Polarization-resolved Raman Spectroscopy Research Articles

High- Tc superconductivity in CaKFe4As4 in absence of nematic fluctuations

We employ polarization-resolved Raman spectroscopy to study multi-band stoichiometric superconductor CaKFe$_4$As$_4$. The B$_{2g}$ symmetry Raman response shows no signatures of Pomeranchuk-like electronic nematic fluctuations which is observed for many other Fe-based superconductors. In the superconducting state, we identify three pair-breaking peaks at 13.8, 16.9 and 21 meV and full spectral weight suppression at low energies. The pair-breaking peak energies in Raman response are about 20% lower than twice the gap energies as measured by single-particle spectroscopy, implying a sub-dominant $d$-wave symmetry interaction. We analyze the superconductivity induced phonon self-energy effects and give an estimation of weak electron-phonon coupling constant $\lambda^\Gamma$=0.0015.

Structural phase transition in monolayer MoTe2 driven by electrostatic doping.

Monolayers of transition-metal dichalcogenides (TMDs) exhibit numerous crystal phases with distinct structures, symmetries and physical properties. Exploring the physics of transitions between these different structural phases in two dimensions may provide a means of switching material properties, with implications for potential applications. Structural phase transitions in TMDs have so far been induced by thermal or chemical means; purely electrostatic control over crystal phases through electrostatic doping was recently proposed as a theoretical possibility, but has not yet been realized. Here we report the experimental demonstration of an electrostatic-doping-driven phase transition between the hexagonal and monoclinic phases of monolayer molybdenum ditelluride (MoTe2). We find that the phase transition shows a hysteretic loop in Raman spectra, and can be reversed by increasing or decreasing the gate voltage. We also combine second-harmonic generation spectroscopy with polarization-resolved Raman spectroscopy to show that the induced monoclinic phase preserves the crystal orientation of the original hexagonal phase. Moreover, this structural phase transition occurs simultaneously across the whole sample. This electrostatic-doping control of structural phase transition opens up new possibilities for developing phase-change devices based on atomically thin membranes.

The structural phases and vibrational properties of Mo1−xWxTe2 alloys

The structural polymorphism in transition metal dichalcogenides (TMDs) provides exciting opportunities for developing advanced electronics. For example, MoTe2 crystallizes in the 2H semiconducting phase at ambient temperature and pressure, but transitions into the 1T′ semimetallic phase at high temperatures. Alloying MoTe2 with WTe2 reduces the energy barrier between these two phases, while also allowing access to the Td Weyl semimetal phase. The WxTe2 alloy system is therefore promising for developing phase change memory technology. However, achieving this goal necessitates a detailed understanding of the phase composition in the MoTe2-WTe2 system. We combine polarization-resolved Raman spectroscopy with x-ray diffraction (XRD) and scanning transmission electron microscopy (STEM) to study bulk WxTe2 alloys over the full compositional range x from 0 to 1. We identify Raman and XRD signatures characteristic of the 2H, 1T′, and Td structural phases that agree with density-functional theory (DFT) calculations, and use them to identify phase fields in the MoTe2–WTe2 system, including single-phase 2H, 1T′, and Td regions, as well as a two-phase 1T′ + Td region. Disorder arising from compositional fluctuations in WxTe2 alloys breaks inversion and translational symmetry, leading to the activation of an infrared 1T′-MoTe2 mode and the enhancement of a double-resonance Raman process in WxTe2 alloys. Compositional fluctuations limit the phonon correlation length, which we estimate by fitting the observed asymmetric Raman lineshapes with a phonon confinement model. These observations reveal the important role of disorder in WxTe2 alloys, clarify the structural phase boundaries, and provide a foundation for future explorations of phase transitions and electronic phenomena in this system.

Simultaneous Acquisition of the Polarized and Depolarized Raman Signal with a Single Detector.

Polarization-resolved Raman spectroscopy provides much more information than its conventional counterpart. However, it usually either requires a complicated setup with two spectrographs and detectors or two measurements must be performed sequentially. This study presents a simple and straightforward approach to recording both polarization components simultaneously with a single spectrograph and detector. The vertically and a horizontally polarized laser beam exiting a Wollaston prism are focused into the sample with a small spatial separation. The scattered light from both beams is imaged onto the slit of an imaging spectrograph as two spatially separated signals, i.e., the polarized and the depolarized Raman signal. Eventually, both spectra are acquired on a single CCD chip simultaneously. Experimental data of ethanol and dimethyl sulfoxide are shown as proof-of-concept. The new method has a number of advantages, for example, laser intensity fluctuations and the polarization dependence of the diffraction grating do not play a role. The proposed approach will be useful for an improved structural analysis and it will be the enabling technology for temporally resolved enantioselective Raman (esR) spectroscopy.

