Electronic properties of phosphorene nanoribbons with nanoholes

Using first-principles calculation based on density-functional theory, the electronic properties of monolayer black phosphorus nanoribbons (PNRs) with and without punched nanoholes (PNRPNHs) and their mechanical stability are studied systematically. We show that while the perfect PNRs and the PNRPNHs have similar properties as semiconductors in both armchair-edge PNR and zigzag-edge PNR structures, the nanoholes can lead to changes in the electronic structure: the zigzag-edge PNRPNH undergoes a direct-to-indirect bandgap transition while the armchair-edge PNRPNH still retains a direct bandgap but with a significant increase in the bandgap as compared to the perfect PNRs. We found also that nanoholes have little influence on the structural stability of PNRs; but the applied external transverse electric field and strain can be more effective in modulating the bandgaps in the PNRPNHs. These new findings show that PNRs are a promising candidate for future nanoelectronic and optoelectronic applications.

Using first-principles calculation based on density-functional theory, the electronic properties of monolayer black phosphorus nanoribbons (PNRs) with and without punched nanoholes (PNRPNHs) and their mechanical stability are studied systematically.     

Charge transport in germanium doped phosphorene nanoribbons

New two dimensional structures containing phosphorus and germanium atoms are introduced for nanoelectronic applications. Under various bias voltages, electronic transport in the systems has been studied with the non-equilibrium Green’s function formalism. I–V characteristics have been extracted. The density of states (DOS) and transmission spectra, T(E,V_bias), have been investigated and it was shown that charge transport occurs when the bias voltage reaches about 1 V. The negative differential resistance (NDR) appears in zigzag phosphorene nanoribbons (zPNRs) while it is completely suppressed after replacing edge phosphorus atoms with germanium ones. The calculated molecular projected self-consistent Hamiltonian (MPSH) shows that the spatial distribution of orbital levels has been affected by the electrodes. The studied structures have a band-gap of about 0.7 eV which absorbs light in the visible range and thus these structures could be interesting contenders for solar cells applications.

New two dimensional structures containing phosphorus and germanium atoms are introduced for nanoelectronic applications.     

Tunnable rectifying performance of in-plane metal–semiconductor junctions based on passivated zigzag phosphorene nanoribbons

Using first principles density functional theory, we perform a systematic study of the band structures of passivated zigzag phosphorene nanoribbons (ZPNRs) and the transport properties of in-plane metal–semiconductor junctions. It is found that the ZPNR passivated by H, Cl or F atoms is a semiconductor, and the ZPNR passivated by C, O or S atoms is a metal. Therefore, ZPNRs with different passivated atoms can be fabricated into an in-plane metal–semiconductor junction. The calculated current–voltage characteristics indicate that these in-plane metal–semiconductor junctions can exhibit excellent rectification behavior. More importantly, we find that the type of passivated atom plays a very important role in the rectification ratio of this in-plane metal–semiconductor junction. The findings are very useful for the further design of functional nanodevices based on ZPNRs.

Using first principles density functional theory, we perform a systematic study of the band structures of passivated zigzag phosphorene nanoribbons (ZPNRs) and the transport properties of in-plane metal–semiconductor junctions.     

Electronic and magnetic properties of a black phosphorene/Tl2S heterostructure with transition metal atom intercalation: a first-principles study

Using density functional theory calculations, the structural, electronic and magnetic properties of a black phosphorene/Tl₂S heterostructure (BP/Tl₂S) and the BP/Tl₂S intercalated with transition metal atoms (TMs) have been detailed investigated. It is demonstrated that the BP/Tl₂S is a type-I van der Waals (vdW) heterostructure with an indirect band gap of approximately 0.79 eV. The BP/Tl₂S experiences a transition from type-I to type-II when various strains are applied. In addition, the BP/Tl₂S intercalated with TMs (TM-BP/Tl₂S) exhibits various kinds of meaningful electronic and magnetic properties. Several TM-BP/Tl₂S systems are still non-magnetic ground states and six TM-BP/Tl₂S (Ti-, V-, Cr-, Mn-, Fe-, Tc-) systems are ferromagnetic. Interestingly, three TM-BP/Tl₂S (V-, Cr-, Mn-) systems display half-metallic character. The Fe-BP/Tl₂S and Tc-BP/Tl₂S are dilute magnetic semiconductors (DMSs), while TM-BP/Tl₂S (Mo-, Pd-, Ni-) systems are semiconductors. The other TM-BP/Tl₂S systems become metals. These results may open a new avenue for application of the BP/Tl₂S in future spintronic and electronic devices.

