天线共振子理论对吡啶分子在铁钴镍衬底上SERS增强因子的计算

天线共振子模型是在研究表面增强拉曼散射增强机理过程中提出的理论.作为一项非常具有代表意义的工作,文章利用天线共振子模型计算了吡啶分子1010 cm-1特征振动模在过渡金属Fe,Co,Ni衬底上的表面增强拉曼散射增强因子:给出了共振时三种金属增强因子与激发光能量的依赖关系;研究了它们的表面粗糙度对增强因子的影响,计算了能量为0.89 eV的入射光在不同表面粗糙度的三种金属衬底上的增强因子.计算结果表明,它们在可见光范围增强因子不大,这与已报道的实验结果一致;但在红外波长却有大的增强因子,可以达到104～107,有待实验检验.     

钴钯铂的表面增强喇曼散射效应研究

利用天线共振子模型对钴钯铂的表面增强喇曼散射特性进行了计算和分析, 计算结果表明钴钯铂的增强分别为1、≤4、2～4, 实验测量的最大增强分别为≤5、105和140, 在考虑化学增强的情况下, 理论同实验是一致的; 在经氧化还原过程处理的钴钯铂片上做了核酸碱基胞嘧啶的SERS谱, 结果反映三种衬底上的SERS谱强弱不同, 以铂最大, 钴最小, 而且, 三种衬底对于胞嘧啶各振动模式的增强基本一致.     

经ORC处理银衬底上核酸碱基的SERS研究

利用天线共振子模型对银的表面增强喇曼散射(SERS)特性进行了计算和分析.结果显示，银增强因子在近红外的1.38 eV处为最大，达140以上；近紫外3.35 eV、3.90 eV、4.30 eV位置处依次减小，分别为60、48、45；而在可见光区，银增强因子的最大值为70. 在经氧化还原过程(ORC)处理的银片上做了核酸碱基腺嘌呤、尿嘧啶的SERS谱，腺嘌呤的SERS谱虽然存在荧光的影响，但SERS效应明显.尿嘧啶的SERS谱出现4个明锐的峰值，1035 cm－1是所出现的最强的模式，该模式应是尿嘧啶在核酸中存在的SERS环呼吸模式，可作为检测尿嘧啶存在的判定依据.     

铑电极在紫外区的表面增强拉曼散射机理

采用波长为 32 5nm的He Cd激光为激发光源 ,首次在粗糙铑电极上获得了高质量的表面增强拉曼信号。基于在紫外区获得SERS信号这一进展 ,以电磁场理论为基础 ,分别从定性和定量的角度对此新的实验结果做了理论分析。分析表明 ,在紫外区获得的铑的SERS信号主要源自于有着特定形貌的铑纳米粒子所引起的避雷针效应及微弱的表面等离子体共振效应的共同作用。对铑纳米粒子的表面平均SERS增强因子的计算结果与实验值较为一致 ,约为两个数量级。我们同时比较分析了在可见光及近红外区有着极佳SERS增强效应的银基底在采用 32 5nm激发光时却得不到任何SERS信号这一实验结果 ,这是因为银在此紫外区间已完全不能满足表面等离子激元共振的条件所致     

化学腐蚀法制作SERS活性衬底

本文给出一种简便的方法——化学腐蚀法,用来制备具有SERS活性的衬底。用这种方法制作的银片衬底,增强因子最大为4×10⁴,而且其SERS特性与腐蚀剂、腐蚀时间有关。同经氧化-还原过程垂处理之银片用化学沉积法制得的眼镜相比较,化学腐蚀之银片衬底增强效果较差。     

密度泛函理论研究黄曲霉素B1的表面增强拉曼散射效应

用密度泛函理论B3LYP方法和6-311G(d,p)/Lanl2DZ优化得到黄曲霉素B₁(AFB₁)分子及其复合物AFB₁-Ag的稳定结构,并计算了复合物的表面增强拉曼光谱和预共振拉曼光谱. 结果表明,AFB₁分子的拉曼光谱很大程度依赖于吸附位点以及入射光的激发波长. 与分子的常规拉曼光谱相比,复合物表面增强拉曼光谱中C=O伸缩振动模的增强因子约为10²～10³复合物的极化率增强而导致的静态化学增强,并分析了振动模式的振动方向与其拉曼强度的关系．选择复合物最大吸收峰附近激发光266和482 nm以及远离共振吸收波长785和1064 nm作为入射光,计算得到不同入射光激发下复合物的预共振拉曼光谱．结果表明其增强因子最大达到10⁴量级,主要是由电荷转移产生的共振增强引起的．     

