Crystal growth rate limited by step length — the case of oxygen-deficient TiO2 exposed to oxygen

We study how an oxygen-deficient crystal of TiO₂ crystal grows when exposed to O₂. While the O flux is external to the crystal, the Ti flux necessary for growth comes from internal (bulk) interstitials (Phys. Rev. Lett. 76 (1996) 791). We address where the reaction between O and Ti to form new crystal takes place in the regime of pure step flow (i.e., surface steps advancing without new-layers nucleating). The detailed partitioning of the growth flux among individual surface steps is studied using low-energy electron microscopy for two geometries on the (110) surface—an array of islands on a terrace and an island stack generated from a dislocation source. For both geometries, the areas of islands larger than the critical size grow at rates strictly proportional to their perimeter length, independent of the local step configuration. In addition, we find that the growth rate is proportional to the O₂ pressure. The step flow represents a simple limiting case of crystal growth (Phil. Trans. R. Soc. A. 243 (1951) 299)—only the growth species near a step edge becomes incorporated into the crystal. That is, only Ti and O reactions near the step edge lead to crystal growth. This case is in marked contrast to crystal growth controlled by species attaching to terraces and diffusing to steps, for which the growth rates depend upon the local step environment. Indeed, simulating the island array as if the growth flux was partitioned among the individual islands by concentration gradients (i.e., diffusion-controlled growth) totally failed to reproduce the experimental rates.     

Growth of EuTe islands on SnTe by molecular beam epitaxy

Semiconductor magnetic quantum dots are very promising structures, with novel properties that find multiple applications in spintronic devices. EuTe is a wide gap semiconductor with NaCl structure, and strong magnetic moments S=7/2 at the half filled 4f⁷ electronic levels. On the other hand, SnTe is a narrow gap semiconductor with the same crystal structure and 4% lattice mismatch with EuTe. In this work, we investigate the molecular beam epitaxial growth of EuTe on SnTe after the critical thickness for island formation is surpassed, as a previous step to the growth of organized magnetic quantum dots. The topology and strain state of EuTe islands were studied as a function of growth temperature and EuTe nominal layer thickness. Reflection high energy electron diffraction (RHEED) was used in-situ to monitor surface morphology and strain state. RHEED results were complemented and enriched with atomic force microscopy and grazing incidence X-ray diffraction measurements made at the XRD2 beamline of the Brazilian Synchrotron. EuTe islands of increasing height and diameter are obtained when the EuTe nominal thickness increases, with higher aspect ratio for the islands grown at lower temperatures. As the islands grow, a relaxation toward the EuTe bulk lattice parameter was observed. The relaxation process was partially reverted by the growth of the SnTe cap layer, vital to protect the EuTe islands from oxidation. A simple model is outlined to describe the distortions caused by the EuTe islands on the SnTe buffer and cap layers. The SnTe cap layers formed interesting plateau structures with easily controlled wall height, that could find applications as a template for future nanostructures growth.     

RHEED studies of the growth of Si(001) by gas source MBE from disilane

The growth of Si(001) from a gas source molecular beam epitaxy system (Si-GSMBE) using disilane (Si₂H₆) was investigated using reflection high-energy electron diffraction (RHEED). The surface reconstructions occurring between 100 and 775°C were studied as a function of both substrate temperature and surface coverage. We report the first observation of (2x2) and c(4x4) reconstructions during growth at substrate temperatures near 645°C using Si₂H₆. All growth was found to be initiated by the formation of three-dimensional (3D) islands which coalesced at substrate temperatures above 600°C. The surface reconstruction was found to change from a disordered to an ordered (2x1)+(1x2) structure at 775°C via intermediate (2x2) and c(4x4) phases. Thereafter, growth was found to proceed in a 2D layer-by-layer fashion, as evidenced by the observation of RHEED intensity oscillations. This technique has been used, for the first time, to calibrate growth rates during Si-GSMBE. The intensity oscillations were measured as a function of both substrate temperature and incident beam flux. Strong and damped oscillations were observed between 610 and 680°C, in the two-dimensional growth regime. At higher temperatures, growth by step propagation dominated while at lower temperatures, growth became increasingly three-dimensional and consequently oscillations were weak or absent. Similarly, there was a minimum flux limit ( <0.16 SCCM), below which no oscillations were recorded.     

Strain dependent growth of silicon on Ge/Si–C heterostructures

We report on structural investigations of strain dependent growth of Si on Ge/Si–C heterostructures. Very small islands of Ge were obtained by using a little C precoverage before the Ge deposition. These islands are visualized by scanning tunneling microscopy (STM) and the subsequent Si epitaxy is pursued. STM pictures taken upon some monolayers of Si epitaxy reveal an inhomogeneous growth mode, which leads to ditch like rings formed around the islands. Pictures of the following Si deposition suggest a strain dependent surface diffusion of Si until sufficient material has been deposited which then flattens the surface resulting in perfect epitaxial structures.     

Tracking atomic processes throughout the formation of heteroepitaxial interfaces

Understanding the atomic processes governing the formation a heteroepitaxial interface is central to predict and control the basic physical and chemical properties of a variety of hetero‐structures. With this perspective, we address in this work the dynamic behavior of Ge atoms deposited on Si‐surfaces by molecular dynamics simulations using enhanced bond order potentials. We demonstrate that the deposition of Ge atoms on Si surface induces the competition between several processes including adsorption, desorption, and bulk and surface diffusion involving atomic exchange, substitution, and clustering. By tracking these process, the simulations provide unprecedented insights onto the assembly of the first atomic layer of Ge on Si, the nucleation, growth, and relaxation of islands and quantum dots as well as of defect generation in the bulk.     

PVT法氮化铝晶体铝面、氮面生长对比分析

在氮气环境下用PVT方法生长氮化铝过程中,氮面和铝面由于表面化学性质不同,生长的主要化学反应速度存在差异。原子在生长表面的迁移能力不同造成单晶表面生长方式差异较大。在基本相同条件下(生长温度、生长温差、生长气压、类似的籽晶、同一台生长设备)进行了铝、氮面氮化铝单晶晶体生长。为了更明显地表现铝氮面的差异,将同一片籽晶分为两半,翻转其中一半让铝氮面同时生长。铝面生长较好的区域形成了明显的晶畴,而氮面生长时生长较好的部分出现了明显的生长台阶,并出现了晶畴边界被生长台阶湮灭的生长现象,进一步通过AFM观测到铝面生长台阶平整但被缺陷所阻隔,晶畴发育明显为各晶畴独立生长。氮面生长台阶没有铝面规则但连续性较强,在原来晶畴边界位置也出现了连续的生长台阶(或台阶簇)。所以籽晶质量不高时氮面生长更容易提高晶体质量,后续的XRD测量结果也证明了氮面生长后的晶体质量明显高于铝面生长的晶体质量。     

Melt growth and post‐grown annealing of semiinsulating (CdZn)Te by vertical gradient freeze method

We present results of development of CdZnTe semi‐insulating crystals prepared by Vertical Gradient Freeze method in a 4‐zone furnace. We applied the way of growth of the crystal from the top when the first crystallization seed is created on the surface of the melt. The typical height of the crystals is 5 cm. Resistivity and photoconductivity profiles measured along the growth axis by contactless method are compared and their mutual correlation is explained based on a model of relative shift of the Fermi level and the midgap level present in the material. The influence of the Fermi level on electron trapping and recombination is summarized. We present here results of a two‐step annealing method aimed at reduction of Te inclusions while keeping the resistivity high. We employed CdTe:Cl VGF grown samples to eliminate Te inclusions observed in as grown crystals by two‐step post grown annealing in Cd and Te atmosphere and present a model of the processes leading to high resistivity material after annealing.     

Misfit Strain Relaxation by Dislocations in InAs Islands and Layers Epitaxially Grown on (001)GaAs Substrates by MOVPE

The misfit dislocation configurations in InAs islands as well as in more or less continuous layers grown on (001) oriented GaAs substrates were studied by weak-beam and high-resolution electron microscopy. The islands are confined by {101} and {111} facets where the aspect ratio (height/lateral extension) can be affected by the growth conditions. It is possible to grow well-defined islands as well as relatively continuous layers by MOVPE under As-stabilized conditions. At constant deposition parameters the growth is characterized by islands of different sizes (but with constant aspect ratio) in various strain states depending on their dislocation content. Coherently strained islands without any dislocation can be observed for heights up to 23 ML InAs, or otherwise, up to a maximal island extension of about 12 nm (for the particular aspect ratio ≈︂0.585). With further increase of island height and lateral extension, the introduction of dislocations becomes favourable. Independent of the island size, the layer thickness and the dislocation density, a residual elastic strain of about ε^r = —0.8% remains after relaxation. This means, about 88% of the total misfit strain of ε = —6.686 × 10^—2 were compensated by Lomer dislocations. These sessile Lomer dislocations lie in the island interior only, where single 60° dislocations were observed exclusively in their near-edge regions. With increasing island size and/or layer thickness some close-spaced 60° dislocations occur additionally within the interfacial region. The Lomer dislocations that are always located 4 monolayers (ML) above the InAs/GaAs interfacial plane result from the well-known fusion of two 60° slip dislocations. These 60° dislocations have been nucleated 7 … 8 ML above the interface at surface steps on the {111} facets confining the islands. Based on our experimental observations a new mechanism is proposed that explains the origin of these 60° dislocations. Their further fusion to sessile Lomer dislocations that compensate the misfit strain most efficiently occurs in the way as commonly accepted.     

Epitaxial growth in the (111)Ag/Cu and (111)Au/Cu systems

The initial stages of epitaxial growth in the (111)Ag/Cu and (111)Au/Cu systems were investigated using UHV-RHEED and TEM on the same specimens. Flat, monocrystalline (111)Cu substrates, 1100 Å thick, were formed in situ in the RHEED system on (111)NaCl/mica bilayers. The latter consisted of air-cleaved mica on which 150 Å of NaCl was vacuum-evaporated to form a (111)NaCl monocrystalline film. The NaCl layer allowed easy removal in water of the subsequently deposited bilayer metal film. RHEED showed that these Cu films grew with extremely flat surfaces at 400°C and 10 Å/sec deposition rates. They were then annealed at 500°C for 15 min to reduce their dislocation content and finally used as substrates for subsequent deposition of thin Ag or Au superlayers. The average Ag and Au superlayer thicknesses were varied from fractions of an Angstrom to approximately 20 Å. It was shown that despite the elongated streaks in the RHEED patterns, film growth occurred by an island mechanism, the islands having flat top surfaces. In the initial growth processes, the islands merely thickened. After a few average monolayers were deposited, the islands began to widen, often by means of much thinner islands, finally coalescing into a continuous film. The Au overgrowths became continuous in the 6–11 Å thickness range. In the case of Ag, there still were some open areas in the overgrowth at 20 Å. In both cases the continuous regions of the Ag and Au overgrowths consisted of sharply delineated thick and thin areas that gave rise to steps on the otherwise flat surface.     

In situ atomic force microscopy studies of surface morphology,growth kinetics,defect structure and dissolution in macromolecular crystallization

Surface morphologies of thaumatin, catalase, lysozyme and xylanase crystals were investigated using in situ atomic force microscopy. For thaumatin, lysozyme and xylanase crystals, growth steps having a height equal to the unit cell parameter were produced both by screw dislocations and two-dimensional nuclei. Growth of catalase crystals proceeded in alternating patterns exclusively by two-dimensional nucleation and the successive deposition of distinctive growth layers, each having a step height equal to half the unit cell parameter. The shapes of islands on successive layers were related by 2-fold rotation axes along the 〈0 0 1〉 direction. Experiments revealed that step bunching on crystalline surfaces occurred either due to two- or three-dimensional nucleation on the terraces of vicinal slopes or as a result of uneven step generation by complex dislocation sources. Growth kinetics for thaumatin and catalase crystals were investigated over wide supersaturation ranges. Strong directional kinetic anisotropy in the tangential step growth rates in different directions was seen. From the supersaturation dependencies of tangential step rates and the rates of two-dimensional nucleation, the kinetic coefficients of the steps and the surface free energy of the step edge were calculated. Adsorption of impurities which formed filaments on the surfaces of catalase and thaumatin crystals was recorded. Cessation of growth of xylanase and lysozyme crystals was also observed and appeared to be a consequence of the formation of dense impurity adsorption layers. Crystal growth resumed upon scarring of the impurity adsorption layer and clearing of the crystal surface with the AFM tip. Adsorption of three-dimensional clusters, which consequently developed into either properly aligned multilayer stacks or misaligned microcrystals was recorded. For catalase crystals, incorporation of misoriented microcrystals as large as 50×3×0.1 μm³ produced elastic deformations in growth layers of ≈0.6%, but did not result in the defect formation. Etching experiments on catalase crystals revealed high defect densities.     

Vapor phase epitaxy of CdTe on sapphire substrates in dependence on the vapor-flow orientation

The growth of cadmium telluride films on a structured (0001) sapphire surface oriented at an angle of 44° to the vapor-flow direction and normal to the steps formed along the \(11\overline 2 0\) direction is studied. It is found that this geometry of the vapor source and a substrate (heated to a temperature of 300°С) provides the growth of single-crystal CdTe films if a step height on the substrate surface is more than 1 nm. The results are explained by the occurrence of a longitudinal component of the diffusion flux of СdTe molecules and atoms toward the steps from the inner side and their high density at the step edge from the outer side due to the presence of the Ehrlich–Schwoebel barrier, which ensures the efficient supply of material and minimum supersaturation necessary for the nucleation at the step edge and growth of oriented CdTe islands. The cadmium telluride films that are grown have the \(\left( {110} \right)\left[ {1\overline 1 0} \right]CdTe\left\| {\left( {0001} \right)} \right.\left[ {11\overline 2 0} \right]A{l_2}{O_3}\) orientation and a composition similar to stoichiometric CdTe.     

Atomic force microscope observation of the initial stage of InAs growth on GaAs substrates

The initial stage of InAs growth on GaAs(001) substrates has been investigated by atomic force microscopy. Three-dimensional (3D) islands of a uniformly small size and high density were observed at the initial stage not only for low substrate temperature (T_s) but also for low V/III ratio. This is explained by a simple model based on the difference in the growth rate between strained and relaxed InAs surfaces. The 3D islands are found to agglomerate after the growth is interrupted under As pressure. We suppress the agglomeration and obtain an atomically flat InAs surface.     

Behaviour of vicinal InP surfaces grown by MOVPE: exploitation of AFM images

InP substrates and epilayers grown by MOVPE have been studied by AFM. For different misorientation angles, we observed the surface of the substrate after annealing under phosphine (PH₃) and of the epilayers under different growth conditions such as growth temperature T_g and trimethylindium (TMI) partial pressure. After annealing the terrace width corresponds to the nominal value of misorientation angle measured by X-ray diffraction. We observed different topographies and roughnesses for the grown layers corresponding to different growth modes. We propose, taking into account the roughness of the surface, a calculation of the step height and terrace width. For 2D nucleation (θ ≤ 0.2° and T_g = 500°C) and step flow mode, the roughness is low while it is increased by step bunching (θ ≥ 0.5° and T_g ≥ 580°C). Moreover we have examined the surface morphology for different misorientation angles and determined the influence of growth conditions (growth temperature, indium partial pressure) on the growth mechanism. At T_g = 580°C the increase of the TMI partial pressure in the reactor enhances the step bunching and leads to larger terraces.     

Nucleation of GaN on sapphire substrates at intermediate temperatures by Hydride Vapor Phase Epitaxy

A novel approach to deposit GaN layers directly on a sapphire substrate by Hydride Vapor Phase Epitaxy is presented. The two‐step deposition process includes the growth of GaN nucleation layers at intermediate temperatures in the range of 750 – 900 °C and subsequent high‐temperature overgrowth at about 1040 °C. Closed and non‐closed nucleation layers with a thickness of up to 2 μm were produced and characterized by scanning and transmission electron microscopy, micro‐Raman spectroscopy and X‐ray diffraction. A growth temperature of 780 °C is found to be optimal with respect to density and size distribution of nucleation islands. Raman measurements performed on the nucleation layers reveal nearly zero residual stress indicating effective stress relaxation on cooling down from growth temperature. The results of first overgrowth experiments demonstrate the possibility to grow 10 μm thick, crack‐free GaN layers of high crystalline quality on the nucleation layers. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Differences in nucleation and properties of InN islands formed using two different deposition procedures

The initial stages of metalorganic chemical vapor deposition of InN have been investigated using two different growth procedures: growth of InN over a GaN buffer layer in one continuous run and growth of InN on a pre-deposited GaN template. While the growth conditions and material quality of the GaN underlying layers are nominally the same, characterization by AFM, X-ray diffraction and PL spectroscopy reveals significantly different material properties of InN islands formed using the two procedures and suggests a different path of evolution during the initial stages of growth. In particular, InN islands grown on a pre-deposited GaN template seem to nucleate directly on the GaN template and are 5 times larger in volume and 2 times lower in surface density as compared with InN growth in one continuous run with the GaN underlying layer. Our studies suggest that the Ga incorporation into the InN during the growth on a GaN buffer layer in one continuous run plays a significant role in altering InN growth mechanisms and material properties.     

扩散过程对自组织生长量子点密度影响的模拟研究

考虑六方格子衬底上的沉积粒子扩散过程,本文利用Monte Carlo方法对自组织生长岛的面密度进行了研究.模拟得到了岛的生长形貌图,结果表明生长的岛数与扩散步数成反比且存在最大23;岛覆盖率,由岛的覆盖率可估算量子点分布的最大面密度.     

Growth and dissolution kinetics of potassium sulfate in pure solutions and in the presence of Cr3+ ions

The growth and dissolution kinetics of potassium sulfate was studied based on single crystal measurements. The growth rate is correlated to the supersaturation with power low equation. At all the temperatures studied, the growth rate order lies in the range of 1‐1.5 with the surface integration process as the controlling step. The estimated value of the activation energy of growth is 39.4 kJ/mol. The dissolution rate order decreases with increasing the temperature. The diffusion step is controlling the dissolution process. The addition of 5 ppm Cr³⁺ ions reduces the growth rate. Both growth rate dispersion and dissolution rate dispersion occur in the growth and dissolution processes of potassium sulfate. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Nucleation of islands in GaAs molecular beam epitaxy studied by in-situ scanning electron microscopy

We studied two-dimensional nucleation of islands in the molecular beam epitaxy (MBE) of GaAs by in-situ scanning electron microscopy and found that the islands do not appear until about 1/3 monolayer is deposited. In contrast to what is expected from the previous simple nucleation and growth model, we observed islands to form continuously.     

The Characteristics of GaP Window Layer Grown by Indium‐added Liquid Phase Epitaxy

The effects of added Indium on the growth characteristics of GaP were systematically studied using conventional liquid phase epitaxy technique with Ga‐rich GaP source melt. The GaP growth rate uniformly increase with the source melt of increasing Indium addition against Gallium solvent. These epilayers have mirror‐like surface morphology examined by optical microscope except several grown films with large amount of Indium addition meet a terrible interface. The surface morphologies examined by AFM showed the ripples in samples of R_0.05 and R_0.4 and distinct islands with elliptical base shape in the sample of R_0.7 (R‐In ratio). The epitaxial layer with incorporation of Indium addition during growth had good performance on the carrier concentrations and resistivity. The composition of compound semiconductor become to InGaP at higher amount of In addition to Ga was examined by double‐crystal X‐ray diffraction and the distribution of Indium examined by SIMS also provided the evidences in sample of R_0.7.     

Initial growth behavior of GaAs on ZnSe in MOVPE

We have used atomic force microscopy to investigate the initial stages of the growth of GaAs on ZnSe by metalorganic vapor phase epitaxy. Underlying ZnSe with an atomically flat surface is achieved by growth at 450°C and post-growth annealing at the same temperature. The growth modes of GaAs on the ZnSe surface strongly depend on growth temperatures. The growth carried out at 450°C is 2-dimensional, while that at 550°C is highly 3-dimensional (3D), where the 3D islands are elongated in the [110] direction. The growth behavior, unlike homoepitaxy, is well interpreted in terms of low sticking coefficient and anisotropic lateral growth rate in the heterovalent heteroepitaxy.