Theoretical Studies on the Geometrical and Electronic Structures of C-Doped ZnO under High Pressure

Russian Journal of Physical Chemistry A - In this work, the geometrical, electronic structures and optical properties of C-doped ZnO under high pressures have been investigated using...     

Photocatalytic degradation of diclofenac sodium in aqueous solution using N,S, and C-doped ZnO

Russian Journal of Applied Chemistry - In this investigation photocatalytic degradation of diclofenac sodium as drug pollutants was studied. N, S, and C-doped ZnO particles were supported from...     

三维分级结构ZnO的制备及光催化性能

以聚乙烯醇/醋酸锌复合纳米纤维为模板, 采用模板辅助共沉积技术制备了三维尖晶石型ZnO纳米线/纳米纤维分级结构, 并采用SEM, XRD对其形貌和晶型结构进行了表征. 在光催化降解乙醛性能实验中, 三维分级结构ZnO表现出比纳米粒子和纤维更好的光催化性能. 这主要归因于ZnO纳米线的次级结构和开放的三维网络结构更有利于乙醛分子和氧分子的扩散和传输, 从而提高了乙醛的光降解速率.     

Dendritic nanowire ultraviolet laser array

Self-organized dendritic crystal growth is explored to assemble uniform semiconductor nanowires into highly ordered one-dimensional microscale arrays that resemble comb structures. The individual ZnO nanowires have uniform diameters ranging from 10 to 300 nm. They are evenly spaced on a stem with a regular periodicity of 0.1-2 micrometer. Under optical excitation, each individual ZnO nanowire serves as a Fabry-Perot optical cavity, and together they form a highly ordered nanowire ultraviolet laser array.     

Inorganic semiconductor nanowires: rational growth, assembly, and novel properties

Rationally controlled growth of inorganic semiconductor nanowires is important for their applications in nanoscale electronics and photonics. In this article, we discuss the rational growth, physical properties, and integration of nanowires based on the results from the authors' laboratory. The composition, diameter, growth position, and orientation of the nanowires are controlled based on the vapor-solid-liquid (VLS) crystal growth mechanism. The thermal stability and optical properties of these semiconductor nanowires are investigated. Particularly, ZnO nanowires with well-defined end surfaces can function as room-temperature ultraviolet nanolasers. In addition, a novel microfluidic-assisted nanowire integration (MANI) process was developed for the hierarchical assembly of nanowire building blocks into functional devices and systems.     

ZnO纳米线阵列的电沉积法制备及表征(英文)

利用直流电沉积方法在多孔氧化铝模板的孔洞中生成锌纳米线,在氧气氛围中,于800°C下氧化2h,将氧化铝中的锌氧化成氧化锌.本研究利用氧气氛围进行锌的氧化,大大提高了传统方法的氧化锌纳米线的制备效率.用场发射扫描电子显微镜(FE-SEM)、透射电子显微镜(TEM)和X射线衍射仪(XRD)对其形貌及成分进行表征和分析,结果表明,氧化铝模板的有序孔洞中填充了大尺寸、均匀连续的多晶态氧化锌纳米线.纳米线具有约1000:1的高纵横比,其长度等于氧化铝模板的厚度,直径约为80nm.光致发光(PL)光谱表明,氧化锌纳米线在504nm处有由于氧空位引起的较强蓝绿光发射.这为进一步研究ZnO/AAO组装体发学性质和开发新型功能器件提供了基础.     

One-dimensional Intrinsic Ferromagnetic Semiconductor CuCl_2: a First-principles Study

One-dimensional nanowires with robust magnetism are desirable for spintronic applications. Herein, on the basis of the first-principles calculations, systematic investigations on the electronic and magnetic properties of the CuCl2 nanowire were performed, which can be potentially tailored from its bulk form. The CuCl2 nanowire exhibits a ferromagnetic ground state. The band structures indicate that the CuCl2 nanowire is a ferromagnetic semiconductor. The spin flip gap is large enough for avoiding spin flip. Phonon dispersion and Born-Oppenheimer molecular dynamics simulation manifest that the CuCl2 nanowire is stable. In addition, distinct magnetic properties of the CuCl2 nanowires inside two types of carbon nanotubes were obtained. The study broadens the family of the existing one-dimensional materials with promising applications for spintronics.     