Using density functional theory calculations, the structural, electronic and magnetic properties of a black phosphorene/Tl₂S heterostructure (BP/Tl₂S) and the BP/Tl₂S intercalated with transition metal atoms (TMs) have been detailed investigated.     

Effect of surface oxidation on the electronic transport properties of phosphorene gas sensors: a computational study

The potential for phosphorene-based devices has been compromised by the material''s fast degradation under ambient conditions. Its tendency to fully oxidize under O₂-rich and humid environments, leads to the loss of its appealing semiconducting properties. However, partially-oxidized phosphorene (po-phosphorene), has been demonstrated to remain stable over significantly longer periods of time, thereby enabling its use in sensing applications. Here, we present a computational study of po-phosphorene-based gas sensors, using the Density-Functional-based Tight Binding (DFTB) method. We show that DFTB accurately predicts the bandgap for the pristine material and po-phosphorene, the electronic transport properties of po-phosphorene at different surface oxygen concentrations, and the appropriate trends in Density-of-States (DOS) contributions caused by adsorbed gas molecules, to demonstrate its potential application in the development of gas sensors. Results are compared against the more traditional and expensive Density Functional Theory (DFT) method using generalized gradient approximation (GGA) exchange–correlation functionals, which significantly underestimates the material''s bandgap.

Computational study of surface oxidation effects on phosphorene-based gas sensors, and potential for nM L⁻¹ detection and measurement of nitrogen–oxygen moieties.     

Enhanced photocatalytic properties of a chemically modified blue phosphorene

It is high time to placate the peak demand for an efficient, economic and green fuel in the form of H₂ through photocatalytic water splitting. Several low dimensional materials have been explored for their photocatalytic properties on account of their surface to volume ratio. The present study illustrates the excellent photocatalytic potential of a two-dimensional material, viz. a chemically tempered blue-phosphorene sheet, with single atom thickness and high carrier mobility. Metal-free element, sulphur, is explored as a dopant in a 32-atom blue-phosphorene sheet. The dopant is inserted at three locations viz. central, edge and central edge positions with varying concentrations from 3.125% to 18.75% (corresponding to n = 1 to 6 sulphur atoms within a 32-atom blue-phosphorene sheet, P_32−nS_n). The cohesive energy studies predict the higher stability of even number S doped sheets as compared to their odd counterparts. Photocatalytic activity is studied in terms of band gap and band alignment for different concentrations of the former. Studies reveal that edge doping demonstrates better water molecule activation independent of S atom concentration. The edge doped systems not only provide the chemical activity to activate water, but also show feasible HER overpotentials of 1.24–1.29 eV at neutral medium. Finally, this work opens up a driving lead of non-corrosive catalysts for water molecule splitting.

Rate of photocatalysis depends on how well the structures can check the electron–hole recombination.     

Novel electrical properties and applications in kaleidoscopic graphene nanoribbons

As one of the representatives of nano-graphene materials, graphene nanoribbons (GNRs) have more novel electrical properties, highly adjustable electronic properties, and optoelectronic properties than graphene due to their diverse geometric structures and atomic precision configurations. The electrical properties and band gaps of GNRs depend on their width, length, boundary configuration and other elemental doping, etc. With the improvement of the preparation technology and level of GNRs with atomic precision, increasing number of GNRs with different configurations are being prepared. They all show novel electrical properties and high tunability, which provides a broad prospect for the application of GNRs in the field of microelectronics. Here, we summarize the latest GNR-based achievements in recent years and summarize the latest electrical properties and potential applications of GNRs.

For quasi-one-dimensional graphene nanoribbons (GNRs), adjusting its length, width, doping and heteroatom adsorption showed novel electronic properties. He has a very wide range of potential applications in the field of microelectronics.     

