Nonequilibrium Green Function Research Articles

First-principles study of highly sensitive graphene/hexagonal boron nitride heterostructures for application in toxic gas-sensing devices.

Graphene-based sensors exhibit high sensitivity, fast response, and good selectivity towards toxic gases but have low mechanical stability. The combination of graphene and two-dimensional hexagonal boron nitride (h-BN) is expected to increase the mechanical stability and enhance the adsorption performance of these gas sensors. Using first-principles calculations, we demonstrate that two-dimensional graphene/h-BN double layers can be used as good substrates for gas sensors with a small lattice mismatch of only 1.78%. Moreover, the presence of a h-BN layer widens the band gap by about 38 meV and considerably increases the work function, thus positively affecting the gas adsorption performance. Although these graphene/h-BN heterostructures do not change the physical adsorption mechanism of these sensors concerning the graphene-based materials, these bilayers significantly enhance the sensitivity of these sensors for detecting CO2, CO, NO, and NO2 toxic gases. Particularly, compared to the pristine graphene-based materials, the gas adsorption energies of graphene/h-BN increased by up to 13.78% for the adsorption of NO, and the shortest distances between the graphene/h-BN substrates and adsorbed gas molecules decreased. We also show that the graphene/h-BN heterostructure is more selective towards NOx gases while more inert towards COx gases, based on the different amounts of charge transferred from the substrate to the adsorbed gas molecules. Using the non-equilibrium Green functions in the context of density functional theory, we quantitatively associated these charge transfers with the reduction of the current passing through these scattering regions. These results demonstrate that graphene/h-BN heterostructures can be exploited as highly sensitive and selective room-temperature gas sensors for detecting toxic gases.

Investigating the enhancement of lung cancer sensing: the effect of edge halogenation in armchair stanene nanoribbons.

In this research, we explore the impact of edge passivation using halogen atoms on armchair stanene nanoribbon (ASNR) for the early detection of lung cancer biomarkers. We employ non-equilibrium green function (NEGF) and density functional theory (DFT) methods to evaluate sensing characteristics. The edges of ASNR are passivated with fluorine, chlorine, bromine, and iodine atoms. Our findings indicate a significant enhancement in sensing performance upon halogenation of ASNR. Notable changes in adsorption energy and current for edge-halogenated ASNR configurations demonstrate improved sensing behavior. Moreover, current curves exhibit greater distinctiveness of halogenated ASNR in comparison to hydrogenated ASNR. The calculations indicate a change in adsorption energy (Eads) of -7.59 eV, -7.6 eV, -8.3 eV, and -8.6 eV for the adsorption by styrene on I-ASnNR, Br-ASnNR, toluene on Cl-ASnNR, and styrene on F-ASnNR, respectively. The corresponding sensitivity improves up to 37.33%, 38.09%, 38.35%, and 45.5%, respectively. These findings highlight that the most significant change occurs with the edge fluorination of ASnNR. Our findings underscore the effectiveness of halogen atom edge passivation in ASNR for heightened sensing performance, making it a promising choice for the development of early-detection lung cancer sensors.

A chiral metal cluster triggers enantiospecific electronic transport.

Chirality is a geometric property of matter that can be present at different scales, especially at the nanoscale. Here, we investigate the manifestation of chirality in electronic transport through a molecular junction. Spinless electronic transport through a chiral molecular junction is not enantiospecific. However, when a chiral metal cluster, C3-Au34, is attached to the source electrode, a different response is obtained in spinless electronic transport between R and L systems: this indicates the crucial role of chiral clusters in triggering enantiospecific spinless electronic transport. In contrast, when an achiral metal cluster, C3v-Au34, is attached, no change in conductance occurs between enantiomeric systems. Using the non-equilibrium green's function method, we characterized this phenomenon by calculating the transmission and conductance of spin-unpolarized electrons. Our theoretical results highlight the importance of metal clusters with specific sizes and chiral structures in electronic transport and support previously published experimental results that exhibited enantiospecific scanning tunneling measurements with intrinsically chiral tips.

