CN103325886A - Preparation method of CIAS membrane with energy band gradient distribution - Google Patents

Preparation method of CIAS membrane with energy band gradient distribution Download PDF

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CN103325886A
CN103325886A CN 201310229778 CN201310229778A CN103325886A CN 103325886 A CN103325886 A CN 103325886A CN 201310229778 CN201310229778 CN 201310229778 CN 201310229778 A CN201310229778 A CN 201310229778A CN 103325886 A CN103325886 A CN 103325886A
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copper
indium
selenium
membrane
aluminum
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CN 201310229778
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CN103325886B (en )
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徐东
徐永清
杨杰
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深圳市亚太兴实业有限公司
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    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50Manufacturing or production processes characterised by the final manufactured product
    • Y02P70/52Manufacturing of products or systems for producing renewable energy
    • Y02P70/521Photovoltaic generators

Abstract

The invention is applied to the technical field of photovoltaic new energy resource materials, and provides a preparation method of a copper indium aluminum selenium membrane with energy band gradient distribution. The method comprises the following steps that copper indium aluminum selenium nano particles are synthesized, copper indium aluminum selenium nanocrystalline ink is prepared, a copper indium aluminum selenium precursor prefabricated membrane is prepared, and the copper indium aluminum selenium membrane is prepared. The preparation method is simple in process, convenient to operate, low in cost and capable of preparing a large-area uniform membrane layer, and promotes the improvement of the conversion rate of a solar thin-film battery.

Description

一种具有能带梯度分布的铜铟铝砸(CIAS)薄膜的制备方法 A method of preparing a copper indium aluminum band hit the gradient (CIAS) film having a

技术领域 FIELD

[0001] 本发明属于光伏太阳电池吸光材料的制备领域,尤其涉及一种具有能带梯度分布的铜铟铝硒薄膜的制备方法。 [0001] The present invention belongs to the field of photovoltaic solar cells prepared light-absorbing material, and particularly to a method for preparing a thin film of copper indium selenide aluminum band having a gradient profile.

背景技术 Background technique

[0002] 太阳能是一种清洁、环保的可再生新能源。 [0002] Solar energy is a clean, renewable energy or environmentally friendly. 它能够取代部分化石燃料,成为未来主要能源之一。 It can replace part of the fossil fuels, has become one of the major energy future. 当前太阳能的利用方式有光热转换和光电转换两种。 Use current photothermal conversion of solar energy and two kinds of photoelectric conversion. 其中光热转化方式被广泛应用,而最有应用前景的光电转化方式,却由于太阳电池的光吸收层材料及其器件制备成本较高,只能在一些特殊要求的领域得到应用。 Wherein a photothermal conversion mode is widely used, a photoelectric conversion of the most promising ways, but because of its higher solar light absorbing layer material preparation device cost, it can only be applied in some fields special requirements. 因此,需要开发一种廉价、高效率的薄膜太阳能电池的制备工艺和技术。 Thus, a need to develop an inexpensive, high-efficiency manufacturing process and technology of thin-film solar cell.

[0003] 目前,铜铟镓硒(CIGS)薄膜太阳能电池是最有应用前景的太阳能电池之一,但是CIGS薄膜太阳能电池光吸收层的制备需要使用大量的In、Ga等稀有金属,这使得CIGS薄膜电池大规模的推广应用在原料供应方面受到很大的限制,随着这些稀有金属原料的日益消耗,CIGS薄膜电池的成本也将会有所增加。 [0003] Currently, copper indium gallium selenide (CIGS) thin film solar cells is one of the most promising solar cells, but the preparation of CIGS thin film solar cell light-absorbing layer requires a large amount of In, Ga and other precious metals, which makes CIGS promote the use of large-scale thin-film batteries is greatly restricted in the supply of raw materials, with the increasing consumption of these rare raw materials, the cost of CIGS thin film cells will also be increased. 因此,一些研究人员就寻找到一种廉价的、储量高的金属Al来取代Ga,制备成铜铟铝硒薄膜电池。 Therefore, some researchers find a cheap, high-Al metal to replace reserves Ga, Al to prepare a copper indium selenide thin film battery.

[0004]目前铜铟铝硒薄膜的制备方法主要有磁控溅射法和电沉积法两种,磁控溅射法需要真空设备,投入成本高,而且金属Al易被氧化,使得制备的薄膜中会含有或多或少的铝氧化物。 [0004] The present method for preparing a thin film copper indium selenide thin film mainly aluminum magnetron sputtering and electrodeposition and French, magnetron sputtering method requires a vacuum equipment, high investment costs, but Al is easily oxidized metal, such prepared It will contain more or less of aluminum oxide. 而电沉积法制备的薄膜致密性和附着型都比较差,且电池的转化效率也较低。 And a film prepared electrodeposition density and relatively poor adhesion type, and the conversion efficiency of the battery is low.

发明内容 SUMMARY

[0005] 本发明实施例的目的在于提供一种具有能带梯度分布的铜铟铝硒(CIAS)薄膜的制备方法,旨在解决现有技术中操作复杂、成本高、纯度低、薄膜致密性和附着型差、以及光电转化率低的问题。 [0005] The object of embodiments of the present invention to provide a method for preparing aluminum copper indium selenide (CIAS) band having a gradient of a thin film, the prior art to solve complex operation, high cost, low purity, the film denseness and differential adhesion type, and the problem of low photoelectric conversion.

[0006] 本发明实施例是这样实现的,一种具有能带梯度分布的的铜铟铝硒薄膜的制备方法,包括以下步骤: [0006] Example embodiments of the present invention is implemented, a process for preparing copper indium selenide thin film of aluminum band having a gradient distribution, comprising the steps of:

[0007] 将铜源化合物、铝源化合物、铟源化合物、硫源和油胺混合,合成铜铟铝硫纳米颗粒; [0007] The copper source compound, an aluminum source compound, an indium compound source, sulfur source and amine blend oil, synthetic aluminum copper indium nanoparticles sulfur;

[0008] 将所述铜铟铝硫纳米颗粒分散在有机溶剂中,配制成铜铟铝硫纳米晶墨水; [0008] The copper indium aluminum sulfur nanoparticles dispersed in an organic solvent to prepare a copper indium aluminum sulfur nanocrystals ink;

[0009] 将所述铜铟铝硫纳米墨水涂敷在镀双层Mo的基体上,形成铜铟铝硒前驱体预制膜,其中,所述镀双层Mo的基体为分别沉积有纯Mo层和掺铝的Mo层的基体; [0009] The copper indium aluminum sulfur nano ink is applied on a substrate of Mo double plating, a copper indium selenide aluminum precursor pre-film, wherein the base plate is double-Mo Mo layer were deposited pure and the base layer is aluminum-doped Mo;

[0010] 将所述铜铟铝硒前驱体预制膜经过硒化、退火处理获得铜铟铝硒薄膜。 [0010] The copper indium selenide aluminum precursor film is subjected to pre-selenide, the annealing process to obtain copper indium selenide thin film aluminum.

[0011] 本发明所述具有能带梯度分布的铜铟铝硒薄膜的制备方法,采用相对廉价的铝化合物作为原料,解决了原料稀少和金属铝易被氧化的问题。 [0011] The method of the present invention is prepared having the copper indium selenide thin film of aluminum with a gradient of energy, use of relatively inexpensive aluminum compound as a starting material, to solve the problem of metallic aluminum and rare material susceptible to oxidation. 此外,本发明是一种非真空制膜技术,它不仅改善了薄膜的能带分布,拓宽薄膜的光吸收范围,促进薄膜对光的吸收和利用,而且采用掺铝的Mo层制备具有梯度分布的铜铟铝硒薄膜,提高了光电转化效率,同时还大大降低了太阳能电池的制造成本,有利于大面积均匀铜铟铝硒薄膜的制备。 Further, the present invention is a non-vacuum film-forming technology, which not only improves the energy band profile of the film, to broaden the range of the light absorption film, a film promoting absorption and utilization of light, and prepared using the Al-doped layer having a gradient distribution of Mo copper indium selenide thin film of aluminum, to improve the photoelectric conversion efficiency, while greatly reducing the manufacturing cost of solar cells, there are prepared a large area uniform film of copper indium selenide aluminum beneficial.

具体实施方式 detailed description

[0012] 为了使本发明要解决的技术问题、技术方案及有益效果更加清楚明白,以下结合实施例,对本发明进行进一步详细说明。 [0012] In order that the present invention is to solve the technical problem, technical solutions and beneficial effects more clearly understood, the following examples, the present invention will be further described in detail. 应当理解,此处所描述的具体实施例仅仅用以解释本发明,并不用于限定本发明。 It should be understood that the specific embodiments described herein are only intended to illustrate the present invention and are not intended to limit the present invention.

