Hyperbolic Dispersion Arising from Anisotropic Excitons in Two-Dimensional Perovskites
Abstract
Excitations of free electrons and optical phonons are known to permit access to the negative real part of relative permittivities (ϵ' < 0) that yield strong light-matter interactions. However, negative ϵ' arising from excitons has been much less explored. Via development of a dielectric-coating based technique described herein, we report fundamental optical properties of two-dimensional hybrid perovskites (2DHPs), composed of alternating layers of inorganic and organic sublattices. Low members of 2DHPs (N = 1 and N = 2) exhibit negative ϵ' stemming from the large exciton binding energy and sizable oscillator strength. Furthermore, hyperbolic dispersion (i.e., ϵ' changes sign with directions) occurs in the visible range, which has been previously achieved only with artificial metamaterials. Such naturally occurring, exotic dispersion stems from the extremely anisotropic excitonic behaviors of 2DHPs, and can intrinsically support a large photonic density of states. Here, we suggest that several other van der Waals solids may exhibit similar behaviors arising from excitonic response.
- Authors:
-
- Argonne National Lab. (ANL), Lemont, IL (United States)
- Northwestern Univ., Evanston, IL (United States)
- Northern Illinois Univ., DeKalb, IL (United States)
- Northwestern Univ., Evanston, IL (United States); Flexterra Corp., Skokie, IL (United States)
- Argonne National Lab. (ANL), Lemont, IL (United States); Northwestern Univ., Evanston, IL (United States)
- Publication Date:
- Research Org.:
- Argonne National Laboratory (ANL), Argonne, IL (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); Air Force Research Laboratory (AFRL), Air Force Office of Scientific Research (AFOSR); Northwestern University, Materials Research Science and Engineering Center (NU-MRSEC); Flexterra, Inc.
- OSTI Identifier:
- 1477741
- Alternate Identifier(s):
- OSTI ID: 1471446
- Grant/Contract Number:
- AC02-06CH11357; SC0012541
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Physical Review Letters
- Additional Journal Information:
- Journal Volume: 121; Journal Issue: 12; Journal ID: ISSN 0031-9007
- Publisher:
- American Physical Society (APS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE
Citation Formats
Guo, Peijun, Huang, Wei, Stoumpos, Constantinos C., Mao, Lingling, Gong, Jue, Zeng, Li, Diroll, Benjamin T., Xia, Yi, Ma, Xuedan, Gosztola, David J., Xu, Tao, Ketterson, John B., Bedzyk, Michael J., Facchetti, Antonio, Marks, Tobin J., Kanatzidis, Mercouri G., and Schaller, Richard D. Hyperbolic Dispersion Arising from Anisotropic Excitons in Two-Dimensional Perovskites. United States: N. p., 2018.
Web. doi:10.1103/PhysRevLett.121.127401.
Guo, Peijun, Huang, Wei, Stoumpos, Constantinos C., Mao, Lingling, Gong, Jue, Zeng, Li, Diroll, Benjamin T., Xia, Yi, Ma, Xuedan, Gosztola, David J., Xu, Tao, Ketterson, John B., Bedzyk, Michael J., Facchetti, Antonio, Marks, Tobin J., Kanatzidis, Mercouri G., & Schaller, Richard D. Hyperbolic Dispersion Arising from Anisotropic Excitons in Two-Dimensional Perovskites. United States. https://doi.org/10.1103/PhysRevLett.121.127401
Guo, Peijun, Huang, Wei, Stoumpos, Constantinos C., Mao, Lingling, Gong, Jue, Zeng, Li, Diroll, Benjamin T., Xia, Yi, Ma, Xuedan, Gosztola, David J., Xu, Tao, Ketterson, John B., Bedzyk, Michael J., Facchetti, Antonio, Marks, Tobin J., Kanatzidis, Mercouri G., and Schaller, Richard D. Wed .
"Hyperbolic Dispersion Arising from Anisotropic Excitons in Two-Dimensional Perovskites". United States. https://doi.org/10.1103/PhysRevLett.121.127401. https://www.osti.gov/servlets/purl/1477741.
