合气(其中氢气小于10％)，反应气压为0.1Pa，气体流量5sccm，功率为100W，靶距为5cm。沉积厚度约为600nm。得到Mo电极。Conductive layer preparation: Sputtering is used to prepare a Mo layer on a PI substrate as an electrode, the temperature of the glass substrate is room temperature, the carrier gas is argon or argon-hydrogen mixed gas (wherein the hydrogen is less than 10%), and the reaction pressure is 0.1Pa. The gas flow rate is 5 sccm, the power is 100W, and the target distance is 5cm. The deposition thickness is about 600nm. Obtain Mo electrode.
吸光区背面纳米线的制备：在基面上的间距可以通过半导体微结构加工方式先在基面上做成具有特定间距微结构模板，使得引导纳米线合成和生长只能占据一些特定的位置，从而控制纳米线沉积位置，可控地制备具有特定间距排列的纳米线。例如，采用模板法电化学沉积铜，银，镍等金属纳米线。上述模板为多孔氧化铝，以该模板为工作电极，金属片(铜、银、镍)为对电极，恒电位沉积法制备金属纳米线(铜、银、镍等)。沉积电位-0.4V至4V，沉积时间为10分钟至6分钟。沉积完毕后，用6mol/L的氢氧化钠溶液去除氧化铝模板，得到金属纳米线。Preparation of nanowires on the back of the light-absorbing region: the spacing on the basal surface can be made into a microstructure template with a specific spacing on the basal surface through semiconductor microstructure processing, so that the guided nanowire synthesis and growth can only occupy some specific positions. Therefore, the deposition position of the nanowires can be controlled, and the nanowires arranged with a specific pitch can be controllably prepared. For example, copper, silver, nickel and other metal nanowires are electrochemically deposited by template method. The template above is porous alumina, the template is used as the working electrode, and the metal sheet (copper, silver, nickel) is used as the counter electrode, and the metal nanowire (copper, silver, nickel, etc.) is prepared by the constant potential deposition method. Deposition potential -0.4V to 4V, deposition time 10 minutes to 6 minutes. After the deposition, the aluminum oxide template was removed with 6 mol/L sodium hydroxide solution to obtain metal nanowires.
吸光层制备：采用共蒸法在衬底上制备CIGS层，衬底温度为200℃，载气为氩气或者氩氢混合气(其中氢气小于10％)，反应气压为0.1Pa，气体流量5sccm，工作距离为5cm。沉积厚度约为1.5μm。得到CIGS吸光层。Preparation of light-absorbing layer: Co-evaporation method is used to prepare CIGS layer on the substrate, the substrate temperature is 200°C, the carrier gas is argon or argon-hydrogen mixed gas (where the hydrogen is less than 10%), the reaction pressure is 0.1Pa, and the gas flow rate is 5 sccm , the working distance is 5cm. The deposition thickness is about 1.5 μm. Obtain CIGS light absorbing layer.
硒化：惰性气体气氛下，以硒金属为硒源，400℃下退火30min。Selenization: Under an inert gas atmosphere, use selenium metal as the selenium source, and anneal at 400°C for 30min.
窗口层制备：采用化学水浴法制备CdS层，反应物为醋酸铵、醋酸镉、氨水以及硫脲。首先将密封容器中加入去离子水，加热至60℃，加入醋酸镉、醋酸铵、氨水，沉积厚度约为70nm。Preparation of the window layer: The CdS layer was prepared by the chemical water bath method, and the reactants were ammonium acetate, cadmium acetate, ammonia water and thiourea. First, add deionized water into a sealed container, heat it to 60°C, add cadmium acetate, ammonium acetate, and ammonia water, and deposit a thickness of about 70nm.
透明缓冲层的制备：采用溅射法制备ZnO层，玻璃衬底温度为室温，载气为氩气或者氩氢混合气(其中氢气小于10％)，反应气压为0.1Pa，气体流量5sccm，功率为50W，靶距为7cm。沉积厚度约为50nm。Preparation of the transparent buffer layer: the ZnO layer is prepared by sputtering, the temperature of the glass substrate is room temperature, the carrier gas is argon or argon-hydrogen mixed gas (wherein the hydrogen is less than 10%), the reaction pressure is 0.1Pa, the gas flow rate is 5 sccm, and the power It is 50W, and the target distance is 7cm. The deposition thickness is about 50nm.
透明电极的制备：采用溅射法制备AZO层，玻璃衬底温度为室温，载气为氩气或者氩氢混合气(其中氢气小于10％)，反应气压为0.1Pa，气体流量5sccm，功率为100W，靶距为5cm。沉积厚度约为500nm。Preparation of transparent electrode: AZO layer is prepared by sputtering method, the temperature of the glass substrate is room temperature, the carrier gas is argon or argon-hydrogen mixed gas (wherein the hydrogen is less than 10%), the reaction pressure is 0.1Pa, the gas flow rate is 5 sccm, and the power is 100W, the target distance is 5cm. The deposition thickness is about 500nm.
