Morphology of InN nanorods using spectroscopic Raman imaging

We report the vibrational properties of vertical and oblique InN nanorods (NRs) grown by molecular beam epitaxy (MBE). Surface optical (SO) Raman mode at 561 cm⁻¹, belonging to E₁ symmetry [SO(E₁)], is identified along with symmetry allowed Raman modes of E₂(low), E₂(high), and E₁(LO) at 87, 489, and 589 cm⁻¹, respectively, corresponding to wurtzite InN phase. Usually, SO phonon modes arise due to breakdown of translational symmetry of surface potential at surface defects, which are attributed by the surface roughness. Intensity distribution of E₁(LO) and SO(E₁) phonon modes over a specified area have been analysed using Raman area mapping with an optical resolution of 400 nm. Imaging with E₁(LO) phonon mode, originating from the bulk of the sample, distinguishes the vertical NRs alone. We are able to resolve NR morphologies in both vertical and oblique cases with additional Raman mapping analysis of SO(E₁) phonon mode, emerging from the surface irregularities, which are confined to the tip of MBE grown NRs. Copyright © 2013 John Wiley & Sons, Ltd.     

Optical properties of laterally overgrown GaN pyramids grown on (1 1 1) silicon substrate

Optical properties of laterally overgrown GaN hexagonal pyramids on (1 1 1) Si substrates are studied by cathodoluminescence (CL) spectroscopy and mapping techniques. The results are compared with structural properties obtained by scanning and transmission electron microscopic techniques. To clarify the origin of the bandedge and yellow-band emissions from the GaN pyramids, wavelength-resolved CL properties of normal and cleaved GaN pyramids are investigated in the top and/or cross-sectional view configurations. The cross-sectional view CL images for cleaved GaN pyramid samples show significant differences between the overgrown areas on top of the mask and the coherently grown regions over the windows. A precise reverse (identical) contrast between bandedge (yellow-band) emission intensity and threading dislocation density is observed by comparing the cross-sectional view CL and transmission electron microscopic images. It is demonstrated that a strong correlation exists between structural defects and optical properties in laterally overgrown GaN hexagonal pyramids.     

Synthesis and optical properties of single crystalline GaN nanorods with a rectangular cross-section

GaN nanorods were synthesized from the reaction of a Ga/Ga₂O₃ mixture with NH₃ on Si substrates by chemical vapor deposition. The synthesized products were characterized by scanning and transmission electron microscopy, X-ray diffraction, photoluminescence and Raman spectroscopy. The nanorods are highly single crystalline and possess uniform smooth surfaces. PL revealed only a strong emission at 3.268 eV, ascribed to free exciton (FX) transitions, at room temperature; while the well-known yellow luminescence band centered at 2.2-2.3 eV was not detected. Four first-order phonon modes, corresponding to the A₁(TO), E₁(TO), E₂(high), and A₁(LO) at ∼531, 554, 564, and 721 cm⁻¹, respectively, were observed by Raman backscattering. The red-shift of the FX emission peak and the down-shifts of the Raman modes by a few wave numbers are attributed to the presence of tensile strain inside GaN nanorods.     

On the mixed nature of the 740 cm band in wurtzite GaN films: A polarized Raman scattering investigation

A detailed study of the polarized Raman scattering of wurtzite GaN films is presented, focusing on the nature of the band centered at 740 cm⁻¹ observed in the X(Z, Z)X configuration. The origin of this band is ascribed to the mixed contribution of the A₁ and E₁ longitudinal phonon modes coupled with the free carrier excitation. The spectral profile of the 740 cm⁻¹ Raman band has been successfully reconstructed through a linear combination of the A₁-E₁ longitudinal phonon plasmon-coupled modes, leading to a free carrier concentration in good agreement with Hall effect measurements.     

