激光诱导多孔硅晶格畸变的Raman光谱和光致发光谱研究

研究了掺钛水热法制备多孔硅的Raman光谱和光致发光谱.实验发现,当激光功率较低时,多孔硅的Raman光谱在略低于520cm^-1附近表现为一锐的单峰,和晶体硅的Raman光谱类似.随激光功率增大,该单峰向低波数移动,Raman和光致发光峰的强度与激光强度的一次方成正比.当激光功率增大到一定值时,该单峰分裂成两个Raman峰,光致发光谱的强度突然增大,与激光强度之间不再满足一次方的关系,位于低波数一侧的Raman峰随激光功率增大进一步向低波数移动.多孔硅Raman光谱随激光功率的变化是 关键词： 多孔硅 Raman光谱 光致发光     

拉曼光谱法计算多孔硅样品的温度

利用457.5nm固体激光器作为激发光源，得到了在不同功率激发下的多孔硅样品的拉曼光谱以及一些谱峰参数随功率的变化关系. 在从前的理论研究中，认为是由于激光功率的增大导致样品局域温度升高，从而使样品局域粒径变小，并由此引起了一系列谱峰参数的变化. 分别由520cm^-1和300cm^-1附近得到的随功率变化的拉曼谱图，详细讨论并计算了激光功率对多孔硅样品局域温度的定量影响，为拉曼光谱用于样品温度的定量测量奠定了实验基础. 关键词： 拉曼光谱 多孔硅 激光功率 样品温度     

激发光强度对多孔硅拉曼光谱的影响①

报道了经较强激发光辐照后的多孔硅呈现出的独特拉曼光谱性质,其一阶拉曼峰随着激发光功率的不同而变化。当激发光功率增大时,其峰位逐渐红移,同时峰的宽度变大,这种变化是可逆的。我们讨论了产生该现象可能机制。     

基于三层模型的多孔硅发光谱双峰结构的研究

基于Litovchenko提出的多孔硅三层模型和在此基础上由Li等人提出的多孔硅三层发光模型,利用半导体异质结理论导出了多孔硅芯部与夹层中载流子浓度、非平衡载流子数目、扩散电流密度、夹层与芯部发光强度的比值等关系式.结果表明:当Egint＞Egcore时,在0.2 eV＜ΔEv+ΔEc＜0.26 eV范围内发光谱将出现双峰,并在ΔEv+ΔEc＞0区域发光峰位不断向高能移动,发生蓝移现象;当Egint＜Egcore时,尽管芯部由于量子限制效应仍将导致发光峰蓝移,但芯部的发光相对夹层的发光相当弱,这时多孔硅发光谱呈现单峰.此模型定量地解释了多孔硅发光峰的蓝移起源于多孔硅量子限制效应,而发光出现发光双峰和发光峰位钉扎是由夹层物质决定,说明了多孔硅的发光存在多种发光机制.     

入射激光功率对硅纳米线拉曼光谱及荧光光谱的影响

一维纳米材料硅纳米线是目前重要的光电材料之一,采用化学气相沉积法制备了硅纳米线,实验研究了不同功率532 nm激光激发下的拉曼光谱和荧光光谱,随着入射激光功率的增加,一阶拉曼光谱出现红移和非对称加宽,而且红移同入射激光功率成正比,光致荧光光谱出现蓝移和双峰结构。使用声子限域效应、应变效应和激光非均匀加热效应对实验结果进行了分析,并采用matlab模拟了入射激光功率同拉曼频移的理论关系曲线,结果表明激光非均匀加热效应是引起拉曼光谱和光致荧光光谱变化的主要原因。     

多孔硅拉曼光谱随激发功率变化的研究

用阳极氧化法新制备了多孔硅样品,以457．5nm固体激光器为激发光源,在不同激发功率下,获得了拉曼谱图和一些谱峰参量随激光功率的变化关系。解释了520cm^-1和300cm^-1附近拉曼峰随功率变化的一系列可逆的实验现象：随激光功率升高出现的红移和非对称性展宽,主要是由于样品局域平均粒径变小而受量子限域效应的影响导致的;样品局域平均粒径在表面上的二维减小与随激光功率升高而导致的局域温升并不违背基本的热力学定律;高功率时520cm^-1附近双峰的出现是由于多孔硅样品局域平均粒径达到一定阈值而导致的纵模和横模双声子模的分裂。     

发射可见光多孔硅的拉曼光谱

本文报导了多孔硅的拉曼散射和光致发光的研究。给出了多孔硅的拉曼和光致发光谱之间的对应关系,根据拉曼峰的移动,估算了多孔硅量子线横截面的平均尺度为2.1～4.2nm。     

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。     

飞秒强激光对二氧化钛金红石晶体相变的影响

该文章报道了利用显微激光拉曼光谱仪研究近红外飞秒强激光脉冲诱导二氧化钛金红石单晶所引起的相变.实验辐照时间为60s,当激光辐照平均功率增加时,锐钛矿相的拉曼振动模式强度增强,金红石相的拉曼振动模式强度减弱.通过金红石相和锐钛矿相粉体等拉曼光谱的实验,肯定了随着辐照激光功率的增大,.可以通过拉曼光谱中锐钛矿A1g B1g(515 cm-1)振动模式标志峰和金红石相Eg(445 cm-1)振动标志峰分别对应面积的比判断其相变量.     

