DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Enhancing ferroelectric photovoltaic effect by polar order engineering

Abstract

Ferroelectric materials for photovoltaics have sparked great interest because of their switchable photoelectric responses and above-bandgap photovoltages that violate conventional photovoltaic theory. However, their relatively low photocurrent and power conversion efficiency limit their potential application in solar cells. To improve performance, conventional strategies focus mainly on narrowing the bandgap to better match the solar spectrum, leaving the fundamental connection between polar order and photovoltaic effect largely overlooked. We report large photovoltaic enhancement by A-site substitutions in a model ferroelectric photovoltaic material, BiFeO3. As revealed by optical measurements and supported by theoretical calculations, the enhancement is accompanied by the chemically driven rotational instability of the polarization, which, in turn, affects the charge transfer at the band edges and drives a direct-to-indirect bandgap transition, highlighting the strong coupling between polarization, lattice, and orbital order parameters in ferroelectrics. Polar order engineering thus provides an additional degree of freedom to further boost photovoltaic efficiency in ferroelectrics and related materials.

Authors:
ORCiD logo [1];  [2]; ORCiD logo [3];  [1]; ORCiD logo [4];  [5];  [5];  [6];  [7];  [8];  [1]; ORCiD logo [4]; ORCiD logo [1]
  1. Nanyang Technological Univ. (Singapore)
  2. Univ. of Pennsylvania, Philadelphia, PA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  3. Soochow Univ., Suzhou (China)
  4. Univ. of Pennsylvania, Philadelphia, PA (United States)
  5. Shanghai Univ., Shanghai (China)
  6. National Univ. of Singapore (Singapore); GLOBALFOUNDRIES, Albany, NY (United States)
  7. National Univ. of Singapore (Singapore)
  8. Nanyang Technological Univ. (Singapore); Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1471238
Alternate Identifier(s):
OSTI ID: 1478347
Grant/Contract Number:  
AC05-76RL01830; AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Science Advances
Additional Journal Information:
Journal Volume: 4; Journal Issue: 7; Journal ID: ISSN 2375-2548
Publisher:
AAAS
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 42 ENGINEERING

Citation Formats

You, Lu, Zheng, Fan, Fang, Liang, Zhou, Yang, Tan, Liang Z., Zhang, Zeyu, Ma, Guohong, Schmidt, Daniel, Rusydi, Andrivo, Wang, Le, Chang, Lei, Rappe, Andrew M., and Wang, Junling. Enhancing ferroelectric photovoltaic effect by polar order engineering. United States: N. p., 2018. Web. doi:10.1126/sciadv.aat3438.
You, Lu, Zheng, Fan, Fang, Liang, Zhou, Yang, Tan, Liang Z., Zhang, Zeyu, Ma, Guohong, Schmidt, Daniel, Rusydi, Andrivo, Wang, Le, Chang, Lei, Rappe, Andrew M., & Wang, Junling. Enhancing ferroelectric photovoltaic effect by polar order engineering. United States. https://doi.org/10.1126/sciadv.aat3438
You, Lu, Zheng, Fan, Fang, Liang, Zhou, Yang, Tan, Liang Z., Zhang, Zeyu, Ma, Guohong, Schmidt, Daniel, Rusydi, Andrivo, Wang, Le, Chang, Lei, Rappe, Andrew M., and Wang, Junling. Fri . "Enhancing ferroelectric photovoltaic effect by polar order engineering". United States. https://doi.org/10.1126/sciadv.aat3438. https://www.osti.gov/servlets/purl/1471238.
@article{osti_1471238,
title = {Enhancing ferroelectric photovoltaic effect by polar order engineering},
author = {You, Lu and Zheng, Fan and Fang, Liang and Zhou, Yang and Tan, Liang Z. and Zhang, Zeyu and Ma, Guohong and Schmidt, Daniel and Rusydi, Andrivo and Wang, Le and Chang, Lei and Rappe, Andrew M. and Wang, Junling},
abstractNote = {Ferroelectric materials for photovoltaics have sparked great interest because of their switchable photoelectric responses and above-bandgap photovoltages that violate conventional photovoltaic theory. However, their relatively low photocurrent and power conversion efficiency limit their potential application in solar cells. To improve performance, conventional strategies focus mainly on narrowing the bandgap to better match the solar spectrum, leaving the fundamental connection between polar order and photovoltaic effect largely overlooked. We report large photovoltaic enhancement by A-site substitutions in a model ferroelectric photovoltaic material, BiFeO3. As revealed by optical measurements and supported by theoretical calculations, the enhancement is accompanied by the chemically driven rotational instability of the polarization, which, in turn, affects the charge transfer at the band edges and drives a direct-to-indirect bandgap transition, highlighting the strong coupling between polarization, lattice, and orbital order parameters in ferroelectrics. Polar order engineering thus provides an additional degree of freedom to further boost photovoltaic efficiency in ferroelectrics and related materials.},
doi = {10.1126/sciadv.aat3438},
journal = {Science Advances},
number = 7,
volume = 4,
place = {United States},
year = {2018},
month = {7}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 15 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Evolution of crystal structure and ferroic properties of La-doped BiFeO3 ceramics near the rhombohedral-orthorhombic phase boundary
journal, April 2013