Cr掺杂ZnO(10(¯1)0)表面的原子结构和电子性质研究

多相催化中ZnO基催化剂广泛应用于甲醇合成、水汽变换和合成气转化等诸多领域.近期发展的ZnCrO_x-分子筛双功能催化剂(OX-ZEO)打破了传统合成气转化的ASF分布,能够高选择性地实现CO加氢转化为低碳烯烃.其中CO在ZnCrO_x表面活化被认为是OX-ZEO催化的关键基元过程,但是ZnCrO_x表面的活性位组成和结构目前仍然缺乏原子尺度上的理解,阻碍了人们对反应机理的研究.因此,本文构建了Cr掺杂ZnO(1010)单晶的模型催化剂,结合低温扫描隧道显微镜(LT-STM)和X射线光电子能谱(XPS),研究不同条件下Cr在ZnO(1010)表面生长的形貌结构,并重点考察了Cr掺杂对表面电子结构和CO吸附的影响.ZnO(101–0)是Zn-O混合终止的非极性面,也是ZnO最稳定的晶面.实验发现室温下沉积Cr在ZnO(1010)表面时,出现多种生长结构.STM显示低覆盖度(<0.1 ML)的沉积Cr在ZnO(1010)台阶面上出现单分散的亮点和暗点,分别为位于表面O原子链上的Cr原子和嵌入ZnO晶格替代Zn²⁺的Cr.XPS显示这些Cr原子与ZnO之间存在电荷转移,呈现出+3价.由于Cr在[0001]方向扩散能垒高于沿着[1210]方向扩散的能垒,能够观察到少量沿着[0001]台阶方向生长的长方形岛,归属为Cr岛.表面单分散Cr原子和Cr岛的密度都会随着Cr沉积量的增加而增多.当在200 K沉积Cr来抑制Cr的表面扩散行为,我们发现Cr主要在ZnO面上形成Cr团簇,均匀分散在表面;而在400 K沉积时,Cr则直接扩散进入ZnO晶格.STM和XPS结果都表明,600 K以上的高温处理能够促进Cr进入ZnO晶格,同时伴随Cr岛的分解,这说明表面负载的Cr原子在高温不能稳定存在;而Cr岛的再分散进入到近表层甚至体相,也表明了Cr和ZnO之间的强相互作用.这种强相互作用有利于Cr在ZnO表层进行原子级分散,形成具有催化活性的结构;与此同时,实验发现Cr扩散到近表层会导致表面能带向上弯曲,从而导致XPS芯能级向低结合能位移.在超高真空条件下,CO与Cr掺杂的ZnO表面作用较弱,室温下只观察到碳酸盐的形成.因此,通过对比不同条件下Cr在ZnO(1010)表面的生长结构,热稳定性以及相应的电子结构变化,发现Cr和ZnO存在强相互作用,在600 K以上Cr以Cr³⁺形式分散到ZnO晶格中.本文通过构建Cr/ZnO(1010)模型催化剂,并研究其原子结构与电子结构的演变,为进一步的分子尺度合成气转化机理研究开辟了道路.     

Control of the ZnO nanowires nucleation site using microfluidic channels

We report on the growth of uniquely shaped ZnO nanowires with high surface area and patterned over large areas by using a poly(dimethylsiloxane) (PDMS) microfluidic channel technique. The synthesis uses first a patterned seed template fabricated by zinc acetate solution flowing though a microfluidic channel and then growth of ZnO nanowire at the seed using thermal chemical vapor deposition on a silicon substrate. Variations the ZnO nanowire by seed pattern formed within the microfluidic channel were also observed for different substrates and concentrations of the zinc acetate solution. The photocurrent properties of the patterned ZnO nanowires with high surface area, due to their unique shape, were also investigated. These specialized shapes and patterning technique increase the possibility of realizing one-dimensional nanostructure devices such as sensors and optoelectric devices.     

Adsorption of atomic hydrogen on ZnO(1010): STM study

The adsorption of atomic hydrogen on a single crystal ZnO(1010) surface has been studied by scanning tunneling microscopy (STM) under ultrahigh vacuum conditions at room temperature and at elevated temperatures. High resolution STM images indicate that a well-ordered (1x1) H adlayer is formed on the ZnO(1010) surface. The STM data strongly indicate that the hydrogen adsorbs on top of the oxygen atoms forming hydroxyl species. Scanning tunneling spectroscopy (STS) studies reveal a H atom induced metallization at room temperature. In contrast to the clean surface for the hydrogen-covered surface distinct defects structures consisting of missing O and Zn atoms could be identified.     