低能d(d,γ)α反应s因子的理论研究

在唯象模型的基础上, 考虑到碰撞氘核的D态分量对跃迁矩阵元的贡献和⁴He基态D态成分,我们从理论上计算了低能d(d,γ)α反应的天体物理学S因子.由理论计算再现d-d系统的结合能和以及由共振群方法计算的d-d弹性散射相移,得到Woods-Saxon势参数. 并由此计算的S因子与实验数据在E_c.m.<3MeV范围符合得较好, 尤其在天体物理学感兴趣的几百keV以下能区, 理论计算结果很好地符合实验数据. 由理论计算结果外推,计算了目前还没有实验数据的使恒星核合成反应过程能够进行的恒星能区(约1—20keV)的S因子.     

用天线共振子模型研究银镜的紫外可见吸收光谱

我们研究了具有不同表面粗糙度银镜的紫外可见吸收光谱,实验结果表明随着表面粗糙度的增加,银粒子的共振吸收峰发生红移。根据天线共振子模型,进行了吸收光谱的理论计算,计算结果与实验相当吻合。     

噻菌灵在纳米银胶表面吸附的表面增强拉曼光谱研究

噻菌灵(TBZ)属苯并咪唑类杀菌剂,容易在水果、蔬菜及相应的果蔬饮品中形成有毒残留。基于密度泛函理论(DFT)的量子化学计算方法和表面增强拉曼光谱(SERS)技术,从理论和实验角度系统研究了噻菌灵在纳米银胶粒子表面的吸附行为和增强效应。采用柠檬酸钠还原法制备了具有表面增强拉曼散射活性的银纳米溶胶,并对水相的噻菌灵进行了SERS光谱研究。利用TBZ-Ag₄四种吸附模型对噻菌灵与银纳米溶胶的相互作用进行了理论分析。结合FT-Raman光谱和B3LYP/6-311G(d)理论计算的结果,借助Gaussian View5.0程序的图形化功能,对噻菌灵分子的振动模式、FT-Raman振动光谱和SERS光谱进行了系统的指认。研究结果表明：噻菌灵分子的所有原子在同一平面上,属于Cs对称性;其在银纳米溶胶表面具有十分显著的表面增强拉曼活性;分子中的S原子与银胶粒子发生吸附作用,并通过该分子的长轴方向垂直于银纳米银胶表面;可利用SERS光谱方法对痕量的噻菌灵进行快速检测。为研究噻菌灵的特性以及其快速检测提供了理论和实验依据。     

P-thiocresol 吸附在银纳米粒子表面系统的表面增强拉曼散射和表面增强共振拉曼散射的增强研究

文中从实验和计算两方面报道了在514.5 nm激发光下P-Thiocresol吸附在银胶表面系统的表面增强拉曼散射(SERS).文中分析了它的增强机制,发现增强主要来自于电磁场增强.如果考虑距离为2nm的两个银纳米粒子的耦舍效应,两粒子之间的SERS的电磁场增强为7.16 × 107.静态化学增强亦起到部分增强作用,它的增强倍数为6.所以,总的SERS增强,包括静态化学增强和电磁场增强,是Gtotal=Gsc ×GEM=4.4×108.我们也理论地研究了此系统的表面增强共振拉曼散射(SERRS).当激发光与P-Thiocresol-Ag3系统的激发态共振时,电荷转移机制(化学增强)也将起到重要作用,最强的增强可迭106.我们使用电荷密度将激发光下p-Thlocresol和Ag团簇问的电荷转移结果可视化,这是电荷转移的直接理论证据.对于SERRS增强,包括电荷转移和电磁场增强机制,能达到1013.     

