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Hexagonal boron nitride (hBN) has emerged as a promising material platform for nanophotonics and quantum sensing, hosting optically-active defects with exceptional properties such as high brightness and large spectral tuning. However, precise control over deterministic spatial positioning of emitters in hBN remained elusive for a long time, limiting their proper correlative characterization and applications in hybrid devices. Recently, focused ion beam (FIB) systems proved to be useful to engineer several types of spatially-defined emitters with various structural and photophysical properties. Here we systematically explore the physical processes leading to the creation of optically-active defects in hBN using FIB, and find that beam-substrate interaction plays a key role in the formation of defects. These findings are confirmed using transmission electron microscopy that reveals local mechanical deterioration of the hBN layers and local amorphization of ion beam irradiated hBN. Additionally, we show that upon exposure to water, amorphized hBN undergoes a structural and optical transition between two defect types with distinctive emission properties. Moreover, using super-resolution optical microscopy combined with atomic force microscopy, we pinpoint the exact location of emitters within the defect sites, confirming the role of defected edges as primary sources of fluorescent emission. This lays the foundation for FIB-assisted engineering of optically-active defects in hBN with high spatial and spectral control for applications ranging from integrated photonics, to quantum sensing to nanofluidics., Comment: 11 pages, 5 figures

Aqueous proton transport at interfaces is ubiquitous and crucial for a number of fields, ranging from cellular transport and signaling, to catalysis and membrane science. However, due to their light mass, small size and high chemical reactivity, uncovering single proton surface transport at room temperature and in aqueous environment has so far remained out-of-reach of conventional atomic-scale surface science techniques, such as STM. Here, we use single-molecule localization microscopy techniques to resolve optically the transport of individual excess protons at the interface of hexagonal boron nitride crystals and aqueous solutions at room temperature. Our label-free approach relies on the successive protonation and activation of optically active defects at the surface of the crystal allowing us to resolve interfacial proton transport at the single molecule scale with nanometric resolution and over micrometer range. Proton trajectories are revealed as a succession of jumps between proton-binding defects, mediated by interfacial water. We demonstrate unexpected interfacial proton mobility under illumination, limited by proton desorption from individual defects. The proposed mechanism is supported by ab initio molecular dynamics simulations of defected and pristine hBN/water interface. Our observations provide direct experimental evidence at the single molecule scale that interfacial water provides a preferential pathway for lateral proton transport. Our findings have fundamental and general implications for water-mediated molecular charge transport at interfaces.

Long-lived interlayer excitons with distinct spin-valley physics in van der Waals heterostructures based on transition metal dichalcogenides make them promising for information processing in next-generation devices. While the emission characteristics of interlayer excitons in different types of hetero stacks have been extensively studied, the manipulation of these excitons required to alter the valley-state or tune the emission energy and intensity is still lacking. Here, we demonstrate such control over interlayer excitons in MoSe2/WSe2 heterostructures. The encapsulation of our stack with h-BN ensures ultraclean interfaces, allowing us to resolve four separate narrow interlayer emission peaks. We observe two main interlayer transitions with opposite helicities under circularly polarized excitation, either conserving or inverting the polarization of incoming light. We further demonstrate control over the wavelength, intensity, and polarization of exciton emission by electrical and magnetic fields. Such ability to manipulate the interlayer excitons and their polarization could pave the way for novel excitonic and valleytronic device applications.

Due to the chemical inertness of 2D hexagonal-Boron Nitride (h-BN), few atomic-layer h-BN is often used to encapsulate air-sensitive 2D crystals such as Black Phosphorus (BP). However, the effects of h-BN on Schottky barrier height, doping and contact resistance are not well known. Here, we investigate these effects by fabricating h-BN encapsulated BP transistors with cobalt (Co) contacts. In sharp contrast to directly Co contacted p-type BP devices, we observe strong n-type conduction upon insertion of the h-BN at the Co/BP interface. First principles calculations show that this difference arises from the much larger interface dipole at the Co/h-BN interface compared to the Co/BP interface, which reduces the work function of the Co/h-BN contact. The Co/h-BN contacts exhibit low contact resistances (~ 4.5 k-ohm), and are Schottky barrier free. This allows us to probe high electron mobilities (4,200 cm2/Vs) and observe insulator-metal transitions even under two-terminal measurement geometry.

Two-dimensional materials offer new opportunities for both fundamental science and technological applications, by exploiting the electron spin. While graphene is very promising for spin communication due to its extraordinary electron mobility, the lack of a band gap restricts its prospects for semiconducting spin devices such as spin diodes and bipolar spin transistors. The recent emergence of 2D semiconductors could help overcome this basic challenge. In this letter we report the first important step towards making 2D semiconductor spin devices. We have fabricated a spin valve based on ultra-thin (5 nm) semiconducting black phosphorus (bP), and established fundamental spin properties of this spin channel material which supports all electrical spin injection, transport, precession and detection up to room temperature (RT). Inserting a few layers of boron nitride between the ferromagnetic electrodes and bP alleviates the notorious conductivity mismatch problem and allows efficient electrical spin injection into an n-type bP. In the non-local spin valve geometry we measure Hanle spin precession and observe spin relaxation times as high as 4 ns, with spin relaxation lengths exceeding 6 um. Our experimental results are in a very good agreement with first-principles calculations and demonstrate that Elliott-Yafet spin relaxation mechanism is dominant. We also demonstrate that spin transport in ultra-thin bP depends strongly on the charge carrier concentration, and can be manipulated by the electric field effect.

