Novel organic dyes containing N-bridged oligothiophene coplanar cores for dye-sensitized solar cells

Three novel organic dyes adopting fully-fused coplanar heteroarene as the donor moieties end-capped with two cyanoacrylic acids as acceptors and anchoring groups have been synthesized, characterized, and used as the sensitizers for dye-sensitized solar cells (DSSCs). The photophysical and electrochemical properties of the novel dyes and the characteristics of the DSSCs based on the novel organic dyes were investigated. The incorporation of the coplanar cores with electron-donating N-bridges are beneficial for the better intramolecular charge transfer (ICT), giving these new dyes good light-harvesting capability. The LUMO energy levels of these coplanar heteroacene-based dyes are sufficiently high for the efficient electron injection to TiO₂ upon photo-excitation, while the suitable HOMOs allow the regeneration of oxidized dyes with the electrolyte redox (I⁻/I₃⁻). The structural features of the coplanar cores (penta vs. hexa heteroarene) as well as the alkyl substitutions play crucial roles in governing the physical properties and device performance. Among these three novel organic sensitizers, the EHTt dye composed of a fully fused hexa-arene core and less bulky N-alkyl groups caused the DSSC to show the best photovoltaic performance with an open-circuit voltage (V_OC) of 0.58 V, a short-circuit photocurrent density (J_SC) of 13.72 mA/cm², and a fill factor (FF) of 0.69, yielding an overall power conversion efficiency (PCE) of 5.52% under AM 1.5G solar irradiation.     

Effect of H2O2 concentration on electrochemical growth and properties of vertically oriented ZnO nanorods electrodeposited from chloride solutions

In this work, ZnO nanostructures are electrodeposited on a transparent conducting glass from chloride baths. The influence of H₂O₂ concentration on the electrochemical characteristics has been studied using cyclic voltammetry (CV) and chronoamperometry (CA) techniques. From the analysis of the current transients on the basis of the Scharifker–Hills model, it is found that nucleation mechanism is progressive with a typical three-dimensional (3D) nucleation and growth process; independently with the concentration of H₂O₂. However, the nucleation rate of the ZnO changes with the increase of H₂O₂ concentration. The Mott–Schottky measurements demonstrate an n-type semiconductor character for all samples with a carrier density varying between 5.14×10¹⁸ cm⁻³ and 1.47×10¹⁸ cm⁻³. Scanning electron microscopy (SEM) observations show arrays of vertically aligned ZnO nanorods (NRs) with good homogeneity. The X-ray diffraction (XRD) patterns show that the ZnO deposited crystallises according to a hexagonal Würtzite-type structure and with the c-axis perpendicular to the electrode surface. The directional growth along (002) crystallographic plane is very important for deposits obtained at 5 and 7 mM of H₂O₂. The high optical properties of the ZnO NRs with a low density of deep defects was checked by UV–vis transmittance analyses, the band gap energy of films varies between 3.23 and 3.31 eV with transparency around 80–90%.     

Sensitive chemically amplified electrochemical detection of ruthenium tris-(2,2′-bipyridine) on tin-doped indium oxide electrode

Optimized combination of chemical agents was selected for sensitive electrochemical detection of dissolved ruthenium tris-(2,2′-bipyridine) (Ru-bipy). The detection was based on the chemical amplification mechanism, in which the anodic current of a redox-active analyte was amplified by a sacrificial electron donor in solution. On indium-doped tin oxide (ITO) electrodes, electrochemical reaction of the analyte was reversible, but that of the electron donor was greatly suppressed. Several transition metal complexes, such as ferrocene and tris-(2,2′-bipyridine) complexes of osmium, iron and ruthenium, were evaluated as model analyte. A correlation between the amplified current and the standard potential of the complex was observed, and Ru-bipy generated the largest current. A variety of organic bases, acids and zwitterions were assessed as potential electron donor. Sodium oxalate was found to produce the largest amplification factor. With Ru-bipy as the model analyte and oxalate as the electron donor, the analyte concentration curve was linear up to 50 μM, with a lower detection limit of approximately 50 nM. Preliminary work was presented in which a Ru-bipy derivative was attached to bovine serum albumin and detected electrochemically. Although the combination of Ru-bipy, oxalate and ITO electrode has been used before for electrochemiluminescent detection of Ru-bipy and oxalate, as well as electrochemical detection of oxalate, its utility in amplified voltammetric detection of Ru-bipy as a potential electrochemical label has not been reported previously.     

