Laser & Optoelectronics Progress, Volume. 60, Issue 9, 0900002(2023)

Application of Transition Metal Doping in Perovskite Photovoltaic Devices

Wenzhen Zou1, Chu Zhang1, Hongmin Jiang1, Liguo Gao2, Meiqiang Fan1, and Tingli Ma1、*
Author Affiliations
  • 1College of Materials and Chemistry, China Jiliang University, Hangzhou 310018, Zhejiang, China
  • 2School of Chemical Engineering, Dalian University of Technology, Panjin 116086, Liaoning, China
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    Figures & Tables(13)
    Mn-doped CsPbI2Br[28]. (a) Schematic structure of device and description of Mn2+ doping modes: interstitial and substitution; scanning electron microscope (SEM) images of (b) original chlorinated paraffins and (c) 0.5%, (d) 1%, and (e) 2% MnCl2; (f) schematic diagram of grain growth driven by surface passivated MnCl2
    Mn-dopded CsPbI3[29]. (a) Structure and crystal junction diagram of Mn-doped CsPbI3 perovskite solar cells; (b) X-ray diffraction (XRD) patterns of Mn-doped PVK films; (c) partial XRD diffraction peak amplified at 14.36°; (d) energy dispersing X-ray spectroscopy (EDS) for 2% Mn-doped perovskite thin films; (e)~(g) X-ray photoelectron spectroscopy (XPS) for Cs, Pb and I in control film and 2% Mn-doped PVK film; (h) optimal current density and voltage (J-V) characteristic curves of PSC based on Mn-doped CsPbI3 in forward and reverse measurements
    Influence of Ag ion doping on PVK[33]. (a) Layout diagram of planar junction solar cell; (b) photovoltaic performance of MAB0.1Pb0.9I3 system with different B elements; (c) UV spectra curves of MAPb1-xHgxI3 films at different Hg2+ doping concentrations; (d) PCE box diagram of solar cells based on MAPb1-xHgxI3; (e) SEM images of perovskite films with different Hg2+ doping concentrations
    Influence of Co ion doping on PVK[34]. (a) Transmission electron microscope (TEM) cross-section image of MA(31Pb∶1Co)I3 thin film; (b)~(d) composite elemental maps performed with energy dispersive X-Ray spectroscopy (EDX) in scanning transmission electron microscopy (STEM) mode. Individual elemental maps of (b) Pb, (c) I, and (e) Co indicate that elements are distributed homogeneously throughout film thickness; (f) SEM images of MAPbI3 and MA(Pb∶Co)I3 thin films; (g) XPS images of MAPbI3 and MA(31Pb∶1Co)I3 thin films; (h) forward and reverse J-V diagrams of solar cell measurements, and average performance of optimized MA(Pb∶Co)I3 solar cells; (i) energy level diagram of MA (Pb∶Co)I3 relative to MAPbI3
    Influence of Cd ion doping on PVK[31]. (a) Lattice relaxation mechanism. a-c are schematic diagram illustrating a local strain, which can be reduced by forming b point defects or c introducing small ions. d is schematic diagram shows strain in (002) plane, which is reduced by introduction of small B/X ions. e is B/X covalent candidate ions; (b) top view SEM images of perovskite thin films on TiO2/ITO substrates and cross-sectional SEM images of perovskite solar cells; (c) PCE statistics for 30 PSCs of each component; (d) evolution of PCE in solar cells as six devices age in ambient air (50 per cent relative humidity); (e) in air environment and (f) in nitrogen environment, unpackaged power factor correction circuit is operated under maximum power point conditions using an UV filter with cut-off wavelength of 420 nm
