Mechanical Exfoliation of Select MAX Phases and Mo4 Ce4 Al7 C3 Single Crystals to Produce MAXenes.

MXenes-2D carbides/nitrides derived from their bulk nanolamellar Mn +1 AXn phase (MAX) counterparts-are, for the most part, obtained by chemical etching. Despite the fact that the MA bonds in the MAX phases are not weak, in this work it is demonstrated that relatively large MAX single crystals can be mechanically exfoliated using the adhesive tape method to produce flakes whose thickness can be reduced down to half a unit cell. The exfoliated flakes, transferred onto SiO2 /Si substrates, are analyzed using electric force microscopy (EFM). No appreciable variation in EFM signal with flake thickness is found. EFM contrast between the flakes and SiO2 not only depends on the contact surface potential, but also on the local capacitance. The contribution of the latter can be used to show the metallic character-confirmed by four-contact resistivity measurements-of even the thinnest of flakes. Because the A-layers are preserved, strictly speaking MXenes are not dealt with in this work, but rather MAXenes. This is important in the case where the "A" layers contain magnetic elements such as Mo4 Ce4 Al7 C3 , whose structure is a derivative of the MAX structure.

Electrical switch to the resonant magneto-phonon effect in graphene.

We report a comprehensive study of the tuning with electric fields of the resonant magneto-exciton optical phonon coupling in gated graphene. For magnetic fields around B ∼ 25 T that correspond to the range of the fundamental magneto-phonon resonance, the electron-phonon coupling can be switched on and off by tuning the position of the Fermi level in order to Pauli block the two fundamental inter-Landau level excitations. The effects of such a profound change in the electronic excitation spectrum are traced through investigations of the optical phonon response in polarization resolved magneto-Raman scattering experiments. We report on the observation of a splitting of the phonon feature with satellite peaks developing at particular values of the Landau level filling factor on the low or on the high energy side of the phonon, depending on the relative energy of the discrete electronic excitation and of the optical phonon. Shifts of the phonon energy as large as ±60 cm(-1) are observed close to the resonance. The intraband electronic excitation, the cyclotron resonance, is shown to play a relevant role in the observed spectral evolution of the phonon response.

Strain superlattices and macroscale suspension of graphene induced by corrugated substrates.

We investigate the organized formation of strain, ripples, and suspended features in macroscopic graphene sheets transferred onto corrugated substrates made of an ordered array of silica pillars with variable geometries. Depending on the pitch and sharpness of the corrugated array, graphene can conformally coat the surface, partially collapse, or lie fully suspended between pillars in a fakir-like fashion over tens of micrometers. With increasing pillar density, ripples in collapsed films display a transition from random oriented pleats emerging from pillars to organized domains of parallel ripples linking pillars, eventually leading to suspended tent-like features. Spatially resolved Raman spectroscopy, atomic force microscopy, and electronic microscopy reveal uniaxial strain domains in the transferred graphene, which are induced and controlled by the geometry. We propose a simple theoretical model to explain the structural transition between fully suspended and collapsed graphene. For the arrays of high density pillars, graphene membranes stay suspended over macroscopic distances with minimal interaction with the pillars' apexes. It offers a platform to tailor stress in graphene layers and opens perspectives for electron transport and nanomechanical applications.

Functional hybrid systems based on large-area high-quality graphene.

The properties of sp² carbon allotropes can be tuned and enriched by their interaction with other materials. The large interface to the outside world in these forms of carbon is ideally suited for combining in an optimal manner several functionalities thanks to this interaction. A wide range of novel materials holding strong promise in energy, optoelectronics, microelectronics, mechanics, or medical applications have been designed accordingly. Graphene, the last representative of this family of sp² carbon materials, has already yielded a wealth of hybrid systems. A new class of these hybrids is emerging, which allows researchers to exploit the properties of truly single-layer graphene. These systems rely on high-quality graphene. In this Account, we describe our recent efforts to develop hybrid systems through various approaches and with various scopes. Depending on the interaction between graphene and molecules, metal clusters, layers, and substrates, either graphene may essentially preserve the electronic properties that make it a unique platform for electronic transport, or new organization and properties in the materials may arise due to the graphene contact at the expense of deep modification of graphene's properties. We prepare our graphene samples by both mechanical exfoliation of graphite and chemical vapor deposition on metals. We use this to study graphene in contact with various species, which either decorate graphene or are intercalated between it and its substrate. We first address the electronic and magnetic properties in systems where graphene is in epitaxy with a metal and discuss the potential to manipulate the properties of both materials, highlighting graphene's role as a protective capping layer in magnetic functional systems. We then present graphene/metal dot hybrids, which can utilize the two-dimensional gas properties of Dirac fermions in graphene. These hybrids allow one to tune the coupling between clusters hosting electronically ordered states such as superconductivity and explore quantum phase transitions controlled by electrostatic back gates. We finally discuss the optical properties of hybrids in which graphene is decorated with optically active molecules. Depending on how close these molecules are to the graphene's electromechanical systems, the interaction of the system with light can be changed. Fields such as spintronics and catalysis could benefit from high-quality graphene based hybrid systems, which have not been fully explored.