取向Zn1-xMgxO纳米线阵列的制备及光学特性

采用化学气相沉积(CVD)法, 以高纯ZnO、Mg和活性C混合粉末为原料, 在Si(111)衬底上制备了不同配比的取向Zn1-xMgxO纳米线阵列. 用X射线衍射仪(XRD), 扫描电镜(SEM), 能量色散X射线分析(EDAX)及光致发光(PL)光谱分析仪对样品的晶体结构、形貌、成分组成和光致发光特性进行了分析. 用霍尔效应测量系统测试了不同配比样品的载流子浓度. 实验发现, 当Zn1-xMgxO纳米线阵列中Mg原子相对Zn原子摩尔比x值较小时(x<0.29), XRD衍射谱中只有ZnO晶体标准衍射峰, 没有MgO晶体衍射峰, 说明此时制备的Zn1-xMgxO纳米线样品晶格结构以ZnO纤锌矿结构为主, Mg原子只是作为替位或填隙原子分布在ZnO晶体中. 但当样品中x>0.53时, ZnO与MgO的特征衍射峰同时出现在样品的衍射谱图中, 说明随原料中Mg原子摩尔比的增加, 制备的Zn1-xMgxO纳米阵列样品中ZnO纤锌矿结构与MgO岩盐结构同时存在, 样品呈现多晶体结构形式. 实验还对比了制备的纯ZnO与不同配比的Zn1-xMgxO纳米线阵列的光致发光光谱和载流子浓度, 发现随Mg含量的增加, Zn1-xMgxO阵列紫光发光峰出现了较明显的蓝移现象, 同时, 测试结果也表明, 随Mg含量的增加, Zn1-xMgxO阵列的紫光和绿光峰发光强度都有所减弱, 样品的载流子浓度也随之下降. 文章对实验结果进行了分析和探讨.     

Spatial determination of gold catalyst residue used in the production of ZnO nanowires by SIMS depth profiling analysis

In this paper we demonstrate how secondary ion mass spectrometry (SIMS) can be applied to ZnO nanowire structures for gold catalyst residue determination. Gold plays a significant role in determining the structural properties of such nanowires, with the location of the gold after growth being a strong indicator of the growth mechanism. For the material investigated here, we find that the gold remains at the substrate–nanowire interface. This was not anticipated as the usual growth mechanism associated with catalyst growth is of a vapour–liquid–solid (VLS) type. The results presented here favour a vapour–solid (VS) growth mechanism instead. Copyright © 2007 John Wiley & Sons, Ltd.     

氮化硼纳米管气敏特性的理论研究

采用密度泛函理论计算研究了氮化硼纳米管及碳掺杂氮化硼纳米管对CH4, CO2, H2, H2O, N2, NH3, NO2, O2, F2等十余种气体小分子的气敏特性. 研究结果表明: 氮化硼纳米管对CH4, CO2, H2, H2O, N2, NH3等气体分子不敏感, 而对O2, NO2, F2等气体分子比较敏感. 虽然碳掺杂氮化硼纳米管可以明显地改变其表面的化学反应活性, 增强了气体分子与氮化硼纳米管之间的相互作用, 但是并不能明显地改变其对所研究气体分子的敏感性.     

Chemical bath deposition of ZnO nanowires at near-neutral pH conditions without hexamethylenetetramine (HMTA): understanding the role of HMTA in ZnO nanowire growth

Chemical bath deposition (CBD) is an inexpensive and reproducible method for depositing ZnO nanowire arrays over large areas. The aqueous Zn(NO(3))(2)-hexamethylenetetramine (HMTA) chemistry is one of the most common CBD chemistries for ZnO nanowire synthesis, but some details of the reaction mechanism are still not well-understood. Here, we report the use of in situ attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopy to study HMTA adsorption from aqueous solutions onto ZnO nanoparticle films and show that HMTA does not adsorb on ZnO. This result refutes earlier claims that the anisotropic morphology arises from HMTA adsorbing onto and capping the ZnO {10 1 0} faces. We conclude that the role of HMTA in the CBD of ZnO nanowires is only to control the saturation index of ZnO. Furthermore, we demonstrate the first deposition of ZnO nanowire arrays at 90 °C and near-neutral pH conditions without HMTA. Nanowires were grown using the pH buffer 2-(N-morpholino)ethanesulfonic acid (MES) and continuous titratation with KOH to maintain the same pH conditions where growth with HMTA occurs. This semi-batch synthetic method opens many new opportunities to tailor the ZnO morphology and properties by independently controlling temperature and pH.     

单晶Ni纳米线阵列的制备与磁性能

采用恒电流沉积方法, 在多孔阳极氧化铝(AAO)模板中制备出了具有单晶结构的Ni纳米线阵列. 采用扫描电子显微镜(SEM)、透射电子显微镜(TEM)和X射线衍射(XRD)技术对制备的Ni纳米线阵列的形貌及结构进行了表征. 利用振动样品磁强计(VSM)对单晶Ni纳米线阵列的磁性能进行了研究. 结果表明, 单晶镍纳米线阵列的易磁化方向为纳米线轴向, 并且与多晶纳米线相比显示出了更高的矫顽力. 直径为30 nm的纳米线具有较高的矫顽力(8.236×104 A/m)和较高的剩磁比(Mr＝0.94Ms).     

