Phonon Confinement Research Articles

Phonon confinement effects in Raman spectra of porous silicon at non‐resonant excitation condition

Light emitting porous silicon samples with different porosities, i.e. crystalline sizes, were produced from the low level doped p‐type silicon wafers by the anodization process. The effects of strong phonon confinement, redshift and broadening, were found on the O(Γ) phonon mode of the Raman spectra recorded at non‐resonant excitation condition using a near infrared 1064 nm laser excitation wavelength. Similarly, the blueshift of the photoluminescence peak was observed by reducing the crystalline sizes. Vibrational and optical findings were analysed within the existing models of confinement on the vibrational and electronic states of silicon nanocrystals. Since the energy of the photoluminescence peak of small nanocrystals also depends on the oxygen content on the surface of nanocrystals, the surface oxidation states were examined using infrared and energy dispersive spectroscopy. The partial coverage of the surface of nanocrystals was found due to the sample exposure to air. As a consequence, the photoluminescence energy did not increase as would be expected from the quantum confinement model. These results further indicate that the oxygen passivation along with the quantum confinement determines the electronic states of the silicon nanocrystals in porous silicon. Copyright © 2014 John Wiley & Sons, Ltd.

Micro-Raman study on the softening and stiffening of phonons in rutile titanium dioxide film: Competing effects of structural defects, crystallite size, and lattice strain

Softening and stiffening of phonons in rutile titanium dioxide films are investigated by in situ micro-Raman studies during energetic ion irradiation. The in situ study minimized other possible mechanisms of phonon dynamics. Initial softening and broadening of Raman shift are attributed to the phonon confinement by structural defects and loss of stoichiometry. The stiffening of A1g mode is ascribed to large distortion of TiO6 octahedra under the influence of lattice strain in the (110) plane, which gives rise to lengthening of equatorial Ti-O bond and shortening of apical Ti-O bond. The shortening of apical Ti-O bond induces stiffening of A1g mode in the framework of the bond-order-length-strength correlation mechanism.

Single-step in-situ synthesis and optical properties of ZnSe nanostructured dielectric nanocomposites

This work provides the evidence of visible red photoluminescent light emission from ZnSe nanocrystals (NCs) grown within a dielectric (borosilicate glass) matrix synthesized by a single step in-situ technique for the first time and the NC sizes were controlled by varying only the concentration of ZnSe in glass matrix. The ZnSe NCs were investigated by UV-Vis optical absorption spectroscopy, Raman spectroscopy, and transmission electron microscopy (TEM). The sizes of the ZnSe NCs estimated from the TEM images are found to alter in the range of 2–53 nm. Their smaller sizes of the NCs were also calculated by using the optical absorption spectra and the effective mass approximation model. The band gap enlargements both for carrier and exciton confinements were evaluated and found to be changed in the range of 0–1.0 eV. The Raman spectroscopic studies showed blue shifted Raman peaks of ZnSe at 295 and 315 cm−1 indicating phonon confinement effect as well as compressive stress effect on the surface atoms of the NCs. Red photoluminescence in ZnSe-glass nanocomposite reveals a broad multiple-peak structure due to overlapping of emission from NC size related electron-hole recombination (∼707 nm) and emissions from defects to traps, which were formed due to Se and Zn vacancies signifying potential application in photonics.

Raman scattering crystalline assessment of polycrystalline Cu2ZnSnS4 thin films for sustainable photovoltaic technologies: Phonon confinement model

Phonon confinement effects in the Raman scattering spectra from polycrystalline Cu2ZnSnS4 thin films synthesized with different crystalline qualities – including photovoltaic grade layers – are investigated in terms of a phonon confinement model. Interpretation of the experimentally obtained spectra required the development of a modified model that includes additional features such as lattice strain. The model has been systematically applied for the simultaneous fitting of the two main A symmetry Raman peaks in the experimental spectra. The experimental data show that the line shape of the Raman peaks is determined mainly by phonon confinement effects, while their frequency is also sensitive to the presence of strain in the lattice. Simultaneous modeling of the A dominant peaks allows a quantitative estimation of the frequency strain shift that has been correlated with the strain measured by X-ray diffraction. Estimation of the correlation length also provides a quantitative indicator of the crystalline quality of the films that is found to correlate with the grain size assessed by scanning electron microscopy. Based on this model, a general and simple methodology for the assessment of the crystalline quality of Cu2ZnSnS4 samples independently of the experimental measurement conditions is proposed through the use of an asymmetry parameter.

