Raman spectroscopy of ZnS nanostructures

We report Raman scattering results of wurtzite ZnS nanowires, nanocombs, and nanobelts. The Raman spectrum obtained from ZnS nanowires exhibits first‐order phonon modes at 272, 284, and 350 cm⁻¹, corresponding to A₁/E₁ transverse optical, E₂ transverse optical, and A₁/E₁ longitudinal optical phonons, respectively. Several multiphonon modes are also observed. The longitudinal optical phonon mode varies in wavenumber for nanocombs and nanobelts, indicating that the residual strain varies during the morphological change from ZnS nanowires to nanocombs and ultimately to nanobelts. Interestingly, a surface optical (SO) phonon mode varies in wavenumber depending on the shape and surface roughness of the ZnS nanostructures. The surface modulation wavelengths of the ZnS nanowires, nanocombs, and nanobelts are estimated using the SO phonon dispersion relations and the observed SO phonon wavenumbers. Copyright © 2012 John Wiley & Sons, Ltd.     

Surface optical phonon modes in ternary aligned crystalline InGaN/GaN multi‐quantum‐well nanopillar arrays

The optical properties of focused ion beam‐engraved, perfectly aligned and spatially controlled multi‐quantum‐well (MQW) InGaN/GaN nanopillars were investigated. Crystalline MQW nanopillars with a diameter of 30–95 nm and high aspect ratios (7:1–16:1) showed a maximum of three‐fold enhancement in emission intensity per unit active area. A light‐emitting contour map of Taiwan is drawn with a nanopillar structure to demonstrate the site control of the technique adopted in the present study. Raman scattering studies were used to characterize the newly created surfaces. Unknown peaks in GaN and InGaN nanostructures are identified for surface optical (SO) phonon modes with proper assignments of wave vectors using multiple excitations, and the SO mode for the ternary phase is reported for the first time. Copyright © 2009 John Wiley & Sons, Ltd.     

Disorder‐induced Raman scattering effects in one‐dimensional ZnO nanostructures by incorporation and anisotropic distribution of Dy and Li codopants

In Dy³⁺ and Li⁺ codoped ZnO nanowires, the additives accumulate preferentially in {0001} planes, resulting in serious breakdown of the translational symmetry in ab plane and modification of the phonon oscillation field. Not only acoustic overtones, silent optical modes, surface optical (SO) phonon modes, and multi‐phonon processes can be effectively observed in the nonresonant Raman scattering (RS) and the Fourier‐transform infrared (FTIR) spectra, but the quasi‐LO and TO modes of mixed A₁ and E₁ symmetry also show a noticeable red shift from E₁ symmetry (in ab plane) to A₁ symmetry (along c axis). The presence of dislocations and internal strain at the surface layer rich in additives, coming from the segregation of additives, forms a quasi‐bilayer system, resulting in the appearance and enhancement of SO phonon modes in RS and FTIR spectra. The Fano interference, originating from the interaction between the discrete scattering from phonons and the continuum scattering from laser‐induced electrons in the doped nanostructures, leads to typical asymmetric lineshapes on the lower wavenumber sides. Copyright © 2010 John Wiley & Sons, Ltd.     

First-order Raman scattering in cylindrical wurtzite nanowire

We have presented a theoretical study on electron resonant Raman scattering (ERRS) process associated with the bulk longitudinal optical (LO), surface optical (SO) and quasi-confined (QC) phonon modes in a free-standing wurtzite nanowire (NW). We consider the Fröhlich electron–phonon interaction in the framework of the dielectric continuum model. Numerical calculations on the GaN material reveal that differential cross-section (DCS) is sensitive to the wire size. The bulk LO and high-frequency quasi-confined (QC₊) phonons make main contributions to the DCS and the impact of the SO phonon can be negligible in the ERRS process. Moreover, scattering intensity of the bulk LO phonon is strongly enhanced as the incident photon energy approaches the energy band-gap of the GaN.     