Ultra-thin van der Waals magnetic tunnel junction based on monoatomic boron vacancy of hexagonal boron nitride.

We present a novel strategy to create a van der Waals-based magnetic tunnel junction (MTJ) comprising a three-atom layer of graphene (Gr) sandwiched with hexagonal boron nitride (hBN) layers by introducing a monoatomic boron vacancy in each hBN layer. The magnetic properties and electronic structure of the system were investigated using density functional theory (DFT) and the transmission probability of the MTJ was investigated using the Landauer-Büttiker formalism within the non-equilibrium Green function method. The Stoner gap was created between the spin-majority channel and the spin-minority channel on the local density of states of the hBN monoatomic boron-vacancy (VB) near the Fermi energy, creating a possible control of the spin valve by considering two magnetic alignment of hBN(VB) layers, anti-parallel configuration (APC) and parallel configuration (PC). The transmission probability calculation results showed a high electron transmission in the PC of the hBN(VB) layers and a low transmission when the APC was considered. A high tunneling magnetoresistance (TMR) ratio of approximately 400% was observed when comparing the APC and PC of the hBN(VB) layers in hBN(VB)/Gr/hBN(VB), giving the highest TMR ratio for the thinnest MTJ system.

Designing van der Waals magnetic tunnel junctions with high tunnel magnetoresistance via Brillouin zone filtering.

Magnetic tunnel junctions (MTJs) consisting of two-dimensional (2D) van der Waals heterostructures have no inter-layer chemical bonds; therefore, their spin tunneling is determined solely by the Brillouin zone (BZ) filtering effect. To obtain high tunnel magnetoresistance (TMR), they should possess transversal momentum-resolved conduction channels for the electrodes and transmission channels for the barriers. Here, we investigate 2D magnets as electrodes whose Curie temperatures approach room temperature and also hexagonal 2D insulators as the barrier. Iron-based compounds such as FexGeTe2 (x = 3 and 4) are calculated to have high transmission coefficients over the entire in-plane BZ for the majority spin channel, while this should only happen around Γ for the minority spin channel. Correspondingly, various 2H-type transition metal dichalcogenides (TMDs) are found to function effectively as spin barriers, where electrons are only allowed to tunnel through them around the K and M points. BZ spin filtering is confirmed to be the major mechanism of the TMR effect by the MTJ transport calculation using the non-equilibrium Green function method. Furthermore, the TMR is calculated to be nearly independent of the barrier layer thickness as the BZ filtering is an interfacial effect. This work sheds light on material selection procedures and designing ultra-thin and robust van der Waals MTJs.

Engineering MOF/carbon nitride heterojunctions for effective dual photocatalytic CO2 conversion and oxygen evolution reactions.

Photocatalysis appears as one of the most promising avenues to shift towards sustainable sources of energy, owing to its ability to transform solar light into chemical energy, e.g. production of chemical fuels via oxygen evolution (OER) and CO2 reduction (CO2RR) reactions. Ti metal-organic frameworks (MOFs) and graphitic carbon nitride derivatives, i.e. poly-heptazine imides (PHI) are appealing CO2RR and OER photo-catalysts respectively. Engineering of an innovative Z-scheme heterojunction by assembling a Ti-MOF and PHI offers an unparalleled opportunity to mimick an artificial photosynthesis device for dual CO2RR/OER catalysis. Along this path, understanding of the photophysical processes controlling the MOF/PHI interfacial charge recombination is vital to fine tune the electronic and chemical features of the two components and devise the optimum heterojunction. To address this challenge, we developed a modelling approach integrating force field Molecular Dynamics (MD), Time-Dependent Density Functional Theory (TD-DFT) and Non-Equilibrium Green Function DFT (NEGF-DFT) tools with the aim of systematically exploring the structuring, the opto-electronic and transport properties of MOF/PHI heterojunctions. We revealed that the nature of the MOF/PHI interactions, the interfacial charge transfer directionality and the absorption energy windows of the resulting heterojunctions can be fine tuned by incorporating Cu species in the MOF and/or doping PHI with mono- or divalent cations. Interestingly, we demonstrated that the interfacial charge transfer can be further boosted by engineering MOF/PHI device junctions and application of negative bias. Overall, our generalizable computational methodology unravelled that the performance of CO2RR/OER photoreactors can be optimized by chemical and electronic tuning of the components but also by device design based on reliable structure-property rules, paving the way towards practical exploitation.