Electronic transport properties of PbSi Schottky-clamped transistors with a surrounding metal–insulator gate

Sustaining Moore''s law requires the design of new materials and the construction of FET. Herein, we investigated theoretically the electronic transport properties of PbSi nanowire Schottky-clamped transistors with a surrounding metal–insulator gate by employing MD simulations and the NEGF method within the extended Hückel frame. The conductance of PbSi nanowire transistors shows ballistic and symmetrical features because of the Schottky contact and the resonance transmission peak, which is gate-controlled. Interestingly, the PbSi(8,17) nanowire FET shows a high ON/OFF ratio and proves to be a typical Schottky contact between atoms as described by the EDD and EDP metrics.

Sustaining Moore''s law requires the design of new materials and the construction of FET.     

A chemical-bond-driven edge reconstruction of Sb nanoribbons and their thermoelectric properties from first-principles calculations

We present a theoretical study on the potential thermoelectric performance of antimony nanoribbons (SNRs). Based on density functional theory and the semiclassical transport model, the thermoelectric figure of merit ZT was calculated for various Sb nanoribbon sizes and different chiralities. The results indicated that the chemical-bond-driven edge reconstruction of nanoribbons (denoted as SNRs-recon) eliminated all of the dangling bonds and passivated all of the boundary antimony atoms with 3-fold coordination. SNRs-recon are the most energy favorable compared to the ribbons with unsaturated edge atoms. Semimetal to semiconductor transition occurred in SNRs-recon. The band gap was width-dependent in armchair SNRs (denoted as ASNRs-recon), whereas it was width-independent in zigzag SNRs (ZSNRs-recon). After nanolization and reconstruction, the TE properties of SNRs were enhanced due to higher Seebeck coefficient and lower thermal conductivity. The thermoelectric properties of n-doped ASNRs-recon and p-doped ZSNRs-recon showed width-dependent odd–even oscillation and eventually resulted in ZT values of 0.75 and 0.60, respectively. Upon increasing the ribbon width, ZT of n-doped ASNRs-recon decreased and approached a constant value of about 0.85. However, n-doped ZSNRs-recon exhibited poor TE performance compared with the others. Importantly, the ZT value could be optimized to as high as 1.91 at 300 K, which was larger than those of Sb-based bulk materials and 100 times that of thin Sb films. These optimizations make the materials promising room-temperature high-performance thermoelectric materials. Furthermore, the proposed new concept of chemical-bond-driven edge reconstruction may be useful for many other related systems.

Chemical-bond-driven edge reconstruction of Sb nanoribbons is energetically favorable and helps to stabilize the whole structure. All the nanoribbons are semiconducting, and their thermoelectric properties are enhanced significantly by the edge reconstruction.     

Sequential BN-doping induced tuning of electronic properties in zigzag-edged graphene nanoribbons: a computational approach

We employed first-principles methods to elaborate doping induced electronic and magnetic perturbations in one-dimensional zigzag graphene nanoribbon (ZGNR) superlattices. Consequently, the incorporation of alternate boron and nitrogen (hole–electron) centers into the hexagonal network instituted substantial modulations to electronic and magnetic properties of ZGNR. Our theoretical analysis manifested some controlled changes to electronic and magnetic properties of the ZGNR by tuning the positions (array) of impurity centers in the carbon network. Subsequent DFT based calculations also suggested that the site-specific alternate electron–hole (B/N) doping could regulate the band-gaps of the superlattices within a broad range of energy. The consequence of variation in the width of ZGNR in the electronic environment of the system was also tested. The systematic analysis of various parameters such as the structural orientations, spin-arrangements, the density of states (DOS), band structures, and local density of states envisioned a basis for the band-gap engineering in ZGNR and attributed to its feasible applications in next generation electronic device fabrication.

Incorporation of an alternate impurity array in the ZGNR don''t break the spin-degeneracy, providing the freedom to tune the electronic behaviors without affecting the spin-dependent properties.     

