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Air-stable CsPbIBr2 photodetector via dual-ligand-assisted solution strategy

Hu Zi-Ting ,  Shu Xin ,  Wang Xiang ,  Li Yue ,  Xu Run ,  Hong Feng ,  Ma Zhong-Quan ,  Jiang Zui-Min ,  Xu Fei

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Air-stable CsPbIBr2 photodetector via dual-ligand-assisted solution strategy

Hu Zi-Ting, Shu Xin, Wang Xiang, Li Yue, Xu Run, Hong Feng, Ma Zhong-Quan, Jiang Zui-Min, Xu Fei
Acta Phys. Sin., 2022, 71(11): 116801.
doi: 10.7498/aps.71.20212143
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  • Abstract

    The CsPbIBr2 perovskite films deposited from the precursor solutions in air, usually suffer poor surface coverage and air-stability due to the uncontrolled nucleation and the existence of I– during the film formation, resulting in terrible photoelectric characteristics and reproducibility. At present, the high-quality CsPbIBr2 films are prepared under nitrogen atmosphere, which results in the increase of the cost and thus impedes their applications in air. Here in this work, we propose a strategy for growing the perovskite films with low defect density and better stability in air via dual-ligand-assisted (ligand 1 (LP) and ligand 2 (NH4SCN)) solution strategy. These ligands contain some organic molecules which have strong interaction with ions on the surface of perovskite thin film in order to regulate the addition of precursor ions onto the films. The high-quality CsPbIBr2 thin films are prepared in air with relative humidity of ≤60% by the spraying method. The results indicate that ligand 1 with hydrophilic group and hydrophobic group, a kind of surfactant, can effectively reduce the surface tension of perovskite precursor solution, improve the coverage of CsPbIBr2 perovskite film, and form a block layer of water and oxygen. However, the addition of ligand 1 in precursor solution inevitably introduces many grain boundaries, which is unfavorable for carrier transport and collection. Thus, ligand 2 is employed to control the nucleation of perovskite film as another ligand, resulting in reducing the point defect formation. Their combination is beneficial to forming the uniform perovskite film with large-size crystal and low-density defect. The high-quality crystallization of the perovskite film is found to simultaneously enhance the response and the durability of photodetectors. Thus, the unpackaged photodetectors (ITO/CsPbIBr2/Au) based on this strategy yield the outstanding photoelectric response under the excitation of 405 nm laser. This device exhibits a low dark current density of 2 × 10–4 mA/cm2, a fast response time of 20–21 µs, and high stability (81%, ≥70 d) in air with a relative humidity of 40%–60%. Hence, this study provides a simple method to prepare high-quality CsPbIBr2 perovskite thin films with low-density defect and realize air-stable and charge-transport-layer-free CsPbIBr2 photodetectors for practical applications in photoelectric detection field.

    Authors and contacts

    • 1.

      SHU-SolarE R&D Lab, Shanghai Key Laboratory of High Temperature Superconductors, Department of Physics, Shanghai University, Shanghai 200444, China

    • 2.

      Department of Electronic Information Materials, Shanghai University, Shanghai 200444, China

    • 3.

      State Key Laboratory of Surface Physics, Ministry of Education Key Laboratory of Micro-Nano Photonic Structure, Department of Physics, Fudan University, Shanghai 200433, China

      • Corresponding author: Xu Fei, feixu@staff.shu.edu.cn
    • Funds: Project supported by the National Natural Science Foundation of China (Grant Nos. 12175131, 61874070) and the Natural Science Foundation of Shanghai of China (Grant No. 17ZR1409600)

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  • 图 1  添加不同浓度的两种配体材料的CsPbIBr2 薄膜的SEM形貌图　(a) 添加不同体积比的LP配体; (b) 添加不同浓度的NH4SCN配体; (c) 固定LP配体体积浓度为10%, 增加NH4SCN配体浓度

    Figure 1.  Top-view SEM images of CsPbIBr2 film with two ligands at different concentrations: (a) Adding different volume ratios of LP ligands; (b) adding different concentrations of NH4SCN ligands; (c) fix the LP ligand volume concentration to 10%, add the NH4SCN ligand concentration.

    DownLoad: Full-Size Img PowerPoint

    图 2  含有不同浓度的两种配体材料的CsPbIBr2 薄膜的AFM形貌图

    Figure 2.  AFM images of CsPbIBr2 film with two ligands at different concentrations.

    DownLoad: Full-Size Img PowerPoint

    图 3  含有两种配体材料的CsPbIBr2 薄膜的XRD和XPS图　(a) XRD; (b) XPS

    Figure 3.  XRD and XPS patterns of CsPbIBr2 thin films containing two ligand materials: (a) XRD; (b) XPS.

    DownLoad: Full-Size Img PowerPoint

    图 4  含有两种配体的 CsPbIBr2 薄膜的稳态 PL 光谱和紫外-可见吸收光谱　(a) Control, Eg = 2.1 eV; (b) L1, Eg = 2.09 eV; (c) L2, Eg = 2.1 eV; (d) L1+L2, Eg = 2.09 eV

    Figure 4.  Steady-state PL and UV-Vis absorption spectra of CsPbIBr2 film with two ligands: (a) Control, Eg = 2.1 eV; (b) L1, Eg = 2.09 eV; (c) L2, Eg = 2.1 eV; (d) L1+L2, Eg = 2.09 eV.

