Gap States in Methylammonium Lead Halides: The Link to Dimethylsulfoxide?

Zhang, Fengyu; Hamill, Jr., J. Clay; Loo, Yueh‐Lin; Kahn, Antoine

doi:10.1002/adma.202003482

Gap States in Methylammonium Lead Halides: The Link to Dimethylsulfoxide?

Journal Article · Thu Sep 03 00:00:00 EDT 2020 · Advanced Materials

DOI:https://doi.org/10.1002/adma.202003482· OSTI ID:1804149

^[1]; Hamill, Jr., J. Clay ^[2]; Loo, Yueh‐Lin ^[3]; ^[1]

Department of Electrical Engineering Princeton University Princeton NJ 08544 USA
Department of Chemical and Biological Engineering Princeton University Princeton NJ 08544 USA
Department of Chemical and Biological Engineering Princeton University Princeton NJ 08544 USA, Andlinger Center for Energy and the Environment Princeton University Princeton NJ 08544 USA

Abstract

Understanding the origin and distribution of electronic gap states in metal halide perovskite (MHP) thin films is crucial to the further improvement of the efficiency and long‐term stability of MHP‐based optoelectronic devices. In this work, the impact of Lewis‐basic additives introduced in the precursor solution on the density of states in the perovskite bandgap is investigated. Ultraviolet photoemission spectroscopy and contact potential difference measurements are conducted on MHP thin films processed from dimethylformamide (DMF)‐based solutions to which either no additive, dimethylsulfoxide (DMSO), or N ‐methylpyrrolidine‐2‐thione (NMPT) is added. The results show the presence of a density of states in the gap of methylammonium lead halide films processed from DMSO‐containing solution. The density of gap states is either suppressed when the methylammonium concentration in mixed cation films is reduced or when NMPT is used as an additive, and eliminated when methylammonium (MA) is replaced with cesium or formamidinium (FA). These results are consistent with the notion that reaction products that result from DMSO reacting with MA ⁺ in the precursor solution are responsible for the formation of gap states.

View Accepted Manuscript (Publisher)

Sponsoring Organization:: USDOE

Grant/Contract Number:: EE0008560

OSTI ID:: 1804149

Alternate ID(s):: OSTI ID: 1848839

Journal Information:: Advanced Materials, Journal Name: Advanced Materials Journal Issue: 42 Vol. 32; ISSN 0935-9648

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

References (33)

