Nanoscale structural and electronic properties of cellulose/graphene interfaces.

The development of electronic devices based on the functionalization of (nano)cellulose platforms relies upon an atomistic understanding of the structural and electronic properties of a combined system, cellulose/functional element. In this work, we present a theoretical study of the nanocellulose/graphene interfaces (nCL/G) based on first-principles calculations. We find that the binding energies of both hydrophobic/G (nCLphob/G) and hydrophilic/G (nCLphil/G) interfaces are primarily dictated by the van der Waals interactions, and are comparable with those of their 2D interface counterparts. We verify that the energetic preference of nCLphob/G has been reinforced by the inclusion of an aqueous medium via an implicit solvation model. Further structural characterization was carried out using a set of simulations of the carbon K-edge X-ray absorption spectra to identify and distinguish the key absorption features of the nCLphob/G and nCLphil/G interfaces. The electronic structure calculations reveal that the linear energy bands of graphene lie in the band gap of the nCL sheet, while depletion/accumulation charge density regions are observed. We show that external agents, i.e., electric field and mechanical strain, allow for tunability of the Dirac cone and charge density at the interface. The control/maintenance of the Dirac cone states in nCL/G is an important feature for the development of electronic devices based on cellulosic platforms.

Simulations of X-ray absorption spectroscopy and energetic conformation of N-heterocyclic carbenes on Au(111).

It has recently been demonstrated that N-heterocyclic carbenes (NHCs) form self-assembled monolayers (SAMs) on metal surfaces. Consequently, it is important to both characterize and understand their binding modes to fully exploit NHCs in functional surface systems. To assist with this effort, we have performed first-principles total energy calculations for NHCs on Au(111) and simulations of X-ray absorption near edge structure (XANES). The NHCs we have considered are N,N-dimethyl-, N,N-diethyl-, N,N-diisopropylbenzimidazolylidene (BNHCX, with X = Me, Et, and iPr, respectively) and the bis-BNHCX-Au complexes derived from these molecules. We present a comprehensive analysis of the energetic stability of both the BNHCX and the complexes on Au(111) and, for the former, examine the role of the wing group in determining the attachment geometry. Further structural characterization is performed by calculating the nitrogen K-edge X-ray absorption spectra. Our simulated XANES results give insight into (i) the relationship between the BNHCX/Au geometry and the N(1s) → π*/σ*, pre-edge/near-edge, absorption intensities, and (ii) the contributions of the molecular deformation and molecule-surface electronic interaction to the XANES spectrum. These simulated spectra work not only as a map to the BNHCX conformation, but also, combined with electronic structure calculations, provide a clear understanding of recent experimental XANES findings on BNHCX/Au.

Topological flat band, Dirac fermions and quantum spin Hall phase in 2D Archimedean lattices.

Materials with properties designed on-demand arise in a synergy between theoretical and experimental approaches. Here, we explore a set of Archimedean lattices, providing a guide to their electronic properties and topological phases. Within these lattices, a rich electronic structure emerges forming type-I and II Dirac fermions, topological flat bands and high-degeneracy points with linear and flat dispersions. Employing a tight-binding model with spin-orbit coupling, we characterize quantum spin Hall (QSH) phases in all Archimedean lattices. Our discussions are validated within density functional theory calculations, where we show the characteristic bands of the studied lattices arising in 2D carbon allotropes.

The role played by the molecular geometry on the electronic transport through nanometric organic films.

The electronic transport properties in molecular heterojunctions are intimately connected with the molecular conformation between the electrodes, and the electronic structure of the molecule/electrode interface. In this work, we perform an ab initio density-functional-theory investigation of the structural and transport properties through self-assembled CuPc molecules sandwiched between gold contacts with (111) surfaces. We demonstrated (i) a tunneling regime ruled by the π orbitals of the aromatic rings of CuPc molecules; and (ii) a high variation (up to two orders of magnitude) of the current density with the orientation of the CuPc molecules relative to the gold surface. The source of this variation is the geometrical dependence of the energy of the highest-occupied-molecular-orbital with respect to the chemical potential of the metal and the generation of intra-molecular transport channels for a configuration with CuPc molecules tilted with respect to the gold surface.

Electronic stripes and transport properties in borophene heterostructures.

