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Limiting factors and improving solutions of P-I-N type tin-lead perovskite solar cells performance

Wang Li-Xuan Li Ren-Jie Liu Hui Wang Peng-Yang Shi Biao Zhao Ying Zhang Xiao-Dan

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Limiting factors and improving solutions of P-I-N type tin-lead perovskite solar cells performance

Wang Li-Xuan, Li Ren-Jie, Liu Hui, Wang Peng-Yang, Shi Biao, Zhao Ying, Zhang Xiao-Dan
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  • In order to break through the limit of Shockley-Queisser (SQ) radiation and further improve the efficiency of perovskite solar cells, tin-lead perovskite solar cells have widely and successfully been used as narrow-bandgap bottom cells in all-perovskite tandem solar cells. The highest efficiency of tin-lead perovskite solar cells has recently reached 21.7%, which, however, is still lower than that of lead-based perovskite solar cells. This article analyzes the main factors that limit the further improving of their performances, and summarizes the effective solutions proposed by researchers in recent years. The main points are as follows: 1) by adding tin-rich additives, strong reducing agents or compounds containing large organic cations, Sn2+ oxidation is inhibited and the p-doped degree of tin-lead perovskite and the open-circuit voltage loss are reduced; 2) through regulating the composition, changing the method of preparing the perovskite film, adding functional groups or solvent engineering, the crystallization rate of tin-lead perovskite film is delayed and the crystallization quality of the film is improved; 3) by selecting an appropriate electron transport layer or hole transport layer the influence of energy level mismatch on carrier transport or the instability of carrier transport layer on devices can be avoided. Finally, the future development of Sn-Pb perovskite solar cells is prospected. It is believed that the tin-lead perovskite solar cells can realize not only the high efficiency and stable single-junction solar cells, but also high efficiency perovskite-perovskite tandem solar cells.
      Corresponding author: Zhang Xiao-Dan, xdzhang@nankai.edu.cn
    • Funds: Project supported by the National Research Program of China (Grant No. 2018YFB1500103), the National Natural Science Foundation of China (Grant No. 61674084), the 111 Project, China (Grant No. B16027), the Tianjin Civil Military Integration Project, China (Grant No. 18ZXJMTG00220), and the Fundamental Research Funds for the Central Universities, China (Grant Nos. 63201171, 63201173)
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  • 图 1  提高P-I-N型锡铅钙钛矿太阳电池性能的解决策略

    Figure 1.  Solutions to improve the performance of P-I-N type tin lead perovskite solar cells.

    图 2  钙钛矿材料的能带结构随着金属比例的变化而调整 (a) Ogomi等[5]表征CH3NH3Sn1–xPbxI3能带结构随金属比例的变化; (b) Eperon等[7]通过Tauc plot、PL及第一性原理计算FASnxPb1–xI3带隙随金属比例的变化趋势; (c) Hao等[8]通过紫外吸收光谱表征CH3NH3Sn1–xPbxI3的带隙变化

    Figure 2.  The energy band of Sn-Pb perovskite changed with the metal ratios: (a) Ogomi et al.[5] characterized the CH3NH3Sn1–xPbxI3 energy band structure changed with the metal ratio; (b) Eperon et al.[7] used the Tauc plot, PL and first-principles calculations to obtain the variable trend of HC(NH2)2SnxPb1–xI3(FASnxPb1–xI3) band gap with metal proportions; (c) Hao et al.[8] characterized the band gap changes of CH3NH3Sn1–xPbxI3 by electronic absorption spectra.

    图 3  不同结构的Sn-Pb钙钛矿太阳电池器件效率进展图, 包括N-I-P型(绿色)和P-I-N型(红色)结构

    Figure 3.  The efficiency progress diagram of Sn-Pb perovskite solar cells in different structures, including N-I-P (green) and P-I-N (red) structures.

