Non-Linear Optics at Twist Interfaces in h-BN/SiC Heterostructures.

Understanding the emergent electronic structure in twisted atomically thin layers has led to the exciting field of twistronics. However, practical applications of such systems are challenging since the specific angular correlations between the layers must be precisely controlled and the layers have to be single crystalline with uniform atomic ordering. Here, an alternative, simple, and scalable approach is suggested, where nanocrystallinetwo-dimensional (2D) film on 3D substrates yields twisted-interface-dependent properties. Ultrawide-bandgap hexagonal boron nitride (h-BN) thin films are directly grown on high in-plane lattice mismatched wide-bandgap silicon carbide (4H-SiC) substrates to explore the twist-dependent structure-property correlations. Concurrently, nanocrystalline h-BN thin film shows strong non-linear second-harmonic generation and ultra-low cross-plane thermal conductivity at room temperature, which are attributed to the twisted domain edges between van der Waals stacked nanocrystals with random in-plane orientations. First-principles calculations based on time-dependent density functional theory manifest strong even-order optical nonlinearity in twisted h-BN layers. This work unveils that directly deposited 2D nanocrystalline thin film on 3D substrates could provide easily accessible twist-interfaces, therefore enabling a simple and scalable approach to utilize the 2D-twistronics integrated in 3D material devices for next-generation nanotechnology.

Phase Stability of Hexagonal/Cubic Boron Nitride Nanocomposites.

Boron nitride (BN) is an exceptional material, and among its polymorphs, two-dimensional (2D) hexagonal and three-dimensional (3D) cubic BN (h-BN and c-BN) phases are most common. The phase stability regimes of these BN phases are still under debate, and phase transformations of h-BN/c-BN remain a topic of interest. Here, we investigate the phase stability of 2D/3D h-BN/c-BN nanocomposites and show that the coexistence of two phases can lead to strong nonlinear optical properties and low thermal conductivity at room temperature. Furthermore, spark-plasma sintering of the nanocomposite shows complete phase transformation to 2D h-BN with improved crystalline quality, where 3D c-BN possibly governs the nucleation and growth kinetics. Our demonstration might be insightful in phase engineering of BN polymorph-based nanocomposites with desirable properties for optoelectronics and thermal energy management applications.

Unravelling the room temperature growth of two-dimensional h-BN nanosheets for multifunctional applications.

The room temperature growth of two-dimensional van der Waals (2D-vdW) materials is indispensable for state-of-the-art nanotechnology. Low temperature growth supersedes the requirement of elevated growth temperatures accompanied with high thermal budgets. Moreover, for electronic applications, low or room temperature growth reduces the possibility of intrinsic film-substrate interfacial thermal diffusion related deterioration of the functional properties and the consequent deterioration of the device performance. Here, we demonstrated the growth of ultrawide-bandgap boron nitride (BN) at room temperature by using the pulsed laser deposition (PLD) process, which exhibited various functional properties for potential applications. Comprehensive chemical, spectroscopic and microscopic characterizations confirmed the growth of ordered nanosheet-like hexagonal BN (h-BN). Functionally, the nanosheets show hydrophobicity, high lubricity (low coefficient of friction), and a low refractive index within the visible to near-infrared wavelength range, and room temperature single-photon quantum emission. Our work unveils an important step that brings a plethora of potential applications for these room temperature grown h-BN nanosheets as the synthesis can be feasible on any given substrate, thus creating a scenario for "h-BN on demand" under a frugal thermal budget.

Temperature Sensitivity of 14N-V and 15N-V Ground-State Manifolds.

