氧化锌叶片状纳米晶的结构和光谱特性

熔盐法对sol-gel法生成的前驱物处理合成新颖的叶片状的氧化锌纳米结构,TEM照片显示其长度300-500nm,宽度为50-80nm,两头尖端约呈25°夹角,形状基本沿中轴呈中心对称。其生长过程进行了研究:弯曲了的ZnO纳米棒闭合形成框架结构,框架内沿中轴方向并排生长的ZnO纳米线填满框架内的空隙形成叶片状的氧化锌纳米结构。Raman谱测量发现该结构是晶化的六角相氧化锌。对叶片状的氧化锌的声子限制效应进行了研究,并与纳米颗粒氧化锌予以比较。435cm-1的E2峰的Fano不对称具有正的Fano耦合系数。发现在585nm处出现光致发光峰,归于ZnO纳米结构中氧缺陷的作用。     

热氧化法制备ZnO纳米晶体、纳米线

以高纯Zn块为源材料,通过热氧化法制备了纳米ZnO薄膜。在950℃的温度和一定的压力条件下,通过改变生长时间,分别制备了ZnO纳米晶体、纳米纤维和纳米线。应用扫描电镜观察发现,在恒温生长条件下,纳米ZnO具有定向生长的趋势。随生长时间的延长,纳米晶体定向生长为纳米纤维,最后生长为超长的纳米线。     

锡催化剂助生长法制备孪晶ZnO纳米线及其结构表征

用SnO和Zn的均匀混合物在高温下共烧通过VLS机制制备出孪晶ZnO纳米线的均匀结构。SEM图像显示孪晶ZnO纳米线的直径在100~200nm之间,长度在几十微米到几百微米之间的范围内,有的甚至达到了毫米级,产率也非常的高。TEM图像中ZnO孪晶纳米线顶端的金属Sn颗粒表明了孪晶结构的Sn催化生长。高分辨电子图谱显示了氧化锌纳米线孪晶结构的特征。电子衍射分析发现孪晶氧化锌的晶带轴的方向是[0110],孪晶面为(1013),并且通过明场像和暗场像分析了孪晶纳米线的晶格关系,确定了孪晶纳米线的汽-液-固(VLS)生长机制。     

异质结型CuO/ZnO复合纳米线的制备及光催化性能

在室温下,通过溶液法在Cu衬底上制备了CuO纳米线,然后采用溶剂热法在CuO纳米线表面生长ZnO纳米颗粒以构建CuO/ZnO复合纳米线异质结构。利用扫描电镜、透射电镜、X射线衍射仪和X射线光电子能谱分析了样品的形貌、结构和元素组成。结果显示CuO/ZnO复合纳米线由ZnO纳米颗粒和CuO纳米线组成。在模拟太阳光照射下,以亚甲基蓝溶液为模拟污染物研究了样品的光催化性能。结果表明,相比纯CuO纳米线,CuO/ZnO复合纳米线能够使亚甲基蓝溶液的光降解效率达到40%,在相同条件下具有更优异的光催化活性。光催化机理研究表明CuO/ZnO纳米复合材料光催化活性的增强主要是由于CuO与ZnO结合形成的p-n异质结有效促进了光生载流子的分离。     

ZnO纳米线紫外探测器的制备和快速响应性能的研究

一维ZnO纳米结构由于具有比表面积大、室温下具有大激子结合能等特点而受到广泛关注. 但是如何实现纳米结构的器件一直是目前研究的一个挑战. 文章通过水热方法, 在玻璃衬底上实现了ZnO纳米线横向生长, 并制备出基于ZnO纳米线的金属-半导体-金属紫外探测器. 测量结果显示器件在365 nm处探测器的响应度达到5 A/W, 并且制备的探测器在空气中对紫外光照具有快速的响应, 其上升时间约4 s, 下降时间约5 s, 这与ZnO纳米线中的氧空位吸附和脱附水分子相关.     

用光声技术研究半导体TiO2,ZnO纳米晶粉的光学特性

应用新型的光声光谱技术,研究了不同种类和不同制备工艺条件的半导体纳米晶粉的光学特性,测量了半导体TiO2、ZnO和掺铝ZnO纳米晶粉的光声光谱,获得了这些半导体纳米晶粉的带隙和光谱吸收系数.研究结果表明,相同种类和相同颗粒形状的半导体纳米晶粉的粒径越小,光学吸收系数越大.半导体纳米晶粉的带隙与相同种类纳米颗粒形状(圆球...     