@article{osti_1477741,
title = {Hyperbolic Dispersion Arising from Anisotropic Excitons in Two-Dimensional Perovskites},
author = {Guo, Peijun and Huang, Wei and Stoumpos, Constantinos C. and Mao, Lingling and Gong, Jue and Zeng, Li and Diroll, Benjamin T. and Xia, Yi and Ma, Xuedan and Gosztola, David J. and Xu, Tao and Ketterson, John B. and Bedzyk, Michael J. and Facchetti, Antonio and Marks, Tobin J. and Kanatzidis, Mercouri G. and Schaller, Richard D.},
abstractNote = {Excitations of free electrons and optical phonons are known to permit access to the negative real part of relative permittivities (ϵ' < 0) that yield strong light-matter interactions. However, negative ϵ' arising from excitons has been much less explored. Via development of a dielectric-coating based technique described herein, we report fundamental optical properties of two-dimensional hybrid perovskites (2DHPs), composed of alternating layers of inorganic and organic sublattices. Low members of 2DHPs (N = 1 and N = 2) exhibit negative ϵ' stemming from the large exciton binding energy and sizable oscillator strength. Furthermore, hyperbolic dispersion (i.e., ϵ' changes sign with directions) occurs in the visible range, which has been previously achieved only with artificial metamaterials. Such naturally occurring, exotic dispersion stems from the extremely anisotropic excitonic behaviors of 2DHPs, and can intrinsically support a large photonic density of states. Here, we suggest that several other van der Waals solids may exhibit similar behaviors arising from excitonic response.},
doi = {10.1103/PhysRevLett.121.127401},
journal = {Physical Review Letters},
number = 12,
volume = 121,
place = {United States},
year = {Wed Sep 19 00:00:00 EDT 2018},
month = {Wed Sep 19 00:00:00 EDT 2018}
}
Web of Science
Figures / Tables:
Works referenced in this record:
Centimeter-Sized Inorganic Lead Halide Perovskite CsPbBr 3 Crystals Grown by an Improved Solution Method
journal, October 2017
- Zhang, Hongjian; Liu, Xin; Dong, Jiangpeng
- Crystal Growth & Design, Vol. 17, Issue 12
Excitons in nanoscale systems
journal, September 2006
- Scholes, Gregory D.; Rumbles, Garry
- Nature Materials, Vol. 5, Issue 9
Influence of the image charge effect on excitonic energy structure in organic-inorganic multiple quantum well crystals
journal, March 2013
- Takagi, Hidetsugu; Kunugita, Hideyuki; Ema, Kazuhiro
- Physical Review B, Vol. 87, Issue 12
Van der Waals Materials for Atomically-Thin Photovoltaics: Promise and Outlook
journal, November 2017
- Jariwala, Deep; Davoyan, Artur R.; Wong, Joeson
- ACS Photonics, Vol. 4, Issue 12
Epsilon-near-zero metamaterials and electromagnetic sources: Tailoring the radiation phase pattern
journal, April 2007
- Alù, Andrea; Silveirinha, Mário G.; Salandrino, Alessandro
- Physical Review B, Vol. 75, Issue 15
Spontaneous Emission inside a Hyperbolic Metamaterial Waveguide
journal, October 2017
- Roth, Diane J.; Krasavin, Alexey V.; Wade, Alexander
- ACS Photonics, Vol. 4, Issue 10
Polaritons in layered two-dimensional materials
journal, November 2016
- Low, Tony; Chaves, Andrey; Caldwell, Joshua D.
- Nature Materials, Vol. 16, Issue 2
Probing optical anisotropy of nanometer-thin van der waals microcrystals by near-field imaging
journal, November 2017
- Hu, Debo; Yang, Xiaoxia; Li, Chi
- Nature Communications, Vol. 8, Issue 1
Electronic and Excitonic Structures of Inorganic–Organic Perovskite-Type Quantum-Well Crystal (C 4 H 9 NH 3 ) 2 PbBr 4
journal, August 2005
- Tanaka, Kenichiro; Takahashi, Takayuki; Kondo, Takashi
- Japanese Journal of Applied Physics, Vol. 44, Issue 8
Sub-diffractional volume-confined polaritons in the natural hyperbolic material hexagonal boron nitride
journal, October 2014
- Caldwell, Joshua D.; Kretinin, Andrey V.; Chen, Yiguo
- Nature Communications, Vol. 5, Issue 1
Influences of evaporation temperature on electronic structures and electrical properties of molybdenum oxide in organic light emitting devices
journal, March 2010
- Lin, Chang-Ting; Yeh, Cheng-Hung; Chen, Mei-Hsin
- Journal of Applied Physics, Vol. 107, Issue 5
Single-crystal-to-single-crystal intercalation of a low-bandgap superatomic crystal
journal, August 2017
- O'Brien, Evan S.; Trinh, M. Tuan; Kann, Rose L.
