Dimer Rows Research Articles

First-principles investigation of hydrogen-related reactions on (100)–(2 × 1)[formula omitted]H diamond surfaces

Hydrogen radical attacks and subsequent hydrogen migrations are considered to play an important role in the atomic-scale mechanisms of diamond chemical vapour deposition growth. We perform a comprehensive analysis of the reactions involving H-radical and vacancies on H-passivated diamond surfaces exposed to hydrogen radical-rich atmosphere. By means of first principles calculations—density functional theory and climbing image nudged elastic band method—transition states related to these mechanisms are identified and characterised. In addition, accurate reaction rates are computed using variational transition state theory. Together, these methods provide—for a broad range of temperatures and hydrogen radical concentrations—a picture of the relative likelihood of the migration or radical attack processes, along with a statistical description of the hydrogen coverage fraction of the (100) H-passivated surface, refining earlier results via a more thorough analysis of the processes at stake. Additionally, the migration of H-vacancy is shown to be anisotropic, and occurring preferentially across the dimer rows of the reconstructed surface. The approach used in this work can be generalised to other crystallographic orientations of diamond surfaces or other semiconductors.

Isolated Pb adstructures on Ge(1 0 0) slabs with variable thickness

The adsorption of an isolated monomer (1 Pb adatom), dimer (2 Pb adatoms), and infinite Pb 1D chain on the Ge(100) oriented slabs of different thickness are studied using density functional theory. It was found that the energetically most favourable atomic configurations of the Pb monomers are independent of the slab thickness. On the other hand, the alternative monomer structure with Pb adatom located between two Ge-up atoms from adjacent dimer rows depends considerably on the slab thickness – the structural and electronic structures of this monomer obtained with the use of 6 and 12 layers slab are very different. The geometry and electronic structure of the parallel inter-dimer-row configuration of Pb on Ge(100) surface are reliably reproduced by relatively thin asymmetric slabs, however, structural and electronic properties of the perpendicular inter-dimer-row configuration of Pb are quite sensitive to the number of layers in the slab.

Dimer Coupling Energies of the Si(001) Surface.

The coupling energies between the buckled dimers of the Si(001) surface were determined through analysis of the anisotropic critical behavior of its order-disorder phase transition. Spot profiles in high-resolution low-energy electron diffraction as a function of temperature were analyzed within the framework of the anisotropic two-dimensional Ising model. The validity of this approach is justified by the large ratio of correlation lengths, ξ_{∥}^{+}/ξ_{⊥}^{+}=5.2 of the fluctuating c(4×2) domains above the critical temperature T_{c}=(190.6±10) K. We obtain effective couplings J_{∥}=(-24.9±1.3) meV along the dimer rows and J_{⊥}=(-0.8±0.1) meV across the dimer rows, i.e., antiferromagneticlike coupling of the dimers with c(4×2) symmetry.

Concurrent Characterization of Surface Diffusion and Intermixing of Ge on Si: A Classical Molecular Dynamics Study

AbstractThe surface diffusion and intermixing of Ge ad‐atoms over Si (001) 2 × 1 substrates using classical molecular dynamics (CMD) simulations are characterized here. Several interatomic potentials, parametrizations, and parameter mixing rules are contemplated. A novel simulation scheme is devised to characterize the effective frequency of surface diffusion and intermixing events overcoming the inherent difficulties related to their interdependency in heteroepitaxial systems. The effective energy barriers of these events encompass different atomistic mechanisms weighted by their occurrence probabilities. The overall description of surface diffusion and intermixing based on Stillinger–Weber (SW) potential is in agreement with ab initio calculations and experimental observations, though some atomistic details differ. This study is extended to Si(001) substrates with stressed Ge monolayers grown on top. It is found that Ge ad‐atom dynamics is accelerated with respect to the case of the pure Si substrate and that diffusion across dimer rows is mainly mediated by the atomic exchange of the Ge ad‐atom with a Ge atom on the surface.

