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Single-molecule magnets (SMMs) with chemically tailorable properties are potential building blocks for quantum computing, high-density magnetic memory, and spintronics.1 2 3,4 These applications require isolated or few molecules on substrates, but studies of SMMs have mainly focused on bulk crystals. Moreover, fabrication of SMM-based devices and electrical detection of the SMM magnetic state are still coveted milestones that have so far been achieved mainly for double-decker rare-earth phthalocyanines at temperatures below 1 K.5-8 Here we demonstrate electrical detection of magnetization switching for a modification of the archetypal SMM Mn12, up to 70 K, based on the supramolecular spin valve effect5 with graphene quantum dots9. Notably, the exchange interaction between the molecules and the graphene, as well as the dot-mediated intermolecular interaction, can be directly extracted from the electrical response, opening the way to an effective characterization of the quantum properties of different types of SMMs in a wide temperature range.

Developing low-power, high-sensitivity photodetectors for the terahertz (THz) band that operate at room temperature is an important challenge in optoelectronics. In this study, we introduce a photo-thermal-electric (PTE) effect detector based on quasi-free standing bilayer graphene (BLG) on a silicon carbide (SiC) substrate, designed for the THz frequency range. Our detector's performance hinges on a quasi-optical coupling scheme, which integrates an aspherical silicon lens, to optimize impedance matching between the THz antenna and the graphene p-n junction. At room temperature, we achieved a noise equivalent power (NEP) of less than 300 $pW/\sqrt{Hz}$. Through an impedance matching analysis, we coupled a planar antenna with a graphene p-n junction, inserted in parallel to the nano-gap of the antenna, via two coupling capacitors. By adjusting the capacitors and the antenna arm length, we tailored the antenna's maximum infrared power absorption to specific frequencies. The sensitivity, spectral properties, and scalability of our material make it an ideal candidate for future development of far-infrared detectors operating at room temperature., Comment: 21 pages, 4 figures

We study quasi-freestanding bilayer graphene on silicon carbide intercalated by calcium. The intercalation, and subsequent changes to the system, were investigated by low-energy electron diffraction, angle-resolved photoemission spectroscopy (ARPES) and density-functional theory (DFT). Calcium is found to intercalate only at the graphene-SiC interface, completely displacing the hydrogen terminating SiC. As a consequence, the system becomes highly n-doped. Comparison to DFT calculations shows that the band dispersion, as determined by ARPES, deviates from the band structure expected for Bernal-stacked bilayer graphene. Instead, the electronic structure closely matches AA-stacked bilayer graphene on Ca-terminated SiC, indicating a spontaneous transition from AB- to AA-stacked bilayer graphene following calcium intercalation of the underlying graphene-SiC interface., Comment: 14 pages, 3 figures

Magnesium intercalated 'quasi-freestanding' bilayer graphene on 6H-SiC(0001) (Mg-QFSBLG) has many favorable properties (e.g., highly n-type doped, relatively stable in ambient conditions). However, intercalation of Mg underneath monolayer graphene is challenging, requiring multiple intercalation steps. Here, we overcome these challenges and subsequently increase the rate of Mg intercalation by laser patterning (ablating) the graphene to form micron-sized discontinuities. We then use low energy electron diffraction to verify Mg-intercalation and conversion to Mg-QFSBLG, and X-ray photoelectron spectroscopy to determine the Mg intercalation rate for patterned and non-patterned samples. By modeling Mg intercalation with the Verhulst equation, we find that the intercalation rate increase for the patterned sample is 4.5$\pm$1.7. Since the edge length of the patterned sample is $\approx$5.2 times that of the non-patterned sample, the model implies that the increased intercalation rate is proportional to the increase in edge length. Moreover, Mg intercalation likely begins at graphene discontinuities in pristine samples (not step edges or flat terraces), where the 2D-like crystal growth of Mg-silicide proceeds. Our laser patterning technique may enable the rapid intercalation of other atomic or molecular species, thereby expanding upon the library of intercalants used to modify the characteristics of graphene, or other 2D materials and heterostructures., Comment: 24 pages, 4 figures

Strong circularly polarized excitation opens up the possibility to generate and control effective magnetic fields in solid state systems, e.g., via the optical inverse Faraday effect or the phonon inverse Faraday effect. While these effects rely on material properties that can be tailored only to a limited degree, plasmonic resonances can be fully controlled by choosing proper dimensions and carrier concentrations. Plasmon resonances provide new degrees of freedom that can be used to tune or enhance the light-induced magnetic field in engineered metamaterials. Here we employ graphene disks to demonstrate light-induced transient magnetic fields from a plasmonic circular current with extremely high efficiency. The effective magnetic field at the plasmon resonance frequency of the graphene disks (3.5 THz) is evidenced by a strong (~1{\deg}) ultrafast Faraday rotation (~ 20 ps). In accordance with reference measurements and simulations, we estimated the strength of the induced magnetic field to be on the order of 0.7 T under a moderate pump fluence of about 440 nJ cm-2.

