Unveiling the Multiradical Character of the Biphenylene Network and Its Anisotropic Charge Transport.

Recent progress in the on-surface synthesis and characterization of nanomaterials is facilitating the realization of new carbon allotropes, such as nanoporous graphenes, graphynes, and 2D π-conjugated polymers. One of the latest examples is the biphenylene network (BPN), which was recently fabricated on gold and characterized with atomic precision. This gapless 2D organic material presents uncommon metallic conduction, which could help develop innovative carbon-based electronics. Here, using first principles calculations and quantum transport simulations, we provide new insights into some fundamental properties of BPN, which are key for its further technological exploitation. We predict that BPN hosts an unprecedented spin-polarized multiradical ground state, which has important implications for the chemical reactivity of the 2D material under practical use conditions. The associated electronic band gap is highly sensitive to perturbations, as seen in finite temperature (300 K) molecular dynamics simulations, but the multiradical character remains stable. Furthermore, BPN is found to host in-plane anisotropic (spin-polarized) electrical transport, rooted in its intrinsic structural features, which suggests potential device functionality of interest for both nanoelectronics and spintronics.

Nonlocal Spin Dynamics in the Crossover from Diffusive to Ballistic Transport.

Improved fabrication techniques have enabled the possibility of ballistic transport and unprecedented spin manipulation in ultraclean graphene devices. Spin transport in graphene is typically probed in a nonlocal spin valve and is analyzed using spin diffusion theory, but this theory is not necessarily applicable when charge transport becomes ballistic or when the spin diffusion length is exceptionally long. Here, we study these regimes by performing quantum simulations of graphene nonlocal spin valves. We find that conventional spin diffusion theory fails to capture the crossover to the ballistic regime as well as the limit of long spin diffusion length. We show that the latter can be described by an extension of the current theoretical framework. Finally, by covering the whole range of spin dynamics, our study opens a new perspective to predict and scrutinize spin transport in graphene and other two-dimensional material-based ultraclean devices.

Universal Spin Diffusion Length in Polycrystalline Graphene.

Graphene grown by chemical vapor deposition (CVD) is the most promising material for industrial-scale applications based on graphene monolayers. It also holds promise for spintronics; despite being polycrystalline, spin transport in CVD graphene has been measured over lengths up to 30 µm, which is on par with the best measurements made in single-crystal graphene. These results suggest that grain boundaries (GBs) in CVD graphene, while impeding charge transport, may have little effect on spin transport. However, to date very little is known about the true impact of disordered networks of GBs on spin relaxation. Here, by using first-principles simulations, we derive an effective tight-binding model of graphene GBs in the presence of spin-orbit coupling (SOC), which we then use to evaluate spin transport in realistic morphologies of polycrystalline graphene. The spin diffusion length is found to be independent of the grain size, and it is determined only by the strength of the substrate-induced SOC. This result is consistent with the D'yakonov-Perel' mechanism of spin relaxation in the diffusive regime, but we find that it also holds in the presence of quantum interference. These results clarify the role played by GBs and demonstrate that the average grain size does not dictate the upper limit for spin transport in CVD-grown graphene, a result of fundamental importance for optimizing large-scale graphene-based spintronic devices.

Spin transport in graphene/transition metal dichalcogenide heterostructures.

Since its discovery, graphene has been a promising material for spintronics: its low spin-orbit coupling, negligible hyperfine interaction, and high electron mobility are obvious advantages for transporting spin information over long distances. However, such outstanding transport properties also limit the capability to engineer active spintronics, where strong spin-orbit coupling is crucial for creating and manipulating spin currents. To this end, transition metal dichalcogenides, which have larger spin-orbit coupling and good interface matching, appear to be highly complementary materials for enhancing the spin-dependent features of graphene while maintaining its superior charge transport properties. In this review, we present the theoretical framework and the experiments performed to detect and characterize the spin-orbit coupling and spin currents in graphene/transition metal dichalcogenide heterostructures. Specifically, we will concentrate on recent measurements of Hanle precession, weak antilocalization and the spin Hall effect, and provide a comprehensive theoretical description of the interconnection between these phenomena.

