Probing charge traps at the 2D semiconductor/dielectric interface.

The family of 2-dimensional (2D) semiconductors is a subject of intensive scientific research due to their potential in next-generation electronics. While offering many unique properties like atomic thickness and chemically inert surfaces, the integration of 2D semiconductors with conventional dielectric materials is challenging. The charge traps at the semiconductor/dielectric interface are among many issues to be addressed before these materials can be of industrial relevance. Conventional electrical characterization methods remain inadequate to quantify the traps at the 2D semiconductor/dielectric interface since the estimations of the density of interface traps, Dit, by different techniques may yield more than an order-of-magnitude discrepancy, even when extracted from the same device. Therefore, the challenge to quantify Dit at the 2D semiconductor/dielectric interface is about finding an accurate and reliable measurement method. In this review, we discuss characterization techniques which have been used to study the 2D semiconductor/dielectric interface. Specifically, we discuss the methods based on small-signal AC measurements, subthreshold slope measurements and low-frequency noise measurements. While these approaches were developed for silicon-based technology, 2D semiconductor devices possess a set of unique challenges requiring a careful re-evaluation when using these characterization techniques. We examine the conventional methods based on their efficacy and accuracy in differentiating various types of trap states and provide guidance to find an appropriate method for charge trap analysis and estimation of Dit at 2D semiconductor/dielectric interfaces.

Large-bias spectroscopy of Yu-Shiba-Rusinov states in a double quantum dot.

We have performed tunnel transport spectroscopy on a quantum dot (QD) molecule proximitized by a superconducting contact. In such a system, the scattering between QD spins and Bogoliubov quasiparticles leads to the formation of Yu-Shiba-Rusinov (YSR) states within the superconducting gap. In this work, we investigate interactions appearing when one- and two-electron spin states in a double-QD energetically align with the superconducting gap edge. We find that the inter-dot spin-triplet state interacts considerably stronger with the superconductor than the corresponding singlet, pointing to stronger screening. By forming a ring molecule with a significant orbital contribution to the effectiveg-factor, we observe interactions of all four spin-orbital one-electron states with the superconductor under a weak magnetic field.

Josephson Junction π-0 Transition Induced by Orbital Hybridization in a Double Quantum Dot.

In this Letter, we manipulate the phase shift of a Josephson junction using a parallel double quantum dot (QD). By employing a superconducting quantum interference device, we determine how orbital hybridization and detuning affect the current-phase relation in the Coulomb blockade regime. For weak hybridization between the QDs, we find π junction characteristics if at least one QD has an unpaired electron. Notably the critical current is higher when both QDs have an odd electron occupation. By increasing the inter-QD hybridization the critical current is reduced, until eventually a π-0 transition occurs. A similar transition appears when detuning the QD levels at finite hybridization. Based on a zero-bandwidth model, we argue that both cases of phase-shift transitions can be understood considering an increased weight of states with a double occupancy in the ground state and with the Cooper pair transport dominated by local Andreev reflection.

Effects of Parity and Symmetry on the Aharonov-Bohm Phase of a Quantum Ring.

We experimentally investigate the properties of one-dimensional quantum rings that form near the surface of nanowire quantum dots. In agreement with theoretical predictions, we observe the appearance of forbidden gaps in the evolution of states in a magnetic field as the symmetry of a quantum ring is reduced. For a twofold symmetry, our experiments confirm that orbital states are grouped pairwise. Here, a π-phase shift can be introduced in the Aharonov-Bohm relation by controlling the relative orbital parity using an electric field. Studying rings with higher symmetry, we note exceptionally large orbital contributions to the effective g-factor (up to 300), which are many times higher than those previously reported. These findings show that the properties of a phase-coherent system can be significantly altered by the nanostructure symmetry and its interplay with wave function parity.

Charged Layered Boron Nitride-Nanoflake Membranes for Efficient Ion Separation and Water Purification.

2D layered nanomaterials have attracted considerable attention for their potential for highly efficient separations, among other applications. Here, a 2D lamellar membrane synthesized using hexagonal boron nitride nanoflakes (h-BNF) for highly efficient ion separation is reported. The ion-rejection performance and the water permeance of the membrane as a function of the ionic radius, ion valance, and solution pH are investigated. The nonfunctionalized h-BNF membranes show excellent ion rejection for small sized salt ions as well as for anionic dyes (>97%) while maintaining a high water permeability, ≈1.0 × 10-3 L m m-2 h-1 bar-1 ). Experiments show that the ion-rejection performance of the membrane can be tuned by changing the solution pH. The results also suggest that the rejection is influenced by the ionic size and the electrostatic repulsion between fixed negative charges on the BN surface and the mobile ions, and is consistent with the Donnan equilibrium model. These simple-to-fabricate h-BNF membranes show a unique combination of excellent ion selectivity and high permeability compared to other 2D membranes.