We performed a theoretical investigation of the structural and electronic properties of (i) pristine and (ii) superlattice structures of borophene. In (i), by combining first-principles calculations, based on the density functional theory (DFT), and simulations of the X-ray Absorption Near-Edge Structure (XANES) spectra we present a comprehensive picture connecting the atomic arrangement of borophene and the X-ray absorption spectra. Once we characterized the electronic properties of the pristine systems, we next examined the electronic confinement effects in 2D borophene superlattices (BSLs) [(ii)]. Here, the BSL structures were made by attaching laterally two different structural phases of borophene. The energetic stability and the electronic properties of these BSLs were examined based on total energy DFT calculations. We find a highly anisotropic electronic structure, characterized by the electronic confinement effects, giving rise to "electronic stripes", and metallic channels ruled by the superlattices. Combining DFT and the Landauer-Büttiker formalism, we investigated the electronic transport properties in BSLs. Our results of the transmission probability reveal that the electronic transport is ruled by π or a combination of π and σ transmission channels, depending on the atomic arrangement and periodicity of the superlattices. Finally, we show that there is a huge magnification of the directional dependence of the electronic transport properties in BSLs, in comparison with the pristine borophene phase. These findings indicate that BSLs are quite interesting systems in order to design conductive nanoribbons on a 2D platform.

Orbital Pseudospin-Momentum Locking in Two-Dimensional Chiral Borophene.

Recently, orbital-textures have been found in Rashba and topological insulator (TI) surface states as a result of the spin-orbit coupling (SOC). Here, we predict a px/py orbital texture, in linear dispersive Dirac bands, arising at the K/K' points of χ-h0 borophene chiral monolayer. Combining "first-principles" calculations with effective Hamiltonians, we show that the orbital pseudospin has its direction locked with the momentum in a similar way as TIs' spin-textures. Additionally, considering a layer pseudospin degree of freedom, this lattice allows stackings of layers with equivalent or opposite chiralities. In turn, we show a control of the orbital textures and layer localization through the designed stacking and external electric field. For instance, for the opposite chirality stacking, the electric field allows for an on/off switch of the orbital-textured Dirac cone.

Layertronic control of topological states in multilayer metal-organic frameworks.

We investigate the layer localization control of two-dimensional states in multilayer metal-organic frameworks (MOFs). For finite stackings of (NiC4S4)3 MOFs, the weak van der Waals coupling between adjacent layers leads to a Fermi level dependent distribution of the electronic states in the monolayers. Such distribution is reflected in the topological edge states of multilayer nanoribbons. Moreover, by applying an external electric field parallel to the stacking direction, the spatial localization of the electronic states can be controlled for a chosen Fermi energy. This localization behavior is studied comparing density functional theory calculations with a kagome lattice tight-binding model. Furthermore, for infinite stacked nanoribbons, a new V-gutter Dirac state is found in the side surfaces, which allows anisotropic current control by tuning the Fermi energy. Our results can be immediately extended to other kagome MOFs with eclipsed stackings, introducing a new degree of freedom (layer localization) to materials design.

Investigating the preservation of π-conjugation in covalently functionalized carbon nanotubes through first principles simulations.

We performed a theoretical investigation of single-walled carbon nanotubes (CNTs) functionalized with triazine molecules. Upon adsorption, the influence of the molecule orientation on the CNTs' electronic properties is examined by combining first-principles density functional theory calculations and simulations of X-ray Absorption Near-Edge Structure (XANES) at the C K-edge. Our calculations show that the electronic properties of functionalized CNTs can preserve the same features of pristine CNTs, for both semiconductor and metallic CNTs, depending on the orientation of the covalently bonded molecule. For that configuration, we observe a breakage of the CNT C-C bond at the molecule adsorption site. Moreover, the XANES spectra reveal that sp2 bonding hybridization is preserved along the CNT network. On the other hand, the electronic properties of pristine CNTs are no longer preserved for adsorbed molecule orientations resulting in intact C-C bond at the adsorption site. In this case, the XANES spectra indicate that the molecule-CNT interactions result in sp3 hybridization. Our findings help to elucidate whether π-conjugation is preserved in functionalized CNTs, demonstrating that calculations of XANES spectra are a powerful tool to resolve such systems.

Quantum anomalous Hall effect in metal-bis(dithiolene), magnetic properties, doping and interfacing graphene.

