Two-dimensional (2D) materials are strongly affected by the dielectric environment including substrates, making it an important factor in designing materials for quantum and electronic technologies. Yet, first-principles evaluation of charged defect energetics in 2D materials typically do not include substrates due to the high computational cost. We present a general continuum model approach to incorporate substrate effects directly in density-functional theory calculations of charged defects in the 2D material alone. We show that this technique accurately predicts charge defect energies compared to much more expensive explicit substrate calculations, but with the computational expediency of calculating defects in free-standing 2D materials. Using this technique, we rapidly predict the substantial modification of charge transition levels of two defects in MoS$_2$ and ten defects promising for quantum technologies in hBN, due to SiO$_2$ and diamond substrates. This establishes a foundation for high-throughput computational screening of new quantum defects in 2D materials that critically accounts for substrate effects.
The growth process of single layer graphene with and without substrate is investigated using ab initio, finite temperature molecular dynamic calculations within density functional theory. An understanding of the epitaxial graphene growth mechanisms in the atomic level is provided by exploring the transient stages which occur at the growing edges of graphene. These stages are formation and collapse of large carbon rings together with the formation and healing of Stone-Wales like pentagon-heptagon defects. The activation barriers for the healing of these growth induced defects on various substra…
GaN-nanorods grown on Si(111) substrates are found strain- and defect-free as characterized by micro Raman spectroscopy, secondary electron (SE) and cathode-luminescence (CL) imaging. The matrix supporting the nanorods bears the brunt of all strains, strain-relaxations, and defect generations, giving the nanorods an ideal environment to grow to perfection. Photo-excitations by the Raman laser source and electron irradiation during CL imaging lead to an increase of non-equilibrium electrons, suggesting an effective approach to photo-emitting or field emitting device applications. The nanorods, …
High-quality Sb2Te3 films are obtained by molecular beam epitaxy on graphene substrate and investigated by in situ scanning tunneling microscopy/spectroscopy. Intrinsic defects responsible for the natural p-type conductivity of Sb2Te3 are identified to be the Sb vacancies and SbTe antisites in agreement with first-principles calculations. By minimizing defect densities, coupled with a transfer doping by the graphene substrate, the Fermi level of Sb2Te3 thin films can be tuned over the entire range of the bulk band gap. This establishes the necessary condition to explore topological insulator b…
A novel bilayer is introduced, consisting of a stiff film adhered to a soft substrate with patterned holes beneath the film and substrate interface. To uncover the transition of surface patterns, two dimensional plane strain simulations are performed on the defected bilayer subjected to uniaxial compression. Although the substrate is considered as the linear elastic material, the presence of defects can directly trigger the formation of locally ridged and then folding configurations from flat surface with a relatively small compressive strain. It is followed by the coexisting phases of folds a…
Precise and scalable defect engineering of 2D nanomaterials is acutely sought-after in contemporary materials science. Here we present defect engineering in monolayer graphene and molybdenum disulfide (MoS$_2$) by irradiation with noble gas ions at 30 keV. Two ion species of different masses were used in a gas field ion source microscope: helium (He$^+$) and neon (Ne$^+$). A detailed study of the introduced defect sizes and resulting inter-defect distance with escalating ion dose was performed using Raman spectroscopy. Expanding on existing models, we found that the average defect size is cons…
Monolayer MoS$_2$ has emerged as an interesting material for nanoelectronic and optoelectronic devices. The effect of substrate screening and defects on the electronic structure of MoS$_2$ are important considerations in the design of such devices. Here, we present ab initio density functional theory (DFT) and GW calculations to study the effect of substrate screening on the quasiparticle band gap and defect charge transition levels (CTLs) in monolayer MoS$_2$. We find a giant renormalization to the free-standing quasiparticle band gap by 350 meV and 530 meV in the presence of graphene and gra…