    Nb ion and Ta ion doping in TiO2[54]. (a) Conduction band diagram of dopant regulated battery; (b) energy graph image of Nb-TiO2 thin film with respect to vacuum level calculated based on UV-VIS spectrum and uninterruptible power source measurement results; (c) top view a and cross section image b of TiO2 films prepared by SEM, and top view of Nb-TiO2 thin films containing 1%, 3%, 5%, 7%, 10%, and 20% mole fraction Nb atoms as shown by c-h; (d) XRD patterns of undoped and doped TiO2 nanowire arrays with different Ta doping levels; (e) a and c are undoped TiO2 nanowire arrays, b and d are TEM and high-resolution transmission electron microscopy (HRTEM) images of 0.1-Ta-TiO2 nanowire arrays; Illustrations in c and d are corresponding fast Fourier transform (FFT) diffraction patterns
    Co ion doping in TiO2[61]. (a) MOF preparation process and perovskite solar cell structure; (b) J-V curves of solar cells with best performance using dye-sol TiO2 and co-doped TiO2 (mass fraction is 1%); (c) SEM images of dye-sol TiO2 and 1% mass fraction co-doped TiO2 on FTO coated glass; (d) EIS curves based on TiO2 and 1% mass fraction co-doped TiO2 thin films
    Ni ion doping in TiO2[66]. (a) Schematic diagram of solution treatment method for preparing Ni-TiO2 thin film; (b) schematic diagram of carbon base plane PSC structure and (c) high resolution cross-section SEM image; (d) energy level diagram; (e) steady-state luminescence spectra of ore on different substrates
    Co ion doping in SiO2[73]. (a) Band diagrams of SnO2, SnO2-CoCl2, and PVK layers and J-V curves of prepared PSCs; (b) cross-sectional SEM images of PSC based on SnO2-CoCl2 at a scale of 500 nm; (c) PSCs PCE histogram based on SnO2 and SnO2-CoCl2; (d) XPS image of Co 2p; XPS image of O 1s for (e) pristine SnO2 and (f) SnO2-CoCl2
    Pd ion doping in HTL[84]. (a) Schematic diagram of PSCs with HTL layer doped Pd nanosheets; (b) TEM image of Pd nanosheets; (c) energy level diagram of materials used in PSCs; (d) schematic of interface of PVK and HTM layers; (e) comparison of PCE distributions of 30 individual devices; (f) EIS plots of devices in dark at 0.8 mV forward bias voltage
    Ag ion doping in NiOx[94]. (a) Device structure; (b) SEM image of cross section of complete solar cell device and (c) Ag-doped lattice structure diagram; (d) Ag 3d XPS image of pristine NiOx thin film and Ag∶NiOx thin film; (e) UV-VIS absorption spectra and (f) time-resolved PL spectra of MAPbI3 thin films grown on pristine NiOx and Ag∶NiOx thin films; (g) J-V curves with reverse direction and (h) IPCE spectra of best performed device based PEDOT∶PSS, NiOx, and Ag∶NiOx as HTLs; (i) normalized PCE of PSCs based on PEDOT∶PSS, pristine NiOx, and Ag∶NiOx HTL as a function of storage time in ambient environment (30±2% humidity, T = 25 °C)
    Cr ion doping in NiOx[97]. (a) Cr/CuGaO2-CC/NiOx HTL device structure and (b) its SEM image; (c) PSC device energy level diagram; (d) SEM images of perovskite on NiOx and Cr/CuGaO2-CC/NiOx HTL, respectively; (e) PL spectrograms of perovskites on NiOx and Cr/CuGaO2-CC/NiOx HTL
    • Table 1. Doping situation of transition metal in each layer of PSCs