The realization of the Quantum anomalous Hall effect (QAHE) in two dimensional (2D) metal organic frameworks (MOFs), (MC4S4)3 with M = Mn, Fe, Co, Ru and Rh, has been investigated based on a combination of first-principles calculations and tight binding models. Our analysis of the magnetic anisotropy energy (MAE) reveals that the out-of-plane (in-plane) magnetization is favored for M = Mn, Fe, and Ru (Co, and Rh). Therefore, we predict that the structural symmetry of (MC4S4)3 yields the QAHE only for M = Mn, Fe and Ru. Such a quantum anomalous Hall phase has been confirmed through the calculation of the Chern number, and examining the formation of topologically protected (metallic) edge states. Furthermore, we show that viable electron (n-type) doping of the MOFs can be used to place the Fermi level within the non-trivial energy gap; where we find that in (RuC4S4)3, in addition to the up-shift of the Fermi level, the MAE energy increases by 40%. Finally, we show that in MOF/graphene (vdW) interfaces, the Fermi level tuning can be done with an external electric field, which controls the charge transfer at the MOF/graphene interface, giving rise to switchable topologically protected edge currents in the MOFs.

Retention of contaminants Cd and Hg adsorbed and intercalated in aluminosilicate clays: A first principles study.

Layered clay materials have been used to incorporate transition metal (TM) contaminants. Based on first-principles calculations, we have examined the energetic stability and the electronic properties due to the incorporation of Cd and Hg in layered clay materials, kaolinite (KAO) and pyrophyllite (PYR). The TM can be (i) adsorbed on the clay surface as well as (ii) intercalated between the clay layers. For the intercalated case, the contaminant incorporation rate can be optimized by controlling the interlayer spacing of the clay, namely, pillared clays. Our total energy results reveal that the incorporation of the TMs can be maximized through a suitable tuning of vertical distance between the clay layers. Based on the calculated TM/clay binding energies and the Langmuir absorption model, we estimate the concentrations of the TMs. Further kinetic properties have been examined by calculating the activation energies, where we found energy barriers of ∼20 and ∼130 meV for adsorbed and intercalated cases, respectively. The adsorption and intercalation of ionized TM adatoms were also considered within the deprotonated KAO surface. This also leads to an optimal interlayer distance which maximizes the TM incorporation rate. By mapping the total charge transfers at the TM/clay interface, we identify a net electronic charge transfer from the TM adatoms to the topmost clay surface layer. The effect of such a charge transfer on the electronic structure of the clay (host) has been examined through a set of X-ray absorption near edge structure (XANES) simulations, characterizing the changes of the XANES spectra upon the presence of the contaminants. Finally, for the pillared clays, we quantify the Cd and Hg K-edge energy shifts of the TMs as a function of the interlayer distance between the clay layers and the Al K-edge spectra for the pristine and pillared clays.

Tuning the p-type Schottky barrier in 2D metal/semiconductor interface:boron-sheet on MoSe2, and WSe2.

Van der Waals (vdW) metal/semiconductor heterostructures have been investigated through first-principles calculations. We have considered the recently synthesized borophene (Mannix et al 2015 Science 350 1513), and the planar boron sheets (S1 and S2) (Feng et al 2016 Nat. Chem. 8 563) as the 2D metal layer, and the transition metal dichalcogenides (TMDCs) MoSe2, and WSe2 as the semiconductor monolayer. We find that the energetic stability of those 2D metal/semiconductor heterojunctions is mostly ruled by the vdW interactions; however, chemical interactions also take place in borophene/TMDC. The electronic charge transfer at the metal/semiconductor interface has been mapped, where we find a a net charge transfer from the TMDCs to the boron sheets. Further electronic structure calculations reveal that the metal/semiconductor interfaces, composed by planar boron sheets S1 and S2, present a p-type Schottky barrier which can be tuned to a p-type ohmic contact by an external electric field.

An ab initio investigation of Bi2Se3 topological insulator deposited on amorphous SiO2.

We use first-principles simulations to investigate the topological properties of Bi2Se3 thin films deposited on amorphous SiO2, Bi2Se3/a-SiO2, which is a promising substrate for topological insulator (TI) based device applications. The Bi2Se3 films are bonded to a-SiO2 mediated by van der Waals interactions. Upon interaction with the substrate, the Bi2Se3 topological surface and interface states remain present, however the degeneracy between the Dirac-like cones is broken. The energy separation between the two Dirac-like cones increases with the number of Bi2Se3 quintuple layers (QLs) deposited on the substrate. Such a degeneracy breaking is caused by (i) charge transfer from the TI to the substrate and charge redistribution along the Bi2Se3 QLs, and (ii) by deformation of the QL in contact with the a-SiO2 substrate. We also investigate the role played by oxygen vacancies ([Formula: see text]) on the a-SiO2, which increases the energy splitting between the two Dirac-like cones. Finally, by mapping the electronic structure of Bi2Se3/a-SiO2, we found that the a-SiO2 surface states, even upon the presence of [Formula: see text], play a minor role on gating the electronic transport properties of Bi2Se3.