双级染料激光放大器泵浦能量分配的数值研究

用染料激光放大器的横向稳态泵浦理论，对不同的入射光能量选择不同的增益计算方法，研究了双级染料放大器的泵浦能量分配比例、泵浦光总能量和信号光能量大小对激光增益的影响。计算结果表明，对于其他参数确定的放大系统，存在着最佳的泵浦能量分配比例，可获得最大增益输出。通过自编程序的计算，可方便地找出特定系统泵浦能量分配比例的最佳值。     

An AFM, XPS and electrochemical study of molecular electroactive monolayers formed by wet chemistry functionalization of H-terminated Si(1 0 0) with vinylferrocene

Molecular electroactive monolayers have been produced from vinylferrocene (VFC) via light-assisted surface anchoring to H-terminated n- and p-Si(1 0 0) wafers prepared via wet chemistry, in a controlled atmosphere. The resulting Si-C bound hybrids have been characterized by means of XPS and AFM. Their performance as semiconductor functionalized electrodes and their surface composition have been followed by combining electrochemical and XPS measurements on the same samples, before and after use in an electrochemical cell. White-light photoactivated anchoring at short (1 h) exposure times has resulted in a mild route, with a very limited impact on the initial quality of the silicon substrate. In fact, the functionalized Si surface results negligibly oxidized, and the C/Fe atomic ratio is close to the value expected for the pure molecular species. The VFC/Si hybrids can be described as (η⁵-C₅H₅)Fe²⁺(η⁵-C₅H₄)-CH₂-CH₂-Si species, on the basis of XPS results. Electrochemical methods have been applied in order to investigate the role played by a robust, covalent Si-C anchoring mode towards substrate-molecule electronic communication, a crucial issue for a perspective development of molecular electronics devices. The response found from cyclic voltammograms for p-Si(1 0 0) functionalized electrodes, run in the dark and under illumination, has shown that the electron transfer is not limited by the number of charge carriers, confirming the occurrence of electron transfer via the Si valence band. The hybrids have shown a noticeable electrochemical stability and reversibility under cyclic voltammetry (cv), and the trend in peak current intensity vs. the scan rate was linear. The molecule-Si bond is preserved even after thousands of voltammetric cycles, although the surface coverage, evaluated from cv and XPS, decreases in the same sequence. An increasingly larger surface concentration of Fe³⁺ at the expenses of Fe²⁺ redox centers has been found at increasing number of cv’s, experimentally associated with the growth of silicon oxide. Surface SiO⁻ groups from deprotonated silanol termination, induced by the electrochemical treatments, are proposed as the associated counterions for the Fe³⁺ species. They could be responsible for the observed decrease in the electron transfer rate constant with electrode ageing.     

Synthesis of Novel Monomeric Dyes with Anthraquinone Residue

Two novel polymerizable dyes with anthraquinone residue have been prepared, and their structures were characterized by FTIR, ^1HNMR and EA.     

Synthesis of paramagnetic BODIPY dyes as new double (spin and fluorescence) sensors

Paramagnetic pyrroline and 1,2,3,6-tetrahydropyridine derivatives of BODIPY and their diamagnetic analogs have been synthesized and characterized as novel redox double sensor and cation sensitive reagents.     

LB膜混合聚集体中极性基团相互作用对光学非线性的影响

通过紫外－可见吸收光谱、压力－面积等温线、二次谐波的测量，研究了不同活性分子混合聚集体的形成对ＬＢ膜光学性质的影响。分子极性基团间的相互作用，使激发态能量及平均偶极矩发生变化，导致ＬＢ膜的光学非线性明显地增强或减弱。     

HoYb:YVO4的上转换发光研究

研究了960nm激光激发下HoYb双掺钒酸钇晶体HoYb:YVO4的直接上转换增敏发光,发现了Ho3+离子的上转换发光现象,HoYb:YVO4晶体的上转换发光是5F5→5I8最强,而5S2→5I8相对小了一个数量级,这是由于YVO4晶体既有很强的振子强度又有很大的多声子无辐射弛豫造成的. 关键词： 上转换发光 直接增敏(敏化) 钒酸钇YVO4晶体 Ho3+离子     

Kinetic Studies of Electrochemical Oxidation of 1,3-Benzenedithiol

The electrochemical oxidation of 1, 3-benzenedithiol was investigated in a 0. 100 mol/L tetrabutylammonium perchlorate/acetonitrile electrolyte. The electrochemical techniques used were potential sweep, bulk electrolysis, rotating disc and the potential step method. The combination of the techniques yielded the number of electrons transferred per molecule, the reaction order, the transfer coefficient, the diffusion coefficient and concentration of dithiol anions, the standard heterogeneous rate constant as well as the formal potential and equilibrium constant of the preceeding dissociation reaction. This paper also illustrates the methods for studying the electrode kinetics of reactions which (a) involve a chemical reaction preceeding the electron-transfer process, (b) have insoluble polymer products, and (c) are totally irreversible.