Direct simulation monte carlo of pulsed laser ablation of metals with clusterization processes in vapor

A mathematical model is proposed to describe laser ablation of metals in vacuum under the action of nanosecond laser pulses of moderate intensity taking into account the processes of cluster formation and decay in the vapor cloud. To describe the laser radiation absorption and metal heating, the thermal model based on the unsteady one-dimensional heat equation with a volume heat source is used, and the method of statistical modelling is employed for modelling vapor expansion and the processes of cluster formation. The efficiency of the proposed complex model is considered by the example of pulsed laser ablation of a niobium target. The work was supported financially by INTAS (grant No. 03-51-5208).     

Mechanisms of small clusters production by short and ultra-short laser ablation

The mechanisms involved into the formation of clusters by pulsed laser ablation are studied both numerically and experimentally. To facilitate the model validation by comparison with experimental results, the time and length scales of the simulation are considerably increased. This increase is achieved by using a combination of molecular dynamics (MD) and the direct simulation Monte Carlo (DSMC) methods. The combined MD-DSMC model is then used to compare the relative contribution of the two channels of the cluster production by laser ablation: (i) direct cluster ejection upon the laser-material interaction, and (ii) collisional sticking and aggregation in the ablated gas flow. Calculation results demonstrate that both of these mechanisms play a role. The initial cluster ejection provides cluster precursors thus eliminating the three-body collision bottleneck in the cluster growth process. The presence of clusters thus facilitates the following collisional condensation and evaporation processes. The rates of these processes become considerable, leading to the modification of not only the plume cluster composition, but also the dynamics of the plume expansion. Calculation results explain several recent experimental findings.     

Modelling chemical kinetics of small clusters after nanosecond laser ablation

Nanoclusters of various materials have recently been obtained by laser ablation. Strong evaporation of a condensed phase caused by laser irradiation is well known to generate an overcooled vapour. Further expansion thereof increases the oversaturation degree and facilitates homogeneous nucleation and cluster growth. To investigate homogeneous nucleation at very high expansion rates attained at nanosecond laser ablation, kinetic equations are applied describing all the possible gas-phase chemical reactions of dissociation and coalescing between small clusters. Additional cooling due to thermal emission by clusters is taken into account. Twenty smallest carbon molecules are considered. The model is applied to nanosecond laser ablation of graphite in vacuum. The resulted vapour molecular composition is characterised by dominating molecules C₃ and C₅ and an exponential drop of heavier clusters concentrations with their mass. The growth of heavier clusters is controlled by the balance between liberating the latent heat of their formation and the energy losses by expansion and thermal emission.     

Thermodynamics of supersaturated vapor nucleation on molecular condensation nuclei

A key problem in the theory of a supersaturated vapor nucleation on molecular condensation nuclei (namely, the work of formation and the equilibrium concentrations of clusters) is considered. To calculate these quantities using the structural models of clusters, which are better suited for this purpose than the classical droplet model, we derive the equation connecting the work of transfer of a molecular condensation nucleus from the gas phase to a homogeneous cluster with a change in the number of contacts between molecules, occurring in the course of this transfer, and with the work of rupture of individual contacts.     

Atom deposition on surface clusters: thin film growth on Pd(111)

We have studied the vapor phase deposition of single metal atoms on two-dimensional clusters at the Pd(111) surface. The system considered here are heptamers and dodecamers for the substrate temperature of 100 K. Using molecular dynamics simulations with the corrected effective medium potentials for Pd, Cu and Rh, we have found that an adatom either diffuses on the cluster or incorporates itself into the cluster depending on the size of clusters and the kind of metals in the gas/cluster system. We also discovered that incorporation of a deposited gas atom into a surface cluster at 100 K was not a consequence of the reduction of the barrier heights at the step edges and that the type of post-impact dynamics for hexagonal heptamers depends on the impact point.     

Cluster formation processes investigated by linearly chirped spectral scattering

By employing linearly chirped spectral scattering technique, the time-resolved formation processes of argon clusters have been investigated. The redshifts of scattering spectra as a function of backing pressure as well as the time delay between the laser and the firing switch of the cluster flow have been measured. It has been found that very large-size cluster sources with very low gas density can be produced by adiabatic expansion of gases at low pressures through a conical nozzle into vacuum. It can be used as clean and important cluster target.     

Modeling cluster jets as targets for high-power ultrashort laser pulses

A hydrodynamic model is formulated that describes the formation of clusters in atomic gas jets expanding into vacuum, which are used as laser plasma targets. Detailed model calculations performed for an argon gas jet describe spatial distributions of the density of gas and cluster phases formed in the Laval nozzle at room temperature in a broad range of entrance gas pressures. The cluster density distribution is significantly inhomogeneous. The cluster distribution features revealed by the model calculations were qualitatively confirmed by the X-ray spectroscopic measurements of the spatial distribution of emission from the plasma created in the jet tar-gets by high-power ultrashort laser pulses.     

