Surface-enhanced Raman Spectroscopic Studies on New Type Nano-scale Rough Substrates

Fleischmann等于1974年在电化学氧化还原粗糙化处理后的银电极表面观察到吡啶吸附分子的高质量拉曼光谱，随后被证实该类电极存在约106的表面增强效应，这一称为表面增强拉曼散射(SurfaceenhancedRamanscattering，简称SERS)效应的发现成功地奠定了将拉曼光谱应用于表面科学研究的实验基础。但是二十多年过去了，表面增强拉曼光谱（SurfaceenhancedRamanspectroscopy,也称SERS）技术并未象最初所预计那样发展成为很重要的表面科学工具而得到广泛应用，究其原因，主要由于以下三方面问题严重制约了它的发展： i）仅有少数几种金属（主要是Ag、A...ABSTRACT Fleischmann et al. observed the high quality Raman spectra of pyridine adsorbed at an electrochemically roughened Ag electrode surface in 1974. The enhancement of the signal for the adsorbate was confirmed later to be about six orders, and the phenomenon was called as surface-enhanced Raman scattering (SERS) effect. This effect is the fundamental for applying Raman spectroscopy in surfac...学位：理学博士院系专业：化学化工学院化学系_物理化学(含化学物理)学号：B19972501

Fluorescence properties and color space of modifying porcelains

目的:探讨色参数差值与荧光发射量的相关性。方法:在Color-Eye7000A分光光谱仪上,用4种模式测定Vita Interno、Shofu Vintage&Unibond和Noritake Super Porcelain EX-3套装染色瓷粉的色参数,建立其CIE LAB色度空间坐标图;计算荧光发射量和反射光谱波长。用完全随机两因素方差分析和SNK-q检验(α=0.05),比较样本荧光发射量之间的差异,建立荧光发射量与色参数差之间的相关性分析(α=0.05)。结果:Vita与Shofu,Vita与Noritake的荧光发射量差别有统计学意义(P<0.05)。荧光发射量与色参数差值之间的相关性有统计学意义(P<0.05)。荧光光谱反射峰值均处于400nm附近。染色瓷粉的色度空间总体分布趋势为:Vita染色瓷粉的明亮度较高,且偏红-黄方向,Noritake偏绿-蓝方向,而Shofu居中。结论:测量模式对测定没有影响;Shofu和Noritake的荧光发射量比Vita大;染色瓷粉所发出的荧光偏紫色;3种套装染色瓷粉的CIE LAB色度空间有差别;荧光发射量与色参数差值总体上相关。Objective:To investigate the correlation between fluorescence emission and color difference (CIE△Eab). Methods:Color and spectral distribution in three kinds of modifying porcelains (Vita Interno, Shofu Vintage & Unibond, Noritake Super Porcelain EX-3) were measured on CIELAB color scale on Color-Eye 7000A spectrophotometer under four measuring modes. CIE△Eab were analyzed by two-way ANVOA and SNK-q test (α=0.05). Correlation analyses were also performed between CIE△Eab and the color parameters difference(α= 0.05). In addition, CIELAB color coordinate was established. Results:Fluorescence emission of Vita and Shofu, Vita and Noritake were significantly different(P<0.05). Fluorescence emission and the color parameters difference showed correlationship(P<0.05). The emission wavelength of fluorescence was about 400 nm. There were differences of three kinds of porcelain in color space. The total tendency of color space as follows: Vita owned higher value and was in red-yellow direction; the shade of Noritake was in blue-green direction, while color scale of Shofu was in the middle of the previous codes.Conclusion:Specular component included versus specular component excluded modes have no effects on fluorescence emission. The fluorescence values of Shofu and Noritake were larger than that of Vita. The shade of fluorescence was purple.福建省卫生厅科技联合攻关项目(编号:3502Z8021

绿色建筑的地域性探索——厦门蓝湾国际住区建筑设计

人类对地球的环境和能源的巨大消耗,使得生态环境在急剧恶化。可持续发展的绿色生态建筑成为建筑发展的必然趋势。生态的、与自然和谐共存的建筑的核心不再是简单的节能、环保,而是更深层次的对自然的尊重和对人性的关怀。本文总结了厦门蓝湾国际对生态设计、节能以及绿色建筑的地域性体现的探索实践

Design and Fabrication of Al_2O_3/SiO_2 Double-Layer Antireflection Coatings on 4H-SiC Substrate