Energy-Level Alignment at Organic/Metal and Organic/Organic Interfaces Braun, Slawomir; Salaneck, William R.; Fahlman, Mats Advanced Materials, Vol. 21, Issue 14-15, p. 1450-1472 https://doi.org/10.1002/adma.200802893	journal	April 2009
Impact of Film Stoichiometry on the Ionization Energy and Electronic Structure of CH ₃ NH ₃ PbI ₃ Perovskites Emara, Jennifer; Schnier, Tobias; Pourdavoud, Neda Advanced Materials, Vol. 28, Issue 3 https://doi.org/10.1002/adma.201503406	journal	November 2015
A Strategy to Simplify the Preparation Process of Perovskite Solar Cells by Co-deposition of a Hole-Conductor and a Perovskite Layer Ye, Senyun; Rao, Haixia; Yan, Weibo Advanced Materials, Vol. 28, Issue 43 https://doi.org/10.1002/adma.201603850	journal	September 2016
Electronic Level Alignment in Inverted Organometal Perovskite Solar Cells Schulz, Philip; Whittaker-Brooks, Luisa L.; MacLeod, Bradley A. Advanced Materials Interfaces, Vol. 2, Issue 7 https://doi.org/10.1002/admi.201400532	journal	March 2015
Elucidating the Role of a Tetrafluoroborate‐Based Ionic Liquid at the n‐Type Oxide/Perovskite Interface Noel, Nakita K.; Habisreutinger, Severin N.; Wenger, Bernard Advanced Energy Materials, Vol. 10, Issue 4 https://doi.org/10.1002/aenm.201903231	journal	December 2019
Ultraviolet Photoemission Spectroscopy and Kelvin Probe Measurements on Metal Halide Perovskites: Advantages and Pitfalls Zhang, Fengyu; Silver, Scott H.; Noel, Nakita K. Advanced Energy Materials, Vol. 10, Issue 26 https://doi.org/10.1002/aenm.201903252	journal	January 2020
The structure and properties of metal-semiconductor interfaces Brillson, L. Surface Science Reports, Vol. 2, Issue 2 https://doi.org/10.1016/0167-5729(82)90001-2	journal	November 1982
Addition of monochromated UV discharge lamp to X-ray photoemission spectrometer Aeppli, G.; Donelon, J. J.; Eastman, D. E. Journal of Electron Spectroscopy and Related Phenomena, Vol. 14, Issue 2 https://doi.org/10.1016/0368-2048(78)85060-9	journal	January 1978
Surface photovoltage phenomena: theory, experiment, and applications Kronik, L. Surface Science Reports, Vol. 37, Issue 1-5 https://doi.org/10.1016/S0167-5729(99)00002-3	journal	December 1999
Acid-Catalyzed Reactions Activate DMSO as a Reagent in Perovskite Precursor Inks Hamill, J. Clay; Sorli, Jeni C.; Pelczer, István Chemistry of Materials, Vol. 31, Issue 6 https://doi.org/10.1021/acs.chemmater.9b00019	journal	June 2018
Halide Perovskites: Is It All about the Interfaces? Schulz, Philip; Cahen, David; Kahn, Antoine Chemical Reviews, Vol. 119, Issue 5 https://doi.org/10.1021/acs.chemrev.8b00558	journal	March 2019
Valence and Conduction Band Densities of States of Metal Halide Perovskites: A Combined Experimental–Theoretical Study Endres, James; Egger, David A.; Kulbak, Michael The Journal of Physical Chemistry Letters, Vol. 7, Issue 14 https://doi.org/10.1021/acs.jpclett.6b00946	journal	June 2016
Constructing the Electronic Structure of CH ₃ NH ₃ PbI ₃ and CH ₃ NH ₃ PbBr ₃ Perovskite Thin Films from Single-Crystal Band Structure Measurements Zu, Fengshuo; Amsalem, Patrick; Egger, David A. The Journal of Physical Chemistry Letters, Vol. 10, Issue 3 https://doi.org/10.1021/acs.jpclett.8b03728	journal	January 2019
Complexities of Contact Potential Difference Measurements on Metal Halide Perovskite Surfaces Zhang, Fengyu; Ullrich, Florian; Silver, Scott The Journal of Physical Chemistry Letters, Vol. 10, Issue 4 https://doi.org/10.1021/acs.jpclett.8b03878	journal	February 2019
Effect of Crystal Grain Orientation on the Rate of Ionic Transport in Perovskite Polycrystalline Thin Films Fassl, Paul; Ternes, Simon; Lami, Vincent ACS Applied Materials & Interfaces, Vol. 11, Issue 2 https://doi.org/10.1021/acsami.8b16460	journal	December 2018
Origin of Open-Circuit Voltage Losses in Perovskite Solar Cells Investigated by Surface Photovoltage Measurement Daboczi, Matyas; Hamilton, Iain; Xu, Shengda ACS Applied Materials & Interfaces, Vol. 11, Issue 50 https://doi.org/10.1021/acsami.9b16394	journal	November 2019
What Limits the Open-Circuit Voltage of Bromide Perovskite-Based Solar Cells? Zohar, Arava; Kulbak, Michael; Levine, Igal ACS Energy Letters, Vol. 4, Issue 1 https://doi.org/10.1021/acsenergylett.8b01920	journal	November 2018
Trap States in Lead Iodide Perovskites Wu, Xiaoxi; Trinh, M. Tuan; Niesner, Daniel Journal of the American Chemical Society, Vol. 137, Issue 5 https://doi.org/10.1021/ja512833n	journal	January 2015
