Piezoelectricity of ZnO films prepared by sol-gel method

ZnO piezoelectric thin films were prepared on crystal substrate Si(111) by sol-gel technology, then characterized by scanning electron microscopy, X-ray diffraction and atomic force microscopy (AFM). The ZnO films characterized by X-ray diffraction are highly oriented in (002) direction with the growing of the film thickness. The morphologies, roughness and grain size of ZnO film investigated by AFM show that roughness and grain size of ZnO piezoelectric films decrease with the increase of the film thickness. The roughness dimension is 2.188-0.914 nm. The piezoelectric coefficient d(33) was investigated with a piezo-response force microscope (PFM). The results show that the piezoelectric coefficient increases with the increase of thickness and (002) orientation. When the force reference is close to surface roughness of the films, the piezoelectric coefficient measured is inaccurate and fluctuates in a large range, but when the force reference is big, the piezoelectric coefficient d(33) changes little and ultimately keeps constant at a low frequency.

微/纳米氧化锌（ZnO）的生长、性质及其应用研究

纳米氧化锌（ZnO）是一种直接宽带隙半导体材料，室温下其禁带隙宽为本3.37 eV，激子束缚能为60 meV。纳米ZnO有明显的尺寸效应、表面和界面效应等，物理化学性能优越。在压电材料、铁电材料、平面显示、表面声波、传感器、场发射器件、激光、光催化等方面有着广泛的用途。近年来，对纳米ZnO材料的研究成为国内外的一个热点。 本论文研究了用化学气相沉积（CVD）法制备微/纳米ZnO材料。通过控制实验条件，合成了多种特殊结构和形貌的微/纳米ZnO材料，并用扫描电子显微镜（SEM）、高分辨率透射电镜（HR-TEM）、X-射线衍射仪（XRD）、Raman光谱和光致发光（PL）等对材料的结构和光学性能进行了表征。采用CVD法，在温度为630 °C，氧气流量为15 sccm，氩气流量为300 sccm的条件下，制备了一种纳米带冠四足状ZnO（T-ZnO）。此结构ZnO材料的每根足顶端均有一规则的六方帽形结构，具有很大的比表面积。实验结果表明：合成的ZnO材料为纤维锌矿结构单晶，并且沿着(0001)方向生长；室温下的PL谱有两个激发峰，一个是在393 nm处相对较弱的近带紫外峰，另一个是在511 nm处强峰。而材料在600 °C下氧气中退火30 min后，511 nm附近的绿光激发辐射峰则基本消失了，这说明在511 nm处的绿光激发辐射峰可能是由于氧空位引起的。此外，通过改变实验条件，还得到了其他多种结构的微/纳米ZnO材料。 通过大量实验，找到了一种在低温下合成微/纳米ZnO材料的新方法，即水蒸气氧化法。用ZnI2作为锌源，水蒸气作为氧化剂，实验温度在300～500 °C范围内，大大低于通常CVD法的500～1500 °C。采用此法，用硅做基底，得到了一系列有趣的实验结果，大多数情况下ZnO纳米晶自组装成很规则的圆。而在瓷舟中收集到的纳米ZnO跟普通CVD法结果相似，可以得到锥状、棒状等结构的纳米晶，但其生长方式与硅基底上的有很大差别。此外，用水蒸气氧化法，还实现了ZnO纳米晶在碳纳米管（CNTs）上的直接生长，而且其PL性能增强，这可能是纳米ZnO和CNTs相互耦合的结果。在700 °C温度下，以锌粉和ZnI2作为锌源，用水蒸气作为氧化剂，在硅基底的正反面分别得到了纳米棒和纳米推子阵列。此外，还对水蒸气氧化法的化学反应机理进行了分析，实验结果证明：固态ZnI2在受热和一定真空度下先蒸发成ZnI2分子，ZnI2分子遇到水蒸气发生反应生成偶极ZnO分子，这些ZnO偶极分子在硅基底上通过静电力自组装成特殊的几何形状。 此外，还通过分子动力学模拟的方法，对材料的力学性能进行了研究，得到了ZnO的弹性常数和体弹性模量，模拟值跟其他研究人员的实验和模拟结果吻合得很好，并估出算了ZnO晶体的表面能和断裂韧性。 本论文还对制备材料的光催化性能进行了系统的研究，采用CVD法制备ZnO，对铬黑T（EBT）进行光催化降解实验。通过正交实验方法，得到了ZnO催化降解EBT的最佳工艺条件，即催化剂用量为5 g/L，光照强度为120 W，反应温度为20 °C，反应时间为120 min，EBT浓度为10 mg/L，溶液pH值为4。 在最佳实验条件下，20分钟内有95%的EBT被降解完，30分钟内则全部降解。因此，ZnO在EBT的降解中催化效率很高，在废水处理中具有潜在的应用前景。

