A review on transport characteristics and bio-sensing applications of silicene.

Silicene, a silicon counterpart of graphene, has been predicted to possess Dirac fermions. The effective spin-orbit interaction in silicene is quite significant compared to graphene; as a result, buckled silicene exhibits a finite band gap of a few meV at the Dirac point. This band gap can be further tailored by applying in plane strain, an external electric field, chemical functionalization and defects. This special feature allows silicene and its various derivatives as potential candidates for device applications. In this topical review, we would like to explore the transport features of the pristine silicene and its possible nano derivatives. As a part of it, Thermoelectric properties as well as several routes for thermoelectric enhancement in silicene are investigated. Besides, the recent progress in biosensing applications of silicene and its hetero-structures will be highlighted. We hope the results obtained from recent experimental and theoretical studies in silicene will setup a benchmark in diverse applications such as in spintronics, bio-sensing and opto-electronic devices.

Spin-state switching: chemical modulation and the impact of intermolecular interactions in manganese(III) complexes.

A series of mononuclear manganese(III) complexes [Mn(X-sal2-323)](ReO4) (X = 5 Cl, 1; X = 5 Br, 2; X = 3,5 Cl, 3; X = 3,5 Br, 4; and X = 5 NO2, 5), containing hexadentate ligands prepared using the condensation of N,N'-bis(3-aminopropyl)ethylenediamine and 5- or 3,5-substituted salicylaldehyde, has been synthesized. Variable temperature single-crystal X-ray diffraction, magnetic, spectroscopic, electrochemical, and spectroelectrochemical analyses, and theoretical calculations have been used to explore the role of various ligand substituents in the spin-state switching behavior of the prepared manganese(III) complexes. All five complexes consist of an analogous distorted octahedral monocationic MnN4O2 surrounding offered by the flexible hexadentate ligand and ReO4- as the counter anion. However, a disordered water molecule was detected in complex 4. Complexes 1 (X = 5 Cl) and 5 (X = 5 NO2) show gradual and complete spin-state switching between the high-spin (HS) (S = 2) and the low-spin (LS) (S = 1) state with T1/2 values of 146 and 115 K respectively, while an abrupt and complete transition at 95 K was observed for complex 2 (X = 5 Br). Alternatively, complex 3 (X = 3, 5 Cl) exhibits an incomplete and sharp transition between the HS and LS states at 104 K, while complex 4 (X = 3, 5 Br) (desolvated) remains almost LS up to 300 K and then displays gradual and incomplete SCO at a higher temperature. The nature of the spin-state switch and transition temperature suggest that the structural effect (cooperativity) plays a more significant role in comparison with the electronic effect coming from various substituents (Cl, Br, and NO2), which is further supported by the detailed structural, electrochemical, and theoretical studies.

Non-equivalent nature of acetylenic bonds in typical square graphynes and intricate negative differential resistance characteristics.

The role of acetylenic linkage in determining the exotic band structures of 4, 12, 2- and 4, 12, 4- graphynes is reported. The Dirac bands, as confirmed by both density functional theory and tight-binding calculations, are robust and stable over a wide range of hopping parameters betweensp-sp-hybridized carbon atoms. The shifting of the crossing points of the Dirac bands along thek-path of these two square graphynes is found to be in opposite direction with the hopping along with the acetylenic bond. A real space decimation scheme has also been adopted for understanding this interesting behavior of the band structure of these two graphynes. The condition for the appearance of a nodal ring in the band structure has been explored and critically tested by appropriate Boron-Nitrogen doping. Moreover, both the graphynes exhibit negative differential resistance in their current-voltage characteristics, with 4, 12, 2- graphynes showing superiority.

Application of the real space decimation method in determining intricate electronic phases of matter: a review.

The real space decimation method has been successfully applied over the years to understand the critical phenomena as well as the nature of single particle excitations in periodic, quasiperiodic, fractal, and decorated lattices in one dimension and beyond. The power of the method is specially revealed through its application in lattice models, leading to an elegant understanding of the nature of the single-particle states and the corresponding transport properties. In this review, we discuss, using a variety of decorated lattices, how the realm of this method is extended to unravel diverse electronic phases of matter, such as the Dirac systems, or lattices exhibiting flat bands and topological phase transitions.