Molecular dynamics study of the role of material properties on nanoparticles formed by rapid expansion of a heated target

Rapid expansion of a heated target and its decomposition into fragments is investigated by using molecular dynamics simulations. Particular attention is focused on the void formation and nucleation that governs the target disintegration. The cluster formation process is investigated as a function of material properties (initial temperature, interaction potential and composition). Calculation results demonstrate the influence of these properties on void nucleation and growth and on the characteristic parameters of nanoparticles to be formed. In particular, larger initial temperature and expansion rate lead to the formation of smaller fragments. These effects are found to be similar for three different materials (silicon, nickel and metal alloy). In addition, the stoichiometrical cluster composition obtained in the expansion of a binary alloy is found to be fairly well preserved. The calculation results can be used for the interpretation of the experimental findings showing the formation of nanoparticles by short and ultra-short pulse laser ablation of both simple and more complex materials.     

Growth analysis of novel ZnO nanotetrapods with tubular legs from aspect of reagent’s vapor pressure and growth temperature

In this article, novel ZnO nanotetrapods with tubular legs was successfully synthesized using mixed powder of Zn, ZnO, and carbon as source. The growth process was analyzed at large, and a two-step growth model, viz. initial deficient-oxidation and latter second-volatilization, was proposed to explain the formation of tubular leg of ZnO nanotetrapod. In the growth model, the high Zn vapor pressure and high growth temperature were considered as two crucial factors determining the growth behavior. Zn-rich ZnO nanotetrapod formed under high Zn vapor pressure at the initial stage. These redundant Zn clusters coexisted in ZnO lattice as interstitial Zn. The following second-volatilization of interstitial Zn under high growth temperature led to formation of tubular leg. Four other experiments were designed to analyze the growth behavior under high and low Zn vapor pressure and growth temperature, respectively, and these experimental results further confirmed the validity of our growth model. Our experiment proposed a feasible synthesis route to prepare hollow nanostructures controlled by the vapor pressure and growth temperature. Furthermore, these novel ZnO nanotetrapods might have potential application as building blocks for functional nanodevices.     

Growth of gas phase nanoparticles with an accretion mechanism

Nano-droplet growth in a supersaturated vapor has been investigated in a gas aggregation source using laser-ionization time-of-flight mass spectrometry. During its propagation into an atomic vapor, a small particle grows by sticking atoms on its surface. This accretion process has been highlighted through the clustering of homogeneous particles M_n and heterogeneous M_n(M₂O) and M_n(MOH)₂ particles in a metallic vapor and a helium buffer gas (M = Na or K). A modelization is introduced so as to connect the measured cluster mass distributions to the pertinent physical parameters. The mass distribution width is particularly sensitive to the efficiency of the first steps in the growth sequence. We used this property to compare the ability of this vapor-condensed matter phase transition to occur around various homogeneous and heterogeneous nucleation seeds.     

Carrier gas effects on the SiGe quantum dots formation

SiGe quantum dots (QDs) grown by ultra-high vacuum chemical vapor deposition using H₂ and He carrier gases are investigated and compared. SiGe QDs using He carrier gas have smaller dot size with a better uniformity in terms of dot height and dot base as compared to the H₂ carrier gas. There is a higher Ge composition and less compressive strain in the SiGe QDs grown in He than in H₂ as measured by Raman spectroscopy. The Ge content is higher for He growth than H₂ growth due to hydrogen induced Si segregation and the lower interdiffusivity caused by the more strain relaxation in the He-grown SiGe dots. The photoluminescence also confirms more compressive strain for H₂ growth than He growth. Hydrogen passivation and Ge-H cluster formation play an important role in the QDs growth.     

Kinetics and energy states of nanoclusters in the initial stage of homogeneous condensation at high supersaturation degrees

The condensation of metal vapor in an inert gas is studied by the molecular dynamics method. Two condensation regimes are investigated: with maintenance of partial pressure of the metal vapor and with a fixed number of metal atoms in the system. The main focus is the study of the cluster energy distribution over the degrees of freedom and mechanisms of the establishment of thermal equilibrium. It is shown that the internal temperature of a cluster considerably exceeds the buffer gas temperature and the thermal balance is established for a time considerably exceeding the nucleation time. It is found that, when the metal vapor concentration exceeds 0.1 of the argon concentration, the growth of clusters with the highest possible internal energy occurs, the condensation rate being determined only by the rate of heat removal from clusters.     

