Due to high tissue penetration depth and low autofluorescence backgrounds, near-infrared (NIR) fluorescence imaging has recently become an advantageous diagnostic technique used in a variety of fields. However, most of the NIR fluorophores do not have therapeutic delivery capabilities, exhibit low photostabilities, and raise toxicity concerns. To address these issues, we developed and tested five types of biocompatible graphene quantum dots (GQDs) exhibiting spectrally-separated fluorescence in the NIR range of 928-1053 nm with NIR excitation. Their optical properties in the NIR are attributed to either rare-earth metal dopants (Ho-NGQDs, Yb-NGQDs, Nd-NGQDs) or defect-states (nitrogen doped GQDS (NGQDs), reduced graphene oxides) as verified by Hartree-Fock calculations. Moderate up to 1.34% quantum yields of these GQDs are well-compensated by their remarkable >4 h photostability. At the biocompatible concentrations of up to 0.5-2 mg ml GQDs successfully internalize into HEK-293 cells and enable imaging in the visible and NIR. Tested all together in HEK-293 cells five GQD types enable simultaneous multiplex imaging in the NIR-I and NIR-II shown for the first time in this work for GQD platforms. Substantial photostability, spectrally-separated NIR emission, and high biocompatibility of five GQD types developed here suggest their promising potential in multianalyte testing and multiwavelength bioimaging of combination therapies.

TiCT MXene is emerging as the enabling material in a broad range of wearable and implantable medical technologies, thanks to its outstanding electrical, electrochemical, and optoelectronic properties, and its compatibility with high-throughput solution-based processing. While the prevalence of TiCT MXene in biomedical research, and in particular bioelectronics, has steadily increased, the long-term stability and degradation of TiCT MXene films have not yet been thoroughly investigated, limiting its use for chronic applications. Here, we investigate the stability of TiCT films and electrodes under environmental conditions that are relevant to medical and bioelectronic technologies: storage in ambient atmosphere (shelf-life), submersion in saline (akin to the environment), and storage in a desiccator (low-humidity). Furthermore, to evaluate the effect of the MXene deposition method and thickness on the film stability in the different conditions, we compare thin (25 nm), and thick (1.0 μm) films and electrodes fabricated via spray-coating and blade-coating. Our findings indicate that film processing method and thickness play a significant role in determining the long-term performance of TiCT films and electrodes, with highly aligned, thick films from blade coating remarkably retaining their conductivity, electrochemical impedance, and morphological integrity even after 30 days in saline. Our extensive spectroscopic analysis reveals that the degradation of TiCT films in high-humidity environments is primarily driven by moisture intercalation, ingress, and film delamination, with evidence of only minimal to moderate oxidation.

Substituting heteroatoms into graphene can tune its properties for applications ranging from catalysis to spintronics. The further recent discovery that covalent impurities in graphene can be manipulated at atomic precision using a focused electron beam may open avenues towards sub-nanometer device architectures. However, the preparation of clean samples with a high density of dopants is still very challenging. Here, we report vacancy-mediated substitution of aluminium into laser-cleaned graphene, and without removal from our ultra-high vacuum apparatus, study their dynamics under 60 keV electron irradiation using aberration-corrected scanning transmission electron microscopy and spectroscopy. Three- and four-coordinated Al sites are identified, showing excellent agreement with predictions including binding energies and electron energy-loss spectrum simulations. We show that the direct exchange of carbon and aluminium atoms predicted earlier occurs under electron irradiation, although unexpectedly it is less probable than the same process for silicon. We also observe a previously unknown nitrogen-aluminium exchange that occurs at Al─N double-dopant sites at graphene divacancies created by our plasma treatment.

Rapid, inexpensive, and easy-to-use coronavirus disease 2019 (COVID-19) home tests are key tools in addition to vaccines in the world-wide fight to eliminate national and local shutdowns. However, currently available tests for SARS-CoV-2, the virus that causes COVID-19, are too expensive, painful, and irritating, or not sufficiently sensitive for routine, accurate home testing. Herein, we employ custom-formulated graphene inks and aerosol jet printing (AJP) to create a rapid electrochemical immunosensor for direct detection of SARS-CoV-2 Spike Receptor-Binding Domain (RBD) in saliva samples acquired non-invasively. This sensor demonstrated limits of detection that are considerably lower than most commercial SARS-CoV-2 antigen tests (22.91 ± 4.72 pg/mL for Spike RBD and 110.38 ± 9.00 pg/mL for Spike S1) as well as fast response time (~30 mins), which was facilitated by the functionalization of printed graphene electrodes in a single-step with SARS-CoV-2 polyclonal antibody through the carbodiimide reaction without the need for nanoparticle functionalization or secondary antibody or metallic nanoparticle labels. This immunosensor presents a wide linear sensing range from 1 to 1000 ng/mL and does not react with other coexisting influenza viruses such as H1N1 hemagglutinin. By combining high-yield graphene ink synthesis, automated printing, high antigen selectivity, and rapid testing capability, this work offers a promising alternative to current SARS-CoV-2 antigen tests.