透明电极区入光面纳微球的制备：采用蒸发自组装法，将实施例一的纳微球的悬浮液涂覆于透明电极区的入光面，在室温至60摄氏度之间的温度蒸发悬浮液的液体，纳微球在悬浮液的气-液相界面处进行高效组装形成致密的纳微球薄膜，沉积在透明电极区入光面上。Preparation of nano-microspheres on the light-incident surface of the transparent electrode area: using the evaporation self-assembly method, coating the suspension of nano-microspheres in Example 1 on the light-incident surface of the transparent electrode area, and evaporating at a temperature between room temperature and 60 degrees Celsius The liquid in the suspension, the nano-microspheres are efficiently assembled at the gas-liquid phase interface of the suspension to form a dense nano-microsphere film, which is deposited on the light incident surface of the transparent electrode area.
本例分别采用了纳微球粒径为50nm、100nm、200nm、300nm、500nm的纳微球进行涂覆，纳微球紧挨致密排列，纳微球间的间距可以为零，也可以随机分布，也可以纳微球在基面上的间距可以通过半导体微结构加工方式先在基面上做成具有特定间距微结构模板，使得纳微球只能占据一些特定的位置，从而控制纳微球沉积位置，可控地制备具有特定间距排列的纳微球薄膜。吸光区背面纳米线的直径为5nm-500nm，长度为50nm-5mm，纳米线之间的间距为10nm-100μm。In this example, nanospheres with diameters of 50nm, 100nm, 200nm, 300nm, and 500nm were used for coating. The nanospheres are closely arranged, and the distance between the nanospheres can be zero or randomly distributed. , it is also possible that the spacing of the nanospheres on the basal surface can be made into a microstructure template with a specific spacing on the basal surface through semiconductor microstructure processing, so that the nanospheres can only occupy some specific positions, thereby controlling the size of the nanospheres. Deposition position, controllable preparation of nano-microsphere films with specific pitch arrangement. The diameter of the nanowires on the back of the light absorption area is 5nm-500nm, the length is 50nm-5mm, and the distance between the nanowires is 10nm-100μm.
实施例十五具有低维材料复合结构的三五族太阳电池，透明电极区入光面纳微球Example 15: III-V solar cells with low-dimensional material composite structure, nano-microspheres on the light-incident surface of the transparent electrode region
吸光层的制备：在n型Ge单晶衬底上，利用MOCVD生长n型GaAs，其中Ga源三甲基镓源(TMG)，温度为-16℃，10ml；掺杂源H2Se，20ml；As源AsH3，50ml；氢气为载气，生长温度600℃，厚度为0.1μm到10μm。Preparation of the light-absorbing layer: On the n-type Ge single crystal substrate, grow n-type GaAs by MOCVD, in which the Ga source is trimethylgallium (TMG), the temperature is -16°C, 10ml; the dopant source is H2 Se, 20ml ; As source AsH3 , 50ml; hydrogen as carrier gas, growth temperature 600°C, thickness 0.1 μm to 10 μm.
窗口层有源层制备：利用MOCVD生长p型GaAs。其中Ga源TMG，温度为-16℃，10ml；掺杂源DEZ，-16℃，2ml；As源AsH3，40ml；氢气为载气，生长温度600℃，沉积厚度约为0.1μm到10μm。Window layer active layer preparation: use MOCVD to grow p-type GaAs. Among them, Ga source TMG, the temperature is -16°C, 10ml; doping source DEZ, -16°C, 2ml; As source AsH3 , 40ml; hydrogen is the carrier gas, the growth temperature is 600°C, and the deposition thickness is about 0.1 μm to 10 μm.
窗口区帽子层：利用MOCVD生长p型AlGaAs。其中Ga源TMG，温度为-16℃，10ml；Al源三甲基铝(TMA)，17℃，20ml；掺杂源DEZ，25℃，2ml；As源AsH3，50ml；氢气为载气，生长温度600℃，沉积厚度约为5nm到10μm。Window area hat layer: grow p-type AlGaAs by MOCVD. Among them, Ga source TMG, temperature is -16°C, 10ml; Al source trimethylaluminum (TMA), 17°C, 20ml; doping source DEZ, 25°C, 2ml; As source AsH3 , 50ml; hydrogen as carrier gas, The growth temperature is 600° C., and the deposition thickness is about 5 nm to 10 μm.
透明电极的制备：采用TiAu材料作为透明电极，利用光刻技术，经过显影，在电池正面做上光刻胶图形。采用蒸镀法，在2×10-2Pa气压下，先后蒸镀40nm的Ti和50nm的Au在电池表面形成栅极电极，去除光刻胶后获得透明电极。Preparation of transparent electrode: TiAu material is used as the transparent electrode, and a photoresist pattern is made on the front of the battery after development by using photolithography technology. Using the evaporation method, under the pressure of 2×10-2Pa, 40nm Ti and 50nm Au were successively evaporated on the surface of the battery to form a gate electrode, and a transparent electrode was obtained after removing the photoresist.
