Growth of ZnO nanoparticles and nanorods with ultrafast pulsed laser deposition

In this work, we study the application of ultrafast pulsed laser deposition (PLD) in ZnO nanomaterial synthesis, including nanoparticles and nanorods. PLD using long pulse (nanosecond) lasers has been widely used as a method for growing prototype materials. The recently-emerged ultrafast PLD is expected to be able to overcome the problem of large liquid droplet formation. Using near infrared and femtosecond laser pulses in ablation, we first characterize the ablation plume using a Langmuir probe and plasma optical emission spectroscopy. We then examine the structural properties of the nanoparticles generated during low-fluence ablation. Finally, we demonstrate that using nanoparticle aggregates as templates, assisted by plume-excited nitrogen radicals at a high fluence, high quality ZnO nanorods can be grown free of metal catalysts.     

Effect of ZnO plasma plume dynamics on laser ablation

The dynamic behaviors and optical properties of a ZnO plasma plume produced by pulsed laser ablation using a Nd:YAG laser (wavelength: 532 nm, pulse width: 3 ns) were studied by fast photography using a commercial gated charge coupled device (CCD) camera linked with a delay circuit and by optical emission spectroscopy at various ambient oxygen pressures. Fast photography was conducted with a resolving power of 0.25 μs and the expansion behaviors of the laser ablation plume were observed. Plasma plume expansion velocity decreased with oxygen partial pressure. The flow of the plasma plume in the early stage of expansion of up to 3 ms agreed well with the drag model.     

Particle diagnostics of a ZnO laser ablation plume for nanostructured material deposition

We report results on the pulsed laser deposition of ZnO obtained with the help of a new apparatus that includes in situ reflectron time-of-flight mass spectrometry, with a view to progress the understanding of the role of clusters in the laser deposition of nanostructured materials. Experiments were carried out using a Nd-YAG laser at its fundamental frequency and frequency tripled, with a fluence on target of ∼7.7 J/cm², in vacuum (10⁻⁴ Pa) or oxygen (1 Pa) atmospheres. The results show that under certain conditions there is preferential clusterisation of the material into certain mass numbers and finally that there exists a correlation between cluster presence in the plume and the deposition of nanostructures.     

ZnO nanoparticles produced by reactive laser ablation

The paper presents the results of theoretical and experimental researches of the analysis of nanopowder ZnO and ZnO-based structures formation mechanisms by means of pulse laser reactive technology (λ = 1.06 μm, τ = 10⁻⁷ to 10⁻⁵ s). The developed 2D model combines non-stationary heat transfer and fluid motion along with the calculated profile of surface deformation. The characteristics of the dispersive and chemical compositions and structural parameters of the synthesized nanopowder together with the influence of the energy of laser impulse evaporation, its duration and gas pressure in the reaction chamber have been studied using X-ray diffractrometry (XRD), energy-dispersive X-ray spectroscopy (EDX), transmission electron microscopy (TEM). Particle size distribution analysis of ZnO has shown that the majority of them range from 5 to 60 nm in size. The photoluminescence emission spectra of the initial ZnO nanopowder at room temperature have been identified.     

Structures of BiInSn nanoparticles formed through laser ablation

The eutectic alloy of BiInSn was ablated in water by UV pulsed radiation. Electron microscopy of the ablated material shows spherical particles that fall into three size regimes: those with diameters of ～0.5 μm, crystalline and amorphous particles with dimensions of ～30 nm, and amorphous particles that are approximately 1 nm across. The 30-nm amorphous particles are homogeneous, while there are two types of 30-nm crystalline particles, those that separate into three phases and those that are homogeneous. The existence of different characteristic sizes is explained by two mechanisms: phase explosion and Rayleigh instability of the ejected melt.     

Fabrication of ZnO nanoparticles by laser ablation of sintered ZnO in aqueous solution

Fabrication of ZnO nanoparticles by laser ablation in liquid medium is reported. The possibility of using a sintered ZnO target for the ablation as well as a Zn plate is demonstrated. The appropriate aqueous solution of sodium dodecyl sulfate is found to be 1 mM for ZnO growing. The shape of ZnO nanoparticles is sphere and its diameter is 30∼60 nm. Fourier transform infrared spectra, Raman scattering spectra, and photoluminescence spectra reveal the optical properties of ZnO nanoparticles. Nanoparticles obtained by using ZnO targets show a smaller defect density compared with those by using Zn targets.     

