Search

Highly transparent Bi4Ti3O12 (BiTO) thin-film photocathodes were fabricated for the ferroelectric-assisted photo-electrochemical (PEC) reduction of CO2, showing the potential of effectively exploiting the ferroelectric properties of BiTO to boost its PEC performance.

An interplay of geometrical frustration and strong quantum fluctuations in a spin-1/2 triangular-lattice antiferromagnet (TAF) can lead to exotic quantum states. Here, we report the neutron-scattering, magnetization, specific heat, and magnetocaloric studies of the recently discovered spin-1/2 TAF Na

Contact resistance effects in n-type organic field-effect transistors (OFETs) based on perylene-diimide thin films and monolayer CVD graphene electrodes have been investigated by using Scanning Kelvin Probe Force Microscopy (SKPFM). SKPFM voltage profiles were acquired as a function of the applied drain–source (Vds) and gate–source (Vgs) voltages and in the temperature range between 300 and 360 K. The results were compared with those obtained for hybrid devices bearing contemporarily a gold and a graphene electrode, in order to highlight the specific behaviors of the graphene/organic and gold/organic interfaces. Despite the fact that overall electrical performances of devices based on gold and graphene contacts are fully comparable, the SKPFM analysis demonstrates unambiguously that the physical mechanisms driving the charge injection and extraction phenomena are distinctive based on the electrode type. While for OFETs with gold electrodes, the RC effect is mainly ascribable to the degraded quality of the charge transport in the semiconducting film regions close to the electrodes, for graphene-based devices, it is related to the presence of a Schottky-like barrier at the injecting electrode.

Here, we exploited the UV light and thermal triggered E Z photoisomerization of an azobenzene compound to fabricate multimodal readable and rewritable data matrix based devices. We first demonstrated that the UV light sensing capabilities can be simultaneously monitored by the change in optical, spectroscopic, and electrical properties. Then we exploited this capability by integrating tetra(azobenzene)methane crystals in a micrometric TAG whose information can be modified and repristinated by local UV treatment and thermal annealing. The system was characterized by polarized optical microscopy, Raman spectroscopy, conductive atomic force microscopy and Kelvin Probe Force Microscopy.

International audience; 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.

We present the fabrication and characterization of all-carbon phototransistors made of graphene three terminal devices, coated with atomically precise graphene quantum dots (GQD). Chemically synthesized GQDs are the light absorbing materials, while the underlying chemical vapor deposition (CVD)-grown graphene layer acts as the charge transporting channel. We investigated three types of GQDs with different sizes and edge structures, having distinct and characteristic optical absorption in the UV–vis range. The photoresponsivity exceeds 106 A/W for vanishingly small incident power (

In this work we report on fully operational sub-micrometric low voltage OFETs by using graphene as the source-drain electrodes pair and a high- κ ultra-thin dielectric in a local gate architecture. The impact of the graphene electrodes on the miniaturization of the organic devices has been assessed, with particular attention to the influence of the contact resistances as well as the parasitic overlap gate capacitance on the device bandwidth. By the use of a modified Transmission-Line-Method, contact resistances have been analyzed as function of the applied voltages, revealing characteristic functional trends that follow the doping state of graphene electrodes. Through impedance spectroscopy of the electrodes, cut-off frequencies as high as 105 Hz have been estimated, highlighting the peculiar role of quantum capacitance of graphene in such architectures.