Emerging properties of carbon based 2D material beyond graphene.

Graphene turns out to be the pioneering material for setting up boulevard to a new zoo of recently proposed carbon based novel two dimensional (2D) analogues. It is evident that their electronic, optical and other related properties are utterly different from that of graphene because of the distinct intriguing morphology. For instance, the revolutionary emergence of Dirac cones in graphene is particularly hard to find in most of the other 2D materials. As a consequence the crystal symmetries indeed act as a major role for predicting electronic band structure. Since tight binding calculations have become an indispensable tool in electronic band structure calculation, we indicate the implication of such method in graphene's allotropes beyond hexagonal symmetry. It is to be noted that some of these graphene allotropes successfully overcome the inherent drawback of the zero band gap nature of graphene. As a result, these 2D nanomaterials exhibit great potential in a broad spectrum of applications, viz nanoelectronics, nanooptics, gas sensors, gas storages, catalysis, and other specific applications. The miniaturization of high performance graphene allotrope based gas sensors to microscopic or even nanosized range has also been critically discussed. In addition, various optical properties like the dielectric functions, optical conductivity, electron energy loss spectra reveal that these systems can be used in opto-electronic devices. Nonetheless, the honeycomb lattice of graphene is not superconducting. However, it is proposed that the tetragonal form of graphene can be intruded to form new hybrid 2D materials to achieve novel superconducting device at attainable conditions. These dynamic experimental prospects demand further functionalization of these systems to enhance the efficiency and the field of multifunctionality. This topical review aims to highlight the latest advances in carbon based 2D materials beyond graphene from the basic theoretical as well as future application perspectives.

Correction: Electric field induced band tuning, optical and thermoelectric responses in tetragonal germanene: a theoretical approach.

Correction for 'Electric field induced band tuning, optical and thermoelectric responses in tetragonal germanene: a theoretical approach' by Supriya Ghosal et al., Phys. Chem. Chem. Phys., 2020, 22, 19957-19968, DOI: 10.1039/D0CP03892J.

Electric field induced band tuning, optical and thermoelectric responses in tetragonal germanene: a theoretical approach.

In this article, we have systematically explored the electronic, optical and thermoelectric properties of tetragonal germanene (T-Ge) using first principles calculations. The ground state geometry of pristine T-Ge is buckled and exhibits nodal line semi-metallic behaviour. In addition, we have proposed a tight binding (TB) model Hamiltonian that efficiently explains the emergence of double Dirac points at the Fermi level of T-Ge. Furthermore, a hopping relation has been explored at which both Dirac points merge and then annihilate resulting in a direct band gap at the Γ point. To exploit the buckling of the system, we have employed a transverse electric field, which invariably breaks the sublattice symmetry and removes the degeneracies at the Fermi surface. Furthermore, the band gap at the Dirac points varies linearly with the external electric field strength. Our TB Hamiltonian adequately satisfies the first principles results even in the presence of an external electric field. Moreover, we have found that T-Ge offers efficient tuning of band gaps at the Dirac points compared to other buckled systems viz. hexagonal silicene and germanene. In addition, the optical behaviour of T-Ge has been explained in accordance with the electronic states of the system. The strong optical responses in a low energy region make the material efficient for optical nanodevice applications. Moreover, T-Ge shows relatively better thermoelectric behaviour than graphene. Therefore, the external electric field induced tunable band gap and intriguing low energy optical signals pave the way to choose T-Ge as a smart choice for optoelectronic device applications. Finally we have suggested probable routes for experimental realization of the T-Ge structure.

A review on role of tetra-rings in graphene systems and their possible applications.