The combination of two-dimensional (2D) materials into heterostructures enabled the formation of atomically thin devices with designed properties. To achieve a high density, bottom-up integration, the growth of these 2D heterostructures via van der Waals epitaxy (vdWE) is an attractive alternative to the currently mostly employed mechanical transfer, which is still problematic in terms of scaling and reproducibility. However, controlling the location of the nuclei formation remains a key challenge in vdWE. Here, we use a focused He ion beam for a deterministic placement of defects in graphene …
We report catalyst-free direct synthesis of vertical graphene nanosheets (VGNs) on SiO2/Si and quartz substrates using microwave electron cyclotron resonance - plasma enhanced chemical vapor deposition. The evolution of VGNs is studied systematically at different growth stages. Raman analysis as a function of growth time reveals that two different disorder-induced competing mechanisms contributing to the defect band intensity. The VGNs grown on SiO2/Si substrates predominantly consists of both vacancy-like and hopping defects. On the other hand, the VGNs grown on quartz substrates contain main…
The engineering of defects in diamond, particularly nitrogen-vacancy (NV) centers, is important for many applications in quantum science. A materials science approach based on chemical vapor deposition (CVD) growth of diamond and in-situ nitrogen doping is a promising path toward tuning and optimizing the desired properties of the embedded defects. Herein, with the coherence of the embedded defects in mind, we explore the effects of substrate miscut on the diamond growth rate, nitrogen density, and hillock defect density, and we report an optimal angle range between 0.66° < θ < 1.16° for the p…
We present Molecular Dynamics simulations of one- and two-dimensional bead-spring models sliding on incommensurate substrates. We investigate how sliding friction is affected by interaction anharmonicity and structural defects. In their absence, we confirm earlier findings, namely, that at special resonance sliding velocities, friction is maximal. When sliding off-resonance, partially thermalized states are possible, whereby only a small number of vibrational modes becomes excited, but whose kinetic energies are already Maxwell-Boltzmann distributed. Anharmonicity and defects typically destroy…
The defect relaxation volumes obtained from density-functional theory (DFT) calculations of charged vacancies and interstitials are much larger than their neutral counterparts, seemingly unphysically large. In this work, we investigate the possible reasons for this and revisit the methods that address the calculation of charged defect structures in periodic DFT. We probe the dependence of the proposed energy corrections to charged defect formation energies on relaxation volumes and find that corrections such as the image charge correction and the alignment correction, which can lead to sizable…
A new pyramidal structural defect, 5 to 8 micron wide, has been discovered in thin films of epitaxial erbium disilicide formed by annealing thin Er films on Si(001) substrates at temperatures of 500 to 800C. Since these defects form even upon annealing in vacuum of TiN-capped films their formation is not due to oxidation. The pyramidal defects are absent when the erbium disilicide forms on amorphous substrates, which suggests that epitaxial strains play an important role in their formation. We propose that these defects form as a result of the separation of the silicide film from the substrate…
Since oxide materials like Sr$_2$FeMoO$_6$ are usually applied as thin films, we studied the effect of biaxial strain, resulting from the substrate, on the electronic and magnetic properties and, in particular, on the formation energy of point defects. From our first-principles calculations, we determined that the probability of forming point defects - like vacancies or substitutions - in Sr$_2$FeMoO$_6$ could be adjusted by choosing a proper substrate. For example, the amount of anti-site disorder can be reduced with compressive strain in order to obtain purer Sr$_2$FeMoO$_6$ as needed for sp…
Charged point defects in materials are widely studied using Density Functional Theory (DFT) packages with periodic boundary conditions. The formation energy and defect level computed from these simulations need to be corrected to remove the contributions from the spurious long-range interaction between the defect and its periodic images. To this effect, the CoFFEE code implements the Freysoldt-Neugebauer-Van de Walle (FNV) correction scheme. The corrections can be applied to charged defects in a complete range of material shapes and size: bulk, slab (or two-dimensional), wires and nanoribbons.…
We propose a new finite-size correction scheme for the formation energy of charged defects and impurities in one-dimensional systems within density functional theory. The energy correction in a supercell geometry is obtained by solving the Poisson equation in a continuum model which is described by an anistrotropic permittivity tensor, with the defect charge distribution derived from first-principles calculations. We implement our scheme to study impurities and dangling bonds in silicon nanowires and demonstrate that the formation energy of charged defects rapidly converges with the supercell …