Ab Initio Study Of Zno-Based Gas-Sensing Mechanisms: Surface Reconstruction And Charge Transfer

Density functional theory (DFT) calculations were employed to explore the gas-sensing mechanisms of zinc oxide (ZnO) with surface reconstruction taken into consideration. Mix-terminated (10 (1) over bar0) ZnO surfaces were examined. By simulating the adsorption process of various gases, i.e., H-2, NH3, CO, and ethanol (C2H5OH) gases, on the ZnO (10 (1) over bar0) surface, the changes of configuration and electronic structure were compared. Based on these calculations, two gas-sensing mechanisms were proposed and revealed that both surface reconstruction and charge transfer result in a change of electronic conductance of ZnO. Also, the calculations were compared with existing experiments.

Femtosecond pulse laser-induced self-organized nanostructures on the surface of ZnO crystal

This paper reports self-organized nanostructures observed on the surface of ZnO crystal after irradiation by a focused beam of a femtosecond Ti:sapphire laser with a repetition rate of 250 kHz. For a linearly polarized femtosecond laser, the periodic nanograting structure on the ablation crater surface was promoted. The period of self-organization structures is about 180 nm. The grating orientation is adjusted by the laser polarization direction. A long range Bragg-like grating is formed by moving the sample at a speed of 10 mu m/s. For a circularly polarized laser beam, uniform spherical nanoparticles were formed as a result of Coulomb explosion during the interaction of near-infrared laser with ZnO crystal.

Femtosecond laser-induced periodic surface structure on ZnO

Three different ZnO nanostructures include nanoparticles, ripples and regular nanogratings were successfully prepared by femtosecond laser irradiation under different experimental conditions. The in-situ observation of the second harmonic generation (SHG) excited in ZnO crystals before, during, and after the formation of the nanostructures was investigated. The obtained results show that the formed nanostructures contribute to the enhancement of the SHG. We propose that the second harmonics in the sample surface plays an important role in the formation of nanostructures. (c) 2007 Published by Elsevier B.V.

Coherent linking of periodic nano-ripples on a ZnO crystal surface induced by femtosecond laser pulses

We demonstrate the coherent linking of periodic nano-ripples formed on the surface of ZnO crystals induced by femtosecond laser pulses. By adjusting the distance between two laser scanning zones, the periodic nano-ripples induced by two separated laser writing processes can be coherently linked and the ZnO nanograting with much longer grooves is therefore produced. The length limitation of this kind of nanograting previously set by the laser focus size is thus overcome. The micro-Raman mapping technique is used to evaluate the quality of coherent linking, and the underlying physics is discussed. The demonstrated scheme is promising for producing large-size self-organized nanogratings induced by femtosecond laser pulses.

Ultrafast dynamics in ZnO thin films irradiated by femtosecond lasers

The damage morphologies, threshold fluences in ZnO films were studied with femtosecond laser pulses. Time-resolved reflectivity and transmissivity have been measured by the pump-probe technique at different pump fluences and wavelengths. The results indicate that two-phase transition is the dominant damage mechanism, which is similar to that in narrow band gap semiconductors. The estimated energy loss rate of conduction electrons is 1.5 eV/ps. (c) 2005 Elsevier Ltd. All rights reserved.

Raman spectroscopy and luminescent properties of ZnO nanostructures fabricated by femtosecond laser pulses

In this paper, we report the laser-induced periodic structure with different spatial characteristics on the surface of polished ZnO single-crystalline by high repetition rate femtosecond laser pulses. This study demonstrates that, using different laser parameters and irradiation conditions, ZnO nanoripples and nanorods were successfully prepared. We have investigated the surface by means of scanning electron microscope (SEM), Raman scattering and photoluminescence (PL). We propose that second-order harmonic has a strong influence on the formation of nanostructures. (c) 2007 Elsevier B.V All rights reserved.

