$N$-Type Surface Doping of MAPbI3 via Charge Transfer from Small Molecules

Perry, Erin E.; Labram, John G.; Venkatesan, Naveen R.; Nakayama, Hidenori; Chabinyc, Michael L.

doi:10.1002/aelm.201800087

Title: $$N$$-Type Surface Doping of MAPbI₃ via Charge Transfer from Small Molecules

Abstract

Organic hole and electron transport materials are regularly employed as electron- and hole-blocking layers in perovskite thin-film solar cells. In order to optimize charge-extraction in the device, these organic layers can be doped using organic small molecules. However, to date there has been little work carried out on direct doping of perovskite surfaces. In this report, we study the change in electrical properties of thin films of MAPbI₃ by surface doping the film with an organic dopant molecule: cobaltocene (Co(C₅H₅)₂). By varying the quantity of cobaltocene deposited, the conductivity of MAPbI3 thin films are observed to be tunable over several orders of magnitude. We observe a tunable shift in the Fermi level illustrating that charge transfer doping enables control over the interfacial energy levels. An increase in photoconductivity is seen at intermediate doping levels, indicating passivation of surface traps confirmed by increased photolumeniscence. In conclusion, this model system provides a means to understand more complex heterointerfaces of doped organic blends at perovskite surfaces.

Authors:

Perry, Erin E. ^[1];

^[1]; Venkatesan, Naveen R. ^[1]; Nakayama, Hidenori ^[2];

^[1]

Univ. of California, Santa Barbara, CA (United States). Dept. of Materials
Mitsubishi Chemical Corporation (Japan). Yokohama R&D Center; Univ. of California, Santa Barbara, CA (United States). Dept. of Materials and Mitsubishi Chemical Center for Advanced Materials

Publication Date:: Sun Jun 10 00:00:00 EDT 2018

Research Org.:: Univ. of California, Santa Barbara, CA (United States)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division

OSTI Identifier:: 1594804

Grant/Contract Number:: SC0012541

Resource Type:: Accepted Manuscript

Journal Name:: Advanced Electronic Materials

Additional Journal Information:: Journal Volume: 4; Journal Issue: 7; Journal ID: ISSN 2199-160X

Publisher:: Wiley

Country of Publication:: United States

Language:: English

Subject:: 36 MATERIALS SCIENCE; charge transfer; interface engineering; ohmic contacts; perovskite solar cells; surface doping; trap passivation

Citation Formats


                    Perry, Erin E., Labram, John G., Venkatesan, Naveen R., Nakayama, Hidenori, and Chabinyc, Michael L. $N$-Type Surface Doping of MAPbI3 via Charge Transfer from Small Molecules.  United States: N. p., 2018. 
Web.  doi:10.1002/aelm.201800087.

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                    Perry, Erin E., Labram, John G., Venkatesan, Naveen R., Nakayama, Hidenori, & Chabinyc, Michael L. $N$-Type Surface Doping of MAPbI3 via Charge Transfer from Small Molecules.  United States.  https://doi.org/10.1002/aelm.201800087

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                    Perry, Erin E., Labram, John G., Venkatesan, Naveen R., Nakayama, Hidenori, and Chabinyc, Michael L. Sun .  
"$N$-Type Surface Doping of MAPbI3 via Charge Transfer from Small Molecules".  United States.  https://doi.org/10.1002/aelm.201800087.  https://www.osti.gov/servlets/purl/1594804.

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@article{osti_1594804,

  title        = {$N$-Type Surface Doping of MAPbI3 via Charge Transfer from Small Molecules},

  author       = {Perry, Erin E. and Labram, John G. and Venkatesan, Naveen R. and Nakayama, Hidenori and Chabinyc, Michael L.},

  abstractNote = {Organic hole and electron transport materials are regularly employed as electron- and hole-blocking layers in perovskite thin-film solar cells. In order to optimize charge-extraction in the device, these organic layers can be doped using organic small molecules. However, to date there has been little work carried out on direct doping of perovskite surfaces. In this report, we study the change in electrical properties of thin films of MAPbI3 by surface doping the film with an organic dopant molecule: cobaltocene (Co(C5H5)2). By varying the quantity of cobaltocene deposited, the conductivity of MAPbI3 thin films are observed to be tunable over several orders of magnitude. We observe a tunable shift in the Fermi level illustrating that charge transfer doping enables control over the interfacial energy levels. An increase in photoconductivity is seen at intermediate doping levels, indicating passivation of surface traps confirmed by increased photolumeniscence. In conclusion, this model system provides a means to understand more complex heterointerfaces of doped organic blends at perovskite surfaces.},

  doi          = {10.1002/aelm.201800087},

  journal      = {Advanced Electronic Materials},

  number       = 7,

  volume       = 4,

  place        = {United States},

  year         = {Sun Jun 10 00:00:00 EDT 2018},

  month        = {Sun Jun 10 00:00:00 EDT 2018}

}

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Works referencing / citing this record:

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journal, December 2018

Yang, Jian-Ming; Luo, Yuxin; Bao, Qinye
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Title: $$N$$-Type Surface Doping of MAPbI3 via Charge Transfer from Small Molecules

Abstract

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Substrate-controlled band positions in CH 3 NH 3 PbI 3 perovskite films journal, January 2014

Heterovalent Dopant Incorporation for Bandgap and Type Engineering of Perovskite Crystals journal, January 2016

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Stable Charge-Transfer Doping of Transparent Single-Walled Carbon Nanotube Films journal, September 2010

Additive engineering for highly efficient organic–inorganic halide perovskite solar cells: recent advances and perspectives journal, January 2017

Structures, Phase Transitions and Tricritical Behavior of the Hybrid Perovskite Methyl Ammonium Lead Iodide journal, October 2016

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A simple rule for determining the band offset at CH 3 NH 3 PbI 3 /organic semiconductor heterojunctions journal, January 2016

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Energy level alignment at the methylammonium lead iodide/copper phthalocyanine interface journal, August 2014

Surface and Interface Aspects of Organometal Halide Perovskite Materials and Solar Cells journal, November 2016

Surface Transfer p-Type Doping of Epitaxial Graphene journal, August 2007

Impact of Film Stoichiometry on the Ionization Energy and Electronic Structure of CH 3 NH 3 PbI 3 Perovskites journal, November 2015

Charge Carrier Trapping at Surface Defects of Perovskite Solar Cell Absorbers: A First-Principles Study journal, January 2017

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Title: $$N$$-Type Surface Doping of MAPbI₃ via Charge Transfer from Small Molecules

Substrate-controlled band positions in CH ₃ NH ₃ PbI ₃ perovskite films
journal, January 2014

Heterovalent Dopant Incorporation for Bandgap and Type Engineering of Perovskite Crystals
journal, January 2016

Surface transfer doping of diamond
journal, July 2004

Electronic structures at the interface between Au and CH ₃ NH ₃ PbI ₃
journal, January 2015

Ultralow Self-Doping in Two-dimensional Hybrid Perovskite Single Crystals
journal, June 2017

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

Trap-Assisted Non-Radiative Recombination in Organic-Inorganic Perovskite Solar Cells
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Stable Charge-Transfer Doping of Transparent Single-Walled Carbon Nanotube Films
journal, September 2010

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journal, October 2016

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journal, May 2009

Impact of Monovalent Cation Halide Additives on the Structural and Optoelectronic Properties of CH ₃ NH ₃ PbI ₃ Perovskite
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journal, January 2017

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Electronic Level Alignment in Inverted Organometal Perovskite Solar Cells
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Band Bending in Semiconductors: Chemical and Physical Consequences at Surfaces and Interfaces
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Surface Transfer Doping of Diamond (100) by Tetrafluoro-tetracyanoquinodimethane
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Carrier trapping and recombination: the role of defect physics in enhancing the open circuit voltage of metal halide perovskite solar cells
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Enhanced Photoluminescence and Solar Cell Performance via Lewis Base Passivation of Organic–Inorganic Lead Halide Perovskites
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Surface and Interface Aspects of Organometal Halide Perovskite Materials and Solar Cells
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Surface Transfer p-Type Doping of Epitaxial Graphene
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Impact of Film Stoichiometry on the Ionization Energy and Electronic Structure of CH ₃ NH ₃ PbI ₃ Perovskites
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Charge Carrier Trapping at Surface Defects of Perovskite Solar Cell Absorbers: A First-Principles Study
journal, January 2017

Valence and Conduction Band Densities of States of Metal Halide Perovskites: A Combined Experimental–Theoretical Study
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journal, November 2016

Surface recombination velocity of silicon wafers by photoluminescence
journal, March 2005

Doped Organic Transistors
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Charge Transfer Doping of Silicon
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Band Tailing and Deep Defect States in CH ₃ NH ₃ Pb(I _{1– x} Br _x ) ₃ Perovskites As Revealed by Sub-Bandgap Photocurrent
journal, February 2017

Determination of the exciton binding energy and effective masses for methylammonium and formamidinium lead tri-halide perovskite semiconductors
journal, January 2016

Incorporation of cobaltocene as an n-dopant in organic molecular films
journal, July 2007

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Recent Advances in Energetics and Stability of Metal Halide Perovskites for Optoelectronic Applications
journal, December 2018

A Review on Additives for Halide Perovskite Solar Cells
journal, April 2020

Efficient CsSnI ₃ -based inorganic perovskite solar cells based on a mesoscopic metal oxide framework via incorporating a donor element
journal, January 2020