Generally adopted design strategies for enhancing the photocatalytic activity are aimed at tuning properties such as the visible light response, the exposed crystal facets, and the nanocrystal shape. Here, we present a different approach for designing efficient photocatalysts displaying a substrate-specific reactivity upon defect engineering. The defective anisotropic brookite TiO2 photocatalyst functionalized with Pt nanocrystals are tested for alcohol photoreforming showing up to an 11-fold increase in methanol oxidation rate, compared to the unreduced one, whilst presenting much lower ethan…
Hybrid halide perovskites such as methylammonium lead iodide (CH3NH3PbI3) exhibit unusually low free carrier concentrations despite being processed at low-temperatures from solution. We demonstrate, through quantum mechanical calculations, that the origin of this phenomenon is a prevalence of ionic over electronic disorder in stoichiometric materials. Schottky defect formation provides a mechanism to self-regulate the concentration of charge carriers through ionic compensation of charged point defects. The equilibrium charged vacancy concentration is predicted to exceed 0.4% at room temperatur…
Chemical, mechanical, thermal and/or electronic properties of bulk or low-dimensional materials can be engineered by introducing structural defects to form novel functionalities. When using particles irradiation, these defects can be spatially arranged to create complex structures, like sensing circuits, where the spatial resolution of the defective areas plays a fundamental role. Here, we show that structural defects can be patterned by low-energy electrons in monolayer graphene sheets with spatial resolution strongly defined by the surface of the supporting substrate. Indeed, two-dimensional…
We propose a direct self-assembly mechanism towards obtaining defect-free perpendicular lamellar phases of diblock copolymer (BCP) thin films. In our numerical study, a thin BCP film having a flat top surface is casted on a uni-directional corrugated solid substrate. The substrate is treated chemically and has a weak preference toward one of the two BCP components. Employing self-consistent field theory (SCFT), we find that there is an enhanced synergy between two substrate characteristics: its topography (geometrical roughness) combined with a weak surface preference. This synergy produces th…
Intrinsic and extrinsic disorder from lattice imperfections, substrate and environment has a strong effect on the local electronic structure and hence the optical properties of atomically thin transition metal dichalcogenides that are determined by strong Coulomb interaction. Here, we examine the role of the substrate material and intrinsic defects in monolayer MoS2 crystals on SiO2 and hBN substrates using a combination of scanning tunneling spectroscopy, scanning tunneling microscopy, optical absorbance, and low-temperature photoluminescence measurements. We find that the different substrate…
A perfectly compliant substrate would allow the monolithic integration of high-quality semiconductor materials such as Ge and III-V on Silicon (Si) substrate, enabling novel functionalities on the well-established low-cost Si technology platform. Here, we demonstrate a compliant Si substrate allowing defect-free epitaxial growth of lattice mismatched materials. The method is based on the deep patterning of the Si substrate to form micrometer-scale pillars and subsequent electrochemical porosification. The investigation of the epitaxial Ge crystalline quality by X-ray diffraction, transmission …
We show the evolution of Raman spectra with number of graphene layers on different substrates, SiO$_{2}$/Si and conducting indium tin oxide (ITO) plate. The G mode peak position and the intensity ratio of G and 2D bands depend on the preparation of sample for the same number of graphene layers. The 2D Raman band has characteristic line shapes in single and bilayer graphene, capturing the differences in their electronic structure. The defects have a significant influence on the G band peak position for the single layer graphene: the frequency shows a blue shift upto 12 cm$^{-1}$ depending on th…
We evaluate the autocorrelation function of the electrostatic potential in doped graphene due to nearby charged impurities. The screening of those impurities is described by a combination of the polarization function for graphene in random phase approximation with the electrostatic Green's function of the surrounding dielectrics. Using the hard-disk model for a two-dimensional distribution of impurities, we show that large correlation lengths between impurities can give rise to anti-correlation in the electrostatic potential, in agreement with recent experiments.
