TY - JOUR
T1 - Tunable Ferroelectricity in Ruddlesden-Popper Halide Perovskites
AU - Zhang, Qiannan
AU - Solanki, Ankur
AU - Parida, Kaushik
AU - Giovanni, David
AU - Li, Mingjie
AU - Jansen, Thomas L.C.
AU - Pshenichnikov, Maxim S.
AU - Sum, Tze Chien
N1 - Funding Information:
*E-mail: [email protected] (M.S.P.). *E-mail: [email protected] (T.C.S.). ORCID Qiannan Zhang: 0000-0002-8139-6160 Thomas L. C. Jansen: 0000-0001-6066-6080 Maxim S. Pshenichnikov: 0000-0002-5446-4287 Tze Chien Sum: 0000-0003-4049-2719 Author Contributions Q.Z. and A.S. contributed equally to this work. T.C.S., A.S., and M.S.P. conceived the idea for the manuscript and designed the experiments. Q.Z. and A.S. prepared and characterized the samples. Q.Z. conducted the microscopic electrical characterization. A.S. and K.P. conducted the macroscopic electrical characterization. Q.Z., M.L., and D.G. conducted the spectroscopic measurement. T.L.C.J. conducted the calculation of MD. T.C.S., A.S., Q.Z., M.S.P., and T.L.C.J. analyzed the data and wrote the paper. All authors discussed the results and commented on the manuscript at all stages. T.C.S. and M.S.P. led this project. Funding Financial support from the Ministry of Education AcRF Tier 1 grant RG173/16; Tier 2 grants MOE2015-T2-2-015, MOE2016-T2-1-034, MOE2017-T2-1-110, and MOE2017-T2-2-002; the Singapore National Research Foundation through the Competitive Research Program NRF-CRP14-2014-03; and the NRF Investigatorship Programme NRF-NRFI-2018-04 are gratefully acknowledged. Notes The authors declare no competing financial interest.
Publisher Copyright:
Copyright © 2019 American Chemical Society.
Copyright:
Copyright 2019 Elsevier B.V., All rights reserved.
PY - 2019/4/10
Y1 - 2019/4/10
N2 - Ruddlesden-Popper (RP) halide perovskites are the new kids on the block for high-performance perovskite photovoltaics with excellent ambient stability. The layered nature of these perovskites offers an exciting possibility of harnessing their ferroelectric property for photovoltaics. Adjacent polar domains in a ferroelectric material allow the spatial separation of electrons and holes. Presently, the structure-function properties governing the ferroelectric behavior of RP perovskites are an open question. Herein, we realize tunable ferroelectricity in 2-phenylethylammonium (PEA) and methylammonium (MA) RP perovskite (PEA) 2 (MA) -rfnet- 1 Pb n I 3n+1 . Second harmonic generation (SHG) confirms the noncentrosymmetric nature of these polycrystalline thin films, whereas piezoresponse force microscopy and polarization-electric field measurements validate the microscopic and macroscopic ferroelectric properties. Temperature-dependent SHG and dielectric constant measurements uncover a phase transition temperature at around 170 °C in these films. Extensive molecular dynamics simulations support the experimental results and identified the correlated reorientation of MA molecules and ion translations as the source of ferroelectricity. Current-voltage characteristics in the dark reveal the persistence of hysteresis in these devices, which has profound implications for light-harvesting and light-emitting applications. Importantly, our findings disclose a viable approach for engineering the ferroelectric properties of RP perovskites that may unlock new functionalities for perovskite optoelectronics.
AB - Ruddlesden-Popper (RP) halide perovskites are the new kids on the block for high-performance perovskite photovoltaics with excellent ambient stability. The layered nature of these perovskites offers an exciting possibility of harnessing their ferroelectric property for photovoltaics. Adjacent polar domains in a ferroelectric material allow the spatial separation of electrons and holes. Presently, the structure-function properties governing the ferroelectric behavior of RP perovskites are an open question. Herein, we realize tunable ferroelectricity in 2-phenylethylammonium (PEA) and methylammonium (MA) RP perovskite (PEA) 2 (MA) -rfnet- 1 Pb n I 3n+1 . Second harmonic generation (SHG) confirms the noncentrosymmetric nature of these polycrystalline thin films, whereas piezoresponse force microscopy and polarization-electric field measurements validate the microscopic and macroscopic ferroelectric properties. Temperature-dependent SHG and dielectric constant measurements uncover a phase transition temperature at around 170 °C in these films. Extensive molecular dynamics simulations support the experimental results and identified the correlated reorientation of MA molecules and ion translations as the source of ferroelectricity. Current-voltage characteristics in the dark reveal the persistence of hysteresis in these devices, which has profound implications for light-harvesting and light-emitting applications. Importantly, our findings disclose a viable approach for engineering the ferroelectric properties of RP perovskites that may unlock new functionalities for perovskite optoelectronics.
KW - and molecular simulation
KW - ferroelectricity
KW - polarization-electric field
KW - Ruddlesden-Popper perovskites
KW - second harmonic generation
UR - http://www.scopus.com/inward/record.url?scp=85064217795&partnerID=8YFLogxK
U2 - 10.1021/acsami.8b21579
DO - 10.1021/acsami.8b21579
M3 - Journal article
C2 - 30854841
AN - SCOPUS:85064217795
SN - 1944-8244
VL - 11
SP - 13523
EP - 13532
JO - ACS Applied Materials and Interfaces
JF - ACS Applied Materials and Interfaces
IS - 14
ER -