Direct Observation of Symmetry-Dependent Electron-Phonon Coupling in Black Phosphorus

Nannan Mao, Xingzhi Wang, Yuxuan Lin, Bobby G. Sumpter, Qingqing Ji, Tomás Palacios, Shengxi Huang, Vincent Meunier, Mildred S. Dresselhaus, William A. Tisdale, Liangbo Liang, Xi Ling, Jing Kong

Research output: Contribution to journalArticle

Abstract

Electron-phonon coupling in two-dimensional nanomaterials plays a fundamental role in determining their physical properties. Such interplay is particularly intriguing in semiconducting black phosphorus (BP) due to the highly anisotropic nature of its electronic structure and phonon dispersions. Here we report the direct observation of symmetry-dependent electron-phonon coupling in BP by performing the polarization-selective resonance Raman measurement in the visible and ultraviolet regimes, focusing on the out-of-plane Ag 1 and in-plane Ag 2 phonon modes. Their intrinsic resonance Raman excitation profiles (REPs) were extracted and quantitatively compared. The in-plane Ag 2 mode exhibits remarkably strong resonance enhancement across the excitation wavelengths when the excitation polarization is parallel to the armchair (Ag 2//AC) direction. In contrast, a dramatically weak resonance effect was observed for the same mode with the polarization parallel to zigzag (Ag 2//ZZ) direction and for the out-of-plane Ag 1 mode (Ag 1//AC and Ag 1//ZZ). Analysis on quantum perturbation theory and first-principles calculations on the anisotropic electron distributions in BP demonstrated that electron-phonon coupling considering the symmetry of the involved excited states and phonon vibration patterns is responsible for this phenomenon. Further analysis of the polarization-dependent REPs for Ag phonons allows us to resolve the existing controversies on the physical origin of Raman anomaly in BP and its dependence on excitation energy, sample thickness, phonon modes, and crystalline orientation. Our study gives deep insights into the underlying interplay between electrons and phonons in BP and paves the way for manipulating the electron-phonon coupling in anisotropic nanomaterials for future device applications.

Original languageEnglish (US)
Pages (from-to)18994-19001
Number of pages8
JournalJournal of the American Chemical Society
Volume141
Issue number48
DOIs
StatePublished - Dec 4 2019

Fingerprint

Phonons
Phosphorus
Observation
Electrons
Polarization
Nanostructured materials
Nanostructures
Excitation energy
Crystal symmetry
Dispersions
Excited states
Crystal orientation
Quantum Theory
Electronic structure
Physical properties
Crystalline materials
Wavelength
Vibration

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Mao, N., Wang, X., Lin, Y., Sumpter, B. G., Ji, Q., Palacios, T., ... Kong, J. (2019). Direct Observation of Symmetry-Dependent Electron-Phonon Coupling in Black Phosphorus. Journal of the American Chemical Society, 141(48), 18994-19001. https://doi.org/10.1021/jacs.9b07974
Mao, Nannan ; Wang, Xingzhi ; Lin, Yuxuan ; Sumpter, Bobby G. ; Ji, Qingqing ; Palacios, Tomás ; Huang, Shengxi ; Meunier, Vincent ; Dresselhaus, Mildred S. ; Tisdale, William A. ; Liang, Liangbo ; Ling, Xi ; Kong, Jing. / Direct Observation of Symmetry-Dependent Electron-Phonon Coupling in Black Phosphorus. In: Journal of the American Chemical Society. 2019 ; Vol. 141, No. 48. pp. 18994-19001.
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Mao, N, Wang, X, Lin, Y, Sumpter, BG, Ji, Q, Palacios, T, Huang, S, Meunier, V, Dresselhaus, MS, Tisdale, WA, Liang, L, Ling, X & Kong, J 2019, 'Direct Observation of Symmetry-Dependent Electron-Phonon Coupling in Black Phosphorus', Journal of the American Chemical Society, vol. 141, no. 48, pp. 18994-19001. https://doi.org/10.1021/jacs.9b07974

Direct Observation of Symmetry-Dependent Electron-Phonon Coupling in Black Phosphorus. / Mao, Nannan; Wang, Xingzhi; Lin, Yuxuan; Sumpter, Bobby G.; Ji, Qingqing; Palacios, Tomás; Huang, Shengxi; Meunier, Vincent; Dresselhaus, Mildred S.; Tisdale, William A.; Liang, Liangbo; Ling, Xi; Kong, Jing.