- Nature Chemistry, Vol. 9, Issue 12
Indefinite by Nature: From Ultraviolet to Terahertz
journal, February 2014
- Sun, Jingbo; Litchinitser, Natalia M.; Zhou, Ji
- ACS Photonics, Vol. 1, Issue 4
High-quality bulk hybrid perovskite single crystals within minutes by inverse temperature crystallization
journal, July 2015
- Saidaminov, Makhsud I.; Abdelhady, Ahmed L.; Murali, Banavoth
- Nature Communications, Vol. 6, Article No. 7586
Nanometre optical coatings based on strong interference effects in highly absorbing media
journal, October 2012
- Kats, Mikhail A.; Blanchard, Romain; Genevet, Patrice
- Nature Materials, Vol. 12, Issue 1, p. 20-24
Ruddlesden–Popper Hybrid Lead Iodide Perovskite 2D Homologous Semiconductors
journal, April 2016
- Stoumpos, Constantinos C.; Cao, Duyen H.; Clark, Daniel J.
- Chemistry of Materials, Vol. 28, Issue 8, p. 2852-2867
Observation of long-range exciton diffusion in highly ordered organic semiconductors
journal, October 2010
- Najafov, H.; Lee, B.; Zhou, Q.
- Nature Materials, Vol. 9, Issue 11
Atomic-scale photonic hybrids for mid-infrared and terahertz nanophotonics
journal, January 2016
- Caldwell, Joshua D.; Vurgaftman, Igor; Tischler, Joseph G.
- Nature Nanotechnology, Vol. 11, Issue 1
Atomically Thin A New Direct-Gap Semiconductor
journal, September 2010
- Mak, Kin Fai; Lee, Changgu; Hone, James
- Physical Review Letters, Vol. 105, Issue 13, Article No.136805
Experimental and theoretical optical properties of methylammonium lead halide perovskites
journal, January 2016
- Leguy, Aurélien M. A.; Azarhoosh, Pooya; Alonso, M. Isabel
- Nanoscale, Vol. 8, Issue 12
Organic-Inorganic Hybrid Materials as Semiconducting Channels in Thin-Film Field-Effect Transistors
journal, October 1999
- Kagan, C. R.; Mitzi, D. B.; Dimitrakopoulos, C. D.
- Science, Vol. 286, Issue 5441, p. 945-947
Light Propagation with Phase Discontinuities: Generalized Laws of Reflection and Refraction
journal, September 2011
- Yu, N.; Genevet, P.; Kats, M. A.
- Science, Vol. 334, Issue 6054
Epitaxial superlattices with titanium nitride as a plasmonic component for optical hyperbolic metamaterials
journal, May 2014
- Naik, G. V.; Saha, B.; Liu, J.
- Proceedings of the National Academy of Sciences, Vol. 111, Issue 21
Electron–Phonon Scattering in Atomically Thin 2D Perovskites
journal, October 2016
- Guo, Zhi; Wu, Xiaoxi; Zhu, Tong
- ACS Nano, Vol. 10, Issue 11
Topological Transitions in Metamaterials
journal, April 2012
- Krishnamoorthy, H. N. S.; Jacob, Z.; Narimanov, E.
- Science, Vol. 336, Issue 6078
Charge-Carrier Dynamics in 2D Hybrid Metal–Halide Perovskites
journal, October 2016
- Milot, Rebecca L.; Sutton, Rebecca J.; Eperon, Giles E.
- Nano Letters, Vol. 16, Issue 11
Hyperbolic metamaterials
journal, December 2013
- Poddubny, Alexander; Iorsh, Ivan; Belov, Pavel
- Nature Photonics, Vol. 7, Issue 12, p. 948-957
Huge exchange energy and fine structure of excitons in an organic-inorganic quantum well material
journal, June 2006
- Ema, K.; Umeda, K.; Toda, M.
