采用高分子自组装ZnO纳米线及其形成机理

介绍了一种能在各种晶面的硅衬底上制备垂直于衬底取向生长的ZnO纳米线阵列的新方法. 该法采用高分子络合和低温氧化烧结反应, 以聚乙烯醇(PVA)高分子材料作为自组装络合载体来控制晶体成核和生长. 首先通过PVA侧链上均匀分布的极性基团羟基(—OH)与锌盐溶液中的Zn²⁺离子发生络合作用, 然后滴加氨水调节络合溶液pH值为8.5±0.1, 使络离子Zn²⁺转变为Zn(OH)₂, 再将硅片浸入此溶液中, 从而在硅衬底表面得到较均匀的Zn(OH)₂纳米点, 随后在125 ℃左右Zn(OH)₂纳米点通过热分解转化为ZnO纳米点, 其后在420 ℃烧结过程中衬底上的ZnO纳米点在PVA高分子网络骨架对其直径的限域下逐渐取向生长成ZnO纳米线, 并且烧结初期PVA碳化形成的碳通过碳热还原ZnO为Zn, 再在氧气氛中氧化为ZnO的方式在纳米线顶端形成了催化活性点, 促进了纳米线顶端ZnO的吸收. 烧结后碳逐渐氧化被完全去除. 采用场发射扫描电镜(FE-SEM)、透射电镜(TEM, HR-TEM)和X射线衍射(XRD)对纳米线的分析结果表明, ZnO纳米线在硅衬底上分布均匀, 具有六方纤锌矿结构, 并且大多沿[0001]方向择优取向生长, 直径为20～80 nm, 长度可从0.5至几微米. 提出了聚合物控制ZnO结晶和形貌的网络骨架限域模型以解释纳米线的生长行为.     

ZnO纳米线的电化学制备研究

High-quality ZnO nanowires have been synthesized at relatively low temperature via one-step electrochemical anodization technique. In this method, Zn sheet acted as the anode and Pb sheet served as the counter electrode, and the complex solution of HF-C₂H₅OH-H₂O was used as electrolyte. ZnO nanowires were characterized by Field Emission Scanning Electron Microscopy (FE-SEM), Transmission Electron Microscopy (TEM) and Selected Area Electron Diffraction (SAED) and X-ray Diffraction (XRD). The results show that the nanowires were wurtzite crystalline ZnO, and the ZnO nanowires with the diameters of 70 nm and 30～40 nm were obtained by adjusting preparation conditions, respectively.     

Co掺杂ZnO纳米棒的水热法制备及其光致发光性能

以Zn(NO3)2·6H2O 和Co(NO3)2·6H2O为原料, 通过水热法在较低温度下制备了纯ZnO和Co掺杂的ZnO(ZnO:Co)纳米棒. 利用XRD、EDS、TEM和HRTEM对样品进行了表征, 结合光致发光(PL)谱研究了样品的PL性能. 结果表明, 水热法制备纯ZnO和ZnO:Co纳米棒均具有较好的结晶度. Co2+是以替代的形式进入ZnO晶格, 掺入量为2%(原子分数)左右. 纯的ZnO纳米棒平均直径约为20 nm, 平均长度约为180 nm; 掺杂样品的平均直径值约为15 nm, 平均长度约为200 nm左右; Co掺杂轻微地影响ZnO纳米棒的生长. 另外, Co掺杂能够调整ZnO纳米棒的能带结构、提高表面态含量, 进而使得ZnO:Co纳米棒的紫外发光峰位红移, 可见光发光能力增强.     

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。     

ZnO纳米粒子自建场的形成及对其光电特性的影响

The effect of built-in field on the surface photovoltage(SPV) response of ZnO nanoparticles was investigated by means of surface photovoltage spectroscopy(SPS). From the results of in situ SPS in atmosphere and in vacuum, we suggest that the built-in field should be a main condition for producing SPV response. By comparison of SPS with PL in vacuum as well as in atmosphere, we deduce that by changing the ambience of ZnO, its functional properties can be modulated.     

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.     

碳化硼纳米线的制备和结构

以碳纳米管为模板，通过加热碳纳米管与硼粉的混合物，获得了笔直的硼碳纳米线.对纳米线的结构和成分进行研究，结果表明纳米线主要为B4C纳米线.在部分B4C纳米线的端部存在Ni颗粒，这些端部具有Ni颗粒的纳米线构成了纳米磁针.讨论了B4C纳米线的生长机制，B4C纳米线的生长主要为硼原子在碳纳米管中扩散并发生化学反应，使得碳纳米管晶格结构发生重组，形成B4C纳米线.反应后，硼原子部分取代了碳纳米管中碳原子，修补了碳纳米管中的晶格缺陷，获得了形态笔直的B4C纳米线.     

聚苯胺／ZnO复合材料纳米线的制备及界面特性研究

为获得优异性能的纳／微米结构的有机一无机复合功能材料,进而探讨在纳／微米结构的电子器件或其它领域的潜在应用,在纳米线聚苯胺（PANi）悬浮液的存在下,采用水热方法进行了ZnO的生长,并用所制得的ZnO／PANi复合材料构筑了叉指结构的聚合物基柔性化学传感器原型器件。采用透射电镜（TEM）、X射线衍射（XRD）、X射线光...     

液相法制备取向ZnO纳米线阵列的场发射特性(英文)

采用水热合成工艺,在不同条件下制备了不同的一维取向ZnO纳米线阵列样品.用X射线衍射仪(XRD)、扫描电镜(SEM)及透射电镜(TEM)对样品的晶体结构和形貌等进行了表征,对样品的场发射特性进行了分析和比较,并用Fowler-Nordheim方程对影响ZnO纳米线场发射的因素进行了研究.结果表明,具有较低生长密度分布、较高的长径比和较尖锐生长端的ZnO纳米线阵列样品具有较好的场发射特性.     

