Phonon Confinement Research Articles

Sound and noisy light: Optical control of phonons in photoswitchable structures

We present a means of controlling phonons via optical tuning. Taking as a model an array of photoresponsive materials (photoswitches) embedded in a matrix, we numerically analyze the vibrational response of an array of bistable harmonic oscillators with stochastic spring constants. Changing the intensity of light incident on the lattice directly controls the composition of the lattice and therefore the speed of sound. Furthermore, modulation of the phonon band structure at high frequencies results in a strong confinement of phonons. The applications of this regime for phonon waveguides, vibrational energy storage, and phononic transistors is examined.

Mesoporosity in doped silicon nanowires from metal assisted chemical etching monitored by phonon scattering

Si nanowires (NWs) are shown to develop internal mesoporosity during metal assisted chemical etching from Si wafers. The onset of internal porosity in n+-Si(100) compared to p-Si(100) is examined through a systematic investigation of etching parameters (etching time, AgNO3 concentration, HF % and temperature). Electron microscopy and Raman scattering show that specific etching conditions reduce the size of the internal Si nanocrystallites in the internal mesoporous structure to 3–5 nm. Mesoporous NWs are found to have diameters as large as 500 nm, compared to ∼100 nm for p-NWs that develop surface roughness. Etching of Si (100) wafers results in (100)-oriented NWs forming a three-fold symmetrical surface texture, without internal NW mesoporosity. The vertical etching rate is shown to depend on carrier concentration and degree of internal mesoporosity formation. Raman scattering of the transverse optical phonon and photoluminescence measurements confirm quantum size effects, phonon scattering and visible intense red light emission between 685 and 720 nm in internally mesoporous NWs associated with the etching conditions. Laser power heating of NWs confirms phonon confinement and scattering, which is demonstrated to be a function of the internal mesoporosity development. We also demonstrate the limitation of mesoporosity formation in n+-Si NWs and development of porosity within p-Si NWs by controlling the etching conditions. Lastly, the data confirm that phonon confinement and scattering often reported for Si NWs is due to surface-bound and internal nanostructure, rather than simply a diameter reduction in NW materials.

Synthesis, characterization and application of electroless metal assisted silicon nanowire arrays

Vertically aligned silicon nanowire arrays (SiNWs) have been synthesized by electroless metal deposition process. The fabricated SiNWs have an average diameter of 75nm and 3.5–4.0μm length, as confirmed from scanning electron microscopy. A characteristic asymmetric peak broadening at 520cm−1 from Raman spectroscopy was obtained for the SiNWs as compared to the bulk silicon crystal due to phonon confinement. The as-prepared SiNWs exhibit good electron field-emission properties with turn-on field of about 8.26Vμm−1 at a current density of 4.9μAcm−2. The SiNWs was functionalized by coating with a thin gold metallic film for 60s, and then used as bio-probe for the detection of bovine serum albumin (BSA) protein molecules. From the linear sweep voltammetry analysis, the Au coated SiNWs, exhibit linear response to the BSA analyte with increase in concentration. The minimum detection limit of the protein molecule was calculated of about 1.16μM by the as-synthesized SiNWs probe.

Electron capture processes in quantum dots due to one-and two-phonon assisted transitions: The role of optical phonon confinement

Electron capture induced by carrier heating in spherical quantum dot-quantum well (QD-QW) structure is studied theoretically. The capture rate (CR) in one- and two-polar- optical-phonon-mediated capture processes has been studied by taking into account the phonon confinement. We have derived the analytic expressions for carrier CRs which can be conveniently applied to practical calculations for the spherical quantum dot systems. The numerical results of the CR as function of dot radius, lattice temperature and electron density in GaAs/AlAs/vacuum and CdSe/ZnS/H2O QD systems are obtained and discussed.

The pronounced role of impurity phases in the optical properties of Mn catalyzed ZnS nanostructures

We report the effect of Mn self-doping in Mn catalyzed ZnS nanostructures grown via vapor liquid solid mechanism, which also resulted in the formation of additional impurity minority phases like ZnO and MnO2. The synthesized ZnS nanostructures were subsequently annealed in the range of 500 °C – 700 °C in an inert environment to remove impurity phases and enhance the incorporation of dopant. Room temperature photoluminescence showed strong defect assisted luminescence. It was observed that green emission due to intrinsic defects of ZnS nanostructures was reduced in magnitude and Mn related orange/red luminescence increased in magnitude in nanostructures annealed at high temperature. The presence of impurity phases led to the observation of surface optical and interface phonon modes as observed in the Raman spectroscopy. Dielectric continuum and phonon confinement models were employed to determine the correlation lengths of the optical phonon modes.