A simplified density functional theory (DFT) method for charged adsorbates on an ultrathin, insulating film supported by a metal substrate is developed and presented. This new method is based on a previous DFT development that uses a perfect conductor (PC) model to approximate the electrostatic response of the metal substrate, while the film and the adsorbate are both treated fully within DFT [I. Scivetti and M. Persson, Journal of Physics: Condensed Matter 25, 355006 (2013)]. The missing interactions between the metal substrate and the insulating film in the PC approximation are modelled by a…
The effects of a step defect and a random array of point defects (such as vacancies or substitutional impurities) on the force of friction acting on a xenon monolayer film as it slides on a silver (111) substrate are studied by molecular dynamic simulations and compared with the results of lowest order perturbation theory in the substrate corrugation potential. For the case of a step, the magnitude and velocity dependence of the friction force are strongly dependent on the direction of sliding respect to the step and the corrugation strength. When the applied force F is perpendicular to the st…
Charged defects in 2D materials have emerging applications in quantum technologies such as quantum emitters and quantum computation. Advancement of these technologies requires rational design of ideal defect centers, demanding reliable computation methods for quantitatively accurate prediction of defect properties. We present an accurate, parameter-free and efficient procedure to evaluate quasiparticle defect states and thermodynamic charge transition levels of defects in 2D materials. Importantly, we solve critical issues that stem from the strongly anisotropic screening in 2D materials, that…
Sol gel obtained YZS (Yttria Stabilized Zirconia) nanocrystals have different morphologies when they grow on an $α$-alumina substrate after thermal treatment. When the substrate has planar defects, the nanocrystals grow in height and are narrow with a crystallographic orientation [111] in the vertical direction, while when the substrate is a perfect plane at the nanometric scale, the nanocrystals are rather extended over the substrate and do not grow in height, with a crystallo- graphic orientation [100] in the vertical direction. We present here a Monte Carlo approach which computes the actio…
A methodology for calculating the contribution of charged defects to the configurational free energy of an ionic crystal is introduced. The temperature-independent Wang-Landau Monte Carlo technique is applied to a simple model of a solid electrolyte, consisting of charged positive and negative defects on a lattice. The electrostatic energy is computed on lattices with periodic boundary conditions, and used to calculate the density of states and statistical-thermodynamic potentials of this system. The free energy as a function of defect concentration and temperature is accurately described by a…
Charged-defect calculation using a periodic supercell is a significant class of problems in solid state physics. However, the finite supercell size induces an undesirable long-range image charge Coulomb interaction. Although a variety of methods have been proposed to eliminate such image Coulomb interaction, most of the previous schemes are based on a rough approximation of the defect charge screening. In this work, we present a rigorous derivation of the image charge interaction with a new defect screening model where the use of bulk macroscopic dielectric constant can be avoided. We have ver…
The healing of graphene grown from a metallic substrate is investigated using tight-binding Monte Carlo simulations. At temperatures (ranging from 1000 to 2500 K), an isolated graphene sheet can anneal a large number of defects suggesting that their healing are thermally activated. We show that in presence of a nickel substrate we obtain a perfect graphene layer. The nickel-carbon chemical bonds keep breaking and reforming around defected carbon zones, providing a direct interaction, necessary for the healing. Thus, the action of Ni atoms is found to play a key role in the reconstruction of th…
We propose the phenomenological description of ferroelectric disordering in ferroelectric-semiconductors caused by charged impurities with the charge density random fluctuations. The material improper conductivity is proportional to the averaged impurity charge density. For high enough conductivity free carriers screen fluctuations in the absence of an external field. When external electric field is applied, inner field fluctuations and dynamical induction fluctuations appear in the inhomogeneously polarized system "charged defect + screening cloud". We show that the macroscopic state of ferro…
Oxygen octahedra tilting is a common structural phenomenon in perovskites and has been subject of intensive studies, particularly in rhombohedral Pb(Zr,Ti)O3 (PZT). Early reports suggest that the tilted octahedra may strongly affect the domain switching behavior, dielectric and piezoelectric properties of PZT ceramics. In a way similar to that proposed for tilts, however, charged defects, associated with oxygen vacancies, may also inhibit the motion of the domain walls, resulting macroscopically in pinched hysteresis loops and reduced piezoelectric response. Here, we revisit the early studies …