Optimize the thermoelectric performance of CdO ceramics by doping Zn

The thermoelectric performance of CdO ceramics was enhanced by simultaneously optimizing the electrical and thermal transport properties via a small amount of Zn doping(≤3%). The introduction of Zn can obviously increase the electrical conductivity of CdO due to the simultaneous increase of carrier concentration and mobility, and eventually results in an improvement in power factor. Zn doping is also effective in suppressing the thermal conductivity of CdO because of stronger phonon scatterings from point defects, Zn-riched second phase, and grain boundaries. A best ZT of about 0.45 has been achieved in the Cd_(1-x)Zn_xO systems at about 1000 K, which is comparable to the highest values reported for other n-type oxide TE materials.     

Enhanced emission of the laser generated plume in Ar gas

We report an effect of enhanced emission of laser generated plume in gas ambi-ent.Nonreactive argon gas was used in the experiment of UV laser ablation of copper plate.The emission of Cu atoms from the plume was increased more than the times.The emission in-tensity is sensitive to the gas pressure,but in a certain region of gas pressure,the enhanced ef-fect can be controlled stably.For the emission lines from other element,Zn,in the plume,the intensities are subjected to the same factor of increasement.     

非晶态Mg_(70)Zn_(30)合金结构因子的预峰

利用X射线衍射仪对非晶态Mg70 Zn30 合金的结构进行了研究 ,获得了强度曲线、结构因子、双体分布函数和原子间最近邻距离 .结果表明 ,Mg70 Zn30 合金在小Q区间存在强烈的预峰现象 .根据预峰的特性 ,提出了Mg70 Zn30 熔体的结构模型 ,即Mg原子位于中心 ,8个Zn原子位于顶角所形成的简单立方结构模型 .该模型以共享顶点的方式相连接 ,能够满足预峰对Mg—Mg原子间距离的要求 .Mg70 Zn30 非晶合金中预峰的产生是相邻原子团中心Mg原子之间相互关联的表现     

Improved surface‐enhanced Raman scattering properties of TiO2 nanoparticles by Zn dopant

In this paper, pure and Zn‐doped TiO₂ nanoparticles (NPs) with various content of Zn were prepared by a sol–hydrothermal method and were employed as active substrates for surface‐enhanced Raman scattering (SERS). On the 3% Zn‐doped TiO₂ substrate, 4‐mercaptobenzoic acid(4‐MBA) molecules exhibit a higher SERS intensity by a factor of 6, as compared with the native enhancement of 4‐MBA adsorbed on undoped TiO₂ NPs. Moreover, the higher SERS activity was still observed on the 3% Zn‐doped TiO₂ NPs at temperature even up to 125 °C. These results indicate that an appropriate amount of Zn doping can improve the SERS performances of TiO₂ SERS‐active substrates. The introduction of Zn dopant can enrich the surface states (defects) of TiO₂ and improve the separation efficiency of photo‐generated charge carriers (electrons and holes) in TiO₂, according to measurements of X‐ray diffraction, UV‐visible diffuse reflectance spectroscopy, and photoluminescence, which are responsible for the influence of Zn dopant on the improved SERS performances of TiO₂ NPs. Copyright © 2009 John Wiley & Sons, Ltd.     

Influence of Zn Ions Codoping on Luminescence Properties of PbWO4:RE(RE=La, Yb, Y)

Zn and RE (RE=La, Yb, Y) ions co-doped PbWO₄ (PWO) single crystal grown by the Czochralski technique are characterized by x-ray diffraction (XRD), opticaltransmission spectra, and photoluminescence (PL). The doping of Zn ions shows distinct effects on the properties of PWO:RE crystals. At low concentration of Zn ions (200ppm), the luminescence intensity is quite weak for (Zn,La)-doped PWO, but is substantially strong for (Zn,Yb)-doped PWO. The blue luminescence intensity is significantly enhanced with the increasing Zn ions doping for PWO:Y. The trivalent ions codoping can increase the ratio of the blue luminescence contributing to the fast components of light yield. Ybions can enhance efficiency of luminescence in PWO:Yb:Zn because they may act as a luminous sensitization agent which can be involved in the efficient energy transfer and storage of the radiative process.     

