Correlation between surface oxide and photoluminescence properties of Si nanoparticles prepared by pulsed laser ablation

Hydrogenated silicon nanoparticles were prepared by pulsed laser ablation (PLA) of Si target in hydrogen gas. We observed native oxidation process for 250 days by infrared (IR) absorption measurement and investigated correlation between native oxidation and photoluminescence (PL) properties. We found three PL peak regions, around 800 nm, 600–700 nm and 400–500 nm. These PL peak wavelengths depended on the Si-O bond density and remarkable correlation with composition of the oxide layer was not observed. The native oxidation is a passive method to modify the surface. We propose plasma surface treatment as an active method. The PL wavelength varied by the surface treatments due to suppression of native oxidation. The surface modification is an important technique to control PL peak wavelength of silicon nanoparticles. PACS 81.15.Fg; 81.07.Bc; 78.67.-n     

Size-selected copper oxide nanoparticles synthesized by laser ablation

Size-tuned copper oxide nanoparticles with sizes of 9, 12, and 15 nm were fabricated by laser ablation and on-line size selection using a differential mobility analyzer at a gas pressure of 666 Pa. The dependence of the particle properties on the in situ annealing temperatures and selection sizes was investigated. The crystalline phases of the nanoparticles fabricated at temperatures below 973 K were assigned to monoclinic cupric oxide (CuO) which converted into cubic cuprous oxide (Cu₂O) when the annealing temperature was above 1,173 K. This indicates that the crystalline phases can be easily controlled by changing the annealing temperature. TEM images confirmed that well-crystallized and well-dispersed CuO and Cu₂O nanoparticles with narrow size distributions were obtained using this method. This fabrication process is useful and promising for the future investigation of the intrinsic size-dependent properties of CuO and Cu₂O.     

Nano-ionic thin films of gadolinia-doped ceria prepared by pulsed laser ablation

Microstructural properties of nano-ionic thin films of gadolinia-doped ceria (GDC) prepared by pulsed laser ablation from sintered targets of gadolinia (5–20 mol%) doped ceria are investigated. The ionic conductivity measurements of the sintered pellets showed a decrease in the activation energy from 1.1 to 0.65 eV for 5 and 30 mol% gadolinia-doped ceria, respectively. The microstructural properties of the GDC films as a function of substrate temperature, oxygen partial pressure, and laser energy show that the films are polycrystalline in the entire range of substrate temperature. The grain size is found to increase with increasing temperature up to 873 K. Further improved crystallinity is noticed for the films grown with oxygen partial pressure of 0.1–0.2 mbar. X-ray diffraction and transmission electron microscopy (TEM) reveal nanocrystalline grains with textured growth along <111> orientation in these films at low substrate temperature and at lower oxygen partial pressure. TEM study shows a uniform distribution of nanocrystal of 8–10 nm for energies ≤200 mJ/pulse, and nanocrystals embedded in a large crystalline matrix of doped ceria for energies in the range 400–600 mJ/pulse. Raman spectroscopy also confirms the defects in these films. The study also reveals that the substrate temperature and oxygen partial pressure could influence preferred orientation, while the laser energy could significantly influence defect concentration in these films. Invited paper presented at the Third International Conference on Ionic Devices (ICID 2006), Chennai, Tamilnadu, India, Dec. 7–9, 2006.     

液相激光烧蚀合成ZnO及Zn/ZnO纳米颗粒及其光致发光性能

利用532 nm脉冲激光对沉浸在去离子水及十二烷基硫酸钠(SDS)水溶液中的金属锌靶进行液相激光烧蚀,合成了ZnO纳米颗粒和Zn/ZnO核壳结构的纳米粒子. 应用X射线衍射仪,透射电子显微镜,紫外可见光分光光度计和荧光光度计表征产物的微观结构和光学性能,并探讨其形成机理. 结果表明:在去离子水中分别烧蚀2 h和4 h生成的ZnO纳米粒子的平均粒径分别为43 nm和19 nm. 激光的长时间作用可以使纳米粒子粒径减小. 在0.005 mol/L的SDS水溶液中合成了Zn/ZnO核壳结构的纳米粒子,这是由于S 关键词： 脉冲激光烧蚀 ZnO纳米粒子 核壳结构 光致发光     

Silver nanoparticles generated by pulsed laser ablation in supercritical CO2 medium