Quantum phase transition in a single-molecule quantum dot.

Quantum criticality is the intriguing possibility offered by the laws of quantum mechanics when the wave function of a many-particle physical system is forced to evolve continuously between two distinct, competing ground states. This phenomenon, often related to a zero-temperature magnetic phase transition, is believed to govern many of the fascinating properties of strongly correlated systems such as heavy-fermion compounds or high-temperature superconductors. In contrast to bulk materials with very complex electronic structures, artificial nanoscale devices could offer a new and simpler means of understanding quantum phase transitions. Here we demonstrate this possibility in a single-molecule quantum dot, where a gate voltage induces a crossing of two different types of electron spin state (singlet and triplet) at zero magnetic field. The quantum dot is operated in the Kondo regime, where the electron spin on the quantum dot is partially screened by metallic electrodes. This strong electronic coupling between the quantum dot and the metallic contacts provides the strong electron correlations necessary to observe quantum critical behaviour. The quantum magnetic phase transition between two different Kondo regimes is achieved by tuning gate voltages and is fundamentally different from previously observed Kondo transitions in semiconductor and nanotube quantum dots. Our work may offer new directions in terms of control and tunability for molecular spintronics.

Surface-confined self-assembled Janus tectons: a versatile platform towards the noncovalent functionalization of graphene.

A general strategy for simultaneously generating surface-based supramolecular architectures on flat sp(2) -hybridized carbon supports and independently exposing on demand off-plane functionality with controlled lateral order is highly desirable for the noncovalent functionalization of graphene. Here, we address this issue by providing a versatile molecular platform based on a library of new 3D Janus tectons that form surface-confined supramolecular adlayers in which it is possible to simultaneously steer the 2D self-assembly on flat C(sp(2))-based substrates and tailor the external interface above the substrate by exposure to a wide variety of small terminal chemical groups and functional moieties. This approach is validated throughout by scanning tunneling microscopy (STM) at the liquid-solid interface and molecular mechanics modeling studies. The successful self-assembly on graphene, together with the possibility to transfer the graphene monolayer onto various substrates, should considerably extend the application of our functionalization strategy.

Electrical control of the superconducting-to-insulating transition in graphene-metal hybrids.

Graphene is a sturdy and chemically inert material exhibiting an exposed two-dimensional electron gas of high mobility. These combined properties enable the design of graphene composites, based either on covalent or non-covalent coupling of adsorbates, or on stacked and multilayered heterostructures. These systems have shown tunable electronic properties such as bandgap engineering, reversible metal-insulating transition or supramolecular spintronics. Tunable superconductivity is expected as well, but experimental realization is lacking. Here, we show experiments based on metal-graphene hybrid composites, enabling the tunable proximity coupling of an array of superconducting nanoparticles of tin onto a macroscopic graphene sheet. This material allows full electrical control of the superconductivity down to a strongly insulating state at low temperature. The observed gate control of superconductivity results from the combination of a proximity-induced superconductivity generated by the metallic nanoparticle array with the two-dimensional and tunable metallicity of graphene. The resulting hybrid material behaves, as a whole, like a granular superconductor showing universal transition threshold and localization of Cooper pairs in the insulating phase. This experiment sheds light on the emergence of superconductivity in inhomogeneous superconductors, and more generally, it demonstrates the potential of graphene as a versatile building block for the realization of superconducting materials.

Quantum and thermal phase slips in superconducting niobium nitride (NbN) ultrathin crystalline nanowire: application to single photon detection.

We present low-temperature electronic transport properties of superconducting nanowires obtained by nanolithography of 4-nm-thick niobium nitride (NbN) films epitaxially grown on sapphire substrate. Below 6 K, clear evidence of phase slippages is observed in the transport measurements. Upon lowering the temperature, we observe the signatures of a crossover between a thermal and a quantum behavior in the phase slip regimes. We find that phase slips are stable even at the lowest temperatures and that no hotspot is formed. The photoresponse of these nanowires is measured as a function of the light irradiation wavelength and temperature and exhibits a behavior comparable with previous results obtained on thicker films.

