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Title: Band Tailing and Deep Defect States in CH3NH3Pb(I1–xBrx)3 Perovskites As Revealed by Sub-Bandgap Photocurrent

Abstract

Organometal halide perovskite semiconductors have emerged as promising candidates for optoelectronic applications because of the outstanding charge carrier transport properties, achieved with low-temperature synthesis. In this paper, we present highly sensitive sub-bandgap external quantum efficiency (EQE) measurements of Au/spiro-OMeTAD/CH3NH3Pb(I1–xBrx)3/TiO2/FTO/glass photovoltaic devices. The room-temperature spectra show exponential band tails with a sharp onset characterized by low Urbach energies (Eu) over the full halide composition space. The Urbach energies are 15–23 meV, lower than those for most semiconductors with similar bandgaps (especially with Eg > 1.9 eV). Intentional aging of CH3NH3Pb(I1–xBrx)3 for up to 2300 h, reveals no change in Eu, despite the appearance of the PbI2 phase due to decomposition, and confirms a high degree of crystal ordering. Moreover, sub-bandgap EQE measurements reveal an extended band of sub-bandgap electronic states that can be fit with one or two point defects for pure CH3NH3PbI3 or mixed CH3NH3Pb(I1–xBrx)3 compositions, respectively. Finally, the study provides experimental evidence of defect states close to the midgap that could impact photocarrier recombination and energy conversion efficiency in higher bandgap CH3NH3Pb(I1–xBrx)3 alloys.

Authors:
ORCiD logo [1];  [2];  [1];  [2];  [3]; ORCiD logo [3];  [2];  [1]
+ Show Author Affiliations
  1. Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  2. Univ. of Oregon, Eugene, OR (United States)
  3. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); LBNL Laboratory Directed Research and Development (LDRD) Program
OSTI Identifier:
1379750
Grant/Contract Number:  
AC02-05CH11231; SC0012363
Resource Type:
Accepted Manuscript
Journal Name:
ACS Energy Letters
Additional Journal Information:
Journal Volume: 2; Journal Issue: 3; Journal ID: ISSN 2380-8195
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE

Citation Formats

Sutter-Fella, Carolin M., Miller, D. Westley, Ngo, Quynh P., Roe, Ellis T., Toma, Francesca M., Sharp, Ian D., Lonergan, Mark C., and Javey, Ali. Band Tailing and Deep Defect States in CH3NH3Pb(I1–xBrx)3 Perovskites As Revealed by Sub-Bandgap Photocurrent. United States: N. p., 2017. Web. doi:10.1021/acsenergylett.6b00727.
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Sutter-Fella, Carolin M., Miller, D. Westley, Ngo, Quynh P., Roe, Ellis T., Toma, Francesca M., Sharp, Ian D., Lonergan, Mark C., & Javey, Ali. Band Tailing and Deep Defect States in CH3NH3Pb(I1–xBrx)3 Perovskites As Revealed by Sub-Bandgap Photocurrent. United States. https://doi.org/10.1021/acsenergylett.6b00727
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Sutter-Fella, Carolin M., Miller, D. Westley, Ngo, Quynh P., Roe, Ellis T., Toma, Francesca M., Sharp, Ian D., Lonergan, Mark C., and Javey, Ali. Wed . "Band Tailing and Deep Defect States in CH3NH3Pb(I1–xBrx)3 Perovskites As Revealed by Sub-Bandgap Photocurrent". United States. https://doi.org/10.1021/acsenergylett.6b00727. https://www.osti.gov/servlets/purl/1379750.
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@article{osti_1379750,
title = {Band Tailing and Deep Defect States in CH3NH3Pb(I1–xBrx)3 Perovskites As Revealed by Sub-Bandgap Photocurrent},
author = {Sutter-Fella, Carolin M. and Miller, D. Westley and Ngo, Quynh P. and Roe, Ellis T. and Toma, Francesca M. and Sharp, Ian D. and Lonergan, Mark C. and Javey, Ali},
abstractNote = {Organometal halide perovskite semiconductors have emerged as promising candidates for optoelectronic applications because of the outstanding charge carrier transport properties, achieved with low-temperature synthesis. In this paper, we present highly sensitive sub-bandgap external quantum efficiency (EQE) measurements of Au/spiro-OMeTAD/CH3NH3Pb(I1–xBrx)3/TiO2/FTO/glass photovoltaic devices. The room-temperature spectra show exponential band tails with a sharp onset characterized by low Urbach energies (Eu) over the full halide composition space. The Urbach energies are 15–23 meV, lower than those for most semiconductors with similar bandgaps (especially with Eg > 1.9 eV). Intentional aging of CH3NH3Pb(I1–xBrx)3 for up to 2300 h, reveals no change in Eu, despite the appearance of the PbI2 phase due to decomposition, and confirms a high degree of crystal ordering. Moreover, sub-bandgap EQE measurements reveal an extended band of sub-bandgap electronic states that can be fit with one or two point defects for pure CH3NH3PbI3 or mixed CH3NH3Pb(I1–xBrx)3 compositions, respectively. Finally, the study provides experimental evidence of defect states close to the midgap that could impact photocarrier recombination and energy conversion efficiency in higher bandgap CH3NH3Pb(I1–xBrx)3 alloys.},
doi = {10.1021/acsenergylett.6b00727},
journal = {ACS Energy Letters},
number = 3,
volume = 2,
place = {United States},
year = {2017},
month = {2}
}
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https://doi.org/10.1021/acsenergylett.6b00727
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Works referenced in this record:

Organometal Halide Perovskites as Visible-Light Sensitizers for Photovoltaic Cells
journal, May 2009

  • Kojima, Akihiro; Teshima, Kenjiro; Shirai, Yasuo
  • Journal of the American Chemical Society, Vol. 131, Issue 17, p. 6050-6051
  • DOI: 10.1021/ja809598r

Metal halide perovskites for energy applications
journal, May 2016

Cesium-containing triple cation perovskite solar cells: improved stability, reproducibility and high efficiency
journal, January 2016

  • Saliba, Michael; Matsui, Taisuke; Seo, Ji-Youn
  • Energy & Environmental Science, Vol. 9, Issue 6
  • DOI: 10.1039/C5EE03874J

Perovskite-perovskite tandem photovoltaics with optimized band gaps
journal, October 2016

Chemical Management for Colorful, Efficient, and Stable Inorganic–Organic Hybrid Nanostructured Solar Cells
journal, March 2013

  • Noh, Jun Hong; Im, Sang Hyuk; Heo, Jin Hyuck
  • Nano Letters, Vol. 13, Issue 4, p. 1764-1769
  • DOI: 10.1021/nl400349b

Blue-Green Color Tunable Solution Processable Organolead Chloride–Bromide Mixed Halide Perovskites for Optoelectronic Applications
journal, August 2015

Defects in perovskite-halides and their effects in solar cells
journal, October 2016

Hysteresis and transient behavior in current–voltage measurements of hybrid-perovskite absorber solar cells
journal, January 2014

  • Unger, E. L.; Hoke, E. T.; Bailie, C. D.
  • Energy Environ. Sci., Vol. 7, Issue 11
  • DOI: 10.1039/C4EE02465F

Organometallic Halide Perovskites: Sharp Optical Absorption Edge and Its Relation to Photovoltaic Performance
journal, March 2014

  • De Wolf, Stefaan; Holovsky, Jakub; Moon, Soo-Jin
  • The Journal of Physical Chemistry Letters, Vol. 5, Issue 6
  • DOI: 10.1021/jz500279b

Preparation of Single-Phase Films of CH 3 NH 3 Pb(I 1– x Br x ) 3 with Sharp Optical Band Edges
journal, July 2014

  • Sadhanala, Aditya; Deschler, Felix; Thomas, Tudor H.
  • The Journal of Physical Chemistry Letters, Vol. 5, Issue 15
  • DOI: 10.1021/jz501332v

Defect states in perovskite solar cells associated with hysteresis and performance
journal, October 2016