Photoelectrochemical and Raman characterization of nanocrystalline CdS grown on ZnO by successive ionic layer adsorption and reaction method

Properties of CdS nanoparticles (NPs) grown by successive ionic layer adsorption and reaction (SILAR) method on the surface of electrodeposited ZnO films were studied by Raman, photocurrent and UV–Vis absorption spectroscopies. The CdS nanoparticles deposited at a SILAR cycle number (N) from 5 to 10 exhibit a broadening of the band gap (Eg) by 0.17–0.31eV as compared with that of the CdS particles grown at N=30. The size quantization of the interband transition energy in CdS nanoparticles is in accordance with the Raman spectroscopic data demonstrating a considerable increase in the LO peak intensity with increasing the N from 5 to 10 as a result of transition to resonant light scattering. The spectral width of the LO peak decreases from 50 to 15cm−1 as the N increases from 5 to 30 reflecting a less pronounced effect of the nanoparticle surface on the phonon scattering. A large spectral width of the Raman peaks is assumed to originate from a complex structure of the CdS nanoparticles comprising crystallinity domains that can affect the phonon confinement. The photocurrent spectroscopy of ZnO/CdS heterostructures showed that the band gap of CdS NPs deposited at N>20 is smaller by ~0.08eV than that of bulk cadmium sulfide. It was concluded that this effect is not associated with photoexcitation of structural defects but rather reflects intrinsic electronic properties of SILAR-deposited CdS nanoparticles.

Thermal Sensitive Quantum and Phonon Confinements for Temperature Mapping in Extreme Environments

Spatial and/or temporal temperature mapping in extreme environments that cannot be physically accessible remains a grand challenge, such as in the interior of high tempeature solid oxide fuel cells and opaque fireballs, where real-time readout of temperature is not feasible. Our study showed that photoluminescence (PL) spectra of ZnO nanoparticles (NPs) and Raman spectra of anatase TiO2 NPs exhibit thermal sensitive quantum confinement and phonon confinement, respectively. Here, we explored the highly temperature sensitive irreversible growth of NPs together with the strong quantum and phonon confinements in these oxide NPs as unique signatures for ex situ temperature sensing, especially for applications in extreme environments. By distributing these NPs, a spatially and temporally nonuniform thermal mapping can be determined by a direct read-off of their PL and Raman spectra at various locations.

Direct evaluation of ballistic phonon transport in a multi-walled carbon nanotube

Phonon confinement and in situ thermal conductance measurements in an individual multi-walled carbon nanotube (MWNT) are reported. Focused ion beam (FIB) irradiation was used to successively shorten a 4.8 μm long MWNT, eventually yielding a 0.3 μm long MWNT. After the first FIB irradiation, a 41% reduction in conductance was achieved, compared with that of the pristine MWNT. This was because the contributions from phonons with long free paths were excluded by scattering at FIB-induced defects. Phonon transport in linked multiple-length nanotubes was also investigated.

Qualitative Evolution of Asymmetric Raman Line-Shape for NanoStructures

A step-by-step evolution of an asymmetric Raman line-shape function from a Lorentzian line-shape is presented here for low dimensional semiconductors. The evolution reported here is based on the phonon confinement model which is successfully used in literature to explain the asymmetric Raman line-shape from semiconductor nano-structures. Physical significance of different terms in the theoretical asymmetric Raman line-shape has been explained here. Better understanding of theoretical reasoning behind each term allows one to use the theoretical Raman line-shape without going into details of theory from first principle. This will enable one to empirically derive a theoretical Raman line-shape function for any material if information about its phonon dispersion, size dependence etc is known.

Evaluation of phonon confinement in ultrathin-film silicon-on-insulator by Raman spectroscopy

Raman spectroscopy is a practical evaluation technique for the quantum effect of phonons in a microcrystalline structure. It is very sensitive to fluctuations of crystalline potential or localized atomic geometry. Phonon confinement is observed as a broadening and desymmetrization of the Raman spectrum. However, Raman spectra also include information on crystal quality, strain, and thermal influence caused by the excitation source. Because these factors have an effect similar to that of phonon confinement on spectra, distinction of the factors is essential for accurate evaluation of the phonon confinement effect. The influence of these effects in the utrathin-film silicon-on-insulator (SOI) was investigated by Raman spectroscopy. Marked broadening and desymmetrization of Raman spectra were confirmed for the SOIs with thickness less than 5 nm. The crystalline quality and strain in the SOI layer were investigated by X-ray diffraction. We developed a precise simulation technique for phonon confinement with consideration of thermal and strain effects. By comparing the simulation with the results of Raman spectroscopy, an exact evaluation of phonon confinement effects in utrathin-film SOI was achieved.

