Finite size effect on Raman frequency of phonons in nano-semiconductors

A comprehensive study on Raman spectroscopy with different excitation wavelengths, sample sizes, and sample shapes for optic phonons (OPs) and acoustic phonons (APs) in polar and non-polar nano-semiconductors has been performed. The study affirms that the finite size effect does not appear in the OPs of polar nano-semiconductors, while it exists in all other types of phonons. The absence of the FSE is confirmed to be originated from the long-range Fröhlich interaction and the breaking of translation symmetry. The result indicates that the Raman spectra of OPs cannot be used as a method to characterize the scale and crystalline property of polar nano-semiconductors.     

Finite size effect on the Raman frequency of phonons in nano-semiconductors

A comprehensive study on Raman spectroscopy with different excitation wavelengths, sample sizes, and sample shapes for optic phonons (OPs) and acoustic phonons (APs) in polar and non-polar nano-semiconductors has been performed. The study affirms that the finite size effect does not appear in the OPs of polar nano-semiconductors, while it exists in all other types of phonons. The absence of the FSE is confirmed to originate from the long-range Fr¨ohlich interaction and the breaking of translation symmetry. The result indicates that the Raman spectra of OPs cannot be used as a method to characterize the scale and crystalline property of polar nano-semiconductors.     

若干低维材料的拉曼光谱学研究--2004年度国家自然科学二等奖获奖项目介绍

文章扼要介绍了2004年国家自然科学二等奖获奖项目：《若干低维材料的拉曼光谱学研究》．用拉曼光谱研究低维纳米材料,必须对传统拉曼光谱学进行改造,创建新的“低维拉曼光谱学”．该项目通过若干低维材料的研究,为创建低维拉曼光谱学作出了系统的创新性贡献,如最先鉴认出典型低维材料的拉曼指纹谱,发现拉曼光谱的两个基本特征出现“反常”,但证明拉曼散射基本原理在低维体系中依然成立．通过低维拉曼光谱和光发射谱的应用研究,发现了材料的许多新奇物性,如发现超晶格和碳纳米管是类缺陷结构,和极性半导体纳米晶材料具有非晶特性,并提出了多孔硅的“量子限制电化学”形成和“多源量子阱”光发射模型,促进了低维材料和半导体器件的制备．     

若干低维材料的拉曼光谱学研究*——2004年度国家自然科学二等奖获奖项目介绍

文章扼要介绍了2004年国家自然科学二等奖获奖项目：《若干低维材料的拉曼光谱学研究》1).用拉曼光谱研究低维纳米材料,必须对传统拉曼光谱学进行改造,创建新的“低维拉曼光谱学”.该项目通过若干低维材料的研究,为创建低维拉曼光谱学作出了系统的创新性贡献,如最先鉴认出典型低维材料的拉曼指纹谱,发现拉曼光谱的两个基本特征出现“反常”,但证明拉曼散射基本原理在低维体系中依然成立.通过低维拉曼光谱和光发射谱的应用研究,发现了材料的许多新奇物性,如发现超晶格和碳纳米管是类缺陷结构,和极性半导体纳米晶材料具有非晶特性,并提出了多孔硅的“量子限制电化学”形成和“多源量子阱”光发射模型,促进了低维材料和半导体器件的制备.     

Longitudinal optical phonon-plasmon coupling in luminescent 3C-SiC nanocrystal films

Glycerol-passivated 3C-SiC nanocrystal (NC) solid films with tunable blue photoluminescence show abnormal longitudinal optical (LO) phonon behavior. As the NC size increases, the LO phonon intensity increases in the Raman spectra of the solid films and is even larger than that of the transverse optical mode. The Raman spectra cannot be fitted by using only the phonon confinement model. When further considering the coupling between the LO phonon and plasmon induced by the surface deformation potential in the glycerol layer, good agreement is achieved between the experiments and theory. This indicates that the coupled LO phonon-plasmon effect arising from the surface bonding structure plays a crucial role in the modified LO phonon behavior.     

