NLO characteristics of D-π-A coumarin-thiophene bridged azo dyes by Z-scan and DFT methods

ABSTRACT

The structural, electronic, intramolecular charge transfer (ICT) and nonlinear optical (NLO) properties of the donor-π-acceptor (D-π-A) azo linked dyes bearing coumarin thiophene bridge with different acceptors were inspected by Z-scan and DFT methods. The dye 3a exhibits bathochromic absorption maxima (649 and 650?nm) in the near IR region in DMF and DMSO. The dye 3a holds low HOMO–LUMO gap elucidated by CV and DFT indicating strong ICT character. The thermal stability is high for 3a and it shows enhanced NLO property by Z-scan and DFT methods as predicted in both global and range-separated hybrid functionals. The molecular geometry was optimised using B3LYP/6-311?+?g(d,p). The ICT characteristics are correlated with NLO properties obtained by Z-scan and DFT techniques.     

Enhancement of modulation depth of an all-optical switch using an azo dye-ethyl red film

The polymethyl methacrylate (PMMA) film doped with an azo dye ethyl-red (ER) film is employed to demonstrate the properties of an all-optical switch by its photoinduced dichroism and birefringence. We show how to enhance remarkably the modulation depth of all-optical switches almost to 100% by using two linear polarization beams: one beam is inclined at 45o with respect to the probing beam and serves as a pumping beam, and the other beam is perpendicular to the probing beam and used as an erasing beam. Furthermore, a maximum-to-minimum output intensity ratio of 2000:1 is achieved in experiment, which is very useful and important for optical storages and image displays.     

Surface‐enhanced Raman scattering of molecules adsorbed on Co‐doped ZnO nanoparticles

Transition‐metal‐doped semiconductor nanoparticles (NPs) have been well studied for their optical and catalytic properties but seldom studied by surface‐enhanced Raman scattering (SERS). In this paper, transition‐metal‐doped semiconductor NPs are investigated for their SERS property. Four groups of Co‐doped (0.5, 1, 3, and 5%) ZnO (Co ZnO) NPs and pure ZnO NPs were synthesized and studied. When 4‐mercaptobenzoic acid was used as probing molecule, significant SERS signals were obtained on all the five samples. Moreover, it is very interesting to observe a relationship between the Co‐doping concentration and enhancement of the SERS signals. SERS intensities first increase with doping concentration (up to 1%), and then decrease with further increase in doping concentration (up to 5%). Charge transfer (CT) is considered to be the main contribution to this phenomenon. Different CT ratios from substrates to molecules seem to induce different intensities of the SERS signals. In our experiments, the crystalline defects of Co ZnO NPs caused by the Co dopant affect the CT ratios. A possible mechanism of CT from the valance band of Co ZnO NPs to the lower unoccupied molecular orbital of the molecules via energy of the surface states is suggested. X‐ray photoelectron spectra, UV vis spectra, and Raman spectra were used to characterize the structure and defects in Co ZnO NPs. Copyright © 2011 John Wiley & Sons, Ltd.     

Nanoscaled ZnO films used as enhanced substrates for fluorescence detection of dyes

The ability of nanoscaled ZnO films to enhance fluorescence was studied. We found that the fluorescence intensities of Cy5, rhodamine 6G, and fluorescein can be enhanced about 10-fold on nanoscaled ZnO films as compared to that on glass substrates. The lifetimes of all samples were measured, and no obvious change in lifetime was observed for dyes on different substrates. The mechanism for the nanoscaled ZnO film enhanced fluorescence appears to be different from that for the metal-fluorophore systems.     

Nanoscaled ZnO films used as enhanced substrates for fluorescence detection of dyes

The ability of nanoscaled ZnO films to enhance fluorescence was studied.We found that the fluorescence intensities of Cy5,rhodamine 6G,and fluorescein can be enhanced about 10-fold on nanoscaled ZnO films as compared to that on glass substrates.The lifetimes of all samples were measured,and no obvious change in lifetime was observed for dyes on different substrates.The mechanism for the nanoscaled ZnO film enhanced fluorescence appears to be different from that for the metal-fluorophore systems.     