We measure electron- and nuclear-spin transition frequencies in the ground state of nitrogen-vacancy (N-V) centers in diamond for two nitrogen isotopes (14N-V and 15N-V) over temperatures ranging from 77 to 400 K. Measurements are performed using Ramsey interferometry and direct optical readout of the nuclear and electron spins. We extract coupling parameters Q (for 14N-V), D, A‖, A⊥, and γe/γn, and their temperature dependences for both isotopes. The temperature dependences of the nuclear-spin transitions within the ms=0 spin manifold near room temperature are found to be 0.52(1) ppm/K for 14N-V(|mI = -1⟩ ↔ |mI = +1⟩) and -1.1(1) ppm/K for 15N-V(|mI = -1/2⟩ ↔ |mI = +1/2⟩). An isotopic shift in the zero-field splitting parameter D between 14N-V and 15N-V is measured to be ~ 120 kHz. Residual transverse magnetic fields are observed to shift the nuclear-spin transition frequencies, especially for 15N-V. We have precisely determined the set of parameters relevant for the development of nuclear-spin-based diamond quantum sensors with greatly reduced sensitivity to environmental factors.

Demonstration of diamond nuclear spin gyroscope.

We demonstrate the operation of a rotation sensor based on the nitrogen-14 (14N) nuclear spins intrinsic to nitrogen-vacancy (NV) color centers in diamond. The sensor uses optical polarization and readout of the nuclei and a radio-frequency double-quantum pulse protocol that monitors 14N nuclear spin precession. This measurement protocol suppresses the sensitivity to temperature variations in the 14N quadrupole splitting, and it does not require microwave pulses resonant with the NV electron spin transitions. The device was tested on a rotation platform and demonstrated a sensitivity of 4.7°/s (13 mHz/Hz), with a bias stability of 0.4 °/s (1.1 mHz).

Structure, Properties and Applications of Two-Dimensional Hexagonal Boron Nitride.

Hexagonal boron nitride (h-BN) has emerged as a strong candidate for two-dimensional (2D) material owing to its exciting optoelectrical properties combined with mechanical robustness, thermal stability, and chemical inertness. Super-thin h-BN layers have gained significant attention from the scientific community for many applications, including nanoelectronics, photonics, biomedical, anti-corrosion, and catalysis, among others. This review provides a systematic elaboration of the structural, electrical, mechanical, optical, and thermal properties of h-BN followed by a comprehensive account of state-of-the-art synthesis strategies for 2D h-BN, including chemical exfoliation, chemical, and physical vapor deposition, and other methods that have been successfully developed in recent years. It further elaborates a wide variety of processing routes developed for doping, substitution, functionalization, and combination with other materials to form heterostructures. Based on the extraordinary properties and thermal-mechanical-chemical stability of 2D h-BN, various potential applications of these structures are described.

Van der Waals interfaces in epitaxial vertical metal/2D/3D semiconductor heterojunctions of monolayer MoS2 and GaN.

A promising approach for high speed and high power electronics is to integrate two-dimensional (2D) materials with conventional electronic components such as bulk (3D) semiconductors and metals. In this study we explore a basic integration step of inserting a single monolayer MoS2 (1L-MoS2) inside a Au/p-GaN junction and elucidate how it impacts the structural and electrical properties of the junction. Epitaxial 1L-MoS2 in the form of 1-2 µm triangle domains are grown by powder vaporization on a p-doped GaN substrate, and the Au capping layer is deposited by evaporation. Transmission electron microscopy (TEM) of the van der Waals interface indicates that 1L-MoS2 remained distinct and intact between the Au and GaN and that the Au is epitaxial to GaN only when the 1L-MoS2 is present. Quantitative TEM analyses of the van der Waals interfaces are performed and yielded the atomic plane spacings in the heterojunction. Electrical characterization of the all-epitaxial, vertical Au/1L-MoS2/p-GaN heterojunctions enables the derivations of Schottky barrier heights (SBH) and drawing of the band alignment diagram. Notably, 1L-MoS2 appears to be electronically semi-transparent, and thus can be considered as a modifier to the Au contact rather than an independent semiconductor component forming a pn-junction. The I-V analysis and our first principles calculation indicated Fermi level pinning and substantial band bending in GaN at the interface. Lastly, we illustrate how the depletion regions are formed in a bipolar junction with an ultrathin monolayer component using the calculated distribution of the charge density across the Au/1L-MoS2/GaN junction.

