Polarization-resolved Raman Spectroscopy Research Articles

Raman signatures of spin-phonon coupling in a self-intercalated van der Waals magnet Mn3Si2Te6

We report the results of Raman spectroscopy on a self-intercalated van der Waals ferrimagnet Mn3Si2Te6. Using polarization-resolved Raman spectroscopy, we identify twelve phonon modes with Eg and A1g symmetries, in agreement with the first principle calculations. Below the ferrimagnetic transition temperature Tc∼ 78 K, we observed a significant deviation of the phonon frequency from the anharmonic model, accompanied by a strong line broadening, indicating a substantial spin-phonon coupling in Mn3Si2Te6. Among twelve phonon modes, this spin-phonon coupling is found to be strong mostly in the out-of-plane vibrational modes. These results highlight the dominant role of the interlayer superexchange interaction in determining the magnetic properties, reflecting the self-intercalated van der Waals structure of Mn3Si2Te6.

Strong electron-phonon coupling and enhanced phonon Grüneisen parameters in valence-fluctuating metal EuPd2Si2

We study the valence crossover and strong electron-phonon coupling of EuPd$_2$Si$_2$ by polarization-resolved Raman spectroscopy. The fully-symmetric phonon mode shows strongly asymmetric lineshape at low temperature, indicating Fano-type interaction between this mode and a continuum of electron-hole excitations. Moreover, the frequency and linewidth of the phonon modes exhibit anomalies across the valence-crossover temperature, suggesting the coupling between valence fluctuations and lattice vibration. In particular, two phonon modes show significantly enhanced Gr\"uneisen parameter, suggesting proximity to a critical elasticity regime. The relative contribution of the structural change and valence change to the phonon anomalies is evaluated by density functional theory calculations.

Phonon polarization deformation in graphene induced by substrate coupling strengths

Displacement in the Raman shift of conventional Raman spectroscopy usually includes an increase in the number of material layers or a strain variation. To distinguish them, polarization-resolved Raman spectroscopy provides an additional degree of freedom to resolve it. In this work, strained graphene induced by different substrates on G band and 2D band phonon modes is studied by polarization-resolved Raman spectroscopy and verified by numerical analysis using Raman tensors and optical Jones calculus. For the strained graphene case, polarization properties of scattered light are obviously different from that in the case of unstrained graphene. Deformation of phonon polarization is seen to originate from different strengths of substrate coupling. This research provides an efficient quantitative method to explore any distortion of strain anisotropy in two-dimensional materials, which is important for the development of straintronics in the future.

Anisotropy and thermal properties in GeTe semiconductor by Raman analysis.

Low-symmetric GeTe semiconductors have attracted wide-ranging attention due to their excellent optical and thermal properties, but only a few research studies are available on their in-plane optical anisotropic nature that is crucial for their applications in optoelectronic and thermoelectric devices. Here, we investigate the optical interactions of anisotropy in GeTe using polarization-resolved Raman spectroscopy and first-principles calculations. After determining both armchair and zigzag directions in GeTe crystals by transmission electron microscopy, we found that the Raman intensity of the two main vibrational modes had a strong in-plane anisotropic nature; the one at ∼88.1 cm-1 can be used to determine the crystal orientation, and the other at ∼124.6 cm-1 can reveal a series of temperature-dependent phase transitions. These results provide a general approach for the investigation of the anisotropy of light-matter interactions in low-symmetric layered materials, benefiting the design and application of optoelectronic, anisotropic thermoelectric, and phase-transition memory devices based on bulk GeTe.

Magnetic and spin-orbit exciton excitations in the honeycomb lattice compound RuBr3

$\mathrm{Ru}{X}_{3}$ trihalides ($\mathit{X}=\text{halogen atoms}$) offer a prominent platform for exploring the Kitaev spin liquid. Using polarization-resolved Raman spectroscopy, we report a comparative study of lattice, magnetic, and electronic excitations on $\mathit{X}=\text{Cl}$ and Br. Our phonon Raman spectra show that ${\mathrm{RuBr}}_{3}$ retains a three-layer honeycomb lattice without structural transition, unlike $\ensuremath{\alpha}\text{\ensuremath{-}}{\mathrm{RuCl}}_{3}$ that undergoes a monoclinic-to-rhombohedral structural transition at $\ensuremath{\sim}150\phantom{\rule{0.16em}{0ex}}\mathrm{K}$. In addition, both $\mathrm{Ru}{X}_{3}$ compounds commonly feature single and double spin-orbit excitons of almost identical energies, alluding to the realization of a ${j}_{\mathrm{eff}}=1/2$ state to the same degree. In contrast to $\ensuremath{\alpha}\text{\ensuremath{-}}{\mathrm{RuCl}}_{3}$ two-magnon scattering dominates over fractionalized excitations in ${\mathrm{RuBr}}_{3}$. Our results suggest that a Br-for-Cl substitution moves $\mathrm{Ru}{X}_{3}$ further away from a pure Kitaev phase despite enhanced $p\text{\ensuremath{-}}d$ hybridization.

Revealing the nanogeometry of WS2 nanoflowers by polarization-resolved Raman spectroscopy

Recent studies of transition metal dichalcogenides (TMDs) have revealed exciting optical properties, such as stable excitons and chiral light–matter interactions. Chemical vapor deposition techniques provide a platform for the fabrication of nanostructures with diverse geometries, ranging from horizontal flakes to flower-like structures. Raman spectroscopy is commonly used to characterize TMDs and their properties. Here, we use polarization-resolved Raman spectroscopy to probe the nanogeometry and orientation of WS2 nanoflower petals. Exciting the nanoflowers with linearly polarized light, we observe an enhanced Raman response from flower petals oriented along the excitation polarization direction. Furthermore, the helicity-resolved Raman response of vertically oriented wall-like flower petals exhibits clear differences with horizontally oriented flakes. Although the photoluminescence from the nanoflowers is strongly reduced, the Raman response upon excitation in resonance with the WS2 excitonic transition does reveal the presence of the exciton, which results in a distinct temperature dependence of the Raman response.

Layered SnSe nanoflakes with anharmonic phonon properties and memristive characteristics

Understanding the phonon anharmonicity and temperature-dependent behavior of phonons that affect the thermal transport properties in 2D materials is crucial for developing efficient thermoelectric and memristor devices. SnSe has attracted significant interest because of its potential applications for developing such novel devices. Here, orthorhombic SnSe nanoflakes with a thickness of less than 100 nm and oriented along the [100] crystal axis were obtained using physical vapor transport at atmospheric pressure. Polarization-resolved Raman spectroscopy of SnSe nanoflakes was performed at a temperature of 5 K. Temperature-dependent frequencies and linewidths of Raman modes in tin selenide were fitted according to the anharmonic phonon coupling theory. The results indicate that both two and three order processes are responsible for the phonon decay in tin selenide. The memristive property was confirmed by electrical measurements of SnSe devices. SnSe memristors have an operating current of 10−4 A, similar to other transition-metal dichalcogenide memristors, but are more energy efficient than memristors based on defect migration, with a threshold voltage of 3 V.

Emergent nematicity and intrinsic versus extrinsic electronic scattering processes in the kagome metal CsV3Sb5

Fermi surface fluctuations and lattice instabilities in the 2D metallic kagome superconductor CsV$_3$Sb$_5$ are elucidated via polarization-resolved Raman spectroscopy. The presence of a weak electronic continuum in high-quality samples marks the cross-over into the charge-density-wave (CDW) ordered phase, while impurity-rich samples promote strong defect-induced electronic scattering processes that affect the coherence of the CDW phase. CDW-induced phonon anomalies appear below $T_{\mathrm{CDW}}$, with emergent $C2$ symmetry for one of the CDW amplitude modes, alluding to nematicity. In conjunction with symmetry-breaking lattice distortions, a kink-like hardening of the A$_{1g}$ phonon energy at $T_{\mathrm{CDW}}$ signifies a concerted interplay of electronic correlations and electron-phonon coupling in the exotic CDW order.

Twist engineering of the two-dimensional magnetism in double bilayer chromium triiodide homostructures

Twist engineering, or the alignment of two-dimensional (2D) crystalline layers with desired orientations, has led to tremendous success in modulating the charge degree of freedom in hetero- and homo-structures, in particular, in achieving novel correlated and topological electronic phases in moir\'e electronic crystals. However, although pioneering theoretical efforts have predicted nontrivial magnetism and magnons out of twisting 2D magnets, experimental realization of twist engineering spin degree of freedom remains elusive. Here, we leverage the archetypal 2D Ising magnet chromium triiodide (CrI3) to fabricate twisted double bilayer homostructures with tunable twist angles and demonstrate the successful twist engineering of 2D magnetism in them. Using linear and circular polarization-resolved Raman spectroscopy, we identify magneto-Raman signatures of a new magnetic ground state that is sharply distinct from those in natural bilayer (2L) and four-layer (4L) CrI3. With careful magnetic field and twist angle dependence, we reveal that, for a very small twist angle (~ 0.5 degree), this emergent magnetism can be well-approximated by a weighted linear superposition of those of 2L and 4L CI3 whereas, for a relatively large twist angle (~ 5 degree), it mostly resembles that of isolated 2L CrI3. Remarkably, at an intermediate twist angle (~ 1.1 degree), its magnetism cannot be simply inferred from the 2L and 4L cases, because it lacks sharp spin-flip transitions that are present in 2L and 4L CrI3 and features a dramatic Raman circular dichroism that is absent in natural 2L and 4L ones. Our results demonstrate the possibility of designing and controlling the spin degree of freedom in 2D magnets using twist engineering.

Bosonic spinons in anisotropic triangular antiferromagnets

Anisotropic triangular antiferromagnets can host two primary spin excitations, namely, spinons and triplons. Here, we utilize polarization-resolved Raman spectroscopy to assess the statistics and dynamics of spinons in Ca3ReO5Cl2. We observe a magnetic Raman continuum consisting of one- and two-pair spinon-antispinon excitations as well as triplon excitations. The twofold rotational symmetry of the spinon and triplon excitations are distinct from magnons. The strong thermal evolution of spinon scattering is compatible with the bosonic spinon scenario. The quasilinear spinon hardening with decreasing temperature is envisaged as the ordering of one-dimensional topological defects. This discovery will enable a fundamental understanding of novel phenomena induced by lowering spatial dimensionality in quantum spin systems.

Heterostrain-enabled dynamically tunable moir\xe9 superlattice in twisted bilayer graphene

The ability to precisely control moiré patterns in two-dimensional materials has enabled the realization of unprecedented physical phenomena including Mott insulators, unconventional superconductivity, and quantum emission. Along with the twist angle, the application of independent strain in each layer of stacked two-dimensional materials—termed heterostrain—has become a powerful means to manipulate the moiré potential landscapes. Recent experimental studies have demonstrated the possibility of continuously tuning the twist angle and the resulting physical properties. However, the dynamic control of heterostrain that allows the on-demand manipulation of moiré superlattices has yet to be experimentally realized. Here, by harnessing the weak interlayer van der Waals bonding in twisted bilayer graphene devices, we demonstrate the realization of dynamically tunable heterostrain of up to 1.3%. Polarization-resolved Raman spectroscopy confirmed the existence of substantial heterostrain by presenting triple G peaks arising from the independently strained graphene layers. Theoretical calculations revealed that the distorted moiré patterns via heterostrain can significantly alter the electronic structure of twisted bilayer graphene, allowing the emergence of multiple absorption peaks ranging from near-infrared to visible spectral ranges. Our experimental demonstration presents a new degree of freedom towards the dynamic modulation of moiré superlattices, holding the promise to unveil unprecedented physics and applications of stacked two-dimensional materials.

Crystal-field excitations and vibronic modes in the triangular-lattice spin-liquid candidate TbInO3

We study the ground-state properties, the electronic excitations, and lattice dynamics in spin-liquid candidate ${\mathrm{TbInO}}_{3}$. By employing polarization-resolved Raman spectroscopy we define the intermultiplet and intramultiplet excitations, and establish the low-energy crystal-field (CF) level scheme. In particular, we demonstrate that the ground state of the ${\mathrm{Tb}}^{3+}$ ions is a non-Kramers doublet, and relate the enhanced linewidth of the CF modes to the magnetic fluctuations near the spin-liquid ground state. We identify the 38 allowed Raman-active phonon modes at low temperature. Moreover, we observe hybrid vibronic excitations involving coupled CF and low-lying phonon modes, suggesting strong spin-lattice dynamics. We develop a model for vibronic states and obtain the parameters of the bare responses and coupling strength. We further demonstrate that the obtained CF level scheme is consistent with specific-heat data.