Raman investigation of defective SiC nanocrystals

Phonon confinement effect and surface optical mode in SiC nanocrystal have been investigated through Raman spectroscopy. Considering high density of stacking faults in SiC grains, the correlation length of RWL (proposed by Richter, Wang, Li to explain phonon confinement in nano silicon) model is determined as a distance between nearby stacking faults. Thus, homogeneous region becomes thin slices in cylindrical SiC grains, which redefines weighting function. Effect of anisotropy of phonon dispersion curve is also analyzed during calculation. The additional 875‐cm−1 band is attributed to defects and amorphous SiC, which is confirmed by transmission electron microscopy. SiC grains are approximated as column array with grain boundary substances regarded as surrounding medium, which explains surface optical phonon mode at 915 cm−1. Copyright © 2015 John Wiley & Sons, Ltd.

Characterization of Nanocrystal Size Distribution using Raman Spectroscopy with a Multi-particle Phonon Confinement Model.

Analysis of the size distribution of nanocrystals is a critical requirement for the processing and optimization of their size-dependent properties. The common techniques used for the size analysis are transmission electron microscopy (TEM), X-ray diffraction (XRD) and photoluminescence spectroscopy (PL). These techniques, however, are not suitable for analyzing the nanocrystal size distribution in a fast, non-destructive and a reliable manner at the same time. Our aim in this work is to demonstrate that size distribution of semiconductor nanocrystals that are subject to size-dependent phonon confinement effects, can be quantitatively estimated in a non-destructive, fast and reliable manner using Raman spectroscopy. Moreover, mixed size distributions can be separately probed, and their respective volumetric ratios can be estimated using this technique. In order to analyze the size distribution, we have formulized an analytical expression of one-particle PCM and projected it onto a generic distribution function that will represent the size distribution of analyzed nanocrystal. As a model experiment, we have analyzed the size distribution of free-standing silicon nanocrystals (Si-NCs) with multi-modal size distributions. The estimated size distributions are in excellent agreement with TEM and PL results, revealing the reliability of our model.

Size and Purity Control of HPHT Nanodiamonds down to 1 nm.

High-pressure high-temperature (HPHT) nanodiamonds originate from grinding of diamond microcrystals obtained by HPHT synthesis. Here we report on a simple two-step approach to obtain as small as 1.1 nm HPHT nanodiamonds of excellent purity and crystallinity, which are among the smallest artificially prepared nanodiamonds ever shown and characterized. Moreover we provide experimental evidence of diamond stability down to 1 nm. Controlled annealing at 450 °C in air leads to efficient purification from the nondiamond carbon (shells and dots), as evidenced by X-ray photoelectron spectroscopy, Raman spectroscopy, photoluminescence spectroscopy, and scanning transmission electron microscopy. Annealing at 500 °C promotes, besides of purification, also size reduction of nanodiamonds down to ∼1 nm. Comparably short (1 h) centrifugation of the nanodiamonds aqueous colloidal solution ensures separation of the sub-10 nm fraction. Calculations show that an asymmetry of Raman diamond peak of sub-10 nm HPHT nanodiamonds can be well explained by modified phonon confinement model when the actual particle size distribution is taken into account. In contrast, larger Raman peak asymmetry commonly observed in Raman spectra of detonation nanodiamonds is mainly attributed to defects rather than to the phonon confinement. Thus, the obtained characteristics reflect high material quality including nanoscale effects in sub-10 nm HPHT nanodiamonds prepared by the presented method.

Microscopic Origin of Thermal Conductivity Reduction in Disordered van der Waals Solids

Films of layered substances like WSe2 can exhibit a reduction in the out-of-plane thermal conductivity of more than 1 order of magnitude compared to that of the bulk, effectively beating the glass limit (Science 2007, 315, 351). Here, we investigate the microscopic contributions that govern this behavior within the framework of Boltzmann transport theory informed by first-principles calculations. To quantitatively reproduce both the magnitude and the temperature dependence of the experimental data, one must account for both phonon confinement effects (softening and localization) and interlayer scattering. Both stacking order and layer spacing are shown to have a pronounced effect on the thermal conductivity that could be exploited to tune the balance between electrical and thermal conductivity.

