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.     

Study of the temperature distribution in Si nanowires under microscopic laser beam excitation

The use of laser beams as excitation sources for the characterization of semiconductor nanowires (NWs) is largely extended. Raman spectroscopy and photoluminescence (PL) are currently applied to the study of NWs. However, NWs are systems with poor thermal conductivity and poor heat dissipation, which result in unintentional heating under the excitation with a focused laser beam with microscopic size, as those usually used in microRaman and microPL experiments. On the other hand, the NWs have subwavelength diameter, which changes the optical absorption with respect to the absorption in bulk materials. Furthermore, the NW diameter is smaller than the laser beam spot, which means that the optical power absorbed by the NW depends on its position inside the laser beam spot. A detailed analysis of the interaction between a microscopic focused laser beam and semiconductor NWs is necessary for the understanding of the experiments involving laser beam excitation of NWs. We present in this work a numerical analysis of the thermal transport in Si NWs, where the heat source is the laser energy locally absorbed by the NW. This analysis takes account of the optical absorption, the thermal conductivity, the dimensions, diameter and length of the NWs, and the immersion medium. Both free standing and heat-sunk NWs are considered. Also, the temperature distribution in ensembles of NWs is discussed. This analysis intends to constitute a tool for the understanding of the thermal phenomena induced by laser beams in semiconductor NWs.     

Temperature dependent phonon confinement in silicon nanostructures

Temperature dependent variation in Raman line-shape from silicon (Si) nanostructures (NSs) is studied here. Asymmetry and red-shift in room temperature Raman spectrum is attributed to phonon confinement effect. Raman spectra recorded at higher temperatures show increase in FWHM and decrease in asymmetry ratio with respect to its room temperature counterpart. Theoretical Raman line-shape analyses of temperature dependence of phonon confinement is done by incorporating the temperature dependence of phonon dispersion relation. Experimental and theoretical temperature dependent Raman spectra are in good agreement.     

Size effects on phonon localization and Raman enhancement in silicon nanotips

Silicon nanotip arrays exhibit a wide variety of interesting optical and electronic properties associated with their dimensionality. We here investigate the effect of size‐induced changes on phonon localization and explain the enhanced Raman response. The occurrence of normally forbidden transitions in the photoluminescence spectra provides evidence for the predicted localization effect. Spatially resolved Raman spectroscopy reveals a continuous change of the silicon Raman peak position and peak width along the nanotip that is attributed to a smooth change between bulk properties at the base to size‐induced phonon confinement in the apex of the nanotip. This approach allows to exclude heating effects that normally overwhelm the phonon confinement signature. The Raman spectra are in excellent agreement with the spatial correlation model and the extracted correlation length is comparable to the tip dimensions. The observed phonon confinement coincides with an enhancement of the Raman scattering efficiency at the tip apex and results in a 40‐fold increase of the sample's Raman intensity compared with bulk silicon. These results provide a step toward the integration of Si based optoelectronic devices. Copyright © 2012 John Wiley & Sons, Ltd.     

Phonons in Ge/Si superlattices with Ge quantum dots

Ge/Si superlattices containing Ge quantum dots were prepared by molecular beam epitaxy and studied by resonant Raman scattering. It is shown that these structures possess vibrational properties of both two-and zero-dimensional objects. The folded acoustic phonons observed in the low-frequency region of the spectrum (up to 15th order) are typical for planar superlattices. The acoustic phonon lines overlap with a broad emission continuum that is due to the violation of the wave-vector conservation law by the quantum dots. An analysis of the Ge and Ge-Si optical phonons indicates that the Ge quantum dots are pseudoamorphous and that mixing of the Ge and Si atoms is insignificant. The longitudinal optical phonons undergo a low-frequency shift upon increasing laser excitation energy (2.54–2.71 eV) because of the confinement effect in small-sized quantum dots, which dominate resonant Raman scattering.     