Introducing a biomimetic coating for graphene neuroelectronics: towardin-vivoapplications.

Electronic micro and nano-devices are suitable tools to monitor the activity of many individual neurons over mesoscale networks. However the inorganic materials currently used in microelectronics are barely accepted by neural cells and tissues, thus limiting both the sensor lifetime and efficiency. In particular, penetrating intracortical probes face high failure rate because of a wide immune response of cells and tissues. This adverse reaction called gliosis leads to the rejection of the implanted probe after few weeks and prevent long-lasting recordings of cortical neurons. Such acceptance issue impedes the realization of many neuro-rehabilitation projects. To overcome this, graphene and related carbon-based materials have attracted a lot of interest regarding their positive impact on the adhesion and regeneration of neurons, and their ability to provide high-sensitive electronic devices, such as graphene field effect transistor (G-FET). Such devices can also be implemented on numerous suitable substrates including soft substrates to match the mechanical compliance of cells and tissues, improving further the biocompatibility of the implants. Thus, using graphene as a coating and sensing device material could significantly enhance the acceptance of intracortical probes. However, such a thin monolayer of carbon atoms could be teared off during manipulation and insertion within the brain, and could also display degradation over time. In this work, we have investigated the ability to protect graphene with a natural, biocompatible and degradable polymeric film derivated from hyaluronic acid (HA). We demonstrate that HA-based coatings can be deposited over a wide range of substrates, including intracortical probes and graphene FET arrays without altering the underlying device material, its biocompatibility and sensitivity. Moreover, we show that this coating can be monitoredin situby quantifying the number of deposited charges with the G-FET arrays. The reported graphene functionalization offers promising alternatives for improving the acceptance of various neural interfaces.

In-Plane Magnetic Domains and Néel-like Domain Walls in Thin Flakes of the Room Temperature CrTe2 Van der Waals Ferromagnet.

The recent discovery of magnetic van der Waals (vdW) materials triggered a wealth of investigations in materials science and now offers genuinely new prospects for both fundamental and applied research. Although the catalog of vdW ferromagnets is rapidly expanding, most of them have a Curie temperature below 300 K, a notable disadvantage for potential applications. Combining element-selective X-ray magnetic imaging and magnetic force microscopy, we resolve at room temperature the magnetic domains and domain walls in micron-sized flakes of the CrTe2 vdW ferromagnet. Flux-closure magnetic patterns suggesting an in-plane six-fold symmetry are observed. Upon annealing the material above its Curie point (315 K), the magnetic domains disappear. By cooling back the sample, a different magnetic domain distribution is obtained, indicating material stability and lack of magnetic memory upon thermal cycling. The domain walls presumably have Néel texture, are preferentially oriented along directions separated by 120°, and have a width of several tens of nanometers. Besides microscopic mapping of magnetic domains and domain walls, the coercivity of the material is found to be of a few millitesla only, showing that the CrTe2 compound is magnetically soft. The coercivity is found to increase as the volume of the material decreases.

Liquid-phase exfoliation of graphite into graphene nanosheets in a hydrocavitating 'lab-on-a-chip'.

Hydrodynamic cavitation 'on a chip' has been used to achieve liquid-phase exfoliation of natural graphite to get graphene. We have taken advantage of the small size of such a 'lab-on-a-chip' (LOC) with low input-power consumption, to produce afterwards few layers of graphene nanosheets in a surfactant suspension. Characterization of the processed material has been performed by TGA analysis, SEM, TEM, AFM and Raman measurements. Observations have demonstrated the presence of monolayers and few layers of graphene with a lateral size around 300 nm, exfoliated from a graphite powder suspension flowing through the microsystem.

Monolayer Graphene Coating of Intracortical Probes for Long-Lasting Neural Activity Monitoring.

The invasiveness of intracortical interfaces currently used today is responsible for the formation of an intense immunoresponse and inflammatory reaction from neural cells and tissues. This leads to a high concentration of reactive glial cells around the implant site, creating a physical barrier between the neurons and the recording channels. Such a rejection of foreign analog interfaces causes neural signals to fade from recordings which become flooded by background noise after a few weeks. Despite their invasiveness, those devices are required to track single neuron activity and decode fine sensory or motor commands. In particular, such quantitative and long-lasting recordings of individual neurons are crucial during a long time period (several months) to restore essential functions of the cortex, disrupted after injuries, stroke, or neurodegenerative diseases. To overcome this limitation, graphene and related materials have attracted numerous interests, as they gather in the same material many suitable properties for interfacing living matter, such as an exceptionally high neural affinity, diffusion barrier, and high physical robustness. In this work, the neural affinity of a graphene monolayer with numerous materials commonly used in neuroprostheses is compared, and its impact on the performance and durability of intracortical probes is investigated. For that purpose, an innovative coating method to wrap 3D intracortical probes with a continuous monolayer graphene is developed. Experimental evidence demonstrate the positive impact of graphene on the bioacceptance of conventional intracortical probes, in terms of detection efficiency and tissues responses, allowing real-time samplings of motor neuron activity during 5 weeks. Since continuous graphene coatings can easily be implemented on a wide range of 3D surfaces, this study further motivates the use of graphene and related materials as it could significantly contribute to reduce the current rejection of neural probes currently used in many research areas, from fundamental neurosciences to medicine and neuroprostheses.

