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.

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.

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.

Single-Molecule Magnetism, Enhanced Magnetocaloric Effect, and Toroidal Magnetic Moments in a Family of Ln4 Squares.

Three cationic [Ln4 ] squares (Ln=lanthanide) were isolated as single crystals and their structures solved as [Dy4 (µ4 -OH)(HL)(H2 L)3 (H2 O)4 ]Cl2 ⋅(CH3 OH)4 ⋅(H2 O)8 (1), [Tb4 (µ4 -OH)(HL)(H2 L)3 (MeOH)4 ]Cl2 ⋅(CH3 OH)4 ⋅(H2 O)4 (2) and [Gd4 (µ4 -OH)(HL)(H2 L)3 (H2 O)2 (MeOH)2 ]Br2 ⋅(CH3 OH)4 ⋅(H2 O)3 (3). The structures are described as hydroxo-centered squares of lanthanide ions, with each edge of the square bridged by a doubly deprotonated H2 L(2-) ligand. Alternating current magnetic susceptibility measurements show frequency-dependent out-of-phase signals with two different thermally assisted relaxation processes for 1, whereas no maxima in χM " appears above 2.0 K for complex 2. For 1, the estimated effective energy barrier for these two relaxation processes is 29 and 100 K. Detailed ab initio studies reveal that complex 1 possesses a toroidal magnetic moment. The ab initio calculated anisotropies of the metal ions in complex 1 were employed to simulate the magnetic susceptibility by using the Lines model (POLY_ANISO) and this procedure yields J1 =+0.01 and J2 =-0.01 cm(-1) for 1 as the two distinct exchange interactions between the Dy(III) ions. Similar parameters are also obtained for complex 1 (and 2) from specific heat measurements. A very weak antiferromagnetic super-exchange interaction (J1 =-0.043 cm(-1) and g=1.99) is observed between the metal centers in 3. The magnetocaloric effect (MCE) was estimated by using field-dependent magnetization and temperature-dependent heat-capacity measurements. An excellent agreement is found for the -ΔSm values extracted from these two measurements for all three complexes. As expected, 3 shows the largest -ΔSm variation (23 J Kg(-1) K(-1) ) among the three complexes. The negligible magnetic anisotropy of Gd indeed ensures near degeneracy in the (2S+1) ground state microstates, and the weak super-exchange interaction facilitates dense population of low-lying excited states, all of which are likely to contribute to the MCE, making complex 3 an attractive candidate for cryogenic refrigeration.

Low temperature magnetic properties and spin dynamics in single crystals of Cr8Zn antiferromagnetic molecular rings.

A detailed experimental investigation of the effects giving rise to the magnetic energy level structure in the vicinity of the level crossing (LC) at low temperature is reported for the open antiferromagnetic molecular ring Cr8Zn. The study is conducted by means of thermodynamic techniques (torque magnetometry, magnetization and specific heat measurements) and microscopic techniques (nuclear magnetic resonance line width, nuclear spin lattice, and spin-spin relaxation measurements). The experimental results are shown to be in excellent agreement with theoretical calculations based on a minimal spin model Hamiltonian, which includes a Dzyaloshinskii-Moriya interaction. The first ground state level crossing at µ0Hc1 = 2.15 T is found to be an almost true LC while the second LC at µ0Hc2 = 6.95 T has an anti-crossing gap of Δ12 = 0.19 K. In addition, both NMR and specific heat measurements show the presence of a level anti-crossing between excited states at µ0H = 4.5 T as predicted by the theory. In all cases, the fit of the experimental data is improved by introducing a distribution of the isotropic exchange couplings (J), i.e., using a J strain model. The peaks at the first and second LCs in the nuclear spin-lattice relaxation rate are dominated by inelastic scattering and a value of Γ âˆ¼ 10(10) rad/s is inferred for the life time broadening of the excited state of the open ring, due to spin phonon interaction. A loss of NMR signal (wipe-out effect) is observed for the first time at LC and is explained by the enhancement of the spin-spin relaxation rate due to the inelastic scattering.

A detailed study of the magnetism of chiral {Cr7M} rings: an investigation into parametrization and transferability of parameters.

Compounds of general formula [Cr7MF3(Etglu)(O2C(t)Bu)15(Phpy)] [H5Etglu = N-ethyl-d-glucamine; Phpy = 4-phenylpyridine; M = Zn (1), Mn (2), Ni (3)] have been prepared. The structures contain an irregular octagon of metal sites formed around the penta-deprotonated Etglu(5-) ligand; the chirality of N-ethyl-d-glucamine is retained in the final product. The seven Cr(III) sites have a range of coordination environments, and the divalent metal site is crystallographically identified and has a Phpy ligand attached to it. By using complementary experimental techniques, including magnetization and specific heat measurements, inelastic neutron scattering, and electron paramagnetic resonance spectroscopy, we have investigated the magnetic features of this family of {Cr7M} rings. Microscopic parameters of the spin Hamiltonian have been determined as a result of best fits of the different experimental data, allowing a direct comparison with corresponding parameters found in the parent compounds. We examine whether these parameters can be transferred between compounds and compare them with those of an earlier family of heterometallic rings.

Controlled positioning of nanoparticles on graphene by noninvasive AFM lithography.

Atomic force microscopy is shown to be an excellent lithographic technique to directly deposit nanoparticles on graphene by capillary transport without any previous functionalization of neither the nanoparticles nor the graphene surface while preserving its integrity and conductivity properties. Moreover this technique allows for (sub)micrometric control on the positioning thanks to a new three-step protocol that has been designed with this aim. With this methodology the exact target coordinates are registered by scanning the tip over the predetermined area previous to its coating with the ink and deposition. As a proof-of-concept, this strategy has successfully allowed the controlled deposition of few nanoparticles on 1 µm(2) preselected sites of a graphene surface with high accuracy.

Dodecanuclear [Cu(II)6Gd(III)6] nanoclusters as magnetic refrigerants.

A novel dodecanuclear complex, [{(HL)(L)(DMF)Cu(II)Gd(III)(DMF)(H(2)O)}(6)]·6DMF (1; DMF = N,N-dimethylformamide), has been obtained using the ligand resulting from the condensation of 3-formylsalicylic acid with hydroxylamine (H(3)L). The exchange interaction between the phenoxo-bridged Cu(II) and Gd(III) ions is weak ferromagnetic (J = +1.01 cm(-1)). The combination of a high-spin ground state with small anisotropy leads to a significant magnetocaloric effect [-ΔS(m)(0-7 T) = 23.5 J K g(-1) K(-1) at ∼2 K].

Molecular spins for quantum information technologies.

Technological challenges for quantum information technologies lead us to consider aspects of molecular magnetism in a radically new perspective. The design of new derivatives and recent experimental results on molecular nanomagnets are covered in this tutorial review through the keyhole of basic concepts of quantum information, such as the control of decoherence and entanglement at the (supra-)molecular level.

Graphene spintronic devices with molecular nanomagnets.

The possibility to graft nano-objects directly on its surface makes graphene particularly appealing for device and sensing applications. Here we report the design and the realization of a novel device made by a graphene nanoconstriction decorated with TbPc(2) magnetic molecules (Pc = phthalocyananine), to electrically detect the magnetization reversal of the molecules in proximity with graphene. A magnetoconductivity signal as high as 20% is found for the spin reversal, revealing the uniaxial magnetic anisotropy of the TbPc(2) quantum magnets. These results depict the behavior of multiple-field-effect nanotransistors with sensitivity at the single-molecule level.

Chemical control of spin propagation between heterometallic rings.

We present a synthetic, structural, theoretical, and spectroscopic study of a family of heterometallic ring dimers which have the formula [{Cr(7)NiF(3)(Etglu)(O(2)CtBu)(15)}(2)(NLN)], in which Etglu is the pentadeprotonated form of the sugar N-ethyl-D-glucamine, and NLN is an aromatic bridging diimine ligand. By varying NLN we are able to adjust the strength of the interaction between rings with the aim of understanding how to tune our system to achieve weak magnetic communication between the spins, a prerequisite for quantum entanglement. Micro-SQUID and EPR data reveal that the magnetic coupling between rings is partly related to the through-bond distance between the spin centers, but also depends on spin-polarization mechanisms and torsion angles between aromatic rings. Density functional theory (DFT) calculations allow us to make predictions of how such chemically variable parameters could be used to tune very precisely the interaction in such systems. For possible applications in quantum information processing and molecular spintronics, such precise control is essential.

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-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.

Magnetic imaging of cyanide-bridged co-ordination nanoparticles grafted on FIB-patterned Si substrates.

Prussian blue CsNiCr nanoparticles are used to decorate selected portions of a Si substrate. For successful grafting to take place, the Si surface needs first to be chemically functionalized. Low-dose focused ion beam patterning on uniformly functionalized surfaces selects those portions that will not participate in the grafting process. Step-by-step control is assured by atomic force and high-resolution scanning electron microscopy, revealing a submonolayer distribution of the grafted nanoparticles. By novel scanning Hall-probe microscopy, an in-depth investigation of the magnetic response of the nanoparticles to varying temperature and applied magnetic field is provided. The magnetic images acquired suggest that low-temperature canted ferromagnetism is found in the grafted nanoparticles, similar to what is observed in the equivalent bulk material.

A ring cycle: studies of heterometallic wheels.

The synthesis of a series of heterometallic rings and chains is reported. The family is based on the octanuclear cages of general formula [H(2)NR(2)][M(7)M'F(8)(O(2)CR')(16)], where M is a trivalent metal (Cr, Fe, V, Al, Ga or In), M' is a divalent metal (Mn, Fe, Co, Ni, Mg, Zn, Cd), R is a linear alkyl chain and O(2)CR' is one of around twenty carboxylates. Other members of the family with nonametallic and decametallic cores are described, and some new physics is outlined, including initial investigations of the proposed application of [Cr(7)Ni] rings as Qubits in quantum information processing.

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.

Electroburning of few-layer graphene flakes, epitaxial graphene, and turbostratic graphene discs in air and under vacuum.

Graphene-based electrodes are very promising for molecular electronics and spintronics. Here we report a systematic characterization of the electroburning (EB) process, leading to the formation of nanometer-spaced gaps, on different types of few-layer graphene (namely mechanically exfoliated graphene on SiO2, graphene epitaxially grown on the C-face of SiC and turbostratic graphene discs deposited on SiO2) under air and vacuum conditions. The EB process is found to depend on both the graphene type and on the ambient conditions. For the mechanically exfoliated graphene, performing EB under vacuum leads to a higher yield of nanometer-gap formation than working in air. Conversely, for graphene on SiC the EB process is not successful under vacuum. Finally, the EB is possible with turbostratic graphene discs only after the creation of a constriction in the sample using lithographic patterning.