Quantum confinement effects in doped two-dimensional Si layers: Novel device design for two-dimensional pn-junction structures

We have experimentally studied the impurity dopant atom effects on band structure modulation (BSM) and phonon confinement effects (PCEs) in a two-dimensional (2D) Si layer. By the photoluminescence (PL) method, the effect of the dopant atom on the bandgap (EG) of 2D-Si is found to be very small. However, the EG narrowing effects of n+ 2D-Si are much smaller than those of conventional 3D n+-Si, which is characteristic of 2D-Si. On the other hand, Raman spectroscopy shows that the PCEs are completely independent of the phosphorous dopant density of n+ 2D-Si. Using the experimental BSM of 2D-Si, we introduce a device design for pn junction structures in 2D-Si for future complementary metal oxide semiconductor (CMOS) devices, to suppress the built-in potential increase of the pn junction, in spite of the EG expansion in the 2D-Si channel region.

Crystal direction dependence of quantum confinement effects of two-dimensional Si layers fabricated on silicon-on-quartz substrates: modulation of phonon spectra and energy band structures

We experimentally studied the crystal direction dependence of phonon confinement effects (PCEs) and bandgap (EG) modulation of a two-dimensional (2D) Si layer fabricated on (100) silicon-on-quartz (SOQ) wafers without a handle Si substrate. For the first time, by polarization Raman spectroscopy, in the case of Raman intensity spectra in the asymmetrical broadening region owing to the PCEs in the 2D Si layer, we demonstrated that the incident laser polarization direction dependence of the Raman intensity deviates from the Raman selection rule. However, a photoluminescence (PL) method shows that the EG expansion is isotropic in the 2D Si layer. On the other hand, the reflectivity of the 2D Si layer in UV region is also modulated. The reflectivity property modulation is possibly attributable to the energy band modulation in the 2D Si layer.

Catalyst-free synthesis of silicon nanowires by oxidation and reduction process

A new process has been developed to grow silicon (Si) nanowires (NWs), and their growth mechanisms were explored and discussed. In this process, SiNWs were synthesized by simply oxidizing and then reducing Si wafers in a high temperature furnace. The process involves H2, in an inert atmosphere, reacts with thermally grown SiO2 on Si at 1100 °C enhancing the growth of SiNWs directly on Si wafers. High-resolution transmission electron microscopy studies show that the NWs consists of a crystalline core of ~25 nm in diameter and an amorphous oxide shell of ~2 nm in thickness, which was also supported by selected area electron diffraction patterns. The NWs synthesized exhibit a high aspect ratio of ~167 and room temperature phonon confinement effect. This simple and economical process to synthesize crystalline SiNWs opens up a new way for large scale applications.

Optical phonons in nanostructured thin films composed by zincblende zinc selenide quantum dots in strong size-quantization regime: Competition between phonon confinement and strain-related effects

Raman scattering in combination with optical spectroscopy and structural studies by X-ray diffraction was employed to investigate the phonon confinement and strain-induced effects in 3D assemblies of variable-size zincblende ZnSe quantum dots close packed in thin film form. Nanostructured thin films were synthesized by colloidal chemical approach, while tuning of the nanocrystal size was enabled by post-deposition thermal annealing treatment. In-depth insights into the factors governing the observed trends of the position and half-width of the 1LO band as a function of the average QD size were gained. The overall shifts in the position of 1LO band were found to result from an intricate compromise between the influence of phonon confinement and lattice strain-induced effects. Both contributions were quantitatively and exactly modeled. Accurate assignments of the bands due to surface optical (SO) modes as well as of the theoretically forbidden transverse optical (TO) modes were provided, on the basis of reliable physical models (such as the dielectric continuum model of Ruppin and Englman). The size-dependence of the ratio of intensities of the TO and LO modes was studied and discussed as well. Relaxation time characterizing the phonon decay processes in as-deposited samples was found to be approximately 0.38ps, while upon post-deposition annealing already at 200°C it increases to about 0.50ps. Both of these values are, however, significantly smaller than those characteristic for a macrocrystalline ZnSe sample.

Communication: three-dimensional model for phonon confinement in small particles: quantitative bandshape analysis of size-dependent Raman spectra of nanodiamonds.

Raman spectroscopy of nano-scale materials is facing a challenge of developing a physically sound quantitative approach for the phonon confinement effect, which profoundly affects the phonon Raman band shapes of small particles. We have developed a new approach based on 3-dimensional phonon dispersion functions. It analyzes the Raman band shapes quantitatively in terms of the particle size distributions. To test the model, we have successfully obtained good fits of the observed phonon Raman spectra of diamond nanoparticles in the size range from 1 to 100 nm.

Surface optical phonons in GaAs nanowires grown by Ga-assisted chemical beam epitaxy

Surface optical (SO) phonons were studied by Raman spectroscopy in GaAs nanowires (NWs) grown by Ga-assisted chemical beam epitaxy on oxidized Si(111) substrates. NW diameters and lengths ranging between 40 and 65 nm and between 0.3 and 1.3 μm, respectively, were observed under different growth conditions. The analysis of the Raman peak shape associated to either longitudinal or surface optical modes gave important information about the crystal quality of grown NWs. Phonon confinement model was used to calculate the density of defects as a function of the NW diameter resulting in values between 0.02 and 0.03 defects/nm, indicating the high uniformity obtained on NWs cross section size during growth. SO mode shows frequency downshifting as NW diameter decreases, this shift being sensitive to NW sidewall oxidation. The wavevector necessary to activate SO phonon was used to estimate the NW facet roughness responsible for SO shift.