[0013] 本发明实施例提供了一种具有能带梯度分布的铜铟铝硒薄膜的溶液制备方法,包括以下步骤: [0013] Example embodiments provide a method for preparing an aluminum solution having a copper indium selenide film band gradient of the present invention, comprising the steps of:

[0014] S01.合成铜铟铝硫纳米颗粒:将铜源化合物、铝源化合物、铟源化合物、硫源和油胺混合,合成铜铟铝硫纳米颗粒; . [0014] S01 Synthesis of copper indium aluminum sulfur nanoparticles: a copper source compound, an aluminum source compound, an indium compound source, sulfur source and amine blend oil, synthetic aluminum copper indium nanoparticles sulfur;

[0015] S02.配制铜铟铝硫纳米晶墨水:将所述铜铟铝硒纳米颗粒分散在有机溶剂中配制成铜钢招硫纳米晶墨水; . [0015] S02 formulated copper indium aluminum sulfur nanocrystals ink: the aluminum copper indium selenide nanoparticles dispersed in an organic solvent formulated nanocrystalline copper sulfur steel ink strokes;

[0016] S03.将所述铜铟铝硫纳米墨水涂敷在镀双层Mo的基体上,形成铜铟铝硒前驱体预制膜,其中,所述镀双层Mo的基体为分别沉积有纯Mo层和掺铝的Mo层的基体; [0016] S03. The copper indium aluminum sulfur nano ink is applied on a substrate of Mo double plating, a copper indium selenide aluminum precursor pre-film, wherein the base plate is double-Mo are deposited pure aluminum-doped Mo layer and the Mo layer of the substrate;

[0017] S04.铜铟铝硒薄膜的制备:将所述铜铟铝硒前驱体预制膜经过硒化、退火处理获得铜铟铝硒薄膜。 [0017] S04 preparing copper indium selenide thin film of aluminum: The aluminum copper indium selenide precursor film is subjected to pre-selenide, the annealing process to obtain copper indium selenide thin film aluminum.

[0018] 具体地,上述步骤SOl中,为了能有效溶解铜源化合物、铝源化合物、铟源化合物和硫源,且在合成温度范围内稳定、挥发性小,本发明实施例选用油胺作为合成铜铟铝硫纳米颗粒的溶剂。 [0018] Specifically, the above step SOl in order to effectively dissolve the copper source compound, an aluminum source compound, an indium compound and a source of sulfur source, and at the synthesis temperature range stability, low volatility, selected embodiments of the present invention as an embodiment of oleylamine copper indium aluminum sulfur compounds were synthesized nanoparticles. 将铜源化合物、铝源化合物、铟源化合物和硫源与油胺混合的方式不受限制,作为优选实施例,可以是将铜源化合物、铝源化合物、铟源化合物和硫源混合后一起加入到油胺中,也可以是分别将铜源化合物、铝源化合物、铟源化合物和硫源加入到油胺中,其加入次序不受限制。 Is not limited to a copper source compound, an aluminum source compound, an indium compound and a sulfur source and a source oleylamine mixed manner, as a preferred embodiment, may be a compound with the copper source, an aluminum source compound, an indium source and a sulfur source compound mixed amine was added to the oil, respectively, may be a copper source compound, an aluminum source compound, an indium source and a sulfur source compound added to the oil-amine, which is the order of addition is not limited. 其中,在优选实施例中,该铜源化合物为氯化盐、醋酸盐、乙酰丙酮盐、氧化物中的至少一种;所述铝源化合物为氯化盐、醋酸盐、乙酰丙酮盐、氧化物中的至少一种;所述铟源化合物为氯化盐、醋酸盐、乙酰丙酮盐、氧化物中的至少一种;所述硫源为硫粉、硫化氢、二硫化碳、硫脲中的至少一种。 Wherein, in a preferred embodiment, the compound is a salt of copper chloride source, at least one of acetate, acetylacetonate, oxide; aluminum source compound is a salt of the chloride, acetate, acetylacetonate , at least one oxide; indium source compound is a salt of the chloride, acetate, acetylacetonate, at least one oxide; the sulfur source is a sulfur powder, hydrogen sulfide, carbon disulfide, thiourea at least one.

[0019] 所述铜铟铝硒薄膜中,各组分的比例对薄膜的能带结构有一定影响,尤其是铟和铝的比例对薄膜宽带结构的影响较大,铝的含量不同,薄膜材料的能带宽度不同,一定比例范围内,铝含量越大薄膜的能带宽度越大,但是,当铝含量太大时,薄膜的性能也会受到影响。 [0019] The copper indium selenide thin film aluminum, the ratio of the components is a band structure of a thin film of an impact, in particular a greater impact on the proportion of indium and aluminum film broadband structures, different contents of aluminum thin film material different energy band gap, a certain proportion of the range, the greater the aluminum content is greater bandgap film, however, when the aluminum content is too large, properties of the film will also be affected. 经发明人反复研究发现,所述铟、铝元素百分含量比为:0〈铝/(铟+铝)〈40%时,薄膜材料的性能较好,其中,当铝/ (铟+铝)=30%时,薄膜的性能最好。 The inventors have found that by repeated, the indium, aluminum element percentage ratio: 0 <Al / (Al + indium) <40%, preferably from properties of the film material, wherein, when the Al / (Al + indium) time = 30%, the best film properties.

[0020] 作为优选实施例,为了隔绝空气、避免其他副反应的产生,加入原料后,在装置中采用通入真空和氮气氛围的方式对反应液进行循环洗气,然后用氮气充满反应容器。 [0020] As a preferred embodiment, in order to cut off the air, to avoid the other side reaction, after addition of the raw material, the apparatus employed into a vacuum and a nitrogen atmosphere to the reaction solution circulated scrubbing, and then filled with nitrogen the reaction vessel. 其中,洗气次数优选为2次,每次洗气时间优选为15min。 Wherein the scrubbing frequency and preferably 2 times, each scrubbing time is preferably 15min. 当然,应当理解,其他在在反应条件下安全、且不与产物发生副反应的其他气体也在本发明的保护范围内。 Of course, it should be understood that, within the scope of the security Other gases under the reaction conditions, side reactions do not occur with the product of the present invention also.

[0021] 该步骤SOl中,作为具体优选实施例,SOl中所述铜铟铝硫纳米颗粒的合成温度优选为180-280° C,反应时间为10-100min。 [0021] In the step SOl, a particularly preferred embodiment, the synthesis temperature copper indium aluminum nanoparticles SOl sulfur is preferably 180-280 ° C, the reaction time is 10-100min. 其中,为了合成反应过程中加热均匀,上述合成反应中加热方式选用磁力搅拌加热方式。 Wherein the synthesis process for uniform heating, heating above synthesis selected magnetic stirring heating.

[0022] 步骤SOl中,SOl中合成反应结束后,将反应液冷却至室温后,过滤反应液得到固体产物,用有机溶剂清洗I〜5次后,获得洁净的铜铟铝硒纳米颗粒。 [0022] In step SOl, SOl after the synthesis reaction, the reaction solution was cooled to room temperature, the reaction solution was filtered to give a solid product, after washing with an organic solvent I~5 times to obtain a clean aluminum copper indium selenide nanoparticles. 作为具体实施例,上述有机溶剂优选为乙醇、异丙醇、己烷或氯仿中的至少一种。 As a specific example, the organic solvent is preferably ethanol, isopropanol, hexane or chloroform, at least one of.

[0023] 其中,上述步骤S02中,为了得到附着力好、杂质残留量少的铜铟镓硒纳米晶墨水,作为进一步优选实施例,所述有机溶剂为胺类、苯类或烷硫醇类化合物中的至少一种。 [0023] wherein the above-described step S02, in order to obtain good adhesion, a small amount of residual impurities copper indium gallium selenide nanocrystals ink, as a further preferred embodiment, the organic solvent is an amine, thiol, or an alkoxy benzene at least one compound. 在该优选实施例中,该有机溶剂同时起到分散剂的作用,使得反应生成的铜铟镓硒纳米颗粒能均匀分散,且能提高铜铟镓硒纳米晶墨水与基体的附着力。 In this preferred embodiment, the organic solvent at the same time acts as a dispersant, such that the CIGS nanoparticles produced by the reaction can be uniformly dispersed, and can improve the adhesion of copper indium gallium selenide nanocrystals ink and the substrate. 作为具体实施例,胺类优选吡啶、丁胺、戊胺、己胺、2-乙基丁胺中的至少一种,苯类优选甲苯、二甲苯、苯、乙苯、丙苯中的至少一种,烷硫醇优选己硫醇、二甲苯、苯、乙苯、丙苯中的至少一种。 As at least one embodiment, the amine is preferably pyridine, butylamine, pentylamine, hexylamine, 2-ethyl-butylamine at least one, preferably benzene, toluene, xylene, benzene, ethylbenzene, propyl benzene species, preferably hexane thiol mercaptan, xylene, benzene, ethylbenzene, propylbenzene at least one of.

[0024] 该S02步骤中,所述铜铟铝硒纳米晶墨水的浓度对薄膜的厚度有直接的影响,单层薄膜的厚度与墨水的浓度成正比关系,浓度越大,单层薄膜的厚度越大。 [0024] In the step S02, the concentration of the selenium ink of nanocrystalline copper indium aluminum has a direct influence on the thickness of the film thickness is proportional to the concentration of the single-layer film of the ink, the greater the concentration, the film thickness of the monolayer greater. 作为优选实施例,为了得到厚度合适、分布均匀的单层铜铟铝硫薄膜,所述铜铟铝硫纳米晶墨水的浓度为10_300mg/mL。 As a preferred embodiment, in order to obtain a suitable thickness, distribution of a single layer film of copper indium aluminum sulfur, the sulfur concentration of the nanocrystalline aluminum copper indium ink is 10_300mg / mL.