The ultrafast dynamics and conductivity of photoexcited graphene can be explained using solely electronic effects., For many of the envisioned optoelectronic applications of graphene, it is crucial to understand the subpicosecond carrier dynamics immediately following photoexcitation and the effect of photoexcitation on the electrical conductivity—the photoconductivity. Whereas these topics have been studied using various ultrafast experiments and theoretical approaches, controversial and incomplete explanations concerning the sign of the photoconductivity, the occurrence and significance of the creation of additional electron-hole pairs, and, in particular, how the relevant processes depend on Fermi energy have been put forward. We present a unified and intuitive physical picture of the ultrafast carrier dynamics and the photoconductivity, combining optical pump–terahertz probe measurements on a gate-tunable graphene device, with numerical calculations using the Boltzmann equation. We distinguish two types of ultrafast photo-induced carrier heating processes: At low (equilibrium) Fermi energy (EF ≲ 0.1 eV for our experiments), broadening of the carrier distribution involves interband transitions (interband heating). At higher Fermi energy (EF ≳ 0.15 eV), broadening of the carrier distribution involves intraband transitions (intraband heating). Under certain conditions, additional electron-hole pairs can be created [carrier multiplication (CM)] for low EF, and hot carriers (hot-CM) for higher EF. The resultant photoconductivity is positive (negative) for low (high) EF, which in our physical picture, is explained using solely electronic effects: It follows from the effect of the heated carrier distributions on the screening of impurities, consistent with the DC conductivity being mostly due to impurity scattering. The importance of these insights is highlighted by a discussion of the implications for graphene photodetector applications.

Molecular spins have shown interesting quantum features, which make them potential candidates for the implementation of quantum information processing. New challenges related to possible applications in the broader class of quantum technologies are currently under discussion. Here, we revisit some key features trying to learn something from experiences in related fields.

Graphene nanodevices, such as ultra-narrow constrictions and nanometer-spaced gaps, are emerging as appealing candidates for various applications, ranging from advanced quantum devices to single-molecule junctions and even DNA sequencing. Here, we present the realization and characterization of nanometer-sized gaps in suspended few-layer graphene devices via feedback-controlled electroburning at room temperature. By analyzing the electrical behavior after the electroburning process, we identify two distinct regimes for the resulting devices, deriving a simple yet effective quantitative criterion to determine the complete opening of the nanogaps.

Proving the preservation of functionality at the molecular scale is still a major challenge, both for the choice of suitable derivatives and protocols and for the employed experimental tools and methods. By using a combined scanning probe (AFM and STM) and spectroscopic methodology (XPS, XAS and XMCD), it is shown that Gd4M8 derivatives (with M = Zn2+, Ni2+) are robust molecular units which preserve their electronic, magnetic, and thermodynamic properties when deposited on a metallic surface. Namely, entropy variation ?S = [S(6 T) - S(0 T)] exceeding 8 R (20 J kg-1 K-1) at 4 K in isolated Gd4Ni8 molecules dispersed on Au(111) surface is measured and a viable route to exploit large magnetocaloric effect at single molecule level is shown.

We investigate the electronic and magnetic properties of TbPc

The molecular magnet Hpyr [Fe17 O16 (OH) 12 (py) 12 Br4] Br4 (" Fe17 ") has a well-defined cluster spin ground state of S=35/2 at low temperatures and an axial molecular anisotropy of only D-0.02K. Dipolar interactions between the molecular spins induce long-range magnetic order below 1.1 K. We report here the magnetic structure of Fe17, as determined by unpolarized neutron diffraction experiments performed on a polycrystalline sample of deuterated Fe17 in zero applied magnetic field. In addition, we report bulk susceptibility, magnetization, and specific heat data. The temperature dependence of the long-range magnetic order has been tracked and is well accounted for within mean-field theory. Ferromagnetic order along the crystallographic c axis of the molecular spins, as determined by the neutron diffraction experiments, is in agreement with ground-state dipolar energy calculations. © 2008 The American Physical Society.

Several technological issues have to be faced to realize devices working at the single molecule level. One of the main challenges consists of defining methods to fabricate electrodes to make contact with single molecules. Here, we report the realization of novel spintronic devices made of a TbPc2 single molecule embedded between two nanometer-separated graphene electrodes, obtained by feedback-controlled electroburning. We demonstrate that this approach allows the realisation of devices working at low temperature. With these, we were able to characterize the magnetic exchange coupling between the electronic spin of the Tb3+ magnetic core and the current passing through the molecular system in the Coulomb blockade regime, thus showing that the use of graphene is a promising way forward in addressing single molecules.

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.

The art of orchestrating molecules on functional and nano-structured surfaces requires the use of complementary approaches, tools and skills. When the design of the molecular architecture puts together different building blocks, these assemblies may disclose novel functionalities of matter at the nano-scale and eventually function as devices. Here we present some basic concepts of this new trend in Nanoscience by using examples from our recent experience.