内分泌干扰物三苯基锡的激光拉曼光谱分析

三苯基锡(TPhT)是目前已知的内分泌干扰物中唯一的两种金属化合物之一,被广泛应用于工业、农业和交通领域,其大量使用会对土壤、海洋和内陆淡水环境造成不同程度的影响。本实验采用激光共聚焦拉曼光谱采集固体TPhT的拉曼光谱信号,尝试将该方法用于TPhT检测,探索该方法的可行性,并进行检测参数的优化选择。将拉曼光谱分析检测方法与TPhT的物性研究相结合,根据TPhT分子中不同官能团振动模式的不同,将拉曼谱图分为高、中、低3个波数区(1 500～3 200,900～1 500和100～900 cm-1)进行拉曼谱峰的归属与分析,得到了TPhT的特征振动模式和拉曼特征峰,并建立一套TPhT的标准拉曼图谱库,光谱范围在100～3 200 cm-1之间。结果表明,当激光功率选择为衰减到原激光功率(500 mW)的0.5%、曝光10 s、累积2次时,得到的拉曼谱图信噪比高且检测时间短。在212,332,657,997和1 577 cm-1处出现的信号强度较高的拉曼峰,可作为固体TPhT拉曼检测的特征峰,657和997 cm-1处拉曼特征峰的同时出现即可认为复杂的环境样品中存在TPhT。实验结果给出了辨别TPhT存在的标志,这些结果将为拉曼光谱用于实际环境样品中TPhT的残留检测提供理论依据和数据基础。     

Luminescence centers in porous silicon

Photoluminescence studies on porous silicon show that there are luminescence centers present in the surface states. By taking photoluminescence spectra of porous silicon with respect to temperature, a distinct peak can be observed in the temperature range 100–150 K. Both linear and nonlinear relationships were observed between excitation laser power and the photoluminescence intensity within this temperature range. In addition, there was a tendency for the photoluminescence peak to red shift at low temperature as well as at low excitation power. This is interpreted as indicating that the lower energy transition becomes dominant at low temperature and excitation power. The presence of these luminescence centers can be explained in terms of porous silicon as a mixture of silicon clusters and wires in which quantum confinement along with surface passivation would cause a mixing of andX band structure between the surface states and the bulk. This mixing would allow the formation of luminescence centers.     

Comparative investigation of photoluminescence of silicon wire structures and silicon oxide films

Photoluminescence spectra and their dependence on temperature as well as Raman scattering spectra and Atomic Force Microscopy investigations have been used to study the peculiarities of the red photoluminescence band in low-dimensional Si structures, such as porous silicon and silicon oxide films. It has been shown that the red photoluminescence band of porous silicon is complex and can be decomposed into two elementary bands. It was discovered that elementary band intensities depend very much on surface morphology of porous silicon. The same positions of the photoluminescence bands are also observed in silicon oxide films for different oxide composition. Comparative investigation of the PL temperature dependences in porous silicon and silicon oxide films indicates that silicon-oxide defect related mechanisms of some elementary photoluminescence bands are involved.     

Enhanced Raman scattering in multilayer structures of porous silicon

Multiple enhancement of the Raman scattering efficiency is observed in porous‐silicon‐based one‐dimensional photonic bandgap (PBG) structures with tunable reflection and dispersion under excitation at 1.06 µm. The experimental results are explained as being due to the resonant increase in the effective Raman susceptibility at light wavelengths close to the PBG edges. This effect is discussed in view of possible applications in the Raman spectroscopy of molecules embedded in porous media as well as in the Raman laser based on silicon. Copyright © 2011 John Wiley & Sons, Ltd.     

Ultraviolet Raman scattering in ZnO nanowires: quasimode mixing and temperature effects

We use near‐resonance Raman scattering to investigate zinc oxide (ZnO) nanowires grown by chemical vapor deposition on Si substrates. We discuss the role of quasimode mixing on the wavenumber of the longitudinal optical (LO) bands, and we perform Raman measurements with different excitation powers to investigate possible laser heating effects. We find that in the Raman spectra of as‐deposited nanowires grown along the c‐axis of wurtzite, the LO bands are located slightly below the E₁(LO) mode of bulk ZnO. We perform a calculation of the expected LO wavenumber in an ensemble of randomly oriented nanowires. Our analysis shows that light refraction, together with the orientation‐dependent cross‐section of the nanowires for the incoming light, counterbalances quasimode mixing effects in the as‐grown product, giving rise to LO bands that are barely redshifted relative to the E₁(LO) mode. In the case of ZnO nanowires that have been mechanically removed (scratched) and subsequently deposited onto separate Si substrates, we observe clear laser‐induced heating. Temperature effects account well for the Raman wavenumber shifts displayed by the LO bands in the Raman spectra of the scratched nanowires. Copyright © 2010 John Wiley & Sons, Ltd.     