[0025] 上述步骤S03中,所述铜铟铝硒前驱体预制膜预制膜通过采用物理方法将铜铟铝硫纳米晶墨水涂敷在镀双层Mo的石英玻璃基体上制备而成,制备得到的铜铟铝硒纳米晶前驱体预制膜厚度为800-3000nm。 [0025] The above-described step S03, the aluminum copper indium selenide film precursor preformed pre-film copper indium aluminum sulfur nanocrystals prepared by coating the ink on the quartz glass substrate coated bilayer Mo by physical means, prepared the thickness of the pre-film copper indium selenide nanocrystals aluminum precursor is 800-3000nm. 采用非真空的物理方法,不需要昂贵的设备,减少了投资成本,且操作简单,便于大规模工业生产。 Using vacuum-physical methods, does not require expensive equipment, reducing the investment cost and simple operation, ease of mass industrial production. 所述物理方法优选为刮涂法、旋涂法、提拉法、滴涂法、丝网印刷法中的一种。 The physical method is preferably knife coating, spin coating method, dip method, a dispenser method, a medium screen printing method. 当然,应当理解,本领域内其他能用于铜铟铝硒纳米晶前驱体预制膜涂膜的物理方法都在本发明的保护范围内。 Of course, it should be understood that other art methods capable of physically coating pre-film copper indium selenide nanocrystals aluminum precursors are used within the scope of the present invention.

[0026] 其中,作为具体优选实施例,上述镀双层Mo的石英玻璃基体为分别采用溅射法和共溅射法在石英基体上沉积纯Mo层和掺铝的Mo层的双层Mo石英玻璃基体。 [0026] wherein, as a specific preferred embodiment, the above-described two-layer plating Mo quartz glass substrate were used as a sputtering method, an Mo layer and the co-sputtering and depositing pure aluminum doped Mo layer on the quartz crystal body bilayer Mo a glass substrate. 作为具体优选实施例,镀Mo石英玻璃基体的制备方法为:选用石英玻璃作为基板,将基体裁剪成边长为 As a specific preferred embodiment, the method for preparing a quartz glass substrate Mo plating is: with quartz glass as the substrate, the substrate is a side cut genre

1.0cmX2.0cm的基体备用,分别用丙酮、乙醇、去离子水超生清洗钙钠玻璃基体,获得表面洁净的基体,接着通过直流磁控溅射在洁净的基体上镀上一层300-800nm的金属Mo薄膜,然后再通过共溅射法沉积一层20-500nm厚含铝的金属Mo薄膜,铝的含量为0.5_15%。 1.0cmX2.0cm backup matrix, respectively, with acetone, ethanol, deionized water bounce washed soda lime glass substrate, to obtain a clean surface of the substrate, by DC magnetron sputtering and then coated with a layer 300-800nm ​​on a clean substrate Mo metal film, a thickness of 20-500nm and then a layer of aluminum deposited by co-sputtering Mo metal thin film, an aluminum content of 0.5_15%. 掺铝的Mo薄膜层通过下述步骤S04中离子的热扩散来实现铝的梯度分布,具体原理为:在热处理中铝的扩散速率比铜、铟的都低,容易在薄膜底部聚集,造成薄膜顶部铝含量过低。 Mo thin film layer of aluminum-doped aluminum gradient distribution is achieved by thermal diffusion of ions in the step S04, specifically principle: the rate of diffusion heat treatment of aluminum are lower than the copper, indium, easily collected at the bottom of the film, causing the film top of the aluminum content is too low. 而采用掺铝的Mo层,既避免了铝被大量氧化,同时也补充薄膜底部的铝,使薄膜底部中铝的浓度加大,在热处理过程铝能向顶部扩散,这样就形成铝梯度分布的薄膜,同时铝向下表面扩散到Mo层与玻璃的接触面与氧气反应形成A1203,促进Mo与玻璃附着性的提高,从而制备具有梯度分布的铜铟铝硒薄膜,进而提高其光电转化效率。 The use of aluminum-doped Mo layer, both to avoid the oxidation of the aluminum is large, while the bottom of the aluminum film also added, so that the base film to increase the concentration of aluminum, can spread to the top of the aluminum during heat treatment, thus forming the gradient of aluminum film, while the diffusion of the aluminum down to the Mo layer and the glass surface of the contact surface reaction with oxygen to form A1203, and Mo promote improved adhesion of glass, thereby preparing an aluminum copper indium selenide film having a gradient distribution, thus improving the photoelectric conversion efficiency.

[0027] 作为具体优选实施例,S04所述硒化处理的具体步骤为:采用管式炉作为热处理工具,先把铜铟铝硒前驱体预制膜和适量的硒源放置在石墨盒中,再把该石墨盒置于管式炉中,并充满Ar气,然后以10-30/min的速度升温,给炉体加热,进行硒化处理,最后获得铜铟铝硒薄膜。 [0027] Specific preferred examples of embodiments, the specific steps S04 selenization treatment is: a tubular furnace using the heat treatment tool, aluminum copper indium selenide first precursor pre-film and the amount of the selenium source is placed in the graphite box, and then the stone the cartridge placed in a tubular furnace, and filled with Ar gas at a rate of 10-30 / min heating, a heating furnace, the selenization process, and finally obtain a copper indium selenide thin film aluminum. 其中,硒化温度为500-600° C,硒化时间为10-90min,其中,硒源为硒粉、硒化氢、二乙基硒中的至少一种。 Wherein the selenization temperature 500-600 ° C, selenide, time 10-90min, wherein the selenium source is selenium powder, hydrogen selenide, at least one of diethyl selenium. 上述步骤中Ar气作为保护气体,用于防止铜铟铝硒前驱体预制膜预制膜发生副反应。 The above steps Ar gas as a shielding gas for preventing copper indium selenide precursor preformed aluminum film pre-film side reactions. 当然,应当理解,本领域内其他在上述条件下能用作铜铟铝硒纳米晶前驱体保护气体的气体,都在本发明的保护范围内。 Of course, it should be understood that other art can be used as aluminum copper indium selenide nanocrystals precursor gas protection gas under the above conditions, are within the scope of the present invention. 本发明实施例中,硒化处理的目的是在薄膜中取代硫的位置,从而形成铜铟铝硒薄膜。 Embodiment of the present invention, the object of the selenization process is replaced with sulfur in position in the film, thereby forming a copper indium selenide thin film aluminum. 硒的用量对硒化处理影响较大,当硒用量太低时,达不到完全取代硫的效果;当硒含量过高时,容易造成浪费。 The amount of selenium large influence on the selenization process, when the amount of selenium are too low to completely replace the effects of sulfur; when selenium content is too high, easily lead to waste. 作为优选实施例,当硒粉用量为l-30mmol,硒量太少会造成薄膜中硒的流失,太多会造成浪费。 As a preferred embodiment, when the selenium powder in an amount of l-30mmol, selenium too can cause the loss of the film of selenium, too wasteful. [0028] 作为优选实施例,制备得到的铜铟铝硒薄膜厚度为800_3000nm。 [0028] As a preferred embodiment, aluminum copper indium selenide film thickness was prepared 800_3000nm. 经发明人反复研究发现,铜铟铝硒薄膜的厚度对光的吸收影响较大:薄膜的厚度太小时,将减少薄膜对光的吸收进而影响薄膜光电转化率,使产品的性能受限;薄膜厚度越厚,薄膜对光的吸收越高,光的利用率越高,产品的性能也就越好,但是厚度太厚将增加薄膜成本。 The inventors have found that by repeated, aluminum copper indium selenide film thickness of the light absorption of greater impact: film thickness is too small, the light absorbing film to reduce thin-film photoelectric conversion rate thereby affecting the performance of the product is limited; film the thicker, the higher the light absorbing film, the higher the utilization of light, the better the performance of the product, but too thick a film will increase the cost. 当铜铟铝硒薄膜厚度为800-3000nm时,既能满足铜铟铝硒薄膜的性能,又能有效地控制成本。 When aluminum copper indium selenide film having a thickness of 800-3000nm, can meet the performance copper indium selenide aluminum film, and can effectively control costs.

[0029] 在本发明实施例采用相对廉价的铝取代稀有金属镓,不仅降低了实验对贵金属的依赖性,还降低了稀有金属的用量,解决了原料稀少和金属铝易被氧化的问题。 [0029] Example use of relatively inexpensive aluminum gallium-substituted rare metal of the present invention, not only reduces the experimental dependence of the noble metal, also reduces the amount of rare metals, rare material solve the problem of metallic aluminum and susceptible to oxidation. 同时,采用掺铝的Mo薄膜层作为背接触电极,制备具有梯度分布的铜铟铝硒薄膜,有利于制备高转化率的铜铟铝硒薄膜电池。 Meanwhile, the use of aluminum-doped Mo thin film layer as a back contact electrode, preparing a thin film copper indium selenide gradient of aluminum, aluminum copper indium selenide facilitate preparation of thin film batteries high conversion. 此外,本发明是一种非真空制膜技术,它不仅改善了薄膜的能带分布,拓宽薄膜的光吸收范围(铜铟铝硒的禁带宽度在1.0-2.7eV),促进薄对光的吸收和利用,进而提高光电转化效率,还大大降低了太阳能电池的制造成本,有利于大面积均匀铜铟铝硒薄膜的制备。 Further, the present invention is a non-vacuum film-forming technology, which not only improves the energy band profile of the film, the film to broaden the range of light absorption (in 1.0-2.7eV bandgap aluminum copper indium selenium), promote thin light absorption and utilization, thus improving the photoelectric conversion efficiency and also greatly reduces the manufacturing cost of solar cells, there are prepared a large area uniform film of copper indium selenide aluminum beneficial.