- Physical Review B, Vol. 73, Issue 24
Plasmonics for improved photovoltaic devices
journal, February 2010
- Atwater, Harry A.; Polman, Albert
- Nature Materials, Vol. 9, Issue 3, p. 205-213
Extreme sensitivity biosensing platform based on hyperbolic metamaterials
journal, March 2016
- Sreekanth, Kandammathe Valiyaveedu; Alapan, Yunus; ElKabbash, Mohamed
- Nature Materials, Vol. 15, Issue 6
Hybrid Dion–Jacobson 2D Lead Iodide Perovskites
journal, February 2018
- Mao, Lingling; Ke, Weijun; Pedesseau, Laurent
- Journal of the American Chemical Society, Vol. 140, Issue 10
Differences between amorphous indium oxide thin films
journal, October 2013
- Buchholz, D. Bruce; Zeng, Li; Bedzyk, Michael J.
- Progress in Natural Science: Materials International, Vol. 23, Issue 5
Formation of Long-Lived Color Centers for Broadband Visible Light Emission in Low-Dimensional Layered Perovskites
journal, December 2017
- Booker, Edward P.; Thomas, Tudor H.; Quarti, Claudio
- Journal of the American Chemical Society, Vol. 139, Issue 51
Phosphorene analogues: Isoelectronic two-dimensional group-IV monochalcogenides with orthorhombic structure
journal, August 2015
- Gomes, Lídia C.; Carvalho, A.
- Physical Review B, Vol. 92, Issue 8
Hyperbolic metamaterials: fundamentals and applications
journal, June 2014
- Shekhar, Prashant; Atkinson, Jonathan; Jacob, Zubin
- Nano Convergence, Vol. 1, Issue 1
CH 3 NH 3 PbCl 3 Single Crystals: Inverse Temperature Crystallization and Visible-Blind UV-Photodetector
journal, September 2015
- Maculan, Giacomo; Sheikh, Arif D.; Abdelhady, Ahmed L.
- The Journal of Physical Chemistry Letters, Vol. 6, Issue 19
Dielectric confinement effect on excitons in -based layered semiconductors
journal, March 1992
- Hong, X.; Ishihara, T.; Nurmikko, A. V.
- Physical Review B, Vol. 45, Issue 12
Electrical Properties of Evaporated Molybdenum Oxide Films
journal, February 1970
- Nadkarni, G. S.; Simmons, J. G.
- Journal of Applied Physics, Vol. 41, Issue 2
Morphological Evolution of Multilayer Ni/NiO Thin Film Electrodes during Lithiation
journal, July 2016
- Evmenenko, Guennadi; Fister, Timothy T.; Buchholz, D. Bruce
- ACS Applied Materials & Interfaces, Vol. 8, Issue 31
Large Excitonic Reflectivity of Monolayer Encapsulated in Hexagonal Boron Nitride
journal, January 2018
- Scuri, Giovanni; Zhou, You; High, Alexander A.
- Physical Review Letters, Vol. 120, Issue 3
Excitons in ultrathin organic-inorganic perovskite crystals
journal, July 2015
- Yaffe, Omer; Chernikov, Alexey; Norman, Zachariah M.
- Physical Review B, Vol. 92, Issue 4
Colloidal nanoplatelets with two-dimensional electronic structure
journal, October 2011
- Ithurria, S.; Tessier, M. D.; Mahler, B.
- Nature Materials, Vol. 10, Issue 12
Reflectance study of the oscillator strength of excitons in semiconductor quantum wells
journal, September 1994
- Zhang, Baoping; Kano, Satoru S.; Shiraki, Yasuhiro
- Physical Review B, Vol. 50, Issue 11
Photon recycling in lead iodide perovskite solar cells
journal, March 2016
- Pazos-Outon, L. M.; Szumilo, M.; Lamboll, R.
- Science, Vol. 351, Issue 6280
Image charge effect on two-dimensional excitons in an inorganic-organic quantum-well crystal
journal, January 2005
- Tanaka, Kenichiro; Takahashi, Takayuki; Kondo, Takashi
- Physical Review B, Vol. 71, Issue 4
Low-Dimensional-Networked Metal Halide Perovskites: The Next Big Thing
journal, March 2017
- Saidaminov, Makhsud I.; Mohammed, Omar F.; Bakr, Osman M.
- ACS Energy Letters, Vol. 2, Issue 4
Electron–phonon coupling in hybrid lead halide perovskites
journal, May 2016
- Wright, Adam D.; Verdi, Carla; Milot, Rebecca L.
- Nature Communications, Vol. 7, Issue 1
Graphene on hexagonal boron nitride as a tunable hyperbolic metamaterial
journal, June 2015
- Dai, S.; Ma, Q.; Liu, M. K.
