CN107706252A - 一种掺杂型铜锌锡硫薄膜材料 - Google Patents

一种掺杂型铜锌锡硫薄膜材料 Download PDF

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CN107706252A
CN107706252A CN201710778008.4A CN201710778008A CN107706252A CN 107706252 A CN107706252 A CN 107706252A CN 201710778008 A CN201710778008 A CN 201710778008A CN 107706252 A CN107706252 A CN 107706252A
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朱建国
况军
徐贤德
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Suzhou Rogart Photoelectric Technology Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
    • H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
    • H01L31/0264—Inorganic materials
    • H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
    • H01L31/0326—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 comprising AIBIICIVDVI kesterite compounds, e.g. Cu2ZnSnSe4, Cu2ZnSnS4
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
    • H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
    • H01L31/0264—Inorganic materials
    • H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
    • H01L31/0326—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 comprising AIBIICIVDVI kesterite compounds, e.g. Cu2ZnSnSe4, Cu2ZnSnS4
    • H01L31/0327—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 comprising AIBIICIVDVI kesterite compounds, e.g. Cu2ZnSnSe4, Cu2ZnSnS4 characterised by the doping material
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy

Abstract

本发明公开了一种掺杂型铜锌锡硫薄膜材料，该方法通过球磨处理得到铜锌锡硫纳米粉末，再与KIO3制备胶体溶液，接着选取导电基底清洗、晾干，分别作为阴极和阳极在胶体溶液中进行电泳沉积，得到前体铜锌锡硫薄膜，随后将其与银粉置于高压反应釜中回流反应，最后经蒸汽反应，退火处理得到掺杂型铜锌锡硫薄膜材料。这一薄膜材料的制备工艺简单快捷，生产成本低，且同样具备优异的光电转化率，同时可利用光的波长范围较宽，适于实用。