[0030] 实施例一 [0030] Example a

[0031 ] (I)铜铟招硫纳米颗粒的制备:将2.0mmol氯化亚铜,1.70mmol三氯化铟,0.30mmol三氯化铝和6.0mmol硫粉加入IOOmL三颈瓶中,再加入35mL油胺,并放入温控加热套中,然后与史莱克换气装置连接好,并加热。 [0031] (I) preparing copper indium nanoparticles sulfur strokes: The cuprous chloride 2.0mmol, 1.70mmol indium trichloride, aluminum trichloride and 0.30 mmol 6.0mmol sulfur powder were added IOOmL three-necked flask was added 35mL oleylamine, and placed in temperature-controlled heating mantle, and then connected to the ventilator Shrek, and heated. 同时通过真空和氩气氛围循环的方式对反应液进行循环洗气2次,每次洗气15min。 At the same time by a vacuum and argon atmosphere circulating reaction liquid circulating scrubbing 2 times scrubbing 15min. 最后用氩气充满反应容器。 Finally, the reaction vessel filled with argon. 在磁力搅拌下,继续加热,当温度升高到220° C,保持不变,60min后停止反应。 Under magnetic stirring and heating was continued, when the temperature was raised to 220 ° C, remains constant, the reaction was stopped after 60min. 随后冷却至室温,过滤离心反应液获得固体产物,并用乙醇、己烷清洗5次,获得洁净的固体产物。 Then cooled to room temperature, the reaction solution was filtered to obtain a solid product was centrifuged and washed with ethanol, washed with hexane 5 times to obtain a solid product was clean.

[0032] (2)制备铜铟铝硫纳米晶墨水:把铜铟铝硫纳米颗粒放入甲苯中形成浓度为20mg/mL稳定的胶体溶液-铜铟铝硫纳米晶墨水。 [0032] (2) Preparation of nanocrystalline copper indium aluminum ink sulfur: sulfur to copper indium aluminum nanoparticles taken up in toluene a concentration of 20mg / mL solution of a stable colloidal - copper indium aluminum sulfur nanocrystals ink.

[0033] (3)镀钥玻璃的制备:把石英玻璃基体裁成1.0cmX2.0cm大小,分别用丙酮、乙醇、去离子水超生清洗干净。 [0033] (3) Preparation of coated glass key: the genre into the silica glass substrate 1.0cmX2.0cm size, respectively, with acetone, ethanol, deionized water bounce clean. 通过直流磁控溅射法在石英玻璃基体上镀金属Mo,厚度为500nm ;接着通过共溅射法沉积一层厚度为200mn的含Al的金属Mo薄膜,其中铝的含量为 By DC magnetron sputtering on a metallized substrate Mo quartz glass, having a thickness of 500 nm; then deposited by co-sputtering to a thickness of the Al-containing metal 200mn the Mo thin film, wherein the content of aluminum is

5% ο 5% ο

[0034] (4)铜铟铝硒薄膜的制备:通过刮涂法把铜铟铝硫纳米晶墨水涂敷在镀Mo的基体上,形成1500nm厚的铜铟铝硒纳米晶前驱体预制膜,随后放在300° C的电热板上干燥。 Preparation of [0034] (4) copper indium selenide thin film of aluminum: the doctor blade method by sulfur nanocrystalline copper indium aluminum ink is applied on a substrate of Mo plating, a copper indium selenide nanocrystals aluminum precursor pre-film 1500nm thick, then placed on a hot plate to 300 ° C and dried. 把干燥后的铜铟铝硒前驱体预制膜预制膜和稍过量(5mmol)的二乙基硒放置在石墨盒中,接着把该石磨盒放在管式炉中,通入Ar气,排尽炉中的空气,并使Ar充满炉腔。 The pre-film pre-film copper indium selenide aluminum precursor after drying and a slight excess (5 mmol of) diethyl selenium ink cartridge is placed in the stone, the stone then the box placed in a tube furnace, an Ar gas into the exhaust make the air in the furnace, and the cavity filled with Ar. 然后以15° C/min的升温速度,给炉体加热,使炉腔温度快速升高到530° C,然后对铜铟铝硒前驱体预制膜进行硒化热火处理。 Then 15 ° C / min heating rate, the heating furnace to the furnace chamber temperature was quickly ramped to 530 ° C, then the pre-film copper indium selenide precursor is an aluminum heat selenization process. 30min后停止加热,并冷却至室温,最后获得具有梯度分布的铜铟铝硒薄膜。 Heating was stopped after 30min, and cooled to room temperature, to obtain the final aluminum copper indium selenide film having a gradient distribution.

[0035] 实施例二 [0035] Second Embodiment

[0036] (I)铜铟招硫纳米颗粒的制备:将2.0mmol氯化亚铜,1.70mmol三氯化铟,0.30mmol三氯化铝和4.0mmol硫粉加入IOOmL三颈瓶中,再加入35mL油胺,并放入温控加热套中,然后与史莱克换气装置连接好,并加热。 [0036] (I) preparing copper indium nanoparticles sulfur strokes: The cuprous chloride 2.0mmol, 1.70mmol indium trichloride, aluminum trichloride and 0.30 mmol 4.0mmol sulfur powder were added IOOmL three-necked flask was added 35mL oleylamine, and placed in temperature-controlled heating mantle, and then connected to the ventilator Shrek, and heated. 同时通过真空和氩气氛围循环的方式对反应液进行循环洗气2次,每次洗气15min。 At the same time by a vacuum and argon atmosphere circulating reaction liquid circulating scrubbing 2 times scrubbing 15min. 最后用氩气充满反应容器。 Finally, the reaction vessel filled with argon. 在磁力搅拌下,继续加热,当温度升高到190° C,保持不变,60min后停止反应。 Under magnetic stirring and heating was continued, when the temperature was increased to 190 ° C, remains constant, the reaction was stopped after 60min. 随后冷却至室温,过滤离心反应液获得固体产物,并用乙醇、己烷清洗5次,获得洁净的固体产物。 Then cooled to room temperature, the reaction solution was filtered to obtain a solid product was centrifuged and washed with ethanol, washed with hexane 5 times to obtain a solid product was clean. [0037] (2)制备铜铟铝硫纳米晶墨水:把铜铟铝硫纳米颗粒放入甲苯中形成浓度为50mg/mL稳定的胶体溶液-铜铟招硫纳米晶墨水。 [0037] (2) Preparation of nanocrystalline copper indium aluminum ink sulfur: sulfur to copper indium aluminum nanoparticles taken up in toluene a concentration of 50mg / mL solution of a stable colloidal - copper indium sulfur nanocrystals ink strokes.

[0038] (3)镀钥玻璃的制备:把石英玻璃基体裁成1.0cmX2.0cm大小,分别用丙酮、乙醇、去离子水超生清洗干净。 [0038] (3) Preparation of coated glass key: the genre into the silica glass substrate 1.0cmX2.0cm size, respectively, with acetone, ethanol, deionized water bounce clean. 通过直流磁控溅射法在石英玻璃基体上镀金属Mo,厚度为500nm ;接着通过共溅射法沉积一层厚度为500mn的含Al的金属Mo薄膜,其中铝的含量为10%。 By DC magnetron sputtering on a metallized substrate Mo quartz glass, having a thickness of 500 nm; and then co-deposited by sputtering to a thickness of a metal containing Al 500mn the Mo thin film, wherein the content of aluminum is 10%.

[0039] (4)铜铟铝硒薄膜的制备:通过刮涂法把铜铟铝硫纳米晶墨水涂敷在镀Mo的基体上,形成1500nm厚的铜铟铝硒纳米晶前驱体预制膜,随后放在300° C的电热板上干燥。 Preparation of [0039] (4) copper indium selenide thin film of aluminum: the doctor blade method by sulfur nanocrystalline copper indium aluminum ink is applied on a substrate of Mo plating, a copper indium selenide nanocrystals aluminum precursor pre-film 1500nm thick, then placed on a hot plate to 300 ° C and dried. 把干燥后的铜铟铝硒前驱体预制膜预制膜和稍过量(5mmol)的二乙基硒放置在石墨盒中,接着把该石磨盒放在管式炉中,通入Ar气,排尽炉中的空气,并使Ar充满炉腔。 The pre-film pre-film copper indium selenide aluminum precursor after drying and a slight excess (5 mmol of) diethyl selenium ink cartridge is placed in the stone, the stone then the box placed in a tube furnace, an Ar gas into the exhaust make the air in the furnace, and the cavity filled with Ar. 然后以20° C/min的升温速度,给炉体加热,使炉腔温度快速升高到560° C,然后对铜铟铝硒前驱体预制膜进行硒化热火处理。 Then 20 ° C / min heating rate, the heating furnace to the furnace chamber temperature was quickly ramped to 560 ° C, then the pre-film copper indium selenide precursor is an aluminum heat selenization process. 20min后停止加热,并冷却至室温,最后获得具有梯度分布的铜铟铝硒薄膜。 Heating was stopped after 20min, and cooled to room temperature, to obtain the final aluminum copper indium selenide film having a gradient distribution.

