Phonon Confinement Research Articles

Phonon Polaritonics in Two-Dimensional Materials.

Extreme confinement of electromagnetic energy by phonon polaritons holds the promise of strong and new forms of control over the dynamics of matter. To bring such control to the atomic-scale limit, it is important to consider phonon polaritons in two-dimensional (2D) systems. Recent studies have pointed out that in 2D, splitting between longitudinal and transverse optical (LO and TO) phonons is absent at the Γ point, even for polar materials. Does this lack of LO-TO splitting imply the absence of a phonon polariton in polar monolayers? To answer this, we connect the microscopic phonon properties with the macroscopic electromagnetic response. Specifically, we derive a first-principles expression for the conductivity of a polar monolayer specified by the wave-vector-dependent LO and TO phonon dispersions. In the long-wavelength (local) limit, we find a universal form for the conductivity in terms of the LO phonon frequency at the Γ point, its lifetime, and the group velocity of the LO phonon. Our analysis reveals that the phonon polariton of 2D is simply the LO phonon of the 2D system. For the specific example of hexagonal boron nitride (hBN), we estimate the confinement and propagation losses of the LO phonons, finding that high confinement and reasonable propagation quality factors coincide in regions that may be difficult to detect with current near-field optical microscopy techniques. Finally, we study the interaction of external emitters with 2D hBN nanostructures, finding an extreme enhancement of spontaneous emission due to coupling with localized 2D phonon polaritons and the possibility of multimode strong and ultrastrong coupling between an external emitter and hBN phonons. This may lead to the design of new hybrid states of electrons and phonons based on strong coupling.

Inhomogeneous crystallization of a‐Si thin films irradiated by femtosecond laser

AbstractRecently, we have carried out a detailed Raman analysis to investigate the inhomogeneous crystallization of a‐Si thin films irradiated by femtosecond (Fs) laser. As expected, there are many etched spots overlapping each other, which features the surface morphology of the irradiated films. It is observed clearly that there has generated an inhomogeneous crystallization inside a‐Si thin film induced by Fs laser, and the crystalline volume fraction in one irradiated spot varies depending on different areas from the center to the edge. It is hard to observe any crystallization at the spot center where maximum energy of Fs laser is injected; however, there is an increasing crystalline volume fraction when the site varies from the center to the edge of the irradiated spot. More importantly, as the site varies from the center to the edge, the TO mode of Si nanocrystals (NCs; first‐order Si–Si peak at ~520.5 cm−1) is asymmetrically broadened towards the low wavenumber and exhibits a dip on the high wavenumber. A model has been proposed to explain this inhomogeneous crystallization inside the a‐Si thin films induced by Fs laser, and both phonon confinement model and Fano model have been employed to discuss the origin of asymmetric line shapes of TO mode of Si NCs, and we prefer to attribute the asymmetry of TO mode to Fano effect. Our present research results provide a deep insight into the origin of asymmetric broadening for the Raman TO mode of Si NCs inside a‐Si thin films irradiated by Fs laser.

Crystallization of Amorphous Germanium Films and Multilayer a-Ge/a-Si Structures upon Exposure to Nanosecond Laser Radiation

The processes of the crystallization of amorphous germanium films and multilayer germanium/silicon structures upon exposure to nanosecond (70 ns) ruby laser radiation (λ = 694 nm) are studied. The samples are grown on silicon and glassy substrates by plasma-enhanced chemical vapor deposition. Pulsed laser annealing of the samples is conducted in the range of pulse energy densities Ep from 0.07 to 0.8 J cm–2. The structure of the films after annealing is determined by analyzing the scanning electron microscopy data and Raman spectra. It is established that, after annealing, the films are completely crystallized and, in this case, contain regions of coarse crystalline grains (>100 nm), whose fraction increases, as Ep is increased, and reaches 40% of the area. From analysis of the position of the Raman peaks, it is conceived that the crystalline grains, whose dimensions exceed 100 nm, either contain structural defects or stretching strains. The correlation length of optical vibrations is determined from the phonon confinement model and found to increase from 5 to 8 nm, as Ep is increased. Pulsed laser annealing of multilayer Ge(10 nm)/Si(5 nm) structures induces partial intermixing of the layers with the formation of Ge–Si alloys.