We perform a femtosecond-THz optical pump-probe spectroscopy to investigate the cooling dynamics of hot carriers in quasi-free standing bilayer epitaxial graphene. We observed longer decay time constants, in the range of 2.6 to 6.4 ps, compared to previous studies on monolayer graphene, which increase nonlinearly with excitation intensity. The increased relaxation times are due to the decoupling of the graphene layer from the SiC substrate after hydrogen intercalation which increases the distance between graphene and substrate. Furthermore, our measurements do not show that the supercollision mechanism is related to the cooling process of the hot carriers, which is ultimately achieved by electron-optical phonon scattering., Comment: 19 pages in lauding the supplemental material. Tree figures and one more in the supplemental material. Nanoscale Advances 2023

The intercalation of epitaxial graphene on SiC(0001) with Ca has been studied extensively, yet precisely where the Ca resides remains elusive. Furthermore, the intercalation of Mg underneath epitaxial graphene on SiC(0001) has not been reported. Here, we use low energy electron diffraction, x-ray photoelectron spectroscopy, secondary electron cut-off photoemission and scanning tunneling microscopy to elucidate the physical and electronic structure of both Ca- and Mg-intercalated epitaxial graphene on 6H-SiC(0001). We find that Ca intercalates underneath the buffer layer and bonds to the Si-terminated SiC surface, breaking the C-Si bonds of the buffer layer i.e. 'freestanding' the buffer layer to form Ca-intercalated quasi-freestanding bilayer graphene (Ca-QFSBLG). The situation is similar for the Mg-intercalation of epitaxial graphene on SiC(0001), where an ordered Mg-terminated reconstruction at the SiC surface and Mg bonds to the Si-terminated SiC surface are formed, resulting in Mg-intercalated quasi-freestanding bilayer graphene (Mg-QFSBLG). Ca-intercalation underneath the buffer layer has not been considered in previous studies of Ca-intercalated epitaxial graphene. Furthermore, we find no evidence that either Ca or Mg intercalates between graphene layers. However, we do find that both Ca-QFSBLG and Mg-QFSBLG exhibit very low workfunctions of 3.68 and 3.78 eV, respectively, indicating high n-type doping. Upon exposure to ambient conditions, we find Ca-QFSBLG degrades rapidly, whereas Mg-QFSBLG remains remarkably stable., Comment: 58 pages, 10 figures, 4 tables. Revised text and figures

At high phonon temperature, defect-mediated electron-phonon collisions (supercollisions) in graphene allow for larger energy transfer and faster cooling of hot electrons than the normal, momentum-conserving electron-phonon collisions. Disorder also affects the heat flow between electrons and phonons at very low phonon temperature, where the phonon wavelength exceeds the mean free path. In both cases, the cooling rate is predicted to exhibit a characteristic cubic power law dependence on the electron temperature, markedly different from the T^4 dependence predicted for pristine graphene. The impact of defect-induced cooling on the performance of optoelectronic devices is still largely unexplored. Here we study the cooling mechanism of hot-electron bolometers based on epitaxial graphene quantum dots where the defect density can be controlled with the fabrication process. The devices with high defect density exhibit the cubic power law. Defect-induced cooling yields a slower increase of the thermal conductance with increasing temperature, thereby greatly enhancing the device responsivity compared to devices with lower defect density and operating with normal-collision cooling.

