碱性介质电催化体系活性氧的生成及其光谱学研究

亚熔盐液相氧化技术可在相对低温下实现难分解两性金属矿物的高效转化,基于此进一步提出了碱性介质电化学活性氧协同强化新方法。利用紫外-可见光光谱和电子自旋共振波谱等手段对电催化体系活性氧的生成与转化机理进行了系统解析。通过阴极电催化的作用,在电极表面定向进行两电子氧气还原反应,原位产生大量的活性氧组分。研究发现过渡金属离子与两电子氧气还原产物HO-₂之间的“自诱发”效应,可生成具有更高氧化活性的羟基自由基,大幅促进两性金属转化过程,实现了碱性介质电化学高级氧化过程。利用紫外-可见光光谱检测到电化学体系活性氧催化氧化低价两性金属氧化物(Cr₂O₃和V₂O₃)的转化过程。与此同时,根据标准自由能变化的热力学数据计算可知,V₂O₃比Cr₂O₃更易在活性氧存在的条件下发生溶出反应。采用电子自旋共振波谱(ESR)对电催化体系内的羟基自由基进行检测,结果表明由V₂O₃引发的电化学-类Fenton反应激发产生的羟基自由基ESR信号比Cr₂O₃信号强。利用猝灭剂实验验证了具有高氧化电位的羟基自由基可以对两性金属液相氧化起到促进作用。该研究为碱性介质电化学矿物溶出实际反应提供理论参考。     

Inverted organic solar cells with solvothermal synthesized vanadium-doped TiO_2 thin films as efficient electron transport layer

We investigated the effects of using different thicknesses of pure and vanadium-doped thin films of TiO_2 as the electron transport layer in the inverted configuration of organic photovoltaic cells based on poly(3-hexylthiophene) P3HT:[6-6] phenyl-(6) butyric acid methyl ester(PCBM). 1% vanadium-doped TiO_2nanoparticles were synthesized via the solvothermal method. Crystalline structure, morphology, and optical properties of pure and vanadium-doped TiO_2 thin films were studied by different techniques such as x-ray diffraction, scanning electron microscopy, transmittance electron microscopy, and UV–visible transmission spectrum. The doctor blade method which is compatible with roll-2-roll printing was used for deposition of pure and vanadium-doped TiO_2 thin films with thicknesses of 30 nm and 60 nm. The final results revealed that the best thickness of TiO_2 thin films for our fabricated cells was 30 nm. The cell with vanadium-doped TiO_2 thin film showed slightly higher power conversion efficiency and great J_(sc) of 10.7 mA/cm~2 compared with its pure counterpart. In the cells using 60 nm pure and vanadium-doped TiO_2 layers, the cell using the doped layer showed much higher efficiency. It is remarkable that the external quantum efficiency of vanadium-doped TiO_2 thin film was better in all wavelengths.     

Correlation between electronic structure and energy band in Eu-doped CuInTe_2 semiconductor compound with chalcopyrite structure

The Eu-doped Cu(In, Eu)Te_2 semiconductors with chalcopyrite structures are promising materials for their applications in the absorption layer for thin-film solar cells due to their wider band-gaps and better optical properties than those of CuInTe_2. In this paper, the Eu-doped CuInTe_2(CuIn_(1-x)Eu_xTe_2, x = 0, 0.1, 0.2, 0.3) are studied systemically based on the empirical electron theory(EET). The studies cover crystal structures, bonding regularities, cohesive energies, energy levels,and valence electron structures. The theoretical values fit the experimental results very well. The physical mechanism of a broadened band-gap induced by Eu doping into CuInTe_2 is the transitions between different hybridization energy levels induced by electron hopping between s and d orbitals and the transformations from the lattice electrons to valence electrons for Cu and In ions. The research results reveal that the photovoltaic effect induces the increase of lattice electrons of In and causes the electric resistivity to decrease. The Eu doping into CuInTe_2 mainly influences the transition between different hybridization energy levels for Cu atoms, which shows that the 3d electron numbers of Cu atoms change before and after Eu doping. In single phase CuIn_(1-x)Eu_xTe_2, the number of valence electrons changes regularly with increasing Eu content,and the calculated band gap E_g also increases, which implies that the optical properties of Eu-doped CuIn_(1-x)Eu_xTe_2 are improved.     

Degradation of flexible thin-film solar cells due to a mechanical strain

Many variants of thin film technology are nowadays part of the photovoltaic market. The most popular are amorphous silicon, CIS (Copper Indium Selenide)/CIGS (Copper Indium Gallium Selenide)/CIGSS (Copper Indium Gallium Sulphur Selenide), and CdS/CdTe (Cadmium Sulphide/Cadmium-Telluride) cells. All mentioned types allow potentially for a flexible cell structure. Most emitter contacts are currently based on TCOs (Transparent Conductive Oxides), however, wider approach with alternative carbon nanoforms, silver nanolayers and polymer materials, called TCLs (Transparent Conductive Layers) are also in use. Authors decided to investigate influence of mechanical stresses on physical and electrical behaviour of these layers. Consequently, the aim of work is to determine the level and possible mechanisms of flexible a-Si cell parameters degradation due to a deterioration of transparent contact properties.     

