CN103746034A - 一种通过界面改性制备铜锌锡硫类薄膜太阳能电池的方法 - Google Patents
一种通过界面改性制备铜锌锡硫类薄膜太阳能电池的方法 Download PDFInfo
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- 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
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Abstract
本发明涉及太阳能电池技术领域,公开了一种通过界面改性制备铜锌锡硫类薄膜太阳能电池的方法。铜锌锡硫类薄膜太阳能电池为多层膜结构:衬底/Mo背接触层/铜锌锡硫类光吸收薄膜层/缓冲层CdS/窗口层ZnO/减反膜MgF2和金属栅电极Ni-Al。本发明通过界面改性,在Mo背接触层上制备Cu2S1-xSex预制层,其中0≤x≤1,在预制层上用铜锌锡硫纳米墨水成膜,经高温退火工艺,使Cu2S1-xSex预制层与铜锌锡硫纳米晶薄膜实现扩散融合及化学反应,在不引入其他杂质元素的基础上,有效克服了铜锌锡硫纳米晶成膜附着力较差的弊端,得到结晶性好,形貌均匀,物相单一,附着力强的铜锌锡硫类光吸收层薄膜,从而制备得到高效率的铜锌锡硫类薄膜太阳能电池。
Description
技术领域
本发明涉及太阳能技术领域,特别涉及铜锌锡硫类薄膜太阳能电池的制备工艺。
背景技术
铜锌锡硫(Cu2ZnSnS4,简称CZTS)为I2–II–IV–VI4族四元锌黄锡矿半导体材料,其组成元素铜、锌、锡、硫无毒,且在地球中含量相对较高。铜锌锡硫为直接带隙半导体,光学带隙Eg为1.4-1.5eV,与光伏电池的理想带隙1.4eV非常接近,具有较大的光吸收系数大于104cm-1,因此CZTS是理想的薄膜太阳能电池吸收层材料。IBM公司采用联氨溶液沉积吸收层的方法构筑了铜锌锡硫硒(CZTSSe)薄膜太阳能电池,其转化效率高达12.6%,是该类电池目前的最高效率。但是在此过程中用到肼作为反应物和溶剂,肼毒性较强,且具有很强的腐蚀性,不利于大规模的工业生产。因此非真空条件下基于纳米墨水的化学湿法制备铜锌锡硫类薄膜太阳能电池,因其低成本、毒性小甚至无毒的特点,近年来成为研究的热点。
现有铜锌锡硫类薄膜太阳能电池中,铜锌锡硫类薄膜处于Mo背接触层与缓冲层CdS之间,基于纳米墨水的化学湿法制备该类电池存在铜锌锡硫类纳米晶成膜形貌粗糙不均匀,薄膜的结晶性差,与Mo背接触层附着力较差的弊端,导致其转化效率较低,因此有必要改善电池结构中的铜锌锡硫类薄膜质量,从而提高铜锌锡硫类薄膜太阳能电池的效率。
发明内容
本发明的发明目的在于:针对上述基于纳米墨水的化学湿法制备该类电池存在铜锌锡硫类纳米晶成膜形貌粗糙不均匀,结晶性差,与Mo背接触层附着力较差的技术问题,提出一种通过界面改性制备铜锌锡硫类薄膜太阳能电池的方法。
本发明阐述的铜锌锡硫类薄膜太阳能电池为多层膜结构:衬底/Mo背接触层/铜锌锡硫类光吸收薄膜层/CdS缓冲层/ZnO窗口层/MgF2减反膜和金属栅电极Ni-Al。
本发明通过在Mo背接触层上以一定的制膜方法(直流磁控溅射、电子束蒸发、溶胶-凝胶、电化学镀)制备一层Cu2S1-xSex预制层,其中0≤x≤1。Cu2S1-xSex预制层与Mo背接触层附着力强,其膜层厚度可控,膜厚在100-500nm,表层为微观粗糙绒面。Cu2S1-xSex预制层的组成成分是铜锌锡硫类吸收层材料的部分组成元素,并且也是半导体薄膜,与铜锌锡硫纳米颗粒的结合力更强,同时Cu2S1-xSex预制层表面的微观粗糙绒面使之与铜锌锡硫纳米晶的结合能力进一步增强;铜锌锡硫纳米墨水成膜后,经过氮气或氩气等惰性气体保护下300-600℃高温退火,使Cu2S1-xSex预制层与贫铜的铜锌锡硫纳米晶薄膜完成扩散融合及化学反应。为达到上述发明目的,本发明采用的技术方案如下:
步骤1:采用直流磁控溅射的方法在衬底上制备电阻率在10-5Ω·cm量级,厚度约为1μm的Mo背接触层。
步骤2:在步骤1制备的Mo背接触层上采用直流磁控溅射、电子束蒸发、电化学镀或溶胶-凝胶制备一层膜层厚度为100nm-500nm,表层为微观粗糙绒面的Cu2S1-xSex预制层,其中0≤x≤1。
步骤3:基于纳米墨水成膜工艺将贫铜富锌的铜锌锡硫纳米晶在步骤2制备的Cu2S1-xSex预制层上沉积贫铜富锌的铜锌锡硫纳米晶薄膜;经氮气或氩气等惰性气体保护下300-600℃退火热处理,使Cu2S1-xSex预制层与铜锌锡硫纳米晶薄膜实现扩散融合及化学反应,得到铜锌锡硫类吸收层薄膜。
步骤4:在步骤3制备的铜锌锡硫类吸收层薄膜上通过化学水浴的方法制备一层厚度约50nm的CdS缓冲层。
步骤5:在步骤4制备的CdS缓冲层上通过射频磁控溅射工艺制备i-ZnO薄膜,再直流磁控溅射Al-ZnO薄膜得到ZnO窗口层。
步骤6:在步骤5制备的ZnO窗口层上射频溅射厚度为80-100nm的MgF2减反膜。
步骤7:在步骤6制备的MgF2减反膜上通过真空蒸发制备Ni-Al栅状电极。
所述步骤2中直流磁控溅射、电子束蒸发、电化学镀、溶胶-凝胶具体制备工艺如下:(1)应用直流磁控溅射***,以铜单质靶材为原料,在背底真空度高于10-4Pa,工作气压为0.3-1Pa,溅射功率为30-100W的条件下,在Mo背接触层上物理气相沉积铜金属前驱,将铜金属前驱在氮气、氩气等惰性气体或其混合气体保护条件下,与含硫单质、硫化氢、硒单质的一种或多种反应物在100-600℃温度条件下热处理得到Cu2S1-xSex,通过控制溅射时间控制膜层厚度。(2)应用电子束蒸发设备,以铜单质的固体材料为原料,在背底真空度高于10-3Pa,基片加热温度为100-300℃,电子枪束流为50-100mA条件下,在Mo背接触层上物理气相沉积铜金属前驱,将铜金属前驱在氮气、氩气等惰性气体或其混合气体保护下,与含硫单质、硫化氢、硒单质的一种或多种反应物在100-600℃温度条件下热处理得到Cu2S1-xSex,通过控制蒸发时间控制膜层厚度。(3)利用电化学工作站,将铜盐和络合物(如柠檬酸盐、酒石酸盐或焦磷酸盐等)溶于水中配制电镀液,铜盐浓度范围为5mM-2M,络合物浓度范围为1M-5M,在Mo层上电镀沉积金属铜前驱,将铜金属前驱在氮气、氩气等惰性气体或其混合气体保护下,与含硫单质、硫化氢、硒单质的一种或多种反应物在100-600℃下热处理得到Cu2S1-xSex;以柠檬酸钠、EDTA等为络合剂、铜盐化合物、硫代硫酸盐、硒代硫酸盐配制电镀液,通过添加酸调节电镀液的PH值为2-5,在Mo层上直接电镀沉积得到Cu2S1-xSex,膜层厚度通过调节电镀液的浓度和电镀时间得到控制。(4)配制含目标Cu、S、Se元素的具有适宜粘度的前驱液,通过旋转涂布、浸渍提拉等方法,制备前驱薄膜,再通过氮气或氩气等惰性气体保护下300-600℃高温退火工艺制备得到Cu2S1-xSex预制层,膜层的厚度可通过控制前驱液浓度及旋涂、提拉次数得到控制。
综上所述,由于采用了上述技术方案,本发明的有益效果是:
在不引入杂质元素的基础上,制备了具有结晶性能好,形貌均匀,物相单一,与Mo背接触层附着力强的铜锌锡硫类吸收层薄膜,从而提高铜锌锡硫类薄膜太阳能电池的效率。
