skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Two Regimes of Bandgap Red Shift and Partial Ambient Retention in Pressure-Treated Two-Dimensional Perovskites

Abstract

The discovery of elevated environmental stability in two-dimensional (2D) Ruddlesden–Popper hybrid perovskites represents a significant advance in low-cost, high-efficiency light absorbers. In comparison to 3D counterparts, 2D perovskites of organo-lead-halides exhibit wider, quantum-confined optical bandgaps that reduce the wavelength range of light absorption. Here, we characterize the structural and optical properties of 2D hybrid perovskites as a function of hydrostatic pressure. We observe bandgap narrowing with pressure of 633 meV that is partially retained following pressure release due to an atomic reconfiguration mechanism. We identify two distinct regimes of compression dominated by the softer organic and less compressible inorganic sublattices. Our findings, which also include PL enhancement, correlate well with density functional theory calculations and establish structure–property relationships at the atomic scale. These concepts can be expanded into other hybrid perovskites and suggest that pressure/strain processing could offer a new route to improved materials-by-design in applications.

Authors:
 [1];  [1]; ORCiD logo [2]; ORCiD logo [3];  [4];  [5];  [6];  [2];  [1]; ORCiD logo [3]; ORCiD logo [7]
  1. Center for High Pressure Science and Technology Advanced Research, Shanghai 201203, China; Geophysical Laboratory, Carnegie Institution of Washington, Washington, DC 20015, United States
  2. Center for Nanoscale Materials, Argonne National Laboratory, Argonne, Illinois 60439, United States
  3. Department of Chemistry, Northwestern University, 2145 Sheridan Road, Evanston, Illinois 60208, United States
  4. Center for High Pressure Science and Technology Advanced Research, Shanghai 201203, China
  5. Geophysical Laboratory, Carnegie Institution of Washington, Washington, DC 20015, United States
  6. Advanced Photon Source, Argonne National Laboratory, Argonne, Illinois 60439, United States
  7. Center for Nanoscale Materials, Argonne National Laboratory, Argonne, Illinois 60439, United States; Department of Chemistry, Northwestern University, 2145 Sheridan Road, Evanston, Illinois 60208, United States
Publication Date:
Research Org.:
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1409634
Report Number(s):
BNL-114686-2017-JA¿¿¿
Journal ID: ISSN 2380-8195
DOE Contract Number:
SC0012704
Resource Type:
Journal Article
Resource Relation:
Journal Name: ACS Energy Letters; Journal Volume: 2; Journal Issue: 11
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE

Citation Formats

Liu, Gang, Kong, Lingping, Guo, Peijun, Stoumpos, Constantinos C., Hu, Qingyang, Liu, Zhenxian, Cai, Zhonghou, Gosztola, David J., Mao, Ho-kwang, Kanatzidis, Mercouri G., and Schaller, Richard D. Two Regimes of Bandgap Red Shift and Partial Ambient Retention in Pressure-Treated Two-Dimensional Perovskites. United States: N. p., 2017. Web. doi:10.1021/acsenergylett.7b00807.
Liu, Gang, Kong, Lingping, Guo, Peijun, Stoumpos, Constantinos C., Hu, Qingyang, Liu, Zhenxian, Cai, Zhonghou, Gosztola, David J., Mao, Ho-kwang, Kanatzidis, Mercouri G., & Schaller, Richard D. Two Regimes of Bandgap Red Shift and Partial Ambient Retention in Pressure-Treated Two-Dimensional Perovskites. United States. doi:10.1021/acsenergylett.7b00807.
Liu, Gang, Kong, Lingping, Guo, Peijun, Stoumpos, Constantinos C., Hu, Qingyang, Liu, Zhenxian, Cai, Zhonghou, Gosztola, David J., Mao, Ho-kwang, Kanatzidis, Mercouri G., and Schaller, Richard D. Mon . "Two Regimes of Bandgap Red Shift and Partial Ambient Retention in Pressure-Treated Two-Dimensional Perovskites". United States. doi:10.1021/acsenergylett.7b00807.
@article{osti_1409634,
title = {Two Regimes of Bandgap Red Shift and Partial Ambient Retention in Pressure-Treated Two-Dimensional Perovskites},
author = {Liu, Gang and Kong, Lingping and Guo, Peijun and Stoumpos, Constantinos C. and Hu, Qingyang and Liu, Zhenxian and Cai, Zhonghou and Gosztola, David J. and Mao, Ho-kwang and Kanatzidis, Mercouri G. and Schaller, Richard D.},
abstractNote = {The discovery of elevated environmental stability in two-dimensional (2D) Ruddlesden–Popper hybrid perovskites represents a significant advance in low-cost, high-efficiency light absorbers. In comparison to 3D counterparts, 2D perovskites of organo-lead-halides exhibit wider, quantum-confined optical bandgaps that reduce the wavelength range of light absorption. Here, we characterize the structural and optical properties of 2D hybrid perovskites as a function of hydrostatic pressure. We observe bandgap narrowing with pressure of 633 meV that is partially retained following pressure release due to an atomic reconfiguration mechanism. We identify two distinct regimes of compression dominated by the softer organic and less compressible inorganic sublattices. Our findings, which also include PL enhancement, correlate well with density functional theory calculations and establish structure–property relationships at the atomic scale. These concepts can be expanded into other hybrid perovskites and suggest that pressure/strain processing could offer a new route to improved materials-by-design in applications.},
doi = {10.1021/acsenergylett.7b00807},
journal = {ACS Energy Letters},
number = 11,
volume = 2,
place = {United States},
year = {Mon Oct 09 00:00:00 EDT 2017},
month = {Mon Oct 09 00:00:00 EDT 2017}
}
  • Bond length and bond angle exhibited by valence electrons is essential to the core of chemistry. Using lead-based organic–inorganic perovskite compounds as an exploratory platform, it is demonstrated that the modulation of valence electrons by compression can lead to discovery of new properties of known compounds. Yet, despite its unprecedented progress, further efficiency boost of lead-based organic–inorganic perovskite solar cells is hampered by their wider bandgap than the optimum value according to the Shockley–Queisser limit. By modulating the valence electron wavefunction with modest hydraulic pressure up to 2.1 GPa, the optimized bandgap for single-junction solar cells in lead-based perovskites, formore » the first time, is achieved by narrowing the bandgap of formamidinium lead triiodide (HC(NH2)2PbI3) from 1.489 to 1.337 eV. Strikingly, such bandgap narrowing is partially retained after the release of pressure to ambient, and the bandgap narrowing is also accompanied with double-prolonged carrier lifetime. With First-principles simulation, this work opens a new dimension in basic chemical understanding of structural photonics and electronics and paves an alternative pathway toward better photovoltaic materials-by-design.« less
  • Bond length and bond angle exhibited by valence electrons is essential to the core of chemistry. Using lead-based organic–inorganic perovskite compounds as an exploratory platform, it is demonstrated that the modulation of valence electrons by compression can lead to discovery of new properties of known compounds. Yet, despite its unprecedented progress, further efficiency boost of lead-based organic–inorganic perovskite solar cells is hampered by their wider bandgap than the optimum value according to the Shockley–Queisser limit. By modulating the valence electron wavefunction with modest hydraulic pressure up to 2.1 GPa, the optimized bandgap for single-junction solar cells in lead-based perovskites, formore » the first time, is achieved by narrowing the bandgap of formamidinium lead triiodide (HC(NH 2) 2PbI 3) from 1.489 to 1.337 eV. Strikingly, such bandgap narrowing is partially retained after the release of pressure to ambient, and the bandgap narrowing is also accompanied with double-prolonged carrier lifetime. With First-principles simulation, this work opens a new dimension in basic chemical understanding of structural photonics and electronics and paves an alternative pathway toward better photovoltaic materials-by-design.« less
  • Tungsten (W) incorporated Ga{sub 2}O{sub 3} films were produced by co-sputter deposition. W-concentration was varied by the applied sputtering-power. The structure and optical properties of W-incorporated Ga{sub 2}O{sub 3} films were evaluated using X-ray diffraction, scanning electron microscopy, and spectrophotometric measurements. No secondary phase formation was observed in W-incorporated Ga{sub 2}O{sub 3} films. W-induced effects were significant on the structure and optical properties of Ga{sub 2}O{sub 3} films. The bandgap of Ga{sub 2}O{sub 3} films without W-incorporation was {approx}5 eV. Red-shift in the bandgap was noted with increasing W-concentration indicating the electronic structure changes in W-Ga{sub 2}O{sub 3} films. Amore » functional relationship between W-concentration and optical property is discussed.« less
  • Two ambient-pressure organic superconductors have recently been synthesized from the sulfur-containing organic donor bis-(ethylenedithio)tetrathiafulvalene (BEDT-TTF or ET). These superconductors ..beta..-(ET)/sub 2/I/sub 3/ (T/sub c/ approx. 1.6 K) and ..beta..-(ET)/sub 2/IBr/sub 7/ (T/sub c/ approx. 2.8 K) have stacks of ET molecules, and each ET stack contains loosely dimerized (ET)/sub 2//sup +/ units. The ET stacks also form molecular sheets. In the ..beta..-(ET)/sub 2/X crystals, the sheets of (ET)/sub 2//sup +/ dimers and X/sup -/ anions (I/sub 3//sup -/ or IBr/sub 2//sup -/) alternate. Between adjacent ET stacks in each ET sheet, numerous short S...S contact distances less than 3.6 A(i.e.,more » the van der Waals radii sum of the S atoms) occur which suggests the presence of strong interstack interactions. In agreement with these structural characteristics, various electrical conductivity and optical measurements and band electronic structure calculations reveal that the ..beta..-(ET)/sub 2/X salts are two-dimensional (2D) metals. In the following, the intermolecular interactions between the ET molecules and their relations to the band structure are examined. In order to better describe the interstack S...S interactions, the s and p orbitals of carbon and sulfur were represented by double-zeta Slater type orbitals as employed in our band electronic structure calculations. Also, the significance of the short interstack S...S contacts for the interactions between ET molecules will be examined. 18 references, 1 figure, 1 table.« less
  • Disorder–order transitions found for CO 2 on titania.