Control of diameter of ZnO nanorods grown by chemical vapor deposition with laser ablation of ZnO

We made a study of controlling diameters of well-aligned ZnO nanorods grown by low-pressure thermal chemical vapor deposition combined with laser ablation of a sintered ZnO target, which was developed by us. Until now, it has been impossible to control diameters of ZnO nanorods, while the growth orientation was maintained well-aligned. In this study we developed a multi-step growth method to fabricate well-aligned nanorods whose diameters could be controlled. Metal Zn vapor and O₂ are used as precursors to grow ZnO nanorods. N₂ is used as a carrier gas for the precursors. A substrate is an n-Si (111) wafer. A sintered ZnO target is placed near the substrate and ablated by a Nd–YAG pulsed laser during ZnO nanorod growth. The growth temperature is 530 C and the pressure is 66.5 Pa. A vertical growth orientation of ZnO nanorods to the substrate is realized in the first-step growth although the diameter cannot be controlled in this step. When an O₂ flow rate is 1.5 sccm, well-aligned nanorods with 100 nm diameter are grown. Next, the second-step nanorods are grown on only the flat tip of the first-step nanorods. The diameters of the second-step nanorods can be controlled by adjusting the O₂ flow rate, and the growth direction is kept the same as that of the first-step nanorods. When the O₂ flow rate in second-step growth is smaller than 0.6 sccm, the diameter of the second-step nanorods is 30–50 nm. When the O₂ flow rate is between 0.75 and 3.0 sccm, the diameter is almost same as that of the first-step nanorods. When the O₂ flow rate is larger than 4.5 sccm, the diameter is increased with increasing O₂ flow rate. Further, the third-step ZnO nanorods with gradually increased diameters can be grown on the second-step nanorods with 1.5 sccm O₂ flow rate and without laser ablation.     

Photoluminescence of ZnO nanoparticles generated by laser ablation in deionized water

Zinc oxide (ZnO) nanoparticles were synthesized using pulsed laser ablation of a Zn metal plate in deionized water without using surfactant. The beam of a Q-switched Nd:YAG laser of 1064-nm and 532-nm wavelengths at 6-ns pulse width and different fluences is employed to irradiate the solid target in water. Transmission electron microscopy images revealed that the size of the ZnO nanoparticles formed by the 532-nm wavelength laser beam is smaller than that of the nanoparticles generated by the 1064-nm wavelength laser beam. The room-temperature photoluminescence spectra of the ZnO nanoparticles show intense violet emission along with emission in blue and green bands. The excellent ultraviolet emission indicates that the ZnO nanostructures have a low defect concentration.     

Fe离子注入ZnO生成超顺磁纳米颗粒

过渡族元素掺杂ZnO生成稀磁半导体, 成为近期国际材料科学研究的热点. 在本文中, 研究Fe离子注入ZnO单晶的结构和磁性变化, 目标是建立磁性和结构的对应关系, 澄清铁磁性的来源. 采用卢瑟福背散射/沟道技术 (RBS/Channelling)、同步辐射X射线衍射 (SR-XRD)和超导量子干涉仪 (SQUID), 研究注入温度和退火对样品的晶格损伤、结构及磁性的影响. 研究表明: 样品注入区损伤随注入温度升高而降低; 低温253 K注入样品中, SR-XRD未检测到新相, Fe离子分布于Zn位, ZnO (0002) 峰右侧肩峰可能属于Zn_1-xFe_xO, 5 K下测试样品不具有铁磁性; 623 K注入和823 K真空退火 (253 K注入) 样品中形成α和γ相金属Fe, 5 K下样品具有明显的剩磁和矫顽力, 零场冷却和场冷却 (ZFC/FC) 曲线和300 K下的磁滞回线显示纳米Fe颗粒具有超顺磁性. Fe离子注入ZnO的磁性源于第二相α-Fe和γ-Fe. 关键词： 离子注入 ZnO 同步辐射X射线衍射 超顺磁性     

Optical emission from disordered multi-branched ZnO nanorods formed by catalyst-free growth

