聚合物基ZnO纳米线的制备和生长机理研究

采用独特的高分子溶液自组装生长方法, 在经化学镀预处理的基底上利用高分子溶液的网络络合效应制备了ZnO纳米线. 通过场发射扫描电子显微镜(FE-SEM), X射线能谱仪(EDS)等对样品的表面形貌及组成进行了观测表征. 结果显示, 纳米线直径约50 nm, 长度达到了数微米; 产物Zn、O化学计量比接近1∶1. 通过Si基底经化学镀工艺预处理和未经化学镀预处理对ZnO纳米结构、紫外吸收和PL性能影响的分析比较, 发现了化学镀Ni对于纳米线长度和直径尺寸的控制更为有效; 在PL图谱中, 经化学镀预处理的样品在中心波长385 nm出现了由激子碰撞复合所形成的近紫外发光峰. 进一步还分析了在不同的pH值和反应时间下样品的紫外吸收和光致发光性能. 通过以上实验, 讨论并提出了ZnO纳米线的生长机理及过程, 认为纳米线的生长是在化学镀催化剂和高分子双重作用下进行的.     

大长径比ZnS纳米线的制备、结构和生长机理

通过碳热辅助化学气相沉积法, 以Au作为催化剂, 在较低温度(800 益)制备了ZnS纳米线, 其尺寸均匀, 表面光滑, 直径约为40 nm, 具有很大的长径比, 是典型的单晶纤锌矿六方结构. 高分辨透射电镜和选区电子衍射分析表明, 纳米线的生长方向为[1100], 与已报道的生长方向不同. 纳米线的生长是由气-液-固(vapor-liquid-solid)机理控制的.     

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.     

高压条件下合成硅纳米线

Silicon nanowires (SiNWs) were synthesized with silicon monoxide as the only starting material. At the beginning, a protective gas argon was charged into the reaction chamber and the temperature ramp was controlled at 3 ℃·min^-1. The growth condition for SiNWs was controlled at 480 ℃ under the pressure of 2.8 MPa. The morphology and the structure of the products were characterized by TEM, HRTEM and XRD. The results revealed that SiNWs were diamond structure and their diameters were distributed from 5 to 25 nm. The SiNW was single crystal in the central core and was coated with amorphous silica shell at the exterior surface. Influenced by the quantum effect, Raman spectrum of the SiNWs was found to be redshifted. The oxide-assisted growth mechanism was suggested to explain the growth model of self-assembled SiNWs.     

ZnO微纳米球的生长机制

ZnO micro-nano spheres covered with ZnO nanowires were synthesized at 650 ℃ without using cataly-sts. Characterizations of the products by TEM, SEM, XRD, SAED and EDS showed that the ZnO nanowires were of high purity and single-crystalline with hexagonal wurtzite structure. The diameter of ZnO nanowires ranges from 60 to 200 nm and the length is longer than 10 μm. The size of the ZnO micro-nano spheres ranges from hundreds of nanometers to tens of microns. At the same time, the growth mechanism of ZnO micro-nano spheres is discussed.     

ZnO纳米电缆的制备、结构和生长机理

以混合的锌粉和锡粉作为原料, 通过热蒸发的方法在沉积有金膜的硅基片上制备出具有“芯线-壳层”同轴结构的ZnO/SiO_x纳米电缆. 扫描和透射电镜的研究表明, 这种纳米电缆的产量很高, 长度达到数个微米, 并且确认了其“芯线-壳层”的独特结构. 不同于以往ZnO一维纳米材料的三个快速生长方向〈0001〉、〈0110〉及〈2110〉, 其ZnO芯线的生长方向为[2021]. 本实验中锡粉和金膜分别作为抑制剂和催化剂, 通过控制锌粉的蒸发速率以及金硅共熔反应使ZnO纳米电缆在硅基片上得到一维生长. 这种纳米电缆可望在纳米尺度的电路、电器以及力学和光学信号的耦合和转换方面得到应用.     