The effects of Stone–Wales defects on the thermal properties of bilayer armchair graphene nanoribbons

We investigate the influence of Stone–Wales (S–W) defects on the thermal properties of bilayer graphene nanoribbons (BGNRs) with armchair edges by nonequilibrium molecular dynamics simulations (NEMD). It is shown that an increasing number of S–W defects leads to a significant decrease of the thermal conductivity of BGNRs at room temperature. Moreover, the AA-stacked BGNRs have significantly higher thermal conductivity than that of the AB-stacked BGNRs for all S–W defect numbers. In the temperature range of 300–700 K, the S–W defects always have a weaker effect on heat transfer of AB-stacked BGNRs than AA-stacked BGNRs, which is closely related to their weaker anharmonic effects induced by structure defects. In addition, the simulation results are further explained by performing an analysis of phonon spectrum properties and phonon vibrational modes.

We investigate the influence of Stone–Wales (S–W) defects on the thermal properties of bilayer graphene nanoribbons (BGNRs) with armchair edges by nonequilibrium molecular dynamics simulations (NEMD).     

Drug selectivity and membrane transport properties of normal human lymphocytes

This study used Interleukin (IL)-stimulated normal human lymphocytes in culture as a model system to examine membrane transport systems and drug cytotoxicity. Normal peripheral blood mononuclear cells were stimulated with either purified IL-1 or phytohemagglutinin (PHA) and maintained for several months in IL-2. Only 'T' lymphocytes grew in culture. Amino acid transport was compared in PHA-stimulated cells and IL-stimulated cells. Both the PHA- and IL-stimulated lymphocyte cell lines had similar generation times and similar uptake and efflux of cisplatin and methotrexate. Yet, PHA-stimulated cells proved 3- to 5-fold more sensitive to the cytotoxic effects of these drugs. The greater drug sensitivity of the PHA-stimulated cell line was associated with enhanced sodium-dependent methionine transport and altered amino acid transport systems. Differences in the nutrient transport systems are comparable to those previously observed between drug sensitive and resistant cells, and may provide the biochemical basis for cisplatin and methotrexate collateral resistance.     

Electronic and optical properties of Janus ZrSSe by density functional theory

In the present work, we investigate systematically the electronic and optical properties of Janus ZrSSe using first-principles calculations. Our calculations demonstrate that the Janus ZrSSe monolayer is an indirect semiconductor at equilibrium. The band gap of the Janus ZrSSe is 1.341 eV using the Heyd–Scuseria–Ernzerhof hybrid functional, larger than the band gap of ZrSe₂ monolayer and smaller than that of ZrS₂ monolayer. Based on the analysis of the band edge alignment, we confirm that the Janus ZrSSe monolayer possesses photocatalytic activities that can be used in water splitting applications. While strain engineering plays an important role in modulating the electronic properties and optical characteristics of the Janus ZrSSe monolayer, the influence of the external electric field on these properties is negligible. The biaxial strain, ε_b, has significantly changed the band of the Janus ZrSSe monolayer, and particularly, the semiconductor–metal phase transition which occurred at ε_b = 7%. The Janus ZrSSe monolayer can absorb light in both visible and ultraviolet regions. Also, the biaxial strain has shifted the first optical gap of the Janus ZrSSe monolayer. Our findings provide additional information for the prospect of applying the Janus ZrSSe monolayer in nanoelectronic devices, especially in water splitting technology.

In the present work, we investigate systematically the electronic and optical properties of Janus ZrSSe using first-principles calculations.     

Oxygen vacancy and doping atom effect on electronic structure and optical properties of Cd2SnO4

The electronic structure and optical properties of oxygen vacancy and La-doped Cd₂SnO₄ were calculated using the plane-wave-based pseudopotential method based on the density functional theory (DFT) within the generalized gradient approximation (GGA). The formation energy of different oxygen vacancies showed that the V_O2 oxygen vacancy was easy to obtain in experiments. The Bader charge analysis is implemented to directly observe the electron transfer and distribution for each atom. The calculated band structures show that when the oxygen vacancy was introduced, the impurity energy level appeared in the band gap. The impurity levels induced by oxygen vacancies were mainly composed of O 2p orbits and a very small amount of Cd 4s orbits. After La doping based on the V_O2 oxygen vacancy of Cd₂SnO₄, the Fermi energy level entered the conduction band and overlapped with the conduction band which increased the conductivity, and the band gap value increased to above 3.0 eV. The optical calculation results showed that the transmittance of the V_O2 oxygen vacancy of Cd₂SnO₄ increased in short wavelength (<600 nm), the reflectivity increased in the infrared region compared with Cd₂SnO₄, and the transmittance increased to 90% in visible light region after La doping.

