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.     

Microscopic phonon theory of Si/Ge nanocrystals

Microscopic phonon theory of semiconductor nanocrystals (NCs) is reviewed in this paper. Phonon modes of Si and Ge NCs with various sizes of up to 7 nm are investigated by valence force field theory. Phonon modes in spherical SiGe alloy NCs approximately 3.6 nm (containing 1147 atoms) in size have been investigated as a function of the Si concentration. Phonon density-of-states, quantum confinement effects, as well as Raman intensities are discussed.      

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.     

Light Harvesting and Enhanced Performance of Si Quantum Dot/Si Nanowire Heterojunction Solar Cells

Si nanowires (Si NWs) structures with good antireflection and enhanced optical‐absorption properties are used to fabricate Si quantum dots/Si NWs heterojunction solar cells. The Si NWs prepared by the metal‐assisted chemical‐etching technique exhibit a very low reflection in a wide spectral range (300–1200 nm). Correspondingly, the optical absorption reaches as high as 88.9% by weighting AM1.5G solar spectrum. Both the short current density and open current voltage are improved compared to the reference flat cell. However, the photovoltaic properties are degraded by varying the Si NWs with long etching time, possibly due to the increased etching‐induced surface states. The optimal Si NWs lead to the best cell with the power conversion efficiency of 11.3%.     

Raman spectrum of Si nanowires: temperature and phonon confinement effects

The Raman spectrum of Si nanowires (NWs) is a matter of controversy. Usually, the one-phonon band appears broadened and shifted. This behaviour is interpreted in terms of phonon confinement; however, similar effects are observed for NWs with dimensions for which phonon confinement does not play any relevant role. In this context, the temperature increase induced by the laser beam is recognized to play a capital role in the shape of the spectrum. The analysis of the Raman spectrum, under the influence of the heating induced by the laser beam, is strongly dependent on the excitation conditions and the properties of the NWs. We present herein an analysis of the Raman spectrum of Si NWs based on a study of the interaction between the laser beam and the NWs, for both ensembles of NWs and individual NWs, taking account of the temperature increase in the NWs under the focused laser beam and the dimensions of the NWs.     

硅纳米线拉曼光谱的研究

声子限制效应会引起本征硅纳米线拉曼光谱红移及不对称宽化,但研究发现其并非引起硅纳米线拉曼光谱改变的主要因素。研究表明,由于在拉曼光谱测量中,通常使用的入射激光功率都在5 mW以上,激光加热会导致很高的局部温度,从而引起拉曼光谱大幅度红移并对称宽化,这是硅纳米线拉曼光谱红移的主要影响因素。另外,激光功率很高时,由激光激发的载流子会与声子发生Fano型干涉,从而使硅纳米线拉曼光谱发生Fano型红移和不对称宽化。除此之外,对小直径本征硅纳米线,声子限制效应导致波矢选择定弛则弛豫,使不在布里渊区中心的声子也可以参与拉曼散射,因而其拉曼光谱中除常见的几个拉曼峰外还会出现新拉曼峰。     

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.     

Raman spectra of CdS nanocrystals in Nafion: longitudinal optical and confined acoustic phonon modes

Quantum confinement effects on the longitudinal optical and acoustic phonons in CdS nanocrystals in the strongly confined regime in the polymer matrix Nafion are studied using Raman spectroscopy. The LO-phonon modes show size-dependent asymmetric broadening though the broadening and asymmetry are less than those predicted by the phonon confinement models. Two types of confined acoustic modes corresponding to n=1, l=0 and n=1, l=2 spheroidal vibrations are observed. Softening of the spheroidal modes is observed in the strongly confined regime.     