Carbon‐Nanotube‐Based Hybrid Materials: Nanopeapods

This review article focuses on the structures and properties of novel hybrid nanocarbon materials, which are created by incorporating atoms and molecules into the hollow spaces of carbon nanotubes (CNTs); thus they are called nanopeapods. After dealing with synthesis procedures, we discuss the structures and electronic properties of the hybrid materials based on high‐resolution transmission electron microscopy (HRTEM), electron energy‐loss spectroscopy (EELS), X‐ray and electron diffraction, scanning tunneling microscopy (STM), and field‐effect transistor transport measurements. Utilization of the low‐dimensional nanosized spaces of CNTs to produce novel low‐dimensional nanocluster, nanowire, and nanotube materials is also discussed.     

Conductivity of ZnO nanowires, nanoparticles, and thin films using time-resolved terahertz spectroscopy

The terahertz absorption coefficient, index of refraction, and conductivity of nanostructured ZnO have been determined using time-resolved terahertz spectroscopy, a noncontact optical probe. ZnO properties were measured directly for thin films and were extracted from measurements of nanowire arrays and mesoporous nanoparticle films by applying Bruggeman effective medium theory to the composite samples. Annealing significantly reduces the intrinsic carrier concentration in the ZnO films and nanowires, which were grown by chemical bath deposition. The complex-valued, frequency-dependent photoconductivities for all morphologies were found to be similar at short pump-probe delay times. Fits using the Drude-Smith model show that films have the highest mobility, followed by nanowires and then nanoparticles, and that annealing the ZnO increases its mobility. Time constants for decay of photoinjected electron density in films are twice as long as those in nanowires and more than 5 times those for nanoparticles due to increased electron interaction with interfaces and grain boundaries in the smaller-grained materials. Implications for electron transport in dye-sensitized solar cells are discussed.     

Length‐Dependent Charge Generation from Vertical Arrays of High‐Aspect‐Ratio ZnO Nanowires

Aqueous chemical growth of zinc oxide nanowires is a flexible and effective approach to obtain dense arrays of vertically oriented nanostructures with high aspect ratio. Herein we present a systematic study of the different synthesis parameters that influence the ZnO seed layer and thus the resulting morphological features of the free‐standing vertically oriented ZnO nanowires. We obtained a homogeneous coverage of transparent conductive substrates with high‐aspect‐ratio nanowire arrays (length/diameter ratio of up to 52). Such nanostructured vertical arrays were examined to assess their electric and piezoelectric properties, and showed an electric charge generation upon mechanical compressive stress. The principle of energy harvesting with these nanostructured ZnO arrays was demonstrated by connecting them to an electronic charge amplifier and storing the generated charge in a series of capacitors. We found that the generated charge and the electrical behavior of the ZnO nanowires are strictly dependent on the nanowire length. We have shown the importance of controlling the morphological properties of such ZnO nanostructures for optimizing a nanogenerator device.     

Synthesis of ordered ultrathin ZnO nanowire bundles on an indium-tin oxide substrate

Ultrathin ZnO nanowire bundles have been synthesized on an indium-tin oxide substrate without any catalyst by using a simple thermal evaporation method, where self-organized ZnO nanowire bundles were grown on the hexagonal heads of ZnO nanocolumns. The nanowires obtained typically have diameters of 8 nm, with lengths extending to 0.25 microm. The size is the same order of magnitude as the ZnO exciton Bohr radius (aB). Room-temperature photoluminescence measurement shows a prominent peak at 374 nm (3.32 eV), which is about 100 meV blue-shifted from the bulk ZnO emission.     

ZnO纳米线基MWNTs/PVDF复合热电材料的制备及特性研究

将不同比例的多壁碳管(MWNTs)与聚偏二氟乙烯(PVDF)聚合物混合后,喷涂于n型ZnO半导体纳米线阵列上,制备了一种新型ZnO纳米线基MWNTs/PVDF热电复合材料.与以往采用价格昂贵的p型与n型单壁碳纳米管(SWNTs)与聚合物混合制备的复合热电材料特性相比,这种新型热电复合材料在降低制造成本的同时,利用分散于聚合物中MWNTs的一维电子传输特性及形成的大量界面势垒,加上ZnO半导体纳米线具有的较高载流子密度与迁移率,提高了复合热电材料中电子的输运特性,增加了材料对声子的散射强度.测试发现,在一定的温度梯度下,随着MWNTs添加质量百分比的增加,热电材料的温差电动势和电导率也随之增加,但其Seebeck系数变化量不大.研究表明,这种热电材料有望替代采用p型与n型SWNTs构建的SWNTs/PVDF复合热电材料.研究结果对开发超轻、无毒、廉价、可应用于各种微纳电子领域的新型电源具有重要的参考价值.