Control of atomic-scale interfaces between materials with distinct electronic structures is crucial for the design and fabrication of most electronic devices. In the case of two-dimensional (2D) materials, disparate electronic structures can be realized even within a single uniform sheet, merely by locally applying different vertical bias voltages. Indeed, it has been suggested that nanoscale electronic patterning in a single sheet can be achieved by placing the 2D material on a suitably pre-patterned substrate, exploiting the sensitivity of 2D materials to their environment via band alignment, screening or hybridization. Here, we utilize the inherently nano-structured single layer (SL) and bilayer (BL) graphene on silicon carbide to laterally tune the electrostatic gating of adjacent SL tungsten disulphide (WS$_2$) in a van der Waals heterostructure. The electronic band alignments are mapped in energy and momentum space using angle-resolved photoemission with a spatial resolution on the order of 500~nm (nanoARPES). We find that the SL WS$_2$ band offsets track the work function of the underlying SL and BL graphene, and we relate such changes to observed lateral patterns of exciton and trion luminescence from SL WS$_2$, demonstrating ultimate control of optoelectronic properties at the nanoscale., Comment: 13 pages, 3 figures

The sensitivity to water of epitaxial graphene is examined in this study.

We directly correlate the local (20-nm scale) and global electronic properties of a device containing mono-, bi- and tri-layer epitaxial graphene (EG) domains on 6H-SiC(0001) by simultaneously performing local surface potential measurements using Kelvin probe force microscopy and global transport measurements. Using well-controlled environmental conditions, where the starting state of the surface can be reproducibly defined, we investigate the doping effects of N2, O2, water vapour and NO2 at concentrations representative of the ambient air. We show that presence of O2, water vapour and NO2 leads to p-doping of all EG domains. However, the thicker layers of EG are significantly less affected by the atmospheric dopants. Furthermore, we demonstrate that the general consensus of O2 and water vapour present in ambient air providing majority of the p-doping to graphene is a common misconception. We experimentally show that even the combined effect of O2, water vapour, and NO2 at concentrations higher than typically present in the atmosphere does not fully replicate the state of the EG surface in ambient air. All doping effects can be reproducibly reversed by vacuum annealing. Thus, for EG gas sensors it is essential to consider naturally occurring environmental effects and properly separate them from those coming from targeted species., Comment: 4 Figures, 1 Table

Graphene is an ideal material for hot-electron bolometers, due to its low heat capacity and weak electron-phonon coupling. Nanostructuring graphene with quantum dot constrictions yields detectors with extraordinarily high intrinsic responsivity, higher than 1x10^9 V/W at 3K. The sensing mechanism is bolometric in nature: the quantum confinement gap causes a strong dependence of the electrical resistance on the electron temperature. Here we show that this quantum confinement gap does not impose a limitation on the photon energy for light detection and these quantum dot bolometers work in a very broad spectral range, from terahertz, through telecom to ultraviolet radiation, with responsivity independent of wavelength. We also measure the power dependence of the response. Although the responsivity decreases with increasing power, it stays higher than 1x10^8 V/W in a wide range of absorbed power, from 1 pW to 0.4 nW.

The individual building blocks of van der Waals (vdW) heterostructures host fascinating physical phenomena, ranging from ballistic electron transport in graphene to striking optical properties of MoSe2 sheets. The presence of bonded and non-bonded cohesive interactions in a vdW heterostructure, promotes diversity in their structural arrangements, which in turn profoundly modulate the properties of their individual constituents. Here, we report on the presence of correlated structural disorder coexisting with the nearly perfect crystallographic order along the growth direction of epitaxial vdW heterostructures of Bi2Se3/graphene/SiC. Using the depth penetration of X-ray diffraction microscopy and scattering, we probed their crystal structure from atomic to mesoscopic length scales, to reveal that their structural diversity is underpinned by spatially correlated disorder states. The presence of the latter induces on a system, widely considered to behave as a collection of nearly independent 2-dimensional units, a pseudo-3-dimensional character, when subjected to epitaxial constraints and ordered substrate interactions. These findings shed new light on the nature of the vast structural landscape of vdW heterostructures and could enable new avenues in modulating their unique properties by correlated disorder., Comment: 17 pages, 4 figures

Among its many outstanding properties, graphene supports terahertz surface plasma waves -- sub-wavelength charge density oscillations connected with electromagnetic fields that are tightly localized near the surface[1,2]. When these waves are confined to finite-sized graphene, plasmon resonances emerge that are characterized by alternating charge accumulation at the opposing edges of the graphene. The resonant frequency of such a structure depends on both the size and the surface charge density, and can be electrically tuned throughout the terahertz range by applying a gate voltage[3,4]. The promise of tunable graphene THz plasmonics has yet to be fulfilled, however, because most proposed optoelectronic devices including detectors, filters, and modulators[5-10] desire near total modulation of the absorption or transmission, and require electrical contacts to the graphene -- constraints that are difficult to meet using existing plasmonic structures. We report here a new class of plasmon resonance that occurs in a hybrid graphene-metal structure. The sub-wavelength metal contacts form a capacitive grid for accumulating charge, while the narrow interleaved graphene channels, to first order, serves as a tunable inductive medium, thereby forming a structure that is resonantly-matched to an incident terahertz wave. We experimentally demonstrate resonant absorption near the theoretical maximum in readily-available, large-area graphene, ideal for THz detectors and tunable absorbers. We further predict that the use of high mobility graphene will allow resonant THz transmission near 100%, realizing a tunable THz filter or modulator. The structure is strongly coupled to incident THz radiation, and solves a fundamental problem of how to incorporate a tunable plasmonic channel into a device with electrical contacts.