Lattice dynamics of the excitonic insulator Ta2Ni(Se1−xSx)5

Recently, we employed electronic polarization-resolved Raman spectroscopy to reveal the strongly correlated excitonic insulator (EI) nature of Ta2NiSe5, Volkov et al. [arXiv:2007.07344], and also showed that for Ta$_2$Ni(Se$_{1-x}$S$_x$)$_5$ alloys the critical excitonic fluctuations diminish with sulfur concentration x exposing a cooperating lattice instability that takes over for large x, Volkov et al. [arXiv:2104.07032]. Here we focus on the lattice dynamics of this EI family. We identify all Raman-active optical phonons of fully symmetric and ac-quadrupole-like symmetries and study their evolution with temperature and sulfur concentration. We demonstrate the change of selection rules at temperatures below the orthorhombic-to-monoclinic transition at Tc(x) that is related to the EI phase. We find that Tc(x) decrease monotonically from 328 K for Ta2NiSe5 to 120 K for Ta2NiS5 and that the magnitude of lattice distortion also decreases with the sulfur concentration x. For x < 0.7, the two lowest-frequency B2g phonon modes show strongly asymmetric lineshapes at high temperatures due to Fano interference with the broad excitonic continuum present in a semimetallic state. Within the framework of extended Fano model, we develop a quantitative description of the interacting exciton-phonon excitation lineshape, enabling us to derive the intrinsic phonon parameters and determine the exciton-phonon interaction strength, that affects the transition temperature Tc(x). We also observe signatures of the acoustic mode scattered assisted by the structural domain walls formed below Tc. Based on our results, we additionally present a consistent interpretation of the origin of oscillations observed in time-resolved pump-probe experiments.

Orbital dichotomy of Fermi liquid properties in Sr2RuO4 revealed by Raman spectroscopy

We report a polarization-resolved Raman spectroscopy study of the orbital dependence of the quasiparticles properties in the prototypical multi-band Fermi liquid Sr\textsubscript{2}RuO\textsubscript{4}. We show that the quasiparticle scattering rate displays $\omega^{2}$ dependence as expected for a Fermi liquid. Besides, we observe a clear polarization-dependence in the energy and temperature dependence of the quasiparticle scattering rate and mass, with the $d_{xz/yz}$ orbital derived quasiparticles showing significantly more robust Fermi liquid properties than the $d_{xy}$ orbital derived ones. The observed orbital dichotomy of the quasiparticles is consistent with the picture of Sr\textsubscript{2}RuO\textsubscript{4} as a Hund's metal. Our study establishes Raman scattering as a powerful probe of Fermi liquid properties in correlated metals.

Structural Monoclinicity and Its Coupling to Layered Magnetism in Few-Layer CrI3.

Using polarization-resolved Raman spectroscopy, we investigate layer number, temperature, and magnetic field dependence of Raman spectra in one- to four-layer CrI3. Layer-number-dependent Raman spectra show that in the paramagnetic phase a doubly degenerated Eg mode of monolayer CrI3 splits into one Ag and one Bg mode in N-layer (N > 1) CrI3 due to the monoclinic stacking. Their energy separation increases in thicker samples until an eventual saturation. Temperature-dependent measurements further show that the split modes tend to merge upon cooling but remain separated until 10 K, indicating a failed attempt of the monoclinic-to-rhombohedral structural phase transition that is present in the bulk crystal. Magnetic-field-dependent measurements reveal an additional monoclinic distortion across the magnetic-field-induced layered antiferromagnetism-to-ferromagnetism phase transition. We propose a structural change that consists of both a lateral sliding toward the rhombohedral stacking and a decrease in the interlayer distance to explain our experimental observations.

Critical charge fluctuations and emergent coherence in a strongly correlated excitonic insulator

Excitonic insulator is a coherent electronic phase that results from the formation of a macroscopic population of bound particle-hole pairs—excitons. With only a few candidate materials known, the collective excitonic behavior is challenging to observe, being obscured by crystalline lattice effects. Here we use polarization-resolved Raman spectroscopy to reveal the quadrupolar excitonic mode in the candidate zero-gap semiconductor Ta2NiSe5 disentangling it from the lattice phonons. The excitonic mode pronouncedly softens close to the phase transition, showing its electronic character, while its coupling to noncritical lattice modes is shown to enhance the transition temperature. On cooling, we observe the gradual emergence of coherent superpositions of band states at the correlated insulator gap edge, with strong departures from mean-field theory predictions. Our results demonstrate the realization of a strongly correlated excitonic state in an equilibrium bulk material.

Direct Observation of the Linear Dichroism Transition in Two-Dimensional Palladium Diselenide.