  • Miller, D. Westley; Eperon, Giles E.; Roe, Ellis T.
  • Applied Physics Letters, Vol. 109, Issue 15
  • DOI: 10.1063/1.4963760

Increased Optoelectronic Quality and Uniformity of Hydrogenated p-InP Thin Films
journal, June 2016

Reversible photo-induced trap formation in mixed-halide hybrid perovskites for photovoltaics
journal, January 2015

  • Hoke, Eric T.; Slotcavage, Daniel J.; Dohner, Emma R.
  • Chemical Science, Vol. 6, Issue 1
  • DOI: 10.1039/C4SC03141E

High Photoluminescence Quantum Yield in Band Gap Tunable Bromide Containing Mixed Halide Perovskites
journal, December 2015

Fabrication of Planar Heterojunction Perovskite Solar Cells by Controlled Low-Pressure Vapor Annealing
journal, January 2015

  • Li, Yanbo; Cooper, Jason K.; Buonsanti, Raffaella
  • The Journal of Physical Chemistry Letters, Vol. 6, Issue 3
  • DOI: 10.1021/jz502720a

Defective TiO2 with high photoconductive gain for efficient and stable planar heterojunction perovskite solar cells
journal, August 2016

  • Li, Yanbo; Cooper, Jason K.; Liu, Wenjun
  • Nature Communications, Vol. 7, Issue 1
  • DOI: 10.1038/ncomms12446

Effect of Ga content on defect states in CuIn 1−x Ga x Se 2 photovoltaic devices
journal, June 2002

  • Heath, J. T.; Cohen, J. D.; Shafarman, W. N.
  • Applied Physics Letters, Vol. 80, Issue 24
  • DOI: 10.1063/1.1485301

Electronically active defects in the Cu 2 ZnSn(Se,S) 4 alloys as revealed by transient photocapacitance spectroscopy
journal, October 2012

  • Miller, D. Westley; Warren, Charles W.; Gunawan, Oki
  • Applied Physics Letters, Vol. 101, Issue 14
  • DOI: 10.1063/1.4754834

Unusual defect physics in CH 3 NH 3 PbI 3 perovskite solar cell absorber
journal, February 2014

  • Yin, Wan-Jian; Shi, Tingting; Yan, Yanfa
  • Applied Physics Letters, Vol. 104, Issue 6
  • DOI: 10.1063/1.4864778

Unique Properties of Halide Perovskites as Possible Origins of the Superior Solar Cell Performance
journal, May 2014

Materials Processing Routes to Trap-Free Halide Perovskites
journal, October 2014

  • Buin, Andrei; Pietsch, Patrick; Xu, Jixian
  • Nano Letters, Vol. 14, Issue 11
  • DOI: 10.1021/nl502612m

Interface energetics in organo-metal halide perovskite-based photovoltaic cells
journal, January 2014

  • Schulz, Philip; Edri, Eran; Kirmayer, Saar
  • Energy & Environmental Science, Vol. 7, Issue 4
  • DOI: 10.1039/c4ee00168k

Band alignment of the hybrid halide perovskites CH 3 NH 3 PbCl 3 , CH 3 NH 3 PbBr 3 and CH 3 NH 3 PbI 3
journal, January 2015

  • Butler, Keith T.; Frost, Jarvist M.; Walsh, Aron
  • Materials Horizons, Vol. 2, Issue 2
  • DOI: 10.1039/C4MH00174E

Recombination Kinetics in Organic-Inorganic Perovskites: Excitons, Free Charge, and Subgap States
journal, September 2014

Optical Properties and Electronic Structure of Amorphous Germanium
journal, January 1966

Photon-Radiative Recombination of Electrons and Holes in Germanium
journal, June 1954

Direct growth of single-crystalline III–V semiconductors on amorphous substrates
journal, January 2016

  • Chen, Kevin; Kapadia, Rehan; Harker, Audrey
  • Nature Communications, Vol. 7, Issue 1
  • DOI: 10.1038/ncomms10502