High thermoelectric figure of merit and thermopower in layered perovskite oxides

We predict high thermoelectric efficiency in the layered perovskite La$_2$Ti$_2$O$_7$, based on calculations (mostly ab-initio) of the electronic structure, transport coefficients, and thermal conductivity in a wide temperature range. The figure of merit $ZT$ computed with a temperature-dependent relaxation time increases monotonically from just above 1 at room temperature to over 2.5 at 1200 K, at an optimal carrier density of around 10$^{20}$ cm$^{-3}$. The Seebeck thermopower coefficient is between 200 and 300 $\mu$V/K at optimal doping, but can reach nearly 1 mV/K at low doping. Much of the potential of this material is due to its lattice thermal conductivity of order 1 W/(K m); using a model based on ab initio anharmonic calculations, we interpret this low value as due to effective phonon confinement within the layered-structure blocks.

Experimental observation of electron-phonon coupling enhancement in Sn nanowires caused by phonon confinement effects

Reducing the size of a superconductor below its characteristic length scales can either enhance or suppress its critical temperature (${T}_{c}$). Depending on the bulk value of the electron-phonon coupling strength, electronic and phonon confinement effects will play different roles in the modification of ${T}_{c}$. Experimentally disentangling each contribution has remained a challenge. We have measured both the phonon density of states and ${T}_{c}$ of Sn nanowires with diameters of 18, 35, and 100 nm in order to quantify the effects of phonon confinement on superconductivity. We observe a shift of the phonon frequency towards the low-energy region and an increase in the electron-phonon coupling constant that can account for the measured increase in ${T}_{c}$.

Phonon confinement and size effect in Raman spectra of ZnO nanoparticles

We study Raman spectra of ZnO nanoparticles of 5–12 nm size in the whole range of the first-order phonon bands. We apply the 3D phonon confinement model (PCM) for the interpretation of the observed Raman spectra. It is found that PCM is well applicable to the acoustic modes as well as to the optical ones, despite the fact that PCM has been thought not to be suitable for acoustic phonons. We show that the asymptotic behavior of PCM for the small-size limit is more consistent with the observation than that of the elastic sphere model (ESM). Furthermore, PCM gives detailed information on the complex size-dependent shapes of the phonon bands.

Coupled elastic membranes model for quantum heat transport in semiconductor nanowires

Presented here is a nanowire model, consisting of coupled elastic membranes with the purpose of investigating thermal transport in quasi-one-dimensional quantum systems. The vibrations of each elastic membrane are quantized and the flow of the vibrational energy between adjacent membranes is allowed. The ends of the nanowire are attached to thermal baths held at different temperatures. We derived quantum master equation for energy flow across the nanowire and obtained thermal currents and other key observables. We study the effects of a disordered boundary on the thermal current by randomizing the membrane radii. We evaluate the model as a nanowire analogue as well as study the effects of a disordered boundary on thermal conductivity. The calculations show that the membrane lattice model demonstrates diameter phonon confinement and a severe reduction in thermal conductivity due to surface roughness which is characteristic of semiconductor nanowires. The surface roughness also produces a length dependence of the thermal conductivity of the form $\kappa=\alpha L^{\beta}$, with $\beta$ dependent on disorder characteristics, in the otherwise ballistic regime. Finally, the parameters of the model are fitted to available experimental data for silicon nanowires and the results of the calculations are assessed against the experimental data.

Dual morphology titanium dioxide for dye sensitized solar cells

Anatase TiO2 displaying dual morphologies were synthesized with a simple chemical route via a single step. A strong correlation between the dye sensitized solar cell (DSSC) device performance and the obtained dual morphologies are highlighted using relevant evidences from UV–vis and diffuse reflectance spectroscopy (DRS), Raman analysis, field emission scanning electron microscope, high resolution transmission electron microscope, current-voltage characteristics and impedance analysis. Structural investigation revealed that the interested medium in this work employed for the synthesis of TiO2 produced different types of dual morphologies such as nanospheres with nanoparticles (NSNP), microsphere decorated with nanoparticles (μSNP) and nanoparticles with stone like features (NPS). UV–vis and DRS results indicated the ability of the materials to assist with diffused reflectance and optical absorption of the screen printed photoanodes. In addition, an investigation of Raman vibrational characteristics was carried out in detail using synchronous and asynchronous 2D correlation analysis. The high intense Eg anatase mode of Raman spectrum was simulated using a phonon confinement model and its normalized spectra are compared with an experimental data. The resultant performances in the DSSCs were not indicative by the material properties; so, the charge transfer resistance (Rct) and recombination properties of the photoanode were investigated. These results showed that the Nyquist plot of NSNP possesses the smallest diameter, which reveals that the device based on NSNP offers the lowest Rct value that accounts for the higher conversion efficiencies when compared with the DSSC device based on photoanodes μSNP and NSP. It can be concluded that the improved power conversion efficiency shown by photoanode fabricated using NSNP has the dual role of optimum surface area for dye loading and light scattering centres. These properties, when optimized along with the offered pathway for electrolyte diffusion to the dye degeneration with less Rct, could lead to better photoelectric conversion efficiency.