Cluster growth processes by direct simulation monte carlo method

Thin films obtained by cluster deposition have attracted strong attention both as a new manufacturing technique to realize high-density magnetic recording media and to create systems with unique magnetic properties. Because the film’s features are influenced by the cluster properties during the flight path, the relevant physical scale to be studied is as large as centimeters. In this paper, a new model of cluster growth processes based on a combination of the Direct Simulation Monte Carlo (DSMC) method and the cluster growth model is introduced to examine the effects of experimental conditions on cluster growth by an adiabatic expansion process. From the macroscopic viewpoint, we simulate the behavior of clusters and inert gas in the flight path under different experimental conditions. The internal energy of the cluster, which consists of rotational and vibrational energies, is limited by the binding energy which depends on the cluster size. These internal and binding energies are used as criteria of the cluster growth. The binding energy is estimated by surface and volume terms. Several types of size distribution of generated clusters under various conditions are obtained by the present model. The results of the present numerical simulations reveal that the size distribution is strongly related to the experimental conditions and can be controlled. Received: 23 January 2001 / Accepted: 3 May 2001 / Published online: 30 August 2001     

On diffusion mixing of vapor and gas

A self-similar solution is obtained for a one-dimensional problem of diffusion mixing of vapor and gas, which is followed by condensation process. Two limiting cases of mixing are considered: in the first one, the vapor and gas occupy in their initial states the volumes of semi-infinite extension, in the second case, the vapor has a semi-infinite extension, and constant values of temperature and gas concentration are maintained at its boundary. The peculiarities of the temperature and concentration fields are analysed versus the vapor and gas temperatures, and the temperature values are found, at which the mixing occurs with the condensate formation.     

Growth of tellurium clusters in presence of metal impurities

The growth of small tellurium clusters in helium and the influence of a metal impurity (dysprosium atoms) on the cluster size distribution are investigated in a double laser vaporization source. A model describing the role of the carrier gas as collision partner is presented, emphasizing the crucial influence of the gas pressure on cluster formation. Changes in cluster reactivity due to dysprosium addition are discussed in terms of ionic structures Dy ^{3 +}(Te _N)^{3 -} containing a radical electron. Received 28 November 2000     

Thin film semiconductor islands and numerical experiment

The distribution functions of island nuclei of germanium melt drops on Si(100) substrate over lateral sizes and heights in the presence of a surface linear defect are obtained in a numerical experiment simulating the initial stage of the first-order phase transition. A similar model of heterogeneous condensation of silicon carbide vapor is discussed. Quasi-linear kinetic partial differential equations are solved by the efficient numerical method of stochastic analogue of nonequilibrium processes. The Volmer-Weber mechanism of cluster formation from melt islands, their crystallization, and island structure formation on the substrate are considered.     

超长定向含铁多壁碳纳米管阵列的制备

采用无模板化学气相沉积法,以二茂铁为催化剂,二甲苯为碳源,利用单温炉加热装置制备了定向碳纳米管阵列。运用扫描电子显微镜、透射电子显微镜、拉曼光谱和X射线衍射仪等对定向碳纳米管阵列的形貌、成分和物相进行细致的分析和表征。结果表明:制得的碳纳米管阵列具有良好的定向性和多壁管状结构,并且石墨化程度高;碳纳米管中除碳元素外,管中包含有少量以纳米颗粒和纳米线形式存在的铁及其化合物,主要成分是铁和碳化铁。结合碳纳米管的制备和透射电子显微镜分析表征结果,认为超长碳纳米管阵列的生长模式为底部生长方式,即经历催化剂分解、催化、成核、长大、中毒、凝聚成粒和连接成线的循环过程,正是由于碳源和催化剂的连续供应促成了碳纳米管阵列的快速定向生长。     

Mechanisms for second harmonic generation in the interaction of a superintense ultrashort laser pulse with cluster plasma

The effects of the interaction of an intense femtosecond laser pulse with large atomic clusters are considered. The pulse intensity is of the order of 10¹⁸ W cm^?2. New effects appear when the magnetic component of the Lorentz force is taken into account. The second harmonic of laser radiation is generated. The second harmonic generation (SHG) efficiency is proportional to the square of the number of atoms in a cluster and the square of the laser radiation intensity. The resonance increase in the SHG efficiency at the Mie frequencies (both at the second harmonic frequency and fundamental frequency) proved to be insignificant because of the fast passage through the resonance during cluster expansion. The mechanisms of the expansion and accumulation of energy by electrons and ions in the cluster are discussed in detail. The energy accumulation by electrons mainly occurs due to stimulated inverse bremsstrahlung upon elastic reflection of the electrons from the cluster surface. The equations describing the cluster expansion take into account both the hydrodynamic pressure of heated electrons and the Coulomb explosion of the ionized cluster caused by outer shell ionization. It is assumed that both inner shell and outer shell ionization is described by the over barrier mechanism. It is shown that atomic clusters are more attractive for the generation of even harmonics than compared to solid and gas targets.     

Morphology evolution of Si nanowires synthesized by gas condensation of SiO without any catalyst

A series of Si nanowires are synthesized at constant temperature of 970 ^○C on Si substrate by gas condensation of pure SiO vapor without any metal catalysts, by controlling the coverage of SiO_x deposits. The morphologies are characterized by scan electron microscopy (SEM) and their evolution during the growth process is observed: from isolated clusters in earlier stage to linked cluster assemblies, and developing to smooth nanowires in the later stage. The growth mechanism is discussed based on the newly proposed clustering-aggregation-sintering model.