掺杂的AgBr胶体上吸附分子的喇曼超增强现象

观察了吡啶和花菁染料D1吸附在掺杂HCOOˉ的AgBr胶体上的表面增强喇曼光谱。与吸附在未掺杂的AgBr胶体表面的增强喇曼光谱相比较 ,掺杂了HCOOˉ的AgBr胶体表面具有喇曼超增强效应。HCOOˉ的双电子转移作用导致AgBr胶体中Ag+n 簇的增加是产生喇曼超增强效应的主要原因 ,符合化学增强机制。     

纳秒脉冲放电处理有机染料废水的实验研究

随着印染行业的快速发展,印染废水的排放与日俱增。由于废水中的有机物具有成分复杂、难以降解的特点,若未经有效处理直接排放,会对生态环境造成严重的污染和危害。试验设计了一种多针-网式反应器循环处理有机组分为酸性红73（AR73）的模拟废水,其采用自行设计的基于TLT（Transmission Line Transformer）的高压重频纳秒脉冲电源驱动。电源可以产生峰值电压为50 kV,脉宽40 ns,上升沿20 ns的纳秒脉冲信号,工作频率可达500 Hz。试验考察了峰值电压、放电频率、染料初始质量浓度及作用时间等因素对AR73降解效果的影响。为评价处理效果,采用紫外分光光度法分别测量了废水中剩余染料浓度、过氧化氢浓度等指标。结果表明,在初始浓度30 mg/L,循环流量3.4 L/min,放电间距30 mm,峰值电压44.26 kV,放电频率200 Hz条件下处理30 min,AR73降解率可以达到83.20%,单次脉冲注入能量为11.73 mJ,过氧化氢浓度为47.36 μmol/L,反应器脱色能效（G₅₀）可以达到31.07 g·kW⁻¹·h⁻¹。增大放电电压可以进一步提高AR73降解率,溶液中活性物质浓度提高,但是能量效率有所下降。     

Excited-state Optical Storage in azo Dye Doped PVA Film by Four-wave mixing

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DFT study and quantitative detection by surface‐enhanced Raman scattering (SERS) of ethyl carbamate

Ethyl carbamate (EC), a potentially toxic compound, is found in alcoholic beverages and fermented foodstuff. A combined experimental and theoretical study of Raman on EC is reported in this work for the first time. The Raman bands observed for EC in solid phase are characteristic for the carbonyl group, C―C, C―H and N―H stretching and deformation vibrations. These spectral features coupled with a pKa study allowed establishing the neutral species of EC present in the aqueous solutions experimentally tested at different concentrations. In addition, by performing a density functional theory study in the gas phase, the calculated geometry, the harmonic vibrational modes, and the Raman scattering activities of EC were found to be in good agreement with our experimental data and helped establish the surface‐enhanced Raman scattering (SERS) behavior and EC adsorption geometry on the silver surfaces. The Raman peak at 1006 cm⁻¹, assigned to the υ_s(CC) + ω(CH) modes, the strongest and best reproducible peak in the SERS spectra, was used for a quantitative evaluation of EC. The limit of detection, which corresponds to a signal‐to‐noise ratio equal to 3, was found to be 2 × 10⁻⁷ M (17.8 µg l⁻¹). SERS spectra obtained by using hydroxylamine hydrochloride‐reduced silver nanoparticles provide a fast and reproducible qualitative and quantitative determination of EC in aqueous solution. Copyright © 2013 John Wiley & Sons, Ltd.     

SERS detection of red organic dyes in Ag‐agar gel

Micro‐Raman spectroscopy has been widely employed in the last few years for the study of artworks, allowing for the characterization of a high class of pictorial materials. However, the detection of organic dyes by conventional Raman spectroscopy is quite difficult, due to the high fluorescence provided by these compounds. Recently, remarkable improvements have been achieved by the introduction of the surface enhanced Raman spectroscopy (SERS) technique for the analysis of organic dyes. In the present work, a new method is presented, based on the use of a SERS probe made of agar‐agar coupled with silver nanoparticles, for a non‐destructive and minimally invasive micro‐extraction of dyes from textiles. Ag‐agar gel has been tested first on textile mock‐ups dyed with alizarin, purpurin and carminic acid. SERS measurements have been performed adopting laser light excitations at 514.5 and 785 nm of a micro‐Raman setup. Highly structured SERS band intensities have been obtained. After having verified the safety of the method by colorimetric, X‐ray fluorescence and attenuated total reflectance Fourier transform infrared techniques, a real case, a pre‐Columbian piece of textile, have been investigated by Ag‐agar gel. This cutting‐edge method offers new possibilities for a sensitive and non‐destructive analysis of fluorescent materials. Copyright © 2012 John Wiley & Sons, Ltd.     