单晶硒纳米线的室温快速生长

本文报道了一个新颖的酸化方法在室温下于聚丙烯酸及其钠盐形成的缓冲体系中制得直径为50nm、长为5μm的单晶硒纳米线。使用此法可将硒纳米线的成核及生长时间缩短为3h。一系列表征结果证明利用这一简单有效的方法在短时间内可成功地生长出均一尺寸的硒纳米线。     

光化学法合成银纳米线及其形成机理的研究

结合晶种法和光化学还原法,在聚乙烯吡咯烷酮(PVP)的诱导下成功地制备出直径为50～120nm,长度约为50μm的银纳米线以及银的树枝状纳米结构．实验表明各种反应条件如聚乙烯吡咯烷酮和硝酸银的摩尔比、晶种的加入量及反应时间等对纳米产物的形貌有影响．根据实验结果提出了一种新的银纳米线的形成机理．     

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。     

锌片上多形貌ZnO微晶的水热合成及生长机理

本文采用水热法以锌片作为锌原料提供ZnO微晶生长的养料,在锌片上制备ZnO微晶。使用蒸馏水、NH3?H2O、NaOH和丁胺作为矿化剂,生长的水热环境呈碱性。实验表明,各种不同碱性矿化剂浓度、分子结构及矿化剂溶液的饱和蒸气压都显著地影响ZnO晶体的生长习性,使得样品的最终晶体形貌呈现不同的特点。研究中利用XRD中各晶面衍射强度值数据对晶体形貌特征进行推测,并以SEM进行形貌验证,同时探讨了以锌片为原料制备ZnO微晶的生长机理。     

Synthesis and Characterization of ZnO Nanowires

Zinc oxide is a wide bandgap (3.37 eV) semiconductor with a hexagonal wurtzite crystal structure. ZnO prepared in nanowire form may be used as a nanosized ultraviolet light-emitting source. In this study, ZnO nanowires were prepared by vapor-phase transport of Zn vapor onto gold-coated silicon substrates in a tube furnace heated to 900 ?C. Gold serves as a catalyst to capture Zn vapor during nanowire growth. Size control of ZnO nanowires has been achieved by varying the gold film thickness…     

溶剂热制备氧化锌纳米线

ZnO nanowires were synthesized mildly through an absolute alcohol solvothermal process at 120 ℃ for 12 h using ZnAc₂·2H₂O and NaOH as raw materials and PEG400 as a soft template. The cyrstal structure and morphology of the nanowires were characterized by XRD, SEM, TEM and HRTEM. The results indicate that the diameter of ZnO nanowires is 40 nm, the length can reach 2 μm and the nanowires are of high purity, homogeneity and well crystallinty. The influence of the various factors on the formation of ZnO nanowires and formation mechanism were also discussed.     

醇热法合成单晶银纳米线及其表征

以硝酸银为前驱物, 聚乙烯醇缩丁醛(PVB)为结构导向剂, 通过醇热法, 反应温度为140 ℃, 反应时间为24 h的条件下制备了银纳米线. 采用X射线衍射(XRD)、扫描电镜(SEM)、透射电镜(TEM)、热重分析(TG)、红外光谱(FT-IR)和激光拉曼光谱(Raman)等手段对产物进行了系统表征, 结果表明: 所得银纳米线具有面心立方结构, 沿着(111)晶面生长, 具有单晶结构; 考察了反应温度和时间对产物形貌的影响, 结果表明: 反应温度和时间在形成银纳米线的过程中起着关键的作用; 银纳米线具有较强的表面增强拉曼散射效应; 同时提出了银纳米线可能的晶化机理.     

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.     

Synthesis, Structure and Growth Mechanism of ZnS Nanowires with High Aspect Ratio

ZnS nanowires were successfully synthesized through the direct reaction of Zn and S vapor via carbon-assisted chemical evaporation deposition method with Au catalyst. The investigations indicated that the size of ZnS nanowires with a diameter of approximately 40 nm was uniform along the axis of the wire and the surfaces were slick. The ZnS nanowire with a hexagonal wurtzite structure was a typical single crystalline structure. HRTEM and SEAD results demonstrated that the nanowire grew along [100] direction, which was different from the common direction reported in literatures. The growth of nanowires was controlled by vapor-liquid-solid (VLS) mechanism.     

软化学法低温合成银纳米线及其生长机制

以AgNO_3为起始物，采用DMF为溶剂和还原剂，无须采用晶种，在低温下 AgNO_3经DMF还原，通过软化学法合成了结构均匀的银纳米线，其直径为15-30nm， 长度高达20μm。通过引入乙酰丙酮，控制钛酸丁酯水解形成的多孔氧化物溶胶为 网络孔道结构，这种孔道结构为银纳米线的控制合成提供了有效的生长模板。