Cheers: A Linear‐Scaling KBE + GKBA Code

The interaction of electrons with quantized phonons and photons underlies the ultrafast dynamics of systems, ranging from molecules to solids, giving rise to a plethora of physical phenomena experimentally accessible using time‐resolved techniques. Green's function methods offer an invaluable interpretation tool since scattering mechanisms of growing complexity can be selectively incorporated in the theory. Cheers is a general‐purpose nonequilibrium Green's function code that implements virtually all known many‐body approximations and is designed for first‐principles studies of ultrafast processes in molecular and model solid‐state systems. The aims of generality, extensibility, efficiency, and user friendliness of the code are achieved through the underlying theory development and the use of modern software design practices. Herein, the necessity for the creation of such a code is motivated and its design and capabilities are overviewed.

Enhancing Spin-Transport Characteristics, Spin-Filtering Efficiency, and Negative Differential Resistance in Exchange-Coupled Dinuclear Co(II) Complexes for Molecular Spintronics Applications.

Single-molecule spintronics, where electron transport occurs via a paramagnetic molecule, has gained wide attention due to its potential applications in the area of memory devices to switches. While numerous organic and some inorganic complexes have been employed over the years, there are only a few attempts to employ exchange coupled dinuclear complexes at the interface, and the advantage of fabricating such a molecular spintronics device in the observation of switchable Kondo resonance was demonstrated recently in the dinuclear [Co2(L)(hfac)4] (1) complex (Wagner et al., Nat. Nanotechnol. 2013, 8, 575-579). In this work, employing an array of theoretical tools such as density functional theory (DFT), the ab initio CASSCF/NEVPT2 method, and DFT combined with nonequilibrium Green Function (NEGF) formalism, we studied in detail the role of magnetic coupling, ligand field, and magnetic anisotropy in the transport characteristics of complex 1. Particularly, our calculations not only reproduce the current-voltage (I-V) characteristics observed in experiments but also unequivocally establish that these arise from an exchange-coupled singlet state that arises due to antiferromagnetic coupling between two high-spin Co(II) centers. Further, the estimated spin Hamiltonian parameters such as J, g values, and D and E/D values are only marginally altered for the molecule at the interface. Further, the exchange-coupled state was found to have very similar transport responses, despite possessing significantly different geometries. Our transport calculations unveil a new feature of the negative differential resistance (NDR) effect on 1 at the bias voltage of 0.9 V, which agrees with the experimental I-V characteristics reported. The spin-filtering efficiency (SFE) computed for the spin-coupled states was found to be only marginal (∼25%); however, if the ligand field is fine-tuned to obtain a low-spin Co(II) center, a substantial SFE of 44% was noted. This spin-coupled state also yields a very strong NDR with a peak-to-valley ratio (PVR) of ∼56 - a record number that has not been witnessed so far in this class of compounds. Additionally, we have established further magnetostructural-transport correlations, providing valuable insights into how microscopic spin Hamiltonian parameters can be associated with SFE. Several design clues to improve the spin-transport characteristics, SFE and NDR in this class of molecule, are offered.

Full statistics of nonequilibrium heat and work for many-body quantum Otto engines and universal bounds: A nonequilibrium Green's function approach.