Optical band gap of BiFeO3 grown by molecular-beam epitaxy
journal, April 2008

  • Ihlefeld, J. F.; Podraza, N. J.; Liu, Z. K.
  • Applied Physics Letters, Vol. 92, Issue 14
  • DOI: 10.1063/1.2901160

Ultrafast carrier dynamics and radiative recombination in multiferroic BiFeO 3
journal, June 2012

  • Sheu, Y. M.; Trugman, S. A.; Park, Y. -S.
  • Applied Physics Letters, Vol. 100, Issue 24
  • DOI: 10.1063/1.4729423

Structural phase transitions of the metal oxide perovskites SrTiO 3 , LaAlO 3 , and LaTiO 3 studied with a screened hybrid functional
journal, January 2013


Bandgap tuning of multiferroic oxide solar cells
journal, November 2014


Role of domain walls in the abnormal photovoltaic effect in BiFeO3
journal, November 2013

  • Bhatnagar, Akash; Roy Chaudhuri, Ayan; Heon Kim, Young
  • Nature Communications, Vol. 4, Issue 1
  • DOI: 10.1038/ncomms3835

QUANTUM ESPRESSO: a modular and open-source software project for quantum simulations of materials
journal, September 2009

  • Giannozzi, Paolo; Baroni, Stefano; Bonini, Nicola
  • Journal of Physics: Condensed Matter, Vol. 21, Issue 39, Article No. 395502
  • DOI: 10.1088/0953-8984/21/39/395502

Surface Space-Charge Layers in Barium Titanate
journal, May 1956


Gap-state engineering of visible-light-active ferroelectrics for photovoltaic applications
journal, August 2017


Structural Evolution of the BiFeO 3 −LaFeO 3 System
journal, January 2011

  • Rusakov, Dmitriy A.; Abakumov, Artem M.; Yamaura, Kazunari
  • Chemistry of Materials, Vol. 23, Issue 2
  • DOI: 10.1021/cm1030975

Wide bandgap tunability in complex transition metal oxides by site-specific substitution
journal, January 2012

  • Choi, Woo Seok; Chisholm, Matthew F.; Singh, David J.
  • Nature Communications, Vol. 3, Issue 1
  • DOI: 10.1038/ncomms1690

Effect of lanthanum doping on tetragonal-like BiFe O 3 with mixed-phase domain structures
journal, October 2014


Temperature dependent photoexcited carrier dynamics in multiferroic BiFeO 3 film: A hidden phase transition
journal, April 2014

  • Zhang, Zeyu; Jin, Zuanming; Pan, Qunfeng
  • Applied Physics Letters, Vol. 104, Issue 15
  • DOI: 10.1063/1.4871689

Theory of Electron Band Tails and the Urbach Optical-Absorption Edge
journal, October 1986


Bulk photovoltaic effect in noncentrosymmetric crystals
journal, July 2001


Ultrahigh strain and piezoelectric behavior in relaxor based ferroelectric single crystals
journal, August 1997

