Novel two-dimensional transition metal chalcogenides created by epitaxial growth

Two-dimensional(2D) materials have been a very important field in condensed matter physics, materials science, chemistry, and electronics. In a variety of 2D materials, transition metal chalcogenides are of particular interest due to their unique structures and rich properties. In this review, we introduce a series of 2D transition metal chalcogenides prepared by epitaxial growth. We show that not only 2D transition metal dichalcogenides can be grown, but also the transition metal chalcogenides that do not have bulk counterparts, and even patterned transition metal chalcogenides can be fabricated. We discuss the formation mechanisms of the novel structures, their interesting properties, and potential applications of these 2D transition metal chalcogenides. Finally, we give a summary and some perspectives on future studies.     

Kinetic model for a step edge in epitaxial growth

A kinetic theory is formulated for the velocity of a step edge in epitaxial growth. The formulation involves kinetic, mean-field equations for the density of kinks and "edge adatoms" along the step edge. Equilibrium and kinetic steady states, corresponding to zero and nonzero deposition flux, respectively, are derived for a periodic sequence of step edges. The theoretical results are compared to results from kinetic Monte Carlo (KMC) simulations of a simple solid-on-solid model, and excellent agreement is obtained. This theory provides a starting point for modeling the growth of two-dimensional islands in molecular-beam epitaxy through motion of their boundaries, as an alternative to KMC simulations.     

Phase-field modeling of epitaxial growth: Applications to step trains and island dynamics

In this paper, we present a new phase-field model including combined effects of edge diffusion, the Ehrlich-Schwoebel barrier, deposition and desorption to simulate epitaxial growth. A new free energy function together with a correction to the initial phase variable profile is used to efficiently capture the morphological evolution when a large deposition flux is imposed. A formal matched asymptotic analysis is performed to show the reduction of the phase-field model to the classical sharp interface Burton-Cabrera-Frank model for step flow when the interfacial thickness vanishes. The phase-field model is solved by a semi-implicit finite difference scheme, and adaptive block-structured Cartesian meshes are used to dramatically increase the efficiency of the solver. The numerical scheme is used to investigate the evolution of perturbed circularly shaped small islands. The effect of edge diffusion is investigated together with the Ehrlich-Schwoebel barrier. We also investigate the linear and nonlinear regimes of a step meandering instability. We reproduce the predicted scaling law for the growth of the meander amplitude, which was based on an analysis of a long wavelength regime. New nonlinear behavior is observed when the meander wavelength is comparable to the terrace width. In particular, a previously unobserved regime of coarsening dynamics is found to occur when the meander wavelength is comparable to the terrace width.     

New approach to the X-ray diffraction analysis of test structures during flow calibration in epitaxial growth reactors

The high-resolution X-ray diffractometry (HRXRD) technique is known as a powerful tool for analyzing epitaxial heterostructures. However, standard analysis procedures do not allow the layer growth time to be used as a fixed parameter during HRXRD spectra analysis. The growth time in modern facilities is measured with a high degree of accuracy, which increases the reliability of HRXRD analysis particularly in the case of spectra with reduced quality or complex heterostructures consisting of a large number of individual homogeneous layers. A new algorithm is based on using flow rates of deposited components as variable parameters, while the layer growth times are taken as fixed parameters. A particular feature of this new approach is associated with the fact that the known growth time for each heterostructure layer is directly included into the algorithm for adjustment of the calculated spectrum to the experimental X-ray diffraction spectrum (HRXRD). The flows of deposited layers are variable parameters and, thus, the algorithm turned out to be very efficient for calibrating flow controllers in epitaxial growth reactors. The algorithm allows for reliable estimation of the flow even in the case of poorly informative HRXRD spectra.     

Kinetic-anisotropy-induced ordering-orientation transition in epitaxial growth: a method to synthesize ordering-orientation superlattices

The epitaxial growth has a distinct kinetic feature that the lateral surface diffusion is faster than the longitudinal bulk diffusion. We show there is an ordering-orientation transition of alloy films with the change of growth rate due to this kinetic anisotropy. As an example, we have calculated the epitaxial growth of CoPt alloy films on the Pt buffer layer. We show the ordered structure of CoPt films changes from the L1(0) [001] (a compositional modulation along the [001] direction) variant to the L1(0) [100] variant with the increase of growth rate. This ordering-orientation transition also occurs with the decrease of temperature at adequate growth rate. Based on this mechanism, we propose a simple method to synthesize the ordering-orientation superlattices.     