The electronic structure and optical properties of oxygen vacancy and La-doped Cd₂SnO₄ were calculated using the plane-wave-based pseudopotential method based on the density functional theory (DFT) within the generalized gradient approximation (GGA).     

Morphology and electrical characteristics of p-type ZnO microwires with zigzag rough surfaces induced by Sb doping

Sb-doped p-type ZnO microwires with zigzag rough surfaces were synthesized by two zone chemical vapor deposition. The zigzag morphology characteristics analyzed by high resolution scanning electron microscopy and transmission electron microscopy show the existence of surface defects caused by Sb doping. The incorporation of Sb into a ZnO lattice induces lattice imperfection, which is the origin of the zigzag rough surface. Photoluminescence and electrical properties of the obtained Sb-doped ZnO microwires were determined. The crossed structure microwire-based p–n homojunction device was fabricated by applying as-synthesized Sb-doped p-type ZnO microwires and undoped n-type ZnO microwires. The doped microwires demonstrate reproducible p-type conduction and enhanced rectifying behavior with increasing Sb doping concentration. The results demonstrated that the optimizable optical and electrical characteristics, controlled by increasing the doping concentration, are reflected in the surface morphology changes which would be helpful for characterizing the doping effects in micro/nanoscale materials.

Sb-doped microwires which have a zigzag rough surface demonstrate p-type conduction and enhanced rectifying behavior with increasing Sb doping concentration.     

Synthesis and gas transport properties of polyamide membranes containing PDMS groups

A series of gas-separation polyamide-poly(dimethylsiloxane) (PA-PDMS) membranes containing PDMS groups were synthesized through the polycondensation reaction. The structural characteristics of polymers were evaluated by ¹H-NMR spectroscopy (NMR), Fourier-transform infrared spectroscopy (FTIR) and UV-vis absorption spectroscopy. The permeability and selectivity behavior was studied at different temperatures (25–55 °C) and pressures (1.0–3.0 atm), using various gases, such as H₂, O₂, CO₂, CH₄, and N₂. The effect of chemical structure, PDMS content, operating pressure and temperature on gas permeability was explored and discussed. Gas-permeation measurements showed that polyamides containing PDMS groups exhibited different separation performance. The PA-PDMS-20 membrane with 20 wt% PDMS exhibited the highest selectivity (CO₂/N₂ = 41.84 and O₂/N₂ = 7.01) at 35 °C and 3.0 atm while CO₂ and O₂ permeability was 29.29 barrer and 4.91 barrer, respectively.

PA-PDMS membranes were synthesized by polycondensation reaction and the gas permeability was found to increase with an increase of PPG content, with the gas permeability of PA-PDMS-20 membrane reaching 29.29 at 35 °C and 3.0 atm.     

Electronic and structural properties of the natural dyes curcumin,bixin and indigo

An optical, electronic and structural characterisation of three natural dyes potentially interesting for application in organic solar cells, curcumin (C₂₁H₂₀O₆), bixin (C₂₅H₃₀O₄) and indigo (C₁₆H₁₀N₂O₂), was performed. X-Ray Diffraction (XRD) measurements, showed that curcumin has a higher degree of crystallinity compared to bixin and indigo. The results from the Pawley unit cell refinements for all dyes are reported. Optical absorption spectra measured by UV-Visible Spectroscopy (UV-Vis) on thermally evaporated films revealed that bixin undergoes chemical degradation upon evaporation, while curcumin and indigo appear to remain unaffected by this process. Combined Ultraviolet Photoemission Spectroscopy (UPS) and Inverse Photoemission Spectroscopy (IPES) spectra measured on the dyes revealed that all of them are hole-conducting materials and allowed for the determination of their electronic bandgaps, and Fermi level position within the gap. UV Photo-Emission Electron Microscopy (PEEM) revealed the workfunction of the dye materials and indicated that indigo has a negative electron affinity. PEEM was also used to study degradation by UV irradiation and showed that they are quite robust to UV exposure.

An optical, electronic and structural characterisation of three natural dyes potentially interesting for application in organic solar cells, curcumin (C₂₁H₂₀O₆), bixin (C₂₅H₃₀O₄) and indigo (C₁₆H₁₀N₂O₂), was performed.     