We have demonstrated catalyst-free fabrication of multi-branched ZnO nanorods and their interesting optical properties. Under Xe lamp excitation (325 nm), it is found that the ethanol rinsing leads to an obviously enhanced ultraviolet emission at room temperature. Moreover, temperature-dependent emission spectra exhibit an anomalous temperature dependence of the ultraviolet emission intensity. This has been analyzed in terms of the competition between the radiative and nonradiative hopping processes using a model developed for disordered porous semiconductors. With femtosecond pulse excitation (640 nm), two-photon-induced photoluminescence is observed, which is confirmed by the quadratic dependence of the emission intensity on the excitation pulse energy.     

Femtosecond laser ablation of ZnO nanorods for two-photon-pumped random lasing and optical data storage

Femtosecond laser ablation based on two-photon absorption was employed to cut ZnO nanorods into uniform ZnO nanoparticles of deep subwavelength size. The fabricated ZnO nanoparticles possess a shorter mean transport length for photons at the emission wavelength and a much smaller scattering cross section at the pump wavelength, leading to highly efficient two-photon-pumped random lasing with a low threshold of ??8?mJ/cm². It was demonstrated that the significant enhancement in two-photon luminescence after the irradiation of femtosecond laser pulses could also be utilized for realizing optical data storage.     

Growth of ZnO nanorods by a simple chemical method

ZnO nanorods were grown by a near-room-temperature, simple, chemical solution method on large-area Zn foils and substrate materials such as silicon, and zinc oxide thin films on silicon and glass. Study of the ZnO nanorods on the different substrates by electron microscopy methods shows that the morphology and size of the ZnO nanorods can be tuned varying the growth parameters and the substrates used. The growth mechanism is briefly discussed. Photoluminescence experiments at room temperature reveal a major emission peak of the nanorods at around 385 nm, which is attributed to the band edge transition of ZnO and weaker defect-related visible band peaks. PACS 81.05.Dz; 78.55.Et; 81.07.-b     

Size classification of Si nanoparticles formed by pulsed laser ablation in helium background gas

We have developed an integrated process system for the formation of nanoparticles by pulsed laser ablation (PLA) in helium background gas, size classification using a differential mobility analyzer (DMA), and deposition on a substrate. The DMA has been improved to operate at pressures of less than 10 Torr. The classification resolution of the low-pressure operating DMA (LP-DMA), transporting properties of nanoparticles under low pressure, have been investigated theoretically in order to evaluate the performance of the size classification for the integrated system. By operating the integrated system at less than 10 Torr, we have measured the size distribution of Si nanoparticles in the gas phase formation field by sweeping the applied voltage to the LP-DMA and counting the charged nanoparticle concentration with an electrometer. Moreover, we successfully deposited the classified Si nanoparticles on a substrate by fixing the voltage. We have verified that the integrated system can be applied to the clean physical vapor deposition process for accurately size-controlled nanoparticles.     

Plasma plume induced during laser ablation of graphite

The plasma plume induced during ArF laser ablation of a graphite target is studied. Velocities of the plasma expansion front are determined by the optical time of flight method. Mass center velocities of the emitting atoms and ions are constant and amount to 1.7×10⁴ and 3.8×10⁴ m s⁻¹, respectively. Higher velocities of ions result probably from their acceleration in electrostatic field created by electron emission prior to ion emission. The emission spectroscopy of the plasma plume is used to determine the electron densities and temperatures at various distances from the target. The electron density is determined from the Stark broadening of the Ca II and Ca I lines. It reaches a maximum of ∼9.5×10²³ m⁻³ 30 ns from the beginning of the laser pulse at the distance of 1.2 mm from the target and next decreases to ∼1.2×10²² m⁻³ at the distance of 7.6 mm from the target. The electron temperature is determined from the ratio of intensities of ionic and atomic lines. Close to the target the electron temperature of ∼30 kK is found but it decreases quickly to 11.5 kK 4 mm from the target.     