Strain in a single wrinkle on an MoS2 flake for in-plane realignment of band structure for enhanced photo-response.

Since 2D transition metal dichalcogenides (TMDs) exhibit strain-tunable bandgaps, locally confining strain can allow lateral manipulation of their band structure, in-plane carrier transport and optical transitions. Herein, we show that a single wrinkle (width = 10 nm-10 µm) on an MoS2 flake can induce confined uniaxial strain to reduce the local bandgap (40-60 meV per % deformation), producing a microscopic exciton funnel with an enhancement in photocurrent over flat MoS2 devices. This study also shows that wrinkles can spatially reconfigure the distribution of dopants and enhance the light absorption in the MoS2 layer via Fabry-Perot interference in its nanocavity. In the field-effect transistor studies on the MoS2 flat-wrinkle-flat device-structure, a higher carrier mobility and an improvement in the on/off ratio were exhibited in the devices with a single wrinkle. This phenomenon is attributed to the built-in potential induced by the bandgap reduction at the wrinkle site and the change in doping of the suspended wrinkle. The wrinkle-induced tunability of the local bandgap and manipulation of the spatial transport barriers, and the enhanced light absorption can enable development of next-generation electronic and optoelectronic devices guided by in-plane deformation of 2D nanomaterials.

WS2-induced enhanced optical absorption and efficiency in graphene/silicon heterojunction photovoltaic cells.

Van Hove singularity (VHS) induced enhancement of visible-frequency absorption in atomically-thin two-dimensional (2D) crystals provides an opportunity for improved light management in photovoltaics; however, it requires the 2D nanomaterial to be in close vicinity of a photojunction. In this report, we design a Schottky junction-based photovoltaic system with single-layer graphene atop n-type silicon (n-Si), which is interfaced directly with a few layers of tungsten disulfide (WS2) via a bottom-up CVD synthesis strategy. An enhanced power conversion efficiency in the architecture of WS2-graphene/n-Si is observed compared to graphene/n-Si. Here, the WS2 induced photon absorption, with only three atoms above the photo-junction, enhanced the short-circuit current density (Jsc), and the reconfiguration of the energy band structure led to effective built-in electric field induced charge carrier transport (enhanced open-circuit voltage (Voc)). Similar to a graphene/n-Si Schottky junction, the WS2-graphene/n-Si double junction exhibited non-linear current density-voltage (J-V) characteristics with a 4-fold increase in Jsc (2.28 mA cm-2 in comparison with 0.52 mA cm-2 for graphene/n-Si) and 40% increase in the Voc (184 mV compared to 130 mV for graphene/n-Si) with a 6-fold increase in the photovoltaic power conversion efficiency. Futuristically, we envision an evolution in 2D heterojunctions with sharp transitions in properties within a few nanometers enabling control on optical absorption, carrier distribution, and band structure for applications including tandem photovoltaic cells and 2D optoelectronic circuit-switches.

Chemical Interaction-Guided, Metal-Free Growth of Large-Area Hexagonal Boron Nitride on Silicon-Based Substrates.

Hexagonal boron nitride (h-BN) is an ideal platform for interfacing with two-dimensional (2D) nanomaterials to reduce carrier scattering for high-quality 2D electronics. However, scalable, transfer-free growth of hexagonal boron nitride (h-BN) remains a challenge. Currently, h-BN-based 2D heterostructures require exfoliation or chemical transfer of h-BN grown on metals resulting in small areas or significant interfacial impurities. Here, we demonstrate a surface-chemistry-influenced transfer-free growth of large-area, uniform, and smooth h-BN directly on silicon (Si)-based substrates, including Si, silicon nitride (Si3N4), and silicon dioxide (SiO2), via low-pressure chemical vapor deposition. The growth rates increase with substrate electronegativity, Si < Si3N4 < SiO2, consistent with the adsorption rates calculated for the precursor molecules via atomistic molecular dynamics simulations. Under graphene with high grain density, this h-BN film acts as a polymer-free, planar-dielectric interface increasing carrier mobility by 3.5-fold attributed to reduced surface roughness and charged impurities. This single-step, chemical interaction guided, metal-free growth mechanism of h-BN for graphene heterostructures establishes a potential pathway for the design of complex and integrated 2D-heterostructured circuitry.

Electrical Transport and Network Percolation in Graphene and Boron Nitride Mixed-Platelet Structures.

