An in-situ room temperature route to CuBiI4 based bulk-heterojunction perovskite-like solar cells

  • Busheng Zhang (张卜生)
  • Yan Lei (雷岩)
  • Ruijuan Qi (齐瑞娟)
  • Haili Yu (余海丽)
  • Xiaogang Yang (杨晓刚)
  • Tuo Cai (蔡拓)
  • Zhi Zheng (郑直)


Both bismuth and copper are non-toxic and earth-abundant elements suitable for lead-free halide perovskite-like photovoltaic devices. Here, we report a highly facile route for in-situ producing copper-bismuth-iodide (CuBiI4) thin films directly on ITO substrate at room temperature, by utilizing a Bi-Cu alloy layer as precursor. X-ray diffraction and transmission electron microscopy (TEM) results verified the formation of well crystallized CuBiI4 thin films with [222] orientation. The transient photovoltage (TPV) analysis revealed that the CuBiI4 is an n-type semiconductor with a suitable band gap of ~1.81 eV, preferable to photoelectric conversion compared with CH3NH3PbI3. It is very interesting that the subsequent spin-coating process of the classical Spiro-MeOTAD organic solution with TBP and acetonitrile resulted in a dense and smooth CuBiI4:Spiro-MeOTAD bulk-heterojunction film. The preliminarily fabricated simple sandwich structures of ITO/CuBiI4:Spiro-MeOTAD/ Au hybrid solar cell devices displayed efficient photovoltaic performance with the PCE up to 1.119% of the best sample. The room temperature direct metal surface elemental reaction (DMSER) method may provide a new insight for all-inorganic lead free perovskite-like AaBbXx compounds and high performance photovoltaic devices.


copper-bismuth-iodide CuBiI4 room temperature lead-free perovskite-like bulk-heterojunction solar cells 



铋和铜作为无毒且储量相对丰富的金属元素, 都非常适合新型无铅卤化物钙钛矿材料及相应光伏器件的设计和制备.本文采用非常简单的气-固反应方法, 以铋铜合金作为前驱体直接在ITO基底上室温原位制备了一种新型铜铋碘(CuBiI4)化合物薄膜材料. XRD和TEM的测试结果证实了这种具有(222)优势晶面取向CuBiI4晶体薄膜的生成. 瞬态表面光电压(TPV)测试表明我们制备的CuBiI4是一种n型半导体材料, 且具有与CH3NH3PbI3钙钛矿材料相当的光生载流子分离与传输性能. UV-Vis, PL和IPCE等结果表明灰黑色CuBiI4的禁带宽度大约为1.81 eV, 适合作为光伏材料. 值得注意的是, 我们利用四叔丁基吡啶(TBP)、乙腈和Spiro-MeOTAD有机混和溶剂旋涂处理后, 得到了一种混合均匀、致密、平滑的CuBiI4:Spiro-MeOTAD本体异质结薄膜. 基于这种新型薄膜, 我们制备了具有简单三明治结构的ITO/Cu-BiI4:Spiro-MeOTAD/Au杂化太阳能电池器件, 并获得了1.119%的光电转化效率. 这种室温下金属表面元素直接反应的方法(DMSER)为未来无铅钙钛矿或类钙钛矿化合物(AaBbXx)的制备及其在高性能光伏器件中的应用提供了一个全新的策略.



This work was supported by the National Natural Science Foundation of China (21673200, 61504117 and U1604121), the Innovation Scientists and Technicians Troop Construction Projects of Henan Province (144200510014).

Supplementary material

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Copyright information

© Science China Press and Springer-Verlag GmbH Germany, part of Springer Nature 2018

Authors and Affiliations

  • Busheng Zhang (张卜生)
    • 1
    • 2
  • Yan Lei (雷岩)
    • 1
  • Ruijuan Qi (齐瑞娟)
    • 3
  • Haili Yu (余海丽)
    • 1
  • Xiaogang Yang (杨晓刚)
    • 1
  • Tuo Cai (蔡拓)
    • 1
  • Zhi Zheng (郑直)
    • 1
  1. 1.Key Laboratory for Micro-Nano Energy Storage and Conversion Materials of Henan Province, College of Advanced Materials and Energy, Institute of Surface Micro and Nano MaterialsXuchang UniversityXuchangChina
  2. 2.School of Civil Engineering and CommunicationNorth China University of Water Resources and Electric PowerZhengzhouChina
  3. 3.Key Laboratory of Polar Materials and Devices, Ministry of Education, Department of Electronic EngineeringEast China Normal UniversityShanghaiChina

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