  • Park, Seung-Eek; Shrout, Thomas R.
  • Journal of Applied Physics, Vol. 82, Issue 4
  • DOI: 10.1063/1.365983

Evidence of bulk photovoltaic effect and large tensor coefficient in ferroelectric BiFeO 3 thin films
journal, September 2011


Physics and Applications of Bismuth Ferrite
journal, June 2009


Chemical Substitution-Induced Ferroelectric Polarization Rotation in BiFeO3
journal, March 2011

  • Kan, Daisuke; Anbusathaiah, Varatharajan; Takeuchi, Ichiro
  • Advanced Materials, Vol. 23, Issue 15
  • DOI: 10.1002/adma.201004503

Revealing the role of organic cations in hybrid halide perovskite CH3NH3PbI3
journal, April 2015

  • Motta, Carlo; El-Mellouhi, Fedwa; Kais, Sabre
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms8026

Massive band gap variation in layered oxides through cation ordering
journal, January 2015

  • Balachandran, Prasanna V.; Rondinelli, James M.
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms7191

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


Charge transfer transitions in multiferroic BiFeO 3 and related ferrite insulators
journal, June 2009


Lead halide perovskites: Crystal-liquid duality, phonon glass electron crystals, and large polaron formation
journal, October 2017

  • Miyata, Kiyoshi; Atallah, Timothy L.; Zhu, X. -Y.
  • Science Advances, Vol. 3, Issue 10
  • DOI: 10.1126/sciadv.1701469

Switchable Ferroelectric Diode and Photovoltaic Effect in BiFeO 3
journal, February 2009


First Principles Calculation of the Shift Current Photovoltaic Effect in Ferroelectrics
journal, September 2012


Composition-driven structural phase transitions in rare-earth-doped bifeo<sub>3</sub> ceramics: a review
journal, January 2015

  • Arnold, Donna
  • IEEE Transactions on Ultrasonics, Ferroelectrics, and Frequency Control, Vol. 62, Issue 1
  • DOI: 10.1109/TUFFC.2014.006668

Phonon softening and direct to indirect band gap crossover in strained single-layer MoSe 2
journal, March 2013


Temperature-dependent dielectric function of bulk SrTiO 3 : Urbach tail, band edges, and excitonic effects
journal, February 2016


What Is Moving in Hybrid Halide Perovskite Solar Cells?
journal, February 2016


The Long-Wavelength Edge of Photographic Sensitivity and of the Electronic Absorption of Solids
journal, December 1953


High‐voltage bulk photovoltaic effect and the photorefractive process in LiNbO 3
journal, August 1974

  • Glass, A. M.; von der Linde, D.; Negran, T. J.
  • Applied Physics Letters, Vol. 25, Issue 4
  • DOI: 10.1063/1.1655453

Direct–indirect character of the bandgap in methylammonium lead iodide perovskite
journal, October 2016

  • Hutter, Eline M.; Gélvez-Rueda, María C.; Osherov, Anna
  • Nature Materials, Vol. 16, Issue 1
  • DOI: 10.1038/nmat4765

Theory of the bulk photovoltaic effect in pure crystals
journal, May 1981


Bulk Photovoltaic Effect at Visible Wavelength in Epitaxial Ferroelectric BiFeO 3 Thin Films
journal, April 2010


Bulk photovoltaic effect in BaTiO3
journal, October 1975


Anisotropic optical properties of rhombohedral and tetragonal thin film BiFeO 3 phases
journal, August 2015


Dielectric Response: Answer to Many Questions in the Methylammonium Lead Halide Solar Cell Absorbers
journal, May 2017

  • Anusca, Irina; Balčiūnas, Sergejus; Gemeiner, Pascale
  • Advanced Energy Materials, Vol. 7, Issue 19
  • DOI: 10.1002/aenm.201700600

Photoconductivity in BiFeO3 thin films
journal, March 2008

  • Basu, S. R.; Martin, L. W.; Chu, Y. H.
  • Applied Physics Letters, Vol. 92, Issue 9
  • DOI: 10.1063/1.2887908