[0040] 实施例三 [0040] Example three

[0041 ] (I)铜铟招硫纳米颗粒的制备:将2.0mmol氯化亚铜,1.70mmol三氯化铟,0.30mmol三氯化铝和5.0mmol硫粉加入IOOmL三颈瓶中,再加入35mL油胺,并放入温控加热套中,然后与史莱克换气装置连接好,并加热。 [0041] (I) preparing copper indium nanoparticles sulfur strokes: The cuprous chloride 2.0mmol, 1.70mmol indium trichloride, aluminum trichloride and 0.30 mmol 5.0mmol sulfur powder were added IOOmL three-necked flask was added 35mL oleylamine, and placed in temperature-controlled heating mantle, and then connected to the ventilator Shrek, and heated. 同时通过真空和氩气氛围循环的方式对反应液进行循环洗气2次,每次洗气15min。 At the same time by a vacuum and argon atmosphere circulating reaction liquid circulating scrubbing 2 times scrubbing 15min. 最后用氩气充满反应容器。 Finally, the reaction vessel filled with argon. 在磁力搅拌下,继续加热,当温度升高到200° C,保持不变,60min后停止反应。 Under magnetic stirring and heating was continued, when the temperature was raised to 200 ° C, remains constant, the reaction was stopped after 60min. 随后冷却至室温,过滤离心反应液获得固体产物,并用乙醇、己烷清洗5次,获得洁净的固体产物。 Then cooled to room temperature, the reaction solution was filtered to obtain a solid product was centrifuged and washed with ethanol, washed with hexane 5 times to obtain a solid product was clean.

[0042] (2)制备铜铟铝硫纳米晶墨水:把铜铟铝硫纳米颗粒放入甲苯中形成浓度为100mg/mL稳定的胶体溶液-铜铟招硫纳米晶墨水。 [0042] (2) Preparation of nanocrystalline copper indium aluminum ink sulfur: sulfur to copper indium aluminum nanoparticles taken up in toluene a concentration of 100mg / mL solution of a stable colloidal - copper indium sulfur nanocrystals ink strokes.

[0043] (3)镀钥玻璃的制备:把石英玻璃基体裁成1.0cmX2.0cm大小,分别用丙酮、乙醇、去离子水超生清洗干净。 [0043] (3) Preparation of coated glass key: the genre into the silica glass substrate 1.0cmX2.0cm size, respectively, with acetone, ethanol, deionized water bounce clean. 通过直流磁控溅射法在石英玻璃基体上镀金属Mo,厚度为500nm ;接着通过共溅射法沉积一层厚度为IOOmn的含Al的金属Mo薄膜,其中铝的含量为15%。 By DC magnetron sputtering on a metallized substrate Mo quartz glass, having a thickness of 500 nm; and then co-deposited by sputtering to a thickness of a metal containing Al IOOmn of Mo thin film, wherein the aluminum content is 15%.

[0044] (4)铜铟铝硒薄膜的制备:通过刮涂法把铜铟铝硫纳米晶墨水涂敷在镀Mo的基体上,形成1500nm厚的铜铟铝硒纳米晶前驱体预制膜,随后放在300° C的电热板上干燥。 Preparation of [0044] (4) copper indium selenide thin film of aluminum: the doctor blade method by sulfur nanocrystalline copper indium aluminum ink is applied on a substrate of Mo plating, a copper indium selenide nanocrystals aluminum precursor pre-film 1500nm thick, then placed on a hot plate to 300 ° C and dried. 把干燥后的铜铟铝硒前驱体预制膜预制膜和稍过量(5mmol)的二乙基硒放置在石墨盒中,接着把该石磨盒放在管式炉中,通入Ar气,排尽炉中的空气,并使Ar充满炉腔。 The pre-film pre-film copper indium selenide aluminum precursor after drying and a slight excess (5 mmol of) diethyl selenium ink cartridge is placed in the stone, the stone then the box placed in a tube furnace, an Ar gas into the exhaust make the air in the furnace, and the cavity filled with Ar. 然后以25。 Then 25. C/min的升温速度,给炉体加热,使炉腔温度快速升高到550° C,然后对铜铟铝硒前驱体预制膜进行硒化热火处理。 Temperature rise rate of C / min, the furnace is heated to the temperature of the furnace chamber quickly rises to 550 ° C, then the pre-film copper indium selenide precursor is an aluminum heat selenization process. 30min后停止加热,并冷却至室温,最后获得具有梯度分布的铜铟铝硒薄膜。 Heating was stopped after 30min, and cooled to room temperature, to obtain the final aluminum copper indium selenide film having a gradient distribution.

[0045] 实施例四 [0045] Fourth Embodiment

[0046] (I)铜铟招硫纳米颗粒的制备:将Immol氯化铜,0.8mmol三氯化铟,0.2mmol三氯化镓和3mmol硫粉加入IOOmL三颈瓶中,再加入35mL油胺,并放入温控加热套中,然后与史莱克换气装置连接好,并加热。 [0046] (I) preparing copper indium nanoparticles sulfur strokes: the Immol copper chloride, indium trichloride 0.8mmol, 0.2mmol gallium trichloride and sulfur powder were added IOOmL 3mmol three-necked flask was added 35mL of oleylamine and placed in temperature-controlled heating mantle, and then connected to the ventilator Shrek, and heated. 同时通过真空和氩气氛围循环的方式对反应液进行循环洗气2次,每次洗气15min。 At the same time by a vacuum and argon atmosphere circulating reaction liquid circulating scrubbing 2 times scrubbing 15min. 最后用氩气充满反应容器。 Finally, the reaction vessel filled with argon. 在磁力搅拌下,继续加热,当温度升高到210° C,保持不变,60min后停止反应。 Under magnetic stirring and heating was continued, when the temperature was raised to 210 ° C, remains constant, the reaction was stopped after 60min. 随后冷却至室温,过滤离心反应液获得固体产物,并用乙醇、己烷清洗5次,获得洁净的固体产物。 Then cooled to room temperature, the reaction solution was filtered to obtain a solid product was centrifuged and washed with ethanol, washed with hexane 5 times to obtain a solid product was clean.

[0047] (2)制备铜铟铝硫纳米晶墨水:把铜铟铝硫纳米颗粒放入甲苯中形成浓度为150mg/mL稳定的胶体溶液-铜铟铝硫纳米晶墨水。 [0047] (2) Preparation of nanocrystalline copper indium aluminum ink sulfur: sulfur to copper indium aluminum nanoparticles taken up in toluene a concentration of 150mg / mL solution of a stable colloidal - copper indium aluminum sulfur nanocrystals ink.

[0048] (3)镀钥玻璃的制备:把石英玻璃基体裁成1.0cmX2.0cm大小,分别用丙酮、乙醇、去离子水超生清洗干净。 [0048] (3) Preparation of coated glass key: the genre into the silica glass substrate 1.0cmX2.0cm size, respectively, with acetone, ethanol, deionized water bounce clean. 通过直流磁控溅射法在石英玻璃基体上镀金属Mo,厚度为500nm ;接着通过共溅射法沉积一层厚度为150mn的含Al的金属Mo薄膜,其中铝的含量为1%。 By DC magnetron sputtering on a metallized substrate Mo quartz glass, having a thickness of 500 nm; and then co-deposited by sputtering to a thickness of a metal containing Al 150mn the Mo thin film, wherein the aluminum content is 1%.

[0049] (4)铜铟铝硒薄膜的制备:通过刮涂法把铜铟铝硫纳米晶墨水涂敷在镀Mo的基体上,形成2000nm厚的铜铟铝硒纳米晶前驱体预制膜,随后放在300° C的电热板上干燥。 Preparation of [0049] (4) copper indium selenide thin film of aluminum: the doctor blade method by sulfur nanocrystalline copper indium aluminum ink is applied on a substrate of Mo plating, a copper indium selenide nanocrystals aluminum precursor pre-film 2000nm thick, then placed on a hot plate to 300 ° C and dried. 把干燥后的铜铟铝硒前驱体预制膜预制膜和稍过量(5mmol)的二乙基硒放置在石墨盒中,接着把该石磨盒放在管式炉中,通入Ar气,排尽炉中的空气,并使Ar充满炉腔。 The pre-film pre-film copper indium selenide aluminum precursor after drying and a slight excess (5 mmol of) diethyl selenium ink cartridge is placed in the stone, the stone then the box placed in a tube furnace, an Ar gas into the exhaust make the air in the furnace, and the cavity filled with Ar. 然后以12° C/min的升温速度,给炉体加热,使炉腔温度快速升高到590° C,然后对铜铟铝硒前驱体预制膜进行硒化热火处理。 Then 12 ° C / min heating rate, the heating furnace to the furnace chamber temperature was quickly ramped to 590 ° C, then the pre-film copper indium selenide precursor is an aluminum heat selenization process. 40min后停止加热,并冷却至室温,最后获得具有梯度分布的铜铟铝硒薄膜。 Heating was stopped after 40min, and cooled to room temperature, to obtain the final aluminum copper indium selenide film having a gradient distribution.