Vertical 2D/3D Semiconductor Heterostructures Based on Epitaxial Molybdenum Disulfide and Gallium Nitride.

When designing semiconductor heterostructures, it is expected that epitaxial alignment will facilitate low-defect interfaces and efficient vertical transport. Here, we report lattice-matched epitaxial growth of molybdenum disulfide (MoS2) directly on gallium nitride (GaN), resulting in high-quality, unstrained, single-layer MoS2 with strict registry to the GaN lattice. These results present a promising path toward the implementation of high-performance electronic devices based on 2D/3D vertical heterostructures, where each of the 3D and 2D semiconductors is both a template for subsequent epitaxial growth and an active component of the device. The MoS2 monolayer triangles average 1 µm along each side, with monolayer blankets (merged triangles) exhibiting properties similar to that of single-crystal MoS2 sheets. Photoluminescence, Raman, atomic force microscopy, and X-ray photoelectron spectroscopy analyses identified monolayer MoS2 with a prominent 20-fold enhancement of photoluminescence in the center regions of larger triangles. The MoS2/GaN structures are shown to electrically conduct in the out-of-plane direction, confirming the potential of directly synthesized 2D/3D semiconductor heterostructures for vertical current flow. Finally, we estimate a MoS2/GaN contact resistivity to be less than 4 Ω·cm(2) and current spreading in the MoS2 monolayer of approximately 1 µm in diameter.

Highly scalable, atomically thin WSe2 grown via metal-organic chemical vapor deposition.

Tungsten diselenide (WSe2) is a two-dimensional material that is of interest for next-generation electronic and optoelectronic devices due to its direct bandgap of 1.65 eV in the monolayer form and excellent transport properties. However, technologies based on this 2D material cannot be realized without a scalable synthesis process. Here, we demonstrate the first scalable synthesis of large-area, mono and few-layer WSe2 via metal-organic chemical vapor deposition using tungsten hexacarbonyl (W(CO)6) and dimethylselenium ((CH3)2Se). In addition to being intrinsically scalable, this technique allows for the precise control of the vapor-phase chemistry, which is unobtainable using more traditional oxide vaporization routes. We show that temperature, pressure, Se:W ratio, and substrate choice have a strong impact on the ensuing atomic layer structure, with optimized conditions yielding >8 µm size domains. Raman spectroscopy, atomic force microscopy (AFM), and cross-sectional transmission electron microscopy (TEM) confirm crystalline monoto-multilayer WSe2 is achievable. Finally, TEM and vertical current/voltage transport provide evidence that a pristine van der Waals gap exists in WSe2/graphene heterostructures.

Strain and structure heterogeneity in MoS2 atomic layers grown by chemical vapour deposition.

Monolayer molybdenum disulfide (MoS2) has attracted tremendous attention due to its promising applications in high-performance field-effect transistors, phototransistors, spintronic devices and nonlinear optics. The enhanced photoluminescence effect in monolayer MoS2 was discovered and, as a strong tool, was employed for strain and defect analysis in MoS2. Recently, large-size monolayer MoS2 has been produced by chemical vapour deposition, but has not yet been fully explored. Here we systematically characterize chemical vapour deposition-grown MoS2 by photoluminescence spectroscopy and mapping and demonstrate non-uniform strain in single-crystalline monolayer MoS2 and strain-induced bandgap engineering. We also evaluate the effective strain transferred from polymer substrates to MoS2 by three-dimensional finite element analysis. Furthermore, our work demonstrates that photoluminescence mapping can be used as a non-contact approach for quick identification of grain boundaries in MoS2.

Electrical transport properties of polycrystalline monolayer molybdenum disulfide.

