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Title: Conductivity Tuning via Doping with Electron Donating and Withdrawing Molecules in Perovskite CsPbI3 Nanocrystal Films

Abstract

Doping of semiconductors enables fine control over the excess charge carriers, and thus the overall electronic properties, crucial to many technologies. Controlled doping in lead-halide perovskite semiconductors has thus far proven to be difficult. However, lower dimensional perovskites such as nanocrystals, with their high surface-area-to-volume ratio, are particularly well-suited for doping via ground-state molecular charge transfer. Here, the tunability of the electronic properties of perovskite nanocrystal arrays is detailed using physically adsorbed molecular dopants. Incorporation of the dopant molecules into electronically coupled CsPbI3 nanocrystal arrays is confirmed via infrared and photoelectron spectroscopies. Untreated CsPbI3 nanocrystal films are found to be slightly p-type with increasing conductivity achieved by incorporating the electron-accepting dopant 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4TCNQ) and decreasing conductivity for the electron-donating dopant benzyl viologen. Time-resolved spectroscopic measurements reveal the time scales of Auger-mediated recombination in the presence of excess electrons or holes. Microwave conductance and field-effect transistor measurements demonstrate that both the local and long-range hole mobility are improved by F4TCNQ doping of the nanocrystal arrays. The improved hole mobility in photoexcited p-type arrays leads to a pronounced enhancement in phototransistors.

Authors:
 [1];  [1];  [1];  [1]; ORCiD logo [1];  [1];  [1];  [2]; ORCiD logo [1]; ORCiD logo [1]
  1. National Renewable Energy Lab. (NREL), Golden, CO (United States)
  2. California Inst. of Technology (CalTech), Pasadena, CA (United States)
Publication Date:
Research Org.:
National Renewable Energy Lab. (NREL), Golden, CO (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22), Solar Photochemistry Program; USDOE National Renewable Energy Laboratory (NREL), Laboratory Directed Research and Development (LDRD) Program
OSTI Identifier:
1514850
Alternate Identifier(s):
OSTI ID: 1511887
Report Number(s):
NREL/JA-5K00-73496
Journal ID: ISSN 0935-9648
Grant/Contract Number:  
AC36-08GO28308; AC36‐08GO28308
Resource Type:
Accepted Manuscript
Journal Name:
Advanced Materials
Additional Journal Information:
Journal Volume: 31; Journal Issue: 27; Journal ID: ISSN 0935-9648
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 77 NANOSCIENCE AND NANOTECHNOLOGY; detectors; doping; nanocrystals; perovskites; transport

Citation Formats

Gaulding, Elizabeth, Hao, Ji, Kang, Hyun Suk, Link, Elisa M., Habisreutinger, Severin N., Zhao, Qian, Hazarika, Abhijit, Sercel, Peter C., Luther, Joseph M., and Blackburn, Jeffrey L. Conductivity Tuning via Doping with Electron Donating and Withdrawing Molecules in Perovskite CsPbI3 Nanocrystal Films. United States: N. p., 2019. Web. doi:10.1002/adma.201902250.
Gaulding, Elizabeth, Hao, Ji, Kang, Hyun Suk, Link, Elisa M., Habisreutinger, Severin N., Zhao, Qian, Hazarika, Abhijit, Sercel, Peter C., Luther, Joseph M., & Blackburn, Jeffrey L. Conductivity Tuning via Doping with Electron Donating and Withdrawing Molecules in Perovskite CsPbI3 Nanocrystal Films. United States. doi:10.1002/adma.201902250.
Gaulding, Elizabeth, Hao, Ji, Kang, Hyun Suk, Link, Elisa M., Habisreutinger, Severin N., Zhao, Qian, Hazarika, Abhijit, Sercel, Peter C., Luther, Joseph M., and Blackburn, Jeffrey L. Fri . "Conductivity Tuning via Doping with Electron Donating and Withdrawing Molecules in Perovskite CsPbI3 Nanocrystal Films". United States. doi:10.1002/adma.201902250. https://www.osti.gov/servlets/purl/1514850.
@article{osti_1514850,
title = {Conductivity Tuning via Doping with Electron Donating and Withdrawing Molecules in Perovskite CsPbI3 Nanocrystal Films},
author = {Gaulding, Elizabeth and Hao, Ji and Kang, Hyun Suk and Link, Elisa M. and Habisreutinger, Severin N. and Zhao, Qian and Hazarika, Abhijit and Sercel, Peter C. and Luther, Joseph M. and Blackburn, Jeffrey L.},
abstractNote = {Doping of semiconductors enables fine control over the excess charge carriers, and thus the overall electronic properties, crucial to many technologies. Controlled doping in lead-halide perovskite semiconductors has thus far proven to be difficult. However, lower dimensional perovskites such as nanocrystals, with their high surface-area-to-volume ratio, are particularly well-suited for doping via ground-state molecular charge transfer. Here, the tunability of the electronic properties of perovskite nanocrystal arrays is detailed using physically adsorbed molecular dopants. Incorporation of the dopant molecules into electronically coupled CsPbI3 nanocrystal arrays is confirmed via infrared and photoelectron spectroscopies. Untreated CsPbI3 nanocrystal films are found to be slightly p-type with increasing conductivity achieved by incorporating the electron-accepting dopant 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4TCNQ) and decreasing conductivity for the electron-donating dopant benzyl viologen. Time-resolved spectroscopic measurements reveal the time scales of Auger-mediated recombination in the presence of excess electrons or holes. Microwave conductance and field-effect transistor measurements demonstrate that both the local and long-range hole mobility are improved by F4TCNQ doping of the nanocrystal arrays. The improved hole mobility in photoexcited p-type arrays leads to a pronounced enhancement in phototransistors.},
doi = {10.1002/adma.201902250},
journal = {Advanced Materials},
number = 27,
volume = 31,
place = {United States},
year = {2019},
month = {5}
}

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