We report the realization of top-gated graphene nanoribbon field effect transistors (GNRFETs) of ~10 nm width on large-area epitaxial graphene exhibiting the opening of a band gap of ~0.14 eV. Contrary to prior observations of disordered transport and severe edge-roughness effects of GNRs, the experimental results presented here clearly show that the transport mechanism in carefully fabricated GNRFETs is conventional band-transport at room temperature, and inter-band tunneling at low temperature. The entire space of temperature, size, and geometry dependent transport properties and electrostatics of the GNRFETs are explained by a conventional thermionic emission and tunneling current model. Our combined experimental and modeling work proves that carefully fabricated narrow GNRs behave as conventional semiconductors, and remain potential candidates for electronic switching devices.

Terahertz (THz) radiation has uses from security to medicine; however, sensitive room-temperature detection of THz is notoriously difficult. The hot-electron photothermoelectric effect in graphene is a promising detection mechanism: photoexcited carriers rapidly thermalize due to strong electron-electron interactions, but lose energy to the lattice more slowly. The electron temperature gradient drives electron diffusion, and asymmetry due to local gating or dissimilar contact metals produces a net current via the thermoelectric effect. Here we demonstrate a graphene thermoelectric THz photodetector with sensitivity exceeding 10 V/W (700 V/W) at room temperature and noise equivalent power less than 1100 pW/Hz^1/2 (20 pW/Hz^1/2), referenced to the incident (absorbed) power. This implies a performance which is competitive with the best room-temperature THz detectors for an optimally coupled device, while time-resolved measurements indicate that our graphene detector is eight to nine orders of magnitude faster than those. A simple model of the response, including contact asymmetries (resistance, work function and Fermi-energy pinning) reproduces the qualitative features of the data, and indicates that orders-of-magnitude sensitivity improvements are possible., Comment: Published 07 September 2014 in Nature Nanotechnology

This letter reports the impact of surface morphology on the carrier transport and RF performance of graphene FETs formed on epitaxial graphene films synthesized on SiC substrates. Such graphene exhibits long terrace structures with widths between 3-5 {\mu}m and steps of 10\pm2 nm in height. While a carrier mobility above 3000 cm2/Vs at a carrier density of 1e12 cm-2 is obtained in a single graphene terrace domain at room temperature, the step edges can result in a vicinal step resistance of ~21 k{\Omega}.{\mu}m. By orienting the transistor layout so that the entire channel lies within a single graphene terrace, and reducing the access resistance associated with the ungated part of the channel, a cut-off frequency above 200 GHz is achieved for graphene FETs with channel lengths of 210 nm, which is the highest value reported on epitaxial graphene thus far.

Variable-field Hall measurements were performed on epitaxial graphene grown on Si-face and C-face SiC. The carrier transport involves essentially a single-type of carrier in few-layer graphene, regardless of SiC face. However, in multi-layer graphene (MLG) grown on C-face SiC, the Hall measurements indicated the existence of several groups of carriers with distinct mobilities. Electrical transport in MLG can be properly described by invoking three independent conduction channels in parallel. Two of these are n- and p-type, while the third involves nearly intrinsic graphene. The carriers in this lightly doped channel have significantly higher mobilities than the other two., Comment: 13 pages, 3 figures, accepted in Appl. Phys. Lett

Epitaxial graphene layers were grown on the C-face of 4H- and 6H-SiC using an argon-mediated growth process. Variations in growth temperature and pressure were found to dramatically affect the morphological properties of the layers. The presence of argon during growth slowed the rate of graphene formation on the C-face and led to the observation of islanding. The similarity in the morphology of the islands and continuous films indicated that island nucleation and coalescence is the growth mechanism for C-face graphene., Comment: 12 pages, 4 figures

