Growth of aligned polypyrrole acicular nanorods and their application as Pt‐free semitransparent counter electrode in dye‐sensitized solar cell

Polypyrrole films on fluorine doped tin oxide (FTO)‐coated glass substrate were prepared in situ by placing FTO/glass substrates where pyrrole was polymerized by methyl orange‐ferric chloride complex. The atomic force microscopy image indicated growth of acicular nanorods of polypyrrole. These films exhibited catalytic activity towards I₃⁻/I⁻ redox couple and have been investigated for counter electrode application in dye‐sensitized solar cell (DSSC). The fabricated DSSC with N719 dye/TiO₂ as photoanode, and PPy/FTO as counter electrode shows ~1.7% efficiency.     

Si衬底上生长的铁硅化合物结构和取向分析

采用分子束外延法分别在650-920 ℃的Si（110）和920 ℃的Si（111）衬底表面生长出铁的硅化物纳米结构,并主要分析了920 ℃高温下纳米结构的形貌、组成相及其与Si 衬底的取向关系. 扫描隧道显微镜（STM）研究表明,920 ℃高温下,Si（110）衬底上生长的铁硅化合物完全以纳米线的形式存在,且其尺寸远大于650 ℃低温下外延生长的纳米线尺寸;Si（111）衬底上生长出三维岛和薄膜两种形貌的铁硅化合物,其中三维岛具有金属特性且直径约300 nm、高约155 nm,薄膜厚度约2 nm. 电子背散射衍射研究表明920 ℃高温下Si（110）衬底上生长的纳米线仅以β-FeSi₂的形式存在,且β-FeSi₂相与衬底之间存在唯一的取向关系：β-FeSi₂（101）//Si（111）;β-FeSi₂ [010]//Si[110];Si（111）衬底上生长的三维岛由六方晶系的Fe₂Si 相组成,Fe₂Si 属于164 空间群,晶胞常数为a=0.405 nm,c=0.509 nm;与衬底之间的取向关系为Fe₂Si（001）∥Si（111）和Fe₂Si[120]//Si[112].     

Uncapped SnO2 quantum dot catalyzed cascade assembling of four components: a rapid and green approach to the pyrano[2,3-c]pyrazole and spiro-2-oxindole derivatives

A new uncapped SnO₂ quantum dots (QDs) catalyzed strategy for the synthesis of substituted pyrano[2,3-c]pyrazole and spiro-2-oxindole derivatives has been developed via a multicomponent one pot approach in aqueous medium. The reactions can be performed at low catalyst loadings with excellent functional group tolerance. This communication also reports a comparative study of the efficiency related to the catalytic activity of uncapped SnO₂ QDs, oleic acid capped SnO₂ QDs, and SnO₂ nanoflower. Uncapped SnO₂ QDs, capped SnO₂ QDs, and SnO₂ nanoflower were prepared by simple solvothermal method and characterized by XRD, FESEM, and TEM images. The easy recovery of the catalyst and high yield of the products make the protocol attractive, sustainable, and economic. The catalyst was reused for six cycles with almost unaltered catalytic activity.     

Atomic Force Microscopy Studies of SnO2 Thin Film Microstruc tures Deposited by Atomic Layer Epitaxy

 ALE-grown, rutile-type SnO₂ thin films and gas sensor structures based thereupon were studied by AFM with main emphasis on cross-sectional investigations (X-AFM). On glass substrates the polycrystalline films showed a preferred orientation which depended on the film thickness and growth temperature while on single crystal sapphire () the growth was heteroepitaxial. For the X-AFM studies various sample preparation techniques were investigated but only ion beam etching gave satisfactory results and revealed substructures in the sensor structure consisting of Pt and SnO₂ layers on a silicon substrate.     

Phase-controlled growth of metastable Fe5Si3 nanowires by a vapor transport method

We report the synthesis of single-crystalline nanowires (NWs) of metastable Fe5Si3 phase via an iodide vapor transport method. Free-standing Fe5Si3 NWs are grown on a sapphire substrate placed on a Si wafer without the use of any catalyst. The typical size of the Fe5Si3 nanowires is 5-15 microm in length and 100-300 nm in diameter. Synthesis of the metastable phase is induced by composition-dependent nucleation from the gas-phase reaction. Depending on the concentration ratio of FeI2(g) to SiI4(g), different phases of iron silicides are formed. The growth of nanowires is facilitated by the initial nucleation of silicide particles on the substrate and further self-seeded growth of the NWs. The present work not only provides a method for the synthesis of metastable Fe5Si3 nanowires but also suggests that the phase controlled synthesis can be further optimized to produce other metal-rich silicide nanostructures for future spintronic devices.     

