氧化锡和氧化锌双层薄膜的XPS研究

用XPS法研究了SnO2 /ZnO及ZnO/SnO2 双层膜中锌和锡的扩散情况 ,结果表明 :锌在SnO2中的扩散比锡在ZnO中的扩散更容易。讨论了锌在SnO2 层中的扩散方式和扩散的结果。在ZnO层留下了较多的氧 ,并使部分的SnO2 还原为SnO。     

Synthesis and thermal stability of ZnO nanowires

ZnO nanowires (NWs) were synthesized on Au-coated Si (100) substrates by vapor transport method. The effect of high temperature annealing on the structural and chemical composition as well as thermal stability was studied. The as-prepared ZnO NWs was nearly stoichiometric and identified as hexagonal ZnO phase. After annealing at 1,473 K, the atomic ratio of O/Zn, the intensity of the diffraction peaks, and the diameter of nanowires were increased. The ZnO NWs were fragmented into nanocrystals and the fragments coalesced with each other after annealing at 1,673 K. The thermal stability of ZnO NWs was studied by thermo-gravimetric (TG) analysis. A sharp increase in the TG curves was observed and can be attributed to the oxidation of some possibly presented Zn atoms. The activation energy of oxidation of Zn interstitial atoms was found to be 484.81 kJ mol^?1. A mass gain peak was observed after annealing at 1,473 K, but it was completely eliminated after annealing at 1,673 K.     

Comparative structure and optical properties of Ga-, In-, and Sn-doped ZnO nanowires synthesized via thermal evaporation

ZnO nanowires doped with a high concentration Ga, In, and Sn were synthesized via thermal evaporation. The doping content defined as X/(Zn + X) atomic ratio, where X is the doped element, is about 15% for all nanowires. The nanowires consist of single-crystalline wurtzite ZnO crystal, and the average diameter is 80 nm. The growth direction of vertically aligned Ga-doped nanowires is [001], while that of randomly tilted In- and Sn-doped nanowires is [010]. A correlation between the growth direction and the vertical alignment has been suggested. The broaden X-ray diffraction peaks indicate the lattice distortion caused by the doping, and the broadening is most significant in the case of Sn doping. The absorption and photoluminescence of Sn-doped ZnO nanowires shift to the lower energy region than those of In- and Ga-doped nanowires, probably due to the larger charge density of Sn.     

Morphological and photoelectrochemical characterization of core-shell nanoparticle films for dye-sensitized solar cells: Zn-O type shell on SnO2 and TiO2 cores

Core-shell type nanoparticles with SnO2 and TiO2 cores and zinc oxide shells were prepared and characterized by surface sensitive techniques. The influence of the structure of the ZnO shell and the morphology ofnanoparticle films on the performance was evaluated. X-ray absorption near-edge structure and extended X-ray absorption fine structure studies show the presence of thin ZnO-like shells around the nanoparticles at low Zn levels. In the case of SnO2 cores, ZnO nanocrystals are formed at high Zn/Sn ratios (ca. 0.5). Scanning electron microscopy studies show that Zn modification of SnO2 nanoparticles changes the film morphology from a compact mesoporous structure to a less dense macroporous structure. In contrast, Zn modification of TiO2 nanoparticles has no apparent influence on film morphology. For SnO2 cores, adding ZnO improves the solar cell efficiency by increasing light scattering and dye uptake and decreasing recombination. In contrast, adding a ZnO shell to the TiO2 core decreases the cell efficiency, largely owing to a loss of photocurrent resulting from slow electron transport associated with the buildup of the ZnO surface layer.     

