Adatom Density Research Articles

Characteristics of high-order silane based Si and SiGe epitaxial growth under 600 ℃

Low temperature Si and SiGe epitaxy have been crucial in the semiconductor industry, prompting interest in high-order silanes as Si precursors. In this study, we investigated the growth characteristics of Si and SiGe epitaxial layers using Si2H6, Si3H8, and Si4H10 precursors by ultra-high vacuum chemical vapor deposition at temperatures between 500℃ and 600 ℃. We examined the effects of each precursor on the growth behaviors through varying temperature and flow rate conditions. For these three precursors, activation energies for Si epitaxy were measured to be below surface H desorption energy, and an increase in the order led to a greater adatom density at equivalent flow rates. In SiGe epitaxy, we observed Ge composition variations with temperature at each Ge-to-Si flow ratio depending on the Si precursors. Si2H6 exhibited almost consistent Ge compositions across temperatures, and the activation energy for SiGe epitaxy was decreased to 1.73 eV when the flow ratio was increased to 1. In comparison, Si3H8 and Si4H10 exhibited negligible changes in Ge compositions for the flow ratios below 0.5, with activation energies of 1.88 and 1.62 eV, respectively. Based on our experimental results, we proposed potential reaction pathways for high-order silane precursors.

Step pinning and hillock formation in (Al,Ga)N films on native AlN substrates

The influence of edge-type threading dislocations (TDs) on the epitaxial growth of AlGaN on native AlN substrates was investigated theoretically and experimentally. In the step flow growth regime, we find that pure edge-type TDs cause a pinning of surface steps, resulting in curved step segments. Theoretical calculations reveal that this pinning mechanism is solely mediated by the altered surface potential due the strain field imposed by the TD. Within the curved step segment, the step width is subject to changes resulting in an altered Ga/Al incorporation rate. According to the density functional theory calculation, this effect is related to the different surface diffusion length of Ga and Al and represents a further destabilization mechanism during step flow growth. Another consequence of surface step pinning is the occurrence of areas where the step width is increased. These areas serve as precursors for 2D nucleation due to an increased adatom density. Once nucleated, these nuclei grow along the c-direction via continuous 2D nucleation, while lateral expansion occurs due to adatom incorporation on the m-facets.

Investigation of the temperature stability of germanium-rich SiGe layers on Si(111) substrates

In this work, we investigated fully relaxed SiGe and pure Ge layers on Si(111) substrates, regarding their temperature stability. The layers were annealed at various temperatures up to 650 °C directly after growth. The Ge content of the Si1−xGex layers was varied between 0.6 and 1. We investigated effects due to surface segregation of Ge in the SiGe layers. During heat treatment, different surface reconstructions were observed. The SiGe layers remained smooth with a root-mean square surface roughness below 0.5 nm up to temperatures of 500 °C and a 7 × 7 surface reconstruction was seen. Annealing at higher temperatures corresponding to a 7 × 7–“1 × 1” phase transition, the surface roughness increased to more than 2 nm and island formation was observed. We measured the in-plane lattice constant of the surface as a function of temperature and confirmed a strong effect of Ge segregation on the surface strain. The Ge accumulation at the surface was confirmed by angle-resolved X-ray photoelectron spectroscopy. The high adatom density of the “1 × 1” reconstruction in combination with compressive strain led to island nucleation when cooling down. Pure Ge layers remained smooth even after annealing up to 650 °C.

Functionalized graphene origami metamaterials with tunable thermal conductivity

Graphene with tunable thermo-mechanical property is of great importance for next-generation thermal management devices. Distinct from previously reported porous graphene materials that tune the thermal conductivity at the cost of degrading their mechanical properties, non-porous hydrogenated graphene origami metamaterial exhibits a unique combination of tunable thermal conductivity, high strength, and enhanced stretchability. Through molecular dynamics simulation, a vast range of thermal conductivity can be found by tuning the geometrical parameters of the Miura-ori graphene origami, altering the adatom types and density, designing new origami patterns, and applying mechanical strains. By analyzing and comparing the numerical results from atomistic and continuum-based simulations, the effect of length scale on the thermal property of graphene origami metamaterials is explored. The temperature distribution, phonon density of states, phonon group velocity, and the atomic heat flux of the graphene origami are examined to illustrate the heat conduction mechanism. Finally, 3D graphene origami metamaterials are constructed by assembling the graphene origami strips, followed by evaluating their thermo-mechanical performance. Negative coefficients of thermal expansion are also observed in the functionalized graphene origami nanotubes. The introduced strategy for controlling the thermo-mechanical properties of graphene metamaterials can open up new avenues for developing thermoelectric devices, heat management systems, and flexible nanoelectronics.