Transparent Ni2+-doped ZnO-Al2O3-SiO2 system glass-ceramics with broadband infrared luminescence

We report transparent Ni2+-doped ZnO-Al2O3-SiO2 system glass-ceramics with broadband infrared luminescence. After heat-treatment, ZnAl2O4 crystallite was precipitated in the glasses, and its average size increased with increasing heat-treatment temperature. No infrared emission was detected in the as-prepared glass samples, while broadband infrared luminescence centered at 1310 nm with full width at half maximum (FWHM) of about 300 nm was observed from the glass-ceramics. The peak position of the infrared luminescence showed a blue-shift with increasing heat-treatment temperature, but a red-shift with an increase in NiO concentration. The mechanisms of the observed phenomena were discussed. These glass-ceramics are promising as materials for super broadband optical amplifier and tunable laser. (c) 2006 Elsevier Ltd. All rights reserved.

A uniform 290 nm periodic square structure on ZnO fabricated by two-beam femtosecond laser ablation

A uniform submicron periodic square structure was fabricated on the surface of ZnO by a technique of two linearly polarized femtosecond laser beams with orthogonal polarizations ablating material alternately. The formed two-dimensional ordering submicron structure consists of close-packed submicron squares with a spacial periodicity of 290 nm, which arises from the intercrossing of two orthogonal submicron ripple structures induced by the two beams respectively. The result demonstrates a noninterference effect of two-beam ablation based on the alternate technique, which should come from the polarization-dependent enhancement of the subwavelength ripple structure and the large interval of two alternate pulses. This two-beam alternate ablation technique is expected to open up prospects for the submicron fabrication of wide-bandgap materials.

Upconversion luminescence and optical power limiting effect based on two- and three-photon absorption processes of ZnO crystal

Near-infrared to UV and visible upconversion luminescence was observed in single-crystalline ZnO under an 800 nm infrared femtosecond laser irradiation. The optical properties of the crystal reveal that the UV and VIS emission band are due to the exciton transition (D0X) bound to neutral donors and the deep luminescent centers in ZnO, respectively. The relationship between the upconversion luminescence intensity and the pump power of the femtosecond laser reveals that the UV emission belongs to three-photon sequential band-to-band excitation and the VIS emission belongs to two-photon simultaneous defect-absorption induced luminescence. A saturation phenomenon and polarization-dependent effect are also observed in the upconversion process of ZnO. A very good optical power limiting performance at 800 nm has been demonstrated. The two- and three-photon absorption coefficients of ZnO crystal were measured to be 0.2018 cm GW(-1) and 7.102 x 10(-3) cm(3) GW(-2), respectively. The two- and three-photon cross sections were calculated to be 1.189 x 10(-51) cm(4) s and 1.040 x 10(-80) cm(6) s(2), respectively. (c) 2007 Elsevier B.V. All rights reserved.

Ni^2＋掺杂透明ZnO-Al2O3-SiO2系微晶玻璃的光学性质

采用传统熔融冷却的方法制备了透明Ni^2＋掺杂ZnO-Al2O3-SiO2系玻璃，结合X-射线、吸收和荧光等测试手段，研究了不同热处理温度对Ni^2＋掺杂透明ZnO-Al2O3-SiO2系微晶玻璃光学性质的影响。由X-射线衍射谱鉴定出微晶玻璃中析出的晶相为ZnAl2O4微晶，其尺寸在13nm以下。玻璃中没有发现近红外发光，而在微晶玻璃中存在宽带近红外发光，其可归属为八面体六配位Ni^2＋离子的^3T2g（^3F）激发态向^3A2g（^3F）基态的跃迁。随热处理温度升高发光强度增强，而发射峰位则发生蓝移；荧

不同烧蚀条件下飞秒激光脉冲诱导ZnO纳米结构研究

烧蚀条件对飞秒激光脉冲诱导氧化锌纳米结构有重要影响。研究了800nm,150fs,250kHz的飞秒激光脉冲分别在空气中,去离子水中以及无水乙醇中垂直聚焦于氧化锌晶体表面,诱导形成不同形态的纳米结构。实验结果表明,在空气中利用飞秒激光脉冲辐照样品表面,形成了周期为180nm的纳米线;在去离子水中辐照诱导形成了由氧化锌纳米线聚集而成的"纳米球";在无水乙醇中形成出现分叉结构的纳米线。拉曼光谱分析辐照前后晶体晶相结果表明,形成的纳米结构相对于辐照前特征峰437cm-1强度有所下降,在570cm-1处的峰值则显著增强。分析了在各种烧蚀条件下诱导形成纳米结构的演化过程以及物理机理。