氧化锌纳米线自组装定向生长动力学研究

研究了以极性高分子(如聚丙烯酰胺)长分子链作为自组装网络, 利用高分子软模板控制ZnO纳米点成核和ZnO纳米线定向生长, 从而使ZnO纳米线在半导体硅衬底上自组装生长的过程; 采用差示扫描量热法(DSC)测试了高分子络合-烧结法制备ZnO纳米线的结晶曲线, 对其结晶动力学进行了研究, 推导出结晶动力学方程为: 1－X_t＝exp(－7.475×10^－2t^1.9); 并利用热重(TG)测试结果, 通过热分解反应, 导出了反应动力学方程: dα/dT＝(3.76×10²³/Φ)e^－21340.8/T(1－α) ^2.8, 从而得到了化学反应速度随时间、浓度和温度变化的关系, 并用结果解释了实验现象.     

金属有机化学气相沉积法制备ZnO和ZnO∶Ni薄膜及其特性分析

采用金属有机化学气相沉积法制备了ZnO和ZnO∶Ni薄膜,并对它们的结构、光学和电学特性进行了对比研究.通过扫描电子显微镜( SEM)和X射线衍射(XRD)对薄膜的表面形貌和晶体结构进行了分析,结果表明,Ni元素的掺杂虽然降低了薄膜的晶体质量,但并未改变ZnO的纤锌矿结构.通过紫外-可见分光光度计对薄膜的光学特性进行了...     

ZnO/SAPO-34组装体的制备及发光性质研究

以微孔分子筛SAPO-34为主体，采用锌盐浸渍-灼烧的方法，在SAPO-34的菱沸石笼中制备出ZnO纳米粒子，并对不同温度下灼烧后得到的ZnO/SAPO-34组装体的发光性质进行了研究。由于SAPO-34菱沸石笼的尺寸所限，制备出来的ZnO粒子粒径小于1 nm。量子尺寸效应使得SAPO-34笼中的ZnO纳米粒子的荧光光谱在近紫外区的发射谱峰有明显的蓝移。     

纳米ZnO的制备及发光特性研究

The samples of nano-size ZnO were prepared by precipitation, hydrolysis, sol-gel method and characterized by X-ray diffraction, Uv-Vis diffuse reflection spectrum, and time resolved luminescent spectrum. The results showed that the crystallite dimensions of all ZnO samples were coarsening with increasing annealing temperature and the grain sizes prepared by sol-gel method were obviously smaller than the others prepared by precipitation and hy-drolysis method. Under excitation of monochromatic light of wavelength 300nm, a strong and broad photolumines-cence (PL) emissions were observed in the wavelength range of 420～780nm. As the grain size decreased, the PL peak positions moved to shorter wavelengths. And as the annealing temperature increased, the peak intensity de-creased. The photoluminescence decay profile of ZnO was well described by three decay components of 46ns, 330ns and 1630ns.     

硅衬底上聚丙烯酰胺/氧化锌纳米线薄膜蓝色发光二极管

采用高分子络合软模板法利用高分子络合和低温氧化烧结反应,在硅衬底上自组装生长出顶面平滑具有六角柱形结构的ZnO纳米线,并基于此聚丙烯酰胺/ZnO纳米线体系构筑了聚合物基ZnO纳米线发光二极管器件,在相对低的阈值电压下实现了常温常压下电场驱动的蓝色发射光,并且其发光颜色可由其应用的激励电压方便地调控.几乎垂直排列的ZnO纳米线/高分子薄膜在器件中被作为发射层.该方法使用聚合物作为LED器件的粘结剂和发光层的分散介质,稳定了硅衬底上埋置在聚合物薄膜中的ZnO纳米线准阵列并对ZnO纳米晶的表面起钝化作用,防止发光猝灭.结果表明,新技术是一种低成本制备ZnO基紫外/蓝色发光材料的工艺,并且减少了以往工艺中要求ZnO薄膜p型掺杂的麻烦.     

均一形貌的ZnO纳米棒的制备及其光催化性能研究

ZnO nanorods were synthesized from high purity Zn granule by a vapor phase deposition in the Ar + O₂ gas. The products were characterized by X-ray diffraction (XRD) and scanning electron microscope (SEM). The ZnO nanorods were typically 1～2 μm in length and 20～30 nm in diameter with an aspect ratio as high as 20. The UV absorption properties were detected and the results show that the ZnO nanorods have an extremely strong absorption at 200～380 nm wavelength. The results were good when the ZnO nanorods were used as photocatalyst.     

纳米氧化锌的制备与发光性能的研究

Nanocrystalline ZnO Powders were prepared by sol-gel process from Zn(Ac)₂·2H₂O and 2-methoxyethanol solutions containing monoethanolamine. It was found that the photoluminescence (PL) spectra of samples (calcined at 250, 350 and 500 ℃, respectively) had two emission bands in UV region (at ～378 nm) and visible region (at ～502 nm) . The intensity of UV emission bands decreased with the increase of the calcination temperature, and the opposite was true for the visible emission band. TEM, TG-DTG, DTA, XRD, FTIR and surface photovoltage spectra (SPS) were used to investigate this competitive phenomenon. The results indicate that the adsorption of organies on the surface of nanoparticles is the key factor responsible for the relative PL intensity of the two emission bands.