Single Rh Adatoms Stabilized on α-Fe2O3(11̅02) by Coadsorbed Water.

Oxide-supported single-atom catalysts are commonly modeled as a metal atom substituting surface cation sites in a low-index surface. Adatoms with dangling bonds will inevitably coordinate molecules from the gas phase, and adsorbates such as water can affect both stability and catalytic activity. Herein, we use scanning tunneling microscopy (STM), noncontact atomic force microscopy (ncAFM), and X-ray photoelectron spectroscopy (XPS) to show that high densities of single Rh adatoms are stabilized on α-Fe2O3(11̅02) in the presence of 2 × 10–8 mbar of water at room temperature, in marked contrast to the rapid sintering observed under UHV conditions. Annealing to 50 °C in UHV desorbs all water from the substrate leaving only the OH groups coordinated to Rh, and high-resolution ncAFM images provide a direct view into the internal structure. We provide direct evidence of the importance of OH ligands in the stability of single atoms and argue that their presence should be assumed when modeling single-atom catalysis systems.

Functionalized Graphene Origami Metamaterials with Tunable Thermal Conductivity

Graphene with tunable thermo-mechanical property is of great importance for next-generation thermal management devices. Distinct from previously reported porous graphene materials that tune the thermal conductivity at the cost of degrading their mechanical properties, non-porous hydrogenated graphene origami metamaterial exhibits a unique combination of tunable thermal conductivity, high strength, and enhanced stretchability. Through molecular dynamics simulation, an extremely broad range of thermal conductivity can be obtained by tuning the geometrical parameters of the Miura-ori nanoarchitecture of graphene origami, altering the adatom types and density, designing new origami patterns, and applying mechanical strains. By analyzing and comparing the results from atomistic and continuum-based simulations, the effect of length scale on the thermal property of graphene origami metamaterials is explored. The temperature distribution and the phonon density of states of the proposed graphene origami are examined to illustrate the heat conduction mechanism. Finally, 3D graphene origami metamaterials are constructed based on the coupling and assembling of graphene origami strips, and their thermo-mechanical performance is elucidated. Negative coefficients of thermal expansion are obtained in graphene origami nanotubes. The introduced strategy for controlling the thermo-mechanical properties of graphene metamaterials can open up new avenues for developing thermoelectric devices, heat management systems, and flexible nanoelectronics.

Enhancement of spin-orbit coupling and magnetic scattering in hydrogenated graphene

Spin-orbit coupling (SOC) can provide essential tools to manipulate electron spins in two-dimensional materials like graphene, which is of great interest for both fundamental physics and spintronics application. In this paper, we report the low-field magnetotransport of in situ hydrogenated graphene where hydrogen atoms are attached to the graphene surface in continuous low temperature and vacuum environment. Transition from weak localization to weak antilocalization with increasing hydrogen adatom density is observed, indicating enhancing Bychkov-Rashba-type SOC in a mirror symmetry broken system. From the low-temperature saturation of phase breaking scattering rate, the existence of spin-flip scattering is identified, which corroborates the existence of magnetic moments in hydrogenated graphene.