H2O incorporation in the phosphorene/a-SiO2 interface: a first-principles study.

Based on first-principles calculations, we investigate (i) the energetic stability and electronic properties of single-layer phosphorene (SLP) adsorbed on an amorphous SiO2 surface (SLP/a-SiO2), and (ii) the further incorporation of water molecules at the phosphorene/a-SiO2 interface. In (i), we find that the phosphorene sheet binds to a-SiO2 through van der Waals interactions, even in the presence of oxygen vacancies on the surface. The SLP/a-SiO2 system presents a type-I band alignment, with the valence (conduction) band maximum (minimum) of the phosphorene lying within the energy gap of the a-SiO2 substrate. The structure and the surface-potential corrugations promote the formation of electron-rich and electron-poor regions on the phosphorene sheet and at the SLP/a-SiO2 interface. Such charge density puddles are strengthened by the presence of oxygen vacancies in a-SiO2. In (ii), because of the amorphous structure of the surface, we consider a number of plausible geometries for H2O embedded in the SLP/a-SiO2 interface. There is an energetic preference for the formation of hydroxyl (OH) groups on the a-SiO2 surface. Meanwhile, in the presence of oxygenated water or interstitial oxygen in the phosphorene sheet, we observe the formation of metastable OH bonded to the phosphorene, and the formation of energetically stable P-O-Si chemical bonds at the SLP/a-SiO2 interface. Further x-ray absorption spectra simulations are performed, which aim to provide additional structural/electronic information on the oxygen atoms forming hydroxyl groups or P-O-Si chemical bonds at the interface region.

A new class of large band gap quantum spin hall insulators: 2D fluorinated group-IV binary compounds.

We predict a new class of large band gap quantum spin Hall insulators, the fluorinated PbX (X = C, Si, Ge and Sn) compounds, that are mechanically stable two-dimensional materials. Based on first principles calculations we find that, while the PbX systems are not topological insulators, all fluorinated PbX (PbXF2) compounds are 2D topological insulators. The quantum spin Hall insulating phase was confirmed by the explicitly calculation of the Z2 invariant. In addition we performed a thorough investigation of the role played by the (i) fluorine saturation, (ii) crystal field, and (iii) spin-orbital coupling in PbXF2. By considering nanoribbon structures, we verify the appearance of a pair of topologically protected Dirac-like edge states connecting the conduction and valence bands. The insulating phase which is a result of the spin orbit interaction, reveals that this new class of two dimensional materials present exceptional nontrivial band gaps, reaching values up to 0.99 eV at the Γ point, and an indirect band gap of 0.77 eV. The topological phase is arisen without any external field, making this system promising for nanoscale applications, using topological properties.

Pyridine intercalated Bi2Se3 heterostructures: controlling the topologically protected states.

We use ab initio simulations to investigate the incorporation of pyridine molecules (C5H5N) in the van der Waals (vdW) gaps of Bi2Se3. The intercalated pyridine molecules increase the separation distance between the Bi2Se3 quintuple layers (QLs), suppressing the parity inversion of the electronic states at the Γ-point. We find that (i) the intercalated region becomes a trivial insulator. By combining the pristine Bi2Se3 region with the one intercalated by the molecules (py-Bi2Se3), we have a trivial/topological heterojunction (py-Bi2Se3/Bi2Se3) characterized by the presence of topologically protected metallic states at the interfacial region. Next, (ii) we apply an external compressive pressure to the system, and the results are a decrease of the separation distance between the QLs intercalated by pyridine molecules, and the metallic states are shifted toward the bulk region, turning the system back to the insulator. Our findings indicate that, through the intercalation of pyridine molecules in Bi2Se3 [(i)], we may have a number of topologically protected metallic channels embedded in (py-Bi2Se3) m /(Bi2Se3) n heterostructures/superlattices, in addition, through suitable tuning of the external pressure [(ii)], we can control its topological properties, turning on and off the topologically protected metallic states in (py-Bi2Se3)m /(Bi2Se3)n.

