Distance Dependence of the Energy Transfer Mechanism in WS_{2}-Graphene Heterostructures.

We report on the mechanism of energy transfer in Van der Waals heterostructures of the two-dimensional semiconductor WS_{2} and graphene with varying interlayer distances, achieved through spacer layers of hexagonal boron nitride (h-BN). We record photoluminescence and reflection spectra at interlayer distances between 0.5 and 5.8 nm (0-16 h-BN layers). We find that the energy transfer is dominated by states outside the light cone, indicative of a Förster transfer process, with an additional contribution from a Dexter process at 0.5 nm interlayer distance. We find that the measured dependence of the luminescence intensity on interlayer distances above 1 nm can be quantitatively described using recently reported values of the Förster transfer rates of thermalized charge carriers. At smaller interlayer distances, the experimentally observed transfer rates exceed the predictions and, furthermore, depend on excess energy as well as on excitation density. Since the transfer probability of the Förster mechanism depends on the momentum of electron-hole pairs, we conclude that, at these distances, the transfer is driven by nonrelaxed charge carrier distributions.

Infrared Resonance Raman of Bilayer Graphene: Signatures of Massive Fermions and Band Structure on the 2D Peak.

Few-layer graphene possesses low-energy carriers that behave as massive Fermions, exhibiting intriguing properties in both transport and light scattering experiments. Lowering the excitation energy of resonance Raman spectroscopy down to 1.17 eV, we target these massive quasiparticles in the split bands close to the K point. The low excitation energy weakens some of the Raman processes that are resonant in the visible, and induces a clearer frequency-separation of the substructures of the resonance 2D peak in bi- and trilayer samples. We follow the excitation-energy dependence of the intensity of each substructure, and comparing experimental measurements on bilayer graphene with ab initio theoretical calculations, we trace back such modifications on the joint effects of probing the electronic dispersion close to the band splitting and enhancement of electron-phonon matrix elements.

Chemically detaching hBN crystals grown at atmospheric pressure and high temperature for high-performance graphene devices.

In this work, we report on the growth of hexagonal boron nitride (hBN) crystals from an iron flux at atmospheric pressure and high temperature and demonstrate that (i) the entire sheet of hBN crystals can be detached from the metal in a single step using hydrochloric acid and that (ii) these hBN crystals allow to fabricate high carrier mobility graphene-hBN devices. By combining spatially-resolved confocal Raman spectroscopy and electrical transport measurements, we confirm the excellent quality of these crystals for high-performance hBN-graphene-based van der Waals heterostructures. The full width at half maximum of the graphene Raman 2D peak is as low as 16 cm-1, and the room temperature charge carrier mobilitiy is around 80 000 cm2/(Vs) at a carrier density 1 × 1012cm-12. This is fully comparable with devices of similar dimensions fabricated using crystalline hBN synthesized by the high pressure and high temperature method. Finally, we show that for exfoliated high-quality hBN flakes with a thickness between 20 and 40 nm the line width of the hBN Raman peak, in contrast to the graphene 2D line width, is not useful for benchmarking hBN in high mobility graphene devices.

Probing Enhanced Electron-Phonon Coupling in Graphene by Infrared Resonance Raman Spectroscopy.

We report on resonance Raman spectroscopy measurements with excitation photon energy down to 1.16 eV on graphene, to study how low-energy carriers interact with lattice vibrations. Thanks to the excitation energy close to the Dirac point at K, we unveil a giant increase of the intensity ratio between the double-resonant 2D and 2D^{'} peaks with respect to that measured in graphite. Comparing with fully ab initio theoretical calculations, we conclude that the observation is explained by an enhanced, momentum-dependent coupling between electrons and Brillouin zone-boundary optical phonons. This finding applies to two-dimensional Dirac systems and has important consequences for the modeling of transport in graphene devices operating at room temperature.

Phonon-mediated room-temperature quantum Hall transport in graphene.