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.

International audience; 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.

We present recent achievements and perspectives for the encoding of qubits with molecular spin clusters.

Future applications of molecular units in quantum information technologies require a fine control at the single molecule level. This includes the choice of each functional element, the intramolecular interaction and the robustness of molecules when dispersed on a substrate. Keeping these goals in mind, we designed and synthesized a heterometallic phthalocyaninato-complex including two different lanthanides in each moiety, namely [PcDyPcTbPc∗] (Pc being phthalocyanines; and Pc∗ being 2,3,9,10,16,17,23,24-octahexyl-substituted phthalocyanines). Full magnetic characterization was performed down to the mK temperature range on bulk microcrystals by means of AC susceptibility, DC magnetization (including microSQUID) and specific heat measurements. A weak, yet sizeable, interaction between the two lanthanides is clearly detected by different techniques, altering the magnetic behavior of the single lanthanide as observed in the parent [LnPc2] complexes. Isolated [PcDyPcTbPc∗] molecules dispersed on HOPG and the Au surface by liquid phase deposition are proven to maintain their main chemical and magnetic features by combined XPS, XAS and XMCD analysis and to lie with one Pc ligand flat to the surface. Opening of a small but sizable hysteresis loop at 1.8 K is directly observed on both Tb and Dy sites proving the retention of magnetization at the single molecule level. This journal is © The Royal Society of Chemistry.

Under the terms of the CC BY license.-- et al., 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 CrZn. 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 μH = 2.15 T is found to be an almost true LC while the second LC at μH = 6.95 T has an anti-crossing gap of Δ = 0.19 K. In addition, both NMR and specific heat measurements show the presence of a level anti-crossing between excited states at μH = 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 ∼ 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., This work was financially supported by the Italian FIRB Project No. RBFR12RPD1 of the Italian MIUR “New Challenges in Molecular Nanomagnetism: From Spin Dynamics to Quantum-Information Processing.”

We report a systematic study on charge transport properties of thermally reduced graphene oxide (rGO) layers, from room temperature to 2 K and in presence of magnetic fields up to 7 T. The most conductive rGO sheets follow different transport regimes: at room temperature they show an Arrhenius-like behavior. At lower temperature they exhibits a thermally activated behavior with resistance R following a R = R0exp(T0/T)p law with p = 1/3, consistently with 2D Mott Variable Range Hopping (VRH) transport mechanism. Below a given temperature Tc, we observe a crossover from VHR to another regime, probably due to a shortening of the characteristic lengths of the disordered 2D system. The temperature Tc depends on the reduction grade of the rGO. Magnetoresistance ?R/R of our rGO films shows as well a crossover between positive and negative and below liquid He temperature ?R/R reaches values larger than ~-60%, surprisingly high for a - nominally - non magnetic material.

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.

Molecular magnets have been recently proposed as possible building blocks for a solid-state quantum computer. In order to substantiate and develop such a proposal, one needs to identify those molecules that are best suited for the qubit encoding and manipulation. Here, we focus on a heterometallic molecular ring, namely Cr7Ni, where the substitution of one Cr3+(S = 3/2) with Ni2+(S = 1) provides an extra spin to the otherwise compensated molecule. We show that its ground state consists in an S = 1/2 doublet, energetically well separated (Δ0/kB ∼ 13 K at zero magnetic field) from the first excited multiplet. This relatively large value of Δ0, together with the reduced mixing of the subspaces corresponding to different values of the total spin S, enables a safe encoding of the |0〉 and |1〉 states with the ground-state doublet, and allows to coherently rotate the effective S = 1/2 spin, while keeping the population loss to the excited states negligible. A further, intriguing challenge is represented by the implementation of the conditional dynamics (two-qubit gates). We present here preliminary characterization of molecular “Cr7Ni-dimers”, i.e., derivatives in which two Cr7Ni rings are linked with each other by means of delocalized aromatic amines. The resulting intercluster couplings are estimated to be ⩽1 K and are expected to be permanent, i.e., not tuneable during gating, as required by the standard approach to quantum computation. We discuss a computational scheme that allows in principle to overcome this limitation. The most relevant decoherence mechanisms for Cr7Ni and possible ways to reduce their effects are discussed as well.