Phonon confinement and spin-phonon coupling in tensile-strained ultrathin EuO films.

Reducing the material sizes to the nanometer length scale leads to drastic modifications of the propagating lattice excitations (phonons) and their interactions with electrons and magnons. In EuO, a promising material for spintronic applications in which a giant spin-phonon interaction is present, this might imply a reduction of the degree of spin polarization in thin films. Therefore, a comprehensive investigation of the lattice dynamics and spin-phonon interaction in EuO films is necessary for practical applications. We report a systematic lattice dynamics study of ultrathin EuO(001) films using nuclear inelastic scattering on the Mössbauer-active isotope 151Eu and first-principles theory. The films were epitaxially grown on YAlO3(110), which induces a tensile strain of ca. 2%. By reducing the EuO layer thickness from 8 nm to a sub-monolayer coverage, the Eu-partial phonon density of states (PDOS) reveals a gradual enhancement of the number of low-energy phonon states and simultaneous broadening and suppression of the peaks. These deviations from bulk features lead to significant anomalies in the vibrational thermodynamic and elastic properties calculated from the PDOS. The experimental results, supported by first-principles theory, unveil a reduction of the strength of the spin-phonon interaction in the tensile-strained EuO by a factor of four compared to a strain-free lattice.

Кристаллизация плeнок аморфного германия и многослойных структур a-Ge/a-Si под действием наносекундного лазерного излучения

AbstractThe processes of the crystallization of amorphous germanium films and multilayer germanium/silicon structures upon exposure to nanosecond (70 ns) ruby laser radiation (λ = 694 nm) are studied. The samples are grown on silicon and glassy substrates by plasma-enhanced chemical vapor deposition. Pulsed laser annealing of the samples is conducted in the range of pulse energy densities E _ p from 0.07 to 0.8 J cm^–2. The structure of the films after annealing is determined by analyzing the scanning electron microscopy data and Raman spectra. It is established that, after annealing, the films are completely crystallized and, in this case, contain regions of coarse crystalline grains (>100 nm), whose fraction increases, as E _ p is increased, and reaches 40% of the area. From analysis of the position of the Raman peaks, it is conceived that the crystalline grains, whose dimensions exceed 100 nm, either contain structural defects or stretching strains. The correlation length of optical vibrations is determined from the phonon confinement model and found to increase from 5 to 8 nm, as E _ p is increased. Pulsed laser annealing of multilayer Ge(10 nm)/Si(5 nm) structures induces partial intermixing of the layers with the formation of Ge–Si alloys.

Acoustic phonon confinement by band inversion

Abstract We study the formation of a topological interface mode between two nanometric acoustic superlattices presenting inverted band structures. That is, the two lattices share a common band gap but present opposite spatial mode symmetries of the two Bloch modes bounding the gap from below and above. We first show that by tuning the acoustic-thickness ratio between the two materials in a unit cell of a GaAs/AlAs superlattice a band structure inversion can be induced at the Brillouin zone center. Secondly, we show that two concatenated superlattices with inverted band structures form a topological interface mode with its strain spatially confined.

Resonance of terahertz phonons in an acoustic nanocavity

We show the resonant behavior of \ensuremath{\sim}0.5-THz longitudinal acoustic (LA) phonons in an acoustic nanocavity of thickness \ensuremath{\sim}28 nm sandwiched between two GaAs/AlAs superlattices (SLs). One of the SLs, upon excitation with an ultrafast optical pulse, acts as a source of coherent LA phonons. These phonons, generated outside the cavity, resonantly drive the cavity mode. The phonon dynamics can be modeled using a driven-damped harmonic oscillator. The confinement and enhancement of phonons in the acoustic nanocavity opens up possibilities in the field of nanophononics.