纳米晶粒在高压下的相转变

本文报道了晶粒尺寸对压力诱导相转变的最新进展。用热力学理论分析了造成纳米晶体材料（纳米晶）的相转变压力与同种大块材料不同的主要因素是体积变化比，表面能差和内能差。通过估算这三个因素的具体大小，可解释文献报道的实验结果，并可确定大块材料和纳米晶之间相转变压力发生差异的控制因素。在纳米晶中，晶粒尺寸对结构稳定性和相转变压力的影响与体系本身有关。     

Ag/ZnO纳米结构的荧光增强效应

利用化学合成方法制备了Ag纳米线和ZnO量子点。对这两种纳米结构的表面形貌、晶体结构和光学性质分别进行了研究。结果表明：Ag纳米线和ZnO量子点均为单晶结构,平均直径分别为160 nm和5 nm左右。将Ag纳米线混入ZnO量子点可以使其紫外荧光显著增强,其中位于345 nm和383 nm 的荧光分别增强30倍和12倍。这与Ag纳米线和ZnO量子点混合体系的局域表面等离子体共振耦合吸收峰位相一致,说明该体系存在两种共振耦合模式。该研究结果为将来开发ZnO基纳米发光器件提供了一条新的途径。     

纳米ZnO在高压下的性质与结构研究

 在金刚石压砧上测量了20 nm的ZnO和体相粉末ZnO的电阻-压力关系。研究结果表明，20 nm的ZnO在7.9 GPa 压力时出现了相变，而体相粉末ZnO在5 GPa 时有相变发生。虽然粒径小的相变压力大于粒径大的，但与以前关于体相粉末ZnO所报道的文献结果有所不同。文中对此作了解释，并对纳米ZnO在压力下的畴破裂进行了研究。     

海胆状ZnO纳米线阵列的制备及其光学性能

采用一种低成本的有效方法制备出了有序排列的海胆状ZnO纳米线阵列。首先利用自组装的方法得到了单层的聚苯乙烯(PS)小球,以其为模板用水热法在小球表面生长ZnO纳米线,得到了由PS小球和ZnO纳米线构成的海胆状结构。纳米线的直径均一,长度可通过水热反应时间进行控制。利用这种方法制备的一维ZnO纳米结构在传感器、太阳能电池及光催化领域有潜在的应用价值。     

The structural and optical properties of ZnO bulk and nanocrystals under high pressure

The elastic properties of high-quality ZnO crystals and nanopowder of grain size of about 65 nm are studied for both wurtzite (low pressure) and rock-salt high pressure phases. The measured values of bulk moduli for wurtzite and rock-salt phases of bulk ZnO crystals are equal to 156±13 and 187±20 GPa, respectively, and considerably larger for ZnO nanocrystals. The phase transition begins at a pressure of about 9 GPa and it is completed at a pressure of about 13.8 GPa for bulk crystals, whereas the values of pressure at which the phase transition occurs are lower for nanocrystals. A carefull Rietveld analysis of the obtained data does not exhibit the presence of any intermediate phases between low pressure wurtzite and high pressure rock-salt phases of ZnO. The phase transition is accompanied by a strong decrease in the near-band-gap photoluminescence intensity. In addition, the pressure coefficient of the near-band-gap luminescence in ZnO nanocrystals exhibits strong deviation from the linearity observed in bulk crystals. An analysis of the results shows that defects present in the nanopowdered sample are responsible for the observed effects.     

纳米晶Si在高压下的电学性质与金属化相变

 在金刚石压砧装置上,采用电阻和电容测量方法,研究了粒径为15~18 nm和80 nm的纳米晶Si在室温下、24 GPa内的电阻、电容与压力的关系。实验结果表明,它们分别在19~17 GPa和14 GPa左右发生了金属化相变。     

Ag掺杂氧化锌纳米材料的制备及高压相变拉曼光谱研究

宽禁带直接带隙半导体材料氧化锌（ZnO）,具有优异的光电性能、机械性能和化学特性。ZnO材料的结构对其性能影响较大,元素掺杂可改变ZnO晶体结构和带隙宽度,是提升ZnO材料性能的有效手段,当前常用Ag掺杂ZnO即为提高光催化反应效率。高压独立于温度、成分,是调控材料结构组织性能的重要手段,是产生新材料、发现新调控原理的重要因素。该研究通过对比纯ZnO晶体和Ag掺杂ZnO晶体的高压相变行为,揭示了元素掺杂对ZnO纳米晶体材料结构性能的影响。研究首先采用水热法辅助制备纯ZnO纳米微球和Ag掺杂ZnO纳米微球（1∶150Ag/ZnO）,表征结果显示水热法合成的纯ZnO和1∶150Ag/ZnO均为六角纤锌矿晶体结构,形貌均为几十纳米尺寸小颗粒堆积形成的微球,ZnO晶格常数随着Ag离子掺杂而变大,Ag掺杂导致ZnO晶格膨胀。随后应用金刚石压腔结合原位拉曼光谱技术测定了纯ZnO和Ag掺杂ZnO的高压结构相变行为。相比于纯ZnO拉曼峰,Ag掺杂ZnO的E₂（high）振动模式439 cm-1拉曼峰峰宽变窄,并呈现向低频方向移动的趋势,与无定形ZnO谱峰相近,表明Ag+取代Zn2+影响了Zn-O键,同时也影响了ZnO晶格结构的长程有序性。随体系压力增大,表征六角纤锌矿结构ZnO的拉曼特征峰439 cm-1出现瞬间弱化和宽化。压力增大至9.0 GPa时,纤锌矿结构ZnO拉曼特征峰439 cm-1消失,585 cm-1处出现新峰,ZnO晶体发生由六角纤锌矿向岩盐矿的结构转变。压力继续增大至11.5 GPa,新的拉曼峰显著增强,峰形变窄,同时向高波数方向移动,相变完成,岩盐矿结构ZnO性能稳定。1∶150 Ag/ZnO从六角纤锌矿结构到立方岩盐结构的相变压力为7.2 GPa,低于纯ZnO。相变压力降低表明晶体结构稳定性下降,可能的原因在于掺杂Ag导致ZnO晶格膨胀,晶体结构松弛,两相相对体积变化增加,从而导致相变势垒降低,使样品在较低压力下发生相变。纳米材料的高压研究揭示了元素掺杂对材料结构稳定性的影响,是纳米材料调控原理的潜在研究手段。     