Electronic and optical properties of silicene on GaAs(111) with hydrogen intercalation: a first-principles study

In this paper, we investigated the electronic and optical properties of silicene on GaAs(111) substrates (silicene/HGaAs) on the basis of first-principles density functional theory. The hydrogen intercalation introduced substantially weakened the interaction between silicene and the GaAs(111) substrate and induced considerable bandgaps in silicene/HGaAs heterostructures. The effects of the interlayer spacing (L) between silicene and the substrate, silicene buckling height (h), biaxial strain (ε), and external electric field (F) on the electronic properties were also considered. Our results showed that the electronic properties of silicene/HGaAs heterostructures could be controlled by adjusting L and h and applying ε and an external F. Silicene/HGaAs heterostructures possessed the typical optical absorption properties of freestanding silicene and had high absorption coefficients. Besides, some strong peaks of absorption spectra and energy loss spectra existed in the ultraviolet light region, which showed that silicene/HGaAs heterostructures had evident enhancement in the ultraviolet light region. Results laid a theoretical foundation for the study of the electronic and optical properties and applications of silicene on semiconductor substrate devices.

In this paper, we investigated the electronic and optical properties of silicene on GaAs(111) substrates (silicene/HGaAs) on the basis of first-principles density functional theory.     

Electronic and optical properties of BxCyNz hybrid α-graphynes

Hybrid two-dimensional (2D) materials composed of carbon, boron, and nitrogen constitute a hot topic of research, as their flexible composition allows for tunable properties. However, while graphene-like hybrid lattices have been well characterized, systematic investigations are lacking for various 2D materials. Hence, in the present contribution, we employ first-principles calculations to investigate the structural, electronic and optical properties of what we call B_xC_yN_z hybrid α-graphynes. We considered eleven structures with stoichiometry BC₂N and varied atomic arrangements. We calculated the formation energy for each arrangement, and determined that it is low (high) when the number of boron-carbon and nitrogen-carbon bonds is low (high). We found that the formation energy of many our structures compared favorably with a previous literature proposal. Regarding the electronic properties, we found that the investigated structures are semiconducting, with band gaps ranging from 0.02 to 2.00 eV. Moreover, we determined that most of the B_xC_yN_z hybrid α-graphynes proposed here strongly absorb infrared light, and so could potentially find applications in optoelectronic devices such as heat sensors and infrared filters.

Hybrid graphynes composed of boron, carbon, and nitrogen are investigated using DFT calculations. The proposed materials are semiconductors and strongly absorb infrared light.     

Rheological and transport properties of airway secretions in cystic fibrosis-relationships with the degree of infection and severity of the disease

It has recently been suggested that in cystic fibrosis (CF), there is no rheological abnormality of airway secretions other than that associated with purulence, and that the apparent inhibition in the mucociliary transport rate might be partly due to a ciliary inhibitor present in these secretions. In order to ascertain this assumption, expectorated airway secretions were collected without salivary contamination in twenty-four CF patients and the rheological properties were measured. Using a photometric method, the effects of CF sputum samples were analysed on the ciliary beat frequency (Fm) of the frog palate, and we measured their mucociliary transport rate (TR). In all but one CF sputum, TR and Fm were lower than that of the control frog mucus (median TR: 18.7 and 11.6 mm min-1; median Fm: 12.3 and 11.3 Hz, respectively). In the eighteen patients in whom the rheological properties were outside the range for optimal mucociliary transport, the clinical Shwachman score was significantly (P less than 0.05) lower (median score: 66.2 points) than in the six patients with optimal rheologic properties (median score: 73 points). In the eleven CF patients with superinfection, the apparent viscosity (eta o) was significantly higher (P less than 0.01; median eta o: 24.4 Pa. s) and TR, expressed as a percentage of the reference value, was significantly lower (P less than 0.05; median Tr: 54.5%) in comparison with the values obtained for the thirteen non-superinfected CF patients (median eta o: 15 Pa. s and median TR: 66% respectively). The CF patients with markedly hyperviscous sputum (eta o higher than 30 Pa. s) exhibited a low Shwachman score.