Spin Proximity Effects in Graphene/Topological Insulator Heterostructures.

Enhancing the spin-orbit interaction in graphene, via proximity effects with topological insulators, could create a novel 2D system that combines nontrivial spin textures with high electron mobility. To engineer practical spintronics applications with such graphene/topological insulator (Gr/TI) heterostructures, an understanding of the hybrid spin-dependent properties is essential. However, to date, despite the large number of experimental studies on Gr/TI heterostructures reporting a great variety of remarkable (spin) transport phenomena, little is known about the true nature of the spin texture of the interface states as well as their role on the measured properties. Here, we use ab initio simulations and tight-binding models to determine the precise spin texture of electronic states in graphene interfaced with a Bi2Se3 topological insulator. Our calculations predict the emergence of a giant spin lifetime anisotropy in the graphene layer, which should be a measurable hallmark of spin transport in Gr/TI heterostructures and suggest novel types of spin devices.

Spin Hall Effect and Weak Antilocalization in Graphene/Transition Metal Dichalcogenide Heterostructures.

We report on a theoretical study of the spin Hall Effect (SHE) and weak antilocalization (WAL) in graphene/transition metal dichalcogenide (TMDC) heterostructures, computed through efficient real-space quantum transport methods, and using realistic tight-binding models parametrized from ab initio calculations. The graphene/WS2 system is found to maximize spin proximity effects compared to graphene on MoS2, WSe2, or MoSe2 with a crucial role played by disorder, given the disappearance of SHE signals in the presence of strong intervalley scattering. Notably, we found that stronger WAL effects are concomitant with weaker charge-to-spin conversion efficiency. For further experimental studies of graphene/TMDC heterostructures, our findings provide guidelines for reaching the upper limit of spin current formation and for fully harvesting the potential of two-dimensional materials for spintronic applications.

Electrical and Thermal Transport in Coplanar Polycrystalline Graphene-hBN Heterostructures.

We present a theoretical study of electronic and thermal transport in polycrystalline heterostructures combining graphene (G) and hexagonal boron nitride (hBN) grains of varying size and distribution. By increasing the hBN grain density from a few percent to 100%, the system evolves from a good conductor to an insulator, with the mobility dropping by orders of magnitude and the sheet resistance reaching the MΩ regime. The Seebeck coefficient is suppressed above 40% mixing, while the thermal conductivity of polycrystalline hBN is found to be on the order of 30-120 Wm-1 K-1. These results, agreeing with available experimental data, provide guidelines for tuning G-hBN properties in the context of two-dimensional materials engineering. In particular, while we proved that both electrical and thermal properties are largely affected by morphological features (e.g., by the grain size and composition), we find in all cases that nanometer-sized polycrystalline G-hBN heterostructures are not good thermoelectric materials.

Giant Spin Lifetime Anisotropy in Graphene Induced by Proximity Effects.

We report on fundamental aspects of spin dynamics in heterostructures of graphene and transition metal dichalcogenides (TMDCs). By using realistic models derived from first principles we compute the spin lifetime anisotropy, defined as the ratio of lifetimes for spins pointing out of the graphene plane to those pointing in the plane. We find that the anisotropy can reach values of tens to hundreds, which is unprecedented for typical 2D systems with spin-orbit coupling and indicates a qualitatively new regime of spin relaxation. This behavior is mediated by spin-valley locking, which is strongly imprinted onto graphene by TMDCs. Our results indicate that this giant spin lifetime anisotropy can serve as an experimental signature of materials with strong spin-valley locking, including graphene-TMDC heterostructures and TMDCs themselves. Additionally, materials with giant spin lifetime anisotropy can provide an exciting platform for manipulating the valley and spin degrees of freedom, and for designing novel spintronic devices.

Effects of Dephasing on Spin Lifetime in Ballistic Spin-Orbit Materials.

We theoretically investigate spin dynamics in spin-orbit-coupled materials. In the ballistic limit, the spin lifetime is dictated by dephasing that arises from energy broadening plus a nonuniform spin precession. For the case of clean graphene, we find a strong anisotropy with spin lifetimes that can be short even for modest energy scales, on the order of a few ns. These results offer deeper insight into the nature of spin dynamics in graphene, and are also applicable to the investigation of other systems where spin-orbit coupling plays an important role.