Dynamics of 3D-island growth on weakly-interacting substrates

The growth dynamics of faceted three-dimensional (3D) Ag islands on weakly-interacting substrates are investigated—using kinetic Monte Carlo (kMC) simulations and analytical modelling—with the objective of determining the critical top-layer radius Rc required to nucleate a new island layer as a function of temperature T, at a constant deposition rate. kMC shows that Rc decreases from 17.3 to 6.0 Å as T is increased at 25 K intervals, from 300 to 500 K. That is, a higher T promotes top-layer nucleation resulting in an increase in island height-to-radius aspect ratios. This explains experimental observations for film growth on weakly-interacting substrates, which are not consistent with classical homoepitaxial growth theory. In the latter case, higher temperatures yield lower top-layer nucleation rates and lead to a decrease in island aspect ratios. The kMC simulation results are corroborated by an analytical mean field model, in which Rc is estimated by calculating the steady-state adatom density on the island side facets and top layer as a function of T. The overall findings of this study constitute a first step toward developing rigorous theoretical models, which can be used to guide synthesis of metal nanostructures, and layers with controlled shape and morphology, on technologically important substrates, including two-dimensional crystals, for nanoelectronic and catalytic applications.

Phase-field method for epitaxial kinetics on surfaces.

We present a procedure for simulating epitaxial growth based on the phase-field method. We consider a basic model in which growth is initiated by a flux of atoms onto a heated surface. The deposited atoms diffuse in the presence of this flux and eventually collide to form islands which grow and decay by the attachment and detachment of migrating atoms at their edges. Our implementation of the phase-field method for this model includes uniform deposition, isotropic surface diffusion, and stochastic nucleation (in both space and time), which creates islands whose boundaries evolve as the surface atoms "condense" into and "evaporate" from the islands. Computations using this model in the submonolayer regime, prior to any appreciable coalescence of islands, agree with the results of kinetic Monte Carlo (KMC) simulations for the coverage-dependence of adatom and island densities and island-size distributions, for both reversible and irreversible growth. The scaling of the island density, as obtained from homogeneous rate equations, agrees with KMC simulations for irreversible growth and for reversible growth for varying deposition flux at constant temperature. For reversible growth with varying temperature but constant flux, agreement relies on an estimate of the formation energy of the critical cluster. Taken together, our results provide a comprehensive analysis of the phase-field method in the submonolayer regime of epitaxial growth, including the verification of the main scaling laws for adatoms and island densities and the scaling functions for island-size distributions, and point to the areas where the method can be extended and improved.

Early stages of growth of Pb, Sn and Ge on Ru(0001): A comparative density functional theory study

As has recently been shown experimentally, adatoms from group 14 exhibit distinct growth characteristics on Ru(0001) at submonolayer coverages. In particular, Pb and Sn atoms agglomerate in dense islands of the c(2 × 4) or c(2 × 8) symmetry with local coverage of 1/2 monolayer (ML), respectively, already for much lower deposition doses, whereas Ge atoms self-assemble in the dilute 21×21 structure with adatom density of 1/7 ML. To trace the observed differences, we employed ab-initio density-functional-theory simulations and followed the early stages of growth of Pb, Sn, and Ge on Ru(0001) in a systematic manner by examining the potential energy surfaces for successive adsorption of up to several atoms of each element within a large surface unit cell. This way the effective lateral interactions between adatoms were recognized in the low-coverage regime, and their most favorable dimer and trimer configurations were identified. Interpreting them as initial building blocks of the adsorbate structure enabled us to clarify the tendency of various considered elements towards formation of a dense or dilute ordered overlayer on Ru(0001) at low nominal coverages.

Nanowire growth and sublimation: CdTe quantum dots in ZnTe nanowires

The role of the sublimation of the compound and of the evaporation of the constituents from the gold nanoparticle during the growth of semiconductor nanowires is exemplified with CdTe-ZnTe heterostructures. Operating close to the upper temperature limit strongly reduces the amount of Cd present in the gold nanoparticle and the density of adatoms on the nanowire sidewalls. As a result, the growth rate is small and strongly temperature dependent, but a good control of the growth conditions allows the incorporation of quantum dots in nanowires with sharp interfaces and adjustable shape, and it minimizes the radial growth and the subsequent formation of additional CdTe clusters on the nanowire sidewalls, as confirmed by photoluminescence. Uncapped CdTe segments dissolve into the gold nanoparticle when interrupting the flux, giving rise to a bulb-like (pendant-droplet) shape attributed to the Kirkendall effect.