银纳米阵列直径对SERS增强效果的影响

采用电化学沉积法分别在不同孔径的阳极氧化铝(AAO)模板上沉积一系列直径不同,排列规则的银纳米阵列。以对氨基苯甲酸(PABA)和三聚氰胺两种分子分别作为探针分子, 研究了银纳米阵列的直径大小对其表面增强拉曼散射(SERS)效果的影响。结果表明, 在波长为514.5 nm的激光激发下, 探针分子的SERS信号强度随银纳米阵列直径的改变而明显变化, 并在银纳米阵列直径约为53 nm时, SERS强度达到最大。利用电磁增强机制对此实验结果进行了分析和解释。     

腺嘌呤/钯体系的电荷转移增强机理研究

腺嘌呤/金属体系中电荷转移(CT)增强机理的深入认识对理解单分子SERS和TERS中的巨大增强效应意义重大。受激发光波长的限制, 关于CT是否存在的实验证据目前还未见报道。本文在获得钯上UV-SERS的基础上, 借助紫外光激发的优势, 研究了腺嘌呤吸附在钯包金体系中的电荷转移增强机理。通过分析三个激发光波长下(325 nm、514.5 nm 和632.8 nm)的电位SERS 谱, 获得了峰值电位与激发光能量hv之间斜率为正的线性关系, 从实验上首次证实了腺嘌呤吸附在钯上的电荷转移增强机理, 电荷转移方向是从金属到分子。这对深入认识SM-SERS 或TERS 中腺嘌呤在金和银上的巨大增强效应起到了一定的指导作用。     

Characterization of undoped and Co doped ZnO nanoparticles synthesized by DC thermal plasma method

ZnO nanopowders doped with 5 and 10 at% cobalt were synthesized and their antibacterial activity was studied. Cobalt doped ZnO powders were prepared using dc thermal plasma method. Crystal structure and grain size of the particles were characterized by X-ray diffractometry and optical properties were studied using UV-vis spectroscopy. The particle size and morphology was observed by SEM and HRTEM, revealing rod like morphology. The antibacterial activity of undoped ZnO and cobalt doped ZnO nanoparticles against a Gram-negative bacterium Escherichia coli and a Gram-positive bacterium Bacillus atrophaeus was investigated. Undoped ZnO and cobalt doped ZnO exhibited antibacterial activity against both E. coli and Staphylococcus aureus but it was considerably more effective in the cobalt doped ZnO.     

Theoretical elucidation of the origin of surface‐enhanced Raman spectra of PCB52 adsorbed on silver substrates

To better understand experimentally observed surface‐enhanced Raman Scattering (SERS) of polychlorinated biphenyls (PCBs) adsorbed on nanoscaled silver substrates, a systematic theoretical study was performed by carrying out density functional theory and time‐dependent density functional theory calculations. 2,2′,5,5′‐tetrachlorobiphenyl (PCB52) was chosen as a model molecule of PCBs, and Ag_n (n = 2, 4, 6, and 10) clusters were used to mimic active sites of substrates. Calculated normal Raman spectra of PCB52–Ag_n (n = 2, 4, 6, and 10) complexes are analogical in profile to that of isolated PCB52 with only slightly enhanced intensity. In contrast, the corresponding SERS spectra calculated at adopted incident light are strongly enhanced, and the calculated enhancement factors are 10⁴ ~ 10⁵. Thus, the experimentally observed SERS phenomenon of PCBs supported on Ag substrates should correspond to the SERS spectra rather than the normal Raman spectra. The dominant enhancement in Raman intensities origins from the charge transfer resonance enhancement between the molecule and clusters. Copyright © 2014 John Wiley & Sons, Ltd.     

Optical and electrical properties of p-type ZnO fabricated by NH3 plasma post-treated ZnO thin films

In this paper, a simple method is reported to obtain nitrogen-doped p-ZnO film. In this method NH₃ plasma, generated in a plasma-enhanced chemical vapor deposition system, was employed to treat ZnO thin film. By Hall-effect measurement, a p-type conductivity was observed for the treated film with the hole density of 2.2 × 10¹⁶ cm⁻³. X-ray photoelectron spectroscopy (XPS) results confirmed that nitrogen was incorporated into ZnO film during the treatment process to occupy the oxygen positions. In low temperature photoluminescence spectra, an emission peak corresponding to acceptor-donor pair was observed. From this emission peak we calculated the N-related acceptor binding energy to be 130 meV.     