Origin of enhancement in open-circuit voltage by adding ZnO to nanocrystalline SnO2 in dye-sensitized solar cells

SnO2 + ZnO working electrodes for dye-sensitized solar cells were made by mixing a nanocrystalline SnO2 colloidal dispersion with ZnO or Zn(CH3COO)2. Addition of ZnO or Zn(CH3COO)2 enhanced the open-circuit voltage (V(oc)) of the cells with respect to cells containing only SnO2. Dependence of the electron lifetime in the electrodes on short-circuit photocurrent density (J(sc)) gave evidence against the assumption that the suppression of back electron transfer to the electrolyte is the origin for the V(oc) enhancement by addition of Zn. V(oc) dependence on temperatures indicated a decrease in the combined capacitance of the mixed electrode. The slope of the V(oc) dependence versus the logarithm of J(sc) indicated that the contribution of unpinning of the band to the enhancement of V(oc) could be neglected. From the cyclic voltammograms of the electrodes, the combined capacitance of the mixed electrode was 1 order of magnitude smaller than that of SnO2. The decrease in the combined capacitance in the mixed electrode could be explained by the decrease in the chemical capacitance of SnO2, thus the shift of the conduction band position toward the vacuum level. X-ray photoelectron spectra of Sn 3d(5/2) peaks showed a shift toward lower binding energy with an increasing amount of added Zn. This was attributed to an increase in the surface potential toward the negative direction, which might have resulted from a dipole moment formed by Zn on the surface of SnO2.     

Size-controllable one-dimensional SnO2 nanocrystals: synthesis, growth mechanism, and gas sensing property

Single crystalline one-dimensional (1-D) SnO(2) nanocrystals with controllable sizes, including the diameter and the aspect ratio, were synthesized by modulating the precursor concentration, reaction time and temperature via a solution method. By regulating the growth in a kinetic regime, a higher temperature range (220-240 degrees C) was beneficial to the growth of SnO(2) nanowires, while reactions below 220 degrees C only resulted in nanorods or even nanoparticles. The aggregates of SnO(2) nanocrystals in the forms of hollow spheres and dendrites were observed as the intermediates for the nanowires. Based on the TEM and SEM observations, the growth mechanism is discussed from the viewpoints of the nature of the reverse micelles and the crystal habit of rutile SnO(2). CO gas sensing measurements were also carried out for SnO(2) nanocrystals with different assembly styles. The results indicate that the sensitivity had close correlation to the specific surface area of the nanocrystals.     

Size-dependent Raman red shifts of semiconductor nanocrystals

The size effects on Raman red shifts in low-dimensional semiconductor nanocrystals are investigated by considering the size-dependent root-mean-square average amplitude associated with the thermal vibration of atoms. The lower limit of vibrational frequency was obtained by matching the calculation results of Raman red shifts with the experimental data of Si, InP, CdSe, CdS0.65Se0.35, ZnO, CeO2, as well as SnO2 nanocrystals. The results indicate the following: (1) the Raman frequency decreases as the nanocrystal size decreases in both narrow and wide bandgap semiconductors; (2) the influence of crystal size on the Raman frequency of nanoparticles is more pronounced than that of nanowires and thin films; and (3) the Raman red shift is ascribed to the size-induced phonon confinement effect and surface relaxation. This model may provide new insights into the fundamental understanding of the underlying mechanism behind the Raman red shifts.     

Synthesis and Photocatalytic Activity of One-dimensional ZnO-Zn2SnO4 Mixed Oxide Nanowires

Mixed oxide photocatalysts, ZnO-Zn2SnO4 (ZnO-ZTO) nanowires with different sizes were prepared by a simple thermal evaporation method. The ZnO-ZTO nanowires were characterized with a scanning electron microscope, X-ray diffraction, high-resolution transmission electron microscopy, energy-dispersive spectrometer, and X-ray photoelectron spectrThe photocatalytic activity of the ZnO-ZTO mixed nanowires were studied by observing the photodegradation behaviors of methyl orange aqueous solution. The results suggest that the ZnO-ZTO mixed oxide nanowires have a higher photocatalytic activity than pure ZnO and Zn2SnO4 nanowires. The photocatalyst concentration in the solution distinctly affects the degradation rate, and our results show that higher photodegradation efficiency can be achieved with a smaller amount of ZnO-ZTO nanowire catalyst, as compared to the pure ZnO and ZTO nanowires. Moreover, the photocatalytic activity can also be enhanced by reducing the average diameter of the nanowires. The activity of pure ZnO and ZTO nanowires are also enhanced by physically mixing them. These results can be explained by the synergism between the two semiconductors.     

