Nucleation of III nitride semiconductors in heteroepitaxy

The nucleation of III nitride semiconductors in heteroepitaxy is theoretically investigated using GaN nucleation on the AlN surface as an example. It is inferred that the mechanism of this process is determined by the temperature at the initial stage of the layer formation (T). At low temperatures (T<500°C), liquid gallium droplets appear and the chemical reaction between the Ga and N atoms results in the formation of GaN nuclei. At substrate temperatures T>650°C, there arise only GaN nuclei. It is revealed that the GaN nucleation is governed by the generalized diffusion coefficient of GaN, which is a combination of the diffusion coefficients for gallium and nitrogen atoms. It is shown that the generalized diffusion coefficient of GaN on the crystal surface increases by seven orders of magnitude as the growth temperature increases from 600 to 800°C. This is accompanied by a change in the growth mechanism of the III nitride semiconductor epitaxial layers.     

Mechanism and kinetics of early growth stages of a GaN film

The growth of GaN islands on the substrate surface covered with an AlN buffer layer is theoretically investigated at the stages of nucleation and Ostwald ripening in the temperature range 480–1000°C. The following inferences are made from analyzing the results obtained. (1) At temperatures T>650°C, the growth of islands is controlled by the chemical reaction of formation of GaN molecules around the periphery of the island surface. Islands nucleated at these temperatures are characterized by a large spread in their sizes. (2) At temperatures T<600°C, the island growth is governed by the surface diffusion of nitrogen atoms. Islands nucleated at these temperatures are virtually identical in size. (3) In the temperature range 600–650°C, the mechanism of island growth gradually changes over from the mechanism associated with the surface diffusion of nitrogen atoms with a large mean free path to the mechanism determined by the diffusion of gallium atoms with a smaller mean free path. The supersaturation, flux, and size distribution functions of GaN nuclei are calculated at different substrate temperatures. The phase diagrams describing the evolution in the phase composition of GaN islands with variations in temperature are constructed.     

Evolution of the optical properties of a silver-doped phosphate glass during thermal treatment

The optical properties of a silver-doped phosphate glass have been monitored during thermal processing at several fixed temperatures by in situ optical microspectroscopy. Silver nanoparticle (NP) formation and growth processes were assessed by analysis of surface plasmon resonance spectral features. Nucleation and growth processes were distinguished, which appeared temperature and time dependent. While nucleation was favored at low temperatures, relatively high temperatures promoted NP growth by silver diffusion. Photoluminescence spectra acquired along with optical absorption data indicated a continuous reduction of Ag⁺-Ag⁰ pairs concomitant with NP precipitation, suggesting their role as nucleation centers. The work of Ag NP formation and the activation energy for silver diffusion were estimated.     

Kinetic Monte Carlo simulations of electrodeposition: Crossover from continuous to instantaneous homogeneous nucleation within Avrami’s law

The influence of lateral adsorbate diffusion on the dynamics of the first-order phase transition in a two-dimensional Ising lattice gas with attractive nearest-neighbor interactions is investigated by means of kinetic Monte Carlo simulations. For example, electrochemical underpotential deposition proceeds by this mechanism. One major difference from adsorption in vacuum surface science is that under control of the electrode potential and in the absence of mass-transport limitations, local adsorption equilibrium is approximately established. We analyze our results using the theory of Kolmogorov, Johnson and Mehl, and Avrami (KJMA), which we extend to an exponentially decaying nucleation rate. Such a decay may occur due to a suppression of nucleation around existing clusters in the presence of lateral adsorbate diffusion. Correlation functions prove the existence of such exclusion zones. By comparison with microscopic results for the nucleation rate I and the interface velocity of the growing clusters v, we can show that the KJMA theory yields the correct order of magnitude for Iv². This is true even though the spatial correlations mediated by diffusion are neglected. The decaying nucleation rate causes a gradual crossover from continuous to instantaneous nucleation, which is complete when the decay of the nucleation rate is very fast on the time scale of the phase transformation. Hence, instantaneous nucleation can be homogeneous, producing negative minima in the two-point correlation functions. We also present in this paper an n-fold way Monte Carlo algorithm for a square lattice gas with adsorption/desorption and lateral diffusion.     

Implementation of an advanced fixed sectional aerosol dynamics model with soot aggregate formation in a laminar methane/air coflow diffusion flame

An advanced fixed sectional aerosol dynamics model describing the evolution of soot particles under simultaneous nucleation, coagulation, surface growth and oxidation processes is successfully implemented to model soot formation in a two-dimensional laminar axisymmetric coflow methane/air diffusion flame. This fixed sectional model takes into account soot aggregate formation and is able to provide soot aggregate and primary particle size distributions. Soot nucleation, surface growth and oxidation steps are based on the model of Fairweather et al. Soot equations are solved simultaneously to ensure convergence. The numerically calculated flame temperature, species concentrations and soot volume fraction are in good agreement with the experimental data in the literature. The structures of soot aggregates are determined by the nucleation, coagulation, surface growth and oxidation processes. The result of the soot aggregate size distribution function shows that the aggregate number density is dominated by small aggregates while the aggregate mass density is generally dominated by aggregates of intermediate size. Parallel computation with the domain decomposition method is employed to speed up the calculation. Three different domain decomposition schemes are discussed and compared. Using 12 processors, a speed-up of almost 10 is achieved which makes it feasible to model soot formation in laminar coflow diffusion flames with detailed chemistry and detailed aerosol dynamics.     

Nucleation and growth mechanisms during electropolymerization of substituted 3-alkylthiophenes

In the present work the electrochemical study of compounds based on 3-((ω-bromoalkyloxy) methyl) thiophene, varying the length of the alkyl chain between 6 and 12 carbon atoms, is reported. Electropolymerization of the monomers was achieved by potentiodynamic (cyclic voltammetry, CV) and potentiostatic (constant potential) techniques. Voltammograms obtained by CV show that all monomers can be electrochemically oxidized at potentials about 1800 mV to synthesize the respective polymer. Besides, the potential shifts to more anodic potentials on successive scans, increasing thus the resistivity of the material. Nucleation and growth mechanism (NGM) of electropolymerization was investigated by a potentiostatic technique (j-t). Deconvolution of the current-time transient data fitted with a theoretical model suggests that at short times the instantaneous nucleation with two-dimensional growth (IN2D) contribution prevails, followed by an instantaneous nucleation with three-dimensional growth controlled by the charge transfer (IN3Dct) contribution and, finally at longer times, the instantaneous nucleation with three-dimensional growth controlled by diffusion (IN3Ddif) contribution becomes important. The predominance of each contribution to the NGM depends on the monomer being electropolymerized, and the electrolysis time. The morphology predicted from these NGMs fully correlates with that determined by SEM.     

Attachment limited versus diffusion limited nucleation of organic molecules: Hexaphenyl on sputter-modified mica

The nucleation and growth of organic molecules is usually discussed in the framework of diffusion limited aggregation (DLA). In this letter we demonstrate for the rod-like organic molecules hexaphenyl (6P) on sputter-modified mica, that under specific experimental conditions the nucleation has to be described by attachment limited aggregation (ALA). The crucial parameter for the growth mode is the roughness of the substrate surface, as induced by ion sputtering. With decreasing surface roughness the diffusion probability of the molecules increases and the growth mode changes from DLA to ALA. This was derived from the deposition rate dependence of the island density. A critical size of i = 7 molecules was determined for the nucleation of 6P on a moderately sputtered mica surface.     

Scaling of submonolayer island growth with reversible adatom exchange in surfactant-mediated epitaxy

Surfactant-mediated epitaxial growth is studied with a realistic model, which includes three main kinetic processes: diffusion of adatoms on the surfactant terrace, exchange of adatoms with their underneath surfactant atoms, and reexchange in which an exchanged adatom resurfaces to the top of the surfactant layer. The scaling behavior of nucleus density and island size distributions in the initial stage of growth is investigated by using kinetic Monte Carlo simulations. The results show that the temperature dependence of nucleus density and island size distributions governed by the reexchanging-controlled nucleation at high temperatures exhibits similar scaling behavior to that obtained by the standard diffusion-mediated nucleation at low temperatures. However, at intermediate temperatures, the exchanging-controlled nucleation leads to an increase of nucleus density with temperature, while the island size distribution scales to a monotonically decreasing function, showing nonstandard scaling behavior.     

Ice nucleation of water droplet containing solid particles under weak ultrasonic vibration

Water with small volume (a few microlitres or less) often maintains its liquid state even at temperatures much lower than 0 °C. In this study, we examine the onset of ice nucleation in micro-sized water droplets with immersed solid particles under weak ultrasonic vibrations. The experimental results show that ice nucleation inside the water droplets can be successfully induced at relatively high temperatures. The experimental observations indicate that the nucleation sites are commonly encountered in the region between the particle and the substrate. A numerical study is conducted to gain insight into the possible underlying phenomenon for ice nucleation in such systems. The simulation results show that the collapse of cavitation bubbles in the crevice at the particle surface is structure sensitive with the hemisphere-shape crevice generating pressures as high as 1.63 GPa, which is theoretically suitable for inducing ice nucleation.     

Kinetic Monte-Carlo simulation of the homoepitaxial growth of MgO{001} thin films by molecular deposition

A lattice-based kinetic Monte-Carlo (KMC) code has been developed to investigate the MgO{001} crystal growth from deposition of MgO molecules, as a prototypical case of the growth of oxide thin films. The KMC approach has been designed on the basis of an extensive database including all possible diffusion mechanisms. The corresponding activation energies have been computed through first-principles calculations at zero temperature or from Arrhenius plots of the frequencies obtained by molecular dynamics simulations with empirical potentials. Crystal growth occurs layer by layer, as experimentally observed, and the diffusion of admolecules leads to a high capacity of nucleation, which is enhanced by vacancy diffusion. We have characterized the growth through surface roughness, size distribution and density of the islands, and filling ratios of the growing layers. Moreover, we have analysed the influence of each elementary mechanism on the growth. The best quality of the deposited layers is reached for temperatures larger than 700 K and for pressures smaller than 0.1 Torr. For these conditions, the simulated surface roughness is fully consistent with available experimental results.     

力和扩散机理下外延形貌的演化分析

本文提出了一个新的基于扩散界面的相场模型来描述外延生长中岛的形核、生长及熟化过程. 该模型同时考虑了弹性场、表面能、沉积、扩散、解吸和能量势垒等热力学及动力学过程对表面纳米形貌的影响. 采用经典的BCF模型来描述生长中的扩散形核过程, 而采用一个新的包含弹性应变能的自由能函数, 通过变分得到一个描述多层岛生长的相场方程, 该方法可以有效地描述外延生长中复杂的外延形貌. 采用有限差分格式对非线性耦合方程组进行求解. 数值结果显示, 该模型可以真实地再现外延生长中多层岛结构(即山丘状形貌)的演化过程, 模拟结果与已有实验结果一致. 同时模拟了生长过程中随外延形貌演化而形成的复杂生长应力, 研究表明, 在生长过程中, 岛中存在着复杂的应力分布, 且在岛边界处应力达到局部最大, 这与实验结果定性一致. 此外, 本文的重要发现是, 外延生长中的应力演化明显地影响原子的扩散过程, 当应力存在时, 外延结构变化较无弹性场时变快. 该项研究对理解外延生长中各物理机理的协同作用有重要的指导意义.     

图形衬底对多周期InGaAs量子点自组装生长的影响

量子点器件技术广泛应用于量子计算和光电器件上.成核位置的均匀性、有序性和尺寸一致性,可以有效提高光电器件性能.为了实现阵列量子点的可控性,本文采用湿法刻蚀制备图形化衬底,理论上解释了铟原子在图形化衬底上成核现象,产生有序的量子点分布特征,发现图形衬底的缺陷诱导在平台边缘和沟壑边缘成核,形成较大的量子点.在Stranski-Krastanow模式下图形衬底制备多周期量子点,发现多周期生长可以弱化台阶结构对量子点分布的限制作用.     

Nanoscale self-organization using standing surface acoustic waves

The diffusion of an adatom on a substrate submitted to a standing surface acoustic wave is theoretically studied. By performing large scale molecular dynamic simulations, we show that the wave dynamically structures the substrate by encouraging the presence of the adatom in the vicinity of the maximum displacements of the substrate. Using an analytical model, we explain this feature introducing an effective potential induced by the wave. Applied in an atomic deposition experiment, this dynamic structuring process should govern the nucleation sites distribution opening the route to accurately control the self-organization process at the nanoscale.     

Kinetic study of copper precipitates under VVER-type reactor conditions

The copper-rich cluster evolution in the neutron-irradiated VVER steels is investigated beginning at the nucleation stage. For this, typical VVER-type reactor conditions are considered. The cluster dynamics approach is used for calculation of the density distribution of copper precipitates related to the number of Cu-atoms or radius, mean radius, volume content, number density of precipitates and the concentration of free Cu-atoms in dependence on the irradiation time. The results for time of one year are compared with the results of small angle neutron scattering experiments which were carried out on specimens irradiated at the surveillance positions of VVER reactors. It has revealed the intermediate type of the evolution kinetics between diffusion and interfacial kinetics limited regimes. The duration of the nucleation and deterministic stages is estimated. The coarsening stage does not occur.     

Nucleation and growth mechanisms of Fe on Au(111) in the sub-monolayer regime

The growth of Fe on Au(111) at 300 K in the sub-monolayer regime has been investigated using scanning tunneling microscopy, focusing on the mechanisms of nucleation, coalescence and interlayer diffusion. Below a coverage of 0.1 ML, Fe growth proceeds in a well-ordered fashion producing regular arrays of islands, while approaching the island coalescence threshold (above 0.35–0.4 ML), we observed a consistent increasing of random island nucleation. These observations have been interpreted through rate equation models for the island densities in the presence of preferred nucleation sites. The evolution of the second layer fraction has also been interpreted in a rate equation scheme. Our results show that the ordered to random growth transition can be explained by including in the model bond breaking mechanisms due to finite Fe–Fe bond energy. A moderate interlayer diffusion has been inferred from data analysis between the second and the first layer, which has been used to estimate the energy barrier of the adatoms descending process.     

On the theory of phase transformations with a nonuniform nucleation rate

An expression for the phase volume fraction in a system with a nonuniform nucleation rate is derived by using the geometrical-probabilistic approach. Examples of such systems considered here are (1) a plane layer (with nucleation in the midplane) and random planes in space, (2) an infinitely long cylinder (with nucleation on the axis) and random lines in space, and (3) a sphere (with nucleation at the center) and nucleation at random points. In each case, an expression for the phase volume fraction is derived for the time-dependent rates of nucleation and growth. The equivalence of homogeneous nucleation and nucleation at points is established.     

Nucleation, growth and properties of Co nanostructures electrodeposited on n-Si(1 1 1)

In the present work, cobalt thin films deposited directly on n-Si(1 1 1) surfaces by electrodeposition in Watts bath have been investigated. The electrochemical deposition and properties of deposits were studied using cyclic voltammetry (CV), chronoamperometry (CA), ex situ atomic force microscopy (AFM), X-ray diffraction (XRD) and alternating gradient field magnetometer (AGFM) techniques. The nucleation and growth kinetics at the initial stages of Co studied by current transients indicate a 3D island growth (Volmer-Weber); it is characterized by an instantaneous nucleation mechanism followed by diffusion limited growth. According to this model, the estimated nucleus density and diffusion coefficient are on the order of magnitude of 10⁶ cm⁻² and 10⁻⁵ cm² s⁻¹, respectively. AFM characterization of the deposits shows a granular structure of the electrodeposited layers. XRD measurements indicate a small grain size with the presence of a mixture of hcp and fcc Co structures. The hysteresis loops with a magnetic field in the parallel and perpendicular direction and showed that the easy magnetization axis of Co thin film is in the film plane.     

非平衡凝固与固态相变中有关形核和长大的竞争研究

非平衡凝固和固态相变作为同热力学和动力学紧密相关的复杂理论体系,在物理冶金和凝聚态物理研究领域占据重要的地位。上述非平衡过程包含形核、生长和碰撞三个微观过程,其发生和发展均由一些竞争过程伴随、辅助甚至驱动。正确理解这些竞争过程决定了能否准确描述整个非平衡过程;材料制备中,其力学和物理/化学性能的提高也归根于这些竞争的发生与发展。因此,很有必要对非平衡凝固和固态相变中的竞争现象进行研究。本综述第一部分从形核/生长类相变角度对非平衡凝固和固态相变进行了概述,并强调了伴随其发生的竞争现象。第二部分立足于经典形核理论,对有关形核热力学、动力学以及形核方式的竞争现象进行了描述。第三部分对凝固中有关热扩散和溶质扩散以及固态相变中有关界面控制和扩散控制的生长方式竞争进行了描述。第四部分对本综述进行了总结性分析和概括,并对本领域的未来发展方向进行了预测。