Mechanism of the formation of metal nanoclusters during pulsed laser deposition

The geometrical structure of Au, Ni, Co and Cr nanoclusters self-assembled on NaCl and HOPG surfaces under pulsed laser deposition (PLD) has been experimentally investigated. The PLD technique is characterized by an extremely high instantaneous deposition rate. Unlike for the thermal evaporation (TE) process, formation of fractal nanoclusters under PLD conditions has been observed with scanning tunneling microscopy (STM). The driving mechanism for this phenomenon occurring at high deposition rate is thought to be the evolution of the initial interacting-adatom states in a system far from thermodynamic equilibrium. The obtained results can be explained by proposing a new mechanism of condensed phase formation under the conditions of strong deviation from thermodynamic equilibrium.     

Thermo-optical response of layered Bi nanostructures produced by pulsed laser deposition

This work reports optical transmission changes in layered Bi nanostructures (NSs) upon heating-cooling cycles up to temperatures above the melting temperature. The nanostructured films prepared by pulsed laser deposition consist of Bi NSs with different characteristic sizes that are organised in layers and embedded in an amorphous Al₂O₃ host. The spectral dependence of the optical transmission as well as its changes upon heating are reported. The combination of Bi NSs layers with more than one characteristic size allows controlling the width of the melting-solidification transition. Eventually, it is shown how a multiple temperature thermo-optical film can be designed and prepared.     

Properties of Zn3N2-doped ZnO films deposited by pulsed laser deposition

The optical properties of N-doped ZnO films grown by pulsed laser deposition are examined for which zinc nitride is used as the source of nitrogen. The motivation for this study is to determine if nitrogen-related acceptor state formation can be achieved in ZnO films using Zn₃N₂ doping in the ablation target. The films were deposited in oxygen or nitrogen on c-plane sapphire. Photoluminescence measurements at 20 K reveal a 3.31 eV acceptor-bound exciton emission due to nitrogen substitution on the oxygen site, donor-acceptor pair emission at 3.23 ± 1 eV and free electron-acceptor at 3.27 eV. The binding energy of the N-related acceptor is estimated to be in the range of 170-15 meV. While the as-deposited films were n-type, thermal annealing in oxygen yielded insulating behavior, consistent with compensating acceptor states.     

An investigation into the effects of high laser fluence on hydroxyapatite/calcium phosphate films deposited by pulsed laser deposition

Pulsed laser deposited mixed hydroxyapatite (HA)/calcium phosphate thin films were prepared at room temperature using KrF laser source with different laser fluence varying between 2.4 J/cm² and 29.2 J/cm². Samples deposited at 2.4 J/cm² were partially amorphous and had rough surfaces with a lot of droplets while higher laser fluences showed higher level of crytallinity and lower roughness of surfaces of obtained samples. Higher laser fluences also decreased ratio Ca/P of as-deposited samples. X-ray photoelectron spectroscopy (XPS) revealed traces of carbonate groups in obtained samples, which were removed after thermal annealing. The decomposition of HA into TCP was observed to start at about 400 °C. The formation of new crystalline phase of HA was found after annealing as well. The cracks observed on surface of sample deposited at 29.2 J/cm² after annealing indicated that the HA/ calcium phosphate films deposited at higher laser energy densities were probably more densed.     

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.     

New aspects on pulsed laser deposition of aligned carbon nanotubes

We have grown carbon nanotubes (CNT) by pulsed laser deposition (PLD) at 1000 °C in Ar atmosphere. A Nd/YAG laser was used for irradiation of a graphite target containing Ni and Co rods. High-resolution scanning electron microscopy (HRSEM) and transmission electron microscopy (TEM) images showed that “closed” carbon nanotubes were grown between clusters of metallic particles, so that the individual nanotubes were arranged in parallel to each other forming a shape of “Rope-Bridge”. The nanotubes structure was analyzed by high-resolution transmission electron microscopy (HRTEM) and their type was found to be of MWNT, containing about five SWNT. Total diameter was 5-20 nm and their length was about 1 μm. High homogeneous distribution carbon nanotubes were grown and different structures were observed such as well-aligned carbon nanotubes, bamboo-like and Y-junction carbon nanotubes.     

