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Title: Chlorine Doping Reduces Electron–Hole Recombination in Lead Iodide Perovskites: Time-Domain Ab Initio Analysis

Rapid development in lead halide perovskites has led to solution-processable thin film solar cells with power conversion efficiencies close to 20%. Nonradiative electron–hole recombination within perovskites has been identified as the main pathway of energy losses, competing with charge transport and limiting the efficiency. Using nonadiabatic (NA) molecular dynamics, combined with time-domain density functional theory, we show that nonradiative recombination happens faster than radiative recombination and long-range charge transfer to an acceptor material. Doping of lead iodide perovskites with chlorine atoms reduces charge recombination. On the one hand, chlorines decrease the NA coupling because they contribute little to the wave functions of the valence and conduction band edges. On the other hand, chlorines shorten coherence time because they are lighter than iodines and introduce high-frequency modes. Both factors favor longer excited-state lifetimes. The simulation shows good agreement with the available experimental data and contributes to the comprehensive understanding of electronic and vibrational dynamics in perovskites. The generated insights into design of higher-efficiency solar cells range from fundamental scientific principles, such as the role of electron–vibrational coupling and quantum coherence, to practical guidelines, such as specific suggestions for chemical doping.
 [1] ;  [2]
  1. Univ. of Rochester, NY (United States). Dept. of Chemical Engineering
  2. Univ. of Southern California, Los Angeles, CA (United States). Dept. of Chemistry
Publication Date:
Grant/Contract Number:
Published Article
Journal Name:
Journal of Physical Chemistry Letters
Additional Journal Information:
Journal Volume: 6; Journal Issue: 22; Journal ID: ISSN 1948-7185
American Chemical Society
Research Org:
Univ. of Southern California, Los Angeles, CA (United States). Dept. of Chemistry
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); Russian Science Foundation
Country of Publication:
United States
14 SOLAR ENERGY; 36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; decoherence; doping; electron−hole recombination; electron−vibrational coupling; lead halide perovskites; nonadiabatic molecular dynamics; nonradiative relaxation; time-domain density functional theory
OSTI Identifier:
Alternate Identifier(s):
OSTI ID: 1437013