Concentration and pH dependent SERS spectra of sulfanilic acid sodium salt on colloidal silver particles

IR, Raman and surface‐enhanced Raman scattering (SERS) spectra of sulfanilic acid sodium salt (SANA) were recorded and analysed. The vibrational wavenumbers were computed by the density functional theory method using the B3LYP/6–31G* basis and found to be in good agreement with the experimental values. The effect of concentration and pH dependence on the SERS intensity of the molecule was also studied. The molecular plane assumes a tilted orientation with respect to the silver surface. The observed changes of the relative intensities of some enhanced bands and the presence of in‐plane and out‐of‐plane modes of the phenyl ring suggest that the molecule assumes a more tilted orientation upon lowering the concentration of the adsorbate. Copyright © 2009 John Wiley & Sons, Ltd.     

银纳米粒子/碳纳米管阵列SERS基底增强因子分析和实验

为了直观、准确地定量分析表面拉曼增强散射基底结构的拉曼增强,利用磁控溅射和高温退火的方法制备了银纳米粒子修饰垂直排列的碳纳米管阵列三维复合结构样品;实验采用罗丹明6G(R6G)溶剂作为探针分子,结合共聚焦显微拉曼系统,开展了表面增强拉曼增强因子(EF)分析计算的相关实验。SEM结果表明：在有序碳纳米管阵列的表面和外壁均匀地负载了大量银纳米粒子。对退火温度为450 ℃,退火时间为30 min的样品进行了EF计算,得到其增强因子约为2.2×103,并分析了EF值低的原因主要是：在碳纳米管上溅射的银膜膜厚不均匀,导致退火后银颗粒分布不均,使得样品粗糙度值偏大,EF值较低;实验中所用的激励光源并非银纳米颗粒的优化光源。     

Structure-controllable synthesis of ZnO nanowires using water vapor in an atmospheric-pressure microwave plasma system

Although the use of atmospheric-pressure microwave plasma to synthesize ZnO nanowires addresses various issues associated with conventional synthesis methods, it is difficult to obtain nanowires with controlled diameters and lengths. Herein, we investigated the effects of microwave input power and water vapor on the structure of ZnO nanowires grown using an atmospheric-pressure microwave plasma system. It was found that the aspect ratio of ZnO nanowires could be controlled by adjusting the plasma temperature and the amount of OH radicals. This method successfully produced ZnO nanowires in a structure-controllable manner with a wide range of aspect ratios from 10 to 340. Interestingly, we found that the sensitivity of the ZnO nanowires to UV irradiation was closely related to the morphology. In particular, the ZnO nanowires with high aspect ratios and densities showed excellent sensing characteristics.     

SERS signal response and SERS/SERDS spectra of fluoranthene in water on naturally grown Ag nanoparticle ensembles

We present experimental results of the time‐dependent Raman signal response of fluoranthene adsorbed on a naturally grown Ag nanoparticle ensemble, which serves as surface enhanced Raman scattering (SERS) substrate. In addition, SERS characteristics such as the concentration‐dependent calibration curves and the limit of detection (LOD) for fluoranthene in distilled water will be shown. The SERS substrate was prepared by Volmer–Weber growth under ultrahigh vacuum condition and exhibits a plasmon resonance wavelength at 491 nm. For the measurement of SERS signal response and SERS/shifted excitation Raman difference spectroscopy spectra of fluoranthene in water, experimental Raman setup containing a microsystem light source with two emission wavelengths (487.61 nm and 487.91 nm) was used. We experimentally demonstrate that the maximum SERS intensity is achieved 9 min after changing the analyte concentration from 0 nmol/l to 600 nmol/l. This response time is explained by a time‐dependent adsorption of the probe molecules onto the nanoparticles. The LOD for fluoranthene in water was evaluated applying shifted excitation Raman difference spectroscopy (SERDS) at different molecule concentrations. For SERDS, two emission wavelengths of a prototype microsystem light source have been used for Raman excitation. The experimental results reveal that the LOD for the probe molecules is very low. Experimentally, we have detected a fluoranthene concentration of only 4 nmol/l, which is very close to our estimated LOD of 2 nmol/l. Thus, the presented Raman setup, with a SERS substrate, whose plasmon resonance coincides with the excitation wavelength for SERS measurements, is well suited for in‐situ trace detection of pollutant chemicals in water. Copyright © 2013 John Wiley & Sons, Ltd.