ZnO掺杂的SnO_2纳米纤维的制备、表征及气敏机理(英文)

以二水氯化亚锡(SnCl2·2H2O)为盐原料,采用静电纺丝的方法制备了SnO2纳米纤维.为了研究ZnO掺杂对SnO2形貌、结构及化学成分的影响,分别制备了不同含量ZnO掺杂的SnO2/ZnO复合材料.利用热重-差热分析(TG-DTA)、X射线衍射(XRD)、傅里叶变换红外(FTIR)光谱仪、扫描电镜(SEM)及能量色散X射线(EDX)光谱对材料的结晶学特性及微结构进行了表征.制备的SnO2/ZnO复合材料是由纳米量级的小颗粒构成的分级结构材料.ZnO含量不同,对应的SnO2/ZnO复合材料结构不同.表征结果表明ZnO的掺杂量对SnO2材料的形貌及结构均起着重要作用.将制备的不同ZnO含量的SnO2/ZnO复合材料进行气敏测试,测试结果表明,Sn:Zn摩尔比为1:1制作的气敏元件对甲醇的灵敏度优于其它摩尔比的气敏元件.讨论了SnO2/ZnO复合材料气敏元件的敏感机理.同时针对Sn:Zn摩尔比为1:1时表现出最好的气敏响应,分析了其原因,包括Zn的替位式掺杂行为、ZnO的催化作用、过量ZnO对SnO2生长的抑制作用以及SnO2与ZnO晶粒界面处的异质结.     

Luminescence and photocatalytic activity of ZnO nanocrystals: correlation between structure and property

Low-dimensional ZnO nanocrystals with controlled size, aspect ratio, and oxygen defects (e.g., type and concentration) are successfully prepared through simple solvothermal and thermal treatment methods. The structure of the as-synthesized samples is characterized by XRD, N2 physical adsorption, TEM, and IR and XPS spectra. The results show that the aspect ratio and size of the as-synthesized ZnO nanocrystals increase with increasing [OH-]/[Zn2+]; the morphology evolves from nanorod to nanoparticle with an increase in the annealing temperature; the BET surface areas of the corresponding samples decrease during these processes, respectively; and different oxygen defects, which are likely to be oxygen vacancy (Vo**) and interstitial oxygen (Oi'), are formed in our experiments accordingly. With evolution of the structure, IR absorption bands and visible photoluminescence emission peaks of the synthesized ZnO nanocrystals shift and split, which is ascribed to the change of oxygen defects. In addition, it is found that the photocatalytic activity of the synthesized ZnO nanocrystals is mainly dependent on the type and concentration of oxygen defects. The relationship of structure-property and the possible photocatalytic mechanism are discussed in detail.     

Colloidal synthesis and structural control of PtSn bimetallic nanoparticles

PtSn bimetallic nanoparticles with different particle sizes (1-9 nm), metal compositions (Sn content of 10-80 mol %), and organic capping agents (e.g., amine, thiol, carboxylic acid and polymer) were synthesized by colloidal chemistry methods. Transmission electron microscopy (TEM) measurements show that, depending on the particle size, the as-prepared bimetallic nanocrystals have quasi-spherical or faceted shapes. Energy-dispersive X-ray (EDX) analyses indicate that for all samples the signals of both Pt and Sn can be detected from single nanoparticles, confirming that the products are actually bimetallic but not only a physical mixture of pure Pt and Sn metal nanoparticles. X-ray diffraction (XRD) measurements were also conducted on the bimetallic particle systems. When compared with the diffraction patterns of monometallic Pt nanoparticles, the bimetallic samples show distinct shifts of the Bragg reflections to lower degrees, which gives clear proof of the alloying of Pt with Sn. However, a quantitative analysis of the lattice parameter shifts indicates that only part of the Sn atoms are incorporated into the alloy nanocrystals. This is consistent with X-ray photoelectron spectroscopy (XPS) measurements that reveal the segregation of Sn at the surfaces of the nanocrystals. Moreover, short PtSn bimetallic nanowires were synthesized by a seed-mediated growth method with amine-capped bimetallic particles as precursors. The resulting nanowires have an average width of 2.3 nm and lengths ranging from 5 to 20 nm.     