Magnetic adatoms in two and four terminal graphene nanoribbons: A comparison between their spin polarized transport

We study the charge and spin transport in two and four terminal graphene nanoribbons (GNR) decorated with random distribution of magnetic adatoms. The inclusion of the magnetic adatoms generates only the z-component of the spin polarized conductance via an exchange bias in the absence of Rashba spin-orbit interaction (SOI), while in presence of Rashba SOI, one is able to create all the three (x, y and z) components. This has important consequences for possible spintronic applications. The charge conductance shows interesting behaviour near the zero of the Fermi energy. Where in presence of magnetic adatoms the familiar plateau at 2e2/h vanishes, thereby transforming a quantum spin Hall insulating phase to an ordinary insulator. The local charge current and the local spin current provide an intuitive idea on the conductance features of the system. We found that, the local charge current is independent of Rashba SOI, while the three components of the local spin currents are sensitive to Rashba SOI. Moreover the fluctuations of the spin polarized conductance are found to be useful quantities as they show specific trends, that is, they enhance with increasing adatom densities. A two terminal GNR device seems to be better suited for possible spintronic applications.

Graphene plasmons in the presence of adatoms

We theoretically investigate graphene plasmons in the presence of a low density of adatoms on the graphene surface. The adatoms can significantly modify the conductivity and plasmonic properties of graphene and may produce a level splitting with the plasmon mode, resulting in two plasmon branches. The high energy branch exhibits large losses and the low energy branch exhibits low losses. Our model may also be considered as a simple model for molecules on graphene and we show that graphene plasmons are sensitive to such changes in the environment. Our microscopic treatment of plasmons and adatoms shows the sensitivity of plasmons and highlights the potential of graphene plasmons for sensing purposes.

Substrate Frequency Effects on Cr x N Coatings Deposited by DC Magnetron Sputtering

Controlled ion bombardment is a popular method to fabricate desirable coating structures and modify their properties. Substrate biasing at high frequencies is a possible technique, which allows higher ion density at the substrate compared with DC current bias. Moreover, high ion energy along with controlled adatom mobility would lead to improved coating growth. This paper focuses on a similar type of study, where effects of coating growth and properties of DC magnetron-sputtered chromium nitride (CrxN) coatings at various substrate bias frequencies are discussed. CrxN coatings were deposited by pulsed DC magnetron sputtering on Inconel 718 and (100) silicon substrates at 110, 160 and 280 kHz frequency at low duty cycle. Coating microstructure and morphology were studied by X-ray diffraction (XRD), atomic force microscopy (AFM), scanning electron microscopy (SEM), scratch adhesion testing and nanoindentation. Results indicate a transformation of columnar into glassy structure of CrxN coatings with the substrate bias frequency increase. This transformation is attributed to preferential formation of the Cr2N phase at high frequencies compared with CrN at low frequencies. Increase in frequency leads to an increase in deposition rate, which is believed to be due to increase in plasma ion density and energy of the incident adatoms. An increase in coating hardness along with decrease in elastic modulus was observed at high frequencies. Scratch tests show a slight increase in coating adhesion, whereas no clear increase in coating roughness can be found with the substrate bias frequency.

Numerical investigation of the submonolayer growth and relaxation of stepped Ag (110) and Au (110) surfaces

The terrace width distribution (TWD) as well as the adatom and island densities for some stepped fcc (110) surfaces with parallel and equidistant steps of equal stiffness are studied by means of kinetic Monte Carlo simulations. Reliable energy barriers for surface diffusion are used. They have been calculated by means of many-body potentials derived within the second moment approximation to the tight-binding model. The effects of the temperature, atom deposition flux and surface diffusion on quantities of interest in the early stage of the surface evolution process have been singled out. In most cases, linear, logarithmic and power-law behaviors are recovered for the evolution of the step width and terrace defects. The TWD is well described by the Gaussian distribution (GD) in the domain of temperature investigated but deviates from the Generalized Wigner Distribution (GWD).