The relationship between the adsorption configuration and fermi energy levels in the conversion process of Li2S6/Li2S8 on the ZrO2 surface

The transition metal oxide ZrO2 can clearly adsorb large lithium-sulfur rings (Li2S6 and Li2S8) and exhibits good conversion performance. To study the adsorption strengths of Li2S6/8, the configuration evolution and adsorption energies of Li2S6 and Li2S8 on the ZrO2 surfaces of tetragonal (t-ZrO2), cubic (c-ZrO2), and monoclinic (m-ZrO2) are calculated by a first-principles method. The results show that the Fermi level controls the adsorption and conversion strength. The relationship between the Fermi level in the partial densities of state (PDOS) and the adsorption strength of the large lithium-sulfur ring is studied for the three surfaces formed by the different crystal structures of ZrO2. The crystal structure of ZrO2 can affect the Fermi energy level of S and Zr when Li2S6/Li2S8 adsorbs on the ZrO2 surface. A change from p-type catalysis for Li2S6 and Li2S8 on the t-ZrO2 surface to the N-type catalysis model on the m-ZrO2 surface is established based on the change in the Fermi level. The c-ZrO2 conversion surface, the Fermi energy of which level is located between the valence and conduction bands, has the moderate adsorption energy. Double Li atoms adsorption on the dimer row of O atoms bridge not only leads to ring opening but also breaks the long chain to degrade Li2S6/Li2S8.

Atomic Imaging of Interface Defects in an Insulating Film on Diamond.

The insulator/semiconductor interface structure is the key to electric device performance, and much interest has been focused on understanding the origin of interfacial defects. However, with conventional techniques, it is difficult to analyze the interfacial atomic structure buried in the insulating film. Here, we reveal the atomic structure at the interface between an amorphous aluminum oxide and diamond using a developed electron energy analyzer for photoelectron holography. We find that the three-dimensional atomic structure of a C-O-Al-O-C bridge between two dimer rows of the hydrogen-terminated diamond surface. Our results demonstrate that photoelectron holography can be used to reveal the three-dimensional atomic structure of the interface between a crystal and an amorphous film. We also find that the photoelectron intensity originating from the C-O bonds is strongly related to the interfacial defect density. We anticipate significant progress in the study of amorphous/crystalline interfaces based on their three-dimensional atomic structures analysis.

Enhanced Atomic Precision Fabrication by Adsorption of Phosphine into Engineered Dangling Bonds on H-Si Using STM and DFT.

The doping of Si using the scanning probe hydrogen depassivation lithography technique has been shown to enable placing and positioning small numbers of P atoms with nanometer accuracy. Several groups have now used this capability to build devices that exhibit desired quantum behavior determined by their atomistic details. What remains elusive, however, is the ability to control the precise number of atoms placed at a chosen site with 100% yield, thereby limiting the complexity and degree of perfection achievable. As an important step toward precise control of dopant number, we explore the adsorption of the P precursor molecule, phosphine, into atomically perfect dangling bond patches of intentionally varied size consisting of three adjacent Si dimers along a dimer row, two adjacent dimers, and one single dimer. Using low temperature scanning tunneling microscopy, we identify the adsorption products by generating and comparing to a catalog of simulated images, explore atomic manipulation after adsorption in select cases, and follow up with incorporation of P into the substrate. For one-dimer patches, we demonstrate that manipulation of the adsorbed species leads to single P incorporation in 12 out of 12 attempts. Based on the observations made in this study, we propose this one-dimer patch method as a robust approach that can be used to fabricate devices where it is ensured that each site of interest has exactly one P atom.

Towards π-wires on a semiconductor surface: Benzyne on Si(001).

Towards the goal of covalently bound molecular wires on silicon, the adsorption of benzyne on Si(001) was studied by means of scanning tunneling microscopy (STM), X-ray photoelectron spectroscopy (XPS), ultraviolet photoelectron spectroscopy (UPS), and density functional calculations (DFT). The benzyne molecule is found to adsorb preferentially via the strained triple bond on one dimer of the Si(001) surface which results in an intact π system covalently bound to the surface. With increasing coverage, the molecules primarily adsorb along the dimer rows; on stepped surfaces, these molecular wires are all oriented in the same direction.

Adsorbate‐Induced Modifications in the Optical Response of the Si(553)–Au Surface

The conductivity of substrate‐supported metallic nanowires can be adjusted, e.g., by strain or adsorbates. In this article, the effect of atomic hydrogen and toluene‐3,4‐dithiol (TDT) adsorption on the quasi‐1D structures of the Si(553)‐(5 × 2)–Au reconstruction is investigated. Reflectance anisotropy spectroscopy (RAS) and infrared ellipsometry reveal optical signatures of the surface. Spectral modifications related to the adsorbate exposure suggest the activation of adsorption‐induced interband transitions. Density functional theory (DFT) calculations reproduce the spectral modifications and explain their origin. Preferential adsorption on sites located at the step edges of the structure occurs independent of the type of adsorbate and induces a charge transfer between electronic states related to the step edges and the Au dimer rows. This charge redistribution modifies the electronic structure close to the Fermi level, enhances the dimerization of the Au chains, and strongly influences the low‐energy region of the RAS spectra. While previous studies employed atomic H as a chief adsorbate, it is shown here that even molecular H deeply modifies the Si(553)–Au optical response. Structural modification of Au–Si(553) by H and TDT adsorbates as suggested from recent ab initio calculations are verified.

