Systematic Absences in Momentum-Resolved Vibrational Spectroscopy

Phonon dispersion is widely used to elucidate the vibrational properties of materials. As an emerging technique, momentum-resolved vibrational spectroscopy in scanning transmission electron microscopy (STEM) offers an unparalleled approach to explore q-dependent phonon behavior at local structures. In this study, we systematically investigate the phonon dispersion of monolayer graphene across several Brillouin zones (BZs) using momentum-resolved vibrational spectroscopy and find that the optical phonon signals vanish at the {\Gamma} points with indices (hk0) satisfying h+2k=3n (n denoted integers). Theoretical analysis reveals that this is due to the complete destructive interference of the scattered waves from different basis atoms. Importantly, we show that the systematic absences should be a general characteristic of materials composed of symmetrically equivalent pairs of the same elements, which have not been appreciated in vibrational spectroscopy before, offering new insights into the experimental assessment of local vibrational properties of materials.

[1]  Shangpeng Gao,et al.  Probing a Defect-Site-Specific Electronic Orbital in Graphene with Single-Atom Sensitivity. , 2023, Physical review letters.

[2]  Jilin Tang,et al.  Direct Observation of Topological Phonons in Graphene. , 2023, Physical review letters.

[3]  J. Barthel,et al.  Lessons from the harmonic oscillator -- a reconciliation of the Frequency-Resolved Frozen Phonon Multislice Method with other theoretical approaches , 2023, 2304.13510.

[4]  S. Pennycook,et al.  Single-atom vibrational spectroscopy with chemical-bonding sensitivity , 2023, Nature Materials.

[5]  C. Elsässer,et al.  Atomic-Resolution Mapping of Localized Phonon Modes at Grain Boundaries. , 2023, Nano letters.

[6]  Xin-Zheng Li,et al.  Phonon transition across an isotopic interface , 2022, Nature communications.

[7]  S. Pantelides,et al.  Direct Visualization of Localized Vibrations at Complex Grain Boundaries , 2022, Advanced materials.

[8]  Xingxu Yan,et al.  Surface vs. Bulk Phonons in Off-axis EELS , 2022, Microscopy and Microanalysis.

[9]  Yung‐Chang Lin,et al.  Imaging of isotope diffusion using atomic-scale vibrational spectroscopy , 2022, Nature.

[10]  T. Beechem,et al.  Emergent interface vibrational structure of oxide superlattices , 2022, Nature.

[11]  T. Taniguchi,et al.  Nanometric phonon spectroscopy for diamond and cubic boron nitride , 2021, Physical Review B.

[12]  Steven J. Plimpton,et al.  LAMMPS - A flexible simulation tool for particle-based materials modeling at the atomic, meso, and continuum scales , 2021, Computer Physics Communications.

[13]  Lai Wang,et al.  Atomic-scale probing of heterointerface phonon bridges in nitride semiconductor , 2021, Proceedings of the National Academy of Sciences.

[14]  Yuanwei Sun,et al.  Measuring phonon dispersion at an interface , 2021, Nature.

[15]  Xiaoqing Pan,et al.  Experimental observation of localized interfacial phonon modes , 2021, Nature Communications.

[16]  Xingxu Yan,et al.  Nanoscale imaging of phonon dynamics by electron microscopy , 2021, Nature.

[17]  J. Rusz,et al.  Simulations of spatially and angle-resolved vibrational electron energy loss spectroscopy for a system with a planar defect , 2021, Physical Review B.

[18]  J. Miao,et al.  Capturing 3D atomic defects and phonon localization at the 2D heterostructure interface , 2021, Science advances.

[19]  J. Rusz,et al.  Frequency-resolved frozen phonon multislice method and its application to vibrational electron energy loss spectroscopy using parallel illumination , 2021, Physical Review B.

[20]  Xiaoqing Pan,et al.  Single-defect phonons imaged by electron microscopy , 2021, Nature.