A simple and accurate approach for calculating the vibration spectra of molecules on surfaces: Comparisons to high resolution electron energy loss data for ethylene on silicon

Peak assignment is a complex but important task for analyzing the vibration spectra of surface-bound molecules. Here we describe a simple approach for calculating infrared and Raman spectra for surface-bound molecules using a cluster model approach with quantum capping potentials (QCPs). The utility of the approach is demonstrated by comparisons to the measured high resolution electron energy loss spectra for ethylene on clean silicon. By capping the silicon cluster with QCPs we computed spectra that agree very well with the HREEL spectrum, allowing us to easily assign the experimental peaks. QCPs are similar to effective core potentials, can be used with any ab initio technique and most computational chemistry packages, and their use requires no special expertise.     

Oxygen vacancy density-dependent transformation from infrared to Raman active vibration mode in SnO2 nanostructures

Raman spectra acquired from spherical, cubic, and cuboid SnO2 nanocrystals (NCs) reveal a morphologically independent Raman mode at ～302?cm(-1). The frequency of this mode is slightly affected by the NC size, but the intensity increases obviously with decreasing NC size. By considering the dipole changes induced by oxygen vacancies and derivation based on the density functional theory and phonon confinement model, an oxygen vacancy density larger than 6% is shown to be responsible for the transformation of the IR to Raman active vibration mode, and the intensity enhancement is due to strong phonon confinement.     

苏氨酸的太赫兹及拉曼光谱研究

采用太赫兹时域光谱和拉曼光谱法对L-苏氨酸多晶粉末进行测试研究,获得了样品在0.2—2.8 THz（6.7—93.2 cm^-1）波段的特征吸收和10—4000 cm^－1波段的拉曼散射谱;分别在6.7—93.2 cm^－1和400—4000 cm^－1两个波段进行了吸收光谱与拉曼散射光谱的对比,根据晶胞分子所属的空间群,对隶属于分子的极性和非极性振动模式（A, B₁, 关键词： 太赫兹光谱 拉曼散射 氨基酸     

ZnO纳米粒子光学模多声子拉曼光谱的尺寸限制效应研究

观察到近均一尺寸的ZnO纳米粒子LO模多声子拉曼频率不随尺寸变化而改变.这为一阶LO模拉曼谱不随尺寸变化的实验结果提供了进一步的证据.参照相关实验工作,本文对ZnO这种极性纳米粒子光学模拉曼谱随尺寸变化而不变的物理根源进行了理论计算和讨论,并认为长程库仑相互作用是其根源.     

拉曼光谱研究n型4H-和6H-SiC晶体的载流子浓度

半导体材料的纵光学声子与等离子体激元耦合模(LOPC模)能够提供材料电学方面的相关信息。本文在室温下测得了n型4H-和6H-SiC的拉曼光谱,分析了掺入的杂质对于SiC晶体拉曼光谱的影响,通过拟合n型4H-和6H-SiC晶体的LOPC模的线型得到等离子体频率,并由此从理论上计算了载流子浓度。载流子浓度的理论计算值与霍尔测量的结果符合得很好。研究结果进一步证实了对于n型4H-和6H-SiC晶体,可以通过分析LOPC模的线形来较准确地给出相关材料的载流子浓度。     

Confined phonons in glasses. A study by nuclear inelastic absorption and Raman scattering

We have applied nuclear inelastic absorption (NIA) to the molecular glass former dibutyl phthalate/ferrocene, both in bulk and in nanoporous matrices having pore sizes of 50 and 25 A. The quantity g(E)/E(2), where g(E) is the vibrational density of states (VDOS) of the iron atoms, exhibits a pronounced maximum around 2 meV. Confinement in pores leads to a suppression of the VDOS below 1.5 meV, independent of the pore size. The influence of local interactions at the pore wall was assessed using Raman scattering. Our observations are discussed in the light of experimental and theoretical results on nanoparticles and for the Boson peak.     