Indirect mechanism of Au adatom diffusion on the Si(100) surface

Calculations of the diffusion of a Au adatom on the dimer reconstructed Si(100)-2x1 surface reveal an interesting mechanism that differs significantly from a direct path between optimal binding sites, which are located in between dimer rows. Instead, the active diffusion mechanism involves promotion of the adatom to higher energy sites on top of a dimer row and then fast migration along the row, visiting ca. a hundred sites at room temperature, before falling back down into an optimal binding site. This top-of-row mechanism becomes more important the lower the temperature is. The calculations are carried out by finding minimum energy paths on the energy surface obtained from density functional theory within the PBEsol functional approximation followed by kinetic Monte Carlo simulations of the diffusion over a range of temperature from 200 K to 900 K. While the activation energy for the direct diffusion mechanism is calculated to be 0.84 eV, the effective activation energy for the indirect mechanism is on average 0.56 eV.

Theoretical study of the initial stages of Ba growth on Si(100) substrate

We present theoretical study based on DFT calculations of the initial stages of Ba growth on Si(100) substrate. The obtained results indicate the possibility of coexistence of the inter-row and intra-row Ba monomers, as predicted by reported earlier STM measurements – the inter-row configuration has only 0.15 eV lower energy than the intra-row system. The detailed analysis of the atomic and electronic structures of both monomers have been performed. It was found that in all cases Ba adatom tends to interact with silicon surface atoms with higher vertical position.Presented study shows that the presence of both types of Ba monomer increases the local chemical reactivity of silicon surface, however this effect is stronger for the inter-row configuration. It was shown that such modification of substrate reactivity influences the form of the further aggregation of Ba adatoms. The obtained results indicate the tendency to formation by adatoms of linear-zigzag chains across the surface dimer rows, which seems to be in the agreement with reported earlier STM data.

A Synchrotron Radiation Photoemission Study of SiGe(001)-2×1 Grown on Ge and Si Substrates: The Surface Electronic Structure for Various Ge Concentrations.

Beyond the macroscopic perspective, this study microscopically investigates Si1−xGex(001)-2×1 samples that were grown on the epi Ge(001) and epi Si(001) substrates via molecular-beam epitaxy, using the high-resolution synchrotron radiation photoelectron spectroscopy (SRPES) as a probe. The low-energy electron diffraction equipped in the SRPES chamber showed 2×1 double-domain reconstruction. Analyses of the Ge 3d core-level spectra acquired using different photon energies and emission angles consistently reveal the ordered spots to be in a Ge–Ge tilted configuration, which is similar to that in epi Ge(001)-2×1. It was further found that the subsurface layer was actually dominated by Ge, which supported the buckled configuration. The Si atoms were first found in the third surface layer. These Si atoms were further divided into two parts, one underneath the Ge–Ge dimer and one between the dimer row. The distinct energy positions of the Si 2p core-level spectrum were caused by stresses, not by charge alternations.

Mechanisms for Graphene Growth on SiO2 Using Plasma-Enhanced Chemical Vapor Deposition: A Density Functional Theory Study.

Plasma-enhanced chemical vapor deposition (PE-CVD) of graphene layers on dielectric substrates is one of the most important processes for the incorporation of graphene in semiconductor devices. Graphene is moving rapidly from the laboratory to practical implementation; therefore, devices may take advantage of the unique properties of such nanomaterial. Conventional approaches rely on pattern transfers after growing graphene on transition metals, which can cause nonuniformities, poor adherence, or other defects. Direct growth of graphene layers on the substrates of interest, mostly dielectrics, is the most logical approach, although it is not free from challenges and obstacles such as obtaining a specific yield of graphene layers with desired properties or accurate control of the growing number of layers. In this work, we use density-functional theory (DFT) coupled with ab initio molecular dynamics (AIMD) to investigate the initial stages of graphene growth on silicon oxide. We select C2H2 as the PE-CVD precursor due to its large carbon contribution. On the basis of our simulation results for various surface models and precursor doses, we accurately describe the early stages of graphene growth, from the formation of carbon dimer rows to the critical length required to undergo dynamical folding that results in the formation of low-order polygonal shapes. The differences in bonding with the functionalization of the silicon oxide also mark the nature of the growing carbon layers as well as shed light of potential flaws in the adherence to the substrate. Finally, our dynamical matrix calculations and the obtained infrared (IR) spectra and vibrational characteristics provide accurate recipes to trace experimentally the growth mechanisms described and the corresponding identification of possible stacking faults or defects in the emerging graphene layers.