Short-period superlattice structure of Sn-doped In(2)O(3)(ZnO)(4) and In(2)O(3)(ZnO)(5) nanowires

Two longitudinal superlattice structures of In(2)O(3)(ZnO)(4) and In(2)O(3)(ZnO)(5) nanowires were exclusively produced by a thermal evaporation method. The diameter is periodically modulated in the range of 50-90 nm. The nanowires consist of one In-O layer and five (or six) layered Zn-O slabs stacked alternately perpendicular to the long axis, with a modulation period of 1.65 (or 1.9) nm. These superlattice nanowires were doped with 6-8% Sn. The X-ray diffraction pattern reveals the structural defects of wurtzite ZnO crystals due to the In/Sn incorporation. The high-resolution X-ray photoelectron spectrum suggests that In and Sn withdraw the electrons from Zn and enhance the number of dangling-bond O 2p states, resulting in the reduction of the band gap. Photoluminescence and cathodoluminescence exhibit the peak shift of near band edge emission to the lower energy and the enhancement of green emission as the In/Sn content increases.     

SiO2/ZnO复合纳米粒子的制备及表征

采用双注控制沉积法(Controlled Double-Jet Precipitation,CDJP)将反应物添加到含有SiO₂的溶液中,通过直接的表面反应来制备单分散的SiO₂/ZnO复合纳米粒子,并对其进行了表征。透射电镜(TEM)观察表明,SiO₂表面有一层ZnO纳米颗粒或薄层。对复合纳米粒子SiO₂/ZnO进行X射线衍射(XRD)分析,复合颗粒的衍射峰与单独的氧化锌的衍射峰完全一致。能量弥散X射线法(EDX)分析表明,复合颗粒中含有Zn、Si、O元素。荧光光谱表明有ZnO的吸收峰。     

Transmission electron microscopy study of pseudoperiodically twinned Zn2SnO4 nanowires

The ternary oxide functional nanomaterial Zn2SnO4 has been synthesized by the thermal evaporation method. The products in general contain numerous kinds of nanowires. In the present work, a remarkable type of Zn2SnO4 nanowires with a pseudoperiodical twinning structure has been investigated by transmission electron microscopy (TEM). These nanowires with a diameter of about 100 nm grow along the 111 direction. High-resolution TEM examinations suggest that a large fraction of the (111) twin boundaries are extended to a thickness of a few nanometers. The twining plane for the perfect case is localized on the Zn atom layer.     

Attachment-driven morphology evolvement of rectangular ZnO nanowires

The rectangular cross-sectional ZnO nanowires were synthesized in a solution method. An attachment-driven growth mechanism was proposed for the morphology evolvement of ZnO nanocrystals from nanoparticles to nanoplates and eventually to nanowires. Due to the pileup attachment of the nanoplates to recrystallize into nanowires, unique one-dimensional (1D) ZnO nanowires with the rectangular cross section were obtained, which is different from those nanowires in the previous reports. It is the first time the evidence that "oriented attachment" can occur not only for nanoparticles but also for nanoplates was obtained, suggesting that "oriented attachment" is an intrinsic behavior for nanosized materials. According to the growth model proposed based on the direct TEM observations, ZnO nanocrystals can be easily controlled as nanoparticles, nanoplates, or nanowires by tuning the synthetic parameters.     

ZnO纳米线形态对其光致发光性能的影响

以多孔氧化铝膜为模板,电化学沉积出Zn纳米线,再通过高温氧化得到ZnO纳米线阵列。通过改变制备多孔氧化铝模板的工艺参数来改变模板纳米孔径,进而改变ZnO纳米线的直径,得到不同形态的ZnO纳米线阵列。应用X射线衍射仪、透射电子显微镜测试技术表征了ZnO纳米线的结构与形貌。结果发现,X射线衍射时会出现随ZnO纳米线直径增大衍射峰增多和增强的现象。采用荧光光谱仪测试样品的光致发光性能,通过Gaussian原理对谱峰的拟合分析了ZnO纳米线形态对其光致发光光谱的影响。结果表明,随着纳米线直径从30nm至60nm依次增大,其结晶性和化学计量比逐渐变好。近紫外区和蓝光区的发射峰随着纳米线直径的增大而蓝移,而纳米线直径为60nm的样品则出现随直径增大而红移的现象。结果可见,直径在55~60nm间的某点将是ZnO纳米线的结构和光致发光性能变化的临界点。     