[21]  P. Rez,et al.  Lattice resolution of vibrational modes in the electron microscope. , 2020, Ultramicroscopy.

[22]  Zhi Xu,et al.  Four-dimensional vibrational spectroscopy for nanoscale mapping of phonon dispersion in BN nanotubes , 2020, Nature Communications.

[23]  C. Hoermann,et al.  Hybrid pixel direct detector for electron energy loss spectroscopy. , 2020, Ultramicroscopy.

[24]  Volker L. Deringer,et al.  An accurate and transferable machine learning potential for carbon. , 2020, The Journal of chemical physics.

[25]  Q. Ramasse,et al.  Single-atom vibrational spectroscopy in the scanning transmission electron microscope , 2020, Science.

[26]  J. Rusz,et al.  Efficient and Versatile Model for Vibrational STEM-EELS. , 2019, Physical review letters.

[27]  J. Hachtel,et al.  Nion Swift: Open Source Image Processing Software for Instrument Control, Data Acquisition, Organization, Visualization, and Analysis Using Python. , 2019, Microscopy and Microanalysis.

[28]  A. Bleloch,et al.  Advances in STEM and EELS: New Operation Modes, Detectors and Software , 2019, Microscopy and Microanalysis.

[29]  V. A. Apkarian,et al.  Visualizing vibrational normal modes of a single molecule with atomically confined light , 2019, Nature.

[30]  F. Mauri,et al.  Position and momentum mapping of vibrations in graphene nanostructures , 2018, Nature.

[31]  Q. Ramasse,et al.  Nanoscale momentum-resolved vibrational spectroscopy , 2018, Science Advances.

[32]  Q. Ramasse,et al.  Theory of momentum-resolved phonon spectroscopy in the electron microscope , 2018, Physical Review B.

[33]  C. Dwyer.  Prospects of spatial resolution in vibrational electron energy loss spectroscopy: Implications of dipolar scattering , 2017 .

[34]  Alexandre Dazzi,et al.  AFM-IR: Technology and Applications in Nanoscale Infrared Spectroscopy and Chemical Imaging. , 2017, Chemical reviews.

[35]  L. Allen,et al.  Modeling energy-loss spectra due to phonon excitation , 2016 .

[36]  D. Seo,et al.  Robust graphene wet transfer process through low molecular weight polymethylmethacrylate , 2016 .

[37]  L. Allen,et al.  Atomic resolution imaging using electron energy-loss phonon spectroscopy , 2015 .

[38]  P. Batson,et al.  Vibrational spectroscopy in the electron microscope , 2014, Nature.

[39]  Andrew V. Martin,et al.  Quantum mechanical model for phonon excitation in electron diffraction and imaging using a Born-Oppenheimer approximation , 2010 .

[40]  Andrew V. Martin,et al.  Model of phonon excitation by fast electrons in a crystal with correlated atomic motion , 2009 .

[41]  S. Banerjee,et al.  Large-Area Synthesis of High-Quality and Uniform Graphene Films on Copper Foils , 2009, Science.

[42]  S. Chaplot,et al.  Inelastic neutron scattering and lattice dynamics of minerals , 2008 .

[43]  E. Burkel.  Phonon spectroscopy by inelastic x-ray scattering , 2000 .

[44]  R. Egerton,et al.  Electron Energy-Loss Spectroscopy in the Electron Microscope , 1995, Springer US.

[45]  Josefsson,et al.  Inelastic scattering of fast electrons by crystals. , 1995, Physical review. B, Condensed matter.

[46]  J. Tersoff,et al.  Modeling solid-state chemistry: Interatomic potentials for multicomponent systems. , 1989, Physical review. B, Condensed matter.

[47]  M. Chisholm,et al.  Atomic-Resolution STEM at Low Primary Energies , 2011 .

[48]  H. Jobic.  Vibrational Spectroscopy with Neutrons , 1997 .