Analysis of Al adatoms random hopping on Si(100)-c(4 [formula omitted] 2) surface observed by STM at low temperature: Determination of the hopping barriers

Mobility of single aluminium atoms adsorbed on Si(100)-c(4×2) surface was studied by means of scanning tunneling microscopy (STM) at a temperature of 115 K. Due to a strongly anisotropic surface migration along silicon dimer rows the hopping in one-dimensional (1-D) bounded areas of various sizes was observed. Distributions of distances traversed in a time between acquisition of two subsequent STM images were obtained. The experimental conditions were interpreted by a model of 1-D random walk of Al adatoms in areas of limited size with reflective boundaries. Kinetic Monte Carlo (KMC) simulations were used for analysing dependence of a calculated activation energy for a single hop on a size of the 1-D bounded area. The developed method allowed restoration of a real value of the activation energy for the Al adatom hopping in a direction parallel to the silicon dimer rows unaffected by the limited size of the bounded area. The activation energy for hops in a direction perpendicular to the dimer rows was estimated from a distribution of time intervals between individual perpendicular hops.

3D kinetic Monte-Carlo simulations of diamond growth on (1 0 0) surfaces

A 3D Kinetic Monte-Carlo (KMC) model is implemented and used to simulate the growth of (1 0 0)-oriented diamond films. The model considers four processes: adsorption and desorption of CH3 radicals, etching of carbon atoms and migration of adsorbed radicals. The atomic structure of diamond is taken into account including the formation of dimer rows on the surface. The model correctly reproduces the step-flow growth mechanism of diamond (1 0 0) surfaces and the obtained growth rates are close to experimental data. The propagation of the steps shows a clear anisotropy. Steps are usually two atomic layers high but step bunching can be observed in presence of defects. The model thus can be used as a predictive tool to obtain growth rates and to understand the effect of atomic interactions on the film morphology.

High-resolution RHEED analysis of dynamics of low-temperature superstructure transitions in Ge/Si(001) epitaxial system

In this paper, we analyze superstructural transitions during epitaxial growth of two-dimensional layers and the formation of quantum dots by the Stranski–Krastanov mechanism in elastically stressed systems by the reflection high-energy electron diffraction method. Detailed dependences of the periodicity parameter N of the 2 × N reconstruction on the effective thickness of the deposited material in a wide range of growth temperatures during epitaxy of germanium on a silicon surface with a crystallographic orientation (001) are obtained. Superstructural transitions and the change in the value of the parameter N at low temperatures of epitaxy in this system have been investigated for the first time. It is shown that the length of dimer rows in such a reconstruction during the growth of pure germanium on silicon can reach a value of no less than N = 11. A relationship is found between the value of the parameter N, determined by elastic strains in the system, and the critical thickness of the transition from two-dimensional to three-dimensional growth. Based on this relationship, a physical mechanism is proposed that explains the nature of the temperature dependence of the critical thickness of the Stranski–Krastanov transition, which has been the subject of constant scientific disputes until now.

Drift of two-dimensional vacancy islands on the Si(100) surface under electromigration conditions

The paper presents an experimental study of morphological changes of the Si(100) surface under electromigration conditions that was carried out using the in situ method involving ultrahigh vacuum reflection electron microscopy. The study aims to determine the temperature dependence of the effective electric charge of an adsorbed atom on the Si(100) surface. A system of concentric two-dimensional vacancy islands was formed on the surface of Si(100) samples by low-energy argon ion sputtering and subsequent high-temperature annealing. Quasi-equilibrium conditions were created on the sample surface by compensating the sublimating flow from the surface from an external silicon source. The video images of the drift of vacancy islands were recorded under the conditions of electromigration with the compensation of sublimation. Based on the processing and analysis of video images, the authors described the dependence of the velocity of motion of vacancy islands on the Si(100) surface for various temperatures and the direction of the electric current along and across the dimer rows with the (2 × 1) superstructure inside the island. It is shown that the drift rate of vacancy islands does not depend on their size under quasi-equilibrium conditions. A simplified one-dimensional theoretical model has been constructed. It includes one atomic step moving by a detachment of atoms from the step and their drift under the force of electromigration in the absence of desorption and deposition of atoms on the surface. Based on the proposed model, the effective electric charge is estimated, and the temperature dependence of the effective charge in the temperature range of 1010 to 1120 °C is obtained. The absolute value of the effective charge decreases linearly with increasing temperature. The sign of the effective charge is negative, and its average value is Z = –0.5 ± 0.3 elementary charges. The obtained results can be used for creating structures with a countable number of atomic steps and act as secondary measures of height with reference to the silicon crystal lattice.