附图说明
本发明将通过例子并参照附图的方式说明,其中:
图1为本发明中铜锌锡硫类薄膜太阳能电池制备工艺流程图;
图2为本发明实施例1中制备的铜锌锡硫薄膜XRD图;
图3为未添加Cu2S预制层制备得到的铜锌锡硫薄膜SEM图;
图4为通过添加Cu2S预制层制备得到的铜锌锡硫薄膜SEM图。
具体实施方式
本说明书(包括任何附加权利要求、摘要和附图)中公开的任一特征,除非特别叙述,每个特征只是一系列等效或类似特征中的一个例子而已。
实施例1
1、Mo背接触层的制备主要分两步,首先在背底真空度高于10-4Pa,在氩气工作气压1-3Pa条件下,130W功率条件下直流磁控溅射2-6分钟,得到与玻璃基底具有较强附着力的Mo薄膜;然后在在氩气工作气压0.1-1Pa条件下,130W功率条件下直流磁控溅射20-40分钟,得到电阻率较小的Mo薄膜,这种双层结构的Mo薄膜形成电池的背电极。
2、在Mo薄膜上采用电化学镀的方法制备Cu2S预制层,具体步骤如下:首先配制配方如下的电解液:柠檬酸钠(0.5mol/L),CuSO4(0.286mol/L),Na2S2O3,加入适量HCl调节电镀溶液的PH值为2.5;然后在-1.0V的电位下在已制备得到的Mo薄膜上沉积Cu2S,通过调整电镀时间控制Cu2S薄膜厚度。
3、铜锌锡硫类吸收层薄膜的制备工艺如下:分别采用CuCl2·2H2O、ZnSO4·7H2O、SnSO4和单质S为Cu源、Zn源、Sn源和S源,溶剂为乙二胺和去离子水。首先配制摩尔比Cu/(Sn+Zn)=0.8,Zn/Sn=1.2,Cu/S=0.5的贫铜富锌的铜锌锡硫前驱液,然后将前驱液转移至聚四氟乙烯耐高温高压反应釜中,在200℃,24小时条件下溶剂热反应制备得到贫铜富锌的铜锌锡硫纳米颗粒,最后将制备得到的铜锌锡硫纳米颗粒用离心机以5000rpm的转速离心4次,清洗掉副产物和未完全反应的反应物,将得到的铜锌锡硫纳米晶溶解于去离子水配制成粘度适中的纳米墨水。将制备好的铜锌锡硫纳米颗粒墨水,旋涂于步骤2中制备好的Cu2S预制层上,在540℃氮气保护条件下进行40分钟退火处理,使Cu2S预制层与铜锌锡硫纳米晶薄膜将实现扩散融合及化学反应,最终生成结晶性良好,物相单一,与Mo背接触层附着力强的铜锌锡硫吸收层薄膜。图2为本实施例中Cu2S1-xSex预制层x取值0时制备的铜锌锡硫吸收层XRD图。图3为未添加Cu2S预制层制备得到的铜锌锡硫薄膜SEM图。图4为通过添加Cu2S预制层制备得到的铜锌锡硫薄膜SEM图。从图2可以分析得到本发明所制备的铜锌锡硫具有很高的相纯度,结晶性好,而且无杂峰,从图3与图4可以对比得到通过添加预制层对Mo层薄膜进行界面改性后,铜锌锡硫膜层均匀性及结晶度得到很大改善。
4、在已经制备得到的铜锌锡硫吸收层薄膜上,经过化学水浴的方法制备一层厚度约50nm的CdS缓冲层,具体步骤如下:称取0.154g CdSO4溶于10ml去离子水中磁力搅拌两分钟得到A溶液;将4.95ml氨水加入A溶液中磁力搅拌2分钟得到B溶液;将0.457g硫脲溶于20ml去离子水中得到C溶液;把C溶液缓慢倒入B溶液中形成D溶液;将步骤3中制备得到的铜锌锡硫吸收层薄膜垂直放入D溶液中,在70℃的恒温水浴锅中保温20分钟,然后取出,用去离子水冲洗后放入真空干燥箱中45℃条件下干燥1小时。
5、制备ZnO窗口层,具体步骤如下:首先在步骤4得到的薄膜基础上,在背底真空度高于10-4Pa,工作气压0.5Pa,50W条件下射频磁控溅射30分钟得到i-ZnO薄膜;再在工作气压0.3-1Pa,200-250W,150-200℃条件下直流磁控溅射30分钟得到Al-ZnO薄膜。