We consider a generic four-stroke quantum Otto engine consisting of two unitary and two thermalization strokes with an arbitrary many-body working medium. Using the Schwinger-Keldysh nonequilibrium Green's function formalism, we provide an analytical expression for the cumulant generating function corresponding to the joint probability distribution of nonequilibrium work and heat. The obtained result is valid up to the second order of the external driving amplitude. We then focus on the linear response limit and obtained Onsager's transport coefficients for the generic Otto cycle and show that the traditional fluctuation-dissipation relation for the total work is violated in the quantum domain, whereas for heat it is preserved. This leads to remarkable consequences in obtaining universal constraints on heat and work fluctuations for engine and refrigerator regimes of the Otto cycle and further allows us to make connections to the thermodynamic uncertainty relations. These findings are illustrated using a paradigmatic model that can be feasibly implemented in experiments.

Investigation of thermoelectric properties of cadmium selenide CdnSen (n= 7, 11, 13) molecular junctions: a DFT study.

The thermoelectric properties of cadmium selenide (CdnSen) molecular junctions (n = 7, 11, 13) were investigated before and after adding hydrogen atoms. The effects of hydrogen passivation on the transmission and thermopower curves were analyzed. CdSe-diamantane (Cd7Se7) and CdSe-tetramantane (Cd11Se11) junctions exhibited the best thermoelectric performance due to their low surface reconstruction energy, which is attributed to the number of dangling and unsaturated bonds. This study guides the design of new molecular junctions with desired thermoelectric properties. The electrical and thermal properties of cadmium selenide (CdnSen) molecular junctions (n = 7, 11, 13) were investigated using a ballistic quantum transport method based on the non-equilibrium Green's function (NEGF) approach. Thermoelectric properties were calculated for the molecular junctions with different structures before and after hydrogen passivation. Density functional theory (DFT) calculations were performed at the B3LYP level with the 3-21G basis set for the Cd atoms and the 6-31G** basis set for the Se atoms. The SIESTA and GOLLUM codes were used to study the effect of changing the shape and size of each structure on its electrical and thermal characteristics.

Modeling of light absorption in self-assembled truncated conical quantum dot structures

Quantum Dots have shown a significant potential as a top candidate for infrared photodetection at higher temperatures. In the presented work, a theoretical model for estimating the coefficient of optical absorption of self-assembled truncated conical quantum dot is developed. This model considers both bound-to-continuum and bound-to-bound absorption mechanisms that increase the accuracy of the absorption coefficient estimation. The developed model is based on estimating the bound states by diagonalizing the Hamiltonian matrix, where the density of states is computed using the Non-Equilibrium Greens function and the effective mass theory to obtain the unbound states. The kinetic equation of Green’s function is solved numerically by finite difference method. Besides, the effects of quantum dot size, height, aspect ratio, and density on the coefficient of the optical absorption are investigated. The results of the developed model are contrasted with those of other alternative QD structures where the truncated conical QD structure results in a higher absorption coefficient in infrared range than semispherical and conical QD structures.

The interfacial properties of 2D metal-monolayer blue phosphorene heterojunctions and transport properties of their field-effect transistors

Monolayer blue phosphorene (BlueP) has attracted much interest as a potential channel material in electronic devices. Searching for suitable two-dimensional (2D) metal materials to use as electrodes is critical to fabricating high-performance nanoscale channel BlueP-based field effect transistors (FETs). In this paper, we adopted first-principles calculations to explore binding energies, phonon calculations and electronic structures of 2D metal-BlueP heterojunctions, including Ti3C2-, NbTe2-, Ga(110)- and NbS2-BlueP, and thermal stability of Ti3C2-BlueP heterojunction at room temperature. We also used density functional theory coupled with the nonequilibrium Green function method to investigate the transport properties of sub-5 nm BlueP-based FETs with Ti3C2-BlueP electrodes. Our calculated results indicate that Ti3C2-BlueP has excellent thermal stability and may be used as a candidate electrode material for BlueP-based FETs. The double-gate can more effectively improve the device performance compared with the single-gate. The estimated source leakage current of sub-5 nm transistors reaches up to 369 µA µm−1, which is expected to meet the requirements of the international technology roadmap for semiconductors for LP (low-power) devices. Our results imply that 2D Ti3C2 may act as an appropriate electrode material for LP BlueP-based FETs, thus providing guidance for the design of future short-gate-length BlueP-based FETs.