Evolution of inter-layer coupling in artificially stacked bilayer MoS2.

In this paper, we show experimentally that for van der Waals heterostructures (vdWh) of atomically-thin materials, the hybridization of bands of adjacent layers is possible only for ultra-clean interfaces. This we achieve through a detailed experimental study of the effect of interfacial separation and adsorbate content on the photoluminescence emission and Raman spectra of ultra-thin vdWh. For vdWh with atomically-clean interfaces, we find the emergence of novel vibrational Raman-active modes whose optical signatures differ significantly from that of the constituent layers. Additionally, we find for such systems a significant modification of the photoluminescence emission spectra with the appearance of peaks whose strength and intensity directly correlate with the inter-layer coupling strength. Our ability to control the intensity of the photoluminescence emission led to the observation of detailed optical features like indirect-band peaks. Our study establishes that it is possible to engineer atomically-thin van der Waals heterostructures with desired optical properties by controlling the inter-layer spacing, and consequently the inter-layer coupling between the constituent layers.

Coherence and Density Dynamics of Excitons in a Single-Layer MoS2 Reaching the Homogeneous Limit.

We measure the coherent nonlinear response of excitons in a single layer of molybdenum disulfide embedded in hexagonal boron nitride, forming a h-BN/MoS2/ h-BN heterostructure. Using four-wave mixing microscopy and imaging, we correlate the exciton inhomogeneous broadening with the homogeneous one and population lifetime. We find that the exciton dynamics is governed by microscopic disorder on top of the ideal crystal properties. Analyzing the exciton ultrafast density dynamics using amplitude and phase of the response, we investigate the relaxation pathways of the resonantly driven exciton population. The surface protection via encapsulation provides stable monolayer samples with low disorder, avoiding surface contaminations and the resulting exciton broadening and modifications of the dynamics. We identify areas localized to a few microns where the optical response is totally dominated by homogeneous broadening. Across the sample of tens of micrometers, weak inhomogeneous broadening and strain effects are observed, attributed to the remaining interaction with the h-BN and imperfections in the encapsulation process.

Self-Assembled UV Photodetector Made by Direct Epitaxial GaN Growth on Graphene.

Hybrid systems based on the combination of crystalline bulk semiconductors with 2D crystals are identified as promising heterogeneous structures for new optoelectronic applications. The direct integration of III-V semiconductors on 2D materials is very attractive to make practical devices but the preservation of the intrinsic properties of the underlying 2D materials remains a challenge. In this work, we study the direct epitaxy of self-organized GaN crystals on graphene. We demonstrate that severe metal-organic chemical vapor deposition growth conditions of GaN (chemically aggressive precursors and high temperatures) are not detrimental to the structural quality and the charge carrier mobility of the graphene base plane. Graphene can therefore be used both as an efficient sensitive material and as a substrate for GaN epitaxy to make a self-assembled UV photodetector. A responsivity as high as 2 A W-1 is measured in the UV-A range without any further postprocessing compared to simple deposition of contact electrodes. Our study opens the way to build new self-assembled 2D/III-V hybrid optoelectronic devices by direct epitaxy.

Recording Spikes Activity in Cultured Hippocampal Neurons Using Flexible or Transparent Graphene Transistors.