Biocompatible film deposition by using Nd:YAG pulsed laser

A Nd:YAG laser operating at the fundamental wavelength (1064 nm) and at the second harmonic (532 nm), with 9 ns pulse duration, 100–900 mJ pulse energy, and 30 Hz repetition rate mode, was employed to ablate in vacuum (10^?6 mbar) biomaterial targets and to deposit thin films on substrate backings. Titanium target was ablated at the fundamental frequency and deposited on near-Si substrates. The ablation yield increases with the laser fluence and at 40 J/cm ² the ablation yield for titanium is 1.2×10¹⁶ atoms/pulse. Thin film of titanium was deposited on silicon substrates placed at different distance and angles with respect to the target and analysed with different surface techniques (optical microscopy, scanning electron spectrosopy (SEM), and surface profile).

Hydroxyapatite (HA) target was ablated to the second harmonic and thin films were deposited on Ti and Si substrates. The ablation yield at a laser fluence of 10 J/cm ² is about 5×10¹⁴ HA molecules/pulse. Thin film of HA, deposited on silicon substrates placed at different distance and angles with respect to the target, was analysed with different surface techniques (optical microscopy, SEM, and Raman spectroscopy).

Metallic films show high uniformity and absence of grains, whereas the bio-ceramic film shows a large grain size distribution. Both films found special application in the field of biomaterial coverage.     

Fabrication of p-type Li-doped ZnO films by pulsed laser deposition

p-Type ZnO thin films have been realized via doping Li as acceptor by using pulsed laser deposition. In our experiment, Li₂CO₃ was used as Li precursor, and the growth temperature was varied from 400 to 600 °C in pure O₂ ambient. The Li-doped ZnO film prepared at 450 °C possessed the lowest resistivity of 34 Ω cm with a Hall mobility of 0.134 cm² V⁻¹ s⁻¹ and hole concentration of 1.37 × 10¹⁸ cm⁻³. X-ray diffraction (XRD) measurements showed that the Li-doped ZnO films grown at different substrate temperatures were of completely (0 0 2)-preferred orientation.     

脉冲激光沉积动力学研究进展

脉冲激光沉积技术是现代常用的先进薄膜材料制备技术之一.文章在简要介绍脉冲激光沉积技术及其进展的基础上,较全面地介绍了脉冲激光沉积动力学的基本物理图像和动力学构架,深入地探讨了激光烧蚀靶材过程、等离子体膨胀过程和薄膜沉积过程的动力学规律,阐述了我国学者在脉冲激光沉积动力学研究方面的贡献,例如包括脉冲激光沉积三个工艺过程自洽的统一模型,等离子体膨胀的冲击波模型,基于局域能量动量守恒定律的新等离子体演化动力学模型,包括热源项、蒸发项、等离子体屏蔽效应和动态物性参数的烧蚀热传导模型,考虑电子碰撞效应和能带结构变化的修正双温模型,能统一描写从纳秒级到飞秒级脉冲激光烧蚀规律的统一双温模型等.     

High temperature growth of InN on various substrates by plasma-assisted pulsed laser deposition

InN has attracted much attention due to its optical and electrical properties that make it suitable for the fabrication of infrared optical devices and high-speed electronic devices. In this work we report on the structural properties and morphology of InN thin films grown on different substrates by radiofrequency plasma beam assisted pulsed laser deposition. Sapphire and silicon substrates were considered for the growth of these films. The influence of substrate type and growth parameters on the morphology and structural properties of the resulting InN thin films is discussed. The structural analysis of the samples was performed by means of X-ray diffraction. The morphology of the thin films was investigated through atomic force microscopy. Although growth of InN from a metallic In target using nitrogen radiofrequency plasma assisted pulsed laser deposition was achieved for all the samples, growth conditions were found to play an important role on the crystal quality of the resulting thin films.     