Metal to insulator transition in epitaxial graphene induced by molecular doping

The capability to control the type and amount of charge carriers in a material and, in the extreme case, the transition from metal to insulator, is one of the key challenges of modern electronics. By employing angle-resolved photoemission spectroscopy we find that a reversible metal to insulator transition and a fine-tuning of the charge carriers from electrons to holes can be achieved in epitaxial bilayer and single layer graphene by molecular doping. The effects of electron screening and disorder are also discussed. These results demonstrate that epitaxial graphene is suitable for electronics applications, as well as provide new opportunities for studying the hole doping regime of the Dirac cone in graphene.     

Instability and wavelength selection during step flow growth of metal surfaces vicinal to fcc(001)

We study the onset and development of ledge instabilities during growth of vicinal metal surfaces using kinetic Monte Carlo simulations. We observe the formation of periodic patterns at [110] close packed step edges on surfaces vicinal to fcc(001) under realistic molecular beam epitaxy conditions. The corresponding wavelength and its temperature dependence are studied in detail. Simulations suggest that the ledge instability on fcc(1,1,m) vicinal surfaces is controlled by the strong kink Ehrlich-Schwoebel barrier, with the wavelength determined by dimer nucleation at the step edge. Our results are in agreement with recent continuum theoretical predictions, and experiments on Cu(1,1,17) vicinal surfaces.     

On the 2D-3D transition in epitaxial thin film growth

The theory is based on the fact that the equilibrium concentration of single atoms adsorbed on the surface of a monolayer island placed on a foreign substrate such that the substrate-deposit interaction is weaker than the deposit-deposit interaction is higher than the equilibrium concentration of atoms adsorbed on the surface of the same island now placed on a substrate of the same material. This higher adatom concentration leads to 2D nucleation on top of the monolayer island. The difference of the above equilibrium adatom concentrations appears as a driving force for the process of transformation of the initial monolayer island into a 3D island by detachment of atoms from the first monolayer island edges and their subsequent attachment to the edges of the second layer nucleus. The kinetics of this process are studied in detail, the following two cases being considered. The first case consists of breaking up and agglomeration of an initially continuous film into 3D crystals upon heating. The second case consists of change of the growth mode from layer to island mode during the vapour deposition when the substrate temperature increases. Expressions for the critical temperatures for these two phenomena to occur are derived. It is shown that they depend strongly on the substrate orientation, the critical temperature being higher for the 〈111〉 orientation in comparison with the 〈110〉 orientation, if substrate and deposit with a fcc lattice are considered. The theoretical results are compared with experimental data for deposition of Au on Mo{110}, Cu on W{110} and W{100} and Fe on Cu{111}.     

Monte Carlo study of the step flow to island nucleation transition for close packed structures

Using joined super-lattice Kinetic Monte Carlo and continuous simulations we study the transition between step flow and two-dimensional island nucleation growth on stepped surfaces for close packed crystalline structures. The numerical analysis is performed in terms of misorientation cut, deposition rate and temperature. We compare the results of the atomistic approach with the predictions of the standard and generalized Burton-Cabrera-Frank (BCF) continuous model. The generalization consists in the explicit inclusion in the theory of the formation and dissolution of mobile dimers on the terraces. We show that the BCF-like continuous theories break down for low temperatures, large off-angle cuts and high deposition rates. In view of these results we critically discuss the basic assumptions of the continuous models.     

Twin boundaries can be moved by step edges during film growth

We track individual twin boundaries in Ag films on Ru(0001) using low-energy electron microscopy. The twin boundaries, which separate film regions whose close-packed planes are stacked differently, move readily during film growth but relatively little during annealing. The growth-driven motion of twin boundaries occurs as film steps advance across the surface--as a new atomic Ag layer reaches an fcc twin boundary, the advancing step edge carries along the boundary. This coupling of the microstructural defect (twin boundary) and the surface step during growth can produce film regions over 10 microm wide that are twin free.     