Semiconducting MoS2 monolayers have shown many promising electrical properties, and the inevitable polycrystallinity in synthetic, large-area films renders understanding the effect of structural defects, such as grain boundaries (GBs, or line-defects in two-dimensional materials), essential. In this work, we first examine the role of GBs in the electrical-transport properties of MoS2 monolayers with varying line-defect densities. We reveal a systematic degradation of electrical characteristics as the line-defect density increases. The two common MoS2 GB types and their specific roles are further examined, and we find that only tilt GBs have a considerable effect on the MoS2 electrical properties. By examining the electronic states and sources of disorder using temperature-dependent transport studies, we adopt the Anderson model for disordered systems to explain the observed transport behaviors in different temperature regimes. Our results elucidate the roles played by GBs in different scenarios and give insights into their underlying scattering mechanisms.

Electric field control of soliton motion and stacking in trilayer graphene.

The crystal structure of a material plays an important role in determining its electronic properties. Changing from one crystal structure to another involves a phase transition that is usually controlled by a state variable such as temperature or pressure. In the case of trilayer graphene, there are two common stacking configurations (Bernal and rhombohedral) that exhibit very different electronic properties. In graphene flakes with both stacking configurations, the region between them consists of a localized strain soliton where the carbon atoms of one graphene layer shift by the carbon-carbon bond distance. Here we show the ability to move this strain soliton with a perpendicular electric field and hence control the stacking configuration of trilayer graphene with only an external voltage. Moreover, we find that the free-energy difference between the two stacking configurations scales quadratically with electric field, and thus rhombohedral stacking is favoured as the electric field increases. This ability to control the stacking order in graphene opens the way to new devices that combine structural and electrical properties.

Electrical transport and low-frequency noise in chemical vapor deposited single-layer MoS2 devices.

We have studied temperature-dependent (77-300 K) electrical characteristics and low-frequency noise (LFN) in chemical vapor deposited (CVD) single-layer molybdenum disulfide (MoS2) based back-gated field-effect transistors (FETs). Electrical characterization and LFN measurements were conducted on MoS2 FETs with Al2O3 top-surface passivation. We also studied the effect of top-surface passivation etching on the electrical characteristics of the device. Significant decrease in channel current and transconductance was observed in these devices after the Al2O3 passivation etching. For passivated devices, the two-terminal resistance variation with temperature showed a good fit to the activation energy model, whereas for the etched devices the trend indicated a hopping transport mechanism. A significant increase in the normalized drain current noise power spectral density (PSD) was observed after the etching of the top passivation layer. The observed channel current noise was explained using a standard unified model incorporating carrier number fluctuation and correlated surface mobility fluctuation mechanisms. Detailed analysis of the gate-referred noise voltage PSD indicated the presence of different trapping states in passivated devices when compared to the etched devices. Etched devices showed weak temperature dependence of the channel current noise, whereas passivated devices exhibited near-linear temperature dependence.

Rapid identification of stacking orientation in isotopically labeled chemical-vapor grown bilayer graphene by Raman spectroscopy.

The growth of large-area bilayer graphene has been of technological importance for graphene electronics. The successful application of graphene bilayers critically relies on the precise control of the stacking orientation, which determines both electronic and vibrational properties of the bilayer system. Toward this goal, an effective characterization method is critically needed to allow researchers to easily distinguish the bilayer stacking orientation (i.e., AB stacked or turbostratic). In this work, we developed such a method to provide facile identification of the stacking orientation by isotope labeling. Raman spectroscopy of these isotopically labeled bilayer samples shows a clear signature associated with AB stacking between layers, enabling rapid differentiation between turbostratic and AB-stacked bilayer regions. Using this method, we were able to characterize the stacking orientation in bilayer graphene grown through Low Pressure Chemical Vapor Deposition (LPCVD) with enclosed Cu foils, achieving almost 70% AB-stacked bilayer graphene. Furthermore, by combining surface sensitive fluorination with such hybrid (12)C/(13)C bilayer samples, we are able to identify that the second layer grows underneath the first-grown layer, which is similar to a recently reported observation.