Application of multi-buffer layer of (Zn,Mg)O/CdS in Cu2ZnSn(S,Se)4 solar cells

(Zn,Mg)O (ZMO) buffer layer has attracted attention for having the potential to control the conduction band offset of buffer layer and large band-gap (Eg) Cu₂ZnSn(S,Se)₄ (CZTSSe) absorber interface, where the ZMO layer is deposited by the sputtering. However, the solar cell efficiency is decreased with the ZMO layer as compared with the CdS layer. The decrease in conversion efficiency is attributed to the sputtering damage on the absorber and high light reflection from the surfaces of CZTSSe solar cells. To completely suppress the damage, a CdS layer with very thin thickness of 20 nm is inserted between the ZMO layer and the CZTSSe layer. In addition, MgF₂ layers are deposited on CZTSSe solar cells as anti-reflection coating. Ultimately, the solar cell with multi-buffer layer of ZMO/thin-CdS is almost same level as that with the CdS layer. Therefore, the multi-buffer layer can be an appropriate buffer layer of the large-Eg CZTSSe layer.     

Electrodeposition of nanocrystalline Zn-Ni alloy from alkaline glycinate bath containing saccharin as additive

Nanocrystalline Zn-Ni (crystallite sizes 13-68 nm) alloy coatings were produced from an alkaline glycinate bath containing saccharin as additive. X-ray diffraction (XRD) was used to determine the phase composition and average crystallite size of nanocrystalline Zn-Ni alloy coatings. The average grain size of a deposit was also studied by transmission electron microscopy (TEM). The effects of saccharin concentration and current density on the crystallite size and surface roughness of the coatings were studied. Crystallite size and average surface roughness were diminished as a result of increasing saccharin concentration. Scanning electron microscopy (SEM) examination showed that coatings had a colony-like morphology and the colony size was increased with increasing current density. Microhardness testing was carried out in order to determine the degree of dependence of this mechanical property on the crystallite size. It was found that microhardness did not depend on crystallite size (Hall-Petch).     

Periodic patterning of silicon by direct nanosecond laser interference ablation

The production of periodic structures in silicon wafers by four-beam is presented. Because laser interference ablation is a single-step and cost-effective process, there is a great technological interest in the fabrication of these structures for their use as antireflection surfaces. Three different laser fluences are used to modify the silicon surface (0.8 J cm⁻², 1.3 J cm⁻², 2.0 J cm⁻²) creating bumps in the rim of the irradiated area. Laser induced periodic surface structures (LIPSS), in particular micro and nano-ripples, are also observed. Measurements of the reflectivity show a decrease in the reflectance for the samples processed with a laser fluence of 2.0 J cm⁻², probably caused by the appearance of the nano-ripples in the structured area, while bumps start to deteriorate.     

Zur quantitativen Auswertung von Mikro-Autoradiogrammen mit dem Densitron

Die vorliegende Arbeit beschāftigt sich mit der Answertung von Autoradiogrammen inhomogen markierter mikroskopischer Strukturen am Densitron. Dazu fertigten wir von herkömmlichen Stripping-Filmen (z. B. ORW O K 106) Mikro-Stufengraukeile an und bestimmten die Schwärzung S_ijeder Stufe photometrisch. Graukeile geeigneten Schwärzungsumfangs dienten dann zur Einstellung der Farbtrigger des Densitrons, so daß sich die bei dieser Einstellung gemessenen Farbflächen F_i des jeweiligen Objektes bestimmten Schwärzungswerten zuordnen ließen.

Als Modellobjekte verwendelen wir erstens Autoradiogramme von ³H-Thymidin-markierten Tumorzellen. Vergleichsmessungen an unterschiedlich lange exponierten, sonst aber identischen Präparaten ergaben eine gute Reproduzierbarkeit der Meßergebnisse. Als zweites Testobjekt dienlen Autoradiogramme einer nur schwach markierten Struktur im Gehirn von Fröschen. Die an diesem Grenzfall erhaltenen Ergebnisse werden mit Meßwerten verglichen, die vom gleichen Objekt mittels Scanning-Photometrie an einem. Mikroskop-Photometer SMP 01 (OPTON, Oberkoches, BRD) gewonnen wurden.     

Band gap tunable and improved microstructure characteristics of Cu2ZnSn(S1−x,Sex)4 thin films by annealing under atmosphere containing S and Se

Cu₂ZnSn(S_xS_1?x)₄ (CZTSSe) thin films were prepared by annealing a stacked precursor prepared on Mo coated glass substrates by the sputtering technique. The stacked precursor thin films were prepared from Cu, SnS₂, and ZnS targets at room temperature with stacking orders of Cu/SnS₂/ZnS. The stacked precursor thin films were annealed using a tubular two zone furnace system under a mixed N₂ (95%) + H₂S (5%) + Se vaporization atmosphere at 580 °C for 2 h. The effects of different Se vaporization temperature from 250 °C to 500 °C on the structural, morphological, chemical, and optical properties of the CZTSSe thin films were investigated. X-ray diffraction patterns, Raman spectroscopy, and X-ray photoelectron spectroscopy results showed that the annealed thin films had a single kesterite crystal structure without a secondary phase. The 2θ angle position for the peaks from the (112) plane in the annealed thin films decreased with increasing Se vaporization temperature. Energy dispersive X-ray results showed that the presence of Se in annealed thin films increased from 0 at% to 42.7 at% with increasing Se vaporization temperatures. UV–VIS spectroscopy results showed that the absorption coefficient of all the annealed thin films was over 10⁴ cm^?1 and that the optical band gap energy decreased from 1.5 eV to 1.05 eV with increasing Se vaporization temperature.