Andreev reflection imaging and longitudinal shift of pseudospin-1 fermions in two-dimensional materials

In this work, the transverse magnetic focusing of pseudospin-1 fermions in two-dimensional materials with a superconducting contact is studied. The transmission coefficient and Andreev reflection coefficient from injector lead to collector lead are calculated based on the Landauer–Büttiker formula combined with the non-equilibrium Green's function method. The local state density diagrams of the electron and hole transmission in the center region are given, which provide a complete image of the ballistic electron–hole cyclotron orbits. Using these images, the positive longitudinal shift in Andreev reflection of the pseudospin-1 fermion can be obviously seen. Furthermore, it is found that the total offset is proportional to the number of Andreev reflection occurrence. This setup provides the possibility of detecting this shift experimentally.

Quantum Transport of Topological and Trivial Edge States in Sn‐Doped SbH Nanoribbons

Although the transport of topological edge states may be insensitive to impurities, impurities may induce the interedge scattering and backscattering in topological nanoribbons due to the finite size effect. It may be interesting to compare the transport of topological edge states with that of trivial edge states in nanoribbons. Here, the quantum transport of edge states in the Sn‐doped SbH nanoribbons using the density functional theory combined with nonequilibrium Green's function method is studied. Both topological and trivial edge states can be found in the zigzag SbH nanoribbons. The impurity generates a higher barrier near the doping position and leads to the scattering of the states. From calculations, the transmission of topological edge states can be smaller than that of trivial edge states due to the antiresonance behavior. Compared with topological edge states, the transport of trivial edge states is more sensitive to the impurity position. Besides, the edge impurity is more likely to induce scattering for both topological and trivial edge states than the central impurity in narrow SbH nanoribbons, since the transport channels are limited to the edges. This study may be helpful for understanding the transport of edge states in nanoribbons.

Enhanced thermoelectric performances in graphene nanoribbons via BN dimers doping: Theoretical study

Improving the thermoelectric performance of designed graphene nanoribbons is a key stage in the production of thermoelectric nanodevices with many applications. The chemical doping allows armchair graphene nanoribbons (AGNRs) to exhibit controllable thermoelectric characteristics. Here, we use density functional theory-based tight-binding (DFTB) coupled with the non-equilibrium Green's function (NEGF) to study the electronic and thermoelectric properties of AGNR with boron nitride (BN) dimers at room temperature. Changing the concentrations (from 4.17 % (BN)1-structure to 12.5 % (BN)3-structure) and geometrical pattern (ortho, meta, and para form) of BN dimers in the graphene nanoribbons may have a significant effect on the thermoelectric (TE) properties. Our results show that the TE properties of AGNR depend not only on the amount of BN dimers but also on the arrangement of the BN dimers in the AGNR. The thermoelectric figure of merit (ZT) of nanoribbons at room temperature has improved from less than 0.7 to more than 2. These results could be used as an indicator to design nanodevices that have good TE applications.