Description

一种掺杂型铜锌锡硫薄膜材料
技术领域
本发明涉及光电薄膜材料这一技术领域，特别涉及到一种掺杂型铜锌锡硫薄膜材料。
背景技术
太阳能作为一种高效的能源，具有照射普遍，储量巨大，使用时间长久的特点，从而成为未来能源的最佳选择。在过去几十年中，碲化镉(CdTe)和铜铟镓硒(CIGS)薄膜太阳能电池在光伏领域受到广泛研究，且铜铟镓硒薄膜电池的光电转化率已达到19.9％，但由于镉有毒，铟和镓为稀有金属，这些都限制了它们的大规模应用，因此寻找一种无毒且成本较低的材料用于薄膜太阳能电池成为研究热点。近几年，四元硫化物铜锌锡硫(CZTS)在下一代薄膜太阳能电池中崛起，锌黄锡矿结构的铜锌锡硫与黄铜矿结构的铜铟镓硒相似，且各元素在地壳中的含量丰富，因此用它们取代铟、镓可大大降低成本，铜锌锡硫为直接带隙材料，其光吸收系数高于10-4cm-1，电池中所需材料厚度较小(约3μm)，禁带宽度约1.05～1.5eV，与太阳能电池所需要的最佳禁带宽度1.5eV相匹配，非常适用于太阳能电池。
中国专利CN106298995A公开了一种银掺杂铜锌锡硫硒光吸收层薄膜材料，该薄膜材料通过以下方法制备得到：1）将0 .07～0 .13 mol/L金属铜盐和金属银盐加入有机溶剂中，搅拌至完全溶解后，加入0 .03～0 .07 mol/L金属锡盐继续搅拌至溶解，然后加入0.03～0.09 mol/L金属锌盐搅拌至完全溶解，最后加入2 mol/L的含硫化合物搅拌至完全溶解形成稳定的ACZTS前驱体溶液；2）将镀钼玻璃依次在丙酮、无水乙醇和去离子水中超声清洗干净；3）将前驱体溶液旋涂到镀钼的玻璃基底上，反复旋涂沉积；4）待旋涂完毕后将样品硒化处理。该发明通过Ag掺杂可改善薄膜的质量，有效提高器件的开路电压、填充因子及光电转换效率，实验可重复性和稳定性也比较好。然而，经过这一工艺改性的掺杂型铜锌锡硫薄膜还带入了硒元素，在国际市场，硒的产量增长一直较为缓慢，年供应量有限，且随着世界经济的发展和新的应用领域的出现，硒的下游需求不断增长，在一定程度上导致硒的价格不断上涨。因此，如何降低生产成本也是光电薄膜材料领域的研究人员应当考虑的内容。
发明内容
为解决上述技术问题，本发明提供一种掺杂型铜锌锡硫薄膜材料，该方法通过球磨处理得到铜锌锡硫纳米粉末，再与KIO3制备胶体溶液，接着选取导电基底清洗、晾干，分别作为阴极和阳极在胶体溶液中进行电泳沉积，得到前体铜锌锡硫薄膜，随后将其与银粉置于高压反应釜中回流反应，最后经蒸汽反应，退火处理得到掺杂型铜锌锡硫薄膜材料。这一薄膜材料的制备工艺简单快捷，生产成本低，且同样具备优异的光电转化率，同时可利用光的波长范围较宽，适于实用。
本发明的目的可以通过以下技术方案实现：
.一种掺杂型铜锌锡硫薄膜材料，由以下步骤制备而成：
（1）以铜、锌、锡纳米粉体为原料，与硫粉、甲基丙烯酸甲酯、对苯二酚、乙酸乙酯均匀混合，经高能震动球磨处理后得铜锌锡硫纳米粉末；
(2) 将铜锌锡硫纳米粉末与KIO3粉末溶于适量丙酮，经搅拌、超声分散后形成均一、稳定的胶体溶液；
(3)选取导电基底清洗、晾干，分别作为阴极和阳极在胶体溶液中进行电泳沉积，得到前体铜锌锡硫薄膜，随后将其与银粉置于高压反应釜中回流反应，得到掺杂型铜锌锡硫薄膜半成品；
(4)将掺杂型铜锌锡硫薄膜半成品进行蒸汽反应，随后退火处理得到掺杂型铜锌锡硫薄膜材料。
特别地，所述步骤（1）中铜、锌、锡纳米粉体及硫粉的摩尔比为3:2:1:2。
特别地，所述步骤（3）中导电基底材料优选为聚萘二甲酸乙二醇酯。
本发明与现有技术相比，其有益效果为：
采用本发明制备的掺杂型铜锌锡硫薄膜材料，制备工艺简单快捷，生产成本低，且同样具备优异的光电转化率，同时可利用光的波长范围较宽，适于实用。
具体实施方式
下面结合具体实施例对发明的技术方案进行详细说明。
实施例
（1）以铜、锌、锡纳米粉体为原料，铜、锌、锡纳米粉体及硫粉的摩尔比为3:2:1:2，将其与硫粉、甲基丙烯酸甲酯、对苯二酚、乙酸乙酯均匀混合，经高能震动球磨处理后得铜锌锡硫纳米粉末；
(2) 将铜锌锡硫纳米粉末与KIO3粉末溶于适量丙酮，经搅拌、超声分散后形成均一、稳定的胶体溶液；
(3)选取聚萘二甲酸乙二醇酯作为导电基底清洗、晾干，分别作为阴极和阳极在胶体溶液中进行电泳沉积，得到前体铜锌锡硫薄膜，随后将其与银粉置于高压反应釜中回流反应，得到掺杂型铜锌锡硫薄膜半成品；
(4)将掺杂型铜锌锡硫薄膜半成品进行蒸汽反应，随后退火处理得到掺杂型铜锌锡硫薄膜材料。
对比例
按照专利CN106298995A中所描述的方法，将0.1 mol/L醋酸铜、0.05 mol/L无水氯化亚锡、0.06 mol/L醋酸锌及2 mol/L硫脲加入至20 mL二甲基亚砜中，搅拌至完全溶解形成透明澄清的CZTS前驱体溶液；利用匀胶机将CZTS溶胶前驱体旋涂到清洗干净的镀钼玻璃基底上，然后在加热板上400℃干燥5分钟，反复旋涂11次；待旋涂完毕后将样品置于快速升温炉中550℃硒化10分钟，升温速率为10℃/s，自然降温，在退火过程中，持续通保护气体N2，流量为15 mL/min，得到ACZTSSe薄膜。
将实施例制得的掺杂型铜锌锡硫薄膜材料和对比例制得的ACZTSSe薄膜材料及常规的CZTS薄膜材料分别按照专利公开号为CN106298995A的文献的方法（即在65 ℃条件下化学浴沉积CdS缓冲层；射频磁控溅射制备本征氧化锌窗口层；直流磁控溅射ITO透明导电层；热蒸发制备金属铝电极）制备成太阳能电池，测试在太阳光下的电池效率以及最大吸收波长，所得的测试结果见表1。可见，本发明所制备的掺杂型铜锌锡硫薄膜材料性能优异，本发明的制备方法与现有技术相比具可以给所制备的产品带来预料不到的技术效果。
表1
电池效率（%） 最大吸收波长（nm）
实施例 8.65 320-800
对比例 4.78 380-800
CZTS薄膜 3.83 480-800
以上所述仅为本发明的实施例，并非因此限制本发明的专利范围，凡是利用本发明说明书内容所作的等效流程变换，或直接或间接运用在其他相关的技术领域，均包括在本发明的专利保护范围内。

Claims (3)

1.一种掺杂型铜锌锡硫薄膜材料，其特征在于，由以下步骤制备而成：
（1）以铜、锌、锡纳米粉体为原料，与硫粉、甲基丙烯酸甲酯、对苯二酚、乙酸乙酯均匀混合，经高能震动球磨处理后得铜锌锡硫纳米粉末；
(2) 将铜锌锡硫纳米粉末与KIO3粉末溶于适量丙酮，经搅拌、超声分散后形成均一、稳定的胶体溶液；
(3)选取导电基底清洗、晾干，分别作为阴极和阳极在胶体溶液中进行电泳沉积，得到前体铜锌锡硫薄膜，随后将其与银粉置于高压反应釜中回流反应，得到掺杂型铜锌锡硫薄膜半成品；
(4)将掺杂型铜锌锡硫薄膜半成品进行蒸汽反应，随后退火处理得到掺杂型铜锌锡硫薄膜材料。
2.根据权利要求1所述的掺杂型铜锌锡硫薄膜材料，其特征在于，所述步骤（1）中铜、锌、锡纳米粉体及硫粉的摩尔比为3:2:1:2。
3.根据权利要求1所述的掺杂型铜锌锡硫薄膜材料，其特征在于，所述步骤（3）中导电基底材料优选为聚萘二甲酸乙二醇酯。
CN201710778008.4A 2017-09-01 2017-09-01 一种掺杂型铜锌锡硫薄膜材料 Pending CN107706252A (zh)

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CN109148267B (zh) * 2018-08-31 2020-11-13 广东工业大学 一种银掺杂铜锌锡硫薄膜的制备方法

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Application publication date: 20180216