Ultrathin films of Ge on the Si(100)2 × 1 surface

The Ge/Si(100)2 × 1 interface was investigated by means of Auger electron spectroscopy, low‐energy electron diffraction, thermal desorption spectroscopy, and work function measurements, in the regime of a few monolayers. The results show that growth of Ge at room temperature forms a thermally stable amorphous interface without significant intermixing and interdiffusion into the substrate, for annealing up to ~1100 K. Therefore, the Ge‐Si interaction most likely takes place at the outmost silicon atomic plane. The charge transfer between Ge and Si seems to be negligible, indicating a rather covalent bonding. Regarding the Ge overlayer morphology, the growth mode depends on the substrate temperature during deposition, in accordance with the literature. Stronger annealing of the germanium covered substrate (>1100 K) causes desorption of not only Ge adatoms, but also SiGe and Ge₂ species. This is probably due to a thermal Ge‐Si interdiffusion. In that case, deeper silicon planes participate in the Ge‐Si interaction. Above 1200 K, a new Ge superstructure (4 × 4)R45^o was observed. Based on that symmetry, an atomic model is proposed, where Ge adatom pairs interact with free silicon dangling bonds.     

Mild Synthesis of Pt/SnO2/Graphene Nanocomposites with Remarkably Enhanced Ethanol Electro‐oxidation Activity and Durability

We have designed a new Pt/SnO₂/graphene nanomaterial by using L ‐arginine as a linker; this material shows the unique Pt‐around‐SnO₂ structure. The Sn²⁺ cations reduce graphene oxide (GO), leading to the in situ formation of SnO₂/graphene hybrids. L ‐Arginine is used as a linker and protector to induce the in situ growth of Pt nanoparticles (NPs) connected with SnO₂ NPs and impede the agglomeration of Pt NPs. The obtained Pt/SnO₂/graphene composites exhibit superior electrocatalytic activity and stability for the ethanol oxidation reaction as compared with the commercial Pt/C catalyst owing to the close‐connected structure between the Pt NPs and SnO₂ NPs. This work should have a great impact on the rational design of future metal–metal oxide nanostructures with high catalytic activity and stability for fuel cell systems.     

Chemical Vapor Deposition of SnO2 Thin Films from Bis(β‐diketonato)tin Complexes

A series of bis(β‐diketonato)tin compounds have been systematically synthesized and examined as precursors for chemical vapor deposition of SnO₂ thin films. These complexes were characterized by elemental analyses and NMR, IR and mass spectroscopic methods. X‐ray single‐crystal determination of Sn(tfac)₂ reveals that the complex possesses a distorted trigonal bipyramidal structure. The SnO₂ films can be deposited on the substrates such as silicon, titanium nitride, and glass by using Sn(hfac)₂, Sn(tfac)₂ and Sn(acac)₂ as CVD precursors at deposition temperatures of 300‐600°C with a carrier gas of O₂. The deposition rates range from 20 to 600 Å/min. Deposited films have been characterized by XRD, SEM, AFM, AES and AAS analyses.     

High-surface-area microporous carbon as the efficient photocathode of dye-sensitized solar cells

This paper reports on the application of cornstalks-derived high-surface-area microporous carbon (MC) as the efficient photocathode of dye-sensitized solar cells (DSCs). The photocathode, which contains MC active material, Vulcan XC–72 carbon black conductive agent, and TiO₂ binder, was obtained by a doctor blade method. Electronic impedance spectroscopy (EIS) of the MC film uniformly coated on fluorine doped SnO₂ (FTO) glass displayed a low charge-transfer resistance of 1.32 Ω cm². Cyclic voltammetry (CV) analysis of the as-prepared MC film exhibited excellent catalytic activity for I₃^?/I^? redox reactions. The DSCs assembled with the MC film photocathode presented a short-circuit photocurrent density (J_sc) of 14.8 mA cm^?2, an open-circuit photovoltage (V_oc) of 798 mV, and a fill factor (FF) of 62.3%, corresponding to an overall conversion efficiency of 7.36% under AM 1.5 irradiation (100 mW cm^?2), which is comparable to that of DSCs with Pt photocathode obtained by conventional thermal decomposition.     