Owing to their unique electrical and optical properties, two-dimensional transition metal dichalcogenides have been extensively studied for their potential applications in biosensing. However, simultaneous utilization of both optical and electrical properties has been overlooked, yet it can offer enhanced accuracy and detection versitility. Here, we demonstrate a dual-mode optoelectronic biosensor based on monolayer molybdenum disulfide (MoS) capable of producing simultaneous electrical and optical readouts of biomolecular signals. On a single platform, the biosensor exhibits a tunable photonic Fano-type optical resonance while also functioning as a field-effect transistor (FET) based on a optically transparent gate electrode. Furthermore, chemical vapor deposition grown MoS provides a clean surface for direct immobilization of a water-soluble variant of the -opioid receptor (wsMOR), via a nickel ion-mediated linker chemistry. We utilize a synthetic opioid peptide to show the operation of the electronic and optical sensing modes. The responses of both modes exhibit a similar trend with dynamic ranges of four orders of magnitude and detection limits of <1 nM. Our work explores the potential of a versatile multimodal sensing platform enabled by monolayer MoS, since the integration of electrical and optical sensors on the same chip can offer flexibility in read-out and improve the accuracy in detection of low concentration targets.

We describe the reversible intercalation of Na under graphene on Ir(111) by photo-dissociation of a previously adsorbed NaCl overlayer. After room temperature evaporation, NaCl adsorbs on top of graphene forming a bilayer. With a combination of electron diffraction and photoemission techniques we demonstrate that the NaCl overlayer dissociates upon a short exposure to an X-ray beam. As a result, chlorine desorbs while sodium intercalates under the graphene, inducing an electronic decoupling from the underlying metal. Low energy electron diffraction shows the disappearance of the moiré pattern when Na intercalates between graphene and iridium. Analysis of the Na 2p core-level by X-ray photoelectron spectroscopy shows a chemical change from NaCl to metallic buried Na at the graphene/Ir interface. The intercalation-decoupling process leads to a n-doped graphene due to the charge transfer from the Na, as revealed by constant energy angle resolved X-ray photoemission maps. Moreover, the process is reversible by a mild annealing of the samples without damaging the graphene.

Monolayer epitaxial graphene (EG), grown on the Si face of SiC, is an advantageous material for a variety of electronic and optical applications. EG forms as a single crystal over millimeter-scale areas and consequently, the large scale single crystal can be utilized as a template for growth of other materials. In this work, we present the use of EG as a template to form millimeter-scale amorphous and hexagonal boron nitride (-BN and -BN) films. The -BN is formed with pulsed laser deposition and the -BN is grown with triethylboron (TEB) and NH precursors, making it the first metal organic chemical vapor deposition (MOCVD) process of this growth type performed on epitaxial graphene. A variety of optical and non-optical characterization methods are used to determine the optical absorption and dielectric functions of the EG, -BN, and -BN within the energy range of 1 eV to 8.5 eV. Furthermore, we report the first ellipsometric observation of high-energy resonant excitons in EG from the 4H polytype of SiC and an analysis on the interactions within the EG and -BN heterostructure.

We report carrier density measurements and electron-electron (-) interactions in monolayer epitaxial graphene grown on SiC. The temperature ()-independent carrier density determined from the Shubnikov-de Haas (SdH) oscillations clearly demonstrates that the observed logarithmic temperature dependence of Hall slope in our system be due to - interactions. Since the electron density determined from conventional SdH measurements does not depend on - interactions based on Kohn's theorem, SdH experiments appear to be more reliable compared with the classical Hall effect when one studies the dependence of the carrier density in the low regime. On the other hand, the logarithmic dependence of the Hall slope δ/δ can be used to probe - interactions even when the conventional conductivity method is not applicable due to strong electron-phonon scattering.

The emerging field of valleytronics aims to exploit the valley pseudospin of electrons residing near Bloch band extrema as an information carrier. Recent experiments demonstrating optical generation and manipulation of exciton valley coherence (the superposition of electron-hole pairs at opposite valleys) in monolayer transition metal dichalcogenides (TMDs) provide a critical step towards control of this quantum degree of freedom. The charged exciton (trion) in TMDs is an intriguing alternative to the neutral exciton for control of valley pseudospin because of its long spontaneous recombination lifetime, its robust valley polarization, and its coupling to residual electronic spin. Trion valley coherence has however been unexplored due to experimental challenges in accessing it spectroscopically. In this work, we employ ultrafast two-dimensional coherent spectroscopy to resonantly generate and detect trion valley coherence in monolayer MoSe demonstrating that it persists for a few-hundred femtoseconds. We conclude that the underlying mechanisms limiting trion valley coherence are fundamentally different from those applicable to exciton valley coherence.