Implementation of a novel low‐noise InGaAs detector enabling rapid near‐infrared multichannel Raman spectroscopy of pigmented biological samples

Pigmented tissues are inaccessible to Raman spectroscopy using visible laser light because of the high level of laser‐induced tissue fluorescence. The fluorescence contribution to the acquired Raman signal can be reduced by using an excitation wavelength in the near infrared range around 1000 nm. This will shift the Raman spectrum above 1100 nm, which is the principal upper detection limit for silicon‐based CCD detectors. For wavelengths above 1100 nm indium gallium arsenide detectors can be used. However, InGaAs detectors have not yet demonstrated satisfactory noise level characteristics for demanding Raman applications. We have tested and implemented for the first time a novel sensitive InGaAs imaging camera with extremely low readout noise for multichannel Raman spectroscopy in the short‐wave infrared (SWIR) region. The effective readout noise of two electrons is comparable to that of high quality CCDs and two orders of magnitude lower than that of other commercially available InGaAs detector arrays. With an in‐house built Raman system we demonstrate detection of shot‐noise limited high quality Raman spectra of pigmented samples in the high wavenumber region, whereas a more traditional excitation laser wavelength (671 nm) could not generate a useful Raman signal because of high fluorescence. Our Raman instrument makes it possible to substantially decrease fluorescence background and to obtain high quality Raman spectra from pigmented biological samples in integration times well below 20 s. Copyright © 2015 John Wiley & Sons, Ltd.     

空间限制与应变对发光多孔硅喇曼光谱的影响

发光多孔硅的喇曼光谱在５２０ｃｍ^－１附近呈现一锐峰，峰位的红移随多孔度的增大而增大采用微晶模型拟合喇曼谱的线形，发现除了光学声子的空间限制效应，硅单晶的应变对峰位的移动也有显著贡献。通过谱形的拟合估算了硅微粒的应变，与已报道的Ｘ射线衍射结果相一致。在多孔硅的喇曼光诸中没有观察到起源于非晶硅的光散射信号。 关键词：     

Theory of the evolution of 2D band in the Raman spectra of monolayer and bilayer graphene with laser excitation energy

A double‐resonance process gives rise to the 2D band in the Raman spectra of monolayer and bilayer graphene. Based on the electronic and vibrational dispersion energies of graphene, the wavenumbers of the 2D band were calculated under different laser excitation energies (from 1.0 to 4.4 eV). Calculated results are in good agreement with experimental data and reproduce the experimental dispersion slope of the 2D band very well. The calculated wavenumbers of the 2D band do not show a linear dependence on the laser excitation energies. Moreover, it is explained that the lowest wavenumber peak of the 2D band of the bilayer graphene, which is composed of four components, has the largest slope with laser excitation energy. Copyright © 2009 John Wiley & Sons, Ltd.     

Tuning SERS for living erythrocytes: Focus on nanoparticle size and plasmon resonance position

Surface‐enhanced Raman spectroscopy (SERS) is a unique technique to study submembrane hemoglobin (Hb_sm) in erythrocytes. We report the detailed design of SERS experiments on living erythrocytes to estimate dependence of the enhancemen t factor for main Raman bands of Hb_sm on silver nanoparticle (AgNP) properties. We demonstrate that the enhancement factor for ν 4/A1g, ν 10/B1g and A2g Raman bands of Hb_sm varies from 10⁵ to 10⁷ under proposed experimental conditions with 473 nm laser excitation. For the first time we show that the enhancement of Raman scattering increases with the increase in the relative amount of small NPs in colloids, with the decrease in AgNP size and with plasmon resonance shift to the shorter wavelength region. Obtained results can be explained by the ability of smaller AgNPs to get deeper into nano‐invaginations of the plasma membrane than larger AgNPs. This shortens the distance between small AgNPs and Hb_sm and, consequently, leads to the higher enhancement of Raman scattering of Hb_sm. The enhancement of higher wavenumber bands ν 10/B1g and A2g is more sensitive to AgNPs’ size and the relative amount of small AgNPs than the enhancement of the lower wavenumber band ν 4/A1g. This can be used for AgNP‐controlled enhancement of the desired Raman bands and should be taken into account in biomedical SERS experiments. Copyright © 2013 John Wiley & Sons, Ltd.