背电极的制备：将Au/Ge/Ni合金蒸镀到电池背电极，工作气压为2×10-2Pa，厚度依次为30nm/20nm/500nm。Preparation of the back electrode: Au/Ge/Ni alloy is vapor-deposited on the back electrode of the battery, the working pressure is 2×10-2 Pa, and the thickness is 30nm/20nm/500nm in sequence.
透明电极区入光面纳微球的制备：在基面上的间距可以通过半导体微结构加工方式先在基面上做成具有特定间距微结构模板，使得引导纳微球合成和生长只能占据一些特定的位置，从而控制纳微球沉积位置，可控地制备具有特定间距排列的纳微球。例如，采用蒸发自组装法，将实施例一的纳微球的悬浮液涂覆于透明电极区的入光面，在室温至60摄氏度之间的温度蒸发悬浮液的液体，纳微球在悬浮液的气-液相界面处进行高效组装形成致密的纳微球薄膜，沉积在透明电极区入光面上。Preparation of nano-microspheres on the light-incident surface of the transparent electrode area: the spacing on the base surface can be made into a microstructure template with a specific spacing on the base surface by semiconductor microstructure processing, so that the guided synthesis and growth of nano-microspheres can only occupy Some specific positions, so as to control the deposition position of the nano-microspheres, controllably prepare the nano-microspheres with a specific pitch arrangement. For example, using the evaporative self-assembly method, the suspension of nano-microspheres in Example 1 is coated on the light-incident surface of the transparent electrode area, and the liquid in the suspension is evaporated at a temperature between room temperature and 60 degrees Celsius, and the nano-microspheres are suspended. High-efficiency assembly at the gas-liquid phase interface of the liquid forms a dense nano-microsphere film, which is deposited on the light-incident surface of the transparent electrode area.
本例分别采用了纳微球粒径为50nm、100nm、200nm、300nm、500nm的纳微球进行涂覆，纳微球紧挨致密排列，纳微球间的间距可以为零，也可以随机分布，也可以纳微球在基面上的间距可以通过半导体微结构加工方式先在基面上做成具有特定间距微结构模板，使得纳微球只能占据一些特定的位置，从而控制纳微球沉积位置，可控地制备具有特定间距排列的纳微球薄膜。吸光区背面纳米线的直径为5nm-500nm，长度为50nm-5mm，纳米线之间的间距为10nm-100μm。In this example, nanospheres with diameters of 50nm, 100nm, 200nm, 300nm, and 500nm were used for coating. The nanospheres are closely arranged, and the distance between the nanospheres can be zero or randomly distributed. , it is also possible that the spacing of the nanospheres on the basal surface can be made into a microstructure template with a specific spacing on the basal surface through semiconductor microstructure processing, so that the nanospheres can only occupy some specific positions, thereby controlling the size of the nanospheres. Deposition position, controllable preparation of nano-microsphere films with specific pitch arrangement. The diameter of the nanowires on the back of the light absorption area is 5nm-500nm, the length is 50nm-5mm, and the distance between the nanowires is 10nm-100μm.
实施例十六具有低维材料复合结构的晶体硅太阳电池Example 16 Crystalline silicon solar cell with composite structure of low-dimensional materials
将p型硅片置于热扩散炉，氮气载气通过液态POCl3，900℃下20分钟，在p型硅表面形成n型区，n型区作为窗口区，p型区作为吸光区，窗口区表面划铝线作为电极，350℃退火30分钟。Place the p-type silicon wafer in a thermal diffusion furnace, nitrogen carrier gas passes through liquid POCl3 , and hold at 900°C for 20 minutes to form an n-type region on the surface of the p-type silicon, the n-type region is used as the window region, the p-type region is used as the light-absorbing region, and the window Scribe aluminum wires on the surface of the area as electrodes, and anneal at 350°C for 30 minutes.
窗口区微纳球的制备：在基面上的间距通过半导体微结构加工方式先在基面上做成具有特定间距微结构模板，使得引导纳微球合成和生长只能占据一些特定的位置，从而控制纳微球沉积位置，可控地制备具有特定间距排列的纳米线。具体的，采用蒸发自组装法，将实施例一的纳微球的悬浮液涂覆于窗口区，在室温至60摄氏度之间的温度蒸发悬浮液的液体，纳微球在悬浮液的气-液相界面处进行高效组装形成致密的纳微球薄膜，沉积在窗口区。Preparation of micro-nanospheres in the window area: the spacing on the basal surface is firstly made into a microstructure template with a specific spacing on the basal surface through semiconductor microstructure processing, so that the synthesis and growth of guided nano-microspheres can only occupy some specific positions. Therefore, the deposition position of the nanospheres can be controlled, and the nanowires arranged with a specific pitch can be controllably prepared. Specifically, using the evaporative self-assembly method, the suspension of nano-microspheres in Example 1 is coated on the window area, and the liquid in the suspension is evaporated at a temperature between room temperature and 60 degrees Celsius. Efficient assembly at the liquid phase interface forms a dense nano-microsphere film, which is deposited in the window area.