Pulsed laser ablation (PLA) has been widely employed in industrial and biological applications and in other fields. The environmental conditions in which PLA is conducted are important parameters that affect both the solid particle cloud and the deposition produced by the plume. In this work, the generation of nanoparticles (NPs) has been developed by performing PLA of silver (Ag) plates in a supercritical CO₂ medium. Ag NPs were successfully generated by allowing the selective generation of clusters. Laser ablation was performed with an excitation wavelength of 532 nm under various pressures and temperatures of CO₂ medium. On the basis of the experimental result, both surface of the irradiated Ag plate and structure of Ag NPs were significantly affected by the changes in supercritical CO₂ pressure and temperature. With increasing irradiation pressure, plume deposited in the surrounding crater created by the ablation was clearly observed. In Field Emission Scanning Electron Microscopy (FE-SEM) the image of the generated Ag NPs on the silicon wafer and the morphology of Ag particles were basically a sphere-like structure. Ag particles contain NPs with large-varied diameter ranging from 5 nm to 1.2 μm. The bigger Ag NPs melted during the ablation process and then ejected smaller spherical Ag NPs, which formed nanoclusters attached on the molten Ag NPs. The smaller Ag NPs were also formed around the bigger Ag NPs. Based on the results, this new method can also be used to obtain advanced nano-structured materials.     

Ag nanoparticles obtained by pulsed laser ablation in water: surface properties and SERS activity

We studied the surface properties and reactivity of silver nanoparticles obtained by picosecond or nanosecond pulsed laser ablation in water and with 1064‐nm wavelength. Ultraviolet–visible spectroscopy results and subsequent modelling by Mie theory indicated the presence of an oxide layer on the nanoparticle surface, which favours the colloidal stability, but reduces the interaction with the environment. The oxide layer is also responsible for the reduced surface enhanced Raman spectroscopy (SERS) activity of these colloids with respect to those obtained by chemical reduction. However, SERS activation can be efficiently obtained by addition of chloride ions to the colloids, leading to SERS enhancement factors that are comparable with those of the chemically prepared counterparts. Copyright © 2015 John Wiley & Sons, Ltd.     

Deposition of zinc oxide thin films by reactive pulsed laser ablation

Thin films of zinc oxide have been deposited by reactive pulsed laser ablation of Zn and ZnO targets in presence of a radio frequency (RF) generated oxygen plasma. The gaseous species have been deposited at several substrate temperatures, using the on-axis configuration, on Si (1 0 0). Thin films have been characterized by scanning electron microscopy, atomic force microscopy, X-ray diffraction, X-ray photoelectron spectroscopy and infrared spectroscopy. A comparison among conventional PLD and reactive RF plasma-assisted PLD has been performed.     

Copper oxide particles produced by laser ablation in water

Laser ablation of copper metal in water was performed in order to obtain copper oxide particles. Scanning electron microscopy, energy dispersive X-ray fluorescence spectrometry, transmission electron microscopy, and electron diffraction were conducted in order to determine the size, shape and structure of the particles. The source of the O atoms in the copper oxide particles is the surrounding water molecules. The copper oxide particles obtained by laser ablation were both crystalline and amorphous. The crystalline particles were determined to be paramelaconite Cu₄O₃.     

Blue luminescent silicon nanocrystals prepared by short pulsed laser ablation in liquid media

The pulsed laser processing in liquid media is an attractive alternative to produce room temperature luminescent silicon nanocrystals (Si-ncs). We report on a blue luminescent Si-ncs preparation by using nanosecond pulsed laser (Nd:YAG, KrF excimer) processing in transparent polymer and water. The Si-ncs fabrication is assured by ablation of crystalline silicon target immersed in liquids. During the processing and following aging in liquids, oxide based liquid media, induce shell formation around fresh nanocrystals that provides a natural and stable form of surface passivation. The stable room temperature blue-photoluminescent Si-ncs are prepared with maxima located around ∼440 nm with corresponding optical band gap around ∼2.8 eV (∼430 nm). Due to the reduction of surface defects, the Si-ncs preparation in water, leads to a narrowing of full-width-half-maxima of the photoluminescence spectra.     

Enhanced photoluminescence of rare-earth doped films prepared by off-axis pulsed laser deposition

Alternate pulsed laser deposition from the host (Al₂O₃) and dopant (Er, Yb) targets has been used to prepare artificially nanostructured films in which the rare earth ion-ion separation is controlled in the nanometer scale in order to control energy transfer between ions. One series of films was prepared in the standard on-axis configuration, i.e. a static substrate being centred with respect to the plasma expansion axis. A second series of films was prepared by rotating the substrate with respect to a shifted axis parallel to the plasma expansion one (off-axis configuration). The latter configuration leads to films with enhanced thickness and Er related photoluminescence intensity uniformity. More interestingly, the Er related photoluminescence lifetime in as-grown films increases up to 2.5 ms, which is much higher than the maximum value of 1 ms obtained for the on-axis configuration films. This enhancement is discussed in terms of a decrease of defect density when using the off-axis configuration.     