Growth and optical study of ZnO nanorods

ZnO nanorods were grown by a simple near room temperature, chemical solution method on ZnO-seeded silicon substrates. Study of the ZnO nanorods over different growth times by electron microscopy methods revealed that the resulting ZnO nanorods were single crystalline with a highly preferential growth perpendicular to the substrate and a very good c-axis alignment. The size of the nanorods increased with increasing growth time. The growth mechanism is briefly discussed. Post-annealing in oxygen slightly improved the surface roughness of the ZnO nanorods. Photoluminescence experiments at 1.6 K revealed a major emission peak of the nanorods at around 3.36 eV which is attributed to the band edge transition of ZnO, while defect-related emission is relatively weak.     

Nanoparticle plume dynamics in femtosecond laser ablation of gold

This paper describes some recent results on femtosecond laser ablation of gold. We have studied both the fast vapour/plasma and slow nanoparticle plumes using Langmuir probe, time-resolved ICCD imaging and time-resolved optical absorption measurements. The nanoparticle plume dynamics was analysed by comparing the optical emission absorption measurements with an adiabatic isentropic model of ablation plume expansion, leading to an estimate of the amount of material in the nanoparticle plume.     

Promoting the yield of nanoparticles from laser ablation in liquid

We have systematically studied the relationship between the preparation of Ge nanoparticles and the thickness of the water layer upon the pulsed-laser ablation of a Ge target in water. It was found that the average size of the prepared nanoparticles decreases with the thickness of water, and there is an optimum the thickness of water for the largest yield of the produced nanopartciles, which means the thickness of water can be regarded as an important parameter to control the size and yield of the prepared nanoparticles from laser ablation in liquid. The relevant physical mechanism was discussed.     

Synthesis of ZnO nanoparticles using nanosecond pulsed laser ablation in aqueous media and their self-assembly towards spindle-like ZnO aggregates

ZnO nanoparticles were fabricated by pulsed laser ablation (PLA) of a Zn metal in aqueous media, and aging effects on the morphology and photoluminescence properties of ZnO nanoparticles were investigated. The crystalline phase and particle morphology were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). It was found that small, well-defined ZnO nanoparticles were obtained by PLA of a Zn plate in aqueous media, and subsequent aging of the obtained ZnO nanoparticle suspension produced in cetyltrimethylammonium bromide (CTAB) solution led to the formation of spindle-like ZnO aggregates. However, in deionized water not the spindle-like ZnO aggregates but fluffy round aggregates were obtained. High-resolution transmission electron microscopic (HRTEM) observation indicated that the spindle-like ZnO aggregates were composed of many well-defined nanoparticles. Spindle-like aggregates exhibited strong exciton emission, while green emission could be suppressed via an aging process in the presence of CTAB. Moreover, thin films prepared by electrophoretic deposition (EPD) of ZnO nanoparticles after PLA in the presence of CTAB also possessed highly elongated aggregate structures that were possibly formed by surrounding the ZnO nanoparticles with double layers of CTAB molecules.     

Analysis of plume deflection in the silicon laser ablation process

Changes in target surface morphology and ablation plume direction have been experimentally observed during the initial stages of the silicon laser ablation process. A relationship between both phenomena can be observed upon analysing the temperature field induced by the laser beam in a rough surface material. Theoretical studies on the deflection of the ablation plume are presented. These analyses are based on the hypothesis that particles that reach evaporation temperature will exit normally to the target surface with a velocity that is proportional to the surface temperature and the amount of the ablated material. Numerical solutions and experimental results of laser ablation process of silicon targets are found to agree with theoretical studies. PACS 42.25.Lc; 79.20.Dc; 02.70.Dc     

氧化锌纳米棒场发射性能研究

采用简单物理气相沉积法制备出取向和非取向的氧化锌纳米棒，他们的场致电子发射性能测量结果表明，ZnO纳米棒具有较好的场发射性能，但是高度取向的ZnO纳米棒阵列并不利于获得高的场致电子发射电流密度.这可能是由于高密度ZnO纳米棒之间具有较高的屏蔽效应，降低了ZnO纳米棒阵列的场放大因子，从而影响了其场发射性能.相反，非取向ZnO纳米棒由于相互之间的屏蔽效应比较弱，而且表面存在容易成为发射中心的微小突起，表现出较好的场发射效果.这些结果不仅有助于加深我们对准一维纳米材料场致电子发射性能的理解，也为未来场发射电子器件的实际应用提供了可靠的依据. 关键词： 氧化锌 场发射 非取向