Phonon Lateral Confinement Enables Thermal Rectification in Asymmetric Single-Material Nanostructures

We show that thermal rectification (TR) in asymmetric graphene nanoribbons (GNRs) is originated from phonon confinement in the lateral dimension, which is a fundamentally new mechanism different from that in macroscopic heterojunctions. Our molecular dynamics simulations reveal that, though TR is significant in nanosized asymmetric GNRs, it diminishes at larger width. By solving the heat diffusion equation, we prove that TR is indeed absent in both the total heat transfer rate and local heat flux for bulk-size asymmetric single materials, regardless of the device geometry or the anisotropy of the thermal conductivity. For a deeper understanding of why lateral confinement is needed, we have performed phonon spectra analysis and shown that phonon lateral confinement can enable three possible mechanisms for TR: phonon spectra overlap, inseparable dependence of thermal conductivity on temperature and space, and phonon edge localization, which are essentially related to each other in a complicated manner. Under such guidance, we demonstrate that other asymmetric nanostructures, such as asymmetric nanowires, thin films, and quantum dots, of a single material are potentially high-performance thermal rectifiers.

Phonon Confinement Using Spirally Designed Elastic Resonators in Discrete Continuum

Periodic and chiral orientation of microstructures, here we call phononic crystals, have extraordinary capabilities to facilitate the innovative design of new generation metamaterials. Periodic arrangements of phononic crystals are capable of opening portals of non-passing, non-dispersive mechanical waves. Defying conventional design of regular periodicity, in this paper spirally periodic but chiral orientation of resonators are envisioned. Dynamics of the spirally connected resonators and the acoustic wave propagation through the spirally connected multiple local resonators are studied using fundamental physics. In present study the spiral systems with local resonators are assumed to be discrete media immersed in fluid. In this paper it is assumed that acoustic or ultrasonic waves in fluid are propagated along the plane of the spiral resonators and thus only the longitudinal wave mode exists due to nonexistence of shear stress in the fluid. Lagrangian formulation of the spiral systems were employed to obtain the governing Euler-Lagrange equation of the system. Discrete element method was employed to verify the equation assuming nearest neighboring effect.

Thermoelectric Nanowire Junction Photoresponse

ABSTRACTRecently there have been reports of hot carrier thermoelectric response in nanostructured materials like graphene and MoS. We report observing that thermoelectric nanowire junctions detect light. In these experiments we employed devices composed of bismuth nanowire arrays which are capped with a transparent indium tin oxide electrode. The incident surface features very low optical reflectivity and enhanced light trapping. The unique attributes of the thermoelectric arrays are the combination of strong temporal and optical wavelength dependences of the photocurrent. Under infrared illumination, the signal can be completely described by “quasi-equilibrium” thermoelectric effects considering cooling rates given by heat diffusion through the array. The thermal diffusivity is found to be less (by a factor of 3.5) than in the bulk, a result that we discuss in terms of phonon confinement effects. In addition to a thermoelectric response, under visible illumination, we observe a photovoltaic response.

Applying an improved phonon confinement model to the analysis of Raman spectra of germanium nanocrystals

The improved phonon confinement model developed previously [11] is applied for definition of germanium nanocrystal sizes from the analysis of its Raman scattering spectra. The calculations based on the model allow determining the sizes of germanium nanocrystals more precisely from the analysis of their Raman spectra. In some cases, the comparative analysis of Raman data and electron microscopy data is carried out, and good agreement is observed.

Effect of sintering temperature on the structural properties of cobalt ferrite nanoparticles

The nanocrystalline CoFe2O4 was prepared by nitrate route at the sintering temperature of 300, 500, 700 and 900°C. The X-ray diffraction (XRD) patterns of all the samples show the single phase spinel structure of nanoparticles. The crystallite sizes vary from 9 to 61 nm as the sintering temperature increases from 300 to 900°C. The FTIR spectra of cobalt ferrite were recorded in the range of 400 to 5,000 cm–1 at room temperature. FTIR spectra of the cobalt ferrite nanoparticles show no residual organic compounds and confirm the formation of the organic free cobalt ferrite nanoparticles above the sintering temperature 500°C. The assigned Raman modes are the characteristics of the spinel structure of the synthesised samples which change slightly with different sintering temperature. The Raman modes of cobalt ferrite nanoparticles at 300°C temperature follow the phonon confinement as the particle size is ~9 nm.