Point defect migration is considered as a mechanism for aging in ferroelectrics. Numerical results are given for the coupled problems of point defect migration and electrostatic energy relaxation in a 2D domain configuration. The peak values of the clamping pressure at domain walls are in the range of $10^6$ Pa, which corresponds to macroscopically observed coercive stresses in perovskite ferroelectrics. The effect is compared to mechanisms involving orientational reordering of defect dipoles in the bulk of domains. Domain clamping is significantly stronger in the drift mechanism than in the o…
Thick CVD diamond layers were successfully grown on (113)-oriented substrates. They exhibited smooth surface morphologies and a crystalline quality comparable to (100) electronic grade material, and much better than (111)-grown layers. High growth rates (15-50 μm/h) were obtained while nitrogen doping could be achieved in a fairly wide range without seriously imparting crystalline quality. Electron spin resonance measurements were carried out to determine NV centers orientation and concluded that one specific orientation has an occurrence probability of 73 % when (100)-grown layers show an equ…
We have proposed the phenomenological description of dielectric hysteresis loops in ferroelectric semiconductors with charged defects and prevailing extrinsic conductivity. Exactly we have modified Landau-Ginsburg approach and shown that the macroscopic state of the aforementioned inhomogeneous system can be described by three coupled equations for three order parameters. Both the experimentally observed coercive field values well below the thermodynamic one and the various hysteresis loop deformations (constricted and double loops) have been obtained in the framework of our model. The obtaine…
The two-dimensional semiconductor phosphorene has attracted extensive research interests for potential applications in optoelectronics, spintronics, catalysis, sensors, and energy conversion. To harness phosphorene's potential requires a better understanding of how intrinsic defects control carrier concentration, character, and mobility. Using density-functional theory and a charge correction scheme to account for the appropriate boundary conditions, we conduct a comprehensive study of the effect of structure on the formation energy, electronic structure, and charge transition level of the cha…
In this paper we investigate the influence of the substrate material and film thickness on the Peierls transition temperature in tetrathiafulvalene-tetracyanoquinodimethane (TTF-TCNQ) thin films, grown by physical vapor deposition. Our analysis shows that the substrate material and the growth conditions strongly influence the film morphology. In particular, we demonstrate that the Peierls transition temperature in thin films is lower than in TTF-TCNQ single crystals. We argue that this effect arises due to defects, which emerge in TTF-TCNQ thin films during the growth process.
We use an atomistic approach to study the electronic properties of monolayer and bilayer black phosphorus in the vicinity of a charged defect. In particular, we combine screened defect potentials obtained from first-principles linear response theory with large-scale tight-binding simulations to calculate the wavefunctions and energies of bound acceptor and donor states. As a consequence of the anisotropic band structure, the defect states in these systems form distorted hydrogenic orbitals with a different ordering than in isotropic materials. For the monolayer, we study the dependence of the …
Photoluminescence (PL) of transition metal dichalcogenide (TMD) monolayers is strongly influenced by the dielectric environment. The defect states present in the substrate induces uncontrollable doping in the TMD monolayer and thereby modifies the PL spectra. There have been enormous efforts to tune and overcome the effect of inevitable subtract defects in PL spectra, but a proper understanding and a convenient way are still lacking. Here, we systematically studied the effect of surface defects by gradually increasing the separation between WS2 monolayer and substrate. Hence, we could precisel…
Fatigue failure in ferroelectrics has been intensively investigated in the past few decades. Most of the mechanisms discussed for ferroelectric fatigue have been built on the "hypothesis of variation in charged defects", which however are rarely evidenced by experimental observation. Here, using a combination of complex impedance spectra techniques, piezoresponse force microscopy and first-principles theory, we examine the microscopic evolution and redistribution of charged defects during the electrical cycling in BiFeO3 thin films. The dynamic formation and melting behaviors of oxygen vacancy…
Few- and single-layer MoS2 host substantial densities of defects. They are thought to influence the doping level, the crystal structure, and the binding of electron-hole pairs. We disentangle the concomitant spectroscopic expression of all three effects and identify to what extent they are intrinsic to the material or extrinsic to it, i.e., related to its local environment. We do so by using different sources of MoS2 -- a natural one and one prepared at high pressure and high temperature -- and different substrates bringing varying amounts of charged impurities and by separating the contributi…
First-principles calculations of charged defects have become a cornerstone of research in semiconductors and insulators by providing insights into their fundamental physical properties. But current standard approach using the so-called jellium model has encountered both conceptual ambiguity and computational difficulty, especially for low-dimensional semiconducting materials. In this Communication, we propose a physical, straightforward, and dimension-independent universal model to calculate the formation energies of charged defects in both three-dimensional (3D) bulk and low-dimensional semic…