Raman investigation of silicon nanocrystals: quantum confinement and laser‐induced thermal effects

We present a detailed experimental and theoretical Raman investigation of quantum confinement and laser‐induced local thermal effects on hydrogenated nanocrystalline silicon with different nanocrystal sizes (3.6–6.2 nm). The local temperature was monitored by measuring the Stokes/anti‐Stokes peak ratio with the laser power density range from ~120 to 960 kW/cm². In combination with the three‐dimensional phonon confinement model and the anharmonic effect, which incorporates the three‐phonon and four‐phonon decay processes, we revealed an asymmetrical decay process with wavenumbers ~170 and 350 cm^–1, an increasing anharmonic effect with nanocrystal sizes, and a shortening lifetime with enhanced temperature and decreasing nanocrystal dimension. Furthermore, we demonstrated experimentally that for Si nanocrystals smaller than 6 nm, the quantum confinement effect is dominant for the peak shift and line broadening. Copyright © 2011 John Wiley & Sons, Ltd.     

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.     

Interplay between phonon confinement effect and anharmonicity in silicon nanowires

Getting light out of silicon is a difficult task since the bulk silicon has an indirect energy electronic band gap structure. It is expected that this problem can be circumvented by silicon nanostructuring, since the quantum confinement effect may cause the increase of the silicon band gap and shift the photoluminescence into the visible energy range. The increase in resulting structural disorder also causes the phonon confinement effect, which can be analyzed with a Raman spectroscopy. The large phonon softening and broadening, observed in silicon nanowires, are compared with calculated spectra obtained by taking into account the anharmonicity, which is incorporated through the three and four phonon decay processes into Raman scattering cross-section. This analysis clearly shows that the strong shift and broadening of the Raman peak are dominated by the anharmonic effects originating from the laser heating, while confinement plays a secondary role.     

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。     

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.     

Direct observation of elemental segregation in InGaN nanowires by X‐ray nanoprobe

Using synchrotron radiation nanoprobe, this work reports on the elemental distribution in single In_x Ga_1–xN nanowires (NWs) grown by molecular beam epitaxy directly on Si(111) substrates. Single NWs dispersed on Al covered sapphire were characterized by nano‐X‐ray fluorescence, Raman scattering and photoluminescence spectroscopy. Both Ga and In maps reveal an inhomogeneous axial distribution inside sin‐ gle NWs. The analysis of NWs from the same sample but with different dimensions suggests a decrease of In segregation with the reduction of NW diameter, while Ga distribution seems to remain unaltered. Photoluminescence and Raman scattering measurements carried out on ensembles of NWs exhibit relevant signatures of the compositional disorder. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Modified phonon confinement model for size dependent Raman shift and linewidth of silicon nanocrystals

A modified phonon confinement model considering the size distribution, an improved phonon dispersion curve and a confinement function is developed for the calculation of size dependent Raman spectra of the silicon (Si) nanocrystals. The model is capable of simultaneous calculations of the Raman shift, intensity and linewidth. The calculated size dependent redshift and linewidth of Raman spectra are in good agreement with the available experimental data in literature and better than previously reported theoretical results. The rapid rise in the redshift and linewidth for relatively smaller Si nanocrystals are well reproduced. The asymmetric behavior of Raman spectra is also obtained from the present model.     

Raman scattering from GaP nanowires

A complete Raman study of GaP nanowires is presented. By comparison with the Raman spectra of GaP bulk material, microcrystals and nanoparticles, we give evidence that the Raman spectrum is affected by the one-dimensional shape of the nanowires. The Raman spectrum is sensitive to the polarization of the laser light. A specific shape of the overtones located between 600 and 800 cm^-1 is actually a signature of the nanowires. Some phonon confinement and thermal behavior is also observed for nanowires.     