One‐Step SnO2 Nanotree Growth

A comparison between Au, TiO₂ and self‐catalysed growth of SnO₂ nanostructures using chemical vapour deposition is reported. TiO₂ enables growth of a nanonetwork of SnO₂, whereas self‐catalysed growth results in nanoclusters. Using Au catalyst, single‐crystalline SnO₂ nanowire trees can be grown in a one‐step process. Two types of trees are identified that differ in size, presence of a catalytic tip, and degree of branching. The growth mechanism of these nanotrees is based on branch‐splitting and self‐seeding by the catalytic tip, facilitating at least three levels of branching, namely trunk, branch and leaf.     

Microstructural Evolution of Electrochemically Cycled Si-Doped SnO2–Lithium Thin-Film Battery

SnO₂ and Si-doped SnO₂ thin-film electrodes were deposited on a Mo/Si substrate with an e-beam evaporator at room temperature. In the voltage range of 0.1–0.8 V, a reversible capacity of 400 mAh/g was attained after 200 cycles with the Si doping whereas the pure SnO₂ exhibited a much faster capacity fade. Transmission electron microscopy (TEM) revealed that Si has segregated to form a Sn–Si solid solution after the first discharge. After subsequent cycling, the tin particles in the Si-doped film were observed to break up in contrast to the particle growth observed in the pure film. TEM study indicated that Si in the tin particles forms a stable amorphous layer whereas in the pure SnO₂, recrystallization of the amorphous material is believed to occur. TEM study showed that there were important differences in the microstructure, which could be responsible for the improvement of the Si addition on the cycling performance.     

不同载体对负载型氧化钨催化剂在己二酸合成反应中的结构及性能影响

以SBA-15、六角介孔二氧化硅（HMS）和SnO₂为载体,通过浸渍法合成了含钨负载型催化剂,并考察了三种催化剂在环氧环己烷选择氧化制备己二酸反应中的催化性能. 通过X射线衍射（XRD）,透射电镜/场发射透射电镜（TEM/FETEM）,紫外-可见漫反射光谱（UV-Vis DRS）,拉曼（Raman）光谱,X射线光电子能谱（XPS）以及傅里叶变换红外（FTIR）光谱等手段对各种催化剂的结构进行表征. 结果表明,载体与催化剂的性能有密切的关系. 以SnO₂为载体的WO₃/SnO₂催化剂活性最高,其次是WO₃/HMS催化剂,WO₃/SBA-15 催化剂的活性最差.XRD 分析显示WO₃/SnO₂催化剂中氧化钨物种的晶化程度最低,TEM 和XPS 结果表明氧化钨物种在WO₃/SnO₂催化剂表面高度分散并且粒径尺寸很小（约2 nm）,UV-Vis DRS结果表明在WO₃/SnO₂催化剂中存在孤立[WO₄]四面体和低聚态的钨物种,这些物种的存在可能是WO₃/SnO₂催化剂具有高活性的主要原因. 此外,WO₃/SnO₂催化剂可以重复使用多次,6 次反应后己二酸（AA）得率仍然保持在80%以上,说明氧化钨物种与SnO₂载体间存在强烈的相互作用,从而提高了催化剂的稳定性.     

Amorphous silicon carbonitride thin‐film coatings produced by remote nitrogen microwave plasma chemical vapour deposition using organosilicon precursor

Amorphous silicon carbonitride (a‐SiCN) films were produced by remote nitrogen plasma chemical vapour deposition (RP‐CVD) from bis(dimethylamino)methylsilane precursor. The effect of substrate temperature (T _S) on the kinetics of RP‐CVD, chemical structure, surface morphology and some properties of the resulting films is reported. The T _S dependence of film growth rate implies that RP‐CVD is an adsorption‐controlled process. Fourier transform infrared spectroscopic examination revealed that an increase in T _S from 30 to 400°C involves the elimination of organic moieties from the film and the formation of Si─C and Si─N network structure. The films were characterized in terms of their surface roughness and basic physical and optical properties, such as density and refractive index, respectively. Reasonably good relationships between the structural parameters represented by relative integrated intensity of infrared absorption bands from the Si─C and Si─N bonds (controlled by T _S) and the film properties are determined. Due to their small surface roughness, high density and high refractive index, the a‐SiCN films produced at T _S ≥ 350°C would seem to be useful protective coatings for metals and optical devices.     