Influence of phonon confinement,surface stress,and zirconium doping on the Raman vibrational properties of anatase TiO2 nanoparticles

We present a comprehensive analysis of the Raman spectra of pure and zirconium‐doped anatase TiO₂ nanoparticles. To account for the wavenumber shifts of the E_g(ν₆) mode as a function of particle size (L) and dopant concentration (x), a modification of the standard phonon confinement model (PCM) is introduced, which takes into account the contribution of surface stress by means of the Laplace–Young equation. Together with X‐ray diffraction (XRD) and transmission electron microscopy data, our analysis shows that the surface stress contribution to the observed blue shift of the Raman wavenumber is of the same magnitude as the spatial phonon confinement effect. Annealing experiments show that Zr‐doped nanoparticles exhibit retarded grain growth and delayed anatase‐to‐rutile phase transition by up to 200 K compared to pure anatase TiO₂. XRD shows that Zr doping leads to a unit cell expansion of the anatase structure. Applying the modified PCM to the x‐dependent variations of the E_g(ν₆) Raman mode, the mode‐Grüneisen parameter is found to increase abruptly at x > 0.07 with a concomitant mode softening. This coincides with the x range over which the Zr cations are reported to be displaced from their position in the tetrahedral lattice, and where Zr precipitation occurs upon annealing. The results have implications for the interpretation of Raman spectra of ionic metal oxide nanoparticles and how these are modified upon cation doping. Copyright © 2011 John Wiley & Sons, Ltd.     

‘Soft’ optical phonons and the morphotropic phase transition of the Pb(Ti1−x, Zrx)O3 system

Room temperature Raman scattering results for the Pb(Ti_1?x, Zr_x)O₃ system in its tetragonal ferroelectric phase are analyzed. For x ≤ 0.25, the square of the frequency of the ‘soft’ E(TO) phonon is linear in the Zr concentration. In addition, we find that the morphotropic phase transition at x = 0.535 may be associated with an instability of this ‘soft’ phonon. It is shown that changes in the short-range harmonic forces play an important role in the x-dependence of the ‘soft’ E(TO) phonon frequency.     

Study on the relationships between Raman shifts and temperature range for a-plane GaN using temperature-dependent Raman scattering

In this paper, Raman shifts of a-plane GaN layers grown on r-plane sapphire substrates by low-pressure metal-organic chemical vapor deposition (LPMOCVD) are investigated. We compare the crystal qualities and study the relationships between Raman shift and temperature for conventional a-plane GaN epilayer and insertion AlN/AlGaN superlattice layers for a-plane GaN epilayer using temperature-dependent Raman scattering in a temperature range from 83 K to 503 K. The temperature-dependences of GaN phonon modes (A₁ (TO), E₂ (high), and E₁ (TO)) and the linewidths of E₂ (high) phonon peak are studied. The results indicate that there exist two mechanisms between phonon peaks in the whole temperature range, and the relationship can be fitted to the pseudo-Voigt function. From analytic results we find a critical temperature existing in the relationship, which can characterize the anharmonic effects of a-plane GaN in different temperature ranges. In the range of higher temperature, the relationship exhibits an approximately linear behavior, which is consistent with the analyzed results theoretically.     

Surface optical Raman modes in GaN nanoribbons

Raman scattering studies were performed in GaN nanoribbons grown along [1 0 0]. These samples were prepared inside Na‐4 mica nanochannels by the ion‐exchange technique and subsequent annealing in NH₃ ambient. Detailed morphological and structural studies including the crystalline orientation were performed by analyzing the vibrational properties in these GaN nanoribbons. Pressure in the embedded structure was calculated from the blue shift of the E₂(high) phonon mode of GaN. Possible red shift of optical phonon modes due to the quantum confinement is also discussed. In addition to the optical phonons allowed by symmetry, two additional Raman peaks were also observed at ∼633 and 678 cm⁻¹ for these nanoribbons. Calculations for the wavenumbers of the surface optical (SO) phonon modes in GaN in Na‐4 mica yielded values close to those of the new Raman modes. The SO phonon modes were calculated in the slab (applicable to belt‐like nanoribbon) mode, as the wavenumber and intensity of these modes depend on the size and the shape of the nanostructures. The effect of surface‐modulation‐assisted electron–SO phonon scattering is suggested to be responsible for the pronounced appearance of SO phonon modes. A scaling factor is also estimated for the interacting surface potential influencing the observed SO Raman scattering intensities. Copyright © 2010 John Wiley & Sons, Ltd.     