ELECTRICAL PROPERTIES, EQUATIONS OF STATE AND PHASE TRANSITION IN SOLID C60 AT HIGH PRESSURE

Electrical properties and equations of state in solid C₆₀ at room temperature and high pressure have been studied in a diamond anvil cell using capacitance and resistance measurements and a piston-cylinder type device using P-V measurements, respectively. Experimental results by capacitance and P-V measurements indicate that solid C₆₀ also undergoes a phase transition at room temperature and a lower pressure, about 2GPa. The phase transition may be from a face-centered-cubic to a simple-cubic structure.     

Semiconductor–metal transition in GaAs nanowires under high pressure

We investigate the structural phase transitions and electronic properties of GaAs nanowires under high pressure by using synchrotron x-ray diffraction and infrared reflectance spectroscopy methods up to 26.2 GPa at room temperature.The zinc-blende to orthorhombic phase transition was observed at around 20.0 GPa.In the same pressure range, pressureinduced metallization of GaAs nanowires was confirmed by infrared reflectance spectra.The metallization originates from the zinc-blende to orthorhombic phase transition.Decompression results demonstrated that the phase transition from zincblende to orthorhombic and the pressure-induced metallization are reversible.Compared to bulk materials, GaAs nanowires show larger bulk modulus and enhanced transition pressure due to the size effects and high surface energy.     

Surface tension and Curie temperature in ferroelectric nanowires and nanodots

The effect of surface tension associated internal pressure on the Curie phase transition in ferroelectric nanowires and nanodots has been investigated using a modified Landau–Ginzburg–Devonshire phenomenological approach. Based on experimental data on the size- dependent phase transition in freely suspended single-crystalline ferroelectric nanocrystals, bulk surface tension coefficients for BaTiO₃ and PbTiO₃ have been determined to be of the order of 1–2 N/m. The present theoretical study reproduces the size dependence of the transition temperature experimentally acquired in individual BaTiO₃ single-crystalline nanowires. In the case of PbTiO₃ single-crystalline nanodots, however, in order to fit the theoretically calculated size-dependent ferroelectric transition with the experimental data, an effective surface tension coefficient has been introduced, which is size dependent and can be much higher than the bulk value. An erratum to this article can be found at     

Position-controlled and catalyst-free growth of ZnO nanocrystals by nanoparticle-assisted pulsed laser deposition

We have synthesized ZnO nanocrystals, such as nanowires, nanorods, and nanosheets, using a nanoparticle-assisted pulsed laser deposition (NAPLD) method. Recently, we achieved position-controlled growth of the ZnO nanocrystals by means of a ZnO buffer layer and laser irradiation without any catalyst. The periodic structure was formed on the ZnO buffer layer by multi-beam interference patterning, and then vertically aligned ZnO nanowalls, corresponding to the patterning, were grown on the buffer layer. It was found that the periodic ZnO nanowalls grew along the c-axis direction by X-ray diffraction measurement. The well-aligned ZnO nanowalls are expected to be utilized as building blocks for field emitters and UV LEDs. The proposed technique can be used as one of the effective methods to control the growth position of the ZnO nanocrystals because various structures can be easily fabricated by a laser writing and a spatial light modulator.     

Mn effect on wurtzite-to-cubic phase transformation in ZnO

Mn doping effect on a wurtzite-to-cubic phase transformation in ZnO has been investigated by in situ high pressure X-ray powder diffraction using synchrotron radiation. Unit cell expansion is clearly observed in Mn-doped ZnO samples. Mn ions sit at Zn site in the wurtzite structure. The onset transition pressure for the wurtzite-to-cubic phase transformation decreases from about 9.5 GPa for pure ZnO to 6 GPa for sintered 2at.% Mn-doped ZnO while the compressibility and volume collapse at transition pressures are not sensitive to the Mn doping in the wurtzite phase. The doping of Mn ions in ZnO increases the onset transition pressure for the cubic-to-wurtzite phase transformation. The results could be explained by a reduction of phase transformation barriers for both transition paths by the Mn doping. The observation of reduction of the wurtzite-to-cubic phase transformation pressure might point out a new direction to synthesize cubic wurtzite phase of ZnO by doping transition element(s).