Small size TiO2 nanoparticles prepared by laser ablation in water

Titanium dioxide nanoparticles in distilled H₂O solvent were prepared by laser ablation. The experiments were performed irradiating a Ti target with a second harmonic (532 nm) output of a Nd:YAG laser varying the operative fluence between 1 and 10 J cm⁻² and for an ablation time ranging from 10 to 30 min. Electron microscopy measurements have evidenced the predominant presence of nanoparticles with diameter smaller than 10 nm together with agglomerations of 100-200 nm whose content increases with the laser fluence. At low laser fluence the particles’ size distribution shows that more than 85% of the nanoparticles have a size smaller than 5 nm while at mid and high fluences the presence of 5-7 nm nanoparticles is predominant. XPS analysis has revealed the presence of different titanium suboxide phases with the prevalence of Ti-O bonds from TiO₂ species. The optical bandgap values, determined by UV-vis absorption measurements, are compatible with the anatase phase.     

Cluster generation under pulsed laser ablation of zinc oxide

Neutral and cationic Zn _n O _m clusters of various stoichiometry have been produced by nanosecond laser ablation of ZnO in vacuum and investigated by time-of-flight mass spectrometry. Particular attention was paid to the effect of laser wavelength (in the range from near-IR to UV) on cluster composition. Under 193-nm laser ablation, the charged clusters are essentially substoichiometric with Zn_nO_n-1⁺\mathrm{Zn}_{n}\mathrm{O}_{n-1}^{+} and Zn_nO_n-3⁺\mathrm{Zn}_{n}\mathrm{O}_{n-3}^{+} being the most abundant series. Both sub- and stoichiometric cationic clusters are generated in abundance at 532- and 1064-nm ablation whose composition depends on the cluster size. The reactivity of small stoichiometric Zn_nO_n⁺\mathrm{Zn}_{n}\mathrm{O}_{n}^{+} clusters (n<11) toward hydrogen is found to be high, while oxygen-deficient species are less reactive. The neutral plume particles are mainly stoichiometric with Zn₄O₄ tetramer being a magic cluster. It is suggested that the Zn₄O₄ loss is the dominant fragmentation channel of large zinc oxide clusters upon electron impact. Plume expansion conditions under ZnO ablation with visible and IR laser pulses are shown to be favorable for stoichiometric cluster formation.     

Investigation of Ag nanoparticles produced by nanosecond pulsed laser ablation in water

A study is presented of the properties of Ag nanoparticles produced by nanosecond pulsed laser ablation in twice-distilled water. An Ag target was immersed in the liquid and irradiated by the fundamental, second, third and fourth harmonics of a Nd:YAG laser system to create different colloids. Two specific boundary values of the laser fluence were applied for each wavelength. The properties of the nanoparticles at different wavelengths of the laser radiation were examined. The characterization of the colloids was performed immediately after their fabrication. Spherical and spherical-like shapes of the nanoparticles created were established. The formation of nanowires was observed when the second and the third harmonics of the laser were used. It is connected with self-absorption of the incident laser light from the already-created nanoparticles and depends also on the laser fluence. The size distribution of the nanoparticles is estimated by transmission electron microscopy. Generally, their mean size and standard deviation decreased as the wavelength of the incident laser light was increased and increased with the increase of the laser fluence. The substantial discrepancy between the results already commented on for both characteristics considered and others, obtained by dynamic light scattering, is discussed. The structure of the nanoparticles was established to be single and polycrystalline, and the phase composition in both cases is identified as consisting of cubic silver. The nanoparticles are slightly oxidized.     

Nickel aluminate oxides/hydroxides by pulsed laser ablation of NiAl2O4 powder in water

Submicron-sized NiAl_2+X O₄ fragments and nanocondensates of Ni-doped γ-Al₂O₃, Al-doped NiO and β-Ni(OH)₂ were synthesized simultaneously by pulsed laser ablation of NiAl₂O₄ powder in water and characterized using X-ray/electron diffraction and optical spectroscopy. The NiAl_2+X O₄ is Al-enriched spinel with dislocations and subgrains. The Ni-doped γ-Al₂O₃ spinel has paracrystalline distribution (i.e., with fair constant longitudinal spacing, but variable relative lateral translations) of defect clusters and intimate intergrowth of θ-Al₂O₃ and 2x( \( \overline{1} \) 3 \( \overline{1} \) ) commensurate superstructure. The Al-doped NiO has perfect cubo-octahedron shape and as small as 5 nm in size. The β-Ni(OH)₂ and 1-D turbostratic hydroxide lamellae occurred as a matrix of these oxide nanoparticles. The colloidal suspension containing the composite phases has a minimum band gap of 5.3 eV for potential photocatalytic applications.     