吸光区背面纳米线的制备：采用模板法电化学沉积铜，银，镍等金属纳米线。上述模板为多孔氧化铝，以该模板为工作电极，金属片(铜、银、镍)为对电极，恒电位沉积法制备金属纳米线(铜、银、镍等)。沉积电位-0.4V至4V，沉积时间为10分钟至6分钟。沉积完毕后，用6mol/L的氢氧化钠溶液去除氧化铝模板，得到金属纳米线。Preparation of nanowires on the back of the light-absorbing region: use the template method to electrochemically deposit copper, silver, nickel and other metal nanowires. The template above is porous alumina, the template is used as the working electrode, and the metal sheet (copper, silver, nickel) is used as the counter electrode, and the metal nanowire (copper, silver, nickel, etc.) is prepared by the constant potential deposition method. Deposition potential -0.4V to 4V, deposition time 10 minutes to 6 minutes. After the deposition, the aluminum oxide template was removed with 6 mol/L sodium hydroxide solution to obtain metal nanowires.
本例分别采用了纳微球粒径为50nm、100nm、200nm、300nm、500nm的纳微球进行涂覆，纳微球紧挨致密排列，纳微球间的间距可以为零，也可以随机分布，也可以纳微球在基面上的间距可以通过半导体微结构加工方式先在基面上做成具有特定间距微结构模板，使得纳微球只能占据一些特定的位置，从而控制纳微球沉积位置，可控地制备具有特定间距排列的纳微球薄膜。吸光区背面纳米线的直径为5nm-500nm，长度为50nm-5mm，纳米线之间的间距为10nm-100μm。In this example, nanospheres with diameters of 50nm, 100nm, 200nm, 300nm, and 500nm were used for coating. The nanospheres are closely arranged, and the distance between the nanospheres can be zero or randomly distributed. , it is also possible that the spacing of the nanospheres on the basal surface can be made into a microstructure template with a specific spacing on the basal surface through semiconductor microstructure processing, so that the nanospheres can only occupy some specific positions, thereby controlling the size of the nanospheres. Deposition position, controllable preparation of nano-microsphere films with specific pitch arrangement. The diameter of the nanowires on the back of the light absorption area is 5nm-500nm, the length is 50nm-5mm, and the distance between the nanowires is 10nm-100μm.
实施例十七具有低维材料复合结构的薄膜硅太阳电池Embodiment 17 Thin-film silicon solar cell with low-dimensional material composite structure
透明电极区入光面纳微球的制备：采用蒸发自组装法，将实施例一的纳微球的悬浮液涂覆于玻璃的表面，在室温至60摄氏度之间的温度蒸发悬浮液的液体，纳微球在悬浮液的气-液相界面处进行高效组装形成致密的纳微球薄膜，沉积在透明电极区的入光面上。纳微球在基面上的间距通过半导体微结构加工方式先在基面上做成具有特定间距微结构模板，使得纳微球只能占据一些特定的位置，从而控制纳微球沉积位置，可控地制备具有特定间距排列的纳微球薄膜。Preparation of nano-microspheres on the light-incident surface of the transparent electrode area: use the evaporation self-assembly method to coat the suspension of nano-microspheres in Example 1 on the surface of the glass, and evaporate the liquid in the suspension at a temperature between room temperature and 60 degrees Celsius , the nano-microspheres are efficiently assembled at the gas-liquid phase interface of the suspension to form a dense nano-microsphere film, which is deposited on the light incident surface of the transparent electrode region. The spacing of the nanospheres on the basal surface is firstly made into a microstructure template with a specific spacing on the basal surface through semiconductor microstructure processing, so that the nanospheres can only occupy some specific positions, thereby controlling the deposition position of the nanospheres, which can Controlled preparation of nano-microsphere thin films with specific pitch arrangement.
透明电极的制备：采用溅射法制备AZO层，玻璃衬底温度为室温，载气为氩气或者氩氢混合气(其中氢气小于10％)，反应气压为0.1Pa，气体流量5sccm，功率为100W，靶距为5cm，其中N2作为载气。沉积厚度约为500nm。Preparation of transparent electrode: AZO layer is prepared by sputtering method, the temperature of the glass substrate is room temperature, the carrier gas is argon or argon-hydrogen mixed gas (wherein the hydrogen is less than 10%), the reaction pressure is 0.1Pa, the gas flow rate is 5 sccm, and the power is 100W, the target distance is 5cm, withN2 as the carrier gas. The deposition thickness is about 500nm.