人胚胎干细胞与急性早幼粒细胞白血病细胞的拉曼光谱特征研究

急性早幼粒细胞白血病(APL)属于急性髓系白血病(AML),是FAB分型中的M3亚型。部分APL患者形成早幼粒细胞白血病/维甲酸受体融合基因,即PML-RARα融合基因。在内外界多种因素的共同作用下,早幼粒细胞白血病发病。胚胎干细胞(ESCs)具有多向分化的能力,在一定诱导条件下, ESCs可以向造血系统分化。早幼粒细胞位于ESCs分化下游,为粒系分化阶段的一种细胞。探索一种非标记的技术方法鉴别不同分化阶段造血细胞具有重要的科研和实践意义。拉曼光谱技术可用于多种类型疾病的鉴别诊断研究,近年来应用前景愈加广阔。实验研究人胚胎干细胞系(ES)、急性早幼粒细胞白血病细胞系(NB4)和急性早幼粒细胞白血病患者(M3)白血病细胞的拉曼光谱特征,建立拉曼光谱非标记鉴别不同分化阶段白血病的方法,为临床实验研究提供基础。分别收集胚胎干细胞系(ES)、急性早幼粒细胞白血病细胞系(NB4)和4例M3患者白血病细胞,使用Horiba Xplora拉曼光谱仪获取拉曼光谱,每组或每例患者采集25~30个白血病细胞光谱。结合应用主成分分析法(PCA)、判别函数分析(DFA)、系统聚类分析和偏最小二乘判别分析(PLS-DA),对三类细胞的光谱进行分析并建立模型,进而对三类细胞进行鉴别,应用交互验证法对模型进行验证。同时结合细胞超微结构分析三种细胞的拉曼光谱特征。M3, NB4和ES细胞的拉曼光谱差别显著,主要表现为M3和NB4细胞光谱中对应核酸、蛋白质及脂类物质的谱峰明显高于ES细胞,其生物学机制包含了APL与PI3K/Akt/mTOR通路的密切关系。PI3K/Akt/mTOR通路在急性早幼粒细胞白血病细胞中存在异常激活,影响白血病细胞的生物大分子代谢;鉴别建模的总体分类准确率达100%(181/181),交互验证的分类准确率达98.9%(179/181),表明鉴别模型预测能力良好。拉曼光谱分析显示M3细胞和NB4细胞增殖代谢明显高于ES细胞,根据PCA-DFA、聚类分析及PLS-DA建立的拉曼光谱鉴别模型能够准确区分3种不同分化阶段白血病相关细胞,其结果与电镜结果相符。     

自发有序Ga_（0．5）In_（0．5）P合金的喇曼光谱研究

在室温和非共振条件下测量了自发有序Ｇａ０．５Ｉｎ０．５Ｐ合金的喇曼散射谱。测得的３８０，３６０和３３０ｃｍ－１附近的三个散射峰分别归结于合金中的类ＧａＰ的ＬＯ模、类ＩｎＰ的ＬＯ模和ＴＯＭ。发现有序合金的类ＧａＰ的ＬＯ模的声子频率随着合金的带隙能量的降低而增大。认为这与在有序合金中形成沿［１１１］方向的（ＧＳＰ）１／（ＩｎＰ）１单层超晶格有一定联系。在几种偏振配置下测得的有序合金的喇曼谱的偏振特性与通常的闪锌矿结构的半导体材料的偏振特性类似。     

分子束外延生长的极性与非极性BeZnO薄膜的比较研究

采用分子束外延设备在不同晶面蓝宝石衬底上(c面,a面,r面)生长BeZnO薄膜。使用复合缓冲层生长得到了高质量的BeZnO薄膜,X射线衍射半高宽达到600 arcsec。在c面与a面蓝宝石衬底上生长得到了极性BeZnO薄膜,在r面蓝宝石上生长得到了非极性BeZnO薄膜。共振拉曼光谱测试结果表明薄膜中的Be含量在同一水平。相对于c面与a面蓝宝石上的极性BeZnO薄膜,生长在r面蓝宝石衬底上的非极性BeZnO薄膜具有较大的表面粗糙度以及较大的半高宽,但是其光致发光谱中的紫外发光峰远远强于极性BeZnO薄膜,并且黄绿光发光峰弱于极性BeZnO薄膜。     

Interaction kinetics of atoms and molecules on carbon nanotube surfaces

We review recent experimental investigations of the interaction of gases with the surface of single-wall carbon nanotube bundles. We discuss thermal desorption spectra of both non-polar and polar adsorbates for low and high coverage. We show experimental results for diffusion processes of Xe along and within carbon nanotube bucky paper material, which is consistent with a recently proposed coupled desorption diffusion (CDD) model. We further discuss details of the interaction of ammonia with carbon nanotube surfaces, including the experimental investigation of the influence of adsorbed ammonia on the electrical transport properties of carbon nanotubes under ultra-high vacuum conditions.     

