Atanu Samanta

Semiconductor to metal transition in bilayer phosphorene under normal compressive strain

Phosphorene, a two-dimensional analog of black phosphorous, has been a subject of immense interest recently, due to its high carrier mobilities and a tunable bandgap. So far, tunability has been predicted to be obtained with very high compressive/tensile in-plane strains, and vertical electric field, which are difficult to achieve experimentally. Here, we show using density functional theory based calculations the possibility of tuning electronic properties by applying normal compressive strain in bilayer phosphorene. A complete and fully reversible semiconductor to metal transition has been observed at [Formula: see text] strain, which can be easily realized experimentally. Furthermore, a direct to indirect bandgap transition has also been observed at [Formula: see text] strain, which is a signature of unique band-gap modulation pattern in this material. The absence of negative frequencies in phonon spectra as a function of strain demonstrates the structural integrity of the sheets at relatively higher strain range. The carrier mobilities and effective masses also do not change significantly as a function of strain, keeping the transport properties nearly unchanged. This inherent ease of tunability of electronic properties without affecting the excellent transport properties of phosphorene sheets is expected to pave way for further fundamental research leading to phosphorene-based multi-physics devices.

Strain-induced electronic phase transition and strong enhancement of thermopower of TiS 2

Using first-principles density functional theory calculations, we show a semimetal to semiconducting electronic phase transition for bulk TiS2 by applying uniform biaxial tensile strain. This electronic phase transition is triggered by charge transfer from Ti to S, which eventually reduces the overlap between Ti-(d) and S-(p) orbitals. The electronic transport calculations show a large anisotropy in electrical conductivity and thermopower, which is due to the difference in the effective masses along the in-plane and out-of-plane directions. Strain-induced opening of band gap together with changes in dispersion of bands lead to threefold enhancement in thermopower for both p-and n-type TiS2. We further demonstrate that the uniform tensile strain, which enhances the thermoelectric performance, can be achieved by doping TiS2 with larger iso-electronic elements such as Zr or Hf at Ti sites.

Fluorinated h-BN as a magnetic semiconductor

A strategic approach toward functionalization can change properties: effect of the “oxidizer of oxygen” on hexagonal boron nitride. We report the fluorination of electrically insulating hexagonal boron nitride (h-BN) and the subsequent modification of its electronic band structure to a wide bandgap semiconductor via introduction of defect levels. The electrophilic nature of fluorine causes changes in the charge distribution around neighboring nitrogen atoms in h-BN, leading to room temperature weak ferromagnetism. The observations are further supported by theoretical calculations considering various possible configurations of fluorinated h-BN structure and their energy states. This unconventional magnetic semiconductor material could spur studies of stable two-dimensional magnetic semiconductors. Although the high thermal and chemical stability of h-BN have found a variety of uses, this chemical functionalization approach expands its functionality to electronic and magnetic devices.

Atomically thin gallium layers from solid-melt exfoliation

A unique way to synthesize innovative 2D gallenene. Among the large number of promising two-dimensional (2D) atomic layer crystals, true metallic layers are rare. Using combined theoretical and experimental approaches, we report on the stability and successful exfoliation of atomically thin “gallenene” sheets on a silicon substrate, which has two distinct atomic arrangements along crystallographic twin directions of the parent α-gallium. With a weak interface between solid and molten phases of gallium, a solid-melt interface exfoliation technique is developed to extract these layers. Phonon dispersion calculations show that gallenene can be stabilized with bulk gallium lattice parameters. The electronic band structure of gallenene shows a combination of partially filled Dirac cone and the nonlinear dispersive band near the Fermi level, suggesting that gallenene should behave as a metallic layer. Furthermore, it is observed that the strong interaction of gallenene with other 2D semiconductors induces semiconducting to metallic phase transitions in the latter, paving the way for using gallenene as promising metallic contacts in 2D devices.

Ultra-sensitive pressure dependence of bandgap of rutile-GeO2 revealed by many body perturbation theory.

The reported values of bandgap of rutile GeO2 calculated by the standard density functional theory within local-density approximation (LDA)/generalized gradient approximation (GGA) show a wide variation (∼2 eV), whose origin remains unresolved. Here, we investigate the reasons for this variation by studying the electronic structure of rutile-GeO2 using many-body perturbation theory within the GW framework. The bandgap as well as valence bandwidth at Γ-point of rutile phase shows a strong dependence on volume change, which is independent of bandgap underestimation problem of LDA/GGA. This strong dependence originates from a change in hybridization among O-p and Ge-(s and p) orbitals. Furthermore, the parabolic nature of first conduction band along X-Γ-M direction changes towards a linear dispersion with volume expansion.