    图 4  (a)不同SnF2添加量的钙钛矿薄膜扫描电子显微镜(scanning electron microscope, SEM)扫描图[34]; (b) Zhu等[39]利用伽伐尼置换反应(GDR)制备MAPbxSn1–xI3钙钛矿溶液的照片和示意图以及薄膜老化过程机制示意图; (c)由于前驱体溶液中存在Sn4+而在Sn-Pb钙钛矿中形成锡空位的示意图[18]; (d) Wei等[42]利用PEAI实现Sn-Pb钙钛矿表面钝化或膜内钝化的处理方法示意图; (e) Ramirez等[43]引入叔丁胺离子n = 4和n = 5的Sn-Pb钙钛矿晶格示意图; (f) Li等[44]引入4-氟苯乙基碘化铵(FPEAI)使(MAPbI3)0.75(FASnI3)0.25晶粒高度垂直排列的示意图及未使用与使用(FPEAI)的器件J-V曲线

    Figure 4.  (a) SEM images of perovskite films with different SnF2 additions[34]; (b) photos and schematic diagrams of preparing MAPbxSn1–xI3 precursor solution using GDR and the schematic diagram of film aging process[39]; (c) the schematic diagram of tin vacancies formation in Sn-Pb perovskite due to the presence of Sn4+ in the precursor solution[18]; (d) Wei et al. [42]used PEAI to achieve surface passivation or in-film passivation of Sn-Pb perovskit; (e) the schematic diagram of Sn-Pb perovskite lattice with n = 4 and n = 5 introduced by Ramirez et al.[43]; (f) Li et al.[44]introduced FPEAI to vertically arrange the (MAPbI3)0.75(FASnI3)0.25 grain height and the J-V curve of unused and used FPEAI devices.

    图 5  (a) AMX3型钙钛矿材料常用元素组分及不同组分的材料性质[45]; (b) FA+掺入对MA1–yFAyPb0.75Sn0.25I3钙钛矿器件稳定性的影响[49]; (c)由计算和实验所得的MASn1–xPbxI3带隙随x的变化[6]; (d)不同Sn-Pb比例的FA0.66MA0.34Pb1–xSnxI3钙钛矿的XRD图谱[24]; (e) Br含量分别为0, 6%和16%的Sn-Pb钙钛矿太阳电池的暗态J-V曲线[53]; (f)未掺入Cl和掺入2.5% Cl对钙钛矿薄膜的SEM扫描图[30]; (g)掺入不同比例(0, 15%, 25%, 40%)MASCN对薄膜钙钛矿薄膜的SEM顶部扫描图及横截面扫描图[54]

    Figure 5.  (a) The commonly used element compositions and their properties of AMX3[45]; (b) FA+-doping effects to the stability of MA1–yFAyPb0.75Sn0.25I3 perovskite devices[49]; (c) the band gap variation with x changes of MASn1–xPbxI3 obtained from calculations and experiments[6]; (d) XRD patterns of FA0.66MA0.34Pb1–xSnxI3 perovskites with different Sn-Pb ratios[24]; (e) dark J-V curves of Sn-Pb perovskite solar cells with Br concentrations of 0, 6% and 16% respectively[53]; (f) SEM images of perovskite films without Cl and with 2.5% Cl[30]; (g) the top and cross-section SEM images of perovskite films mixed with 0, 15%, 25%, 40% of MASCN[54].

    图 6  (a)两步顺序沉积结合DMSO溶剂蒸气处理的方式制备MASn0.1Pb0.9I3的过程示意图[59]; (b)两步顺序沉积FA0.66MA0.34Pb0.5Sn0.5I3的过程示意及原位吸收光谱图[24]

    Figure 6.  (a) The schematic diagram of the two-step sequential depositions combined with DMSO solvent vapor treatment method to prepare MASn0.1Pb0.9I3 perovskite films[59]; (b) the schematic diagram of the two-step sequential deposition process of FA0.66MA0.34Pb0.5Sn0.5I3 and in-situ absorption spectra[24].

    图 7  (a)真空辅助热退火结合一步溶液法制备的器件结构及原理示意图[60]; (b)使用/不使用真空辅助热退火所制备的薄膜形貌顶部SEM图[60]; (c)真空辅助生长(VAGC)方法的原理示意图及横截面SEM图像[61]; (d)双源共蒸法制备FA1–xCsxSn1–yPbyI3钙钛矿薄膜过程示意图及晶体结构示意图[62]

    Figure 7.  (a) Device architecture and schematic diagram that combined the vacuum-assisted thermal annealing process and one-step solution method[60]; (b) the top SEM images of the film prepared with/without vacuum-assisted thermal annealing[60]; (c) the schematic diagram and cross-section SEM image of the film prepared by VAGC method[61]; (d) the schematic diagram and crystal structure of FA1–xCsxSn1–yPbyI3 perovskite films prepared by dual-source co-evaporation method[62].