The observation of micron size spin relaxation makes graphene a promising material for applications in spintronics requiring long distance spin communication. However, spin dependent scatterings at the contact/graphene interfaces affect the spin injection efficiencies and hence prevent the material from achieving its full potential. While this major issue could be eliminated by nondestructive direct optical spin injection schemes, graphenes intrinsically low spin orbit coupling strength and optical absorption place an obstacle in their realization. We overcome this challenge by creating sharp artificial interfaces between graphene and WSe2 monolayers. Application of a circularly polarized light activates the spin polarized charge carriers in the WSe2 layer due to its spin coupled valley selective absorption. These carriers diffuse into the superjacent graphene layer, transport over a 3.5 um distance, and are finally detected electrically using BN/Co contacts in a non local geometry. Polarization dependent measurements confirm the spin origin of the non local signal.

The elimination of extrinsic sources of spin relaxation is key in realizing the exceptional intrinsic spin transport performance of graphene. Towards this, we study charge and spin transport in bilayer graphene-based spin valve devices fabricated in a new device architecture which allows us to make a comparative study by separately investigating the roles of substrate and polymer residues on spin relaxation. First, the comparison between spin valves fabricated on SiO2 and BN substrates suggests that substrate-related charged impurities, phonons and roughness do not limit the spin transport in current devices. Next, the observation of a 5-fold enhancement in spin relaxation time in the encapsulated device highlights the significance of polymer residues on spin relaxation. We observe a spin relaxation length of ~ 10 um in the encapsulated bilayer with a charge mobility of 24000 cm2/Vs. The carrier density dependence of spin relaxation time has two distinct regimes; n<4 x 1012 cm-2, where spin relaxation time decreases monotonically as carrier concentration increases, and n>4 x 1012 cm-2, where spin relaxation time exhibits a sudden increase. The sudden increase in the spin relaxation time with no corresponding signature in the charge transport suggests the presence of a magnetic resonance close to the charge neutrality point. We also demonstrate, for the first time, spin transport across bipolar p-n junctions in our dual-gated device architecture that fully integrates a sequence of encapsulated regions in its design. At low temperatures, strong suppression of the spin signal was observed while a transport gap was induced, which is interpreted as a novel manifestation of impedance mismatch within the spin channel.

The preservation and manipulation of a spin state mainly depends on the strength of the spin-orbit interaction. For pristine graphene, the intrinsic spin-orbit coupling (SOC) is only in the order of few ueV, which makes it almost impossible to be used as an active element in future electric field controlled spintronics devices. This stimulates the development of a systematic method for extrinsically enhancing the SOC of graphene. In this letter, we study the strength of SOC in weakly fluorinated graphene devices. We observe high non-local signals even without applying any external magnetic field. The magnitude of the signal increases with increasing fluorine adatom coverage. From the length dependence of the non-local transport measurements, we obtain SOC values of ~ 5.1 meV and ~ 9.1 meV for the devices with ~ 0.005% and ~ 0.06% fluorination, respectively. Such a large enhancement, together with the high charge mobility of fluorinated samples (u~4300 cm2/Vs - 2700 cm2/Vs), enables the detection of the spin Hall effect even at room temperature., Comment: 15 pages, 3 figures, 1 table

The presence of finite bandgap and high mobility in semiconductor few-layer black phosphorus offers an attractive prospect for using this material in future two-dimensional electronic devices. Here we demonstrate for the first time fully encapsulated ultrathin (down to bilayer) black phosphorus field effect transistors in Van der Waals heterostructures to preclude their stability and degradation problems which have limited their potential for applications. Introducing monolayer graphene in our device architecture for one-atom-thick conformal source-drain electrodes enables a chemically inert boron nitride dielectric to tightly seal the black phosphorus surface. This architecture, generally applicable for other sensitive two-dimensional crystals, results in stable transport characteristics which are hysteresis free and identical both under high vacuum and ambient conditions. Remarkably, our graphene electrodes lead to contacts not dominated by thermionic emission, solving the issue of Schottky barrier limited transport in the technologically relevant two-terminal field effect transistor geometry.

The development of a spintronics device relies on efficient generation of spin polarized currents and their electric field controlled manipulation. While observation of exceptionally long spin relaxation lengths make graphene an intriguing material for spintronics studies, modulation of spin currents by gate field is almost impossible due to negligibly small intrinsic spin orbit coupling (SOC) of graphene. In this work, we create an artificial interface between monolayer graphene and few-layers semiconducting tungsten disulfide (WS2). We show that in such devices graphene acquires a SOC as high as 17meV, three orders of magnitude higher than its intrinsic value, without modifying any of the structural properties of the graphene. Such proximity SOC leads to the spin Hall effect even at room temperature and opens the doors for spin FETs. We show that intrinsic defects in WS2 play an important role in this proximity effect and that graphene can act as a probe to detect defects in semiconducting surfaces.

We demonstrate injection, transport and detection of spins in spin valve arrays patterned in both copper based chemical vapor deposition (Cu-CVD) synthesized wafer scale single layer (SLG) and bilayer graphene (BLG). We observe spin relaxation times comparable to those reported for exfoliated graphene samples demonstrating that CVD specific structural differences such as nano-ripples and grain boundaries do not limit spin transport in the present samples. Our observations make Cu-CVD graphene a promising material of choice for large scale spintronic applications., Comment: 23 pages, 7 figures