窗口层的制备：采用PECVD制备p层Si薄膜，射频功率60W，衬底温度250，工作气压130Pa；反应气体为1.5sccm流量的SiH4，和0.1％到5％的掺杂气体B2H6；载气为Ar和H2，Ar流量1到100sccm，H2流量1到100sccm。p层窗口区厚度为20nm到500nm。Preparation of the window layer: PECVD is used to prepare the p-layer Si thin film, the radio frequency power is 60W, the substrate temperature is 250, and the working pressure is 130Pa; the reaction gas is SiH4 with a flow rate of 1.5 sccm, and the doping gas B2H6 of 0.1% to 5%; the carrier gas For Ar and H2 , the flow rate of Ar is 1 to 100 sccm, and the flow rate of H2 is 1 to 100 sccm. The thickness of the p-layer window region is 20nm to 500nm.
本征层的制备：采用PECVD制备i层Si薄膜，射频功率60W，衬底温度250，工作气压130Pa；反应气体SiH流量为1.5sccm；载气为Ar和H2，Ar流量1到100sccm，H2流量1到100sccm。p层窗口区厚度为20nm到5μm。Preparation of intrinsic layer: Prepare i-layer Si film by PECVD, RF power 60W, substrate temperature 250, working pressure 130Pa; reaction gas SiH flow rate 1.5 sccm; carrier gas Ar and H2 , Ar flow rate 1 to 100 sccm, H2Flow 1 to 100sccm. The thickness of the p-layer window region is 20nm to 5μm.
吸收层的制备：采用PECVD制备n层Si薄膜，射频功率60W，衬底温度250，工作气压130Pa；反应气体SiH4流量为1.5sccm，和0.1％到5％的掺杂气体PH3；载气为Ar和H2，Ar流量1到100sccm，H2流量1到100sccm。p层窗口区厚度为20nm到500nm。Preparation of absorbing layer: adopt PECVD to prepare n-layer Si film, radio frequency power 60W, substrate temperature 250, working pressure 130Pa; reaction gas SiH4 flow rate is 1.5 sccm, and 0.1% to 5% doping gas PH3 ; carrier gas For Ar and H2 , the flow rate of Ar is 1 to 100 sccm, and the flow rate of H2 is 1 to 100 sccm. The thickness of the p-layer window region is 20nm to 500nm.
吸光区背面纳米线的制备：采用模板法电化学沉积铜，银，镍等金属纳米线。上述模板为多孔氧化铝，以该模板为工作电极，金属片(铜、银、镍)为对电极，恒电位沉积法制备金属纳米线(铜、银、镍等)。沉积电位-0.4V至4V，沉积时间为10分钟至6分钟。沉积完毕后，用6mol/L的氢氧化钠溶液去除氧化铝模板，得到金属纳米线。Preparation of nanowires on the back of the light-absorbing region: use the template method to electrochemically deposit copper, silver, nickel and other metal nanowires. The template above is porous alumina, the template is used as the working electrode, and the metal sheet (copper, silver, nickel) is used as the counter electrode, and the metal nanowire (copper, silver, nickel, etc.) is prepared by the constant potential deposition method. Deposition potential -0.4V to 4V, deposition time 10 minutes to 6 minutes. After the deposition, the aluminum oxide template was removed with 6 mol/L sodium hydroxide solution to obtain metal nanowires.
本例分别采用了纳微球粒径为50nm、100nm、200nm、300nm、500nm的纳微球进行涂覆，纳微球紧挨致密排列，纳微球间的间距可以为零，也可以随机分布，也可以纳微球在基面上的间距可以通过半导体微结构加工方式先在基面上做成具有特定间距微结构模板，使得纳微球只能占据一些特定的位置，从而控制纳微球沉积位置，可控地制备具有特定间距排列的纳微球薄膜。吸光区背面纳米线的直径为5nm-500nm，长度为50nm-5mm，纳米线之间的间距为10nm-100μm。In this example, nanospheres with diameters of 50nm, 100nm, 200nm, 300nm, and 500nm were used for coating. The nanospheres are closely arranged, and the distance between the nanospheres can be zero or randomly distributed. , it is also possible that the spacing of the nanospheres on the basal surface can be made into a microstructure template with a specific spacing on the basal surface through semiconductor microstructure processing, so that the nanospheres can only occupy some specific positions, thereby controlling the size of the nanospheres. Deposition position, controllable preparation of nano-microsphere films with specific pitch arrangement. The diameter of the nanowires on the back of the light absorption area is 5nm-500nm, the length is 50nm-5mm, and the distance between the nanowires is 10nm-100μm.
实施例十八具有低维材料复合结构的染料敏化太阳电池Example 18 Dye-sensitized solar cell with low-dimensional material composite structure
透明电极的制备：采用溅射法制备AZO层，玻璃衬底温度为室温，载气为氩气或者氩氢混合气(其中氢气小于10％)，反应气压为0.1Pa，气体流量5sccm，功率为100W，靶距为5cm，其中N2作为载气。沉积厚度约为500nm。Preparation of transparent electrode: AZO layer is prepared by sputtering method, the temperature of the glass substrate is room temperature, the carrier gas is argon or argon-hydrogen mixed gas (wherein the hydrogen is less than 10%), the reaction pressure is 0.1Pa, the gas flow rate is 5 sccm, and the power is 100W, the target distance is 5cm, withN2 as the carrier gas. The deposition thickness is about 500nm.