Morphological symmetry breaking during epitaxial growth at grazing incidence

It is shown that, in submonolayer growth at off-normal incidence, even much less than 1% of transfer from the condensation energy of the deposited atoms into adatom motion is sufficient to induce a net adatom current from the illuminated edge of a two-dimensional island to the other edges, thereby breaking the island symmetry. Such a symmetry breaking phenomenon is most pronounced for deposition at grazing incidence. Comparison between our theoretical predictions and existing experimental results confirms the general validity of the model.     

Kinetic step bunching instability during surface growth

We study the step bunching kinetic instability in a growing crystal surface characterized by anisotropic diffusion. The instability is due to the interplay between the elastic interactions and the alternation of step parameters. This instability is predicted to occur on a vicinal semiconductor surface Si(001) or Ge(001) during epitaxial growth. The maximal growth rate of the step bunching increases like F4, where F is the deposition flux. Our results are complemented with numerical simulations which reveal a coarsening behavior in the long time evolution for the nonlinear step dynamics.     

Low energy electron oscillations during epitaxial growth of thin films

We have measured the specularly reflected intensity of low energy (12 eV) electrons as a function of the deposition time during the growth of Cu-thin films on fcc-Co(100) and Co-thin films on Cu(100). The measured curves show pronounced periodical oscillations. The origin of these oscillations is identified as arising from the interference of the electron waves reflected at the vacuum-film and film-substrate boundaries.     

Impact of the growth on the stability–instability transition at Si (111) during step bunching induced by electromigration

The central result of this work is the definite proof that the mechanisms of the direct current induced step bunching in the middle and high temperature domains are different. We used the recently developed technique for reflection electron microscopy (REM) observation of Si surfaces during equilibrium and during crystal growth to document the impact of the growth on the process of step bunching induced by direct current heating of an Si crystal. We found completely different effects of crystal growth on the stability of the vicinal surfaces in the two temperature domains 1160–1240°C and 1260–1320°C. In the high temperature domain step bunching takes place at step-down direction of the electric current during sublimation, equilibrium and growth; whereas in the 1160–1240°C domain bunching takes place at step-up current during sublimation and at step-down current during growth. These findings support the concept of local mass transport in the high temperature domain — the surface migration of adatoms is effectively interrupted at each step by a high rate exchange between the adlayer and the crystal phase. At 1160–1240°C the mass transport is global — adatoms easily cross the steps without taking part in the crystal–adlayer exchange. Since earlier studies of other researchers support the concept of local mass transport in the low temperature domain, 900–1050°C, a difficult question arises — why do the properties of the steps, with respect to the mass transport over the crystal surface, have a temperature dependence which is not monotonous? To explain the transition from local mass transport in the low temperature domain to global mass transport in the middle temperature domain we advance a hypothesis for a transition from a low temperature state of adsorption (Takayanagi-like adatoms, existing above the (7×7)↔(1×1) transition) to a high temperature state of adsorption (adatom with three dangling bonds) with much lower activation energy for desorption.     

Numerical simulation of the laminar-turbulent transition in the flow over a backward-facing step

The capabilities of the quasi-gasdynamic equations as applied to the simulation of laminar-turbulent transitions are demonstrated by computing the viscous compressible gas flow in a channel with an abrupt expansion.     

Optimization of carbon incorporation in GaAs during molecular beam epitaxial growth

Carbon-doped GaAs with dopant concentrations up to about 10²⁰ cm^–3 has been grown by molecular beam epitaxy. Above a critical carbon concentration, which depends on the deposition parameters, the surface deteriorates and loses its mirror-like appearance. From X-ray diffractometry and scanning electron microscopy, a diagram is established separating two areas with rough and mirror-like surface morphologies. The electrical properties as well as the morphology of GaAs : C can be simultaneously improved by a careful adjustment of the deposition parameters according to this diagram. On leave at: Tokyo Institute of Technology, Research Center for Quantum Effect Electronics, 2-12-1 O-okayama, Meguro-ku, Tokyo 152, Japan