Effect of surface ZnO coatings on oxidation and thermal stability of zinc films

The effect of thin ZnO coatings grown on Zn films on further oxidation and thermal stability of Zn films deposited on Mo(110) substrate was in situ investigated under ultrahigh vacuum by photoelectron spectrometries and low-energy electron diffraction. The results indicated that ZnO layers formed by oxidizing Zn films had at least a thickness of 3–5 monolayers. Further oxidation of Zn films was confined by as-formed ZnO coatings due to a surface passivation. It was of advantage to explain the difficulty in growing low oxygen-deficient ZnO films. The surface ZnO coatings strongly enhanced the thermal stability of Zn films, which was useful for understanding the underlying application of Zn/ZnO materials, such as Zn/ZnO nanocables with Zn core and ZnO shell.     

超导材料的正常态下杂质锌引起的非均匀性

本文采用含有非磁性杂质的二维t-J模型来描述掺锌的高温氧化物超导材料,并利用非均匀双时格林函数理论对有限尺寸的材料进行了数值计算.在 Fermion-Spin 理论框架下,我们分别研究了非磁性杂质引起的电荷和自旋的不均匀性及对材料正常态特性的影响.我们发现:一方面非磁性杂质锌对其附近的自旋反铁磁关联有强烈的影响,能使周围的最近邻关联函数的绝对值比均匀情况增加很多;另一方面,空位子会受到其周围自旋的影响而出现相应的分布不均匀性,进而又影响自旋关联的不均匀性.并且,围绕杂质锌能够形成自旋激发和空位激发的局域态.     

Microstructural evolution of SiC joints soldered using Zn–Al filler metals with the assistance of ultrasound

SiC ceramics were successfully soldered with the assistance of ultrasound. Two kinds of filler metals, namely non-eutectic Zn–5Al–3Cu and eutectic Zn–5Al alloys, were used. The effects of ultrasonic action on the microstructure and mechanical properties of the soldered joints were investigated. The results showed that ultrasound could promote the wetting and bonding between the SiC ceramic and filler metals within tens of seconds. For the Zn–5Al–3Cu solder, a fully grain-refined structure in the bond layer was obtained as the ultrasonic action time increased. This may lead to a substantial enhancement in the strength of the soldered joints. For the Zn–5Al solder, the shear strength of the soldered joints was only ∼102 MPa when the ultrasonic action time was shorter, and fractures occurred in the brittle lamellar eutectic phases in the center of the bond layer. With increasing ultrasonic action time, the lamellar eutectic phase in the bond layer of SiC joints could be completely transformed to a fine non-lamellar eutectic structure. Meanwhile, the grains in the bond layer were obviously refined. Those results led to the remarkable enhancement of the shear strength of the joints (∼138 MPa) using the Zn–5Al solder, which had approached that enhancement using the Zn–5Al–3Cu solder. The enhanced mechanical properties of the joints were attributed to the significant refinement of the grains and the change in the eutectic structure in the bond layer. Prolonged enhanced heterogeneous nucleation triggered by ultrasonic cavitation is the predominant refinement mechanism of the bond metals of the SiC joints.     

Effect of lattice strain on the Debye-Waller factors of Mg, Zn and Cd

Lattice strains in Mg, Zn and Cd powders produced by grinding have been analyzed by X-ray powder diffraction. The lattice strain (ɛ) and Debye-Waller factor (B) are determined from the half-widths and integrated intensities of the Bragg reflections. In all three cases viz. Mg, Zn and Cd, the Debye-Waller factor is found to increase with the lattice strain. From the correlation between the strain and effective Debye-Waller factor, the Debye-Waller factors for zero strain have been estimated for Mg, Zn and Cd. The variation of energy of vacancy formation as a function of lattice strain has been studied.     

锌电极表面氧化成膜过程的现场拉曼光谱研究

利用电化学氧化还原法获得了具有SERS活性的粗糙锌电极,现场检测了其在不同浓度氢氧化钾溶液中随电位变化的表面拉曼光谱。锌氧化物拉曼信号在不同浓度氢氧化钾溶液中存在着很大的差异,说明氢氧根离子浓度对锌的氧化过程有很大的影响。根据所得拉曼谱图,作者尝试着给出不同浓度氢氧化钾溶液中锌的成膜过程及机理。