Topological phase transitions of (BixSb1-x)2Se3 alloys by density functional theory.

We have performed an ab initio total energy investigation of the topological phase transition, and the electronic properties of topologically protected surface states of (BixSb1-x)2Se3 alloys. In order to provide an accurate alloy concentration for the phase transition, we have considered the special quasirandom structures to describe the alloy system. The trivial â†’ topological transition concentration was obtained by (i) the calculation of the band gap closing as a function of Bi concentration (x), and (ii) the calculation of the Z2 topological invariant number. We show that there is a topological phase transition, for x around 0.4, verified for both procedures (i) and (ii). We also show that in the concentration range 0.4 < x < 0.7, the alloy does not present any other band at the Fermi level besides the Dirac cone, where the Dirac point is far from the bulk states. This indicates that a possible suppression of the scattering process due to bulk states will occur.

Surface and near surface defects in δ-doped Si(1 1 1).

The B/Si(1 1 1)- (√3 x √3)R30° surface reconstruction has recently been used as a platform for supramolecular assembly. However, our understanding of the native defects in this delta-doped system and their corresponding scanning tunnelling microscopy (STM) signatures is incomplete. So we have studied this system using ab initio total energy calculations and scanning tunneling microscopy. We find that although perturbations to the equilibrium geometry of the surface are in general weak, the perturbations to the electronic structure can be quite strong due to the presence of dangling bonds composed of Si-3p(z) orbitals. Additionally, we propose a possible structure for a previously unidentified defect that appears in positive bias constant-current STM images as an equilateral triangular arrangement of Si adatoms with attenuated intensity.

Organic molecules deposited on graphene: a computational investigation of self-assembly and electronic structure.

We use ab initio simulations to investigate the adsorption and the self-assembly processes of tetracyanoquinodimethane (TCNQ), tetrafluoro-tetracyanoquinodimethane (F4-TCNQ), and tetrasodium 1,3,6,8-pyrenetetrasulfonic acid (TPA) on the graphene surface. We find that there are no chemical bonds at the molecule-graphene interface, even at the presence of grain boundaries on the graphene surface. The molecules bond to graphene through van der Waals interactions. In addition to the molecule-graphene interaction, we performed a detailed study of the role played by the (lateral) molecule-molecule interaction in the formation of the, experimentally verified, self-assembled layers of TCNQ and TPA on graphene. Regarding the electronic properties, we calculate the electronic charge transfer from the graphene sheet to the TCNQ and F4-TCNQ molecules, leading to a p-doping of graphene. Meanwhile, such charge transfer is reduced by an order of magnitude for TPA molecules on graphene. In this case, it is not expected a significant doping process upon the formation of self-assembled layer of TPA molecules on the graphene sheet.

Electronic confinement in graphene ruled by N doped extended defects.

We investigate by means of ab-initio simulations the formation energy and the electronic properties of substitutional N doping in graphene with distinct grain boundary defects as a function of the N concentration. Our results show that the presence of substitutional N atoms along the defective regions is quite likely for several N concentrations. Also, we find either semiconducting or metallic structures, depending on the N concentration. Confinement effects were also investigated for the semiconducting structures. We find that the distance between the defect lines can modulate the band structure of those semiconducting N doped lines. This opens an interesting possibility to produce two-dimensional heterojunctions composed by N doped grain boundaries with different distances between the defect lines.

Lithium incorporation at the MoS2/graphene interface: an ab initio investigation.

Based on ab initio calculations, we examine the incorporation of Li atoms in the MoS2/graphene interface. We find that the intercalated Li atoms are energetically more stable than Li atoms adsorbed on the MoS2 surface. The intercalated atoms interact with both graphene sheet and MoS2 layer, increasing the Li binding energies. However, the equilibrium geometries are ruled by the MoS2 layer, where the intercalated Li atoms lie on the top (LiT) and hollow (LiH) sites of the MoS2 layer. We calculate the Li diffusion barriers, along the LiT → LiH diffusion path, where we find similar energy barriers compared with that obtained for Li adatoms on the MoS2 surface. Our results allow us to infer that the Li storage capacity increases at MoS2/G interfaces, in comparison with Li adatoms on the MoS2 surface-however, with no reduction on the mobility of the intercalated Li atoms. Those properties are interesting/useful to the development of Li batteries based on MoS2.