Oxygen reduction activity of N-doped carbon-based films prepared by pulsed laser deposition

Carbon-based films with nitrogen species on their surface were prepared on a glassy carbon (GC) substrate for application as a non-platinum cathode catalyst for polymer electrolyte fuel cells. Cobalt and carbon were deposited in the presence of N₂ gas using a pulsed laser deposition method and then the metal Co was removed by HCl-washing treatment. Oxygen reduction reaction (ORR) activity was electrochemically determined using a rotating disk electrode system in which the film samples on the GC substrate were replaceable. The ORR activity increased with the temperature of the GC substrate during deposition. A carbon-based film prepared at 600 °C in the presence of N₂ at 66.7 Pa showed the highest ORR activity among the tested samples (0.66 V vs. NHE). This film was composed of amorphous carbons doped with pyridine type nitrogen atoms on its surface.     

Ar环境下脉冲激光烧蚀粒子阻尼系数的空间分布

在10 Pa的Ar环境气体中,采用脉冲激光烧蚀技术,分别在半径为2.0,2.5,3.0,3.5和4.0 cm的半圆环不同角度处的衬底上制备了一系列含有纳米晶粒的Si晶薄膜。使用扫描电子显微镜、X射线衍射仪和拉曼光谱仪对其表面形貌和微观结构进行分析表征。结果表明,纳米Si晶粒的平均尺寸和烧蚀粒子的阻尼系数均相对于羽辉轴向呈对称分布,并随着与羽辉轴向夹角的增大而减小;同时,随着衬底半径的增加,晶粒平均尺寸和阻尼系数均逐渐减小。     

Ar环境下脉冲激光烧蚀粒子阻尼系数的空间分布

在10 Pa的Ar环境气体中,采用脉冲激光烧蚀技术,分别在半径为2.0,2.5,3.0,3.5和4.0 cm的半圆环不同角度处的衬底上制备了一系列含有纳米晶粒的Si晶薄膜。使用扫描电子显微镜、X射线衍射仪和拉曼光谱仪对其表面形貌和微观结构进行分析表征。结果表明,纳米Si晶粒的平均尺寸和烧蚀粒子的阻尼系数均相对于羽辉轴向呈对称分布,并随着与羽辉轴向夹角的增大而减小;同时,随着衬底半径的增加,晶粒平均尺寸和阻尼系数均逐渐减小。     

CEMS study on diluted magneto titanium oxide films prepared by pulsed laser deposition

6% ⁵⁷Fe doped titanium oxide films, prepared by pulsed laser deposition (PLD) on sapphire substrate at 650°C under various vacuum conditions, were characterized mainly by conversion electron Mössbauer spectrometry (CEMS). Two magnetic sextets with hyperfine fields 33 and 29 T, and one doublet were observed in the CEMS spectra of TiO₂ films prepared under PO₂ = 10^?6 and 10^?8 torr, which showed ferromagnetism at room temperature, whereas only the doublet of paramagnetic Fe³⁺ species was observed for the film prepared under PO₂ = 10^?1 torr.     

Microstructural study of thin films of 5 mol% gadolinia-doped ceria prepared by pulsed laser ablation

Microstructural characterization of thin films of 5 mol% gadolinia-doped ceria films deposited by pulsed laser ablation in the energy range 100–600 mJ/pulse has been investigated. As-deposited films were found to be nanocrystalline with preferred orientation. X-ray diffraction (XRD) analysis revealed that the size of the nanocrystals of doped ceria does not vary significantly with increasing laser energy, while transmission electron microscopy (TEM) study showed a uniform distribution of nanocrystals of 8–10 nm for energies ≤200 mJ/pulse and nanocrystals embedded in a large crystalline matrix of doped ceria for energies in the range 400–600 mJ/pulse. Though, the laser-ablated films were totally free from secondary phases, lattice imaging of the large grained doped ceria showed growth-induced defects such as dislocations and ledges. This artice was accidentally published twice. This is the second publication, please cite only the authoritative first one which is available at . An additional erratum is available at . An erratum to this article can be found at     

电场中不同能量密度激光烧蚀制备纳米硅晶粒分布特性

在室温和10 Pa氩气环境中,引入平行于靶面方向的直流电场,通过改变脉冲激光能量密度烧蚀单晶硅靶,在与羽辉轴线呈不同角度的衬底上沉积纳米硅晶薄膜。利用扫描电子显微镜和拉曼散射谱对沉积样品进行分析,结果表明:随着激光能量密度的增加,位于相同角度衬底上的晶粒尺寸和面密度逐渐变大;在同一激光能量密度下,零度角处衬底上的晶粒尺寸和面密度最大,且靠近接地极板处的值比与之对称角度处略大。通过朗缪尔探针对不同能量密度下烧蚀羽辉中硅离子密度变化的诊断、结合成核区内晶粒成核生长动力学过程,对晶粒分布特性进行了分析。