The quantum Hall (QH) effect in two-dimensional electron systems (2DESs) is conventionally observed at liquid-helium temperatures, where lattice vibrations are strongly suppressed and bulk carrier scattering is dominated by disorder. However, due to large Landau level (LL) separation (~2000 K at B = 30 T), graphene can support the QH effect up to room temperature (RT), concomitant with a non-negligible population of acoustic phonons with a wave-vector commensurate to the inverse electronic magnetic length. Here, we demonstrate that graphene encapsulated in hexagonal boron nitride (hBN) realizes a novel transport regime, where dissipation in the QH phase is governed predominantly by electron-phonon scattering. Investigating thermally-activated transport at filling factor 2 up to RT in an ensemble of back-gated devices, we show that the high B-field behaviour correlates with their zero B-field transport mobility. By this means, we extend the well-accepted notion of phonon-limited resistivity in ultra-clean graphene to a hitherto unexplored high-field realm.

Putting High-Index Cu on the Map for High-Yield, Dry-Transferred CVD Graphene.

Reliable, clean transfer and interfacing of 2D material layers are technologically as important as their growth. Bringing both together remains a challenge due to the vast, interconnected parameter space. We introduce a fast-screening descriptor approach to demonstrate holistic data-driven optimization across the entirety of process steps for the graphene-Cu model system. We map the crystallographic dependences of graphene chemical vapor deposition, interfacial Cu oxidation to decouple graphene, and its dry delamination across inverse pole figures. Their overlay enables us to identify hitherto unexplored (168) higher index Cu orientations as overall optimal orientations. We show the effective preparation of such Cu orientations via epitaxial close-space sublimation and achieve mechanical transfer with a very high yield (>95%) and quality of graphene domains, with room-temperature electron mobilities in the range of 40000 cm2/(V s). Our approach is readily adaptable to other descriptors and 2D material systems, and we discuss the opportunities of such a holistic optimization.

Experimental Observation of ABCB Stacked Tetralayer Graphene.

In tetralayer graphene, three inequivalent layer stackings should exist; however, only rhombohedral (ABCA) and Bernal (ABAB) stacking have so far been observed. The three stacking sequences differ in their electronic structure, with the elusive third stacking (ABCB) being unique as it is predicted to exhibit an intrinsic bandgap as well as locally flat bands around the K points. Here, we use scattering-type scanning near-field optical microscopy and confocal Raman microscopy to identify and characterize domains of ABCB stacked tetralayer graphene. We differentiate between the three stacking sequences by addressing characteristic interband contributions in the optical conductivity between 0.28 and 0.56 eV with amplitude and phase-resolved near-field nanospectroscopy. By normalizing adjacent flakes to each other, we achieve good agreement between theory and experiment, allowing for the unambiguous assignment of ABCB domains in tetralayer graphene. These results establish near-field spectroscopy at the interband transitions as a semiquantitative tool, enabling the recognition of ABCB domains in tetralayer graphene flakes and, therefore, providing a basis to study correlation physics of this exciting phase.

CVD Bilayer Graphene Spin Valves with 26 µm Spin Diffusion Length at Room Temperature.

We present inverted spin-valve devices fabricated from chemical vapor deposition (CVD)-grown bilayer graphene (BLG) that show more than a doubling in device performance at room temperature compared to state-of-the-art bilayer graphene spin valves. This is made possible by a polydimethylsiloxane droplet-assisted full-dry transfer technique that compensates for previous process drawbacks in device fabrication. Gate dependent Hanle measurements reveal spin lifetimes of up to 5.8 ns and a spin diffusion length of up to 26 µm at room temperature combined with a charge carrier mobility of about 24 000 cm2(V s)-1 for the best device. Our results demonstrate that CVD-grown BLG shows equally good room temperature spin transport properties as both CVD-grown single-layer graphene and even exfoliated single-layer graphene.

Electrical Control over Phonon Polarization in Strained Graphene.