Steps roughening in thermal relaxation and low-coverage growth of sloped Pt(110) and Ir(110) surfaces: A numerical study

The dynamical roughening of [001] steps on sloped Pt (110) and Ir (110) surfaces is investigated by kinetic Monte Carlo simulations. Our model includes deposition, diffusion and fully reversible aggregation on these surfaces with both anisotropic barriers and anisotropic attachment. The barriers for the diffusion processes have been calculated by means of classical molecular dynamics simulations where both metals are modeled by realistic many-body potentials. The roughness is evaluated through calculations of the step width in thermal relaxation of the surface and low-coverage growth conditions. Results indicated a non-trivial behavior of the width in time during relaxation. In growth, power-law behavior is recovered for both metal surfaces. Defects population on terraces is investigated through calculations of adatom and island densities. It is found that at very low temperature (T = 200K for Pt and 400K for Ir and below), a power-law behavior with the growth time is got. Beyond, fluctuations in generated data become important and do not allow to correctly access the true trend of both quantities. Their behavior with the diffusion length at low temperature is singled out.

Permeability and kinetic coefficients for mesoscale BCF surface step dynamics: Discrete two-dimensional deposition-diffusion equation analysis

A discrete version of deposition-diffusion equations appropriate for description of step flow on a vicinal surface is analyzed for a two-dimensional grid of adsorption sites representing the stepped surface and explicitly incorporating kinks along the step edges. Model energetics and kinetics appropriately account for binding of adatoms at steps and kinks, distinct terrace and edge diffusion rates, and possibly asymmetric barriers for attachment to steps. Analysis of adatom attachment fluxes as well as limiting values of adatom densities at step edges for non-uniform deposition scenarios allows determination of both permeability and kinetic coefficients. Behavior of these quantities is assessed as a function of key system parameters including kink density, step attachment barriers, and the step edge diffusion rate.

Graphene Flakes in Arc Plasma: Conditions for the Fast Single-Layer Growth

The results of systematic numerical studies of graphene flakes growth in low-temperature arc discharge plasmas are presented. Diffusion-based growth model was developed, verified using the previously published experiments, and used to investigate the principal effects of the process parameters such as plasma density, electron temperature, surface temperature and time of growth on the size and structure of the plasma-grown graphene flakes. It was demonstrated that the higher growth temperatures result in larger graphene flakes reaching 5 μm, and simultaneously, lead to much lower density of the carbon atoms adsorbed on the flake surface. The low density of the carbon adatoms reduces the probability of the additional graphene layer nucleation on surface of growing flake, thus eventually resulting in the synthesis of the most valuable single-layered graphenes.

Impact of boron on the step-free area formation on Si(111) mesa structures

We report about the influence of boron (B) on surface morphology of Si layers grown by molecular beam epitaxy on Si(111) mesas. Dimension of step-free mesa areas is reduced in comparison to pristine Si and scales with the B-coverage. This can be explained by a reduced mass transport on the Si surface in the presence of B-induced √3 × √3 surface structure which is due to a reduced Si equilibrium free adatom density. We demonstrate that a suitable combination of initial B coverage and Si layer thickness results in large step free areas and B doping concentration up to 4 × 1018 cm−3.

Refined BCF-type boundary conditions for mesoscale surface step dynamics

Deposition on a vicinal surface with alternating rough and smooth steps is described by a solid-on-solid model with anisotropic interactions. Kinetic Monte Carlo (KMC) simulations of the model reveal step pairing in the absence of any additional step attachment barriers. We explore the description of this behavior within an analytic Burton-Cabrera-Frank (BCF)-type step dynamics treatment. Without attachment barriers, conventional kinetic coefficients for the rough and smooth steps are identical, as are the predicted step velocities for a vicinal surface with equal terrace widths. However, we determine refined kinetic coefficients from a two-dimensional discrete deposition-diffusion equation formalism which accounts for step structure. These coefficients are generally higher for rough steps than for smooth steps, reflecting a higher propensity for capture of diffusing terrace adatoms due to a higher kink density. Such refined coefficients also depend on the local environment of the step and can even become negative (corresponding to net detachment despite an excess adatom density) for a smooth step in close proximity to a rough step. Our key observation is that incorporation of these refined kinetic coefficients into a BCF-type step dynamics treatment recovers quantitatively the mesoscale step-pairing behavior observed in the KMC simulations.