Synthesis and characterization of GaN nanowires by a catalyst assisted chemical vapor deposition

GaN nanowires have been fabricated on Si(1 1 1) substrates by chemical vapor deposition (CVD) method with NiCl₂ as catalyst and their compositions, microstructures, morphologies and light emitting properties were characterized by X-ray diffraction (XRD), FT-IR spectrophotometer (FTIR), scanning electron microscope (SEM), high-resolution transmission electron microscope (HRTEM), Raman spectroscopy and photoluminescence (PL). The results demonstrate that the nanowires are single-crystal GaN with hexagonal wurtzite structure and high crystalline quality, having the size of 20-50 nm in diameter and several tens of microns in length with some nano-droplets on their tips, which reveals that the growth mechanism of GaN nanowires agrees with vapor-liquid-solid (VLS) process. Five first-order Raman active phonon bands move to low shift and A₁(TO), E₁(TO), and E₂ (high) bands are overlapped and broaden, which is caused by uncertainty in the phonon wave vector. Five non-first-order active Raman phonons also appear, which is caused by the small dimension and high surface disorder degree. A blue-shift of the band-gap emission occurs due to quantum confinement effect.     

Temperature dependence of Raman scattering in Co-doped AlN whiskers

Raman studies are reported for the A ₁ (TO), E ₂ (high) and E ₁ (LO) phonons of Co-doped AlN whiskers from 78 K to 778 K. The temperature dependence of the Raman shifts and line widths of these phonons can be well described by an empirical model which takes into account the contribution of the thermal expansion of the lattice and the symmetric decay of phonons into two and three identical phonons with lower energy. Our results show that the three-phonon process is the dominant decay channel in A ₁ (TO), E ₂ (high) and E ₁ (LO). The symmetric decay of A ₁ (TO) may be attributed to the production of two LA phonons near the M symmetry point of the Brillouin zone. For E ₂ (high), the symmetric decay may be near the M and L symmetry points. The E ₁ (LO) phonon, whose decay behavior has not been identified in AlN, may decay near the H and K symmetry points of the Brillouin zone. Compared with undoped AlN, the stronger temperature dependence of the A ₁ (TO) and E ₂ (high) phonons in Co-doped AlN whiskers was observed, which is probably due to the distortion of the lattice and the much larger tensile stress after doping Co into AlN.     

Raman scattering study of IrxRu1−xO2 mixed metal oxide nanowires (0 ≤ x ≤ 1)

Recent interests in mixed metal oxide nanostructured materials especially Ir_xRu_1−xO₂ compounds have been mainly driven by the technological application as electrocatalyst and electrode materials. We present room temperature Raman scattering results of single crystalline Ir_xRu_1−xO₂ (0 ≤ x ≤ 1) nanowires grown by atmospheric pressure chemical vapor deposition. We observed that the E_g, the A_1g, and the B_2g phonon modes of a single Ir_xRu_1−xO₂ nanowire are blue-shifted linearly with respect to the Ir contents from which we could get stoichiometry information. We also observed that the asymmetric lineshape and the broadening of the full width at half maximum of the E_g mode that involves the out-of-plane oxygen vibration. The unusual asymmetric broadening of the E_g phonon can be explained by the activation of the non-zone-center phonons due to substitutional disorder present in the system. We also found that there is a mixed mode of the A_1g and the B_2g phonons due to the substitutional disorder, in the range of 630–750 cm⁻¹.     