Enhanced room temperature ferromagnetism in antiferromagnetic NiO nanoparticles

We report systematic investigations of structural, vibrational, resonance and magnetic properties of nanoscale NiO powders prepared by ball milling process under different milling speeds for 30 hours of milling. Structural properties revealed that both pure NiO and as-milled NiO powders exhibit face centered cubic structure, but average crystallite size decreases to around 11 nm along with significant increase in strain with increasing milling speed. Vibrational properties show the enhancement in the intensity of one-phonon longitudinal optical (LO) band and disappearance of two-magnon band due to size reduction. In addition, two-phonon LO band exhibits red shift due to size-induced phonon confinement effect and surface relaxation. Pure NiO powder exhibit antiferromagnetic nature, which transforms into induced ferromagnetic after size reduction. The average magnetization at room temperature increases with decreasing the crystallite size and a maximum moment of 0.016 μB/f.u. at 12 kOe applied field and coercivity of 170 Oe were obtained for 30 hours milled NiO powders at 600 rotation per minute milling speed. The change in the magnetic properties is also supported by the vibrational properties. Thermomagnetization measurements at high temperature reveal a well-defined magnetic phase transition at high temperature (TC) around 780 K due to induced ferromagnetic phase. Electron paramagnetic resonance (EPR) studies reveal a good agreement between the EPR results and magnetic properties. The observed results are described on the basis of crystallite size variation, defect density, large strain, oxidation/reduction of Ni and interaction between uncompensated surfaces and particle core with lattice expansion. The obtained results suggest that nanoscale NiO powders with high TC and moderate magnetic moment at room temperature with cubic structure would be useful to expedite for spintronic devices.

Structural and optical properties of ZnSe quantum dots in glass nanocomposites

Zinc selenide (ZnSe) quantum dots (QDs) were synthesized in a dielectric (borosilicate glass) matrix for the first time by melt-quenching process followed by thermal treatment. Sizes of the quantum dots were varied by post thermal treatment. UV–Vis optical absorption spectroscopy, transmission electron microscopy (TEM) and Raman spectroscopy were deployed to investigate the ZnSe QDs. TEM analysis reveals QD sizes of the order of 2–4 nm and relatively larger nanocrystals having sizes of the order of 15–26 nm. The sizes of the QDs have also been verified with the help of effective mass approximation model and optical absorption spectroscopy. The quantum confinement effect has been observed for both variation of heat treatment temperature and time. The Raman spectra of the nanocomposites reveal blue-shifted Raman peaks of ZnSe at 295 and 315 cm−1 due to phonon confinement effect. The decrease in Raman intensity with heat treatment indicates increase in size of the QDs. Red luminescence from the ZnSe-glass nanocomposites peaking at 708 nm due to the size related as well as traps related states makes their applications towards luminescent solar concentrators (LSCs).

(Invited) Phonon Dispersion Engineering and Thermal Transport in Si Membranes

Present silicon technology provides single crystal films and membranes with thicknesses on the order of 10 nm and below. Along the years, the thermal studies on such structures have shown a reduction of the thermal conductivity consistent with the decrease of the characteristic size. Although the lowering of thermal conductivity is detrimental for heat dissipation processes in nanoelectronic devices, it becomes advantageous to increase the figure of merit (ZT) of Si and turning it as a promising material for thermoelectric applications. It is widely accepted that, for submicrometer thicknesses and down to 20 nm, the reduction of the in-plane thermal conductivity is mainly determined by the shortening of the phonon mean free path due to the diffusive scattering of phonons at the boundaries. In this case an analytical model that adopts the phonon bulk properties and includes the boundary scattering by a conductivity reduction factor is shown to match the experimental trend of systematical reduction of the thermal conductivity as the thickness of the film or membrane decreases. In this talk we will report on the modification of the phonon properties in Si membranes, such as the dispersion relation, and its dependence on the thickness. The thermal conductivity in Si results from the cumulative contribution of the transport of phonons with a broad range of wavevectors and mainly from long-wavevector phonons. Thus, heat transport at room temperature can be influenced by the reduction of the membrane thickness as the dispersion relation of the short-wave-phonons starts to be affected by emerging new vibrational modes arising from the boundary conditions at the membrane surface. Our measurements of the thermal conductivity in ultra-thin sub-20 nm Si membranes have demonstrated this extreme and, in fact, we have been able to disentangle the effects of phonon confinement from those related to surface morphology and chemical composition. Finally, we will discuss the prospects of employing the increased modification of phonon dispersion relation achieved in phononic crystals in controlling heat transport. While some applications require the existence of absolute band gaps, the approach to reduce the thermal conductivity is more linked to the decrease of phonon’s group velocity and phonon-phonon interactions in an extended range of frequencies.

