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Title: 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:
 [1];  [2];  [2];  [2];  [3];  [2];  [1];  [1];  [1];  [1];  [3];  [2];  [2];  [4];  [2];  [2];  [5]
+ Show Author Affiliations
  1. Argonne National Lab. (ANL), Lemont, IL (United States)
  2. Northwestern Univ., Evanston, IL (United States)
  3. Northern Illinois Univ., DeKalb, IL (United States)
  4. Northwestern Univ., Evanston, IL (United States); Flexterra Corp., Skokie, IL (United States)
  5. 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.
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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
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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.
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@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}
}
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https://doi.org/10.1103/PhysRevLett.121.127401
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Figures / Tables:

FIG. 1 FIG. 1: (a) Schematic of the crystal structures of $N$ = 1 (left, 3D view) and $N$ = 2 (right, 2D view). (b) Optical micrographs of an $N$ = 3 single crystal flake before and after coating with MoOx, viewed along $\vec{c}$. The reflectivity spectrum was acquired from the regionmore » indicated by the black square. The white scale bar is 40 μm. (c) Calculated dependence of reflectivity ($R$; color-coded) on the values of n and k of an infinitely-thick, optically absorbing medium. (d) Calculated change of reflectivity ($ΔR$; color-coded) as a function of n and k of an optically absorbing medium, due to an 11-nm thick coating of MoOx. Both (c) and (d) are calculated for normal incidence, with a representative contour of $R$ = 0.2 plotted.« less
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    Works referencing / citing this record:

    Layered‐Perovskite Nanowires with Long‐Range Orientational Order for Ultrasensitive Photodetectors
    journal, January 2020

    Giant Nonlinear Optical Response in 2D Perovskite Heterostructures
    journal, May 2019

    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
    • DOI: 10.1002/crat.201900011

    In‐Plane Isotropic/Anisotropic 2D van der Waals Heterostructures for Future Devices
    journal, February 2019

    Layer-edge device of two-dimensional hybrid perovskites
    journal, December 2018

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