    图 8  (a)不同DMSO/DMF溶剂比的Sn-Pb钙钛矿反应机理示意图[56]; (b) MAPb1–xSnxI3 (0 ≤ x ≤ 1)薄膜的形成机理以及相应的晶体结构示意图[64]; (c)在不同偏置电压下未掺杂及掺杂C60的MAPb0.75Sn0.25I3钙钛矿器件的本体复合寿命和表面复合寿命[65]

    Figure 8.  (a) The mechanism diagram of Sn-Pb perovskite reactions with different DMSO/DMF solvent ratio[56]; (b) the formation mechanisms of MAPb1–xSnxI3 (0 ≤ x ≤ 1) film and corresponding crystal structures[64]; (c) bulk recombination life and surface recombination life of MAPb0.75Sn0.25I3 perovskite devices with or without C60-doped under different amplitude voltages[65].

    图 9  (a)含GABr的FA0.7MA0.3Pb0.7Sn0.3I3表面的电荷密度分布图(等电势为0.03 eÅ–3)以及未添加与添加12%的GABr的钙钛矿SEM扫描图[66]; (b)添加CdI2的1.22 eV窄带隙钙钛矿与1.80 eV宽带隙钙钛矿叠层太阳电池的结构示意图和SEM横截面扫描图[68]; (c) (4AMP)2+, 哌嗪离子和PEA+阳离子的结构式及用(4AMP)I2, 碘化哌嗪和PEAI表面处理的CsPb0.6Sn0.4I3钙钛矿太阳电池的J-V曲线[67]

    Figure 9.  (a) The charge density distribution on the FA0.7MA0.3Pb0.7Sn0.3I3 surface containing GABr (the isopotential is 0.03 eÅ–3) and the SEM images of the perovskite without and with 12% GABr[66]; (b) structure diagram and cross-section SEM inage of 1.22 eV narrow-bandgap perovskite with CdI2 added and 1.80 eV wide-bandgap perovskite tandem solar cell[68]; (c) structure of(4AMP)2+, piperazine ion and PEA+ and J-V curves of CsPb0.6Sn0.4I3 perovskite solar cell that absorber film surface treated with (4AMP)I2, piperazine iodide and PEAI, respectively[67].

    图 10  (a) Kapil等[69]对比传统无PCBM层和带PCBM层的电荷提取和复合过程示意图, τr表示从FAMA到C60的载流子注入时间; (b)添加DF-C60形成的梯度异质结(GHJ)结构示意图[72]; (c)在NiOx及PEDOT:PSS上沉积钙钛矿膜的SEM顶部扫描图及截面扫描图[27]; (d)使用BHJ PBDB-T:ITIC中间层形成的逐步升高的HOMO能级结构示意图[82]; (e) S-乙酰硫代胆碱氯化物分子锚定在缺陷部位的示意图, 其中红色、黄色和蓝色符号分别代表S-乙酰硫代胆碱氯化物分子中的O原子、S原子和N原子[71]

    Figure 10.  (a) The diagram of Kapil et al[69]. compared the traditional charge extraction and recombination process without and with PCBM, τr represents the carrier injection time from FAMA to C60; (b) the schematic diagram of the gradient heterojunction (GHJ) with DF-C60[72]; (c) the top and cross-section SEM images of the perovskite films deposited on NiOx and PEDOT:PSS[27]; (d) the schematic diagram of the gradually increasing HOMO energy level structure formed by BHJ PBDB-T:ITIC intermediate layer[82]; (e) the schematic diagram of the S-acetylthiocholine chloride molecule anchored at the defect sites, where the red, yellow and blue symbols represent the O atom, S atom and N atom in the acetylthiocholine chloride molecule, respectively[71].