Designed nonlocal pseudopotentials for enhanced transferability
journal, May 1999


Mechanism of the Switchable Photovoltaic Effect in Ferroelectric BiFeO3
journal, June 2011


First-principles study of spontaneous polarization in multiferroic Bi Fe O 3
journal, January 2005


First-Principles Calculation of the Bulk Photovoltaic Effect in Bismuth Ferrite
journal, December 2012


Restoring the Density-Gradient Expansion for Exchange in Solids and Surfaces
journal, April 2008


First-principles investigation of the structural phases and enhanced response properties of the BiFeO 3 -LaFeO 3 multiferroic solid solution
journal, February 2012

  • González-Vázquez, O. E.; Wojdeł, Jacek C.; Diéguez, Oswaldo
  • Physical Review B, Vol. 85, Issue 6
  • DOI: 10.1103/PhysRevB.85.064119

Perovskite oxides for visible-light-absorbing ferroelectric and photovoltaic materials
journal, November 2013

  • Grinberg, Ilya; West, D. Vincent; Torres, Maria
  • Nature, Vol. 503, Issue 7477, p. 509-512
  • DOI: 10.1038/nature12622

Band structure and optical transitions in LaFeO 3 : theory and experiment
journal, November 2014


Above-bandgap voltages from ferroelectric photovoltaic devices
journal, January 2010


Tip-enhanced photovoltaic effects in bismuth ferrite
journal, March 2011

  • Alexe, Marin; Hesse, Dietrich
  • Nature Communications, Vol. 2, Issue 1
  • DOI: 10.1038/ncomms1261

Universal Behavior and Electric-Field-Induced Structural Transition in Rare-Earth-Substituted BiFeO3
journal, March 2010

  • Kan, Daisuke; Pálová, Lucia; Anbusathaiah, Varatharajan
  • Advanced Functional Materials, Vol. 20, Issue 7
  • DOI: 10.1002/adfm.200902017

Non-volatile memory based on the ferroelectric photovoltaic effect
journal, June 2013

  • Guo, Rui; You, Lu; Zhou, Yang
  • Nature Communications, Vol. 4, Issue 1
  • DOI: 10.1038/ncomms2990

Optimized pseudopotentials
journal, January 1990

  • Rappe, Andrew M.; Rabe, Karin M.; Kaxiras, Efthimios
  • Physical Review B, Vol. 41, Issue 2
  • DOI: 10.1103/PhysRevB.41.1227

Band gap and Schottky barrier heights of multiferroic BiFeO3
journal, March 2007

  • Clark, S. J.; Robertson, J.
  • Applied Physics Letters, Vol. 90, Issue 13
  • DOI: 10.1063/1.2716868

Theory of Electron Band Tails and the Urbach Optical-Absorption Edge
journal, December 1986


Lead halide perovskites: Crystal-liquid duality, phonon glass electron crystals, and large polaron formation
text, January 2017

  • Miyata, Kiyoshi; Atallah, Timothy Luke; Zhu, Xiaoyang
  • Columbia University
  • DOI: 10.7916/d8281kg3

Direct-indirect character of the bandgap in methylammonium lead iodide perovskite.
text, January 2017

  • Hutter, Em; Gélvez-Rueda, Mc; Osherov, A.
  • Apollo - University of Cambridge Repository
  • DOI: 10.17863/cam.12468

Ultrafast carrier dynamics and radiative recombination in multiferroic BiFeO$_{3}$
text, January 2012


Revealing the role of organic cations in hybrid halide perovskites CH3NH3PbI3
text, January 2014


Designed nonlocal pseudopotentials for enhanced transferability
preprint, January 1997


Works referencing / citing this record:

Conjuncted Pyro‐Piezoelectric Effect for Self‐Powered Simultaneous Temperature and Pressure Sensing
journal, June 2019


Functional Oxides for Photoneuromorphic Engineering: Toward a Solar Brain
journal, June 2019


Optically Controlled Abnormal Photovoltaic Current Modulation with Temperature in BiFeO 3
journal, February 2019