    DownLoad: Full-Size Img PowerPoint

    图 5  (a) Au/CsPbIBr2/ITO器件结构和能带图; (b) 含有两种配体材料的CsPbIBr2 薄膜器件在黑暗条件和405 nm激光下的J-V曲线; (c) L1+ L2组器件在50 Hz下的时间响应和该组器件线光电流和响应率随入射光功率变化关系图

    Figure 5.  (a) Device structure and band diagram of Au/CsPbIBr2/ITO detector; (b) J-V characteristics of the film with different ligands-based photodetector under dark and 405 nm laser conditions; (c) the time response of the L1+ L2 group of devices at 50 Hz, and the relationship between the line photocurrent and responsivity of the devices with incident light power.

    DownLoad: Full-Size Img PowerPoint

    图 6  (a) 含有两种配体材料的CsPbIBr2 薄膜形貌随时间变化图; (b) 含有两种配体材料的CsPbIBr2 薄膜器件在大气环境下的电学稳定性测试

    Figure 6.  (a) The changes of morphology of CsPbIBr2 film with two ligands with time; (b) stability tests of the CsPbIBr2 film with two ligands-based photodetectors stored in ambient air.

    DownLoad: Full-Size Img PowerPoint

    表 1  采用双配体策略的无机 CsPbIBr2 薄膜光电探测器与其他CsPbIBr2探测器的性能比较

    Table 1.  Performance comparisons of inorganic CsPbIBr2 photodetector using dual ligand with other reports.

    器件结构方法配体环境
    		偏压
    /V    		响应时间
    /μs    		暗电流
    /(10–9 A)    		开光比稳定性文献
    Au/CsPbIBr2/ITO旋涂DEN20.1320, 2302.00103—[10]
    Au/CsPbIBr2/FTO旋涂TAair, 10% RH—3900, 5600—10582%, 56 d
    (air, 30% RH)    		[9]
    Carbon/CsPbIBr2/Ga2O3/TiO2/FTO旋涂—N201.834.15——[1]
    Carbon/CsPbIBr2/FTO旋涂PEIN201.212.03——[8]
    Au/Spiro/CsPbIBr2/TiO2/ITO旋涂AgI2N2022.4, 25.7582.00——[11]
    Au/CsPbIBr2/ITO喷涂LP+
    NH4SCN    		air, 60% RH–520, 211.6010281%, 70 d
    (air, 40%—60% RH)    		This work
    DownLoad: CSV
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    [3]

    Ou Z, Yi Y, Hu Z, Zhu J, Wang W, Meng H, Zhang X, Jing S, Xu S, Hong F, Huang J, Qin J, Xu F, Xu R, Zhu Y, Wang L 2020 J. Alloys Compd. 821 153344Google Scholar

    [4]

    Cen G, Liu Y, Zhao C, Wang G, Fu Y, Yan G, Yuan Y, Su C, Zhao Z, Mai W 2019 Small 15 1902135Google Scholar

    [5]

    Zhu W, Deng M, Zhang Z, Chen D, Xi H, Chang J, Zhang J, Zhang C, Hao Y 2019 ACS Appl. Mater. Inter. 11 22543Google Scholar

    [6]

    Wang Y, Yang F, Li X, Ru F, Liu P, Wang L, Ji W, Xia J, Meng X 2019 Adv. Funct. Mater. 29 1904913Google Scholar

    [7]

    Tang M, He B, Dou D, Liu Y, Duan J, Zhao Y, Chen H, Tang Q 2019 Chem. Eng. J. 375 121930Google Scholar

    [8]

    Zhang Z, Zhang W, Jiang Q, Wei Z, Zhang Y, You H L, Deng M, Zhu W, Zhang J, Zhang C, Hao Y 2020 IEEE Electr. Device. L 41 1532Google Scholar

    [9]

    Chen G, Feng J, Gao H, Zhao Y, Pi Y, Jiang X, Wu Y, Jiang L 2019 Adv. Funct. Mater. 29 1808741Google Scholar

    [10]

    Li Y W, Wang X, Li G W, Wu Y, Pan Y Z, Xu Y B, Chen J, Lei W 2020 Chin. Phys. Lett. 37 018101Google Scholar

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    Zhang Z, Zhang W, Jiang Q, Wei Z, Deng M, Chen D, Zhu W, Zhang J, You H 2020 ACS Appl. Mater. Inter. 12 6607Google Scholar

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    [13]

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    Eze V O, Adams G R, Braga Carani L, Simpson R J, Okoli O I 2020 J. Phys. Chem. C 124 20643Google Scholar

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    Jeon N J, Noh J H, Kim Y C, Yang W S, Ryu S, Seok S I 2014 Nat. Mater. 13 897Google Scholar

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    Zhang H, Nazeeruddin M K, Choy W C H 2019 Adv. Mater. 31 1805702Google Scholar

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    Uličná S, Dou B, Kim D H, Zhu K, Walls J M, Bowers J W, van Hest M F A M 2018 ACS Appl. Energy Mater. 1 1853Google Scholar

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    Zhu W, Zhang Z, Chai W, Chen D, Xi H, Chang J, Zhang J, Zhang C, Hao Y 2019 ACS Appl. Energy Mater. 2 5254Google Scholar

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  • Abstract views:  5011
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Publishing process
  • Received Date:  22 November 2021
  • Accepted Date:  21 December 2021
  • Available Online:  01 March 2022
  • Published Online:  05 June 2022

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