Multiple quantum phases in graphene with enhanced spin-orbit coupling: from the quantum spin Hall regime to the spin Hall effect and a robust metallic state.

We report an intriguing transition from the quantum spin Hall phase to the spin Hall effect upon segregation of thallium adatoms adsorbed onto a graphene surface. Landauer-Büttiker and Kubo-Greenwood simulations are used to access both edge and bulk transport physics in disordered thallium-functionalized graphene systems of realistic sizes. Our findings not only quantify the detrimental effects of adatom clustering in the formation of the topological state, but also provide evidence for the emergence of spin accumulation at opposite sample edges driven by spin-dependent scattering induced by thallium islands, which eventually results in a minimum bulk conductivity ∼4e²/h, insensitive to localization effects.

Tailoring giant quantum transport anisotropy in nanoporous graphenes under electrostatic disorder.

During the last 15 years bottom-up on-surface synthesis has been demonstrated as an efficient way to synthesize carbon nanostructures with atomic precision, opening the door to unprecedented electronic control at the nanoscale. Nanoporous graphenes (NPGs) fabricated as two-dimensional arrays of graphene nanoribbons (GNRs) represent one of the key recent breakthroughs in the field. NPGs interestingly display in-plane transport anisotropy of charge carriers, and such anisotropy was shown to be tunable by modulating quantum interference. Herein, using large-scale quantum transport simulations, we show that electrical anisotropy in NPGs is not only resilient to disorder but can further be massively enhanced by its presence. This outcome paves the way to systematic engineering of quantum transport in NPGs as a novel concept for efficient quantum devices and architectures.

Observation of giant and tunable thermal diffusivity of a Dirac fluid at room temperature.

Conducting materials typically exhibit either diffusive or ballistic charge transport. When electron-electron interactions dominate, a hydrodynamic regime with viscous charge flow emerges1-13. More stringent conditions eventually yield a quantum-critical Dirac-fluid regime, where electronic heat can flow more efficiently than charge14-22. However, observing and controlling the flow of electronic heat in the hydrodynamic regime at room temperature has so far remained elusive. Here we observe heat transport in graphene in the diffusive and hydrodynamic regimes, and report a controllable transition to the Dirac-fluid regime at room temperature, using carrier temperature and carrier density as control knobs. We introduce the technique of spatiotemporal thermoelectric microscopy with femtosecond temporal and nanometre spatial resolution, which allows for tracking electronic heat spreading. In the diffusive regime, we find a thermal diffusivity of roughly 2,000 cm2 s-1, consistent with charge transport. Moreover, within the hydrodynamic time window before momentum relaxation, we observe heat spreading corresponding to a giant diffusivity up to 70,000 cm2 s-1, indicative of a Dirac fluid. Our results offer the possibility of further exploration of these interesting physical phenomena and their potential applications in nanoscale thermal management.

Tailoring emergent spin phenomena in Dirac material heterostructures.

Dirac materials such as graphene and topological insulators (TIs) are known to have unique electronic and spintronic properties. We combine graphene with TIs in van der Waals heterostructures to demonstrate the emergence of a strong proximity-induced spin-orbit coupling in graphene. By performing spin transport and precession measurements supported by ab initio simulations, we discover a strong tunability and suppression of the spin signal and spin lifetime due to the hybridization of graphene and TI electronic bands. The enhanced spin-orbit coupling strength is estimated to be nearly an order of magnitude higher than in pristine graphene. These findings in graphene-TI heterostructures could open interesting opportunities for exploring exotic physical phenomena and new device functionalities governed by topological proximity effects.

Spin dynamics and relaxation in graphene dictated by electron-hole puddles.