We explore the tunability of the phonon polarization in suspended uniaxially strained graphene by magneto-phonon resonances. The uniaxial strain lifts the degeneracy of the LO and TO phonons, yielding two cross-linearly polarized phonon modes and a splitting of the Raman G peak. We utilize the strong electron-phonon coupling in graphene and the off-resonant coupling to a magneto-phonon resonance to induce a gate-tunable circular phonon dichroism. This, together with the strain-induced splitting of the G peak, allows us to controllably tune the two linearly polarized G mode phonons into circular phonon modes. We are able to achieve a circular phonon polarization of up to 40% purely by electrostatic fields and can reverse its sign by tuning from electron to hole doping. This provides unprecedented electrostatic control over the angular momentum of phonons, which paves the way toward phononic applications.

Unveiling Valley Lifetimes of Free Charge Carriers in Monolayer WSe2.

We report on nanosecond-long, gate-dependent valley lifetimes of free charge carriers in monolayer WSe2, unambiguously identified by the combination of time-resolved Kerr rotation and electrical transport measurements. While the valley polarization increases when tuning the Fermi level into the conduction or valence band, there is a strong decrease of the respective valley lifetime consistent with both electron-phonon and spin-orbit scattering. The longest lifetimes are seen for spin-polarized bound excitons in the band gap region. We explain our findings via two distinct, Fermi-level-dependent scattering channels of optically excited, valley-polarized bright trions either via dark or bound states. By electrostatic gating we demonstrate that the transition-metal dichalcogenide WSe2 can be tuned to be either an ideal host for long-lived localized spin states or allow for nanosecond valley lifetimes of free charge carriers (>10 ns).

Spin States Protected from Intrinsic Electron-Phonon Coupling Reaching 100 ns Lifetime at Room Temperature in MoSe2.

We present time-resolved Kerr rotation measurements, showing spin lifetimes of over 100 ns at room temperature in monolayer MoSe2. These long lifetimes are accompanied by an intriguing temperature-dependence of the Kerr amplitude, which increases with temperature up to 50 K and then abruptly switches sign. Using ab initio simulations, we explain the latter behavior in terms of the intrinsic electron-phonon coupling and the activation of transitions to secondary valleys. The phonon-assisted scattering of the photoexcited electron-hole pairs prepares a valley spin polarization within the first few ps after laser excitation. The sign of the total valley magnetization, and thus the Kerr amplitude, switches as a function of temperature, as conduction and valence band states exhibit different phonon-mediated intervalley scattering rates. However, the electron-phonon scattering on the ps time scale does not provide an explanation for the long spin lifetimes. Hence, we deduce that the initial spin polarization must be transferred into spin states, which are protected from the intrinsic electron-phonon coupling, and are most likely resident charge carriers, which are not part of the itinerant valence or conduction band states.

Quantum transport through MoS2 constrictions defined by photodoping.

We present a device scheme to explore mesoscopic transport through molybdenum disulfide (MoS2) constrictions using photodoping. The devices are based on van-der-Waals heterostructures where few-layer MoS2 flakes are partially encapsulated by hexagonal boron nitride (hBN) and covered by a few-layer graphene flake to fabricate electrical contacts. Since the as-fabricated devices are insulating at low temperatures, we use photo-induced remote doping in the hBN substrate to create free charge carriers in the MoS2 layer. On top of the device, we place additional metal structures, which define the shape of the constriction and act as shadow masks during photodoping of the underlying MoS2/hBN heterostructure. Low temperature two- and four-terminal transport measurements show evidence of quantum confinement effects.

Spin Lifetimes Exceeding 12 ns in Graphene Nonlocal Spin Valve Devices.

We show spin lifetimes of 12.6 ns and spin diffusion lengths as long as 30.5 µm in single layer graphene nonlocal spin transport devices at room temperature. This is accomplished by the fabrication of Co/MgO-electrodes on a Si/SiO2 substrate and the subsequent dry transfer of a graphene-hBN-stack on top of this electrode structure where a large hBN flake is needed in order to diminish the ingress of solvents along the hBN-to-substrate interface. Interestingly, long spin lifetimes are observed despite the fact that both conductive scanning force microscopy and contact resistance measurements reveal the existence of conducting pinholes throughout the MgO spin injection/detection barriers. Compared to previous devices, we observe an enhancement of the spin lifetime in single layer graphene by a factor of 6. We demonstrate that the spin lifetime does not depend on the contact resistance area products when comparing all bottom-up devices indicating that spin absorption at the contacts is not the predominant source for spin dephasing.