Fe、Ni共掺杂ZnO基稀磁半导体光学性能与铁磁性研究

采用水热法成功制备了不同掺杂浓度的Zn_1-2xFe_xNi_xO（x=0,0.025,0.05,0.1）稀磁半导体材料,利用X射线衍射（XRD）、透射电子显微镜（TEM）和X射线能量色散分析仪（XEDS）对样品进行表征,并结合拉曼（Raman）光谱、光致发光光谱（PL）和振动样品磁强计（VSM）研究样品的光学性能和磁学性能。结果表明,水热法制备的样品具有结晶性良好的纤锌矿结构,没有杂峰出现,形貌为纳米棒状结构,分散性良好。Fe²⁺、Ni²⁺是以替代的形式进入ZnO晶格中,Fe和Ni的掺杂使得晶体中的缺陷和应力增加,拉曼光谱峰位发生红移,光致发光光谱发生猝灭现象。另外,共掺杂样品在室温条件下存在明显的铁磁性,饱和磁化强度随着掺杂量的增加而增强。     

Raman spectral studies of Zr4+‐rich BaZrxTi1−xO3(0.5⩽x⩽1.00) phase diagram

This paper reports a systematic study of the composition and the temperature‐dependent‐Raman spectra of Zr⁴⁺‐rich BaZr_xTi_1−xO₃ (BZT) ceramic compositions (0.50⩽x⩽1.00). On the basis of the dielectric behavior of Zr rich BZT ceramics, the observed relaxor behavior has been hypothesized as a result of increasing long‐range interactions of nanosized, Ti⁴⁺‐rich polar regions in a Zr⁴⁺‐rich nonpolar matrix. Beyond an optimum concentration of BaTiO₃ (BT) in the nonpolar matrix of BaZrO₃ (x⩽0.75), a critical size and density of the polar regions is reached when the polar clusters start showing the relaxor like behavior, which finally show classical relaxor behavior for compositions with x = 0.5 and 0.6. This hypothesis is strongly supported from the Raman data on Zr‐rich BZT presented in this paper. Well‐defined BT Raman spectra for 5% BT in BZT composition were recorded, which followed completely up to the 50% Ti addition in the BZT samples. The temperature‐dependent Raman spectra collected on the BZT ceramics far beyond the dielectric transition temperatures supported the existence of the nano‐polar BT regions, like in typical relaxor samples. The full width at half‐maximum (FWHM), integrated intensity of the peaks in the Raman spectra has been analyzed to further support the conclusions. Copyright © 2008 John Wiley & Sons, Ltd.     

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.     

Size-dependent intrinsic radiative decay rates of silicon nanocrystals at large confinement energies

We study ultrafast photoluminescence (PL) dynamics of Si nanocrystals (NCs). The early-time PL spectra (<1 ns), which show strong dependence on NC size, are attributed to emission involving NC quantized states. The PL spectra recorded for long delays (>10 ns) are almost independent of NC size and are likely due to surface-related recombination. Based on instantaneous PL intensities measured 2 ps after excitation, we determine intrinsic radiative rate constants for NCs of different sizes. These constants sharply increase for confinement energies greater than approximately 1 eV indicating a fast, exponential growth of the oscillator strength of zero-phonon, pseudodirect transitions.     

亚乙基硫脲的表面增强拉曼极化率研究：电磁和电荷转移机制

测量了吸附在银电极表面的亚乙基硫脲分子在不同电位下的表面增强拉曼光谱，对光谱强度变化进行了分析.从拉曼光谱强度计算出分子的键极化率数值，分析极化率大小和变化情况，提出了分子在不同电位下表面增强效应的增强机制. 关键词： 亚乙基硫脲 表面增强拉曼极化率 电磁增强 电荷转移增强