A study of 8 MeV e-beam on localized defect states in ZnO nanostructures and its role on photoluminescence and third harmonic generation

In this article we have explored an effect of electron beam irradiation (EBI) on physical and nonlinear optical properties ZnO thin nano films. Nanostructured ZnO thin films were grown by low cost spray pyrolysis technique. The irradiation dosage has been fixed at 5 kGy, 10kGY, 15 kGy and 20 kGy. The structural investigation by Glancing angle X-Ray Diffractometer (GAXRD) confirms a polycrystalline phase of ZnO with wurtzite structure. The variation in the surface morphology upon EBI has been demonstrated using 2D and 3D Atomic force microscopy (AFM) images. Nanoscope software analysis quantifies the variation in surface roughness and average particle height upon EBI. The defect states created in the films upon irradiation experiments were investigated using UV–visible spectrophotometer, Room temperature Photoluminescence (RTPL), Raman and X-ray photoelectron spectroscopy (XPS). The increase in urbach tail validates the creation of localized defect states in the films The Gaussian fitting on RTPL spectra shows the quenching in the luminescent centers upon irradiation arised as result of recombination of vacancy defects. Phonon confinement model fitting on Raman spectra endorses that shift in the phonon modes observed on irradiation is due to spatial confinement of phonons. The elemental composition and impurity states of the EBI ZnO thin films were studied using XPS spectra. The shift in the binding energy of Zn and O elements infers the electron beam induced changes in the films. The electron beam irradiation has resulted in the increment of third order optical susceptibility χ(3) 3.5 × 10−4 esu to 8.13 × 10−3 esu due to the enhancement of electronic transition to different defect levels formed in the films and through local heating effects arising due to continuous wave (CW) laser illumination. The enhanced THG signal investigated using Nd:YAG laser at 1064 nm and 8 ns pulse width shows the promising features of EBI ZnO films for frequency tripling applications.

Photocatalytic response of Fe, Co, Ni doped ZnO based diluted magnetic semiconductors for spintronics applications

Novel attempts were made to prepare diluted magnetic semiconductors separately with 10 at.% each of Fe, Co and Ni doped ZnO by sol-gel method. The XRD analysis of the films detect wurtzite ZnO as the pure phase present in the synthesized films. The average particle size of 10 at.% Fe, Co, Ni doped and pristine ZnO derived films are found as 10.01 nm, 12.03 nm, 15.36 nm and 16.16 nm respectively. The absorbance spectra of the oxides reveal intrinsic band gap of ZnO, Fe2O3, CoO and NiO are 3.29 eV, 2.53 eV, 2.42 eV and 3.64 eV respectively. The near band edge absorbance of pure ZnO was recorded as about 377 nm (∼3.29 eV) which shifts to lower wavelength with reduction in particle size in Ni, Co and Fe doped ZnO sample as the effect of quantum confinement. The PL spectra of the developed films reveal multiple peaks between 450 nm and 500 nm, on excitation wavelength at 370 nm, as the evidence of photochemical properties of the samples. Vibrating sample magnetometer analysis reveals 10 at.% Fe doped ZnO posses minimum value of squareness 0.118 and coersivity 177.738 Oe which prove it to be the best magnetic material among all four samples prepared. Raman spectra show evidence of phonon confinement for 10 at.% Fe doped ZnO sample by broadening of Eg, T2g and A1g peaks, which is not so prominent for other samples. In addition, the photochemical degradation reaction is maximum for 10 at.% Fe doped ZnO sample which proves to be most suitable material for optoelectronic devices.

Raman spectrum of nanocrystals: Phonon dispersion splitting and anisotropy

The effects of anisotropy and splitting of the phonon dispersions in the Raman spectrum of nanocrystals are investigated. We describe the different branches of the optical phonon dispersion curves along each high-symmetry direction by fitting a simple empirical model to experimental data. These curves are then used to calculate the Raman spectrum in the framework of the phonon confinement model and the results are compared with a wide range of available experimental data as well as with the spectra predicted by currently available models based on a single isotropic dispersion curve. We show that by considering the anisotropy and splitting of rigorously obtained optical phonon dispersions, the commonly observed deviations between experimental and theoretical data are strongly reduced. Our work enables the extraction of significantly more accurate information about relevant physical properties of nanocrystals from Raman spectroscopy.

Remote Phononic Effects in Epitaxial Ruddlesden-Popper Halide Perovskites.

Despite their weak nature, van der Waals (vdW) interactions have been shown to effectively control the optoelectronic and vibrational properties of layered materials. However, how vdW effects exist in Ruddlesden-Popper layered halide perovskites remains unclear. Here we reveal the role of interlayer vdW force in Ruddlesden-Popper perovskite in regulating phase-transition kinetics and carrier dynamics based on high-quality epitaxial single-crystalline (C4H9NH3)2PbI4 flakes with controlled dimensions. Both substrate-perovskite epitaxial interaction and interlayer vdW interaction play significant roles in suppressing the structural phase transition. With reducing flake thickness from ∼100 to ∼20 nm, electron-phonon coupling strength decreases by ∼30%, suggesting the ineffectiveness of phonon confinement of the natural quantum wells. Therefore, the conventional understanding that vdW perovskite is equivalent to a multiple quantum well has to be substantially amended due to significant nonlocal phononic effects in the layered crystal, where intralayer interaction is not drastically different from the interlayer force.

