Giant Electron-Phonon Coupling Induced Band-Gap Renormalization in Anharmonic Silver Chalcohalide Antiperovskites

Fuente: arXiv
Saved in:
Bibliographic Details
Main Authors: Benítez, Pol, Chen, Siyu, Jiang, Ruoshi, López, Cibrán, Tamarit, Josep-Lluís, Íñiguez-González, Jorge, Saucedo, Edgardo, Monserrat, Bartomeu, Cazorla, Claudio
Format: Preprint
Published: 2024
Subjects:
Online Access:
Tags: Add Tag
No Tags, Be the first to tag this record!
_version_ 1866913585207181312
author Benítez, Pol
Chen, Siyu
Jiang, Ruoshi
López, Cibrán
Tamarit, Josep-Lluís
Íñiguez-González, Jorge
Saucedo, Edgardo
Monserrat, Bartomeu
Cazorla, Claudio
author_facet Benítez, Pol
Chen, Siyu
Jiang, Ruoshi
López, Cibrán
Tamarit, Josep-Lluís
Íñiguez-González, Jorge
Saucedo, Edgardo
Monserrat, Bartomeu
Cazorla, Claudio
contents Silver chalcohalide antiperovskites (CAP), Ag$_{3}$XY (X = S, Se; Y = Br, I), are a family of highly anharmonic inorganic compounds with great potential for energy applications. However, a substantial and unresolved discrepancy exists between the optoelectronic properties predicted by theoretical first-principles methods and those measured experimentally at room temperature, hindering the fundamental understanding and rational engineering of CAP. In this work, we employ density functional theory, tight-binding calculations, and anharmonic Fröhlich theory to investigate the optoelectronic properties of CAP at finite temperatures. Near room temperature, we observe a giant band-gap ($E_{g}$) reduction of approximately $20$-$60$\% relative to the value calculated at $T = 0$ K, bringing the estimated $E_{g}$ into excellent agreement with experimental measurements. This relative $T$-induced band-gap renormalization is roughly twice the largest value previously reported in the literature for similar temperature ranges. Low-energy optical polar phonon modes, which break inversion symmetry and promote the overlap between silver and chalcogen $s$ electronic orbitals in the conduction band, are identified as the primary contributors to this giant $E_{g}$ reduction. Furthermore, when considering temperature effects, the optical absorption coefficient of CAP increases by nearly an order of magnitude for visible light frequencies. These insights not only bridge a crucial gap between theory and experiment but also open pathways for future technologies where temperature, electric fields, or light dynamically tailor optoelectronic behavior, positioning CAP as a versatile platform for next-generation energy applications.
format Preprint
id arxiv_https___arxiv_org_abs_2411_16279
institution arXiv
publishDate 2024
record_format arxiv
spellingShingle Giant Electron-Phonon Coupling Induced Band-Gap Renormalization in Anharmonic Silver Chalcohalide Antiperovskites
Benítez, Pol
Chen, Siyu
Jiang, Ruoshi
López, Cibrán
Tamarit, Josep-Lluís
Íñiguez-González, Jorge
Saucedo, Edgardo
Monserrat, Bartomeu
Cazorla, Claudio
Materials Science
Silver chalcohalide antiperovskites (CAP), Ag$_{3}$XY (X = S, Se; Y = Br, I), are a family of highly anharmonic inorganic compounds with great potential for energy applications. However, a substantial and unresolved discrepancy exists between the optoelectronic properties predicted by theoretical first-principles methods and those measured experimentally at room temperature, hindering the fundamental understanding and rational engineering of CAP. In this work, we employ density functional theory, tight-binding calculations, and anharmonic Fröhlich theory to investigate the optoelectronic properties of CAP at finite temperatures. Near room temperature, we observe a giant band-gap ($E_{g}$) reduction of approximately $20$-$60$\% relative to the value calculated at $T = 0$ K, bringing the estimated $E_{g}$ into excellent agreement with experimental measurements. This relative $T$-induced band-gap renormalization is roughly twice the largest value previously reported in the literature for similar temperature ranges. Low-energy optical polar phonon modes, which break inversion symmetry and promote the overlap between silver and chalcogen $s$ electronic orbitals in the conduction band, are identified as the primary contributors to this giant $E_{g}$ reduction. Furthermore, when considering temperature effects, the optical absorption coefficient of CAP increases by nearly an order of magnitude for visible light frequencies. These insights not only bridge a crucial gap between theory and experiment but also open pathways for future technologies where temperature, electric fields, or light dynamically tailor optoelectronic behavior, positioning CAP as a versatile platform for next-generation energy applications.
title Giant Electron-Phonon Coupling Induced Band-Gap Renormalization in Anharmonic Silver Chalcohalide Antiperovskites
topic Materials Science
url https://arxiv.org/abs/2411.16279