6、在ZnO窗口层上射频溅射厚度为80-100nm的MgF2减反膜。
7、最后通过真空蒸发工艺在MgF2减反膜上制备Ni-Al栅状电极。
实施例2
1、Mo背接触层的制备主要分两步,首先在背底真空度高于10-4Pa,在氩气工作气压1-3Pa条件下,130W功率条件下直流磁控溅射2-6分钟,得到与玻璃基底具有较强附着力的Mo薄膜;然后在在氩气工作气压0.1-1Pa条件下,130W功率条件下直流磁控溅射20-40分钟,得到电阻率较小的Mo薄膜,这种双层结构的Mo薄膜形成电池的背电极。
2、在Mo薄膜上采用直流磁控溅射的方法制备Cu2Se预制层,应用直流磁控溅射***,以铜单质靶材为原料,在背底真空度高于10-4Pa,工作气压为0.3-1Pa,溅射功率为30-100W的条件下,直流磁控溅射20-30分钟,在Mo背接触层上物理气相沉积铜金属前驱,将铜金属前驱在氮气惰性气体保护条件下,与0.3g硒单质在400℃条件下热处理得到Cu2Se。
3、铜锌锡硫硒吸收层薄膜的制备工艺如下:分别采用CuCl2·2H2O、ZnSO4·7H2O、SnSO4和单质S为Cu源、Zn源、Sn源和S源,溶剂为乙二胺和去离子水。首先配制摩尔比Cu/(Sn+Zn)=0.8,Zn/Sn=1.2,Cu/S=0.5的贫铜富锌的铜锌锡硫前驱液,然后将前驱液转移至聚四氟乙烯耐高温高压反应釜中,在200℃,24小时条件下溶剂热反应制备得到贫铜富锌的铜锌锡硫纳米颗粒,最后将制备得到的铜锌锡硫纳米颗粒用离心机以5000rpm的转速离心4次,清洗掉副产物和未完全反应的反应物,将得到的铜锌锡硫纳米晶溶解于去离子水配制成粘度适中的纳米墨水。将制备好的铜锌锡硫纳米颗粒墨水,旋涂于步骤2中制备好的Cu2Se预制层上,在540℃氮气保护条件下进行40分钟退火处理,使Cu2Se预制层与铜锌锡硫纳米晶薄膜将实现扩散融合及化学反应,最终生成结晶性良好,物相单一,与Mo背接触层附着力强的铜锌锡硫硒吸收层薄膜。
4、在已经制备得到的铜锌锡硫硒吸收层薄膜上,经过化学水浴的方法制备一层厚度约50nm的CdS缓冲层,具体步骤如下:称取0.154g CdSO4溶于10ml去离子水中磁力搅拌两分钟得到A溶液;将4.95ml氨水加入A溶液中磁力搅拌2分钟得到B溶液;将0.457g硫脲溶于20ml去离子水中得到C溶液;把C溶液缓慢倒入B溶液中形成D溶液;将步骤3中制备得到的铜锌锡硫硒吸收层薄膜垂直放入D溶液中,在70℃的恒温水浴锅中保温20分钟,然后取出,用去离子水冲洗后放入真空干燥箱中45℃条件下干燥1小时。
5、制备ZnO窗口层,具体步骤如下:首先在步骤4得到的薄膜基础上,在背底真空度高于10-4Pa,工作气压0.5Pa,50W条件下射频磁控溅射30分钟得到i-ZnO薄膜;再在工作气压0.3-1Pa,200-250W,150-200℃条件下直流磁控溅射30分钟得到Al-ZnO薄膜。
6、在ZnO窗口层上射频溅射厚度为80-100nm的MgF2减反膜。
7、最后通过真空蒸发工艺在MgF2减反膜上制备Ni-Al栅状电极。
本发明并不局限于前述的具体实施方式。本发明扩展到任何在本说明书中披露的新特征或任何新的组合,以及披露的任一新的方法或过程的步骤或任何新的组合。
Claims (6)
1.一种通过界面改性制备铜锌锡硫类薄膜太阳能电池的方法,其特征在于,包括如下步骤:
步骤1:在衬底上制备Mo背接触层;
步骤2:在步骤1制备的Mo背接触层上制备Cu2S1-xSex预制层,其中0≤x≤1;
步骤3:在步骤2所述Cu2S1-xSex预制层上用铜锌锡硫纳米墨水成膜,经高温退火工艺,使Cu2S1-xSex与铜锌锡硫纳米晶实现扩散融合及化学反应制备铜锌锡硫类吸收层薄膜;