In order to make graphene technologically viable, the transfer of graphene films to substrates appropriate for specific applications is required. We demonstrate the dry transfer of epitaxial graphene (EG) from the C-face of 4H-SiC onto SiO2, GaN and Al2O3 substrates using a thermal release tape. We further report on the impact of this process on the electrical properties of the EG films. This process enables EG films to be used in flexible electronic devices or as optically transparent contacts., Comment: 8 pages, 4 figures and supplementary info regarding procedure for transfer

Graphene was epitaxially grown on both the C- and Si-faces of 4H- and 6H-SiC(0001) under an argon atmosphere and under high vacuum conditions. Following growth, samples were imaged with Nomarski interference contrast and atomic force microscopies and it was found that growth under argon led to improved morphologies on the C-face films but the Si-face films were not significantly affected. Free carrier transport studies were conducted through Hall effect measurements, and carrier mobilities were found to increase and sheet carrier densities were found to decrease for those films grown under argon as compared to high vacuum conditions. The improved mobilities and concurrent decreases in sheet carrier densities suggest a decrease in scattering in the films grown under argon., Comment: 215th Meeting of the Electrochemical Society (ECS 215), 14 pages, 6 figures

Epitaxial graphene films were grown in vacuo by silicon sublimation from the (0001) and (000-1) faces of 4H- and 6H-SiC. Hall effect mobilities and sheet carrier densities of the films were measured at 300 K and 77 K and the data depended on the growth face. About 40% of the samples exhibited holes as the dominant carrier, independent of face. Generally, mobilities increased with decreasing carrier density, independent of carrier type and substrate polytype. The contributions of scattering mechanisms to the conductivities of the films are discussed. The results suggest that for near-intrinsic carrier densities at 300 K epitaxial graphene mobilities will be ~150,000 cm2V-1s-1 on the (000-1) face and ~5,800 cm2V-1s-1 on the (0001) face., Comment: Accepted for publication in Applied Physics Letters, 10 pages, 2 figures

An in vacuo thermal desorption process has been accomplished to form epitaxial graphene (EG) on 4H- and 6H-SiC substrates using a commercial chemical vapor deposition reactor. Correlation of growth conditions and the morphology and electrical properties of EG are described. Raman spectra of EG on Si-face samples were dominated by monolayer thickness. This approach was used to grow EG on 50 mm SiC wafers that were subsequently fabricated into field effect transistors with fmax of 14 GHz., Comment: 215th Meeting of the Electrochemical Society, 8 pages, 8 figures

Graphene layers were created on both C and Si faces of semi-insulating, on-axis, 4H- and 6H-SiC substrates. The process was performed under high vacuum (<10-4 mbar) in a commercial chemical vapor deposition SiC reactor. A method for H2 etching the on-axis sub-strates was developed to produce surface steps with heights of 0.5 nm on the Si-face and 1.0 to 1.5 nm on the C-face for each polytype. A process was developed to form graphene on the substrates immediately after H2 etching and Raman spectroscopy of these samples confirmed the formation of graphene. The morphology of the graphene is described. For both faces, the underlying substrate morphology was significantly modified during graphene formation; sur-face steps were up to 15 nm high and the uniform step morphology was sometimes lost. Mo-bilities and sheet carrier concentrations derived from Hall Effect measurements on large area (16 mm square) and small area (2 and 10 um square) samples are presented and shown to compare favorably to recent reports., Comment: European Conference on Silicon Carbide and Related Materials 2008 (ECSCRM '08), 4 pages, 4 figures

We report a direct correlation between carrier mobility and Raman topography of epitaxial graphene (EG) grown on silicon carbide (SiC). We show the Hall mobility of material on the Si-face of SiC [SiC(0001)] is not only highly dependent on thickness uniformity but also on monolayer strain uniformity. Only when both thickness and strain are uniform over a significant fraction (> 40%) of the device active area does the mobility exceed 1000 cm2/V-s. Additionally, we achieve high mobility epitaxial graphene (18,100 cm2/V-s at room temperature) on the C-face of SiC [SiC(000-1)] and show that carrier mobility depends strongly on the graphene layer stacking. These findings provide a means to rapidly estimate carrier mobility and provide a guide to achieve very high mobility in epitaxial graphene. Our results suggest that ultra-high mobilities (>50,000 cm2/V-s) are achievable via the controlled formation of uniform, rotationally faulted epitaxial graphene., Comment: 13 pages including supplimental material. Submitted to Nature Materials 2/23/2009