Perovskites with d-block metals for solar energy applications
journal, January 2019

  • Theofylaktos, Lazaros; Kosmatos, Kyro Odysseas; Giannakaki, Eleni
  • Dalton Transactions, Vol. 48, Issue 26
  • DOI: 10.1039/c9dt01485c

Anomalous polarization switching and permanent retention in a ferroelectric ionic conductor
journal, January 2020

  • Zhou, Shuang; You, Lu; Chaturvedi, Apoorva
  • Materials Horizons, Vol. 7, Issue 1
  • DOI: 10.1039/c9mh01215j

High performance bulk photovoltaics in narrow-bandgap centrosymmetric ultrathin films
journal, January 2020

  • Mai, Haoxin; Lu, Teng; Sun, Qingbo
  • Materials Horizons, Vol. 7, Issue 3
  • DOI: 10.1039/c9mh01744e

Controllable defect driven symmetry change and domain structure evolution in BiFeO 3 with enhanced tetragonality
journal, January 2019

  • Chen, Chao; Wang, Changan; Cai, Xiangbin
  • Nanoscale, Vol. 11, Issue 17
  • DOI: 10.1039/c9nr00932a

Improved ferroelectric properties and band-gap tuning in BiFeO 3 films via substitution of Mn
journal, January 2019


Enhanced photovoltaic effect in Bi 2 FeMo 0.7 Ni 0.3 O 6 ferroelectric thin films by tuning the thickness
journal, January 2020

  • Cui, Xiaxia; Li, Yong; Li, Xiaowei
  • Journal of Materials Chemistry C, Vol. 8, Issue 4
  • DOI: 10.1039/c9tc04973h

Polarization controlled photovoltaic and self-powered photodetector characteristics in Pb-free ferroelectric thin film
journal, January 2019

  • Swain, Atal Bihari; Rath, Martando; Biswas, Pranab Parimal
  • APL Materials, Vol. 7, Issue 1
  • DOI: 10.1063/1.5064454

Self-polarization effect on large photovoltaic response in lead free ferroelectric 0.5Ba(Zr 0.2 Ti 0.8 )O 3 -0.5(Ba 0.7 Ca 0.3 )TiO 3 epitaxial film
journal, December 2018

  • Swain, Atal Bihari; Rath, Martando; Pal, Subhajit
  • Applied Physics Letters, Vol. 113, Issue 23
  • DOI: 10.1063/1.5068699

Large photovoltaic response in rare-earth doped BiFeO 3 polycrystalline thin films near morphotropic phase boundary composition
journal, April 2019

  • Biswas, Pranab Parimal; Pal, Subhajit; Subramanian, V.
  • Applied Physics Letters, Vol. 114, Issue 17
  • DOI: 10.1063/1.5090911

Photovoltaic, photo-impedance, and photo-capacitance effects of the flexible (111) BiFeO 3 film
journal, September 2019

  • Xie, Zhongshuai; Yang, Yuxi; Fang, Liang
  • Applied Physics Letters, Vol. 115, Issue 11
  • DOI: 10.1063/1.5120484

Enhanced pyroelectric properties of Bi 1−x La x FeO 3 thin films
journal, November 2019

  • Zhang, Lei; Huang, Yen-Lin; Velarde, Gabriel
  • APL Materials, Vol. 7, Issue 11
  • DOI: 10.1063/1.5128413

Tailoring the photovoltaic effect in (1 1 1) oriented BiFeO 3 /LaFeO 3 superlattices
journal, December 2019

  • Belhadi, J.; Yousfi, S.; El Marssi, M.
  • Journal of Physics: Condensed Matter, Vol. 32, Issue 13
  • DOI: 10.1088/1361-648x/ab5e11

A Ferroelectric-Photovoltaic Effect in SbSI Nanowires
journal, April 2019

  • Mistewicz, Krystian; Nowak, Marian; Stróż, Danuta
  • Nanomaterials, Vol. 9, Issue 4
  • DOI: 10.3390/nano9040580

Tailoring the photovoltaic effect in (111) oriented BiFeO3/LaFeO3 superlattices
text, January 2020