对电极的制备：在氩气气氛下将Pt涂在FTO导电玻璃表面。Preparation of counter electrode: Pt was coated on the surface of FTO conductive glass under argon atmosphere.
对电极入光面纳米线的制备：采用模板法电化学沉积铜，银，镍等金属纳米线。上述模板为多孔氧化铝，以该模板为工作电极，金属片(铜、银、镍)为对电极，恒电位沉积法制备金属纳米线(铜、银、镍等)。沉积电位-0.4V至4V，沉积时间为10分钟至6分钟。沉积完毕后，用6mol/L的氢氧化钠溶液去除氧化铝模板，得到金属纳米线。Preparation of nanowires on the light-incident surface of the counter electrode: copper, silver, nickel and other metal nanowires are electrochemically deposited by template method. The template above is porous alumina, the template is used as the working electrode, and the metal sheet (copper, silver, nickel) is used as the counter electrode, and the metal nanowire (copper, silver, nickel, etc.) is prepared by the constant potential deposition method. Deposition potential -0.4V to 4V, deposition time 10 minutes to 6 minutes. After the deposition, the aluminum oxide template was removed with 6 mol/L sodium hydroxide solution to obtain metal nanowires.
染料的制备：将30mM的碘、0.3M的碘化钾、亚胺铥盐和吡啶诱导体加入乙腈溶剂得到电解质溶液。Preparation of dye: 30 mM iodine, 0.3 M potassium iodide, thulium imide and pyridine inducer were added into acetonitrile solvent to obtain electrolyte solution.
在光电极上滴几滴染料，用对电极封住。完成染料敏化电池。Put a few drops of dye on the photoelectrode and seal it with the counter electrode. Complete the dye-sensitized cell.
透明电极区背面纳微球的制备：在基面上的间距通过半导体微结构加工方式先在基面上做成具有特定间距微结构模板，使得引导纳米线合成和生长只能占据一些特定的位置，从而控制纳米线沉积位置，可控地制备具有特定间距排列的纳米线。具体的，采用蒸发自组装法，将实施例一的纳微球的悬浮液涂覆于透明电极区背面，在室温至60摄氏度之间的温度蒸发悬浮液的液体，纳微球在悬浮液的气-液相界面处进行高效组装形成致密的纳微球薄膜，沉积在透明电极区上。Preparation of nanospheres on the back of the transparent electrode area: the spacing on the basal surface is firstly made into a microstructure template with a specific spacing on the basal surface through semiconductor microstructure processing, so that the guided nanowire synthesis and growth can only occupy some specific positions , so as to control the deposition position of nanowires, and controllably prepare nanowires with specific pitch arrangement. Specifically, using the evaporative self-assembly method, the suspension of nano-microspheres in Example 1 is coated on the back of the transparent electrode area, and the liquid in the suspension is evaporated at a temperature between room temperature and 60 degrees Celsius. Efficient assembly at the gas-liquid phase interface forms a dense nano-microsphere film, which is deposited on the transparent electrode area.
本例分别采用了纳微球粒径为50nm、100nm、200nm、300nm、500nm的纳微球进行涂覆，纳微球紧挨致密排列，纳微球间的间距可以为零，也可以随机分布，也可以纳微球在基面上的间距可以通过半导体微结构加工方式先在基面上做成具有特定间距微结构模板，使得纳微球只能占据一些特定的位置，从而控制纳微球沉积位置，可控地制备具有特定间距排列的纳微球薄膜。In this example, nanospheres with diameters of 50nm, 100nm, 200nm, 300nm, and 500nm were used for coating. The nanospheres are closely arranged, and the distance between the nanospheres can be zero or randomly distributed. , it is also possible that the spacing of the nanospheres on the basal surface can be made into a microstructure template with a specific spacing on the basal surface through semiconductor microstructure processing, so that the nanospheres can only occupy some specific positions, thereby controlling the size of the nanospheres. Deposition position, controllable preparation of nano-microsphere films with specific pitch arrangement.
实施例十九具有低维材料复合结构的有机高分子太阳能电池Embodiment 19 Organic polymer solar cell with low-dimensional material composite structure
透明电极的制备：采用溅射法制备AZO层，玻璃衬底温度为室温，载气为氩气或者氩氢混合气(其中氢气小于10％)，反应气压为0.1Pa，气体流量5sccm，功率为100W，靶距为5cm，其中N2作为载气。沉积厚度约为500nm。Preparation of transparent electrode: AZO layer is prepared by sputtering method, the temperature of the glass substrate is room temperature, the carrier gas is argon or argon-hydrogen mixed gas (wherein the hydrogen is less than 10%), the reaction pressure is 0.1Pa, the gas flow rate is 5 sccm, and the power is 100W, the target distance is 5cm, withN2 as the carrier gas. The deposition thickness is about 500nm.
