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近空间升华工艺制备高晶化硒化亚锗光电薄膜及其在太阳能电池中的应用

周静 贺伟兰 杨盛文 高莉 曲鹏 蔡永茂 曹宇

周静, 贺伟兰, 杨盛文, 等. 近空间升华工艺制备高晶化硒化亚锗光电薄膜及其在太阳能电池中的应用[J]. 复合材料学报, 2024, 41(5): 2575-2584. doi: 10.13801/j.cnki.fhclxb.20231102.001
引用本文: 周静, 贺伟兰, 杨盛文, 等. 近空间升华工艺制备高晶化硒化亚锗光电薄膜及其在太阳能电池中的应用[J]. 复合材料学报, 2024, 41(5): 2575-2584. doi: 10.13801/j.cnki.fhclxb.20231102.001
ZHOU Jing, HE Weilan, YANG Shengwen, et al. Preparation of highly crystalline germanous selenide photoelectronic thin films byclose-space sublimation process and its application in solar cells[J]. Acta Materiae Compositae Sinica, 2024, 41(5): 2575-2584. doi: 10.13801/j.cnki.fhclxb.20231102.001
Citation: ZHOU Jing, HE Weilan, YANG Shengwen, et al. Preparation of highly crystalline germanous selenide photoelectronic thin films byclose-space sublimation process and its application in solar cells[J]. Acta Materiae Compositae Sinica, 2024, 41(5): 2575-2584. doi: 10.13801/j.cnki.fhclxb.20231102.001

近空间升华工艺制备高晶化硒化亚锗光电薄膜及其在太阳能电池中的应用

doi: 10.13801/j.cnki.fhclxb.20231102.001
基金项目: 国家自然科学基金(52172185);吉林省教育厅科学技术研究项目(JJKH20210084KJ);吉林市科技创新发展计划(20230103006);吉林省创新创业人才资助项目(2022QN15)
详细信息
    通讯作者:

    曹宇,博士,教授,研究方向为锑基微纳米材料及其在储能与能源转换中的应用 E-mail: ycao@neepu.edu.cn

  • 中图分类号: TB332

Preparation of highly crystalline germanous selenide photoelectronic thin films byclose-space sublimation process and its application in solar cells

Funds: National Natural Science Foundation of China (52172185); Jilin Provincial Department of Education Science and Technology Research Project (JJKH20210084KJ); Jilin City Science and Technology Innovation Development Plan (20230103006); Jilin Province Innovation and Entrepreneurship Talent Funding Project (2022QN15)
  • 摘要: 硒化亚锗(GeSe)由于具有原材料储量丰富、绿色无毒、制备工艺简单和性质稳定等优势,近几年得到了广泛关注。采用近空间升华法制备了GeSe薄膜,对GeSe薄膜的结晶行为进行分析,并将其应用到器件结构为FTO/CdS/GeSe/聚(3-己基噻吩)(P3 HT)/C的太阳能电池中进行优化。首先,在蒸发步骤完成后引入退火工艺,能够有效促进GeSe薄膜晶化,使GeSe太阳能电池的光电转换效率(PCE)提高至0.743%。随后,通过衬底温度调节GeSe薄膜的晶化特性,发现衬底温度的提高有利于GeSe薄膜的晶化,但当衬底温度在300℃以上时,过高的温度会使GeSe从衬底上脱附,导致晶化程度下降,器件性能快速退化。在最佳的280℃衬底温度下,GeSe薄膜具有最大的晶粒尺寸和最强的光吸收、最高的电子寿命(τ)和电导率(σ),获得了2.130%的PCE,其中开路电压(VOC)为0.299 V,短路电流密度(JSC)为16.815 mA·cm−2,填充因子(FF)为42.137%。以上研究为高晶化GeSe太阳能电池的制备和优化提供了可行的技术路线。

     

  • 图  1  GeSe太阳能电池结构图

    P3 HT—Poly(3-hexylthiophene)

    Figure  1.  Structure diagram of GeSe solar cell

    图  2  近空间升华法制备GeSe薄膜示意图

    Figure  2.  Preparation of GeSe thin films by close-space sublimation method

    图  3  (a)未退火与退火GeSe薄膜的XRD图谱;未退火GeSe薄膜(b)和退火GeSe薄膜(c)的SEM图像

    Figure  3.  (a) XRD patterns of unannealed and annealed GeSe films; SEM images of unannealed GeSe film (b) and annealed GeSe film (c)