Percolating network of mixed 2D nanomaterials (2DNs) can leverage the unique electronic structures of different 2DNs, their interfacial doping, manipulable conduction pathways, and local traps. Here, we report on the percolation mechanism and electro-capacitive transport pathways of mixed-platelet network of hexagonal boron nitride (hBN) and reduced graphene oxide (rGO), two isostructural and isoelectronic 2DNs. The transport mechanism is explained in terms of electron hopping through isolated hBN defect traps between rGO (possibly via electron tunneling/hopping through "funneling" points). With optical bandgaps of 4.57 and 4.08 eV for the hBN-domains and 2.18 eV for the rGO domains, the network of hBN with rGO exhibits Poole-Frenkel emission-based transport with mean hopping gap of 1.12 nm (∼hBN trilayer) and an activation barrier of ∼15 ± 0.7 meV. Further, hBN (1.7 pF) has a 6-fold lower capacitance than 1:1 hBN:rGO, which has a resistance 2 orders of magnitude higher than that of rGO (1.46 MΩ). These carrier transport results can be applied to other multi-2DN networks for development of next-generation functional 2D-devices.

Comparative Study of Water Adsorption on a H(+) and K(+) Ion Exposed Mica Surface: Monte Carlo Simulation Study.

Clay minerals are used in variety of applications ranging from composites to electronic devices. For their efficient use in such areas, understanding the effect of surface-active agents on interfacial properties is essential. We investigated the role of surface ions in the adsorption of water molecules by using a muscovite mica surface populated with two different, H(+) and K(+), surface ions. A series of grand canonical Monte Carlo (GCMC) simulations at various relative vapor pressures (p/p0) were performed to obtain the water structure and adsorption isotherm on the H(+)-exposed mica (H-mica) surface. The obtained results were compared to the recent simulation data of water adsorption on the K(+)-exposed mica (K-mica) surface reported by Malani and Ayyappa (Malani, A.; Ayappa, K. G. J. Phys. Chem. B 2009, 113, 1058-1067). Water molecules formed two prominent layers adjacent to the H-mica surface, whereas molecular layering was observed adjacent to the K-mica surface. The adsorption isotherm of water on the K-mica surface was characterized by three stages that corresponded to rapid adsorption in the initial regime below p/p0 = 0.1, followed by a linear development regime for p/p0 = 0.1-0.7 and rapid film thickening for p/p0 ≥ 0.7, whereas only latter two regimes were observed in the H-mica system. In addition, the film thickness of adsorbed water molecules for p/p0 < 0.7 was lower as compared to that for the K-mica surface and comparable beyond. The film thickness obtained from the MC simulations was in excellent agreement with the interferometry experimental data of Balmer et al. (Balmer, T. E.; Christenson, H. K.; Spencer, N. D.; Heuberger, M. Langmuir 2008, 24, 1566-1569). It was observed that the hydration behaviors of the two ions were completely different and depended on the size of their hydration shell and their ability to form hydrogen bonds. The behavior of water adsorption between these two cases was illustrated using the water density distribution, orientational distributions, hydrogen bonding, and isosteric heats of adsorption.

Large-Area, Transfer-Free, Oxide-Assisted Synthesis of Hexagonal Boron Nitride Films and Their Heterostructures with MoS2 and WS2.

Ultrasmooth hexagonal boron nitride (h-BN) can dramatically enhance the carrier/phonon transport in interfaced transition metal dichalcogenides (TMDs), and amplify the effect of quantum capacitance in field-effect gating. All of the current processes to realize h-BN-based heterostructures involve transfer or exfoliation. Rational chemistries and process techniques are still required to produce large-area, transfer-free, directly grown TMDs/BN heterostructures. Here, we demonstrate a novel boron-oxygen chemistry route for oxide-assisted nucleation and growth of large-area, uniform, and ultrathin h-BN directly on oxidized substrates (B/N atomic ratio = 1:1.16 ± 0.03 and optical band gap = 5.51 eV). These intimately interfaced, van der Waals heterostructures of MoS2/h-BN and WS2/h-BN benefit from 6.27-fold reduced roughness of h-BN in comparison to SiO2. This leads to reduction in scattering from roughness and charged impurities, and enhanced carrier mobility verified by an increase in electrical conductivity (5 times for MoS2/h-BN and 2 times for WS2/h-BN). Further, the heterostructures are devoid of wrinkles and adsorbates, which is critical for 2D nanoelectronics. The versatile process can potentially be extrapolated to realize a variety of heterostructures with complex sandwiched 2D electronic circuitry.