In: Journal of the American Chemical Society, Vol. 141, No. 48, 04.12.2019, p. 18994-19001.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Direct Observation of Symmetry-Dependent Electron-Phonon Coupling in Black Phosphorus

AU - Mao, Nannan

AU - Wang, Xingzhi

AU - Lin, Yuxuan

AU - Sumpter, Bobby G.

AU - Ji, Qingqing

AU - Palacios, Tomás

AU - Huang, Shengxi

AU - Meunier, Vincent

AU - Dresselhaus, Mildred S.

AU - Tisdale, William A.

AU - Liang, Liangbo

AU - Ling, Xi

AU - Kong, Jing

PY - 2019/12/4

Y1 - 2019/12/4

N2 - Electron-phonon coupling in two-dimensional nanomaterials plays a fundamental role in determining their physical properties. Such interplay is particularly intriguing in semiconducting black phosphorus (BP) due to the highly anisotropic nature of its electronic structure and phonon dispersions. Here we report the direct observation of symmetry-dependent electron-phonon coupling in BP by performing the polarization-selective resonance Raman measurement in the visible and ultraviolet regimes, focusing on the out-of-plane Ag 1 and in-plane Ag 2 phonon modes. Their intrinsic resonance Raman excitation profiles (REPs) were extracted and quantitatively compared. The in-plane Ag 2 mode exhibits remarkably strong resonance enhancement across the excitation wavelengths when the excitation polarization is parallel to the armchair (Ag 2//AC) direction. In contrast, a dramatically weak resonance effect was observed for the same mode with the polarization parallel to zigzag (Ag 2//ZZ) direction and for the out-of-plane Ag 1 mode (Ag 1//AC and Ag 1//ZZ). Analysis on quantum perturbation theory and first-principles calculations on the anisotropic electron distributions in BP demonstrated that electron-phonon coupling considering the symmetry of the involved excited states and phonon vibration patterns is responsible for this phenomenon. Further analysis of the polarization-dependent REPs for Ag phonons allows us to resolve the existing controversies on the physical origin of Raman anomaly in BP and its dependence on excitation energy, sample thickness, phonon modes, and crystalline orientation. Our study gives deep insights into the underlying interplay between electrons and phonons in BP and paves the way for manipulating the electron-phonon coupling in anisotropic nanomaterials for future device applications.

AB - Electron-phonon coupling in two-dimensional nanomaterials plays a fundamental role in determining their physical properties. Such interplay is particularly intriguing in semiconducting black phosphorus (BP) due to the highly anisotropic nature of its electronic structure and phonon dispersions. Here we report the direct observation of symmetry-dependent electron-phonon coupling in BP by performing the polarization-selective resonance Raman measurement in the visible and ultraviolet regimes, focusing on the out-of-plane Ag 1 and in-plane Ag 2 phonon modes. Their intrinsic resonance Raman excitation profiles (REPs) were extracted and quantitatively compared. The in-plane Ag 2 mode exhibits remarkably strong resonance enhancement across the excitation wavelengths when the excitation polarization is parallel to the armchair (Ag 2//AC) direction. In contrast, a dramatically weak resonance effect was observed for the same mode with the polarization parallel to zigzag (Ag 2//ZZ) direction and for the out-of-plane Ag 1 mode (Ag 1//AC and Ag 1//ZZ). Analysis on quantum perturbation theory and first-principles calculations on the anisotropic electron distributions in BP demonstrated that electron-phonon coupling considering the symmetry of the involved excited states and phonon vibration patterns is responsible for this phenomenon. Further analysis of the polarization-dependent REPs for Ag phonons allows us to resolve the existing controversies on the physical origin of Raman anomaly in BP and its dependence on excitation energy, sample thickness, phonon modes, and crystalline orientation. Our study gives deep insights into the underlying interplay between electrons and phonons in BP and paves the way for manipulating the electron-phonon coupling in anisotropic nanomaterials for future device applications.

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