Molecular beam epitaxy offers an exciting avenue for investigating the behavior of topological semimetal Cd3As2, by providing routes for doping, alloying, strain engineering, and heterostructure formation. To date, however, minimal exploration has been devoted to the impact of defects that are incorporated into epilayers due to contraints imposed by the substrate and narrow growth window. Here, we use a combination of lattice-matched ZnxCd1-xTe buffer layers, miscut substrates and broadband illumination to study how dislocations, twins and point defects influence the electron mobility of Cd3As…
The thermodynamics and kinetics of tip-induced polarization switching in Piezoresponse Force Microscopy in the presence of surface charge defects is studied using the combination of analytical and numerical techniques. The signature of the defects in hysteresis loop fine structure and Switching Spectroscopy PFM images is identified and compared to experimental observations. An approach for the deconvolution of PFM spectroscopy measurements to extract relevant defect parameters is derived. This methodology is universal and can be extended to switching in other ferroics and in reversible electro…
Topological insulator (TI) materials are exciting candidates for integration into next-generation memory and logic devices because of their potential for efficient, low-energy-consumption switching of magnetization. Specifically, the family of bismuth chalcogenides offers efficient spin-to-charge conversion because of its large spin-orbit coupling and spin-momentum locking of surface states. However, a major obstacle to realizing the promise of TIs is the thin-film materials' quality, which lags behind that of epitaxially grown semiconductors. In contrast to the latter systems, the Bi-chalcoge…
Defects in 2D materials are becoming prominent candidates for quantum emitters and scalable optoelectronic applications. However, several physical properties that characterize their behavior, such as charged defect ionization energies, are difficult to simulate with conventional first-principles methods, mainly because of the weak and anisotropic dielectric screening caused by the reduced dimensionality. We establish fundamental principles for accurate and efficient calculations of charged defect ionization energies and electronic structure in ultrathin 2D materials. We propose to use the vacu…
Homoepitaxial chemical vapour deposition (CVD) on high pressure high temperature (HPHT) synthetic diamond substrates allows production of diamond material with controlled point defect content. In order to minimize the extended defect content, however, it is necessary to minimize the number of substrate extended defects that reach the initial growth surface and the nucleation of dislocations at the interface between the CVD layer and its substrate. X-ray topography has indicated that when type IIa HPHT synthetic substrates are used the density of dislocations nucleating at the interface can be …
We show that the orientation of nitrogen-vacancy (NV) defects in diamond can be efficiently controlled through chemical vapor deposition (CVD) growth on a (111)-oriented diamond substrate. More precisely, we demonstrate that spontaneously generated NV defects are oriented with a ~ 97 % probability along the [111] axis, corresponding to the most appealing orientation among the four possible crystallographic axes. Such a nearly perfect preferential orientation is explained by analyzing the diamond growth mechanism on a (111)-oriented substrate and could be extended to other types of defects. Thi…
A detailed understanding of charged defects in two-dimensional semiconductors is needed for the development of ultrathin electronic devices. Here, we study negatively charged acceptor impurities in monolayer WS$_2$ using a combination of scanning tunnelling spectroscopy and large-scale atomistic electronic structure calculations. We observe several localized defect states of hydrogenic wave function character in the vicinity of the valence band edge. Some of these defect states are bound, while others are resonant. The resonant states result from the multi-valley valence band structure of WS$_…
Thanks to its high refractive index contrast, band gap and polarization mismatch compared to GaN, In0.17Al0.83N layers lattice-matched to GaN are an attractive solution for applications such as distributed Bragg reflectors, ultraviolet light-emitting diodes, or high electron mobility transistors. In order to study the structural degradation mechanism of InAlN layers with increasing thickness, we performed metalorganic vapor phase epitaxy of InAlN layers of thicknesses ranging from 2 to 500 nm, on free-standing (0001) GaN substrates with a low density of threading dislocations, for In compositi…
The mechanical integrity of composite materials depends primarily on the interface strength and the defect density of the reinforcement which is the provider of enhanced strength and stiffness. In the case of graphene/ polymer nanocomposites which are characterized by an extremely large interface region, any defects in the inclusion (such as folds, cracks, holes etc.) will have a detrimental effect to the internal strain distribution and the resulting mechanical performance. This conventional wisdom, however, can be challenged if the defect size is reduced beyond the critical size for crack fo…