Polar interface and surface optical vibration spectra in multi-layer wurtzite quantum wires： transfer matrix method

The polar interface optical （IO） and surface optical （SO） phonon modes and the corresponding Froehlich electron phonon-interaction Hamiltonian in a freestanding multi-layer wurtzite cylindrical quantum wire （QWR） are derived and studied by employing the transfer matrix method in the dielectric continuum approximation and Loudon＇s uniaxial crystal model. A numerical calculation of a freestanding wurtzite GaN/AlN QWR is performed. The results reveal that for a relatively large azimuthal quantum number m or wave-number kz in the free z-direction, there exist two branches of IO phonon modes localized at the interface, and only one branch of SO mode localized at the surface in the system. The degenerating behaviours of the IO and SO phonon modes in the wurtzite QWR have also been clearly observed for a small kz or m. The limiting frequency properties of the IO and SO modes for large kz and m have been explained reasonably from the mathematical and physical viewpoints. The calculations of electron-phonon coupling functions show that the high-frequency IO phonon branch and SO mode play a more important role in the electron phonon interaction.     

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.     

First-order Raman scattering in a free-standing GaN nanowire with ring geometry

We have investigated one phonon resonant Raman scattering in GaN nanowires (NWs) with ring geometry. We consider the Fröhlich electron–phonon interaction in the framework of the dielectric continuum approach. The selection rules are studied. For the GaN NWs with small radius, results reveal that the main contribution to the differential cross-section (DCS) stems from the surface optical (SO) phonons especially from the high-frequency of SO phonons, with a minor contribution from the longitudinal optical (LO) phonons. Meanwhile, dispersions of the two branches of the SO phonon modes are obvious when the wire is thin. Moreover, compared to GaAs NWs, the GaN NWs make more contribution to the DCS in the small quantum size.     

Structural modifications of GaN after cerium implantation

Among the family of rare earth (RE) dopants, the doping of first member Ce into GaN is the least studied system. This article reports structure properties of Ce‐doped GaN realized by technique of ion implantation. Ce ions were implanted into metal organic chemical vapor deposition grown n‐ and p‐GaN/sapphire thin films at doses 3 × 10¹⁴ and 2 × 10¹⁵ cm⁻². X‐ray diffraction scans and Raman scattering measurements exhibited expansion of lattice in the implanted portion of the samples. First order Raman scattering spectra show appearance of several disorder‐activated Raman scattering modes in addition to typical GaN features. A dose‐dependent decrease in intensity of E₂ mode was observed in Raman the spectra of the implanted samples. Ultraviolet Raman spectra of implanted samples show complete quenching of photoluminescence emission and appearance of multiple A₁(LO) phonon scattering modes up to fifth order. Moreover, a decrease in intensity and an increase in line width of LO modes as a function of wavenumber were observed for implanted samples. Copyright © 2012 John Wiley & Sons, Ltd.     

Size‐dependent Raman and infrared studies of PbSe nanoparticles

Micro‐probe Raman and far‐infrared absorption spectroscopies were used to prove the existence of optical phonon modes of PbSe nanoparticles prepared by colloidal chemistry and preliminarily characterized by transmission electron microscopy. To the best of our knowledge, this is the first time that evidence of the surface phonon (SP) mode by Raman spectroscopy has been experimentally observed. The wavenumber of the SP mode is consistent with its prediction by a dielectric continuum model. While for different PbSe nanoparticle sizes the observed SP mode does not show any obvious change in its position, there is a clear shift by approximately 4 cm⁻¹ toward higher wavenumber in the appearance of the LO(Γ) in the Raman spectra from the 3 nm to the 7 nm PbSe nanoparticles. Far‐infrared measurements demonstrate the presence of the transverse optical TO(Γ) and of the coupled phonon modes. Copyright © 2008 John Wiley & Sons, Ltd.     

Raman study of structural disorder in ZnO nanopowders

Raman scattering spectroscopy has been used for the characterization of zinc oxide nanoparticles obtained by mechanical activation in a high‐energy vibro‐mill and planetary ball mill. Raman modes observed in spectra of nonactivated sample are assigned to Raman spectra of the ZnO monocrystal, while the spectra of mechanically activated samples point out to the structural and stoichiometric changes, depending on the milling time and the choice of equipment. Observed redshift and peak broadening of the E₂^high and E₁ (LO) first‐order Raman modes are attributed to increased disorder induced by mechanical milling, followed by the effects of phonon confinement due to correlation length decrease. The additional modes identified in Raman spectra of activated ZnO samples are related to the surface optical phonon modes, due to the intrinsic surface defects and presence of ZrO₂as extrinsic defects introduced by milling in zirconia vials. Copyright © 2009 John Wiley & Sons, Ltd.     