Effects of passage of 200 MeV Ag9+ ions in indium phosphide at different depths

Indium phosphide sample was irradiated with 200 MeV Ag9+ ions for the fluence of 2 × 1013 ions cm−2. The sample was chemically etched down up to 240 nm depth to investigate the distribution of defects at different regions. Raman scattering and glancing incidence X-ray diffraction spectra were recorded at different depths. The stress estimated from Raman shift was found to increase with depth up to 160 nm and thereafter it decreased and at a depth of 224 nm sample did not show any stress. Phonon coherence length estimated from the Phonon Confinement Model was found to vary between 43 and 18 nm with respect to depth. Glancing incidence X-ray diffraction results revealed the decrease in crystallite size from 16.12 to 1.00 nm in different depth regions.

Mechanisms Of Composite-hydroxide-mediated Approach For The Synthesis Of Functional ZnO Nanostructures And Morphological Dependent Optical Emissions

We report synthesis of the functional ZnO nanostructures (nanowires, nanorods) by a cost effective and efficient method; called composite­hydroxide­mediated (CHM) approach. Effect of the processing temperature on the particle size, morphology, and subsequently morphological dependent optical emissions is investigated. Needle shaped nanowires are obtained at 200 and 220C, of about (500­1500) nm in length, while at 250C; nanorods are formed with length in the range of (200­460) nm and width (10­30) nm. Optical study reveals that ZnO nanorods show only ultra­violet (UV) emission while bent nanowires demonstrate both UV and green emissions simultaneously. The week green emission at 2.4 eV indicates no efficient trapping of the photo­ generated hole in the nanostructures. Phase purity, crystalline structure, size and chemical nature of the product are probed by XRD, EDX, Raman spectroscopy and FT­IR. The particle size estimated from the spatial correlation phonon confinement model for the E2 (high) phonon mode. The applied approach is believed to be an efficient, and a direct route for the synthesis of a wide range simple and complex oxide nanostructures for novel electro­optical nanodevices.

Behavior of porous silicon crystallite size analized by Raman spectroscopy and phonon confinement model

Porous silicon samples, obtained by electrochemical process in a solution containing HF-Ethanol were prepared varying etching time and current density. Using the phonon confinement model the crystallite size was estimated on the porous layer through the best fit of the Raman spectrum of first order. The experimental and theoretical points were better adjusted in order to obtain more accurate results in relation to previous works. For the samples with varying the anodization time and keeping constant the current density the crystallite size had an oscillating behavior and tendency to decrease as a function of the anodization time. Varying current density, keeping constant the anodization time, was observed an increase in the crystallite size as a function current density.

Size‐dependent evolution of phonon confinement in colloidal Si nanoparticles

A size‐dependent evolution of phonon confinement is revealed in Si nanoparticles (NPs) via Raman spectroscopy. By introducing a variable confinement factor, α, into a well‐known phenomenological phonon confinement model (PCM) developed by Richter et al., acceptable fits are achieved to downshifted and asymmetrically broadened Raman spectra of Si NPs with different diameters, d, from 2.4 nm to 6.3 nm. A comparative study using Raman spectra of colloidal Si NPs, for the first time, shows an apparent positive linear correlation between α and the Si NP size. Based on the PCM, the amplitude of the atomic vibration (phonon) at the real physical boundary of NPs is proportional to e−α/2, which indicates that the amplitude of the first order optical phonon is relatively larger at the edges for smaller Si nanostructures despite of their stronger phonon confinement weighed by α/d2. Copyright © 2015 John Wiley & Sons, Ltd.