Phonon confinement in individual titanium dioxide nanowires

Size effects on the phonon modes have been unambiguously observed on single individual titanium dioxide (TiO₂) nanowire using Raman spectroscopy. A template-free oxidation process using ethanol vapor was developed to control the growth and the density, length, and size distribution of the TiO₂ nanowires. Scanning electron microscopy, transmission electron microscopy, and X-ray diffraction were used to characterize the morphology, crystalline phases and microstructures. Using a confocal laser probe, Raman spectroscopy revealed in the individual rutile TiO₂ nanowire, the E_g, A_1g vibration modes which are confined in the radial directions. Along the single-crystalline nanowire axis, the systematic size-dependent variations in the center-shift, broadening as well as the shape asymmetry of the Raman peaks can be well explained in terms of the phonon confinement model.     

Resonance Raman spectroscopic study for radial vibrational modes in ultra‐thin walled TiO2 nanotubes

The study reports the observation of radial vibrational modes in ultra‐thin walled anatase TiO₂ nanotube powders grown by rapid breakdown anodization technique using resonant Raman spectroscopic study. The as‐grown tubes in the anatase phase are around 2–5 nm in wall thickness, 15–18 nm in diameter and few microns in length. The E_{g(ν1,ν5,ν6)} phonon modes with molecular vibrations in the radial direction are predominant in the resonance Raman spectroscopy using 325 nm He–Cd excitation. Multi‐phonons including overtones and combinational modes of E_{g(ν1,ν5,ν6)} are abundantly observed. Fröhlich interaction owing to electron–phonon coupling in the resonance Raman spectroscopy of ultra‐thin wall nanotubes is responsible for the observation of radial vibrational modes. Finite size with large surface energy in these nanotubes energetically favor only one mode, B_1g(ν4) with unidirectional molecular vibrations in the parallel configuration out of the three Raman modes with molecular vibration normal to the radial modes. Enhanced specific heat with increasing temperatures in these nanotubes as compared to that reported for nanoparticles of similar diameter may possibly be related to the presence of the prominent radial mode along with other energetic phonon mode. The findings elucidate the understanding of total energy landscape for TiO₂ nanotubes. Copyright © 2015 John Wiley & Sons, Ltd.     

Raman imaging and stress quantification in self‐assembled graphene oxide fiber ‘Latin Letters’

To probe the intrinsic stress distribution in terms of spatial Raman shift (ω) and change in the phonon linewidth (Γ), here we analyze self‐assembled graphene oxide fibers (GOF) ‘Latin letters’ by confocal Raman spectroscopy. The self‐assembly of GOF ‘Latin letters’ has been explained through surface tension, π–π stacking, van der Waals interaction at the air–water interface and by systematic time‐dependent investigation using field emission scanning electron microscopy analysis. Intrinsic residual stress due to structural joints and bending is playing a distinct role affecting the E_2g mode (G band) at and away from the physical interface of GOF segments with broadening of phonon linewidth, indicating prominent phonon softening. Linescan across an interface of the GOF ‘letters’ reveals Raman shift to lower wavenumber in all cases but more so in ‘Z’ fiber exhibiting a broader region. Furthermore, intrinsic stress homogeneity is observed for ‘G’ fiber distributed throughout its curvature with negligible shift corresponding to E_2g mode vibration. This article demonstrates the significance of morphology in stress distribution across the self‐assembled and ‘smart‐integrable’ GOF ‘Latin letters’. Copyright © 2016 John Wiley & Sons, Ltd.     

Infrared ellipsometry and Raman studies of hexagonal InN films: correlation between strain and vibrational properties

The vibrational properties of InN films with different strain have been studied using Infrared ellipsometry and Raman scattering spectroscopy. We have established a correlation between the phonon mode parameters and the strain, which allows the determination of the deformation potentials and the strain-free frequencies of the InN E₁(TO) and E₂ modes. The LO phonons and their coupling to the free-carrier plasmon excitations are also discussed in relation to the carrier concentration in the films.     

Second order resonant Raman scattering at the E1 and E1 + Δ1 edges of germanium

The resonance of the 2TO phonon second order Raman band of germanium was investigated in the vicinity of the E₁, E₁ + Δ₁ gaps. The peak reported earlier for 2TO phonons at Γ is interpreted as due to a resonant process of the iterative type, involving two first order electron-phonon vertices. The rest of the 2TO band is interpreted as a process involving a second order electron-two phonon interaction vertex. From these measurements three phonon coupling constants for the electron-two phonon interaction are obtained.     