Low‐temperature photoluminescence studies of In‐rich InAlN nanocolumns

High‐quality In_x Al_1–xN (0.71 ≤ x_In ≤ 1.00) nanocolumns (NCs) have been grown on Si(111) substrates by rf‐plasma‐assisted molecular‐beam epitaxy (rf‐MBE). Low‐temperature photoluminescence (LT‐PL) spectra of various In‐rich InAlN NCs were measured at 4 K and single peak PL emissions were observed in the wavelength region from 0.89 µm to 1.79 µm. Temperature‐dependent PL spectra of In_0.92Al_0.08N NCs were studied and the so‐called “S‐shape” (decrease–increase–decrease) PL peak energy shift was observed with increasing temperature. This shift indicates the carrier localization induced by the In segregation effect and is different from the anomalous blue shift frequently observed in InN films and nanowires with high residual carrier concentra‐ tions. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Etching temperature dependence of optical properties of the electrochemically etched n-GaAs

The GaAs granular films have been prepared by electrochemical anodic etching of n-GaAs in HCl electrolyte at different etching temperatures. The microstructure and optical properties of the films were investigated by micro-Raman spectrum, atomic force microscopy (AFM) and photoluminescence (PL) spectroscopy. Raman spectra reveal marked redshift and broadening, which could be explained by phonon confinement model. Results show the GaAs nanocrystalline films have formed during the anodic etching process under certain chemical conditions. Two “infrared” PL bands at ∼860 nm and ∼920 nm and a strongly enhanced visible PL band envelope around 550 nm were observed in the film prepared at etching temperature of 50 °C. The “green” PL band envelope is attributed to both quantum confinement in GaAs nanocrystals and PL of Ga₂O₃ and As₂O₃. The results reveal that the energy band structure of GaAs granular films is closely related to the etching temperatures. PACS 81.07.Bc; 78.30.Fs; 78.55.Cr     

Raman spectroscopy for study of interplay between phonon confinement and Fano effect in silicon nanowires

A combined effect of doping (type and species) and size on Raman scattering from silicon (Si) nanowires (NWs) has been presented here to study interplay between quantum confinement and Fano effects. The SiNWs prepared from low doping Si wafers show only confinement effect, as evident from the asymmetry in the Raman line‐shape, irrespective of the doping type. On the other hand SiNWs prepared from wafer with high doping shows the presence of electron–phonon interaction in addition to the phonon confinement effect as revealed from the presence of asymmetry and antiresonence in the corresponding Raman spectra. This combined effect induces an extra asymmetry in the lower energy side of Raman peak for n‐type SiNWs whereas the asymmetry flips from lower energy side to the higher energy side of the Raman peak in p‐type SiNWs. Such an interplay can be represented by considering a general Fano‐Raman line‐shape equation to take care of the combined effect in SiNWs. Copyright © 2015 John Wiley & Sons, Ltd.     

Self-catalytic growth of horizontal and straight Si nanowires on Si substrates using a sputter deposition technique

We report on the growth of horizontal and straight Si nanowires (NWs) on Si substrate using sputter deposition of the Si layer followed by thermal annealing at 1000 °C and above. The growth of horizontal NWs was achieved without the use of any metal catalyst. Uniform cylindrical shaped Si NWs with a diameter in the range of 50–60 nm and a length of up to 8 μm were synthesized. The as-synthesized Si NWs have a Si core covered with a thin amorphous native oxide layer, as revealed by high resolution transmission electron microscopy. The aspect ratio of these Si NWs is in the range of 100–160. Micro-Raman studies on the NWs reveal a tensile strain on the Si NW core due to presence of a thin oxide layer. From the Raman shift, we calculate a strain of 1.0% for the catalyst free Si NW. FTIR analysis indicates the presence of interstitial oxygen atoms in the Si NWs, as expected from oxidation of Si NWs. For comparison, metal catalyst (Au) assisted Si NWs have also been grown on Si(100) substrate by a similar process. These NWs have a similar diameter and a marginally higher aspect ratio. A model for the growth mechanism of horizontal NWs is presented. This represents one of the first examples of direct horizontal growth of straight Si NWs on commonly used Si substrates suitable for nanoelectronic device fabrication.     

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.     