- Nature Nanotechnology, Vol. 10, Issue 8
Optical properties due to electronic transitions in two-dimensional semiconductors (
journal, December 1990
- Ishihara, Teruya; Takahashi, Jun; Goto, Takenari
- Physical Review B, Vol. 42, Issue 17
Role of Organic Counterion in Lead- and Tin-Based Two-Dimensional Semiconducting Iodide Perovskites and Application in Planar Solar Cells
journal, October 2016
- Mao, Lingling; Tsai, Hsinhan; Nie, Wanyi
- Chemistry of Materials, Vol. 28, Issue 21
Fundamentals of Semiconductors
book, January 2010
- Yu, Peter Y.; Cardona, Manuel
- Graduate Texts in Physics
Polaritons in van der Waals materials
journal, October 2016
- Basov, D. N.; Fogler, M. M.; Garcia de Abajo, F. J.
- Science, Vol. 354, Issue 6309
Measurement of the optical dielectric function of monolayer transition-metal dichalcogenides: , , , and
journal, November 2014
- Li, Yilei; Chernikov, Alexey; Zhang, Xian
- Physical Review B, Vol. 90, Issue 20
Decreasing the electronic confinement in layered perovskites through intercalation
journal, January 2017
- Smith, Matthew D.; Pedesseau, Laurent; Kepenekian, Mikaël
- Chemical Science, Vol. 8, Issue 3
Monolayer behaviour in bulk ReS2 due to electronic and vibrational decoupling
journal, February 2014
- Tongay, Sefaattin; Sahin, Hasan; Ko, Changhyun
- Nature Communications, Vol. 5, Issue 1
Manipulating polarization of light with ultrathin epsilon-near-zero metamaterials
journal, January 2013
- Ginzburg, P.; Fortuño, F. J. Rodríguez; Wurtz, G. A.
- Optics Express, Vol. 21, Issue 12
Topological Transitions in Metamaterials
conference, January 2012
- Krishnamoorthy, Harish N.; Jacob, Zubin; Narimanov, Evgenii
- Quantum Electronics and Laser Science Conference, Conference on Lasers and Electro-Optics 2012
Formation of Long-Lived Color Centers for Broadband Visible Light Emission in Low-Dimensional Layered Perovskites.
text, January 2017
- Booker, Edward; Thomas, Tudor; Quarti, Claudio
- Apollo - University of Cambridge Repository
Fundamentals of Semiconductors: Physics and Materials Properties
book, January 2005
- Yu, Peter Y.; Cardona, Manuel
- Graduate Texts in Physics
Hyperbolic metamaterials: fundamentals and applications
text, January 2014
- Shekhar, Prashant; Atkinson, Jonathan; Jacob, Zubin
- arXiv
Sub-diffractional, volume-confined polaritons in a natural hyperbolic material: hexagonal boron nitride
text, January 2014
- Caldwell, Joshua D.; Kretinin, Andrey; Chen, Yiguo
- arXiv
Epsilon-Near-Zero (ENZ) Metamaterials and Electromagnetic Sources: Tailoring the Radiation Phase Pattern
text, January 2006
- Alu, Andrea; Silveirinha, Mario; Salandrino, Alessandro
- arXiv
Works referencing / citing this record:
Layered‐Perovskite Nanowires with Long‐Range Orientational Order for Ultrasensitive Photodetectors
journal, January 2020
- Zhao, Yingjie; Qiu, Yuchen; Gao, Hanfei
- Advanced Materials, Vol. 32, Issue 9
Giant Nonlinear Optical Response in 2D Perovskite Heterostructures
journal, May 2019
- Wang, Jun; Mi, Yang; Gao, Xian
- Advanced Optical Materials, Vol. 7, Issue 15
Refractive Index Dispersion of Organic-Inorganic Hybrid Halide Perovskite CH 3 NH 3 PbX 3 (X═Cl, Br, I) Single Crystals
journal, March 2019
- He, Chongjun; Zha, Guoan; Deng, Chenguang
- Crystal Research and Technology, Vol. 54, Issue 5
In‐Plane Isotropic/Anisotropic 2D van der Waals Heterostructures for Future Devices
journal, February 2019
- Neupane, Guru Prakash; Zhou, Kai; Chen, Songsong
- Small, Vol. 15, Issue 11
Layer-edge device of two-dimensional hybrid perovskites
journal, December 2018
- Cheng, Bin; Li, Ting-You; Wei, Pai-Chun
- Nature Communications, Vol. 9, Issue 1
Figures / Tables found in this record: