Phonon Wavenumber Research Articles

GeSn-on-GaAs with photoconductive carrier lifetime >400 ns: role of substrate orientation and atomistic simulation.

Group IV GeSn quantum material finds application in electronics and silicon-compatible photonics. Synthesizing these materials with low defect density and high carrier lifetime is a potential challenge due to lattice mismatch induced defects and tin segregation at higher growth temperature. Recent advancements in the growth of these GeSn materials on Si, Ge, GaAs, and with substrate orientations, demonstrated different properties using epitaxial and chemical deposition methods. This article addresses the effect of GaAs substrate orientation and misorientation on the materials' properties and carrier lifetimes in epitaxial Ge0.94Sn0.06 layers. With starting GaAs substrates of (100)/2°, (100)/6°, (110) and (111)A orientations, Ge0.94Sn0.06 epitaxial layers were grown with an intermediate Ge buffer layer by molecular beam epitaxy and analyzed by several analytical tools. X-ray analysis displayed good crystalline quality, and Raman spectroscopy measurements showed blue shifts in phonon wavenumber due to biaxial compressive strain in Ge0.94Sn0.06 epilayers. Cross-sectional transmission electron microscopy analysis confirmed the defect-free heterointerface of Ge0.94Sn0.06/Ge/GaAs heterostructure. Minority carrier lifetimes of the unintentionally doped n-type Ge0.94Sn0.06 epilayers displayed photoconductive carrier lifetimes of >400 ns on (100)/6°, 319 ns on (100)/2°, and 434 ns on (110) GaAs substrate at 1500 nm excitation wavelength. On the other hand, Ge0.94Sn0.06 layer showed poor carrier lifetime on (111)A GaAs substrate. The observed differences in carrier lifetimes were correlated with the formation energy of the Ge on (100)/6° and (100)/2° GaAs heterointerface using Stillinger-Weber interatomic potential model-based atomistic simulation with different heterointerfacial bonding by Synopsys QuantumATK tool. Total energy computation of 6280-atom Ge/GaAs supercell on (100)/6° leads to lower formation energy than (100)/2°, making it more thermodynamically stable. Hence, the growth of the GeSn/III-V material system using misoriented (100) substrates that are more thermodynamically stable will enhance the performances of optoelectronic devices.

Molecular Mechanism of the Piezoelectric Response in the β-Phase PVDF Crystals Interpreted by Periodic Boundary Conditions DFT Calculations.

A theoretical approach based on Periodic Boundary Conditions (PBC) and a Linear Combination of Atomic Orbitals (LCAO) in the framework of the density functional theory (DFT) is used to investigate the molecular mechanism that rules the piezoelectric behavior of poly(vinylidene fluoride) (PVDF) polymer in the crystalline β-phase. We present several computational tests highlighting the peculiar electrostatic potential energy landscape the polymer chains feel when they change their orientation by a rigid rotation in the lattice cell. We demonstrate that a rotation of the permanent dipole through chain rotation has a rather low energy cost and leads to a lattice relaxation. This justifies the macroscopic strain observed when the material is subjected to an electric field. Moreover, we investigate the effect on the molecular geometry of the expansion of the lattice parameters in the (a, b) plane, proving that the rotation of the dipole can take place spontaneously under mechanical deformation. By band deconvolution of the IR and Raman spectra of a PVDF film with a high content of β-phase, we provide the experimental phonon wavenumbers and relative band intensities, which we compare against the predictions from DFT calculations. This analysis shows the reliability of the LCAO approach, as implemented in the CRYSTAL software, for calculating the vibrational spectra. Finally, we investigate how the IR/Raman spectra evolve as a function of inter-chain distance, moving towards the isolated chain limit and to the limit of a single crystal slab. The results show the relevance of the inter-molecular interactions on the vibrational dynamics and on the electro-optical features ruling the intensity pattern of the vibrational spectra.

Nickel Slag/Laterite Soil and Nickel Slag/Iron Sand Nanocomposites: Structural, Optical, and Electromagnetic Absorption Properties.

Efforts to produce microwave absorber materials that are inexpensive and environmentally friendly have become a means of greening the environment. The breakthrough can be focused on industrial waste and natural materials for functional purposes and how to enhance their performance. We successfully synthesized nickel slag/laterite soil (NS/LS) and nickel slag/iron sand (NS/IS) nanocomposites using a simple mechanical alloying technique, and the electromagnetic (EM) wave absorption capacities of the nanocomposites were measured using a vector network analyzer. The structural properties of the nanocomposites were analyzed by X-ray diffraction spectroscopy, where the results of the analysis showed that NS/IS has the largest crystallite size (15.69 nm) and the highest EM wave absorption performance. The optical properties of the nanocomposites were determined from their Fourier transform infrared spectra using the Kramers-Kronig relation. As determined through a quantitative analysis of the optical properties, the distance between the longitudinal and transversal optical phonon wavenumber positions (Δ(LO - TO) = 65 cm-1) is inversely proportional to the reflection loss. The surface morphologies of the nanocomposites were analyzed by scanning electron microscopy, and the particle diameters were observed by binary image and Gaussian distribution analyses. The nanocomposite surface exhibits a graded-like morphology, which indicates multiple reflections of the EM radiation, consequently reducing the EM interference. The best nanocomposite for an attenuated EM wave achieved a reflection loss of -39.14 dB at 5-8 GHz. A low penetration depth has implications for the electrical charge tuning of the storage and composite magnets. Finally, the EM absorption properties of NS/IS and NS/LS indicate a 2-mm-thick environmentally friendly nanocomposite for EM absorption.

Lattice vibrational modes in changchengite from Raman spectroscopy and first principles electronic structure

AbstractWe measured room‐temperature phonon Raman spectra of changchengite (IrBiS) and compared the experimental phonon wavenumbers to the theoretical ones obtained by means of the ab initio density‐functional‐theory calculations in the presence and absence of the spin‐orbit coupling effects. Combining two different excitation photon energies all the symmetry predicted Raman modes are experimentally observed. The electronic properties of IrBiS are found to be similar to the recently studied isostructural compound IrBiSe showing a large Dresselhaus spin‐orbit valence band splitting. A good agreement between the experimental and theoretically predicted Raman phonon wavenumbers is found only when the lattice parameter is constrained to the experimental value. The inclusion of the spin orbit coupling does not significantly affect the phonon wavenumbers.

Order-disorder phase transition and molecular dynamics in the hybrid perovskite [(CH3)3NH][Mn(N3)3

We present a temperature-dependent Raman scattering study of a [(CH3)3NH][Mn(N3)3] hybrid organic–inorganic azide-perovskite, in which we have analysed in detail the wavenumber and full width at half-maximum (FWHM) of lattice modes and internal modes of the NC3 skeleton, N3– and CH3 molecular groups. In general, the modes exhibited unusual behaviour during the phase transitions, including discontinuity in the phonon wavenumber, bandwidth, and unconventional shifts upon temperature variation. Spectral features on heating reveal the absence of significant distortions in the NC3 skeleton and a relatively restricted order–disorder process of the TrMA+ cations. On the other hand, linewidth anomalies of the δNC3 and νasNC3 modes have been attributed to the molecular dynamics of encapsulated cations. The unconventional blue shift of the symmetric stretching modes of azide ligands indicates the weakening of the intermolecular interactions between the TrMA+ cations and azido-bridges, and the strengthening of the intramolecular bonds. Additionally, we have used differential scanning calorimetry to confirm the subtle monoclinic to monoclinic (P21/c → C2/c) phase transition at around 330 K; and the phase transition to trigonal structure (R3¯m) above 359 K, whose associated entropy variation turns to be |ΔS| ∼ 22.3 J·kg−1 K−1 and displays a barocaloric (BC) tunability |δTt/δP| ∼ 3.17 K kbar−1, according to our estimations using the Clausius-Clapeyron method. Although the obtained values of entropy change and BC tunability are very close to those reported on formate-perovskites and other important caloric materials, those parameters are much lower than the giant entropy change of ∼80 Jkg−1 K−1 and large BC tunability ∼12 K kbar−1 observed for the analogue azide-perovskite [(CH3)4N][Mn(N3)]3 (TMAMnN3). Very interestingly, our combined study shed light to understand such different behaviour, as they reveal that the hydrogen bonds created between the TrMA+ cations and the framework prevent an extensive order–disorder process that is needed to obtain large entropy changes and large BC coefficients as it occurs in the case of related azide-perovskites with no H-bonds between the A cations (for example TMA) and the framework.

Lattice dynamics and Raman spectrum of supertetragonal PbVO3

Lead vanadate PbVO3 is a polar crystal with a P4mm space group under ambient conditions. PbVO3 is isostructural with the model soft mode-driven ferroelectric PbTiO3, but it differs due to the so-called “supertetragonal” elongation of its unit cell. In this study, we investigated the lattice dynamics of PbVO3 based on Raman spectroscopy at room temperature and first-principle calculations. All zone-center transverse optical phonon modes were identified by polarized, angle-dependent Raman spectroscopy and assigned as follows: E modes at 136, 269, 374, and 508 cm−1; A1 modes at 188, 429, and 874 cm−1, and B1 mode at 319 cm−1. The calculations confirmed the experimental symmetry assignment and allowed us to obtain the longitudinal optical phonon wavenumbers. In addition, we analyzed the mode eigenvectors in detail in order to identify the atomic displacements associated with each mode and compare them with PbTiO3. Despite differences in chemistry and strain, the phonon eigenvectors were found to be highly comparable in both compounds. We investigated the position of the ferroelectric soft mode in PbVO3 compared with PbTiO3. Sizeable splitting of the B1+E modes appeared as a characteristic feature of supertetragonal phases. The peculiarity of the vanadyl V–O bond frequency in PbVO3 was also addressed.

Raman activity of the longitudinal optical phonons of the LiNbO3 crystal: Experimental determination and quantum mechanical simulation

AbstractIn this study, the and the two equivalent / polarized Raman spectra of a LiNbO3 single crystal have been recorded and used as a benchmark test for the density functional theory (DFT) calculation of the longitudinal modes and of their Raman activity. The theoretical approach, based on periodic boundary conditions and a linear combination of atomic orbitals (LCAO), provides excellent predictions of phonon wavenumbers and relative bands intensities for both A1 and E Longitudinal Optical (LO) modes and complements a previous paper limited to the study of Transverse Optical (TO) modes. Overall, the present investigation demonstrates that the LCAO approach, as implemented in the CRYSTAL software, gives results of similar accuracy for the TO and the LO phonons features. By means of a band deconvolution scheme applied to the experimental spectra, we present, for the first time, a quantitative comparison between experimental and theoretically predicted polarized Raman band intensities of LiNbO3 LO modes. This analysis highlights the role of the suitable determination of the static and high‐frequency dielectric matrices that are needed for the prediction of the TO/LO frequency split but also the first nonlinear electric susceptibility tensor for an accurate description of the Raman intensity pattern.

Flexomagnetic effects on inhomogeneously strained multiferroics composites

Herein, the origin of flexomagnetic effect in Pb[(Zr0.52Ti0.48)0.60(Fe0.67W0.33)0.40]O3]0.80-[CoFe2O4]0.20 (PZTFW–CFO) multiferroic composite is demonstrated. An external inhomogeneous strain on thick composite films significantly changes the crystal lattice constants and phonon wave numbers related to single-phase PZTFW and CFO ceramics. Surface morphology indicates that inhomogeneous strain modified the magnetic dipole moments that partly regain their original position after removing external inhomogeneous strain. The magnitude of magnetic susceptibility increased under inhomogeneous strain for a small probe of the magnetic field. The magnetic anisotropic energy (MAE) supports that under-applied inhomogeneous strain reduces surface spin disorders and is responsible for the enhancement of zero field cooled (ZFC) and field cooled (FC) magnetization. Under a high external magnetic field (>100 Oe), it would be hard to detect the weak flexomagnetic effects. This work provides a framework for the effect of macroscopic inhomogeneous strain gradient on magnetic moments in multiferroics composites suggesting its suitability for the sensors and actuators applications.

Laser‐induced phonon and magnon properties of NiO nanoparticles: A Raman study

AbstractIn the present study, the influence of laser intensity on phonon and magnon properties of nickel oxide (NiO) nanoparticles were extensively studied using room temperature Raman spectroscopy. The required NiO nanoparticles were synthesized using a simple sol–gel method. The structural and morphological properties were characterized using powder X‐ray diffraction (XRD), field emission scanning electron microscopy (FE‐SEM), and transmission electron microscopy (TEM) techniques. The rarely reported surface optical (SO) phonon modes of NiO nanoparticles were observed and well‐studied using the dielectric continuum (DC) model. A mismatch between the experimental and DC model SO phonon wavenumbers were observed and is attributed to one magnon‐induced first order phonon shift. The difference between the experimental and DC model SO phonon wavenumbers were reduced with increase in laser power, which indicates the diminishing behavior of magnon excitations. The laser power dependency of highly distinguishable two magnon (2 M) excitation of NiO nanoparticles were well studied. The 2 M modes were experienced a red shift and decrease in intensity with increase in laser power.

Ternary CdS1–xSexnanocrystals formed in Cd‐doped As–Se–S films due to photoenhanced diffusion during micro‐Raman measurement

AbstractMicro‐Raman spectra of amorphous As–Se–S:Cd films prepared by thermal evaporation on silicon and silicate glass substrates measured at different laser power densities show the formation of CdS1–xSexnanocrystals in the As–Se–S:Cd film under laser beam illumination due to a photoinduced material transfer and photoenhanced diffusion in the laser spot area. The material transfer and the photoenhanced diffusion are caused by a non‐thermal interaction of light with the amorphous As–Se–S:Cd films. The chemical composition of the CdS1–xSexnanocrystals can be determined from the difference of the CdSe‐like and CdS‐like LO phonon wavenumbers in the Raman spectra. The photoluminescence peak energies are in agreement with the CdS1–xSexcomposition, with the average nanocrystal size being somewhat above the exciton Bohr radius.

Raman spectrum of layered tilkerodeite (Pd2HgSe3) topological insulator: the palladium analogue of jacutingaite (Pt2HgSe3)

The layered mineral tilkerodeite (Pd2HgSe3), the palladium analogue of jacutingaite (Pt2HgSe3), is a promising quantum spin hall insulator for low-power nanospintronics. In this context, a fast and reliable assessment of its structure is key for exploring fundamental properties and architecture of new Pd2HgSe3-based devices. Here, we investigate the first-order Raman spectrum in high-quality, single-crystal bulk tilkerodeite, and analyze the wavenumber relation to its isostructural jacutingaite analogue. By using polarized Raman spectroscopy, symmetry analysis, and first-principles calculations, we assigned all the Raman-active phonons in tilkerodeite, unveiling their wavenumbers, atomic displacement patterns, and symmetries. Our calculations used several exchange–correlation functionals within the density functional perturbation theory framework, reproducing both structure and Raman-active phonon wavenumbers in excellent agreement with experiments. Also, it was found that the influence of the spin–orbit coupling can be neglected in the study of these properties. Finally, we compared the wavenumber and atomic displacement patterns of corresponding Raman-active modes in tilkerodeite and jacutingaite, and found that the effect of the Pd and Pt masses can be neglected on reasoning their wavenumber differences. From this analysis, tilkerodeite is found to be mechanically weaker than jacutingaite against the atomic displacement patterns of these modes. Our findings advance the understanding of the structural properties of a recently discovered layered topological insulator, fundamental to further exploring its electronic, optical, thermal, and mechanical properties, and for device fabrication.

Raman Spectroscopy Studies on the Barocaloric Hybrid Perovskite [(CH3)4N][Cd(N3)3

Temperature-dependent Raman scattering and differential scanning calorimetry were applied to the study of the hybrid organic-inorganic azide-perovskite [(CH3)4N][Cd(N3)3], a compound with multiple structural phase transitions as a function of temperature. A significant entropy variation was observed associated to such phase transitions, |∆S| ~ 62.09 J·kg−1 K−1, together with both a positive high barocaloric (BC) coefficient |δTt/δP| ~ 12.39 K kbar−1 and an inverse barocaloric (BC) coefficient |δTt/δP| ~ −6.52 kbar−1, features that render this compound interesting for barocaloric applications. As for the obtained Raman spectra, they revealed that molecular vibrations associated to the NC4, N3– and CH3 molecular groups exhibit clear anomalies during the phase transitions, which include splits and discontinuity in the phonon wavenumber and lifetime. Furthermore, variation of the TMA+ and N3– modes with temperature revealed that while some modes follow the conventional red shift upon heating, others exhibit an unconventional blue shift, a result which was related to the weakening of the intermolecular interactions between the TMA (tetramethylammonium) cations and the azide ligands and the concomitant strengthening of the intramolecular bondings. Therefore, these studies show that Raman spectroscopy is a powerful tool to gain information about phase transitions, structures and intermolecular interactions between the A-cation and the framework, even in complex hybrid organic-inorganic perovskites with highly disordered phases.

Structure and vibrational spectra of ReSe2 nanoplates

AbstractTheoretical and experimental vibrational spectra of ReSe2 nanocrystals, synthesized by self‐limited chemical vapor deposition (CVD), are reported. Scanning electron microscopy reveals that the nanocrystals have the shape of polygon nanoplates (NPs), 20 nm thick and about 100–300 nm wide. X‐ray diffraction studies determined their triclinic structure (space group, P‐1 [no. 2]). The wavenumbers of the Raman‐ and infrared (IR)‐active phonon modes were calculated using the density functional perturbation theory (DFPT), along with the dispersion curves and phonon density of states. The set of theoretical phonon wavenumbers is found to correlate well with the experimental Raman and IR spectra. We established that, unlike ReS2, ReSe2 does not exhibit a “phonon gap.” Several “extra” bands in the experimental Raman spectrum of ReSe2 are argued to be defect‐induced contributions of phonons from F and Q critical points of the Brillouin zone. In addition, the effect of Fermi resonance is observed in the Raman spectrum of the ReSe2 NPs, which manifests itself in an increase of the intensity of second‐order bands due to their interaction with first‐order phonons.

New insights on the structural and optical-vibration properties of noncentrosymmetric lanthanides pyrogermanates

A complete series of noncentrosymmetric Ln2Ge2O7 materials (Ln = lanthanides) were obtained by the molten-salts processing route. Triclinic (P1 space group) as well as tetragonal (P41212 space group) structures were observed, respectively, for the La–Eu compounds (larger ions) and for the Gd–Lu ones (smaller ions). The optical-vibration properties of both groups of samples were well investigated by Raman spectroscopy besides group-theory calculations. All the predicted phonon modes were discerned for the triclinic polar phase, while the most significant phonon modes of the tetragonal phase were determined. Beside the well-known classical dependence of the phonon wavenumbers with the ionic radii of the lanthanide (hardening of the higher-frequency modes from La to Lu), it was observed an opposite softening of the low-frequency modes within the triclinic phase (La–Eu samples). This result could be related to the contribution of the increasing lanthanide masses, added to the high lattice anharmonicity near the phase boundary between the triclinic and tetragonal phases, which can be a consequence of the strong changes in the coordination numbers of the Ln-polyhedra. Once the polar triclinic phase and the noncentrosymmetric tetragonal structure are thermally stable, and owing to the low-temperature magnetic features already shown by of non-cubic Ln2Ge2O7 compounds, we believe that some of these materials could present magnetoelectric or related properties.

Superior stiffness and vibrational spectroscopic signature of two-dimensional diamond-like carbon nitrides

Abstract Carbon nitride materials are promising for applications in electronics, clean energy production, and heat dissipation. Two-dimensional (2D) diamond-like carbon nitrides α -C 2 N 2 , β -C 2 N 2 , and γ -C 4 N 4 rise as beyond graphene semiconductors. Here, we apply first-principles calculations and group theory to study their structure, mechanical properties, and vibrational signature. The α -C 2 N 2 is the strongest among them, with a 2D Young’s modulus E 2D equal to 616(6) N/m, followed by the γ -C 4 N 4 with an E 2D equal to 632(6) N/m and 581(7) N/m along its zigzag and armchair directions, respectively, and the β -C 2 N 2 with an E 2D equal to 582(9) N/m. These materials are about 2 times stiffer than graphene, and are the stiffest among 2D networks of carbon and nitrogen atoms. The zigzag direction of 2D γ -C 4 N 4 is approximately 8% stronger than its armchair direction, unusual for in-plane anisotropic 2D materials, where the armchair direction is considerably weaker than the zigzag direction. These findings from stress–strain analysis are consistent with the high sound speed and elastic constants values we found by using 2D density-functional perturbation theory framework, suggesting them for mechanical reinforcement. We report the phonon wavenumber, atomic vibrational pattern, and Raman and infrared spectra for all polytypes. The longitudinal and transverse optical modes of the in-plane isotropic polytypes display the breakdown of LO–TO splitting, characteristic of 2D polar crystals. We found that the difference between their phonon wavenumbers can be probed in their unpolarized Raman and infrared spectra. The simulated angular dependency of the Raman intensity under backscattering parallel and cross polarizations show how to assign the A 1 ′ and E ′ modes of the α -C 2 N 2 , the A 1 g and E g modes of the β -C 2 N 2 , and of the A g and B 1 g modes of the γ -C 4 N 4 , being key for polytype identification. These results provide comprehensive information on the emerging 2D diamond-like carbon nitrides, necessary for further developments on their synthesis, characterization, and future device fabrication.

Acoustoelectric Effect in Fluorinated Carbon Nanotube in the Absence of External Electric Field

Acoustoelectric effect (AE) in a non-degenerate Fluorine modified single walled carbon nanotube (FSWCNT) semiconductor is studied theoretically using the Boltzmann’s transport equation. The study is done in the hypersound regime i.e. , where q is the acoustic phonon wavenumber and is the electron mean free path. The results obtained are compared with that of undoped single walled carbon nanotube (SWCNT). The AE current density for FSWCNT is observed to be four orders of magnitude smaller than that of undoped SWCNT with increasing temperature, that is . This is because the electron-phonon interactions in SWCNT are stronger than FSWCNT. Thus, there are more intra-mini-band electrons interacting with the acoustic phonons to generate a higher AE current in SWCNT than in FSWCNT. This has been observed experimentally, where the electrical resistance of FSWCNT is higher than pristine SWCNT i.e. . The study shows the potential for FSWCNT as an ultrasound current source density imaging (UCSDI) and AE hydrophone material. However, FSWCNT offers the potential for room temperature applications of acoustoelectric device but other techniques are needed to reduce the resistance.

Raman spectrum of layered jacutingaite (Pt2HgSe3) crystals—Experimental and theoretical study

AbstractJacutingaite (Pt2HgSe3) is a recently discovered layered platinum‐group mineral. Recent experimental studies have shown that it displays the properties of a quantum spin Hall insulator (QSHI), and theoretical studies indicate that its two‐dimensional monolayer is a QSHI with a robust topological gap of ∼0.5 eV. Jacutingaite is thus promising for potential applications to nanoelectronics and spintronics. The Raman spectrum of three‐dimensional bulk jacutingaite and the symmetries of its vibrational modes, fundamental for understanding structural modifications of this material, are still unexplored. Here, we address the zone‐center Raman optical phonons of bulk jacutingaite by experiments, symmetry, and first‐principles calculations. The improved synthesis used here provided crystals of higher purity and of micrometer size, allowing the study of single crystals. Polarized Raman spectroscopy was used to assign the symmetries of nine out of the 11 Raman‐active modes expected by group theory and their respective selection rules. The calculated wavenumbers of the Raman‐active modes, in addition to their atomic displacements, are in very good agreement with experiments. In addition, we discuss the use of different exchange correlation functionals within density functional theory, as local functionals and nonlocal functionals that best describe van der Waals interactions. The influence of the inclusion of spin–orbit coupling on calculated vibrational phonon wavenumbers and lattice parameters is commented, and it was found that the local density approximation provides a good description. Our results are of paramount importance to further exploitation of the effects of jacutingaite's structural modifications to tune its properties, as well as for its structural, optical, electronic, mechanical, and thermal applications.

Temperature dependent X‐ray diffraction and Raman spectroscopy studies of polycrystalline YCrO3 ceramics across the TC ~ 460 K

AbstractIn this paper, we report the X‐ray diffraction studies over the temperature range of 300–900 K and subsequent Rietveld refinement of the diffraction patterns shows that there is no evidence of any structural phase transition in YCrO3 (YCO) across the paraelectric to ferroelectric phase transitions (TC ~ 460 K), and the material retains the orthorhombic structure with Pnma space group. However, a detailed analysis reveals local distortions in the CrO6 octahedra. To probe the local structural distortion, we have carried out temperature‐dependent, unpolarized Raman measurements, from 300 to 600 K. YCrO3 shows a strong anomalous deviation in both phonon wavenumbers and line widths around TC. YCrO3 is reported to possess as an incipient ferroelectric material to show that there are two competing phenomenon—onset of ferroelectricity due to rotation of CrO6 octahedra and displacement of Y atom leading to suppression of ferroelectricity. This competition reveals that although the octahedral rotations favor a lower symmetry state, the Y atom displacement opposes it leaving YCO to exhibit only an incipient ferroelectric state. These results while being in agreement with the earlier theoretical predictions can also help suggest a pathway to a more stable ferroelectric state in these oxides by using a larger cationic substitution at the Y site.

Efficient ab initio quantum mechanical simulations of structural stability and vibrational properties of bulk, monolayer and (n,0) nanotubes: Yttrium sesquioxide Y2O3

AbstractIn this contribution, we report reliable ab initio quantum mechanical simulations of a variety of physical properties concerning yttrium sesquioxide (Y2O3) in different arrangements from the bulk, the monolayer (h‐Y2O3), to the (n,0) single‐walled nanotubes in the range from n = 6 to 32, for geometry optimization and vibrational properties. Structural parameters, phonon wavenumbers, infrared (IR) and Raman intensities, and elastic constants are computed via density functional theory (DFT/B3LYP) where the trend towards the (h‐Y2O3) monolayer for large nanotube radius is discussed. We firstly report combined experimental and computational studies on the structural and vibrational properties of the bulk Y2O3. Then, IR and Raman spectra of all arrangements are simulated via the coupled perturbed Hartree–Fock and Kohn–Sham (CPHF/KS) computational schemes. For the (n,0) Y2O3 nanotube family, two sets of IR active phonon modes in the (200–400 cm−1) and (600–900 cm−1) ranges are determined. Both of them tend smoothly with different slope, towards the optical vibrational modes of the h‐Y2O3 single layer. Three sets of active phonon bands are obtained in their Raman spectrum. The first one, in the 0–100 cm−1 range contains two phonon modes, their vibration wavenumbers tend to zero at very large tube radius and are found to be connected to the elastic constants C11 and C66 of the h‐Y2O3 monolayer as the 1D → 2D transition is approached. The second one, in 200–400 cm−1 range tends to the optical mode E′ (ν = 308 cm−1) of the monolayer. The third set, in the 600–900 cm−1 range contains two active modes, their intensities tend to zero in the limit of large nanotube without change in their vibration wavenumbers.

Temperature dependence of the double‐resonance Raman bands in monolayer MoS2

AbstractThis work reports a detailed study of the double‐resonance (DR) Raman bands of single‐layer MoS2 as a function of temperature, using many different laser energies in the region of the excitonic transitions and at different temperatures between 80 and 300 K. Our measurements show that the DR bands are strongly affected by temperature and the results are explained in terms of the temperature dependence of both the phonon wavenumber and the excitonic energy. In order to distinguish these two effects, the excitonic transitions were directly measured by photoluminescence as a function of temperature. It was observed from the multiple‐excitation results that the dispersion of the DR bands measured with different laser lines depends on temperature. The resonance condition was evidenced by considering the difference between energies of the laser excitation and the excitonic transition, at a given temperature. Our findings for the temperature dependence of the DR process in single‐layer MoS2 can be extended to other classes of transition metal dichalcogenide materials.