Negative differential resistance in armchair silicene nanoribbons

Due to dimensional confinement of carriers and non-trivial changes in the electronic structure, novel tunable transport properties manifest in nanoscale materials. Here, we report using first-principles density functional theory and non-equilibrium Greens function formalism, the occurrence of negative differential resistance (NDR) in armchair silicene nanoribbons (ASNRs). Interestingly, NDR manifests only in pristine [Formula: see text] ASNRs, where [Formula: see text]. We show that the origin of such a novel transport phenomenon lies in the bias-induced changes in the density of states of this particular family of nanoribbons. With increasing width of the nanoribbons belonging to this family, the peak-to-valley ratios of current decrease due to the increase in the number of sub-bands leading to a reduction in NDR. NDR is possible not only in [Formula: see text] ASNRs, but also in mixed configurations of armchair and zigzag silicene nanoribbons. This universality of NDR along with its unprecedented width-induced tunability can be useful for silicene-based low-power logic and memory applications.

Resonant domain-wall-enhanced tunable microwave ferroelectrics

Ordering of ferroelectric polarization1 and its trajectory in response to an electric field2 are essential for the operation of non-volatile memories3, transducers4 and electro-optic devices5. However, for voltage control of capacitance and frequency agility in telecommunication devices, domain walls have long been thought to be a hindrance because they lead to high dielectric loss and hysteresis in the device response to an applied electric field6. To avoid these effects, tunable dielectrics are often operated under piezoelectric resonance conditions, relying on operation well above the ferroelectric Curie temperature7, where tunability is compromised. Therefore, there is an unavoidable trade-off between the requirements of high tunability and low loss in tunable dielectric devices, which leads to severe limitations on their figure of merit. Here we show that domain structure can in fact be exploited to obtain ultralow loss and exceptional frequency selectivity without piezoelectric resonance. We use intrinsically tunable materials with properties that are defined not only by their chemical composition, but also by the proximity and accessibility of thermodynamically predicted strain-induced, ferroelectric domain-wall variants8. The resulting gigahertz microwave tunability and dielectric loss are better than those of the best film devices by one to two orders of magnitude and comparable to those of bulk single crystals. The measured quality factors exceed the theoretically predicted zero-field intrinsic limit owing to domain-wall fluctuations, rather than field-induced piezoelectric oscillations, which are usually associated with resonance. Resonant frequency tuning across the entire L, S and C microwave bands (1–8 gigahertz) is achieved in an individual device—a range about 100 times larger than that of the best intrinsically tunable material. These results point to a rich phase space of possible nanometre-scale domain structures that can be used to surmount current limitations, and demonstrate a promising strategy for obtaining ultrahigh frequency agility and low-loss microwave devices.The domain-wall structure and dynamics are found to enhance, rather than inhibit, the high-frequency performance of an intrinsically tunable material, obtaining ultralow loss and exceptional frequency selectivity.

First-Principles Investigation of Black Phosphorus Synthesis

Black phosphorus (BP) is a layered semiconductor with outstanding properties, making it a promising candidate for optoelectronic and other applications. BP synthesis is an intriguing task largely due to the insufficient understanding of the synthesis mechanism. In this work, we use density functional theory calculations to examine BP and its precursor red phosphorus as they are formed from P4 building blocks. Our results suggest that, without external effects such as pressure or addition of a catalyst, the precursor is energetically favored in the initial steps of the synthesis, even though BP is the more stable allotrope. The higher energy of BP is dictated by its 2D geometry that gives rise to the higher number of high-energy strained bonds at the edge compared to the 1D geometry of red phosphorus. The elucidated BP formation pathway provides a natural explanation for the effectiveness of the recently discovered Sn/I catalyst used in BP synthesis.

Metal Immiscibility Route to Synthesis of Ultrathin Carbides, Borides, and Nitrides

Ultrathin ceramic coatings are of high interest as protective coatings from aviation to biomedical applications. Here, a generic approach of making scalable ultrathin transition metal-carbide/boride/nitride using immiscibility of two metals is demonstrated. Ultrathin tantalum carbide, nitride, and boride are grown using chemical vapor deposition by heating a tantalum-copper bilayer with corresponding precursor (C2 H2 , B powder, and NH3 ). The ultrathin crystals are found on the copper surface (opposite of the metal-metal junction). A detailed microscopy analysis followed by density functional theory based calculation demonstrates the migration mechanism, where Ta atoms prefer to stay in clusters in the Cu matrix. These ultrathin materials have good interface attachment with Cu, improving the scratch resistance and oxidation resistance of Cu. This metal-metal immiscibility system can be extended to other metals to synthesize metal carbide, boride, and nitride coatings.

Strain-induced phenomena in layered materials

Using first principles density functional theory (DFT), we investigate the effect of normal compressive strain on the bilayers of MoS2, SnS2, and their van der Waals heterostructure. These materials and the corresponding heterostructure show a universal phenomenon of reversible semiconductor-metal (S-M) transition under applied strain. Most interestingly, a van der Waals heterostructure of MoS2 and SnS2 is found to have an effective direct band gap of 0.71 eV at Γ-point. This inherent ease of tunability of electronic properties of these materials by applying strain or heterostructuring is expected to pave way for further fundamental research leading to multi-physics devices.