One and two-phonon Raman scattering from nanostructured silicon

Raman scattering from highly/low resistive nanostructured silicon films prepared by metal-assisted chemical etching was investigated. Raman spectrum of obtained silicon nanostructures was measured. Interpretation of observed one and two-phonon Raman peaks are presented. First-order Raman peak has a redshift and broadening. This phenomenon is analyzed in the framework of the phonon confinement model taking into account mechanical stress effects. Second-order Raman peaks were found to be shifted and broadened in comparison to those in the bulk silicon. The peak shift and broadening of two-phonon Raman scattering relates to phonon confinement and disorder. A broad Raman peak between 900 and 1100cm−1 corresponds to superposition of three transverse optical phonons ∼2TO (X), 2TO (W) and 2TO (L). Influence of excitation wavelength on intensity redistribution of two-phonon Raman scattering components (2TO) is demonstrated and preliminary theoretical explanation of this observation is presented.

Effect of disorder on Raman scattering of single-layerMoS2

We determine the effect of defects induced by ion bombardment on the Raman spectrum of single-layer molybdenum disulfide. The evolution of both the linewidths and frequency shifts of the first-order Raman bands with the density of defects is explained with a phonon confinement model, using density functional theory to calculate the phonon dispersion curves. We identify several defect-induced Raman scattering peaks arising from zone-edge phonon modes. Among these, the most prominent is the $\mathrm{LA}(M)$ peak at $\ensuremath{\sim}227\phantom{\rule{0.16em}{0ex}}\mathrm{c}{\mathrm{m}}^{\ensuremath{-}1}$ and its intensity, relative to the one of first-order Raman bands, is found to be proportional to the density of defects. These results provide a practical route to quantify defects in single-layer $\mathrm{Mo}{\mathrm{S}}_{2}$ using Raman spectroscopy and highlight an analogy between the $\mathrm{LA}(M)$ peak in $\mathrm{Mo}{\mathrm{S}}_{2}$ and the $D$ peak in graphene.

Soft chemistry based sponge-like indium tin oxide (ITO) — a prospective component of photoanode for solar cell application

Previously we reported the synthesis of novel organic-inorganic composite indium tin oxide (ITO) foam precursor leading to the formation of “sponge-like” ITO by burning away the organics. This newly made sponge-like ITO possesses relatively high electrical conductivity due to phonon confinement with reasonable pore structure and may have potential application as functional materials in semiconducting dye absorbing layer in dye-sensitized solar cell (DSSC) and also as the receptor of electrons injected from the quantum dots (QDs) of organic-inorganic hybrid QD based solar cell. This report is a short review of “sponge-like” ITO described as a lecture note on its future use as an alternative new prospective material for photoanode of solar cell in the domain of sustainable energy.

Quantitative analysis of the phonon confinement effect in arbitrarily shaped Si nanocrystals decorated on Si nanowires and its correlation with the photoluminescence spectrum

Arrays of single‐crystalline Si nanowires (NWs) decorated with arbitrarily shaped Si nanocrystals (NCs) are grown by a metal‐assisted chemical etching process using silver (Ag) as the noble metal catalyst. The metal‐assisted chemical etching‐grown Si NWs exhibit strong photoluminescence (PL) emission in the visible and near infrared region at room temperature. Quantum confinement of carriers in the Si NCs is believed to be primarily responsible for the observed PL emission. Raman spectra of the Si NCs decorated on Si NWs exhibit a red shift and an asymmetric broadening of first‐order Raman peak as well as the other multi‐phonon modes when compared with that of the bulk Si. Quantitative analysis of confinement of phonons in the Si NCs is shown to account for the measured Raman peak shift and asymmetric broadening. To eliminate the laser heating effect on the phonon modes of the Si NWs/NCs, the Raman measurement was performed at extremely low laser power. Both the PL and Raman spectral analysis show a log‐normal distribution for the Si NCs, and our transmission electron microscopy results are fully consistent with the results of PL and Raman analyses. We calculate the size distribution of these Si NCs in terms of mean diameter (D0) and skewness (σ) by correlating the PL spectra and Raman spectra of the as‐grown Si NCs decorated on Si NWs. Copyright © 2015 John Wiley & Sons, Ltd.