Raman theory of quantum wires. Evidence of ripples in Raman spectra of thin wall Si nanotubes

In the present paper we develop for the first time a general theory calculating the Raman spectrum of a quantum wire, using the phonon modes active in the wire. No Raman theory is at present available for quantum wires. In fact, to date only phenomenological models with arbitrary parameters, or unidimensional approaches have been published specifically for quantum dots. In our approach the confinement effects due to the reduced size are introduced directly by means of the Heisenberg Uncertainty Principle. The present theory, applied to silicon nanowires, permits the evaluation of Raman frequency shift and linewidth broadening as a function of the size. The results obtained by this model for Si nanowires are in close agreement with the few experimental data available in the literature. The model also shows evidence of ripples in the Raman spectra of thin wall Si nanotubes. This theory can be applied as well to any semiconductor of known phonon branches.     

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.     

Confirming the lattice contraction in CdSe nanocrystals grown in a glass matrix by Raman scattering

This work gives the evidence of the lattice contraction in CdSe nanocrystals (NCs) grown in a glass matrix. The CdSe NCs were investigated by atomic force microscopy (AFM), optical absorption (OA), and Raman spectroscopy. The average size of CdSe NCs can be estimated by AFM images. Using the OA spectra and the effective‐mass approximation, it was also possible to estimate the average sizes of CdSe NCs, which agree very well with the AFM data. These results showed that the CdSe NCs grow with increasing time of heat treatment. The blue shift of the longitudinal optical (LO) modes and surface optical (SO) phonon modes with an increase in the average radius of the NCs, shown in the Raman spectra, was explained by the lattice contraction in CdSe NCs caused by thermodynamic interactions at the interface with the host glass matrix. Copyright © 2010 John Wiley & Sons, Ltd.     

Photoluminescence properties of GaAs nanowire ensembles with zincblende and wurtzite crystal structure

Self‐standing III–V nanowires (NWs) are promising building blocks for future optoelectronic devices such as LEDs, lasers, photodetectors and solar cells. In this work, we present the results of low temperature photoluminescence (PL) characterization of GaAs NWs grown by Au‐assisted molecular beam epitaxy (MBE), coupled with the transmission electron microscopy (TEM) structural analysis. PL spectra contain exci‐ ton peaks from zincblende (ZB) and wurtzite (WZ) crystal structures of GaAs. The peaks are influenced by the quantum confinement effects. PL bands corresponding to the exciton emission from ZB and WZ crystal phases are identified, relating to the PL peaks at 1.519 eV and 1.478 eV, respectively. The obtained red shift of 41 meV for WZ GaAs should persist in thin NWs as well as in bulk materials. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

光学声子色散关系对多孔硅喇曼谱的影响

测量了多孔硅的喇曼光谱,观察到谱峰有明显的红移和非对称性展宽效应。用微晶模型对此现象进行了解释:认为谱峰的这种变化不完全是由尺寸的空间限制效应和多孔硅的应变造成的,更主要的是多孔硅的色散关系发生了变化。采用不同的色散关系对谱峰进行了拟合,发现色散关系对喇曼谱的拟合有较大的影响。     

Mechanism and enhancement of photoluminescence from silicon nanocrystals implanted in SiO2 matrix

Photoluminescence (PL) spectra of Si nanocrystals (NCs) prepared by 130 keV Si ions implantation onto SiO2 matrix were investigated as a function of annealing temperature and implanted ion dose. PL spectra consist of two PL peaks, originated from smaller Si NCs due to quantum confinement effect (QCE) and the interface states located at the surface of larger Si NCs. The evolution of number of dangling bonds (DBs) on Si NCs was also investigated. For hydrogen-passivated samples, a monotonic increase in PL peak intensity with the dose of implanted Si ions up to 3×1017 ions /cm2 is observed. The number of DBs on individual Si NC, the interaction between DBs at the surface of neighbouring Si NCs and their effects on the efficiency of PL are discussed.