Temperature characterization of Raman scattering in an AlGaN/GaN heterostructure

Raman scattering from an AlGaN/GaN heterostructure was performed in the temperature range from 77 to 773 K. The first- and second-order Raman scattering of the A₁ longitudinal-optical phonon–plasmon coupled mode from an AlGaN/GaN interface as well as the Raman scattering from the GaN layer were observed. All the modes downshift, and their intensities weaken with increasing temperature. The free-carrier concentration estimated by the frequency of the coupled mode from an AlGaN/GaN interface is 7.5 times as high as that of n-AlGaN, indicating mass free-carrier transfer from the AlGaN barrier to the GaN well. Moreover, the temperature dependence of the phonon frequency is well described by an empirical formula. PACS 78.30.Fs; 63.20.Ls; 61.82.Fk; 68.60.Dv; 81.15.Gh     

Electrical field analysis of metal‐surface plasmon resonance using a biaxially strained Si substrate

Electrical field components of metal‐surface plasmon resonance were analyzed in detail. Both longitudinal optical (LO) and transverse optical (TO) phonon modes of a biaxially strained Si layer can be excited by surface‐enhanced Raman spectroscopy (SERS). The z to y polarization ratio in SERS measurements was calculated to be 0.78 using the intensity ratio of TO to LO phonon modes. The electrical field components of SERS were also calculated by the finite‐difference time‐domain method. Copyright © 2014 John Wiley & Sons, Ltd.     

气相外延GaN的拉曼散射

测量了在蓝宝石衬底上气相外延生长GaN的拉曼散射谱.除观察到已被确认的两个E2,一个A1(TO)和一个E1(TO)声于振动以外,在734±3cm-1处观察到一个散射峰且从实验上确认其为GaN的纵向光学声子模E1(LO).而且发现其强度与外延层晶体质量密切相关.A1(TO)和高频E2散射峰相对强度变化显示不同生长条件引起的外延层质量的变化.     

Surface-enhanced Raman spectroscopy of semiconductor nanostructures

We review our recent results concerning surface-enhanced Raman scattering (SERS) by confined optical and surface optical phonons in semiconductor nanostructures including CdS, CuS, GaN, and ZnO nanocrystals, GaN and ZnO nanorods, and AlN nanowires. Enhancement of Raman scattering by confined optical phonons as well as appearance of new Raman modes with the frequencies different from those in ZnO bulk attributed to surface optical modes is observed in a series of nanostructures having different morphology located in the vicinity of metal nanoclusters (Ag, Au, and Pt). Assignment of surface optical modes is based on calculations performed in the frame of the dielectric continuum model. It is established that SERS by phonons has a resonant character. A maximal enhancement by optical phonons as high as 730 is achieved for CdS nanocrystals in double resonant conditions at the coincidence of laser energy with that of electronic transitions in semiconductor nanocrystals and localized surface plasmon resonance in metal nanoclusters. Even a higher enhancement is observed for SERS by surface optical modes in ZnO nanocrystals (above 10⁴). Surface enhanced Raman scattering is used for studying phonon spectrum in nanocrystal ensembles with an ultra-low areal density on metal plasmonic nanostructures.     

Size dependence of surface optical mode and electron–phonon coupling in ZnO nanocombs

ZnO nanocombs with different sizes are synthesized by simple thermal evaporation methods. Scanning electron microscopy and transmission election microscopy testify the growth of single crystal ZnO nanocombs along [0 0 0 2] direction. The temperature-dependent Raman spectra show that the intensity of surface optical (SO) modes in ZnO nanocombs obviously increases with declining measure temperatures. With the decrease of diameters, the frequency of SO modes shows a blue shift due to the passivation of surface states. The resonant Raman scattering shows that the strength of electron–phonon coupling increases with decreasing size. Calculated on size-dependent electron–phonon interaction energy agrees well with measured values for a large size range. The origin of electron–phonon coupling in ZnO nanocombs is also discussed.     