Spatial Control of Laser-Induced Doping Profiles in Graphene on Hexagonal Boron Nitride.

We present a method to create and erase spatially resolved doping profiles in graphene-hexagonal boron nitride heterostructures. The technique is based on photoinduced doping by a focused laser beam and does neither require masks nor photoresists. This makes our technique interesting for rapid prototyping of unconventional electronic device schemes, where the spatial resolution of the rewritable, long-term stable doping profiles is limited by only the laser spot size (≈600 nm) and the accuracy of sample positioning. Our optical doping method offers a way to implement and to test different, complex doping patterns in one and the very same graphene device, which is not achievable with conventional gating techniques.

Ballistic Transport Exceeding 28 µm in CVD Grown Graphene.

We report on ballistic transport over more than 28 µm in graphene grown by chemical vapor deposition (CVD) that is fully encapsulated in hexagonal boron nitride. The structures are fabricated by an advanced dry van-der-Waals transfer method and exhibit carrier mobilities of up to three million cm(2)/(Vs). The ballistic nature of charge transport is probed by measuring the bend resistance in cross- and square-shaped devices. Temperature-dependent measurements furthermore prove that ballistic transport is maintained exceeding 1 µm up to 200 K.

Ultrahigh-mobility graphene devices from chemical vapor deposition on reusable copper.

Graphene research has prospered impressively in the past few years, and promising applications such as high-frequency transistors, magnetic field sensors, and flexible optoelectronics are just waiting for a scalable and cost-efficient fabrication technology to produce high-mobility graphene. Although significant progress has been made in chemical vapor deposition (CVD) and epitaxial growth of graphene, the carrier mobility obtained with these techniques is still significantly lower than what is achieved using exfoliated graphene. We show that the quality of CVD-grown graphene depends critically on the used transfer process, and we report on an advanced transfer technique that allows both reusing the copper substrate of the CVD growth and making devices with mobilities as high as 350,000 cm(2) V(-1) s(-1), thus rivaling exfoliated graphene.

Low B field magneto-phonon resonances in single-layer and bilayer graphene.

Many-body effects resulting from strong electron-electron and electron-phonon interactions play a significant role in graphene physics. We report on their manifestation in low B field magneto-phonon resonances in high-quality exfoliated single-layer and bilayer graphene encapsulated in hexagonal boron nitride. These resonances allow us to extract characteristic effective Fermi velocities, as high as 1.20 × 10(6) m/s, for the observed "dressed" Landau level transitions, as well as the broadening of the resonances, which increases with the Landau level index.

Nanosecond spin lifetimes in single- and few-layer graphene-hBN heterostructures at room temperature.

We present a new fabrication method of graphene spin-valve devices that yields enhanced spin and charge transport properties by improving both the electrode-to-graphene and graphene-to-substrate interface. First, we prepare Co/MgO spin injection electrodes onto Si(++)/SiO2. Thereafter, we mechanically transfer a graphene-hBN heterostructure onto the prepatterned electrodes. We show that room temperature spin transport in single-, bi-, and trilayer graphene devices exhibit nanosecond spin lifetimes with spin diffusion lengths reaching 10 µm combined with carrier mobilities exceeding 20,000 cm(2)/(V s).

Electrically conducting nanopatterns formed by chemical e-beam lithography via gold nanoparticle seeds.

We report the formation of thiol nanopatterns on SAM covered silicon wafers by converting sulfonic acid head groups via e-beam lithography. These thiol groups act as binding sites for gold nanoparticles, which can be enhanced to form electrically conducting nanostructures. This approach serves as a proof-of-concept for the combination of top-down and bottom-up processes for the generation of electrical devices on silicon.

Toward wafer scale fabrication of graphene based spin valve devices.

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 and bilayer graphene. We observe spin relaxation times comparable to those reported for exfoliated graphene samples demonstrating that chemical vapor deposition specific structural differences such as nanoripples 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.