步骤4:在步骤3所述的铜锌锡硫类吸收层薄膜上制备CdS缓冲层;
步骤5:在步骤4所述的CdS缓冲层上制备ZnO窗口层;
步骤6:在步骤5所述的ZnO窗口层上射频溅射MgF2减反膜;
步骤7:在步骤6所述的MgF2减反膜上制备Ni-Al栅状电极。
2.如权利要求1所述一种通过界面改性制备铜锌锡硫类薄膜太阳能电池的方法,其特征在于:所述步骤1中制备的Mo背接触层电阻率在10-5Ω·cm量级,厚度约为1μm。
3.如权利要求1所述一种通过界面改性制备铜锌锡硫类薄膜太阳能电池的方法,其特征在于:所述步骤2中Cu2S1-xSex预制层采用直流磁控溅射、电化学镀、溶胶-凝胶或电子束蒸发制备。
4.如权利要求1所述一种通过界面改性制备铜锌锡硫类薄膜太阳能电池的方法,其特征在于:所述预制层的膜厚为100nm-500nm,表层为微观粗糙绒面。
5.如权利要求1所述一种通过界面改性制备铜锌锡硫类薄膜太阳能电池的方法,其特征在于:所述步骤3中铜锌锡硫类吸收层薄膜的制备基于纳米墨水成膜工艺在Cu2S1-xSex预制层上沉积贫铜富锌的铜锌锡硫纳米晶薄膜,再经过惰性气体保护下300℃-600℃退火热处理实现扩散融合及化学反应得到。
6.如权利要求1所述一种通过界面改性制备铜锌锡硫类薄膜太阳能电池的方法,其特征在于:所述步骤5的ZnO窗口层在步骤4制备的CdS缓冲层上通过射频磁控溅射工艺制备i-ZnO薄膜,再通过直流磁控溅射得到Al-ZnO薄膜从而获得ZnO窗口层。
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CN105633198A (zh) * | 2014-11-06 | 2016-06-01 | 中物院成都科学技术发展中心 | 铜锌锡硫薄膜太阳电池吸收层表面刻蚀的电化学处理方法 |
CN105633198B (zh) * | 2014-11-06 | 2017-05-10 | 中物院成都科学技术发展中心 | 铜锌锡硫薄膜太阳电池吸收层表面刻蚀的电化学处理方法 |
CN105023961A (zh) * | 2015-08-24 | 2015-11-04 | 中国工程物理研究院材料研究所 | 一种柔性铜锌锡硫薄膜太阳能电池及其制备方法 |
CN105023961B (zh) * | 2015-08-24 | 2018-04-03 | 中国工程物理研究院材料研究所 | 一种柔性铜锌锡硫薄膜太阳能电池及其制备方法 |
CN105821384A (zh) * | 2015-09-24 | 2016-08-03 | 云南师范大学 | 多元靶双靶共溅射制备铜锌锡硫薄膜的方法 |
CN105821384B (zh) * | 2015-09-24 | 2018-08-28 | 云南师范大学 | 多元靶双靶共溅射制备铜锌锡硫薄膜的方法 |
CN108511328A (zh) * | 2018-05-10 | 2018-09-07 | 河南科技大学 | 一种双层钼薄膜及其制备方法、薄膜太阳能电池 |
CN113471332A (zh) * | 2021-07-01 | 2021-10-01 | 南开大学 | 一种载流子有效分离的铜基薄膜太阳电池p-n结结构设计的方法及制备得到的太阳电池 |
CN114843355A (zh) * | 2022-04-21 | 2022-08-02 | 福州大学 | 一种大面积CZTSSe太阳电池及其制备方法 |
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