Mesoscopic 3D Charge Transport in Solution-Processed Graphene-Based Thin Films: A Multiscale Analysis.

Graphene and related 2D material (GRM) thin films consist of 3D assembly of billions of 2D nanosheets randomly distributed and interacting via van der Waals forces. Their complexity and the multiscale nature yield a wide variety of electrical characteristics ranging from doped semiconductor to glassy metals depending on the crystalline quality of the nanosheets, their specific structural organization ant the operating temperature. Here, the charge transport (CT) mechanisms are studied that are occurring in GRM thin films near the metal-insulator transition (MIT) highlighting the role of defect density and local arrangement of the nanosheets. Two prototypical nanosheet types are compared, i.e., 2D reduced graphene oxide and few-layer-thick electrochemically exfoliated graphene flakes, forming thin films with comparable composition, morphology and room temperature conductivity, but different defect density and crystallinity. By investigating their structure, morphology, and the dependence of their electrical conductivity on temperature, noise and magnetic-field, a general model is developed describing the multiscale nature of CT in GRM thin films in terms of hopping among mesoscopic bricks, i.e., grains. The results suggest a general approach to describe disordered van der Waals thin films.

Tetrairon(II) extended metal atom chains as single-molecule magnets.

Iron-based extended metal atom chains (EMACs) are potentially high-spin molecules with axial magnetic anisotropy and thus candidate single-molecule magnets (SMMs). We herein compare the tetrairon(ii), halide-capped complexes [Fe4(tpda)3Cl2] (1Cl) and [Fe4(tpda)3Br2] (1Br), obtained by reacting iron(ii) dihalides with [Fe2(Mes)4] and N2,N6-di(pyridin-2-yl)pyridine-2,6-diamine (H2tpda) in toluene, under strictly anhydrous and anaerobic conditions (HMes = mesitylene). Detailed structural, electrochemical and Mössbauer data are presented along with direct-current (DC) and alternating-current (AC) magnetic characterizations. DC measurements revealed similar static magnetic properties for the two derivatives, with χMT at room temperature above that for independent spin carriers, but much lower at low temperature. The electronic structure of the iron(ii) ions in each derivative was explored by ab initio (CASSCF-NEVPT2-SO) calculations, which showed that the main magnetic axis of all metals is directed close to the axis of the chain. The outer metals, Fe1 and Fe4, have an easy-axis magnetic anisotropy (D = -11 to -19 cm-1, |E/D| = 0.05-0.18), while the internal metals, Fe2 and Fe3, possess weaker hard-axis anisotropy (D = 8-10 cm-1, |E/D| = 0.06-0.21). These single-ion parameters were held constant in the fitting of DC magnetic data, which revealed ferromagnetic Fe1-Fe2 and Fe3-Fe4 interactions and antiferromagnetic Fe2-Fe3 coupling. The competition between super-exchange interactions and the large, noncollinear anisotropies at metal sites results in a weakly magnetic non-Kramers doublet ground state. This explains the SMM behavior displayed by both derivatives in the AC susceptibility data, with slow magnetic relaxation in 1Br being observable even in zero static field.

Multiscale Charge Transport in van der Waals Thin Films: Reduced Graphene Oxide as a Case Study.

Large area van der Waals (vdW) thin films are assembled materials consisting of a network of randomly stacked nanosheets. The multiscale structure and the two-dimensional (2D) nature of the building block mean that interfaces naturally play a crucial role in the charge transport of such thin films. While single or few stacked nanosheets (i.e., vdW heterostructures) have been the subject of intensive works, little is known about how charges travel through multilayered, more disordered networks. Here, we report a comprehensive study of a prototypical system given by networks of randomly stacked reduced graphene oxide 2D nanosheets, whose chemical and geometrical properties can be controlled independently, permitting to explore percolated networks ranging from a single nanosheet to some billions with room-temperature resistivity spanning from 10-5 to 10-1 Ω·m. We systematically observe a clear transition between two different regimes at a critical temperature T*: Efros-Shklovskii variable-range hopping (ES-VRH) below T* and power law behavior above. First, we demonstrate that the two regimes are strongly correlated with each other, both depending on the charge localization length ξ, calculated by the ES-VRH model, which corresponds to the characteristic size of overlapping sp2 domains belonging to different nanosheets. Thus, we propose a microscopic model describing the charge transport as a geometrical phase transition, given by the metal-insulator transition associated with the percolation of quasi-one-dimensional nanofillers with length ξ, showing that the charge transport behavior of the networks is valid for all geometries and defects of the nanosheets, ultimately suggesting a generalized description on vdW and disordered thin films.

Microwave Photon Detectors Based on Semiconducting Double Quantum Dots.

Detectors of microwave photons find applications in different fields ranging from security to cosmology. Due to the intrinsic difficulties related to the detection of vanishingly small energy quanta ℏ ω , significant portions of the microwave electromagnetic spectrum are still uncovered by suitable techniques. No prevailing technology has clearly emerged yet, although different solutions have been tested in different contexts. Here, we focus on semiconductor quantum dots, which feature wide tunability by external gate voltages and scalability for large architectures. We discuss possible pathways for the development of microwave photon detectors based on photon-assisted tunneling in semiconducting double quantum dot circuits. In particular, we consider implementations based on either broadband transmission lines or resonant cavities, and we discuss how developments in charge sensing techniques and hybrid architectures may be beneficial for the development of efficient photon detectors in the microwave range.

Microwave-Assisted Tunneling in Hard-Wall InAs/InP Nanowire Quantum Dots.