    图  4  未退火与退火GeSe太阳能电池电流密度-电压(J-V)曲线

    VOC—Open circuit voltage; JSC—Short circuit current density; FF—Filling factor; PCE—Photoelectric conversion efficiency

    Figure  4.  Current density-voltage (J-V) curves of unannealed and annealed GeSe solar cells

    图  5  GeSe薄膜的拉曼图谱(a)和XPS图谱((b), (c))

    Figure  5.  Raman spectra (a) and XPS spectra ((b), (c)) of GeSe thin films

    图  6  不同衬底温度下GeSe薄膜的XRD图谱(a)和SEM图像((b)~(f))

    Figure  6.  XRD patterns (a) and SEM images ((b)-(f)) of GeSe films under different substrate temperatures

    图  7  不同衬底温度下GeSe薄膜太阳能电池的光态J-V曲线(a)、暗态J-V曲线(b)、外部量子效率(EQE)曲线(c)和EIS曲线(d)

    Rs—Series resistance; Rrec—Composite resistance; Rco—Contact resistance; Z'—The real part of the impedance; Z'' —The imaginary part of the impedance; CPE—Constant phase element

    Figure  7.  Light J-V curves (a), dark state J-V curves (b), external quantum efficiency (EQE) curves (c) and EIS impedance fitting curves (d) of GeSe thin film solar cells under different substrate temperatures

    图  8  不同衬底温度下GeSe吸光层的电流-电压(I-V)曲线

    Figure  8.  Current-voltage (I-V) curves of GeSe absorbent layer at different substrate temperatures

    图  9  不同衬底温度下GeSe吸光层紫外-可见吸收光谱图(插图为对应GeSe薄膜的光学带隙图)

    α—Absorption coefficient; hv—Photon energy

    Figure  9.  Ultraviolet-visible absorption spectra of the GeSe absorbent layer at different substrate temperatures (The illustration is the optical band gap diagram of the corresponding GeSe film)

    表  1  不同衬底温度下GeSe薄膜太阳能电池的性能参数

    Table  1.   Performance parameters of GeSe thin film solar cells under different substrate temperatures

    Substrate temperature/℃ VOC/V JSC/(mA·cm−2) FF/% PCE/% Grain size/nm τ/μs J0/(mA·cm−2)
    220 0.228 0.211 22.571 0.011 18.855 34 3.123×10−5
    240 0.242 7.747 33.749 0.632 23.353 67 9.912×10−7
    260 0.269 10.892 40.137 1.178 48.079 89 8.091×10−7
    280 0.299 16.815 42.137 2.130 54.490 108 6.891×10−8
    300 0.225 5.583 31.906 0.401 40.867 42 1.328×10−6
    Notes: τ—Specific conductance; J0—Reverse saturation current density.
    下载: 导出CSV

    表  2  EIS阻抗图中拟合阻抗参数

    Table  2.   Impedance parameters fitted in the EIS impedance diagram

    Substrate temperature/℃ Rs Rrec Rco
    220 147 6290 178
    240 141 11500 167
    260 135 14600 127
    280 108 17420 60
    300 140 6470 77
    下载: 导出CSV

    表  3  不同制备方法GeSe薄膜太阳能电池的特征参数

    Table  3.   Characteristic parameters of GeSe thin film solar cells prepared by different methods

    Method VOC/V JSC/(mA·cm−2) FF/% PCE/% Ref.
    Thermal evaporation0.13512.6138.200.65[25]
    Magnetron sputtering deposition0.22 0.8226.500.05[24]
    Rapid thermal sublimation0.3626.6575.5[26]
    0.3320.147.13.1[29]
    0.2414.4842.601.48[23]
    Close-space sublimation0.29916.81542.1372.130This work
    下载: 导出CSV
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出版历程
  • 收稿日期:  2023-08-01
  • 修回日期:  2023-10-01
  • 录用日期:  2023-10-19
  • 网络出版日期:  2023-11-02
  • 刊出日期:  2024-05-01

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