Preparation and thermal properties of palmitic acid/polyaniline/copper nanowires form-stable phase change materials

Form-stable phase change materials (PCMs) with high thermal conductivity are essential for thermal energy storage systems, which in turn are indispensible in solar thermal energy applications and efficient use of energy. In this paper, a new palmitic acid (PA)/polyaniline (PANI) form-stable PCMs were prepared by surface polymerization. The highest loading of PA in the form-stable PCMs was 80 mass% with the phase change enthalpy (ΔH _melting) of 175 J g^?1. Copper nanowires (Cu NWs) were introduced to the form-stable PCM by mixing the Cu NWs with PA and ethanol prior to the emulsifying of PA in surfactant solution. The Cu NWs would remain intact in case the ethanol was eliminated before the PA/Cu NWs mixture was mixed with surfactant solution. Otherwise, the Cu NWs would be partially oxidized under the attack of ethanol and ammonium persulfate. The ΔH _melting of the form-stable PCMs containing Cu NWs decreased linearly with the increasing of Cu NWs loading. The ΔH _melting of the form-stable PCMs doped with 11.2 mass% Cu NWs was 149 J g^?1. The thermal conductivity of the form-stable PCMs could be effectively improved by Cu NWs. By adding 11.2 mass% Cu NWs, the thermal conductivity of the form-stable PCM could attain 0.455 W m^?1 K^?1.     

Interfacial properties of thermally oxidized Ta2Si on Si

Many refractory metal silicides have received great attention due to their potential for innovative developments in the silicon‐based microelectronic industry. However, tantalum silicide, Ta₂Si, has remained practically unnoticed since its successful application in silicon carbide technology as a simple route for a high‐k dielectric formation. The thermal oxidation of Ta₂Si produces high‐k dielectric layers, (O? Ta₂Si)‐based on a combination of Ta₂O₅ and SiO₂. In this work, we investigate the interfacial properties of thermally oxidized (850–1050 °C) Ta₂Si on commercial silicon substrates. The implications of diffusion processes in the dielectric properties of an oxidized layer are analyzed. In particular, we observe migration of tantalum pentoxide nanocrystals into the substrate with increasing oxidation temperature. An estimation of the insulator charge and interfacial O? Ta₂Si/Si trap density is also presented. Copyright © 2008 John Wiley & Sons, Ltd.     

Thin Film Growth of 3D Sr-based Metal-Organic Framework on Conductive Glass via Electrochemical Deposition

Integration of metal-organic frameworks (MOFs) as components of advanced electronic devices is at a very early phase of development and the fundamental issues related to their crystal growth on conductive substrate need to be addressed. Herein, we report on the structural characterization of a newly synthesized Sr-based MOF {[Sr(2,5-Pzdc)(H₂O)₂] ⋅ 3 H₂O}_n ( 1 ) and the uniform crystal growth of compound 1 on a conducting glass (fluorine doped tin oxide (FTO)) substrate using electrochemical deposition techniques. The Sr-based MOF 1 was synthesized by the reaction of Sr(NO₃)₂ with 2,5-pyrazinedicarboxylic acid dihydrate (2,5-Pzdc) under solvothermal conditions. A single-crystal X-ray diffraction analysis revealed that 1 has a 3D structure and crystallizes in the triclinic P space group. In addition, the uniform crystal growth of this MOF on a conducting glass (FTO) substrate was successfully achieved using electrochemical deposition techniques. Only a handful of MOFs have been reposed to grown on conductive surfaces, which makes this study an important focal point for future research on the applications of MOF-based devices in microelectronics.     