With downscaling of electronic circuits, components based on semiconductor quantum dots are assuming increasing relevance for future technologies. Their response under external stimuli intrinsically depend on their quantum properties. Here we investigate single-electron tunneling in hard-wall InAs/InP nanowires in the presence of an off-resonant microwave drive. Our heterostructured nanowires include InAs quantum dots (QDs) and exhibit different tunnel-current regimes. In particular, for source-drain bias up to few mV Coulomb diamonds spread with increasing contrast as a function of microwave power and present multiple current polarity reversals. This behavior can be modelled in terms of voltage fluctuations induced by the microwave field and presents features that depend on the interplay of the discrete energy levels that contribute to the tunneling process.

Aggregation of [Ln] clusters by the dianion of 3-formylsalicylic acid. Synthesis, crystal structures, magnetic and luminescence properties.

Three isostrucutral dodecanuclear clusters with the general formula [Ln12(fsa)12(µf3-OH)12(DMF)12]·nDMF (fsa2- is the dianion of 3-formylsalicylic acid; Ln = Eu 1, Gd 2, Dy 3) have been obtained from the reaction of fromylsalicyclic acid (H2fsa), tetrabutylammonium hydroxide and Ln(NO3)3·6H2O in methanol/DMF. Their structure consists of four vertex-sharing heterocubanes. Each heterocubane unit is assembled from four LnIII ions, three µ3-OH groups and one µ3-oxygen atom arising from the fsa2- carboxylato group. The photophysical properties of the europium derivative investigated at both 300 and 80 K sustain a relative intense emission obtained under low power LED excitation at 420 nm. The dysprosium derivative shows a SMM behavior with an effective energy barrier Ueff of 22.9 cm-1, while the thermodynamical properties of Gd12 confirm a large magnetocaloric effect: S(7 T) - S(0 T) = 20R = 166 J mol-1 K), typical for isotropic GdIII derivatives, with ΔS = S(7 T) - S(0 T) = 1.7R for each GdIII ion.

Synthesis of Graphene Nanoribbons by Ambient-Pressure Chemical Vapor Deposition and Device Integration.

Graphene nanoribbons (GNRs), quasi-one-dimensional graphene strips, have shown great potential for nanoscale electronics, optoelectronics, and photonics. Atomically precise GNRs can be "bottom-up" synthesized by surface-assisted assembly of molecular building blocks under ultra-high-vacuum conditions. However, large-scale and efficient synthesis of such GNRs at low cost remains a significant challenge. Here we report an efficient "bottom-up" chemical vapor deposition (CVD) process for inexpensive and high-throughput growth of structurally defined GNRs with varying structures under ambient-pressure conditions. The high quality of our CVD-grown GNRs is validated by a combination of different spectroscopic and microscopic characterizations. Facile, large-area transfer of GNRs onto insulating substrates and subsequent device fabrication demonstrate their promising potential as semiconducting materials, exhibiting high current on/off ratios up to 6000 in field-effect transistor devices. This value is 3 orders of magnitude higher than values reported so far for other thin-film transistors of structurally defined GNRs. Notably, on-surface mass spectrometry analyses of polymer precursors provide unprecedented evidence for the chemical structures of the resulting GNRs, especially the heteroatom doping and heterojunctions. These results pave the way toward the scalable and controllable growth of GNRs for future applications.

Relay-Like Exchange Mechanism through a Spin Radical between TbPc2 Molecules and Graphene/Ni(111) Substrates.

We investigate the electronic and magnetic properties of TbPc2 single ion magnets adsorbed on a graphene/Ni(111) substrate, by density functional theory (DFT), ab initio complete active space self-consistent field calculations, and X-ray magnetic circular dichroism (XMCD) experiments. Despite the presence of the graphene decoupling layer, a sizable antiferromagnetic coupling between Tb and Ni is observed in the XMCD experiments. The molecule-surface interaction is rationalized by the DFT analysis and is found to follow a relay-like communication pathway, where the radical spin on the organic Pc ligands mediates the interaction between Tb ion and Ni substrate spins. A model Hamiltonian which explicitly takes into account the presence of the spin radical is then developed, and the different magnetic interactions at play are assessed by first-principle calculations and by comparing the calculated magnetization curves with XMCD data. The relay-like mechanism is at the heart of the process through which the spin information contained in the Tb ion is sensed and exploited in carbon-based molecular spintronics devices.

Heterodimers of heterometallic rings.

Nine new complexes are reported involving linked heterometallic rings; one ring is designed as a ligand for the second, and the compounds produced can be regarded as molecular prototypes for implementing quantum gates featuring two subtly different qubits.

Coherent Spin Dynamics in Molecular Cr8Zn Wheels.

Controlling and understanding transitions between molecular spin states allows selection of the most suitable ones for qubit encoding. Here we present a detailed investigation of single crystals of a polynuclear Cr8Zn molecular wheel using 241 GHz electron paramagnetic resonance (EPR) spectroscopy in high magnetic field. Continuous wave spectra are well reproduced by spin Hamiltonian calculations, which evidence that transitions in correspondence to a well-defined anticrossing involve mixed states with different total spin. We studied, by means of spin echo experiments, the temperature dependence of the dephasing time (T2) down to 1.35 K. These results are reproduced by considering both hyperfine and intermolecular dipolar interactions, evidencing that the dipolar contribution is completely suppressed at the lowest temperature. Overall, these results shed light on the effects of the decoherence mechanisms, whose understanding is crucial to exploit chemically engineered molecular states as a resource for quantum information processing.