Extended carrier lifetimes and diffusion in hybrid perovskites revealed by Hall effect and photoconductivity measurements Chen, Y.; Yi, H. T.; Wu, X. Nature Communications, Vol. 7, Issue 1 https://doi.org/10.1038/ncomms12253	journal	August 2016
Solvent engineering for high-performance inorganic–organic hybrid perovskite solar cells Jeon, Nam Joong; Noh, Jun Hong; Kim, Young Chan Nature Materials, Vol. 13, Issue 9, p. 897-903 https://doi.org/10.1038/nmat4014	journal	July 2014
Performance-limiting nanoscale trap clusters at grain junctions in halide perovskites Doherty, Tiarnan A. S.; Winchester, Andrew J.; Macpherson, Stuart Nature, Vol. 580, Issue 7803 https://doi.org/10.1038/s41586-020-2184-1	journal	April 2020
Clean, cleaved surfaces of the photovoltaic perovskite Kollár, Márton; Ćirić, Luka; Dil, J. Hugo Scientific Reports, Vol. 7, Issue 1 https://doi.org/10.1038/s41598-017-00799-0	journal	April 2017
The identification and characterization of defect states in hybrid organic–inorganic perovskite photovoltaics Duan, Hsin-Sheng; Zhou, Huanping; Chen, Qi Physical Chemistry Chemical Physics, Vol. 17, Issue 1 https://doi.org/10.1039/C4CP04479G	journal	January 2015
Spectral dependence of direct and trap-mediated recombination processes in lead halide perovskites using time resolved microwave conductivity Guse, Joanna A.; Soufiani, Arman M.; Jiang, Liangcong Physical Chemistry Chemical Physics, Vol. 18, Issue 17 https://doi.org/10.1039/C5CP07360J	journal	January 2016
Efficient charge extraction and slow recombination in organic–inorganic perovskites capped with semiconducting single-walled carbon nanotubes Ihly, Rachelle; Dowgiallo, Anne-Marie; Yang, Mengjin Energy & Environmental Science, Vol. 9, Issue 4 https://doi.org/10.1039/C5EE03806E	journal	January 2016
How far does the defect tolerance of lead-halide perovskites range? The example of Bi impurities introducing efficient recombination centers Yavari, Mozhgan; Ebadi, Firouzeh; Meloni, Simone Journal of Materials Chemistry A, Vol. 7, Issue 41 https://doi.org/10.1039/C9TA01744E	journal	January 2019
Interface energetics in organo-metal halide perovskite-based photovoltaic cells Schulz, Philip; Edri, Eran; Kirmayer, Saar Energy & Environmental Science, Vol. 7, Issue 4 https://doi.org/10.1039/c4ee00168k	journal	January 2014
Electronic structure of the CsPbBr ₃ /polytriarylamine (PTAA) system Endres, James; Kulbak, Michael; Zhao, Lianfeng Journal of Applied Physics, Vol. 121, Issue 3 https://doi.org/10.1063/1.4974471	journal	January 2017
Origin of the energy level alignment at organic/organic interfaces: The role of structural defects Bussolotti, Fabio; Yang, Jinpeng; Hinderhofer, Alexander Physical Review B, Vol. 89, Issue 11 https://doi.org/10.1103/PhysRevB.89.115319	journal	March 2014
Gap states in Pentacene Thin Film Induced by Inert Gas Exposure Bussolotti, Fabio; Kera, Satoshi; Kudo, Kazuhiro Physical Review Letters, Vol. 110, Issue 26 https://doi.org/10.1103/PhysRevLett.110.267602	journal	June 2013
High-efficiency solution-processed perovskite solar cells with millimeter-scale grains Nie, W.; Tsai, H.; Asadpour, R. Science, Vol. 347, Issue 6221, p. 522-525 https://doi.org/10.1126/science.aaa0472	journal	January 2015
Low trap-state density and long carrier diffusion in organolead trihalide perovskite single crystals Shi, D.; Adinolfi, V.; Comin, R. Science, Vol. 347, Issue 6221 https://doi.org/10.1126/science.aaa2725	journal	January 2015
A vacuum flash–assisted solution process for high-efficiency large-area perovskite solar cells Li, Xiong; Bi, Dongqin; Yi, Chenyi Science, Vol. 353, Issue 6294 https://doi.org/10.1126/science.aaf8060	journal	June 2016

Similar Records

Sulfur-Donor Additives Preferentially Coordinate Pb²⁺ in Perovskite Precursor Solutions

Conference · Thu Dec 05 23:00:00 EST 2019 · OSTI ID:1659408

Degradation of Highly Alloyed Metal Halide Perovskite Precursor Inks: Mechanism and Storage Solutions

Journal Article · Tue Mar 13 20:00:00 EDT 2018 · ACS Energy Letters · OSTI ID:1432603

Solvent and A-Site Cation Control Preferred Crystallographic Orientation in Bromine-Based Perovskite Thin Films

Journal Article · Wed May 24 20:00:00 EDT 2023 · Chemistry of Materials · OSTI ID:1988607

Gap States in Methylammonium Lead Halides: The Link to Dimethylsulfoxide?

Citation Formats

References (33)

Similar Records

Related Subjects