One phonon resonant Raman scattering in a quantized spherical film

We have presented a theoretical calculation of the differential cross section (DCS) for the electron Raman scattering (ERS) process associated with surface optical (SO) phonon modes in a semiconductor quantized spherical film. We consider the Fröhlich electron–phonon interaction in the framework of the dielectric continuum approach. We study the selection rules for the processes. Singularities are found to be size-dependent and by varying the size of the QDs, it is possible to control the frequency shift in the Raman spectrum. A discussion of the phonon behavior for the films with large and small size is presented. The numerical results are also compared with that of experiments.     

One-phonon resonant electron Raman scattering in a cylindrical semiconductor quantum dot

We have presented a theoretical calculation of the differential cross section (DCS) for the electron Raman scattering (ERS) process associated with the surface optical (SO) phonon modes in semiconductor quantum dots (QDs). We consider the Fröhlich electron-phonon interaction in the framework of the dielectric continuum approach. Different scattering configurations are discussed and the selection rules for the processes are also studied. Singularities are found to be sensitively size-dependent and by varying the size of the QDs, it is possible to control the frequency shift in the Raman spectra. A discussion of the phonon behavior for QDs with large and small size is presented. The numerical results are also compared with that of experiments.     

Surface and interface optical phonon modes and electron-phonon interaction in a multi-shell spherical system

Within the framework of the dielectric continuum model, interface optical(IO) and surface optical(SO) phonon modes and the Fr?hlich electron-IO (SO) phonon interaction Hamiltonian in a multi-shell spherical system were derived and studied. Numerical calculation on CdS/HgS/H₂O and CdS/HgS/CdS/H₂O spherical systems have been performed. Results reveal that there are two IO modes and one SO mode for the CdS/HgS/H₂O system, one SO mode and four IO modes whose frequencies approach the IO phonon frequencies of the single CdS/HgS heterostructure with the increasing of the quantum number l for CdS/HgS/CdS/H₂O. It also showed that smaller l and SO phonon compared with IO phonon, have more significant contribution to the electron-IO (SO) phonon interaction. Received 16 October 2001 and Received in final form 23 January 2002 Published online 25 June 2002     

Resonant Raman scattering in CdSxSe1−x nanocrystals: effects of phonon confinement,composition, and elastic strain

Optical phonon modes, confined in CdS_xSe_1−x nanocrystal (NC) quantum dots (≈2 nm in radius) grown in a glass matrix by the melting‐nucleation method, were studied by resonant Raman scattering (RRS) spectroscopy and theoretical modeling. The formation of nanocrystalline quantum dots (QDs) is evidenced by the observation of absorption peaks and theoretically expected resonance bands in the RRS excitation spectra. This system, a ternary alloy, offers the possibility to investigate the interplay between the effects of phonon localization by disorder and phonon confinement by the NC/matrix interface. Based on the concept of propagating optical phonons, which is accepted for two‐mode pseudo‐binary alloys in their bulk form, we extended the continuous lattice dynamics model, which has successfully been used for nearly spherical NCs of binary materials, to the present case. After determining the alloy composition for NCs (that was evaluated with only 2–3% uncertainty using the bulk longitudinal optical phonon wavenumbers) and the NC size (using atomic force microscopy and optical absorption data), the experimental RRS spectra were described rather well by this theory, including the line shape and polarization dependence of the scattering intensity. Even though the presence of a compressive strain in the NCs (introduced by the matrix) masks the expected downward shift owing to the phonons' spatial quantization, the asymmetric broadening of both Raman peaks is similar to that characteristic of NCs of pure binary materials. Although with some caution, we suggest that both CdSe‐like and CdS‐like optical phonon modes indeed are propagating within the NC size unless the alloy is considerably heterogeneous. Copyright © 2011 John Wiley & Sons, Ltd.     

GaN直纳米线的光学性能

对 Ga N直纳米线的拉曼光谱及光致发光光谱进行了研究。拉曼光谱表明 ,与计算值相比 ,E2 ( high)声子频率在 560 cm- 1有 -9cm- 1的移动 ,这种声子频率显示出向低能带频移及带变宽的特征 ,是由于纳米尺寸效应所引起的结果。体系的光致发光光谱在 3 44 .8nm附近的近带隙发光 ,与文献报道的 Ga N体材料的数值3 65nm相比有一蓝移 ,这是由于量子限制效应造成的