Size-Dependent Localized Phonon Population in Semiconducting Si Nanowires.

The optical phonons in semiconductor nanostructures play an indispensable role in fundamental phenomenon and device applications based on these nanostructures. We study the Raman spectroscopy of optical phonons in Si nanowires (NWs) whose sizes are beyond the phonon confinement regime. The peak shift and unusual asymmetric broadening by one-phonon mode in Si NWs is observed during far-field Raman studies. Using an appropriate thermal anchoring and localized Raman measurements on single NWs by near-field tip-enhanced Raman spectroscopy (TERS), we demonstrate the decoupling of multiple origins responsible for the peak shift accompanied by asymmetric broadening of the one-phonon mode and the appearance of multiple phonon peaks from a single measurement area. A model based on the localized phonon population induced by NW size-dependent charge depletion is proposed to explain the observed dependence of phonon characteristics on NW size. The scanning Kelvin probe force microscopy measurements confirm the size-dependent intrinsic semiconductor surface and interface states-induced charge depletions in single Si NWs. The study clearly suggests the size-dependent phonon characteristics of Si NWs which are crucial for several NW-based photovoltaic and thermoelectric devices.

Theoretical Investigation of the Shubnikov-de Haas Magnetoresistance Oscillations in a Quantum well under the Influence of Confined Acoustic Phonons

The Shubnikov – de Haas magnetoresistance oscillations in the Quantum well (QW) under the influence of confined acoustic phonons, The theoretical results show that the conductivity tensor, the complex magnetic impedance of the magnetic field, the frequency, the amplitude of the laser radiation, the QW width, the temperature of the system and especially the quantum index m characterizes the confinement of the phonon. The amplitude of the oscillations of the Shubnikov-de Haas impedance decreases with the increase of the influence of the confined acoustic phonons. The results for bulk phonons in a QW could be achieved, when m goes to zero. We has been compared with other studies when perform the numerical calculations are also achieved for the GaAs/AlGaAs in the QW. Results show that The Shubnikov-de Haas magnetoresistance oscillations amplitude decrease when phonon confinement effect increasing and when width L of the QW increases to a certain value, The Shubnikov – de Haas magnetoresistance oscillations amplitude completely disappears can not be observed.

Raman Spectra of Nonpolar Crystalline Nanoparticles: Elasticity Theory-like Approach for Optical Phonons

A simple way to investigate theoretically the Raman spectra (RS) of nonpolar nanoparticles is proposed. For this aim we substitute the original lattice optical phonon eigenproblem by the continuous Klein-Fock-Gordon-like equation with Dirichlet boundary conditions. This approach provides the basis for the continuous description of optical phonons in the same manner how the elasticity theory describes the longwavelength acoustic phonons. Together with continuous reformulation of the bond polarization model it allows to calculate the RS of nanoparticles without referring to their atomistic structure. It ensures the powerful tool for interpreting the experimental data, studying the effects of particle shape and their size distribution. We successfully fit recent experimental data on very small diamond and silicon particles, for which the commonly used phonon confinement model fails. The predictions of our theory are compared with recent results obtained within the dynamical matrix method - bond polarization model (DMM-BPM) approach and an excellent agreement between them is found. The advantages of the present theory are its simplicity and the rapidity of calculations. We analyze how the RS are affected by the nanoparticle faceting and propose a simple power law for Raman peak position dependence on the facets number. The method of powder RS calculations is formulated and the limitations on the accuracy of our analysis are discussed.

\u201cGreen\u201d Aqueous Synthesis and Advanced Spectral Characterization of Size-Selected Cu2ZnSnS4 Nanocrystal Inks

Structure, composition, and optical properties of colloidal mercaptoacetate-stabilized Cu2ZnSnS4 (CZTS) nanocrystal inks produced by a “green” method directly in aqueous solutions were characterized. A size-selective precipitation procedure using 2-propanol as a non-solvent allows separating a series of fractions of CZTS nanocrystals with an average size (bandgap) varying from 3 nm (1.72 eV) to 2 nm (2.04 eV). The size-selected CZTS nanocrystals revealed also phonon confinement, with the main phonon mode frequency varying by about 4 cm−1 between 2 nm and 3 nm NCs.