Transverse Optical Modes Research Articles

Measurement of temporal evolution of antiferromagnetic domain change in nickel oxide driven by 2TO phonon mode excitation via pump-probe experiment

Abstract The temporal evolution of antiferromagnetic domain pattern changes under resonant excitation of the second-order transverse optical (2TO) phonon mode in nickel oxide was investigated using mid-infrared free electron laser (MIR-FEL) pulses and visible nanosecond probe laser pulses at room temperature. We visualized the domain patterns through magneto-optical polarized microscopy in transmission and observed their temporal variation after the phonon excitation via MIR-FEL. We evaluated the differences throughout the timeline using the structural similarity index measure (SSIM) technique from domain images with and without MIR-FEL irradiation. We found that the MIR-FEL irradiation induces significant structural changes in the domain patterns. The maximum difference was observed at the timing of the MIR-FEL irradiation and exponentially recovered with the time constant of 1.4 ± 0.2 ms. This rather long-time constant could be owing to the spin relaxation, whilst further investigation is needed to confirm the underlying mechanism.

Modulating phononic landscapes: The role of silicon ion bombardment in tailoring Si/Si+Ge and SiO2/SiO2+Ge superlattices for advanced neutron superreflector applications

This study investigates the effects of silicon ion bombardment on the phononic properties of Si/Si+Ge and SiO2/SiO2+Ge superlattices to enhance neutron superreflector technology. Through precise ion implantation and Fourier Transform Infrared Spectroscopy (FTIR), we observed significant alterations in transverse and longitudinal optical phonon modes. The Si/Si+Ge system exhibited notable blueshifts and intensity changes, while SiO2/SiO2+Ge showed increased lattice disorder and peak broadening. These findings highlight ion bombardment's potential to optimize phononic landscapes for improved nuclear reactor safety and efficiency via advanced phonon engineering.

Bose–Einstein condensation of photons in a vertical-cavity surface-emitting laser

Many bosons can occupy a single quantum state without a limit. It is described by the quantum-mechanical Bose–Einstein statistic, which allows Bose–Einstein condensation at low temperatures and high particle densities. Photons, historically the first considered bosonic gas, were late to show this phenomenon, observed in rhodamine-filled microcavities and doped fibre cavities. These findings have raised the question of whether condensation is also common in other laser systems with potential technological applications. Here we show the Bose–Einstein condensation of photons in a broad-area vertical-cavity surface-emitting laser with a slight cavity-gain spectral detuning. We observed a Bose–Einstein condensate in the fundamental transversal optical mode at a critical phase-space density. The experimental results follow the equation of state for a two-dimensional gas of bosons in thermal equilibrium, although the extracted spectral temperatures were lower than the device’s. This is interpreted as originating from the driven-dissipative nature of the photon gas. In contrast, non-equilibrium lasing action is observed in the higher-order modes in more negatively detuned device. Our work opens the way for the potential exploration of superfluid physics of interacting photons mediated by semiconductor optical nonlinearities. It also shows great promise for enabling single-mode high-power emission from a large-aperture device.

(Invited) Ultrathin Gap Nanoantenna: Crystal Phase Transitions and Luminescent Properties

We report Te-doped GaP nanowires (NWs) with positive tapering and radii measuring as low as 5 nm grown by the self-assisted vapor-liquid-solid mechanism using selective-area molecular beam epitaxy. The occurrence of the ultrathin nanoantenna showed a dependence on pattern pitch (separation between NWs) with a predominance at 600 nm pitch, and exhibited radius oscillations that correlate with polytypic zincblende/wurtzite segments. A growth model explains the positive tapering of the NW leading to an ultrathin tip from the suppression of surface diffusion of Ga adatoms on the NW sidewalls by Te dopant flux. The model also provides a relationship between the radius modulations and the oscillations of the droplet contact angle, predicting the quasi-periodic radius oscillations and corresponding crystal phase transitions. The GaP NWs showed strong low temperature micro-photoluminescence exciton-related emission, indicating a bandgap difference between the zincblende/wurtzite segments, with phonon replicas due to the transverse optical phonon mode. These results establish a link between dopants and the ability to control NW morphology, crystal phase and luminescent properties with possible applications in thermoelectrics, quantum emitters and photodetectors.

Generation of multiple user-defined dispersive waves in a silicon nitride waveguide

The quest for a wide and bright supercontinuum source has received significant attention, addressing pivotal challenges in ultra-fast spectroscopy, imaging, and frequency metrology. Among the diverse optical nonlinear mechanisms steering supercontinuum generation, dispersive waves emerge as crucial contributors, providing heightened spectral intensity, wavelength tunability, and superior temporal coherence. Nevertheless, their generation is tightly bound by waveguide geometry, limiting both their numbers and the wavelengths at which they manifest. In this paper, we demonstrate the controlled generation of multiple dispersive waves in fundamental optical transverse mode by leveraging quasi phase-matching in an integrated silicon nitride (Si3N4) waveguide. This approach involves modulating the group velocity dispersion through varying the width of the Si3N4 waveguide crossing anomalous and normal dispersion, which facilitates the creation of diverse dispersive waves in fundamental transverse electromagnetic (TE) polarization at multiple phase-matched wavelengths. A wide nonlinear optical spectral broadening surpassing conventional approaches is achieved with good temporal and spatial coherence. Remarkably, the generation of the multiple dispersive waves and the supercontinuum is achieved by a 190-fs pulse duration pump with peak power as low as 110 W (24 pJ). This work offers flexibility to manipulate dispersive waves in an integrated platform beyond current dispersion engineering. It represents a significant step forward in developing an integrated broadband source with a user-defined spectral shape, accomplished with minimal pump power requirements.

Phonon dispersion of quantum paraelectric SrTiO3 in electric fields

Here we report on an elastic and inelastic neutron scattering study addressing the effect of electric fields on quantum paraelectric SrTiO3. Our elastic scattering results find small changes as a function of field in a superlattice reflection that sample the octahedral rotations, which is indicative of only weak coupling of octahedral rotation and electric polarization. Using inelastic neutron scattering, we measured the dispersion of the transverse acoustic and transverse optic phonon in SrTiO3 as a function of applied electric fields. By collecting not only the change in gap, but also of the dispersion, we can better quantify the changes in the lattice dynamics. The findings are put in context to recent DFT calculations predicting the E-field effect on the atomic motions of the lowest lying transverse optical (soft) mode. We find hints of nonlinear coupling to the acoustic mode and to the phonon with polarization perpendicular to the E field, which shows the nonlinearity in the chemical potential that is also relevant when SrTiO3 is excited by strong E-field (THz) pulses. Published by the American Physical Society 2024

Hyper-Raman scattering from the LO modes of perovskite ferroelectric relaxors

Hyper-Raman scattering is used to study the temperature dependence of the longitudinal optic (LO) modes of three prototypical ferroelectric relaxors in a broad temperature range from 20 to 800 K. The three LO bands observed in all spectra of the three materials are linked to the three transverse optic (TO) modes in cubic relaxors where LOi is linked to TOi, with i = 1 to 3. The Last, Slater, and Axe eigenvector pictures of the TO modes are consistent with our observations on LO1, LO2, and LO3, respectively. Within this framework, the splitting of LO2 would mostly be linked to a structural disorder on the site while the strength of an anomaly of LO1 near the freezing temperature Tf relies on the ability of the material to develop a long-range ordering. Moreover, the more pronounced the splitting, the more important the structural disorder and the lower the value of the dielectric constant. Published by the American Physical Society 2024

Impact of Cu2+ precursor on physical and photoelectrochemical properties of electrodeposited nanostructured CuS thin films for biosensor applications

Nanostructured CuS films were synthesized on FTO substrates employing low-cost electro deposition technique. XRD, Raman, SEM, UV–visible spectroscopy, photocurrent, PL, Mott-Schottky, and electrochemical impedance spectroscopy (EIS) measurements were used to examine physical and photoelectrochemical properties of samples. XRD results indicated that CuS films have hexagonal crystal structure where the crystallite size raises from 32 to 53 nm with increasing the Cu2+ molarity. Raman results displayed two peaks at 270 and 450 cm−1 that related to A1g transverse optical mode (TO) and A1g longitudinal optical (LO) mode for the vibrations of the S–S stretching and Cu–S bonds, respectively. SEM images displayed that fabricated CuS cover the substrate surface entirely, where grains are distributed uniformly with increasing the Cu+2 molarity. UV–visible measurements exhibited an absorption band edge between 450 and 550 nm as a characteristic of CuS films direct band gap. PL results presented strong blue-green emission at about 500 nm for CuS thin films. The photocurrent studies demonstrated that the CuS films are p-type semiconductors where the current density increases from 0.8 mA/cm2 to 1.1 mA/cm2 with the Cu2+ molarity increasing. The EIS analysis confirmed that charge transfer resistance reduces with increasing molarity. Mott- Schottky measurements established that carrier concentrations and the flat band varied from 5 × 1019 to 6.7 × 1019 cm−3 and from 1.1 to 0.75V, respectively. The fabricated CuS film was tested as glucose biosensor where a fast response and higher stability were noticed. Our results indicated that nanostructured CuS films are gifted candidates for optoelectronics applications especially biosensors.

Observation of the nonanalytic behavior of optical phonons in monolayer hexagonal boron nitride

Phonon splitting of the longitudinal and transverse optical modes (LO-TO splitting), a ubiquitous phenomenon in three-dimensional polar materials, will break down in two-dimensional (2D) polar systems. Theoretical predictions propose that the LO phonon in 2D polar monolayers becomes degenerate with the TO phonon, displaying a distinctive “V-shaped” nonanalytic behavior near the center of the Brillouin zone. However, the full experimental verification of these nonanalytic behaviors has been lacking. Here, using monolayer hexagonal boron nitride (h-BN) as a prototypical example, we report the comprehensive and direct experimental verification of the nonanalytic behavior of LO phonons by inelastic electron scattering spectroscopy. Interestingly, the slope of the LO phonon in our measurements is lower than the theoretically predicted value for a freestanding monolayer due to the screening of the Cu foil substrate. This enables the phonon polaritons in monolayer h-BN/Cu foil to exhibit ultra-slow group velocity (~5 × 10−6c, c is the speed of light) and ultra-high confinement (~ 4000 times smaller wavelength than that of light). These exotic behaviors of the optical phonons in h-BN presents promising prospects for future optoelectronic applications.

3D self-assembled polar vs. non-polar NiO nanoparticles nanoengineered from turbostratic Ni3(OH)4(NO3)2 and ordered β-Ni(OH)2 intermediates.

A surfactant-free ammonia and carbamide precursor-modulated engineering of self-assembled flower-like 3D NiO nanostructures based on ordered β-Ni(OH)2 and turbostratic Ni3(OH)4(NO3)2 nanoplate-structured intermediates is reported. By employing complementary structural and spectroscopic techniques, fundamental insights into structural and chemical transformations from intermediates to NiO nanoparticles (NPs) are provided. FTIR, Raman and DSC analyses show that the transformation of intermediates to NiO NPs involves subsequent loss of NO3- and OH- species through a double-step phase transformation at 306 and 326 °C corresponding to the loss of free interlayer ions and H2O species, respectively, followed by the loss of chemically bonded OH- and NO3- ions. Transformation to NiO NPs via the ammonia route proceeds as single-phase transition, accompanied with a loss of OH- species at 298 °C. The full transformation to NiO NPs of both intermediates is achieved at 350 °C through annealing in the air atmosphere. Ammonia-derived NPs maintain nanoflower morphology by self-assembling into nanoplates, which is enabled by H2O-mediated adhesion on the NiO NPs' {100} neutral surfaces. Structural transformations of turbostratic Ni3(OH)4(NO3)2 nanoplates result in the formation of NiO NPs dominantly shaped by inert polar OH-terminated (111) atomic planes, leading to the loss of the initial self-assembled 3D structure. DFT calculations support these observations, confirming that H2O adsorbs dissociatively on polar {111} surfaces, while only physisorption is energetically feasible on {100} surfaces. NiO NPs obtained via two different routes have overall different properties: carbamide-derived NPs are 3 times larger (15.5 vs. 5.4 nm), possess a larger band gap (3.6 vs. 3.2 eV) and are more Ni deficient. The intensity ratio of surface optical (SO) modes to transversal and longitudinal optical modes is ∼40 times higher in the NiO NPs obtained from β-Ni(OH)2 compared to Ni3(OH)4(NO3)2-derived NPs. The SO phonon lifetime is an order of magnitude shorter in NiO obtained from β-Ni(OH)2, reflecting a much smaller NP size. The choice of a precursor defines the size, morphology, crystallographic surface orientations and band gap of the NiO NPs, with Ni deficiency providing pathways for utilizing them as p-type materials, allowing for the precise nanoengineering of polar and neutral surface-dominated NiO NPs, which is of exceptional importance for use in catalysis.

Evaluation of Anisotropic Biaxial Stress in Extremely-Thin Body (100) Silicon-Germanium-on-Insulator p-Type Metal-Oxide-Semiconductor Field-Effect-Transistor by Oil-Immersion Raman Spectroscopy

Background and ObjectiveSilicon germanium (SiGe)-on-insulator (SGOI) p-MOSFETs are expected for obtaining low power consumption and high current drive of CMOS since SiGe has higher hole career mobility than Si and the compressive strain can be induced in the SiGe channel without complicated heterostructures. In addition, the buried oxide between the Si substrate and the SiGe layer realizes suppression of leak current, and an extremely thin body (ETB) SGOI prevents short-channel effects. Strain engineering is important for improving the performance of p-MOSFETs because the hole mobility increases due to the compressive strain in the channel region. In previous studies, we have reported that anisotropic strain in ETB GOI channels of p-MOSFET improved electrical properties [1]. However, there are few reports regarding the detailed stress evaluation in ETB SGOI p-MOSFETs. The strain state has changed complicatedly by the SiGe device process. Therefore, a detailed stress measurement is indispensable to determine career mobility enhancement in the actual channel fabrication. In this study, we evaluated the anisotropic biaxial stress in the channel region of the ETB (100) SGOI p-MOSFETs by oil-immersion Raman spectroscopy.Experiments We prepared (100) SGOI p-MOSFETs along <110> with a channel thickness of approximately 10 nm by applying the Ge condensation process with slow cooling on the 60 nm-thick Si0.75Ge0.25 films epitaxially grown on SOI substrates with 10 nm-thick superficial Si layer [2]. We used the Ge condensation process that combined oxidation and intermixing annealing in order to suppress strain relaxation in the Ge-rich region [3] and obtained Ge-rich SiGe layer (Ge fraction: from 65 to 70%). For the evaluation of anisotropic biaxial stress in the SiGe channel region, we measured longitudinal optical (LO) and transverse optical (TO) phonon modes of Raman spectra for Ge-Ge vibration mode derived from SiGe by using oil-immersion Raman spectroscopy. In the oil-immersion Raman measurements, the wavelength of the excitation light source was 532 nm, the laser power at the sample surface was less than 1 mW, and the focal length of the spectrometer was 2,000 mm. The numerical aperture of the oil-immersion lens was 1.4, and the reflective index of oil was 1.5. We measured p-MOSFETs with different channel widths to examine the channel width dependence.Results and DiscussionFigure 1(a) and (b) show the Raman spectra of the LO and TO phonon modes obtained from the SiGe channel region at channel width (Wch) = 738 nm, respectively. We observed that Raman peaks of LO phonon mode shifted toward the higher wavenumber side compared to the Raman peak of strain-free SiGe. These results suggest that the high compressive strain is induced in the SiGe channel.Figure 1(c) shows the calculated transverse stress (σxx) and longitudinal stress (σyy) of the samples using LO and TO Raman shift for four different channel widths under the assumption of the anisotropic biaxial stress and Ge fraction 68% in the SiGe layer. From Fig. 1(c), we observed transverse stress (σxx) decreases with narrowing channel width. On the other hand, the longitudinal stress (σyy) did not significantly change regardless of channel width. These results suggest that the strain states in the SiGe channel region became closer to the uniaxial strain with narrowing the channel width. These changes are in good agreement with the previous electrical characteristics studies of the GOI p-MOSFETs [1], and it is expected that the compressive strain enhances the hole mobility in the ETB SGOI p-MOSFETs as well.AcknowledgementsThis work was supported by JSPS KAKENHI Grant Number 22H00208, Japan. A part of this work was conducted at Takeda Sentanchi Supercleanroom, The University of Tokyo, supported by "Nanotechnology Platform Program" of MEXT, Japan, Grant Number JPMXP09F-20-UT-0007. Reference [1] C. -T. Chen et al., IEEE Trans. Electron Devices 69, 1 (2022).[2] C. -T. Chen et al., Proc. IEEE Symp. VLSI Technology (2021).[3] K. -W. Jo et al., Appl. Phys. Lett. 114, 062101 (2019). Figure 1

Investigation of effects of interlayer interaction and biaxial strain on the phonon dispersion and dielectric response of hexagonal boron arsenide

In this study, the effects of interlayer interaction and biaxial strain on the electronic structure, phonon dispersion and optical properties of monolayer and bilayer BAs are studied, using first-principles calculations within the framework of density functional theory. The interlayer coupling in bilayer BAs causes the splitting of out-of-plane acoustic (ZA) and optical (ZO) mode. For both structures, positive phonon modes across the Brillouin zone have been observed under biaxial tensile strain from 0 to 8%, which indicate their dynamical stability under tensile strain. Also, the phonon band gap between longitudinal acoustic (LA) and longitudinal optical (LO)/transverse optical (TO) modes for monolayer and bilayer BAs decreases under tensile strain. An appreciable degree of optical anisotropy is noticeable in the materials for parallel and perpendicular polarizations, accompanied by significant absorption in the ultraviolet and visible regions. The absorption edge of bilayer BAs is at a lower energy with respect to the monolayer BAs. The results demonstrate that the phonon dispersion and optoelectronic properties of BAs sheet could as well be tuned with both interlayer interaction and biaxial strain that are promising for optoelectronic and thermoelectric applications.

Synthesis and Characterization of Ag/CdO Nanocomposite for the Photocatalytic Degradation of Methyl Orange Dye

Well crystalline Ag/CdO nanocomposite has been synthesized via the solution combustion synthesis (SCS) route. The Ag/CdO nanocomposite has been characterized in term of X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM) and Raman spectroscopy. The crystallinity of the as-synthesized nanocomposite was obtained by using XRD technique. The crystallite size of the nanocomposite was calculated by the Scherrer equation and was found to be 47 nm. The surface morphology was obtained by FESEM spectroscopy. The particles appear to be porous in nature and wool-like morphology was obtained. Raman band at about 278 cm[Formula: see text] is because of the combination of transverse acoustic and optical phonon modes of cadmium oxide (CdO). Further, the Ag/CdO nanocomposite was used as a photocatalyst for the degradation of methyl orange (MO) dye. Results revealed that the photocatalytic activity of Ag/CdO nanocomposite for the degradation of MO dye increases with increasing the amount of photocatalyst. The rate constant, [Formula: see text] values for 100 mg, 150 mg and 200 mg of photocatalyst were 0.83, 2.21 × 10[Formula: see text] min[Formula: see text] and 3.81 × 10[Formula: see text] min[Formula: see text], respectively.

Thickness-Dependent Terahertz Permittivity of Epitaxially Grown PbTe Thin Films

The exceptional thermoelectric properties of PbTe are believed to be associated with the incipient ferroelectricity of this material, which is caused by strong electron–phonon coupling that connects phononic and electronic dynamics. Here, we have used terahertz time-domain spectroscopy measurements to generate complex permittivity spectra for a set of epitaxially grown PbTe thin films with thicknesses between 100 and 500 at temperatures from 10K to 300K. Using a Drude–Lorentz model, we retrieved the physical parameters of both the phononic and electronic contributions to the THz permittivity. We observed a strong decrease, or softening, of the transverse optical phonon mode frequency with decreasing temperature, determining a thickness-independent negative ferroelectric-transition critical temperature, while we found a thickness-dependent anharmonic phonon decay lifetime. The electronic contribution to the permittivity was larger in thinner films, and both the carrier density and mobility increased with decreasing temperature in all films. Finally, we detected a thickness-dependent longitudinal optical phonon mode frequency, indicating the presence of plasmon–phonon coupling.

Phonon Characteristics of Gas-Source Molecular Beam Epitaxy-Grown InAs1−xNx/InP (001) with Identification of Si, Mg and C Impurities in InAs and InN

The lattice dynamical properties of dilute InAs1−xNx/InP (001) epilayers (0 ≤ x ≤ 0.03) grown by gas-source molecular beam epitaxy were carefully studied experimentally and theoretically. A high-resolution Brüker IFS 120 v/S spectrometer was employed to measure the room-temperature infrared reflectivity (IRR) spectra at near-normal incidence (θi = 0). The results in the frequency range of 180–500 cm−1 revealed accurate values of the characteristic In-As-like and In-N-like vibrational modes. For InAs1−xNx alloys, a classical “Drude–Lorentz” model was constructed to obtain the dielectric functions ε~ω in the far IR regions by incorporating InAs-like and InN-like transverse optical ωTO modes. Longitudinal optical ωLO phonons were achieved from the imaginary parts of the simulated dielectric loss functions. The theoretical results of IRR spectra for InAs1−xNx/InP (001) epilayers using a multi-layer optics methodology provided a very good agreement with the experimental data. At oblique incidence (θi ≠ 0), our study of s- and p-polarized reflectance (Rs,p(ω)) and transmission (Ts,p(ω)) spectra allowed the simultaneous perception of the ωTO and ωLO phonons of the InAs, InN and InAs0.97N0.03 layers. Based on the average t-matrix Green’s function theory, the results of local vibrational modes for light SiIn+ donors and SiAs−, CAs− acceptors in InAs were found in good agreement with the existing Raman scattering and infrared spectroscopy data. InInN, however, the method predicted an in-band mode for the MgIn− acceptor while projecting an impurity mode of the SiIn+ donor to appear just above the maximum ωmaxInN[≡595 cm−1] phonon frequency region. In InAs1−xNx/InP (001) epifilms, the comparison of reflectivity/transmission spectra with experiments and the predictions of impurity modes for isoelectronic donor and acceptor impurities in InAs and InN can be valuable for appraising the role of defects in other technologically important semiconductors.

Evaluation of Anisotropic Biaxial Stress in Extremely-Thin Body (100) Silicon-Germanium-on-Insulator p-Type Metal-Oxide-Semiconductor Field-Effect-Transistor by Oil-Immersion Raman Spectroscopy

We evaluated the anisotropic biaxial strain in the channel region of extremely-thin body silicon-germanium-on-insulator p-MOSFETs by oil-immersion Raman spectroscopy. Oil-immersion Raman spectroscopy can measure the transverse optical (TO) phonon mode which cannot be detected by conventional Raman spectroscopy under the backscattering configuration for (001) substrate. Therefore, we can calculate the anisotropic biaxial stress in the SiGe channel region and investigate the channel width dependence of stress. From the Raman spectra obtained in the polarization configurations of longitudinal optical (LO)-active and TO-active, we confirmed that compressive stress is induced in the SiGe channel region. In addition, we observed that the strain state of the SiGe channel region becomes quasi-uniaxial strain by narrowing the channel width.

Molecular Dynamics Simulation of Thermal Conductivity and Vibrational Density of States of Cadmium Telluride

This study aims to calculate the thermal conductivity and vibrational density of states of CdTe using MD simulation. The lengths of CdTe varied from 10 nm, 20 nm, 30 nm, 40 nm, and 50 nm, with fixed width and height of 10 nm at room temperature (300 K). The results show the decrease of thermal conductivity as a function of length due to phonon-phonon interaction. The width varied from 10 nm, 20 nm, 30 nm, 40 nm, and 50 nm at room temperature (300 K) with a fixed length and height of 10 nm. Similarly, the height varied from 10 nm, 20 nm, 30 nm, 40 nm, and 50 nm with fixed length and width at room temperature (300 K). It was found that the phonon spread less in the boundaries of the mean free path which follows the creation processes resulting to the decrease of thermal conductivity. The temperatures varied from 50 K, 75 K, 100 K, 300 K, 500 K, 700 K, 900 K, 1,000 K, and 1,365 K with fixed dimensions of 50 nm in length, 50 nm in width, and 50 nm in height. As observed, the thermal conductivity decreases with a further increase in temperature. There were four major peaks found in the vibrational density of states of cadmium telluride: ~1.3 THz and ~3.5 THz which corresponds to transverse and longitudinal acoustic modes, ~4.5 THz and ~5 THz which corresponds to transverse and longitudinal optical modes.

Raman scattering studies of Si/B4C periodic multilayer mirrors with an operating wavelength of 13.5 nm

In order to obtain mirrors with a minimum value of residual stress, periodic multilayer mirrors composed of Si/B4C were deposited by magnetron sputtering with change in pressure of sputtering Ar gas. The microstructure and phase of Si and B4C was manipulated by the pressure of Ar gas which overall affected the stress in the mirrors. The minimum stress was obtained at higher pressure of sputter Ar gas, which showed the formation of amorphous boron, amorphous B4C, free carbon atoms and amorphous carbon structure in the B4C layers, investigated by Raman scattering spectroscopy. In Raman spectroscopy, a transverse optical (TO) mode of amorphous Si was shifted to lower frequency with increase in Ar gas pressure, which indicated relaxation of stress, also confirmed by the curvature measurement of mirrors. However, in the case of high residual stress, the amorphous B4C was a prominent phase in this layer and the frequency of the TO mode of amorphous Si was blue-shifted. Microstructure and stress affected the interfaces and modulation of the periodicity of the Si/B4C mirrors, investigated by secondary ion mass spectroscopy, which influenced the reflectivity of the mirrors.

Composition-driven structural phase transition in ferroelectric PbZrxTi1-xO3 across the morphotropic phase boundary

Materials with coexisting ferroelectric, piezoelectric, and pyroelectric properties have taken a great scientific attraction owing to their potential technological applications. In this work, employing X-ray diffraction and Raman scattering measurements combined with a photoluminescence investigation at room temperature, we report a composition-driven structural phase transition in the ferroelectric PbZrxTi1-xO3 (PZT) system by tuning the Zr content close to the morphotropic phase boundary (MPB) in the range of 0.44≤x≤0.58. The Ti-rich compound (x = 0.44) crystallizes in a tetragonal structure while the Zr-rich compound (x = 0.58) belongs to the rhombohedral symmetry. The system exhibits a phase coexistence region composed of these tetragonal and rhombohedral phases in the vicinity of MPB for compositions with x = 0.50, 0.52, and 0.53. We reveal strong and systematic evolution of the Raman shift, Raman strength, and damping constants for the Raman active phonon modes associated with the aforementioned structural transition and the increased local disorder of Ti4+ or Zr4+ cations as a function of x. We further uncover a resonance Raman phenomenon with 633 nm (1.96 eV) excitation, enhancing the Raman strength and damping constants of certain low-lying transverse optical (TO) phonon modes in the Raman spectra. The photoluminescence emission spectrum shows evidence of in-gap energy levels that could be ascribed to self-trapped excitons, explaining the origin of the resonance Raman effect in PZT ceramics.

Intrinsic Control of Interlayer Exciton Generation in Van der Waals Materials via Janus Layers

We demonstrate the possibility of engineering the optical properties of transition metal dichalcogenide heterobilayers when one of the constitutive layers has a Janus structure. We investigate different MoS2@Janus layer combinations using first-principles methods including excitons and exciton-phonon coupling. The direction of the intrinsic electric field from the Janus layer modifies the electronic band alignments and, consequently, the energy separation between dark interlayer exciton states and bright in-plane excitons. We find that in-plane lattice vibrations strongly couple the two states, so that exciton-phonon scattering may be a viable generation mechanism for interlayer excitons upon light absorption. In particular, in the case of MoS2@WSSe, the energy separation of the low-lying interlayer exciton from the in-plane exciton is resonant with the transverse optical phonon modes (40 meV). We thus identify this heterobilayer as a prime candidate for efficient generation of charge-separated electron-hole pairs.