窗口区的入光面纳米线的制备：在基面上的间距通过半导体微结构加工方式先在基面上做成具有特定间距微结构模板，使得引导纳米线合成和生长只能占据一些特定的位置，从而控制纳米线沉积位置，可控地制备具有特定间距排列的纳米线。具体的，采用模板法电化学沉积铜，银，镍等金属纳米线。上述模板为多孔氧化铝，以该模板为工作电极，金属片(铜、银、镍)为对电极，恒电位沉积法制备金属纳米线(铜、银、镍等)。沉积电位-0.4V至4V，沉积时间为10分钟至6分钟。沉积完毕后，用6mol/L的氢氧化钠溶液去除氧化铝模板，得到金属纳米线。纳米线的直径可以为5nm-500nm，可以长度为50nm-5mm，可以纳米线之间的间距为10nm-100μm。Preparation of nanowires on the light incident surface in the window area: the spacing on the basal surface is firstly made into a microstructure template with a specific spacing on the basal surface through semiconductor microstructure processing, so that the guided nanowire synthesis and growth can only occupy some specific space. position, thereby controlling the deposition position of the nanowires, and controllably preparing nanowires with a specific pitch arrangement. Specifically, copper, silver, nickel and other metal nanowires are electrochemically deposited using a template method. The template above is porous alumina, the template is used as the working electrode, and the metal sheet (copper, silver, nickel) is used as the counter electrode, and the metal nanowire (copper, silver, nickel, etc.) is prepared by the constant potential deposition method. Deposition potential -0.4V to 4V, deposition time 10 minutes to 6 minutes. After the deposition, the aluminum oxide template was removed with 6 mol/L sodium hydroxide solution to obtain metal nanowires. The diameter of the nanowires can be 5nm-500nm, the length can be 50nm-5mm, and the distance between the nanowires can be 10nm-100μm.
窗口区的制备：利用旋涂机，将聚合物聚3，4-乙撑二氧噻吩(PEDOT:PSS，739332Sigma-Aldrich)水溶剂旋涂在透明电极上，形成窗口区。旋涂速度为1000-2000转每分钟。Preparation of the window area: using a spin coating machine, the polymer poly-3,4-ethylenedioxythiophene (PEDOT:PSS, 739332 Sigma-Aldrich) was spin-coated on the transparent electrode with an aqueous solution to form the window area. The spin coating speed is 1000-2000 revolutions per minute.
高分子有机光电涂料的制备：将聚噻吩和富勒烯(巴溪仪器有限公司的P-100)按1∶1的质量配比溶入三氯甲烷有机溶剂液中，形成有机光电涂料。Preparation of polymer organic photoelectric coating: polythiophene and fullerene (P-100 from Baxi Instrument Co., Ltd.) are dissolved in chloroform organic solvent in a mass ratio of 1:1 to form an organic photoelectric coating.
有机高分子太阳能电池薄膜的制备：将高分子有机光电涂料滴在带有透明导电电极的导电玻璃上，利用旋涂剂，经过40-60秒1000-2000转每分钟旋涂成有机太阳能电池薄膜。Preparation of organic polymer solar cell film: drop the polymer organic photoelectric coating on the conductive glass with transparent conductive electrodes, use spin coating agent, and spin-coat organic solar cell film at 1000-2000 revolutions per minute for 40-60 seconds .
背电极的制备：将铝、镁、钙等金属用真空热蒸镀方法蒸镀到电池背电极，工作气压为2×10-2Pa，厚度依次为1000nm。Preparation of the back electrode: aluminum, magnesium, calcium and other metals were vapor-deposited on the back electrode of the battery by vacuum thermal evaporation, the working pressure was 2×10-2 Pa, and the thickness was 1000nm in order.
实施例二十具有低维材料复合结构的有机高分子太阳能电池Example 20 Organic polymer solar cell with low-dimensional material composite structure
透明电极的制备：采用溅射法制备AZO层，玻璃衬底温度为室温，载气为氩气或者氩氢混合气(其中氢气小于10％)，反应气压为0.1Pa，气体流量5sccm，功率为100W，靶距为5cm，其中N2作为载气。沉积厚度约为500nm。Preparation of transparent electrode: AZO layer is prepared by sputtering method, the temperature of the glass substrate is room temperature, the carrier gas is argon or argon-hydrogen mixed gas (wherein the hydrogen is less than 10%), the reaction pressure is 0.1Pa, the gas flow rate is 5 sccm, and the power is 100W, the target distance is 5cm, withN2 as the carrier gas. The deposition thickness is about 500nm.