Inspired by the success of graphene, various two-dimensional (2D) non-hexagonal graphene allotropes having sp2-bonded tetragonal rings in free-standing (hypothetical) form and on different substrates have been proposed recently. These systems have also been fabricated after modifying the topology of graphene by chemical processes. In this review, we would like to indicate the role of tetra-rings and the local symmetry breaking on the structural, electronic and optical properties of the graphene system. First-principles computations have demonstrated that the tetragonal graphene (TG) allotrope exhibits appreciable thermodynamic stability. The band structure of the TG nanoribbons (TGNRs) strongly depends on the size and edge geometry. This fact has been supported by the transport properties of TGNRs. The optical properties and Raman modes of this graphene allotrope have been well explored for characterisation purposes. Recently, a tight-binding model was used to unravel the metal-to-semiconductor transition under the influence of external magnetic fluxes. Even the introduction of transition metal atoms into this non-hexagonal network can control the magnetic response of the TG sheet. Furthermore, the collective effect of B-N doping and confinement effect on the structural and electronic properties of TG systems has been investigated. We also suggest future directions to be explored to make the synthesis of T graphene and its various derivatives/allotropes viable for the verification of theoretical predictions. It is observed that these doped systems act as a potential candidate for carbon monoxide gas sensing and current rectification devices. Therefore, all these experimental, numerical and analytical studies related to non-hexagonal TG systems are extremely important from a basic science point of view as well as for applications in sensing, optoelectronic and photonic devices.

The topology and robustness of two Dirac cones in S-graphene: A tight binding approach.

Present work reports an elegant method to address the emergence of two Dirac cones in a non-hexagonal graphene allotrope S-graphene (SG). We have availed nearest neighbour tight binding (NNTB) model to validate the existence of two Dirac cones reported from density functional theory (DFT) computations. Besides, the real space renormalization group (RSRG) scheme clearly reveals the key reason behind the emergence of two Dirac cones associated with the given topology. Furthermore, the robustness of these Dirac cones has been explored in terms of hopping parameters. As an important note, the Fermi velocity of the SG system (vF [Formula: see text] c/80) is almost 3.75 times that of the graphene. It has been observed that the Dirac cones can be easily shifted along the symmetry lines without breaking the degeneracy. We have attained two different conditions based on the sole relations of hopping parameters and on-site energies to break the degeneracy. Further, in order to perceive the topological aspect of the system we have obtained the phase diagram and Chern number of Haldane model. This exact analytical method along with the supported DFT computation will be very effective in studying the intrinsic behaviour of the Dirac materials other than graphene.

Acetylenic linkage dependent electronic and optical behaviour of morphologically distinct '-ynes'.

We have critically examined the key role of acetylenic linkages (-C[triple bond, length as m-dash]C-) in determining the opto-electronic responses of dynamically stable tetragonal (T) '-ynes' with the help of a density functional theory method. The presence of -C[triple bond, length as m-dash]C- between two tetra-rings invariably flips the electronic bands about the Fermi level. The underlying physics has been critically addressed with the help of a real space renormalization group (RSRG) scheme under a tight binding (TB) approximation. Besides, we have proposed an elegant approach to introduce and tune a band gap in the customarily metallic T graphene allotrope. The quantum dots of these systems exhibit diode like current-voltage (I-V) characteristics and can be used in negative differential resistance devices. In addition, the anisotropic optical properties evidently support the electronic states of the systems. In particular, the static dielectric constants for some of these '-ynes' are enhanced compared to graphene and T graphene. The effective number of electrons participating in an interband transition shows saturation over 30 eV. Furthermore, electron energy loss spectra (EELS) peaks are consistent with the plasma frequencies of the corresponding systems. The intrinsic responses of the -C[triple bond, length as m-dash]C- in these systems are extremely important for basic science and nanodevice research.

Optical properties and magnetic flux-induced electronic band tuning of a T-graphene sheet and nanoribbon.

Tetragonal graphene (T-graphene) is a theoretically proposed dynamically stable, metallic allotrope of graphene. In this theoretical investigation, a tight binding (TB) model is used to unravel the metal to semiconductor transition of this 2D sheet under the influence of an external magnetic flux. In addition, the environment under which the sheet exposes an appreciable direct band gap of 1.41 ± 0.01 eV is examined. Similarly, the electronic band structure of the narrowest armchair T-graphene nanoribbon (NATGNR) also gets modified with different combinations of magnetic fluxes through the elementary rings. The band tuning parameters are critically identified for both systems. It is observed that the induced band gaps vary remarkably with the tuning parameters. We have also introduced an exact analytical approach to address the band structure of the NATGNR in the absence of any magnetic flux. Finally, the optical properties of the sheet and NATGNR are also critically analysed for both parallel and perpendicular polarizations with the help of density functional theory (DFT). Our study predicts that this material and its nanoribbons can be used in optoelectronic devices.