Femtosecond pulsed laser deposition of diamond-like carbon films: The effect of double laser pulses

The bonding structure of carbon films prepared by pulsed laser deposition is determined by the plasma properties especially the change of the kinetic energy. Using double laser pulses the ablation process and the characteristics of the generated plasma can be controlled by the setting of the delay between the pulses. In our experiments, amorphous carbon films have been deposited in vacuum onto Si substrates by double pulses from a Ti:sapphire laser (180 fs, λ = 800 nm, at 1 kHz) and a KrF laser system (500 fs, λ = 248 nm, at 5 Hz). The intensities have been varied in the range of 3.4 × 10¹² to 2 × 10¹³ W/cm². The morphology and the main properties of the thin layers were investigated as a function of the time delay between the two ablating pulses (0-116.8 ps) and as a function of the irradiated area on the target surface. Atomic force microscopy, spectroscopic ellipsometry and Raman-spectroscopy were used to characterize the films. It was demonstrated that the change of the delay and the spot size results in the modification of the thickness distribution of the layers, and the carbon sp²/sp³ bonding ratio.     

Characterization of polymer thin films obtained by pulsed laser deposition

The development of laser techniques for the deposition of polymer and biomaterial thin films on solid surfaces in a controlled manner has attracted great attention during the last few years. Here we report the deposition of thin polymer films, namely Polyepichlorhydrin by pulsed laser deposition. Polyepichlorhydrin polymer was deposited on flat substrate (i.e. silicon) using an NdYAG laser (266 nm, 5 ns pulse duration and 10 Hz repetition rate).The obtained thin films have been characterized by atomic force microscopy, scanning electron microscopy, Fourier transform infrared spectroscopy and spectroscopic ellipsometry.It was found that for laser fluences up to 1.5 J/cm² the chemical structure of the deposited polyepichlorhydrin polymer thin layers resembles to the native polymer, whilst by increasing the laser fluence above 1.5 J/cm² the polyepichlorohydrin films present deviations from the bulk polymer.Morphological investigations (atomic force microscopy and scanning electron microscopy) reveal continuous polyepichlorhydrin thin films for a relatively narrow range of fluences (1-1.5 J/cm²).The wavelength dependence of the refractive index and extinction coefficient was determined by ellipsometry studies which lead to new insights about the material.The obtained results indicate that pulsed laser deposition method is potentially useful for the fabrication of polymer thin films to be used in applications including electronics, microsensor or bioengineering industries.     

Radio-frequency assisted pulsed laser deposition of nanostructured WOx films

The synthesis of tungsten oxide films with large surface area is promising for gas sensing applications. Thin WO_x films were obtained by radio-frequency assisted pulsed laser deposition (RF-PLD). A tungsten target was ablated at 700 and 900 Pa in reactive oxygen, or in a 50% mixed oxygen-helium atmosphere at the same total pressure values. Corning glass was used as substrate, at temperatures including 673, 773 and 873 K. Other deposition parameters such as laser fluence (4.5 J cm⁻²), laser wavelength (355 nm), radiofrequency power (150 W), target to substrate distance (4 cm), laser spot area (0.7 mm²), and number of laser shots (12,000) were kept fixed. The sensitivity on the deposition conditions of morphology, nanostructure, bond coordination, and roughness of the obtained films were analyzed by scanning and transmission electron microscopy, micro-Raman spectroscopy, and atomic force microscopy.     

脉冲激光气相沉积法制备钴纳米薄膜实验研究

 采用脉冲激光沉积技术制备了钴纳米薄膜，分析和讨论了不同背景气压和脉冲频率对钴纳米薄膜表面形貌的影响及纳米微粒的形成机理。实验结果表明：在低背景气压下，等离子体羽辉自身粒子之间的碰撞占主导作用，容易形成液滴；在较高背景气压下，等离子体羽辉边缘粒子和背景气体粒子之间的碰撞占主导作用，容易形成小岛并凝聚成微颗粒；在4Hz的脉冲重复频率和5Pa背景气压下生长出单分散性良好的钴纳米颗粒。     

Effects of deposition temperature on the structural and morphological properties of thin ZnO films fabricated by pulsed laser deposition

ZnO thin films were grown on Si(1 0 0) substrates using pulsed laser deposition in O₂ gas ambient (10 Pa) and at different substrate temperatures (25, 150, 300 and 400 °C). The influence of the substrate temperature on the structural and morphological properties of the films was investigated using XRD, AFM and SEM. At substrate temperature of T=150 °C, a good quality ZnO film was fabricated that exhibits an average grain size of 15.1 nm with an average RMS roughness of 3.4 nm. The refractive index and the thickness of the thin films determined by the ellipsometry data are also presented and discussed.     