Optimization of the synthesis and characterizations of chemical bath deposited Cu2S thin films

Semiconducting copper sulphide (Cu₂S) thin films have been deposited on various substrates (SnO₂:F/glass, glass) by the simple and economical chemical bath deposition technique. The depositions were carried out during a deposition time of about 32.5 min in the pH range of 9.4 to 11. The synthesized Cu₂S thin films were characterized using various techniques without any annealing treatment. X-ray diffraction study shows that Cu₂S films exhibit the best crystallinity for pH = 10.2. For this pH value, Auger electron spectroscopy investigations show that Cu₂S thin films grown on an SnO₂/glass substrate exhibit stochiometric composition with [Cu]/[S] concentrations ratio equal to 2.02. Using the Kelvin method, the work function difference (Ф_material– Ф_probe) for the Cu₂S films deposited on SnO₂/glass substrates at the optimum pH value was found to be equal to 145 meV. Hall measurements confirm the p-type electrical conductivity of the obtained films. The electrical resistivity was of the order of 3.85 × 10⁻⁴ Ω-cm. The transmission and reflection coefficients vary in the range of [35–60] % and [5–15] % respectively, in the visible range, and the band gap energy is about 2.37 eV.     

Low‐Temperature Molten‐Salt Production of Silicon Nanowires by the Electrochemical Reduction of CaSiO3

Silicon is an extremely important technological material, but its current industrial production by the carbothermic reduction of SiO₂ is energy intensive and generates CO₂ emissions. Herein, we developed a more sustainable method to produce silicon nanowires (Si NWs) in bulk quantities through the direct electrochemical reduction of CaSiO₃, an abundant and inexpensive Si source soluble in molten salts, at a low temperature of 650 °C by using low‐melting‐point ternary molten salts CaCl₂–MgCl₂–NaCl, which still retains high CaSiO₃ solubility, and a supporting electrolyte of CaO, which facilitates the transport of O²⁻ anions, drastically improves the reaction kinetics, and enables the electrolysis at low temperatures. The Si nanowire product can be used as high‐capacity Li‐ion battery anode materials with excellent cycling performance. This environmentally friendly strategy for the practical production of Si at lower temperatures can be applied to other molten salt systems and is also promising for waste glass and coal ash recycling.     

Engineering of SnO2/TiO2 heterojunction compact interface with efficient charge transfer pathway for photocatalytic hydrogen evolution

Fabricating an efficient charge transfer pathway at the compact interface between two kinds of semiconductors is an important strategy for designing hydrogen production heterojunction photocatalysts. In this work, we prepared a compact, stable and oxygen vacancy-rich photocatalyst (SnO₂/TiO₂ heterostructure) via a simple and reasonable in-situ synthesis method. Briefly, SnCl₂–2H₂O is hydrolyzed on the TiO₂ precursor. After the pyrolysis process, SnO₂ nanoparticles (5 nm) were dispersed on the surface of ultrathin TiO₂ nanosheets uniformly. Herein, the heterojunction system can offer abundant oxygen vacancies, which can act as active sites for catalytic reactions. Meanwhile, the interfacial contact of SnO₂/TiO₂ grading semiconductor oxide is uniform and tight, which can promote the separation and migration of photogenerated carriers. As shown in the experimental results, the hydrogen production rate of SnO₂/TiO₂ is 16.7 mmol h^?1 g^?1 (4.4 times higher than that of TiO₂), which is owing to its good dynamical properties. This work demonstrates an efficient strategy of tight combining SnO₂/TiO₂ with abundant oxygen vacancies to improve catalytic efficiency.     

Mn掺杂SnO_2一维纳米结构的制备、形貌及光学性质

用化学气相沉积(CVD)法制备了Mn掺杂的SnO2一维纳米结构(纳米线及纳米带),X射线衍射(XRD)显示样品为金红石型SnO2晶体,其生长机理可分别归结为气-液-固(VLS)和气-固(VS)机理,生长温度和气态原料浓度的差别是造成样品形貌及生长机理不同的主要原因.样品的拉曼谱出现了500、543、694和720cm-1四个新拉曼谱峰,分别是由活性的红外模和表面模引起的.纳米线及纳米带发光峰位于520nm处,发光强度随样品中氧空位的增减出现由强到弱的变化.