The understanding of spin dynamics and relaxation mechanisms in clean graphene, and the upper time and length scales on which spin devices can operate, are prerequisites to realizing graphene-based spintronic technologies. Here we theoretically reveal the nature of fundamental spin relaxation mechanisms in clean graphene on different substrates with Rashba spin-orbit fields as low as a few tens of µeV. Spin lifetimes ranging from 50 picoseconds up to several nanoseconds are found to be dictated by substrate-induced electron-hole characteristics. A crossover in the spin relaxation mechanism from a Dyakonov-Perel type for SiO2 substrates to a broadening-induced dephasing for hBN substrates is described. The energy dependence of spin lifetimes, their ratio for spins pointing out-of-plane and in-plane, and the scaling with disorder provide a global picture about spin dynamics and relaxation in ultraclean graphene in the presence of electron-hole puddles.

Near-field photocurrent nanoscopy on bare and encapsulated graphene.

Optoelectronic devices utilizing graphene have demonstrated unique capabilities and performances beyond state-of-the-art technologies. However, requirements in terms of device quality and uniformity are demanding. A major roadblock towards high-performance devices are nanoscale variations of the graphene device properties, impacting their macroscopic behaviour. Here we present and apply non-invasive optoelectronic nanoscopy to measure the optical and electronic properties of graphene devices locally. This is achieved by combining scanning near-field infrared nanoscopy with electrical read-out, allowing infrared photocurrent mapping at length scales of tens of nanometres. Using this technique, we study the impact of edges and grain boundaries on the spatial carrier density profiles and local thermoelectric properties. Moreover, we show that the technique can readily be applied to encapsulated graphene devices. We observe charge build-up near the edges and demonstrate a solution to this issue.

Charge transport in polycrystalline graphene: challenges and opportunities.

Graphene has attracted significant interest both for exploring fundamental science and for a wide range of technological applications. Chemical vapor deposition (CVD) is currently the only working approach to grow graphene at wafer scale, which is required for industrial applications. Unfortunately, CVD graphene is intrinsically polycrystalline, with pristine graphene grains stitched together by disordered grain boundaries, which can be either a blessing or a curse. On the one hand, grain boundaries are expected to degrade the electrical and mechanical properties of polycrystalline graphene, rendering the material undesirable for many applications. On the other hand, they exhibit an increased chemical reactivity, suggesting their potential application to sensing or as templates for synthesis of one-dimensional materials. Therefore, it is important to gain a deeper understanding of the structure and properties of graphene grain boundaries. Here, we review experimental progress on identification and electrical and chemical characterization of graphene grain boundaries. We use numerical simulations and transport measurements to demonstrate that electrical properties and chemical modification of graphene grain boundaries are strongly correlated. This not only provides guidelines for the improvement of graphene devices, but also opens a new research area of engineering graphene grain boundaries for highly sensitive electro-biochemical devices.

Broadband, polarization-sensitive photodetector based on optically-thick films of macroscopically long, dense, and aligned carbon nanotubes.

Increasing performance demands on photodetectors and solar cells require the development of entirely new materials and technological approaches. We report on the fabrication and optoelectronic characterization of a photodetector based on optically-thick films of dense, aligned, and macroscopically long single-wall carbon nanotubes. The photodetector exhibits broadband response from the visible to the mid-infrared under global illumination, with a response time less than 32 µs. Scanning photocurrent microscopy indicates that the signal originates at the contact edges, with an amplitude and width that can be tailored by choosing different contact metals. A theoretical model demonstrates the photothermoelectric origin of the photoresponse due to gradients in the nanotube Seebeck coefficient near the contacts. The experimental and theoretical results open a new path for the realization of optoelectronic devices based on three-dimensionally organized nanotubes.

Enhanced performance of short-channel carbon nanotube field-effect transistors due to gate-modulated electrical contacts.

We use numerical simulations to analyze recent experimental measurements of short-channel carbon nanotube field-effect transistors with palladium contacts. We show that the gate strongly modulates the contact properties, an effect that is distinct from that observed in Schottky barrier carbon nanotube transistors. This modulation of the contacts by the gate allows for the realization of superior subthreshold swings for short channels, and improved scaling behavior. These results further elucidate the behavior of carbon nanotube-metal contacts, and should be useful in the optimization of high-performance carbon nanotube electronics.