窗口区入光面纳微球的制备：在基面上的间距通过半导体微结构加工方式先在基面上做成具有特定间距微结构模板，使得引导纳微球合成和生长只能占据一些特定的位置，从而控制纳微球沉积位置，可控地制备具有特定间距排列的纳微球。具体的，采用蒸发自组装法，将实施例一的纳微球的悬浮液涂覆于透明电极区背面，在室温至60摄氏度之间的温度蒸发悬浮液的液体，纳微球在悬浮液的气-液相界面处进行高效组装形成致密的纳微球薄膜，沉积在透明电极区背面上。需要说明的是，由于透明电极区与窗口区紧邻，因此，在透明电极区背面的纳微球也可以理解为是与窗口区点接触的。Preparation of nano-microspheres on the light-incident surface of the window area: the spacing on the basal surface is firstly made into a microstructure template with a specific spacing on the basal surface through semiconductor microstructure processing, so that the guided synthesis and growth of nano-microspheres can only occupy some specific space. The position of nano-microspheres can be controlled to control the deposition position of nano-microspheres, and the nano-microspheres with specific spacing can be prepared controllably. Specifically, using the evaporative self-assembly method, the suspension of nano-microspheres in Example 1 is coated on the back of the transparent electrode area, and the liquid in the suspension is evaporated at a temperature between room temperature and 60 degrees Celsius. Efficient assembly at the gas-liquid phase interface forms a dense nano-microsphere film, which is deposited on the back of the transparent electrode area. It should be noted that since the transparent electrode region is adjacent to the window region, the nanospheres on the back of the transparent electrode region can also be understood as being in point contact with the window region.
窗口区的制备：利用旋涂机，将聚合物聚3，4-乙撑二氧噻吩(PEDOT:PSS，739332Sigma-Aldrich)水溶剂旋涂在透明电极上，形成窗口区。旋涂速度为1000-2000转每分钟。Preparation of the window area: using a spin coating machine, the polymer poly-3,4-ethylenedioxythiophene (PEDOT:PSS, 739332 Sigma-Aldrich) was spin-coated on the transparent electrode with an aqueous solution to form the window area. The spin coating speed is 1000-2000 revolutions per minute.
高分子有机光电涂料的制备：将聚噻吩和富勒烯(巴溪仪器有限公司的P-100)按1∶1的质量配比溶入三氯甲烷有机溶剂液中，形成有机光电涂料。Preparation of polymer organic photoelectric coating: polythiophene and fullerene (P-100 from Baxi Instrument Co., Ltd.) are dissolved in chloroform organic solvent in a mass ratio of 1:1 to form an organic photoelectric coating.
有机高分子太阳能电池薄膜的制备：将高分子有机光电涂料滴在带有透明导电电极的导电玻璃上，利用旋涂剂，经过40-60秒1000-2000转每分钟旋涂成有机太阳能电池薄膜。Preparation of organic polymer solar cell film: drop the polymer organic photoelectric coating on the conductive glass with transparent conductive electrodes, use spin coating agent, and spin-coat organic solar cell film at 1000-2000 revolutions per minute for 40-60 seconds .
背电极的制备：将铝、镁、钙等金属用真空热蒸镀方法蒸镀到电池背电极，工作气压为2×10-2Pa，厚度依次为1000nm。Preparation of the back electrode: aluminum, magnesium, calcium and other metals were vapor-deposited on the back electrode of the battery by vacuum thermal evaporation, the working pressure was 2×10-2 Pa, and the thickness was 1000nm in order.
本例分别采用了纳微球粒径为50nm、100nm、200nm、300nm、500nm的纳微球进行涂覆，纳微球紧挨致密排列，纳微球间的间距可以为零，也可以随机分布，也可以纳微球在基面上的间距可以通过半导体微结构加工方式先在基面上做成具有特定间距微结构模板，使得纳微球只能占据一些特定的位置，从而控制纳微球沉积位置，可控地制备具有特定间距排列的纳微球薄膜。In this example, nanospheres with diameters of 50nm, 100nm, 200nm, 300nm, and 500nm were used for coating. The nanospheres are closely arranged, and the distance between the nanospheres can be zero or randomly distributed. , it is also possible that the spacing of the nanospheres on the basal surface can be made into a microstructure template with a specific spacing on the basal surface through semiconductor microstructure processing, so that the nanospheres can only occupy some specific positions, thereby controlling the size of the nanospheres. Deposition position, controllable preparation of nano-microsphere films with specific pitch arrangement.
以上内容是结合具体的实施方式对本申请所作的进一步详细说明，不能认定本申请的具体实施只局限于这些说明。对于本申请所属技术领域的普通技术人员来说，在不脱离本申请构思的前提下，还可以做出若干简单推演或替换，都应当视为属于本申请的保护范围。The above content is a further detailed description of the present application in conjunction with specific implementation modes, and it cannot be considered that the specific implementation of the present application is limited to these descriptions. For those of ordinary skill in the technical field to which this application belongs, some simple deduction or substitutions can be made without departing from the concept of this application, which should be deemed to belong to the protection scope of this application.
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| CN201210095940.4ACN102646745B (en) | 2012-04-01 | 2012-04-01 | Photovoltaic device and solar battery |
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