Temperature dependence of the Urbach edge in GaAs
journal, November 1995

  • Johnson, S. R.; Tiedje, T.
  • Journal of Applied Physics, Vol. 78, Issue 9
  • DOI: 10.1063/1.359683

The effect of copper on the sub-bandgap density of states of CdTe solar cells
journal, May 2015

  • Warren, Charles W.; Li, Jiaojiao; Wolden, Colin A.
  • Applied Physics Letters, Vol. 106, Issue 20
  • DOI: 10.1063/1.4921577

Beneficial effect of a low deposition temperature of hot-wire deposited intrinsic amorphous silicon for solar cells
journal, January 2003

  • van Veen, M. K.; Schropp, R. E. I.
  • Journal of Applied Physics, Vol. 93, Issue 1
  • DOI: 10.1063/1.1527208

Temperature dependence of the optical properties of AlInN
journal, July 2009

  • Jiang, L. F.; Shen, W. Z.; Guo, Q. X.
  • Journal of Applied Physics, Vol. 106, Issue 1
  • DOI: 10.1063/1.3160299

High In-content InGaN layers synthesized by plasma-assisted molecular-beam epitaxy: Growth conditions, strain relaxation, and In incorporation kinetics
journal, December 2014

  • Valdueza-Felip, S.; Bellet-Amalric, E.; Núñez-Cascajero, A.
  • Journal of Applied Physics, Vol. 116, Issue 23
  • DOI: 10.1063/1.4903944

Recent Advances in Improving the Stability of Perovskite Solar Cells
journal, November 2015

  • Tiep, Nguyen Huy; Ku, Zhiliang; Fan, Hong Jin
  • Advanced Energy Materials, Vol. 6, Issue 3
  • DOI: 10.1002/aenm.201501420

Controllable Self-Induced Passivation of Hybrid Lead Iodide Perovskites toward High Performance Solar Cells
journal, June 2014

  • Chen, Qi; Zhou, Huanping; Song, Tze-Bin
  • Nano Letters, Vol. 14, Issue 7
  • DOI: 10.1021/nl501838y
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    Works referencing / citing this record:

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    journal, November 2019

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    • DOI: 10.1002/aenm.201903258

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    journal, February 2018

    • Lin, Qianqian; Wang, Zhiping; Snaith, Henry J.
    • Advanced Science, Vol. 5, Issue 4
    • DOI: 10.1002/advs.201700792

    Defect Activity in Lead Halide Perovskites
    journal, September 2018

    • Motti, Silvia G.; Meggiolaro, Daniele; Martani, Samuele
    • Advanced Materials, Vol. 31, Issue 47
    • DOI: 10.1002/adma.201901183

    Photovoltaic solar cell technologies: analysing the state of the art
    journal, March 2019

    • Nayak, Pabitra K.; Mahesh, Suhas; Snaith, Henry J.
    • Nature Reviews Materials, Vol. 4, Issue 4
    • DOI: 10.1038/s41578-019-0097-0

    Enhanced Moisture Stability by Butyldimethylsulfonium Cation in Perovskite Solar Cells
    journal, December 2019

    Highly efficient all-inorganic perovskite solar cells with suppressed non-radiative recombination by a Lewis base
    journal, January 2020

    High stress-driven voltages in net-like layer-supported organic–inorganic perovskites
    journal, January 2020

    • Tusiime, Rogers; Zabihi, Fatemeh; Tebyetekerwa, Mike
    • Journal of Materials Chemistry C, Vol. 8, Issue 8
    • DOI: 10.1039/c9tc05468e

    Understanding macroscale functionality of metal halide perovskites in terms of nanoscale heterogeneities
    journal, December 2018

    • Song, Tze-Bin; Sharp, Ian D.; Sutter-Fella, Carolin M.
    • Journal of Physics: Energy, Vol. 1, Issue 1
    • DOI: 10.1088/2515-7655/aaeee5

    A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu
    journal, April 2010

    • Grimme, Stefan; Antony, Jens; Ehrlich, Stephan
    • The Journal of Chemical Physics, Vol. 132, Issue 15
    • DOI: 10.1063/1.3382344
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