[0050] 实施例五 [0050] Embodiment V

[0051] (I)铜铟招硫纳米颗粒的制备:将3.0mmol醋酸铜,2.6OmmoI醋酸铟,0.40mmol硝酸铝铝和9.0mmol硫尿加入IOOmL三颈瓶中,再加入35mL油胺,并放入温控加热套中,然后与史莱克换气装置连接好,并加热。 [0051] (I) preparing copper indium nanoparticles sulfur strokes: the 3.0mmol copper acetate, indium 2.6OmmoI acetate, 0.40 mmol of aluminum and aluminum nitrate was added thiourea 9.0mmol IOOmL three-necked flask was added 35mL oleylamine, and Temperature placed in a heating mantle and connected with Shrek ventilator and heating. 同时通过真空和氩气氛围循环的方式对反应液进行循环洗气2次,每次洗气15min。 At the same time by a vacuum and argon atmosphere circulating reaction liquid circulating scrubbing 2 times scrubbing 15min. 最后用氩气充满反应容器。 Finally, the reaction vessel filled with argon. 在磁力搅拌下,继续加热,当温度升高到250° C,保持不变,60min后停止反应。 Under magnetic stirring and heating was continued, when the temperature was increased to 250 ° C, remains constant, the reaction was stopped after 60min. 随后冷却至室温,过滤离心反应液获得固体产物,并用乙醇、己烷清洗5次,获得洁净的固体产物。 Then cooled to room temperature, the reaction solution was filtered to obtain a solid product was centrifuged and washed with ethanol, washed with hexane 5 times to obtain a solid product was clean.

[0052] (2)制备铜铟铝硫纳米晶墨水:把铜铟铝硫纳米颗粒放入甲苯中形成浓度为200mg/mL稳定的胶体溶液-铜铟铝硫纳米晶墨水。 [0052] (2) Preparation of nanocrystalline copper indium aluminum ink sulfur: sulfur to copper indium aluminum nanoparticles taken up in toluene a concentration of 200mg / mL solution of a stable colloidal - copper indium aluminum sulfur nanocrystals ink.

[0053] (3)镀钥玻璃的制备:把石英玻璃基体裁成1.0cmX2.0cm大小,分别用丙酮、乙醇、去离子水超生清洗干净。 [0053] (3) Preparation of coated glass key: the genre into the silica glass substrate 1.0cmX2.0cm size, respectively, with acetone, ethanol, deionized water bounce clean. 通过直流磁控溅射法在石英玻璃基体上镀金属Mo,厚度为500nm ;接着通过共溅射法沉积一层厚度为300mn的含Al的金属Mo薄膜,其中铝的含量为10%。 By DC magnetron sputtering on a metallized substrate Mo quartz glass, having a thickness of 500 nm; and then co-deposited by sputtering to a thickness of a metal containing Al 300mn the Mo thin film, wherein the content of aluminum is 10%.

[0054] (4)铜铟铝硒薄膜的制备:通过刮涂法把铜铟铝硫纳米晶墨水涂敷在镀Mo的基体上,形成3000nm厚的铜铟铝硒纳米晶前驱体预制膜,随后放在300° C的电热板上干燥。 Preparation of [0054] (4) copper indium selenide thin film of aluminum: the doctor blade method by sulfur nanocrystalline copper indium aluminum ink is applied on a substrate of Mo plating, a copper indium selenide nanocrystals aluminum precursor pre-film 3000nm thick, then placed on a hot plate to 300 ° C and dried. 把干燥后的铜铟铝硒前驱体预制膜预制膜和稍过量(5mmol)的二乙基硒放置在石墨盒中,接着把该石磨盒放在管式炉中,通入Ar气,排尽炉中的空气,并使Ar充满炉腔。 The pre-film pre-film copper indium selenide aluminum precursor after drying and a slight excess (5 mmol of) diethyl selenium ink cartridge is placed in the stone, the stone then the box placed in a tube furnace, an Ar gas into the exhaust make the air in the furnace, and the cavity filled with Ar. 然后以15° C/min的升温速度,给炉体加热,使炉腔温度快速升高到580° C,然后对铜铟铝硒前驱体预制膜进行硒化热火处理。 Then 15 ° C / min heating rate, the heating furnace to the furnace chamber temperature was quickly ramped to 580 ° C, then the pre-film copper indium selenide precursor is an aluminum heat selenization process. SOmin后停止加热,并冷却至室温,最后获得具有梯度分布的铜铟铝硒薄膜。 SOmin stopped heating, cooled to room temperature and, finally obtained aluminum copper indium selenide film having a gradient distribution.

[0055] 实施例六 [0055] Sixth Embodiment

[0056] (I)铜铟招硫纳米颗粒的制备:将1.0mmol乙酰丙酮铜,0..70mmol乙酰丙酮铟, [0056] Preparation of copper-indium-sulfur nanoparticles strokes (I): The 1.0mmol copper acetylacetonate, 0..70mmol indium acetylacetonate,

0.30mmol硝酸招和3.0mmol硫粉加入IOOmL三颈瓶中,再加入35mL油胺,并放入温控加热套中,然后与史莱克换气装置连接好,并加热。 0.30mmol strokes nitric acid and sulfur powder were added 3.0mmol IOOmL three-necked flask was added 35mL of oleylamine and placed in temperature-controlled heating mantle, and then connected to the ventilator Shrek, and heated. 同时通过真空和氩气氛围循环的方式对反应液进行循环洗气2次,每次洗气15min。 At the same time by a vacuum and argon atmosphere circulating reaction liquid circulating scrubbing 2 times scrubbing 15min. 最后用氩气充满反应容器。 Finally, the reaction vessel filled with argon. 在磁力搅拌下,继续加热,当温度升高到200° C,保持不变,80min后停止反应。 Under magnetic stirring and heating was continued, when the temperature was raised to 200 ° C, remains constant, the reaction was stopped after 80min. 随后冷却至室温,过滤离心反应液获得固体产物,并用乙醇、己烷清洗5次,获得洁净的固体产物。 Then cooled to room temperature, the reaction solution was filtered to obtain a solid product was centrifuged and washed with ethanol, washed with hexane 5 times to obtain a solid product was clean.

[0057] (2)制备铜铟铝硫纳米晶墨水:把铜铟铝硫纳米颗粒放入甲苯中形成浓度为280mg/mL稳定的胶体溶液-铜铟铝硫纳米晶墨水。 [0057] (2) Preparation of nanocrystalline copper indium aluminum ink sulfur: sulfur to copper indium aluminum nanoparticles taken up in toluene a concentration of 280mg / mL solution of a stable colloidal - copper indium aluminum sulfur nanocrystals ink.

[0058] (3)镀钥玻璃的制备:把石英玻璃基体裁成1.0cmX2.0cm大小,分别用丙酮、乙醇、去离子水超生清洗干净。 [0058] (3) Preparation of coated glass key: the genre into the silica glass substrate 1.0cmX2.0cm size, respectively, with acetone, ethanol, deionized water bounce clean. 通过直流磁控溅射法在石英玻璃基体上镀金属Mo,厚度为500nm ;接着通过共溅射法沉积一层厚度为250mn的含Al的金属Mo薄膜,其中铝的含量为10%。 By DC magnetron sputtering on a metallized substrate Mo quartz glass, having a thickness of 500 nm; and then depositing a layer thickness by a co-sputtering method 250mn Mo Al-containing metal film, wherein the aluminum content is 10%.

[0059] (4)铜铟铝硒薄膜的制备:通过刮涂法把铜铟铝硫纳米晶墨水涂敷在镀Mo的基体上,形成1500nm厚的铜铟铝硒纳米晶前驱体预制膜,随后放在300° C的电热板上干燥。 Preparation of [0059] (4) copper indium selenide thin film of aluminum: the doctor blade method by sulfur nanocrystalline copper indium aluminum ink is applied on a substrate of Mo plating, a copper indium selenide nanocrystals aluminum precursor pre-film 1500nm thick, then placed on a hot plate to 300 ° C and dried. 把干燥后的铜铟铝硒前驱体预制膜预制膜和稍过量(5mmol)的二乙基硒放置在石墨盒中,接着把该石磨盒放在管式炉中,通入Ar气,排尽炉中的空气,并使Ar充满炉腔。 The pre-film pre-film copper indium selenide aluminum precursor after drying and a slight excess (5 mmol of) diethyl selenium ink cartridge is placed in the stone, the stone then the box placed in a tube furnace, an Ar gas into the exhaust make the air in the furnace, and the cavity filled with Ar. 然后以15° C/min的升温速度,给炉体加热,使炉腔温度快速升高到530° C,然后对铜铟铝硒前驱体预制膜进行硒化热火处理。 Then 15 ° C / min heating rate, the heating furnace to the furnace chamber temperature was quickly ramped to 530 ° C, then the pre-film copper indium selenide precursor is an aluminum heat selenization process. 30min后停止加热,并冷却至室温,最后获得具有梯度分布的铜铟铝硒薄膜。 Heating was stopped after 30min, and cooled to room temperature, to obtain the final aluminum copper indium selenide film having a gradient distribution.

[0060] 实施例七 [0060] Seventh Embodiment

[0061] (I)铜铟招硫纳米颗粒的制备:将2.0mmol醋酸铜,1.70mmol醋酸铟,0.3OmmoI醋酸铝和5.0mmol硫粉加入IOOmL三颈瓶中,再加入35mL油胺,并放入温控加热套中,然后与史莱克换气装置连接好,并加热。 [0061] (I) preparing copper indium nanoparticles sulfur strokes: the 2.0mmol copper acetate, indium acetate 1.70mmol, 0.3OmmoI 5.0mmol sulfur powder and aluminum acetate were added IOOmL three-necked flask was added 35mL of oleylamine and placed the temperature-controlled heating mantle, and then connected to the ventilator Shrek, and heated. 同时通过真空和氩气氛围循环的方式对反应液进行循环洗气2次,每次洗气15min。 At the same time by a vacuum and argon atmosphere circulating reaction liquid circulating scrubbing 2 times scrubbing 15min. 最后用氩气充满反应容器。 Finally, the reaction vessel filled with argon. 在磁力搅拌下,继续加热,当温度升高到230° C,保持不变,60min后停止反应。 Under magnetic stirring and heating was continued, when the temperature was increased to 230 ° C, remains constant, the reaction was stopped after 60min. 随后冷却至室温,过滤离心反应液获得固体产物,并用乙醇、己烷清洗5次,获得洁净的固体产物。 Then cooled to room temperature, the reaction solution was filtered to obtain a solid product was centrifuged and washed with ethanol, washed with hexane 5 times to obtain a solid product was clean.