Analogy Between the "Hidden Order" and the Orbital Antiferromagnetism in URu_{2-x}Fe_{x}Si_{2}.

We study URu_{2-x}Fe_{x}Si_{2}, in which two types of staggered phases compete at low temperature as the iron concentration x is varied: the nonmagnetic "hidden order" (HO) phase below the critical concentration x_{c}, and unconventional antiferromagnetic (AFM) phase above x_{c}. By using polarization resolved Raman spectroscopy, we detect a collective mode of pseudovectorlike A_{2g} symmetry whose energy continuously evolves with increasing x; it monotonically decreases in the HO phase until it vanishes at x=x_{c}, and then reappears with increasing energy in the AFM phase. The mode's evolution provides direct evidence for a unified order parameter for both nonmagnetic and magnetic phases arising from the orbital degrees-of-freedom of the uranium-5f electrons.

Raman spectroscopic signature of fractionalized excitations in the harmonic-honeycomb iridates β- and γ-Li2IrO3.

The fractionalization of elementary excitations in quantum spin systems is a central theme in current condensed matter physics. The Kitaev honeycomb spin model provides a prominent example of exotic fractionalized quasiparticles, composed of itinerant Majorana fermions and gapped gauge fluxes. However, identification of the Majorana fermions in a three-dimensional honeycomb lattice remains elusive. Here we report spectroscopic signatures of fractional excitations in the harmonic-honeycomb iridates β- and γ-Li2IrO3. Using polarization-resolved Raman spectroscopy, we find that the dynamical Raman response of β- and γ-Li2IrO3 features a broad scattering continuum with distinct polarization and composition dependence. The temperature dependence of the Raman spectral weight is dominated by the thermal damping of fermionic excitations. These results suggest the emergence of Majorana fermions from spin fractionalization in a three-dimensional Kitaev–Heisenberg system.

Critical quadrupole fluctuations and collective modes in iron pnictide superconductors

The multiband nature of iron pnictides gives rise to a rich temperature-doping phase diagram of competing orders and a plethora of collective phenomena. At low dopings, the tetragonal-to-orthorhombic structural transition is closely followed by a spin density wave transition both being in close proximity to the superconducting phase. A key question is the nature of high-$T_c$ superconductivity and its relation to orbital ordering and magnetism. Here we study the NaFe$_{1-x}$Co$_{x}$As superconductor using polarization-resolved Raman spectroscopy. The Raman susceptibility displays critical enhancement of non-symmetric charge fluctuations across the entire phase diagram which are precursors to a $d$-wave Pomeranchuk instability at temperature $\theta(\mbox{x})$. The charge fluctuations are interpreted in terms of quadrupole inter-orbital excitations in which the electron and hole Fermi surfaces breathe in-phase. Below $T_c$, the critical fluctuations acquire coherence and undergo a metamorphosis into a coherent ingap mode of extraordinary strength.

Assessment of crystal quality and unit cell orientation in epitaxial Cu₂ZnSnSe₄ layers using polarized Raman scattering.

We use polarization-resolved Raman spectroscopy to assess the crystal quality of epitaxial kesterite layers. It is demonstrated for the example of epitaxial Cu₂ZnSnSe₄ layers on GaAs(001) that "standing" and "lying" kesterite unit cell orientations (c'-axis parallel / perpendicular to the growth direction) can be distinguished by the application of Raman tensor analysis. From the appearance of characteristic intensity oscillations when the sample is rotated one can distinguish polycrystalline and epitaxial layers. The method can be transferred to kesterite layers oriented in any crystal direction and can shed light on the growth of such layers in general.

Measurement of Filling-Factor-Dependent Magnetophonon Resonances in Graphene Using Raman Spectroscopy

We perform polarization-resolved Raman spectroscopy on graphene in magnetic fields up to 45 T. This reveals a filling-factor-dependent, multicomponent anticrossing structure of the Raman G peak, resulting from magnetophonon resonances between magnetoexcitons and E(2g) phonons. This is explained with a model of Raman scattering taking into account the effects of spatially inhomogeneous carrier densities and strain. Random fluctuations of strain-induced pseudomagnetic fields lead to increased scattering intensity inside the anticrossing gap, consistent with the experiments.

Polarized ultraviolet Raman spectroscopy of β-Si3N4

We have studied single crystals of β-Si3N4 with polarization-resolved Raman spectroscopy in order to unambiguously obtain the symmetry character of zone center optical phonon modes. By applying ultraviolet excitation radiation, approaching resonance condition, we have overcome the usual difficulties with overwhelming fluorescence obscuring Raman spectra of β-Si3N4 in the visible. Superior extinction ratios have been achieved and the application of group theory allows us to assign ten out of eleven Raman-active modes in excellent correlation with recent theoretical results. The probable nature of the eleventh mode is discussed.