      View table

      Table 1. Doping situation of transition metal in each layer of PSCs

      ElementDoped materialPCE /%FunctionReference
      All inorganic perovskite layerMn2+CsPbI316.52Reduce crystal lattice,expand grain,reduce hysteresis phenomenon,reduce composite18
      CsPbI2Br13.47Enlarged grain size14
      CsPbIBr219.9017
      Mn2+、Ni2+、Cu2+、Zn2+CsPbBr36.37-9.18Enlarged grain size,charge composite decreases19
      Organic inorganic perovskite layerCu2+、Ag+、(Na+MAPbI3Successfully incorporated into lattice,regulating valence band,with good band gap arrangement24
      Mn2+MAPbI317.68-19.09Insert into octahedron,suppress vacancy defect,enlarge grain size,adjustable band gap27
      Cd2+、Zn2+、Fe2+、Ni2+、Co2+、Ti4+MAPbI3It causes lattice shrinkage and changes energy band. Fe3+ has a negative effect on battery performance28
      Mn2+、Fe2+、Co2+、Ni2+、Cu2+、Zn2+MAPbI3Co2+ can change energy level and band gap,while Fe2+ has a reaction29
      Cd2+CsMAFAIncrease grain size,reduce defects,and improve stability33
      Cd2+、Zn2+、Fe2+11.70-13.76(0.1% Zn)For Cd2+,Zn2+,grain size will be enlarged,crystallinity will be improved,composite sites will be reduced,and battery performance will be improved. Fe2+ will introduce flight radiation defects50
      TiO2 electron transport materialNb2+m-TiO212.20-13.40Similar band gap,improves electron transmission52
      compact -TiO2Improve electron transport,reduce hysteresis,make the potential positive shift53
      TiO220.40-21.40Can control conduction band,improve photocurrent density54
      Nb2+、Ta2+m-/c-TiO212.40-14.80(Nb)/15.00(Ta)Improve electronic transmission at interface55-56
      Ta2+TiO2 nanowire19.11Electronic structure of crystal can be adjusted to speed up charge transfer57
      Y2+c-TiO2 nanorods18.32Improved electronic transport and reduced recombination58
      TiO219.30Increase electron transfer,lower Schottky barrier59
      Co2+TiO2Band edges are enhanced,defects are reduced,and charge transport is improved60
      Co2+TiO2Improve charge transfer,reduce point defects,improve quality of perovskite film,overcome energy band25
      Co2+m-TiO215.73It can improve light absorption ability,promote charge transmission and reduce electron hole recombination61
      Zr2+TiO218.16Improved TiO2 electrical conductivity,enhanced charge collection,inhibited recombination and defects,adjusted band,good band alignment62
      Ru2+c-TiO214.83-18.35Provides suitable band gap,low resistivity,and improved carrier density63
      Ag+、Zn2+c-TiO211.00-14.10Improve performance64
      Fe3+c-TiO216.02-18.60Defect density is reduced,and conductivity and charge mobility are improved65
      Ni2+TiO217.46Charge transfer is promoted,recombination is inhibited,Fermi level is positively shifted,energy level is adjusted,and defect density is reduced66
      Pt2+TiO220.02Electron transport performance and membrane coverage are improved,and trap state is inhibited67
      Other electronic transport materialsNb2+SnO220.50Better surface coverage of perovskite films reduces series resistance and inhibits hysteresis68
      SnO218.64-20.07Improvement of electrical conductivity and improvement of electron transport motion mechanics66
      Y2+SnO2 GNPs16.25-17.29Speed up charge transfer,restrain electron hole recombination,adjust band arrangement,restrain hysteresis69
      Co2+SnO2Improve band arrangement,improve charge extraction,inhibit compound,improve voltage and efficiency70
      Zr2+SnO2 NPs17.30-19.54Adjust energy level,reduce defect density,reduce interface resistance,inhibit recombination71
      Ru2+SnO220.00-22.00Fermi level of SnO2 is adjusted and increased,charge transfer is improved,and defect density is reduced72
      Ni2+ZnO210.37-12.77It is beneficial to carrier extraction and reduce recombination75
      Ni2+、Ag2+ZnO26.57-7.25Doped with 5% Ag helps charge transfer and reduces recombination rate76
      NiOx hole transport layerCu2+NiOx15.40Increase conductivity,reduce loss of Jsc and FF,improve PCE84
      Cu2+NiOx15.52-17.74Low temperature treatment results in high temperature effect86
      NiOx
      NiOx18.02-20.41Higher carrier concentration,higher hole mobility and higher work function improve hole extraction and reduce compound losses88
      NiOx9.08-11.45Low conductivity,accelerated hole extraction89
      NiOx21.19-23.17Higher conductivity and faster charge transfer and extraction85
      NiOx15.40Improve perovskite hole transmission capacity and reduce series resistance of device91
      Fe3+NiOx15.41-17.57Improvement in conductivity and work function87
      Ag+NiOx13.46-16.86Improve optical transparency,work function,conductivity and hole mobility of nickel oxide thin films92
      Y2+NiOx12.32-16.31Improved hole mobility,effective charge extraction and lower probability of carrier recombination93
      Zn2+NiOx10.43-13.72Defect density at grain boundary is reduced,charge recombination is inhibited,and hysteresis is improved94
      Cr2+NiOx17.60-19.91It has enhanced electrical conductivity,more efficient charge transport,more favorable energy level arrangement and promotes perovskite crystal growth95
      V2+NiOx13.48-13.82Electrical conductivity and surface adhesion are improved,and PCE effect and stability are enhanced96
      Other hole transport materialsTi2+MoO215.10-15.80Better stability for humidity97
      Ni2+、Ti2+MoO217.50-18.10Better reduction stability98
      Pd2+P3HT17.80-18.90Improve electrical conductivity99
      Au+、Ag+PEDOT:PSS11.33-12.18(Au)/12.68(Ag)Improve power conversion efficiency100
      Cu2+CrOx11.48It can inhibit oxidation state of Cr6+,providing a new HTL system101-102
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    Wenzhen Zou, Chu Zhang, Hongmin Jiang, Liguo Gao, Meiqiang Fan, Tingli Ma. Application of Transition Metal Doping in Perovskite Photovoltaic Devices[J]. Laser & Optoelectronics Progress, 2023, 60(9): 0900002

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    Paper Information

    Category: Reviews

    Received: Jan. 25, 2022

    Accepted: Mar. 9, 2022

    Published Online: Apr. 24, 2023

    The Author Email: Ma Tingli (matingli123@cjlu.edu.com)

    DOI:10.3788/LOP220620

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