    表 A1  P-I-N型Sn-Pb钙钛矿太阳电池性能统计

    Table A1.  Statistics of P-I-N type tin-lead perovskite solar cells performance

    YearPerovskiteDevice structureEg/eVVOC/VJSC/(mA·cm–2)FF/%PCE/(%)Ref.
    2016MA0.5FA0.5Pb0.75Sn0.25I3ITO/PEDOT:PSS/PVK/PCBM/Bis-C60/Ag1.330.7823.037914.19[49]
    2016(FASnI3)0.6(MAPbI3)0.4ITO/PEDOT:PSS/PVK/C60/BCP/Ag1.250.79526.8670.615.08[26]
    2017MA0.5FA0.5Pb0.5Sn0.5I3ITO/PEDOT:PSS/PVK/PCBM/Bis-C60/Ag1.20.7825.697014.01[38]
    2017MAPb0.5Sn0.5I3ITO/PEDOT:PSS/PVK-DF-C60/ICBA/Bis-C60/Ag1.220.8726.16915.61[72]
    2018(t-BUA)2(FA0.85Cs0.15)n–1 Pb0.6Sn0.4)nI3n+1ITO/PEDOT:PSS/2 D-PVK/PCBM/BCP/Ag1.240.7024.26310.6[43]
    2018FA0.6MA0.4Sn0.6Pb0.4I3ITO/PFI-(PEDOT:PSS)/PVK/PCBM/BCP/Ag1.220.78427.2274.3615.85[81]
    2018(FAPbI3)0.7(CsSnI3)0.3ITO/PEDOT:PSS/PVK/C60/BCP/Al1.30.7425.8981.415.6[36]
    2018(FASnI3)0.6(MAPbI3)0.34(MAPbBr3)0.06ITO/PEDOT:PSS/PVK/C60/BCP/Ag1.2720.88828.7274.619.03[53]
    2018(FASnI3)0.6(MAPbI3)0.4ITO/PEDOT:PSS/PVK/C60/BCP/Ag1.250.84129.074.418.1[30]
    2018FAPb0.7Sn0.3I3ITO/PEDOT:PSS/PVK/PEAI/PC61BM/BCP/Ag1.340.7826.467916.26[54]
    2018FAPb0.75Sn0.25I3ITO/NiOX/PVK/PC60BM/BCP/Ag1.360.8128.2375.417.25[27]
    2018(FASnI3)0.6(MAPbI3)0.4ITO/PEDOT:PSS/PBDBT:ITIC/PVK/C60/BCP/Ag1.250.8627.9275.118.03[82]
    2019FA0.8MA0.2Sn0.5Pb0.5I3ITO/PEDOT:PSS/PVK/PCBM/BCP/Ag1.270.81307518.2[61]
    2019(FAPb0.6Sn0.4I3)0.85(MAPb0.6Sn0.4Br3)0.15ITO/PEDOT:PSS/PVK/PCBM/Bis­C60/Ag1.280.8726.4579.118.21[39]
    2019FA0.7MA0.3Pb0.5Sn0.5I3ITO/PEDOT:PSS/PVK/PC60BM/BCP/Cu1.220.83131.480.821.1[18]
    2019Cs0.1MA0.2FA0.7Pb0.5Sn0.5I3ITO/NiOX/PVK/C60/BCP/Cu1.20.77131.173.317.6[52]
    2019FA0.75Cs0.25Sn0.4Pb0.6I3ITO/PVK/C60/BCP/Ag1.250.7232.5969.816.4[51]
    2019(FASnI3)0.6(MAPbI3)0.4ITO/PEDOT:PSS/PVK/C60/BCP/Ag1.250.83430.480.820.5[55]
    2019Cs0.1MA0.2FA0.7Sn0.5Pb0.5I3ITO/NiOX/PVK/C60/BCP/Cu1.20.77131.173.317.6[52]
    2020(MAPbI3)0.75(FASnI3)0.25ITO/PEDOT:PSS/PVK/BCP/Ag1.330.7928.427817.51[44]
    2020Cs0.1MA0.2FA0.7Pb0.5Sn0.5I3ITO/PEDOT:PSS/PVK/PCBM/PEIE/Ag1.250.8130.378.919.4[42]
    2020FA0.83Cs0.17Pb0.7Sn0.3I3ITO/PEDOT:PSS/PVK/PCBM/BCP/Ag1.30.8230.378.418.1[9]
    2020FA0.7MA0.3Pb0.7Sn0.3I3ITO/PEDOT:PSS(EMIC)/PVK/S-acetylthiocholine chlorde/C60/BCP/Ag1.351.0226.617620.63[66]
    2020FA0.66MA0.34Pb0.5Sn0.5I3ITO/PEDOT:PSS/PVK/C60/BCP/Ag1.230.7827.87315.8[54]
    2020FA0.5MA0.45Cs0.05Pb0.5Sn0.5I3ITO/PEDOT:PSS/PTAA/Cd-PVK/C60/BCP/Cu1.220.8530.27920.3[68]
    2020FA0.7MA0.3Pb0.5Sn0.5I3ITO/PEDOT:PSS/PVK/C60/BCP/Cu1.240.8531.680.821.7[4]
    DownLoad: CSV
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Metrics
  • Abstract views:  8880
  • PDF Downloads:  253
  • Cited By: 0
Publishing process
  • Received Date:  11 October 2020
  • Accepted Date:  23 December 2020
  • Available Online:  26 May 2021
  • Published Online:  05 June 2021

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