B3C2P3 monolayers based highly sensitive and selective room-temperature gas sensors for reusable NO and NO2 detection

Motivated by the development of high-performance gas sensors using two-dimensional (2D) nanomaterials, herein using the combination methods of density functional theory (DFT) and nonequilibrium Green's function (NEGF), the structural, electronic, transport, and gas sensing properties of the B3C2P3 monolayer adsorbed with various gases (NO2, NO, NH3, SO2, H2S, CO2, CO, H2O, O2 and CH2O) have been systematically studied. The NO2 (or NO) molecules were chemically adsorbed (or strong physisorbed) on the B3C2P3 monolayer, while other molecules were weak-physically adsorbed on the substrate. Furthermore, only the NO2 and NO adsorption results in the remarkable change in electronic properties of B3C2P3. The transport properties such as current-voltage (I–V) characteristics and transmission functions indicate the B3C2P3 monolayer is highly sensitive and selective towards NO2 and NO gases. The recovery times of NO2 and NO were calculated to be 2.27 and 0.0785 ms at 300 K, indicating the reusability of the B3C2P3-based NO2 (NO) sensors. The existence of moisture hardly influences the adsorption of NO and NO2 on the B3C2P3 monolayer. Our results indicated that the B3C2P3 monolayer, as a room-temperature reusable gas sensor, is highly sensitive and selective for NO2 and NO detection regardless of the existence of moisture, O2 and CO2.

Mechanistic Insights into Electronic Current Flow through Quinone Devices.

Molecular switches based on functionalized graphene nanoribbons (GNRs) are of great interest in the development of nanoelectronics. In experiment, it was found that a significant difference in the conductance of an anthraquinone derivative can be achieved by altering the pH value of the environment. Building on this, in this work we investigate the underlying mechanism behind this effect and propose a general design principle for a pH based GNR-based switch. The electronic structure of the investigated systems is calculated using density functional theory and the transport properties at the quasi-stationary limit are described using nonequilibrium Green's function and the Landauer formalism. This approach enables the examination of the local and the global transport through the system. The electrons are shown to flow along the edges of the GNRs. The central carbonyl groups allow for tunable transport through control of the oxidation state via the pH environment. Finally, we also test different types of GNRs (zigzag vs. armchair) to determine which platform provides the best transport switchability.

Josephson current across a Double Quantum Dot Josephson junction in T-Shape Configuration

By implementing the Keldysh non-equilibrium Green's function equation of motion approach, Josephson current has been examined across a T-shaped uncorrelated double quantum dot Josephson junction. The behavior of the Josephson current as a function of the main quantum dot energy level for varied interdot tunneling and different dot-lead coupling strengths is examined. With this configuration, we illustrate that the side-attached quantum dot offers an alternative route for electron transmission, which modifies the Josephson current by varying interdot tunneling. Further, we also investigate how the dot-lead coupling strengths affect the Josephson current.

Automatic differentiable nonequilibrium Green's function formalism: An end-to-end differentiable quantum transport simulator

Automatic differentiable nonequilibrium Green's function formalism: An end-to-end differentiable quantum transport simulator

Coupling effects in bipyridines linked to carbon nanowires

In this work, we conducted an investigation into the electronic transport properties of four distinct devices formed by bipyridines (BPY) as the central region, linked to carbon nanowires (polyyne-type carbyne) electrodes. These four devices have two symmetrical (2,2′ and 4,4′ BPY) and two asymmetrical (2,4′ and 2,6′ BPY) configurations. We employed Density Functional Theory combined with Non-Equilibrium Green's Function (DFT-NEGF) to calculate the molecular geometry and the electronic transport properties. Our analysis, using Fowler-Nordheim (F-N) and Millikan-Lauritsen (M-L) plots, reveals that electronic transport primarily occurs through direct tunneling without any inflection points, indicating the absence of nonlinear effects such as resonance or negative differential resistance (NDR). This demonstrates the importance of the study including an analysis of Transition Voltage Spectroscopy (TVS) which shows that the presence of nitrogen atoms in the electrode-molecule contacts, specifically in the cases 2,4′ and 4,4′ BPY, significantly alters the structural and electronic characteristics of the devices. This alteration leads to a strong coupling of the junction, improved structural and electronic properties. These findings are supported by the Device Density of States (DDOS) and Frontier Molecular Orbitals (FMOs). Moreover, we observed that the electronic characteristics of all four devices remain consistent even under bias voltage (Ve).