[0062] (2)制备铜铟铝硫纳米晶墨水:把铜铟铝硫纳米颗粒放入甲苯中形成浓度为180mg/mL稳定的胶体溶液-铜铟招硫纳米晶墨水。 [0062] (2) Preparation of nanocrystalline copper indium aluminum ink sulfur: sulfur to copper indium aluminum nanoparticles taken up in toluene a concentration of 180mg / mL solution of a stable colloidal - copper indium sulfur nanocrystals ink strokes.

[0063] (3)镀钥玻璃的制备:把石英玻璃基体裁成1.0cmX2.0cm大小,分别用丙酮、乙醇、去离子水超生清洗干净。 [0063] (3) Preparation of coated glass key: the genre into the silica glass substrate 1.0cmX2.0cm size, respectively, with acetone, ethanol, deionized water bounce clean. 通过直流磁控溅射法在石英玻璃基体上镀金属Mo,厚度为500nm ;接着通过共溅射法沉积一层厚度为280mn的含Al的金属Mo薄膜,其中铝的含量为 By DC magnetron sputtering on a metallized substrate Mo quartz glass, having a thickness of 500 nm; then deposited by co-sputtering to a thickness of the Al-containing metal 280mn the Mo thin film, wherein the content of aluminum is

8% ο 8% ο

[0064] (4)铜铟铝硒薄膜的制备:通过刮涂法把铜铟铝硫纳米晶墨水涂敷在镀Mo的基体上,形成2000nm厚的铜铟铝硒纳米晶前驱体预制膜,随后放在300° C的电热板上干燥。 Preparation of [0064] (4) copper indium selenide thin film of aluminum: the doctor blade method by sulfur nanocrystalline copper indium aluminum ink is applied on a substrate of Mo plating, a copper indium selenide nanocrystals aluminum precursor pre-film 2000nm thick, then placed on a hot plate to 300 ° C and dried. 把干燥后的铜铟铝硒前驱体预制膜预制膜和稍过量(5mmol)的二乙基硒放置在石墨盒中,接着把该石磨盒放在管式炉中,通入Ar气,排尽炉中的空气,并使Ar充满炉腔。 The pre-film pre-film copper indium selenide aluminum precursor after drying and a slight excess (5 mmol of) diethyl selenium ink cartridge is placed in the stone, the stone then the box placed in a tube furnace, an Ar gas into the exhaust make the air in the furnace, and the cavity filled with Ar. 然后以15° C/min的升温速度,给炉体加热,使炉腔温度快速升高到530° C,然后对铜铟铝硒前驱体预制膜进行硒化热火处理。 Then 15 ° C / min heating rate, the heating furnace to the furnace chamber temperature was quickly ramped to 530 ° C, then the pre-film copper indium selenide precursor is an aluminum heat selenization process. 30min后停止加热,并冷却至室温,最后获得具有梯度分布的铜铟铝硒薄膜。 Heating was stopped after 30min, and cooled to room temperature, to obtain the final aluminum copper indium selenide film having a gradient distribution.

[0065] 实施例八 [0065] The eighth embodiment

[0066] (I)铜铟招硫纳米颗粒的制备:将2.0mmol硝酸铜,1.70mmol硝酸铟,0.3OmmoI硝酸铝和6.0mmol硫粉加入IOOmL三颈瓶中,再加入35mL油胺,并放入温控加热套中,然后与史莱克换气装置连接好,并加热。 [0066] (I) preparing copper indium nanoparticles sulfur strokes: the 2.0mmol copper nitrate, indium nitrate 1.70mmol, 0.3OmmoI 6.0mmol sulfur powder and aluminum nitrate was added IOOmL three-necked flask was added 35mL of oleylamine and placed the temperature-controlled heating mantle, and then connected to the ventilator Shrek, and heated. 同时通过真空和氩气氛围循环的方式对反应液进行循环洗气2次,每次洗气15min。 At the same time by a vacuum and argon atmosphere circulating reaction liquid circulating scrubbing 2 times scrubbing 15min. 最后用氩气充满反应容器。 Finally, the reaction vessel filled with argon. 在磁力搅拌下,继续加热,当温度升高到235° C,保持不变,IOOmin后停止反应。 Under magnetic stirring and heating was continued, when the temperature was raised to 235 ° C, remains constant, the reaction was stopped after IOOmin. 随后冷却至室温,过滤离心反应液获得固体产物,并用乙醇、己烷清洗5次,获得洁净的固体产物。 Then cooled to room temperature, the reaction solution was filtered to obtain a solid product was centrifuged and washed with ethanol, washed with hexane 5 times to obtain a solid product was clean.

[0067] (2)制备铜铟铝硫纳米晶墨水:把铜铟铝硫纳米颗粒放入甲苯中形成浓度为80mg/mL稳定的胶体溶液-铜铟招硫纳米晶墨水。 [0067] (2) Preparation of nanocrystalline copper indium aluminum ink sulfur: sulfur to copper indium aluminum nanoparticles taken up in toluene a concentration of 80mg / mL solution of a stable colloidal - copper indium sulfur nanocrystals ink strokes.

[0068] (3)镀钥玻璃的制备:把石英玻璃基体裁成1.0cmX2.0cm大小,分别用丙酮、乙醇、去离子水超生清洗干净。 [0068] (3) Preparation of coated glass key: the genre into the silica glass substrate 1.0cmX2.0cm size, respectively, with acetone, ethanol, deionized water bounce clean. 通过直流磁控溅射法在石英玻璃基体上镀金属Mo,厚度为500nm ;接着通过共溅射法沉积一层厚度为500mn的含Al的金属Mo薄膜,其中铝的含量为12%。 By DC magnetron sputtering on a metallized substrate Mo quartz glass, having a thickness of 500 nm; and then co-deposited by sputtering to a thickness of a metal containing Al 500mn the Mo thin film, wherein the content of aluminum is 12%.

[0069] (4)铜铟铝硒薄膜的制备:通过刮涂法把铜铟铝硫纳米晶墨水涂敷在镀Mo的基体上,形成1500nm厚的铜铟铝硒纳米晶前驱体预制膜,随后放在300° C的电热板上干燥。 Preparation of [0069] (4) copper indium selenide thin film of aluminum: the doctor blade method by sulfur nanocrystalline copper indium aluminum ink is applied on a substrate of Mo plating, a copper indium selenide nanocrystals aluminum precursor pre-film 1500nm thick, then placed on a hot plate to 300 ° C and dried. 把干燥后的铜铟铝硒前驱体预制膜预制膜和稍过量(5mmol)的二乙基硒放置在石墨盒中,接着把该石磨盒放在管式炉中,通入Ar气,排尽炉中的空气,并使Ar充满炉腔。 The pre-film pre-film copper indium selenide aluminum precursor after drying and a slight excess (5 mmol of) diethyl selenium ink cartridge is placed in the stone, the stone then the box placed in a tube furnace, an Ar gas into the exhaust make the air in the furnace, and the cavity filled with Ar. 然后以18° C/min的升温速度,给炉体加热,使炉腔温度快速升高到520° C,然后对铜铟铝硒前驱体预制膜进行硒化热火处理。 Then 18 ° C / min heating rate, the heating furnace to the furnace chamber temperature was quickly ramped to 520 ° C, then the pre-film copper indium selenide precursor is an aluminum heat selenization process. 30min后停止加热,并冷却至室温,最后获得具有梯度分布的铜铟铝硒薄膜。 Heating was stopped after 30min, and cooled to room temperature, to obtain the final aluminum copper indium selenide film having a gradient distribution.

[0070] 以上所述仅为本发明的较佳实施例而已,并不用以限制本发明,凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等,均应包含在本发明的保护范围之内。 [0070] The foregoing is only preferred embodiments of the present invention but are not intended to limit the present invention, any modifications within the spirit and principle of the present invention, equivalent substitutions and improvements should be included in the present within the scope of the invention.