Investigating the effect of ultrasonic irradiation on preparation and properties of conductive nanocomposites

In the present study, the ultrasonic irradiation technique was employed as a new approach to prepare 0-3-dimensional polyaniline/ZnO shell-core composite particles. By taking advantage of the multiple effects of ultrasound, one can break down the aggregates of nanocrystalline ZnO particles. The polymerization of aniline proceeded while the nanoparticles were redispersed by ultrasound, and the synthesized polyaniline deposited on the ZnO particle, which formed polyaniline-coated nanocrystalline composite particles. The material was characterized by using transmission electron microscopy, XRD, scanning electron microscopy (SEM), fourier transform infrared spectroscopy (FTIR), and Thermogravimetric analysis (TGA). With increased ZnO content, the H-bonding interaction is strengthened and the characteristic peaks of benzoid and quinoid are shifted. X-ray photoelectron spectroscopy (XPS) shows that the ratio of the number of Zn and N atoms (Zn/N) on the surface is lower than that in the bulk. This is strong evidence for a PANI-encapsulated ZnO nanoparticles structure. The conductivity of the composites obtained through ultrasonic irradiation decreases with increasing ZnO content. Ultrasonic irradiation contributes to the increase in the conductivity compared with conventional stirring. Photocatalytic properties of PANI/ZnO nanocomposites were examined by degrading Reactive Black 5 (RB5) dye under visible light irradiation.     

化学气相沉积法制备氧化锡自组装纳米结构

采用化学气相沉积法在镀有5-10 nm厚金膜的SiO2衬底上, 通过控制生长条件, 实现了二氧化锡纳米结构的自组装生长, 成功制备出了莲花状和菊花状的二氧化锡自组装纳米结构. 利用扫描电子显微镜、X射线衍射等表征分析手段对样品的表面形貌、结构及成份进行表征和研究. 并在此基础上, 讨论了两种自组装纳米结构的生长机制.     

Growth mechanism of ZnO nanocrystals with Zn-rich from dots to rods

ZnO nanocrystals from dot to rod were synthesized by simply changing Zn2+ concentration in ZnO seed solutions. The growth of ZnO nanocrystals was sensitive to the amount of Zn2+ in the solution. The growth process of ZnO from dot to rod was observed by optical spectra, transmission electron microscopy and X-ray diffraction spectra. From these results, the growth mechanism of ZnO from dots to rods was discussed.     

Incorporating Zn(2) SnO(4) Quantum Dots and Aggregates for Enhanced Performance in Dye-Sensitized ZnO Solar Cells

The performance of dye-sensitized ZnO solar cells was improved by a facile surface-treatment approach through chemical-bath deposition. After the surface treatment, the quantum dots of Zn(2) SnO(4) were deposited onto ZnO nanoparticles accompanied by the aggregations of Zn(2) SnO(4) nanoparticles. The ZnO film displayed a better resistance to acidic dye solution on account of the deposited Zn(2) SnO(4) nanoparticles. Meanwhile, the open-circuit photovoltage was greatly enhanced, which can be ascribed to the increased conduction-band edge of ZnO and inhibited interfacial charge recombination. Although the deposition of Zn(2) SnO(4) decreased the adsorption amounts of N719 dye, the aggregates of Zn(2) SnO(4) with a size of 350-450?nm acted as the effective light-scattering layer, thereby resulting in an improved short-circuit photocurrent. By co-sensitizing 10?μm-thick ZnO film with N719 and D131 dyes, a top efficiency of 4.38?% was achieved under the illumination of one sun (AM?1.5, 100?mW?cm(-2) ).