Bioactive glass and hydroxyapatite thin films obtained by pulsed laser deposition

Bioactive glass (BG), calcium hydroxyapatite (HA), and ZrO₂ doped HA thin films were grown by pulsed laser deposition on Ti substrates. An UV KrF^* (λ = 248 nm, τ ≥ 7 ns) excimer laser was used for the multi-pulse irradiation of the targets. The substrates were kept at room temperature or heated during the film deposition at values within the (400-550 °C) range. The depositions were performed in oxygen and water vapor atmospheres, at pressure values in the range (5-40 Pa). The HA coatings were heat post-treated for 6 h in a flux of hot water vapors at the same temperature as applied during deposition. The surface morphology, chemical composition, and crystalline quality of the obtained thin films were studied by scanning electron microscopy, atomic force microscopy, and X-ray diffractometry. The films were seeded for in vitro tests with Hek293 (human embryonic kidney) cells that revealed a good adherence on the deposited layers. Biocompatibility tests showed that cell growth was better on HA than on BG thin films.     

Preparation and characterization of pulsed laser deposition (PLD) SiC films

Si K-edge XAFS was used to characterize a stoichiometric SiC film prepared by pulsed KrF laser deposition. The film was deposited on a p-type Si(1 0 0) wafer at a substrate temperature of 250 °C in high vacuum with a laser fluence of ∼5 J/cm². The results reveal that the film contains mainly a SiC phase with an amorphous structure in which the Si atoms are bonded to C atoms in its first shell similar to that of crystalline SiC powder but with significant disorder.     

How the dynamics of an ablation plume is affected by ambient gas ionisation

The influence of inert gas ionisation on the expansion dynamics of a laser ablation plume propagating through an inert gas is studied. Charge transfer reactions between ionised ablated species and gas neutrals lead to the formation of a charged layer of ionised gas atoms in contact with the plume expansion front. The energy lost by fast ablated ions when the plume is slowed down is calculated. For the exemplary carbon ablation in helium and argon atmospheres, where background gas ionisation plays a different role, model predictions agree with the observed microstructural differences of deposited films.     

Structural characterization of AlN films synthesized by pulsed laser deposition

We obtained AlN thin films by pulsed laser deposition (PLD) from a polycrystalline AlN target using a pulsed KrF* excimer laser source (248 nm, 25 ns, intensity of ∼4 × 10⁸ W/cm², repetition rate 3 Hz, 10 J/cm² laser fluence). The target-Si substrate distance was 5 cm. Films were grown either in vacuum (10⁻⁴ Pa residual pressure) or in nitrogen at a dynamic pressure of 0.1 and 10 Pa, using a total of 20,000 subsequent pulses. The films structure was characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM) and spectral ellipsometry (SE). Our TEM and XRD studies showed a strong dependence of the film structure on the nitrogen content in the ambient gas. The films deposited in vacuum exhibited a high quality polycrystalline structure with a hexagonal phase. The crystallite growth proceeds along the c-axis, perpendicular to the substrate surface, resulting in a columnar and strongly textured structure. The films grown at low nitrogen pressure (0.1 Pa) were amorphous as seen by TEM and XRD, but SE data analysis revealed ∼1.7 vol.% crystallites embedded in the amorphous AlN matrix. Increasing the nitrogen pressure to 10 Pa promotes the formation of cubic (≤10 nm) crystallites as seen by TEM but their density was still low to be detected by XRD. SE data analysis confirmed the results obtained from the TEM and XRD observations.