The linear dichroism (LD) transition within anisotropic photonic materials displays promising prospects for applications in polarization-wavelength-selective detectors, optical switching, and optical communication. In conventional two-dimensional (2D) anisotropic materials, the LD is predominantly uniaxial over a broad spectrum of wavelengths and arises principally from the reduced symmetry of the materials. However, the LD transition behavior in crystalline 2D materials remains elusive. Here, we demonstrate the observation of a unique LD conversion phenomenon at a wavelength of 472 nm in palladium diselenide (PdSe2) using polarization-resolved absorption spectroscopy. This material exhibits prominent anisotropic responses and a high absorption ratio of αy/αx ≈ 1.11 at 364 nm, 1.15 at 532 nm, and 0.84 at 633 nm. We propose that this abnormal LD conversion behavior originates from the forceful localization rules at different parallel energy bands that exist within this material. Furthermore, the robust periodicity of Ag and B1g modes in polarization-resolved Raman spectroscopy is in good agreement with the theoretical structure symmetry analysis. This indicates the strong intrinsic LD effect in the anisotropic nature of PdSe2, which offers a macrolevel determination of crystal orientations. Such unique LD conversion features, in combination with strong LD effects, enable the air-stable PdSe2 to be a potential candidate for technological innovations in multispectral imaging, sensing, and polarization-sensitive and wavelength-controllable photoelectronic applications.

Low-temperature monoclinic layer stacking in atomically thin CrI3 crystals

Chromium triiodide, CrI3, is emerging as a promising magnetic two-dimensional semiconductor where spins are ferromagnetically aligned within a single layer. Potential applications in spintronics arise from an antiferromagnetic ordering between adjacent layers that gives rise to spin filtering and a large magnetoresistance in tunnelling devices. This key feature appears only in thin multilayers and it is not inherited from bulk crystals, where instead neighbouring layers share the same ferromagnetic spin orientation. This discrepancy between bulk and thin samples is unexpected, as magnetic ordering between layers arises from exchange interactions that are local in nature and should not depend strongly on thickness. Here we solve this controversy and show through polarization resolved Raman spectroscopy that thin multilayers do not undergo a structural phase transition typical of bulk crystals. As a consequence, a different stacking pattern is present in thin and bulk samples at the temperatures at which magnetism sets in and, according to previous first-principles simulations, this results in a different interlayer magnetic ordering. Our experimental findings provide evidence for the strong interplay between stacking order and magnetism in CrI3, opening interesting perspectives to design the magnetic state of van der Waals multilayers.

Polarization-resolved Raman spectroscopy of α−RuCl3 and evidence of room-temperature two-dimensional magnetic scattering

Polarization-resolved Raman spectroscopy was performed and analyzed from large, high quality, mono-domain single crystal of {\alpha}-RuCl3, a proximate Kitaev quantum spin liquid. Spectra were collected with laser polarizations parallel and perpendicular to the honeycomb plane. Pairs of nearly degenerate phonons were discovered and show either a 4-fold or 2-fold polarization angle dependence in their Raman intensity, thereby providing evidence to definitively assign the bulk crystal point group as C2h. The low frequency continuum that is often attributed to scattering from pairs of Majorana fermions was also examined and found to disappear when the laser excitation and scattered photon polarizations were perpendicular to the honeycomb plane. This disappearance, along with the behavior of the phonon spectrum in the same polarization configuration, strongly suggests that the scattering continuum is 2-dimensional. We argue that this scattering continuum originates from the Kitaev magnetic interactions that survives up to room temperature, a scale larger than the bare Kitaev exchange energy of approximately 50 K.

Tuning the Fr\xf6hlich exciton-phonon scattering in monolayer MoS2

Charge carriers in semiconducting transition metal dichalcogenides possess a valley degree of freedom that allows for optoelectronic applications based on the momentum of excitons. At elevated temperatures, scattering by phonons limits valley polarization, making a detailed knowledge about strength and nature of the interaction of excitons with phonons essential. In this work, we directly access exciton-phonon coupling in charge tunable single layer MoS2 devices by polarization resolved Raman spectroscopy. We observe a strong defect mediated coupling between the long-range oscillating electric field induced by the longitudinal optical phonon in the dipolar medium and the exciton. This so-called Fröhlich exciton phonon interaction is suppressed by doping. The suppression correlates with a distinct increase of the degree of valley polarization up to 20% even at elevated temperatures of 220 K. Our result demonstrates a promising strategy to increase the degree of valley polarization towards room temperature valleytronic applications.