在4H-SiC基底上设计并制备了Al2O3/SiO2紫外双层减反射膜,通过扫描电镜(SEM)和实测反射率谱来验证理论设计的正确性。利用编程计算得到Al2O3和SiO2的最优物理膜厚分别为42.0nm和96.1nm以及参考波长λ=280nm处最小反射率为0.09%。由误差分析可知,实际镀膜时保持双层膜厚度之和与理论值一致有利于降低膜系反射率。实验中应当准确控制SiO2折射率并使Al2O3折射率接近1.715。用电子束蒸发法在4H-SiC基底上淀积Al2O3/SiO2双层膜,厚度分别为42nm和96nm。SEM截面图表明淀积的薄膜和基底间具有较强的附着力。实测反射率极小值为0.33%,对应λ=276nm,与理论结果吻合较好。与传统SiO2单层膜相比,Al2O3/SiO2双层膜具有反射率小,波长选择性好等优点,从而论证了其在4H-SiC基紫外光电器件减反射膜上具有较好的应用前景。Al2O3/SiO2 double-layer UV antireflection coatings were designed and fabricated on 4H-SiC substrate,and the validity of theoretical design was further verified by scanning electron microscope (SEM) and reflection spectrum. The optimal physical thickness of Al2O3 and SiO2 is 42.0 nm and 96.1 nm respectively by programming calculation. And then the minimum reflectance of 0.09% is obtained at reference wavelength λ=280 nm. According to error analysis,keeping the sum of double-layer thickness consistent with theoretical value is helpful to reduce the reflectance. In addition,the refractive index of SiO2 should more accurate and the refractive index of Al2O3 should be controlled close to 1.715 in the experiment. Al2O3/SiO2 double-layer coatings were deposited on 4H-SiC substrate by electron beam evaporation and the physical thickness is 42 nm and 96 nm respectively. SEM images show that the deposited layers and the substrate perform good adhesion to each other. The practical minimum reflectance is 0.33% at λ=276 nm which is close to theoretical value. Compared with conventional SiO2 single layer,Al2O3/SiO2 double-layer coatings show low reflectance and better wavelength selectivity. These results make the possibility for 4H-SiC based UV optoelectronic devices with Al2O3/SiO2 films as antireflection coatings

The Response Rate of The SERS Intensity When A Potential Step is Applied

SErS谱峰强度对电位阶跃的响应速率顾仁敖，吴芸，乔专虹，姚建林（苏州大学化学系苏州215006）田中群，李五湖（厦门大学化学系厦门361005）THErESPOnSErATEOfTHESErSInTEnSITyWHEnAPOTEnTIAlSTEPI...Abstract Time-resolved surFace-enhanced Raman spectroscopy（TRSERS）has been combined with the potential step method to study thiourea and ClO coadsorbed at Ag electrodes.When a potential is applied， the response rate of the SERS intensity depends on the potential being stepped the stepping direc-tion, the concentration of TU and the diFFerent SERS band

The Dependence of The SERS Intensities Rate on The Potential

SErS谱峰强度比与电位的关系顾仁敖，吴芸，乔专虹，姚建林（苏州大学化学系215006）田中群，李五湖（厦门大学化学系361005）THEdEPEndEnCEOfTHESErSInTEnSITIESrATEOnTHEPOTEnTIAl￥gurEnAO...Abstract Time-resolved surFace－enhanced Raman spectroscopy （ TRSERS）has been combined with the potental step inethod to study thiourea and ClO coadsorbed at Ag electrodes.When the potential changed， iF the ratio of two SERS bands intensities were stable， the two bands must have some common properties.The two bands at 932cm--(-1) and 1094cm--(-1) have similar properties

表面增强拉曼光谱研究硫脲及其衍生物在银电极上的共吸附行为

用表面增强拉曼光谱技术（ＳＥＲＳ）研究了ＨＣｌＯ４介质中硫脲（ＴＵ），一甲基硫脲（ＭＴＵ）和烯丙基硫脲（ＡＴＵ）在银电极表面的共吸附行为．首次报道了它们的混合物在银电极表面上竞争共吸附随电极电位变化的行为以及在所研究的共吸附体系中作为支持电解质的弱吸附ＣｌＯ－４离子被诱导物理共吸附的现象．作者联系地址：江西师范大学化学

Measurement Method of Logical Gate in Bulk Spin Quantum Computer

提出一种核磁共振量子计算机两量子位逻辑门测量的方案。该方案通过设置适当的标记量子位可显著缩减测量所需输入态数目,给出量子门和具体输入状态集合的实验脉冲序列。包含较少J偶合演化的脉冲序列设计可有效减少操作时间,削弱环境对量子系统的退相干影响。A scheme of measuring two-qubit logical gate is proposed based on nuclear magnetic resonance,which includes the specific input states and complete pulse sequences.In comparison with the approach not using ancillary qubit,this method remarkably reduces the number of the inputs at the cost of flag qubit resource.The pulse sequence with fewer J-coupling evolution can effectively shorten the experiment time and weaken the quantum system decoherence effect by environment.福建省自然科学基金(2008J0219;2009J05152