Optical phonons in Ge quantum dots obtained on Si(111)

The Raman light scattering from optical phonons of Ge quantum dots grown by molecular beam epitaxy on a Si(111) surface is studied. A series of Raman lines related to the quantization of phonon spectrum is observed. It is shown that phonon frequencies are adequately described in terms of the elastic properties and the dispersion of the optical phonons of bulk Ge. The strain experienced by the Ge quantum dots is estimated.     

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.     

Annealing temperature dependence of Raman scattering in Si/SiO2 superlattice prepared by magnetron sputtering

Si/SiO₂ superlattices were prepared by magnetron sputtering, and the deposition temperature and annealing temperature had a great influence on the superlattice structure. In terms of SEM images, the mean size of Si nanocrystals annealed at 1100 °C is larger than that of nanocrystals annealed at 850 °C. It was found that the films deposited at room temperature are amorphous. With increasing deposition temperature, the amorphous and crystalline phases coexist. With increasing annealing temperature, the Raman intensity of the peak near 470 cm⁻¹ decreases, and the intensity of that at 520 cm⁻¹ increases. Also, on increasing the annealing temperature, the Raman peak near 520 cm⁻¹ shifts and narrows, and asymmetry emerges. A spherical cluster is used to model the nanocrystals in Si/SiO₂ superlattices, and the observed Raman spectra are analyzed by combining the effects of confinement on the phonon frequencies. Raman spectra from a variety of nanocrystalline silicon structures were successfully explained in terms of the phonon confinement effect. The fitted results agreed well with the experimental observations from SEM images.     

Micro-Raman scattering by laser-modified structures with Ge/Si quantum dots

Structures with self-assembled Ge/Si quantum dots grown by molecular-beam epitaxy are exposed to pulsed radiation of a picosecond laser. Changes in the vibrational spectrum of nanostructures under an external action are studied by Raman spectroscopy. An analysis of the Raman spectra measured with a micron spatial resolution along the exposed region indicates a mixing of Ge and Si atoms and a change in the induced mechanical stresses in quantum dots.     

n-SiC拉曼散射光谱的温度特性

测量了采用离子注入法得到掺N的n-SiC晶体从100—450 K的拉曼光谱. 研究了SiC一级拉曼谱、电子拉曼散射谱及二级拉曼谱的温度效应. 实验结果表明,大部分SiC一级拉曼峰会随温度升高向低波数方向移动,但声学模红移(峰值位置向低频方向移动)的幅度较光学模小. 重掺杂4H-SiC的纵光学声子等离子体激元耦合(LOPC)模频率随温度升高表现出先蓝移(峰值位置向高频方向移动)后红移的变化趋势,表明LOPC模的温度特性不仅会受到非简谐效应的影响,还与实际已离化杂质浓度有关. 电子拉曼散射峰线宽随温度升高而增 关键词： 碳化硅 温度 纵光学声子等离子体激元耦合模 电子拉曼散射     

激光显微拉曼技术检测晶体管工作电流导致的器件自加热现象

随着晶体管尺寸的日益缩小,不良热效应成为晶体管失效重要原因之一.现有的检测器件热分布的手段的空间分辨率较低,不能原位直观地获得这些尺寸越来越小的晶体管的工作过程中的热分布情况.本文针对以上问题,在变温系统上探索利用激光显微拉曼光谱技术原位检测晶体管的自热效应,结果表明可以通过器件衬底上硅的一阶声子振动的拉曼谱峰频率随温...     

Superheating of silicon nanocrystals observed by Raman spectroscopy

In the Raman spectra of silicon nanocrystals a new anomalous component was detected. Close to the usual first order Raman peak situated for a bulk crystal at 521 cm⁻¹ at room temperature, two peaks arise shifting towards lower energy and demonstrating a huge temperature increase, as measured by the ratio of the Stokes/anti-Stokes peak intensities. This behavior is dependent on the laser power and on the morphology of the nanocrystals. We can exclude, however, confinement effects, although surface enhanced phonon modes could be responsible of such superheating. Alternative explanations are also suggested and discussed.