Atomic surface control of Ge(100) in MOCVD reactors coated with (Ga)As residuals

Heteroepitaxy of planar, low-defect III-V semiconductor layers on Ge(100) requires a single-domain substrate surface, where dimer rows are aligned in parallel on atomically well-ordered terraces, which are separated by steps of even numbered atomic height. The presence of Ga and As in the sample ambience crucially impacts the preparation of such Ge(100) surfaces. Ga and As are commonly omnipresent, when applying metalorganic chemical vapor deposition (MOCVD), either directly supplied by precursors, in the form of MOCVD reactor residuals, or both. We study the impact of the growth conditions on the Ge(100) surface formation in situ, in dependence on the reactor pre-conditioning, the type of As supply, and/or temperature, utilizing surface-sensitive reflection anisotropy spectroscopy. We benchmark the in situ spectra to in system X-ray photoelectron spectroscopy, low energy electron diffraction and scanning tunneling microscopy. We find that interaction of tertiarybutylarsine (TBAs) with a coating of the inner MOCVD reactor walls by GaAs residuals favors desorption of As from reactor parts resulting in As-dimers on the Ge(100) surface, which are rotated by 90° compared to preparation routes employing TBAs in Ga-free ambience. The optical in situ control enables precise adjustment and switching between distinct Ge(100) surface reconstructions for subsequent III-V heteroepitaxy.

AlCl3-Dosed Si(100)-2 × 1: Adsorbates, Chlorinated Al Chains, and Incorporated Al

The adsorption of AlCl$_{3}$ on Si(100) and the effect of annealing the AlCl$_{3}$-dosed substrate was studied to reveal key surface processes for the development of atomic-precision acceptor-doping techniques. This investigation was performed via scanning tunneling microscopy (STM), X-ray photoelectron spectroscopy (XPS), and density functional theory (DFT) calculations. At room temperature, AlCl$_{3}$ readily adsorbed to the Si substrate dimers and dissociated to form a variety of species. Annealing of the AlCl$_{3}$-dosed substrate at temperatures below 450 $^{\circ}$C produced unique chlorinated aluminum chains (CACs) elongated along the Si(100) dimer row direction. An atomic model for the chains is proposed with supporting DFT calculations. Al was incorporated into the Si substrate upon annealing at 450 $^{\circ}$C and above, and Cl desorption was observed for temperatures beyond 450 $^{\circ}$C. Al-incorporated samples were encapsulated in Si and characterized by secondary ion mass spectrometry (SIMS) depth profiling to quantify the Al atom concentration, which was found to be in excess of 10$^{20}$ cm$^{-3}$ across a $\sim$2.7 nm thick $\delta$-doped region. The Al concentration achieved here and the processing parameters utilized promote AlCl$_{3}$ as a viable gaseous precursor for novel acceptor-doped Si materials and devices for quantum computing.

Determination of the preferred reaction pathway of acetophenone on Si(001) using photoelectron diffraction

The adsorption configurations of a technologically relevant model organic adsorbate on the silicon (001) surface were studied using energy scanned x-ray photoelectron diffraction (PhD). Previous work has established the existence of an interesting vertically-aligned (‘flagpole’) configuration, where the acetophenone attaches to Si(001) via the acetyl group carbon and oxygen atoms. Density functional theory calculations have predicted two energetically similar variants of this structure, where the phenyl ring is orientated parallel or perpendicular to the rows of silicon dimers on this reconstructed surface. However, previously published experimental measurements, including scanning tunnelling microscopy, x-ray photoelectron spectroscopy, and near-edge x-ray absorption fine structure investigations were unable to distinguish between these two configurations. Here, we apply the unique experimental capabilities of the PhD technique to this system and demonstrate that the dominant adsorption configuration has the phenyl ring parallel to the dimer rows (the end-bridge structure). This information in turn facilitates the determination of the dominant reaction pathway for acetophenone on Si(001), which has remained elusive until now. Information about subtle preferences in reaction pathways that affect the alignment and orientation of organic adsorbates such as acetophenone on technologically-relevant semiconductor surfaces such as Si(001) is critical for the fabrication of future atomically-precise atomic and molecular-scale electronic devices utilising the organic-silicon interface, and this work demonstrates the unique and complementary capabilities of PhD for providing this information.