Claims (10)

  1. 1.一种具有能带梯度分布的铜铟铝硒薄膜的制备方法,包括以下步骤: 将铜源化合物、铝源化合物、铟源化合物、硫源和油胺混合,合成铜铟铝硫纳米颗粒; 将所述铜铟铝硫纳米颗粒分散在有机溶剂中,配制成铜铟铝硫纳米晶墨水; 将所述铜铟铝硫纳米墨水涂敷在镀双层Mo的基体上,形成铜铟铝硒前驱体预制膜,其中,所述镀双层Mo的基体为分别沉积有纯Mo层和掺铝的Mo层的基体; 将所述铜铟铝硒前驱体预制膜经过硒化、退火处理获得铜铟铝硒薄膜。 1. A method for preparing a band of copper indium aluminum selenide film having a gradient distribution, comprising the steps of: a copper source compound, an aluminum source compound, an indium compound source, sulfur source and amine blend oil, synthetic aluminum copper indium sulfur nanoparticles ; sulfur the copper indium aluminum nanoparticles dispersed in an organic solvent to prepare a copper indium aluminum sulfur nanocrystals ink; the copper indium aluminum sulfur nano ink is applied on a substrate of Mo coated bilayer, forming a copper indium aluminum selenium precursor pre-film, wherein the coating substrate is a bilayer Mo were deposited pure Mo Mo layer and the substrate layer doped aluminum; aluminum copper indium selenide to the precursor film is subjected to pre-selenide, the annealing process is obtained aluminum, copper indium selenide film.
  2. 2.根据权利要求1所述的具有能带梯度分布的铜铟铝硒薄膜的制备方法,其特征在于:铜铟铝硒前驱体预制膜的制备过程中,所述镀双层Mo的基体中,掺铝Mo层中铝的百分含量为0.5-15%。 The method for preparing an aluminum copper indium selenide film having an energy band profile of the gradient of claim 1, wherein: the preparation of the pre-film copper indium selenide aluminum precursor, the plating base in the bilayer Mo , the percentage of aluminum in the aluminum-doped Mo layer is 0.5 to 15%.
  3. 3.根据权利要求1或2所述的具有能带梯度分布的铜铟铝硒薄膜的制备方法,其特征在于:铜铟铝硒前驱体预制膜的制备过程中,所述镀双层Mo的基体中,掺铝Mo层厚度为20_500nm。 The method of preparing an aluminum copper indium selenide film having an energy band profile of the gradient of claim 1 or claim 2, wherein: the preparation of the pre-film copper indium selenide aluminum precursor, the coating of bilayer Mo matrix, an Mo layer having a thickness of the aluminum doped 20_500nm.
  4. 4.如权利要求1所述的具有能带梯度分布的铜铟铝硒薄膜的制备方法,其特征在于:所述合成铜铟铝硫纳米颗粒的步骤中,所述铜源化合物、铝源化合物、铟源化合物分别为含有铜、铝、铟的氯化盐、醋酸盐、乙酰丙酮盐、氧化物中的至少一种;所述硫源为硫粉、硫化氢、二硫化碳、硫脲中的至少一种。 4. A method of preparing a copper indium aluminum selenide film having an energy band profile of the gradient of claim 1, wherein: said step of synthesizing a copper indium aluminum sulfur nanoparticles, the copper source compound, an aluminum source compound , respectively, the indium source compound containing copper, aluminum, indium chloride salts, acetates, acetylacetonates, oxides of at least one of; the sulfur source is a sulfur powder, hydrogen sulfide, carbon disulfide, thiourea at least one.
  5. 5.如权利要求1所述的具有能带梯度分布的铜铟铝硒薄膜的制备方法,其特征在于:合成铜铟铝硫纳米颗粒的步骤中,铝、铟元素百分含量比为:0〈铝/ (铟+铝)〈40%。 As claimed in claim 1, the method for preparing a copper indium aluminum band selenide film having a gradient distribution, which is characterized in that: the step of synthesizing a copper indium aluminum nanoparticles sulfur, aluminum, indium element percentage ratio: 0 <Al / (Al + indium) <40%.
  6. 6.如权利要求1所述的具有能带梯度分布的铜铟铝硒薄膜的制备方法,其特征在于:所述合成铜铟铝硫纳米颗粒的步骤中,所述铜铟铝硫纳米颗粒的合成温度为180-280° C。 6. A method of preparing a copper indium aluminum selenide film having an energy band profile of the gradient of claim 1, wherein: said step of synthesizing a copper indium aluminum nanoparticles of sulfur, the sulfur copper indium aluminum nanoparticles synthesis temperature of 180-280 ° C.
  7. 7.根据权利要求1所述的具有能带梯度分布的铜铟铝硒薄膜的制备方法,其特征在于:所述配制铜钢招硫纳米晶墨水的步骤中,铜钢招硫纳米晶墨水浓度为10-300mg/mL。 The method for preparing an aluminum copper indium selenide film having an energy band profile of the gradient of claim 1, wherein: said step of formulating steel Copper sulfur nanocrystals ink strokes, the strokes sulfur steel nanocrystalline copper ink density of 10-300mg / mL.
  8. 8.根据权利要求1所述的具有能带梯度分布的铜铟铝硒薄膜的制备方法,其特征在于:所述配制铜铟铝硫纳米晶墨水的步骤中,所述有机溶剂为胺类、苯类或烷硫醇类化合物中的至少一种。 8. A method for preparing a copper indium aluminum selenide film having an energy band profile of the gradient of claim 1, wherein: said step of formulating a sulfur nanocrystalline copper indium aluminum ink, the organic solvent is an amine, or at least one alkyl benzene thiol compound.
  9. 9.根据权利要求1所述的具有能带梯度分布的铜铟铝硒薄膜的制备方法,其特征在于:所述硒化处理中,硒化温度为500-600° C,硒化时间为10-90min。 9. A method of preparing a copper indium aluminum selenide film having an energy band profile of the gradient of claim 1, wherein: the selenization process, the selenization temperature of 500-600 ° C, for 10 selenide -90min.
  10. 10.根据权利要求1或9所述的具有能带梯度分布的铜铟铝硒薄膜的制备方法,其特征在于:所述硒化处理中采用的硒源为硒粉、硒化氢、二乙基硒中的至少一种。 10. A method of preparing a copper indium aluminum selenide film having an energy band profile of the gradient of claim 1 or claim 9, wherein: a source of selenium uses the selenium treatment is selenium powder, hydrogen selenide, diethyl at least one group of selenium.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104709885A (en) * 2015-02-15 2015-06-17 深圳先进技术研究院 Photovoltaic material as well as preparation method and application thereof

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101471394A (en) * 2007-12-29 2009-07-01 中国科学院上海硅酸盐研究所 Method for preparing optical absorption layer of copper indium gallium sulphur selenium film solar battery
CN102011194A (en) * 2010-10-11 2011-04-13 中国科学院青岛生物能源与过程研究所 Photovoltaic semiconductor nanocrystalline and preparation method and application thereof
CN102044577A (en) * 2010-11-18 2011-05-04 深圳丹邦投资集团有限公司 Flexible thin film solar cell and production method thereof
CN102361830A (en) * 2009-01-21 2012-02-22 珀杜研究基金会 Selenization of precursor layer containing culns2 nanoparticles
CN102365752A (en) * 2009-03-26 2012-02-29 富士胶片株式会社 Photoelectric conversion semiconductor layer, manufacturing method thereof, photoelectric conversion device, and solar cell
US20120067407A1 (en) * 2010-09-15 2012-03-22 Precursor Energetics, Inc. Deposition processes and photovoltaic devices with polymeric precursors
CN102458832A (en) * 2009-05-26 2012-05-16 珀杜研究基金会 Thin films for photovoltaic cells
US20120178205A1 (en) * 2011-01-06 2012-07-12 Electronics And Telecommunications Research Institute Methods of manufacturing solar cell
CN102694068A (en) * 2012-05-23 2012-09-26 中南大学 Method for surface modification of copper indium gallium diselenide (Cu(In, Ga)Se2) film
CN102983222A (en) * 2012-12-06 2013-03-20 许昌天地和光能源有限公司 Preparation method for absorption layer with gradient band gap distribution
US20130112108A1 (en) * 2009-07-28 2013-05-09 Chi-Jie Wang Producing method of ink composition for forming absorption layer of thin film cells

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101471394A (en) * 2007-12-29 2009-07-01 中国科学院上海硅酸盐研究所 Method for preparing optical absorption layer of copper indium gallium sulphur selenium film solar battery
CN102361830A (en) * 2009-01-21 2012-02-22 珀杜研究基金会 Selenization of precursor layer containing culns2 nanoparticles
CN102365752A (en) * 2009-03-26 2012-02-29 富士胶片株式会社 Photoelectric conversion semiconductor layer, manufacturing method thereof, photoelectric conversion device, and solar cell
CN102458832A (en) * 2009-05-26 2012-05-16 珀杜研究基金会 Thin films for photovoltaic cells
US20130112108A1 (en) * 2009-07-28 2013-05-09 Chi-Jie Wang Producing method of ink composition for forming absorption layer of thin film cells
US20120067407A1 (en) * 2010-09-15 2012-03-22 Precursor Energetics, Inc. Deposition processes and photovoltaic devices with polymeric precursors
CN102011194A (en) * 2010-10-11 2011-04-13 中国科学院青岛生物能源与过程研究所 Photovoltaic semiconductor nanocrystalline and preparation method and application thereof
CN102044577A (en) * 2010-11-18 2011-05-04 深圳丹邦投资集团有限公司 Flexible thin film solar cell and production method thereof
US20120178205A1 (en) * 2011-01-06 2012-07-12 Electronics And Telecommunications Research Institute Methods of manufacturing solar cell
CN102694068A (en) * 2012-05-23 2012-09-26 中南大学 Method for surface modification of copper indium gallium diselenide (Cu(In, Ga)Se2) film
CN102983222A (en) * 2012-12-06 2013-03-20 许昌天地和光能源有限公司 Preparation method for absorption layer with gradient band gap distribution

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
向华等: ""前驱膜Al含量对铜铟铝硒薄膜成分和结构的影响"", 《太阳能学报》 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104709885A (en) * 2015-02-15 2015-06-17 深圳先进技术研究院 Photovoltaic material as well as preparation method and application thereof

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