Large-area growth of monolayer films of the transition metal dichalcogenides is of the utmost importance in this rapidly advancing research area. The mechanical exfoliation method offers high quality monolayer material but it is a problematic approach when applied to materials that are not air stable. One important example is 1T'-WTe, which in multilayer form is reported to possess a large non saturating magnetoresistance, pressure induced superconductivity, and a weak antilocalization effect, but electrical data for the monolayer is yet to be reported due to its rapid degradation in air. Here we report a reliable and reproducible large-area growth process for obtaining many monolayer 1T'-WTe flakes. We confirmed the composition and structure of monolayer 1T'-WTe flakes using x-ray photoelectron spectroscopy, energy-dispersive x-ray spectroscopy, atomic force microscopy, Raman spectroscopy and aberration corrected transmission electron microscopy. We studied the time dependent degradation of monolayer 1T'-WTe under ambient conditions, and we used first-principles calculations to identify reaction with oxygen as the degradation mechanism. Finally we investigated the electrical properties of monolayer 1T'-WTe and found metallic conduction at low temperature along with a weak antilocalization effect that is evidence for strong spin-orbit coupling.

Direct growth of graphene films on dielectric substrates (quartz and silica) is reported, by means of remote electron cyclotron resonance plasma assisted chemical vapor deposition r-(ECR-CVD) at low temperature (650°C). Using a two step deposition process- nucleation and growth- by changing the partial pressure of the gas precursors at constant temperature, mostly monolayer continuous films, with grain sizes up to 500 nm are grown, exhibiting transmittance larger than 92% and sheet resistance as low as 900 Ω·sq. The grain size and nucleation density of the resulting graphene sheets can be controlled varying the deposition time and pressure. In additon, first-principles DFT-based calculations have been carried out in order to rationalize the oxygen reduction in the quartz surface experimentally observed. This method is easily scalable and avoids damaging and expensive transfer steps of graphene films, improving compatibility with current fabrication technologies.

The structural polymorphism in transition metal dichalcogenides (TMDs) provides exciting opportunities for developing advanced electronics. For example, MoTe crystallizes in the 2H semiconducting phase at ambient temperature and pressure, but transitions into the 1T' semimetallic phase at high temperatures. Alloying MoTe with WTe reduces the energy barrier between these two phases, while also allowing access to the T Weyl semimetal phase. The Mo WTe alloy system is therefore promising for developing phase change memory technology. However, achieving this goal necessitates a detailed understanding of the phase composition in the MoTe-WTe system. We combine polarization-resolved Raman spectroscopy with x-ray diffraction (XRD) and scanning transmission electron microscopy (STEM) to study bulk MoWTe alloys over the full compositional range from 0 to 1. We identify Raman and XRD signatures characteristic of the 2H, 1T', and T structural phases that agree with density-functional theory (DFT) calculations, and use them to identify phase fields in the MoTe-WTe system, including single-phase 2H, 1T', and T regions, as well as a two-phase 1T' + T region. Disorder arising from compositional fluctuations in MoWTe alloys breaks inversion and translational symmetry, leading to the activation of an infrared 1T'-MoTe mode and the enhancement of a double-resonance Raman process in 2H-Mo WTe alloys. Compositional fluctuations limit the phonon correlation length, which we estimate by fitting the observed asymmetric Raman lineshapes with a phonon confinement model. These observations reveal the important role of disorder in MoWTe alloys, clarify the structural phase boundaries, and provide a foundation for future explorations of phase transitions and electronic phenomena in this system.

Graphene oxide (GO) forms well ordered liquid crystal (LC) phases in polar solvents. Here, we map the lyotropic phase diagram of GO as a function of the lateral dimensions of the GO flakes, their concentration, geometrical confinement configuration and solvent polarity. GO flakes were prepared in water and transferred into other polar solvents. Polarising optical microscopy (POM) was used to determine the phase evolution through the isotropic-biphasic-nematic transitions of the GO LC. We report that the confinement volume and geometry relative to the particle size is critical for the observation of the lyotropic phase, specifically, this determines the low-end concentration limit for the detection of the GO LC. Additionally, a solvent with higher polarisability stabilises the LC phases at lower concentrations and smaller flake sizes. GO LCs have been proposed for a range of applications from display technologies to conductive fibres, and the behaviour of LC phase formation under confinement imposes a limit on miniaturisation of the dimensions of such GO LC systems which could significantly impact on their potential applications.

Experiments in gated bilayer graphene with stacking domain walls present topological gapless states protected by no-valley mixing. Here we research these states under gate voltages using atomistic models, which allow us to elucidate their origin. We find that the gate potential controls the layer localization of the two states, which switches non-trivially between layers depending on the applied gate voltage magnitude. We also show how these bilayer gapless states arise from bands of single-layer graphene by analyzing the formation of carbon bonds between layers. Based on this analysis we provide a model Hamiltonian with analytical solutions, which explains the layer localization as a function of the ratio between the applied potential and interlayer hopping. Our results open a route for the manipulation of gapless states in electronic devices, analogous to the proposed writing and reading memories in topological insulators.

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 () inside a -GaN junction and elucidate how it impacts the structural and electrical properties of the junction. Epitaxial in the form of 1-2 m triangle domains are grown by powder vaporization on a -doped GaN substrate, and the Au capping layer is deposited by evaporation. Transmission electron microscopy (TEM) of the van der Waals interface indicates that remained distinct and intact between the Au and GaN and that the Au is epitaxial to GaN only when the 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 /-GaN heterojunctions enables the derivations of Schottky barrier heights (SBH) and drawing of the band alignment diagram. Notably, 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 -junction. The 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 /GaN junction.