The emergence of nanoelectronics applied to neural interfaces has started few decades ago, and aims to provide new tools for replacing or restoring disabled functions of the nervous systems as well as further understanding the evolution of such complex organization. As the same time, graphene and other 2D materials have offered new possibilities for integrating micro and nano-devices on flexible, transparent, and biocompatible substrates, promising for bio and neuro-electronics. In addition to many bio-suitable features of graphene interface, such as, chemical inertness and anti-corrosive properties, its optical transparency enables multimodal approach of neuronal based systems, the electrical layer being compatible with additional microfluidics and optical manipulation ports. The convergence of these fields will provide a next generation of neural interfaces for the reliable detection of single spike and record with high fidelity activity patterns of neural networks. Here, we report on the fabrication of graphene field effect transistors (G-FETs) on various substrates (silicon, sapphire, glass coverslips, and polyimide deposited onto Si/SiO2 substrates), exhibiting high sensitivity (4 mS/V, close to the Dirac point at VLG < VD) and low noise level (10-22 A2/Hz, at VLG = 0 V). We demonstrate the in vitro detection of the spontaneous activity of hippocampal neurons in-situ-grown on top of the graphene sensors during several weeks in a millimeter size PDMS fluidics chamber (8 mm wide). These results provide an advance toward the realization of biocompatible devices for reliable and high spatio-temporal sensing of neuronal activity for both in vitro and in vivo applications.

Light Control of Charge Transfer and Excitonic Transitions in a Carbon Nanotube/Porphyrin Hybrid.

Carbon nanotube-chromophore hybrids are promising building blocks in order to obtain a controlled electro-optical transduction effect at the single nano-object level. In this work, a strong spectral selectivity of the electronic and the phononic response of a chromophore-coated single nanotube transistor is observed for which standard photogating cannot account. This paper investigates how light irradiation strongly modifies the coupling between molecules and nanotube within the hybrid by means of combined Raman diffusion and electron transport measurements. Moreover, a nonconventional Raman enhancement effect is observed when light irradiation is on the absorption range of the grafted molecule. Finally, this paper shows how the dynamics of single electron tunneling in the device at low temperature is strongly modified by molecular photoexcitation. Both effects will be discussed in terms of photoinduced excitons coupled to electronic levels.

Tunable transmission of quantum Hall edge channels with full degeneracy lifting in split-gated graphene devices.

Charge carriers in the quantum Hall regime propagate via one-dimensional conducting channels that form along the edges of a two-dimensional electron gas. Controlling their transmission through a gate-tunable constriction, also called quantum point contact, is fundamental for many coherent transport experiments. However, in graphene, tailoring a constriction with electrostatic gates remains challenging due to the formation of p-n junctions below gate electrodes along which electron and hole edge channels co-propagate and mix, short circuiting the constriction. Here we show that this electron-hole mixing is drastically reduced in high-mobility graphene van der Waals heterostructures thanks to the full degeneracy lifting of the Landau levels, enabling quantum point contact operation with full channel pinch-off. We demonstrate gate-tunable selective transmission of integer and fractional quantum Hall edge channels through the quantum point contact. This gate control of edge channels opens the door to quantum Hall interferometry and electron quantum optics experiments in the integer and fractional quantum Hall regimes of graphene.

Gate-controlled reversible rectifying behaviour in tunnel contacted atomically-thin MoS2 transistor.

Atomically thin two-dimensional semiconducting materials integrated into van der Waals heterostructures have enabled architectures that hold great promise for next generation nanoelectronics. However, challenges still remain to enable their applications as compliant materials for integration in logic devices. Here, we devise a reverted stacking technique to intercalate a wrinkle-free boron nitride tunnel layer between MoS2 channel and source drain electrodes. Vertical tunnelling of electrons therefore makes it possible to suppress the Schottky barriers and Fermi level pinning, leading to homogeneous gate-control of the channel chemical potential across the bandgap edges. The observed features of ambipolar pn to np diode, which can be reversibly gate tuned, paves the way for future logic applications and high performance switches based on atomically thin semiconducting channel.Van der Waals heterostructures of atomically thin materials hold promise for nanoelectronics. Here, the authors demonstrate a reverted stacking fabrication method for heterostructures and devise a vertical tunnel-contacted MoS2 transistor, enabling gate tunable rectification and reversible pn to np diode behaviour.

A synthetic redox biofilm made from metalloprotein-prion domain chimera nanowires.

Engineering bioelectronic components and set-ups that mimic natural systems is extremely challenging. Here we report the design of a protein-only redox film inspired by the architecture of bacterial electroactive biofilms. The nanowire scaffold is formed using a chimeric protein that results from the attachment of a prion domain to a rubredoxin (Rd) that acts as an electron carrier. The prion domain self-assembles into stable fibres and provides a suitable arrangement of redox metal centres in Rd to permit electron transport. This results in highly organized films, able to transport electrons over several micrometres through a network of bionanowires. We demonstrate that our bionanowires can be used as electron-transfer mediators to build a bioelectrode for the electrocatalytic oxygen reduction by laccase. This approach opens opportunities for the engineering of protein-only electron mediators (with tunable redox potentials and optimized interactions with enzymes) and applications in the field of protein-only bioelectrodes.