Raman and AFM Characterization of Au and Cu Nanorod and Nanowire Arrays

通过电化学氧化法制备具有不同孔径氧化铝模板 ,利用交流电镀的方法在模板中沉积金属 ,再用酸溶解模板可以得到相应尺度的金属纳米线或纳米棒的阵列 .本文利用原子力显微镜和表面增强拉曼技术分别表征了金和铜两种金属纳米线阵列 .研究结果表明 ,作为探针分子的硫氰(SCN )在金属纳米线上的碳氮三键的振动频率随纳米线直径的增大而蓝移 .这一现象可能是因为尺寸效应对纳米线的费米能级造成影响 ,使不同直径的金属纳米线电子结构存在微小的差别 .Recently metal nanowires (nanorods) have aroused tremendous interest because of their novel properties and potential applications in wide fields [1] . Many two?dimensional nanowire arrays of semiconductors and metals with different diameter and length have been made by using template synthesis method. To characterize the novel optical, electronic and magnetic properties of these materials, UV?Vis and fluorescence spectroscopies are two of the most wildly used methods [2, 3] . Raman spectroscopy has, however, only been applied to the characterizing of semiconductor nanowires and carbon nanotubes [4,5] . Important and meaningful information can be obtained in these cases, as some forbidden Raman modes in the bulk materials become Raman active [4, 5] . Raman spectroscopy is apparently not suitable to study metal nanowires since it can only detect the mechanical vibration bands located in the extremely low frequency region. Consequently, an alternative way has to be established to study the metal nano?wires (?rods) with Raman spectroscopy. In the present work, we have taken the probe molecule strategy and used surface?enhanced Raman spectroscopy (SERS) to characterize metal nanorods (nanowires). It is well known that for a molecule which interacts strongly with a surface, its vibrational band frequency and shape are very sensitive to the electronic property, the chemical environment and the morphology of the surface. Hence Raman spectroscopy has long been used to analyze the atomic structures and the electronic properties of the surface indirectly through assessing carefully the spectral changes of the adsorbate known as a probe molecule. On that account, it is of great interest to diagnose the electronic structures of the metal nanorods with the vibrational spectrum of a probe molecule. We have examined the changes in the electronic properties of the nanorods through analyzing the spectral changes of the probe molecule. For this purpose a typical SERS molecule of SCN - was employed. The nanorod arrays of Au and Cu with different diameter from about 15 nm to 130 nm were fabricated electrochemically by means of the anodic aluminum oxide (AAO) templates. To partially expose metal nanowires with various lengths, the AAO template was chemically etched off to a certain extent by an aqueous solution of phosphoric acid or sodium hydroxide as shown in Fig. 1. After the template was etched off, the nanowires can be characterized by TEM, see Fig. 2. The tapping mode AFM image was obtained on a scanning probe microscope (Nanoscope IIIa). SERS measurements were performed on a confocal microprobe Raman system (LabRam I).作者联系地址：厦门大学固体表面物理化学国家重点实验室!化学系福建厦门361005,厦门大学固体表面物理化学国家重点实验室!化学系福建厦门361005,南京师范大学化学系!江苏南京,210097,厦门大学固体表面物理化学国家重点实验室!化学系福建厦门361005,厦门大学固体表面物理化学国家重点实验室!Author's Address: State Key Lab.for Phys.Chem.of Solid Surf.,Xiamen Univ.,Xiamen 361005, China; 1 Dept. of Chem., Nanjing Norm

Charge transport performance of Nafion-based redox polymer in atmosphere

The charge transport performance of the Nafion-based redox polymer films prepared under different conditions was investigated by cyclic voltammetry in the sandwiched cells. The results showed that the apparent charge transfer diffusion coefficient(D-a) of the Nafion[M(bpy)(3)(2+), PEG (polyethylene glycol)] (M=Ru or Fe) films is about 10(-6)-10(-7) cm(2) . s(-1) and the mobility of the electron or hole (mu) was about 10(-4)-10(-5) cm(2) . V-1 . s(-1). In order to decrease the resistance of the interface, a polyaniline (PANI) layer was added to the interface of indium tin oxide coated conducting glass (ITO) electrode and the redox polymer. Consequentially, the D-a could be increased to about 10(-5)-10(-6) cm(2) . s(-1) and mu to about 10(-3)-10(-4) cm(2) . V-1 . s(-1), and the operating current of the cells under 600 mV bias could be increased by almost 100 times. In addition, the D-a and mu of this redox polymer film had just reduced slightly after 30 d kept in atmosphere. Therefore, the redox polymer film is sufficiently stable