Role of Fe doping on structural and vibrational properties of ZnO nanostructures

In this report, Raman and Fourier Transform Infrared (FTIR) measurements were carried out to study the phonon modes of pure and Fe doped ZnO nanoparticles. The nanoparticles were prepared by sol–gel technique at room temperature. The X-ray diffraction measurements reveal that the nanoparticles are in hexagonal wurtzite structure and doping makes the shrinkage of the lattice parameters, whereas there is no alteration in the unit cell. Raman measurements show both E₂^lowE_{2}^{\mathrm{low}} and E₂^HighE_{2}^{\mathrm{High}} optical phonon mode is shifted towards lower wave number with Fe incorporation and explained on the basis of force constant variation, stress measurements, respectively. In addition, Fe related local vibrational modes (LVM) were observed for higher concentration of Fe doping. FTIR spectra reveal a band at 444 cm⁻¹ which is specific to E ₁ (TO) mode; a red-shift of this mode in Fe doped samples and some surface phonon modes were observed. Furthermore, the observation of additional IR modes, which is considered to have an origin related to Fe dopant in the ZnO nanostructures, is also reported. These additional mode features can be regarded as an indicator for the incorporation of Fe ions into the lattice position of the ZnO nanostructures.     

Comparative Analysis of Temperature-dependent Raman Spectra of GaN and GaN/Mg Films

The Raman spectra of unintentionally doped gallium nitride (GaN) and Mg-doped GaN films were investigated and compared at room temperature and low temperature. The differences of E₂ and A₁(LO) mode in two samples are discussed. Stress relaxation is observed in Mg-doped GaN, and it is suggested that Mg-induced misfit dislocation and electron–phonon interaction are the possible origins. A peak at 247 cm^?1 is observed in both the Raman spectra of GaN and Mg-doped GaN. Temperature-dependent Raman scattering experiment of Mg-doped GaN shows the frequency and intensity changes of this peak with temperature. This peak is attributed to the defect-induced vibrational mode.     

Prediction of superconductivity of Ta2AlC: in situ Raman spectrometry and density functional investigations

In this paper, in situ Raman spectra of Ta₂AlC are measured in the temperature range of 80–500 K at ambient pressure. The frequencies of the Raman modes decrease with increasing temperature, which have been explained by the anharmonic and thermal expansion effects. The line‐width of E_2g (ω₃) mode increases at elevated temperatures, which is found to be due to the anharmonic phonon–phonon scatterings. On the other hand, the line‐widths of E_2g (ω₁) and A_1g (ω₄) modes decrease continuously with increasing temperature, which is explained by the electron–phonon couplings of these two phonon modes with the Ta 5d electrons. The electron–phonon coupling strengths are obtained both in experiments and density functional calculations. Finally, Ta₂AlC is predicted to be a new superconductive MAX phase. Copyright © 2014 John Wiley & Sons, Ltd.     

Micro‐Raman analysis of GaAs Schottky barrier solar cell

Gallium arsenide (GaAs) cells have been in the race with silicon single‐crystal cells for the highest efficiency photovoltaic devices. The annealed, irradiated Schottky barrier (SB) solar cells were characterised using micro‐Raman spectroscopy at three different regions: namely, at the (1) ohmic contact region, (2) unirradiated region and (3) irradiated region. We also present a micro‐Raman study of the damage process in annealed GaAs SB solar cells bombarded by high‐energy ions. A Gaussian line shape was fitted to the Raman spectra of the longitudinal optical phonon A₁(LO), and parameters such as intensity, full width at half maximum (FWHM) and the area under the peak were obtained for the different annealing temperatures. Biaxial stress (σ), carrier concentration (n), depletion length (L_d), dislocation velocity (ν) and life time of the first‐order optical phonon (τ) of the A₁(LO) mode of the irradiated region of the samples annealed at different temperatures were calculated. Copyright © 2010 John Wiley & Sons, Ltd.