The interface spin coupling mechanism is studied in a hybrid structure made of Fe phthalocyanine molecules sublimed in ultrahigh vacuum on graphene grown on the magnetic substrate Ni(111). By using synchrotron X-ray magnetic circular dichroism, the field-dependent magnetization of the isolated FePc molecules and of the Ni substrate has been measured at low temperature (8 K). Along with density functional theory calculations, the role of the graphene interlayer in transmitting the magnetic coupling is addressed. Both experiments and theory show a ferromagnetic coupling between the molecules and the substrate which is weakened by the insertion of graphene. DFT calculations indicate that the key role is played by the ? orbitals of graphene, which hybridize with the underlying magnetic Ni, giving rise to a sizable spin polarized continuum at the molecular interface. The resulting overlap with the Fe orbitals favors a direct coupling of ferromagnetic nature, as evidenced by our spin density distribution plots. © 2014 American Chemical Society.

With element-specific X-ray absorption spectroscopy and X-ray magnetic circular dichroism we have investigated submonolayer coverages of TbPc2 and DyPc2 molecules sublimated on highly ordered pyrolytic graphite. We have studied the field dependence of the magnetization of the central lanthanide ion at very low temperatures. Even in zero applied magnetic field we still observe a remanence in the magnetization. Since there are neither intermolecular coupling nor magnetic interactions with the substrate, this remanent behaviour results just from single-ion anisotropy. On the very inert surface of graphite at temperatures between 0.5 K and 2 K the spin relaxation is slow enough to observe a memory effect in the timescale of the experimental measurements.

By means of focused ion beam milling, we fabricate Hall magnetometers with active areas as small as 100 × 100 nm 2 . The constituent material can either be metallic (Au), semimetallic (Bi) or doped bulk semiconducting (Si doped GaAs). We experimentally show that Au nano-probes can work from room temperature down to liquid helium with magnetic flux sensitivity 10 - 1 Φ 0 .

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. © 2012 American Chemical Society., We thank the Spanish government for the project MAT2009-13977-C03-03. N.D. and E.B. thank the Spanish government for a Ramon y Cajal grant and a FPI grant, respectively. This work has been partially supported by FP7-ICT FET Open “MolSpinQIP” project, Contract No. 211284.

International audience; 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.

The ability to assemble weakly interacting subsystems is a prerequisite for implementing quantum information processing and generating controlled entanglement. In recent years, molecular nanomagnets have been proposed as suitable candidates for qubit encoding and manipulation. In particular, antiferromagnetic Cr7Ni rings behave as effective spin-1/2 systems at low temperature and show long decoherence times. Here, we show that these rings can be chemically linked to each other and that the coupling between their spins can be tuned by choosing the linker. We also present calculations that demonstrate how realistic microwave pulse sequences could be used to generate maximally entangled states in such molecules. The ability to assemble weakly-interacting subsystems is a prerequisite for implementing quantum-information processing. In recent years, molecular nanomagnets have been proposed as suitable candidates for qubit encoding and manipulation, with antiferromagnetic Cr7Ni rings of particular interest. It has now been shown that such rings can be chemically linked to each other and the coupling between their spins tuned through the choice of chemical linker.

The molecular magnet Hpyr[Fe 17O16OH12py12Br4Br4] “Fe17” has a well-defined cluster spin ground state of S=35/2 at low temperatures and an axial molecular anisotropy of only D ≈−0.02 K. Dipolar interactions between the molecular spins induce long-range magnetic order below 1.1 K. We report here the magnetic structure of Fe17, as determined by unpolarized neutron diffraction experiments performed on a polycrystalline sample of deuterated Fe17 in zero applied magnetic field. In addition, we report bulk susceptibility, magnetization, and specific heat data. The temperature dependence of the long-range magnetic order has been tracked and is well accounted for within mean-field theory. Ferromagnetic order along the crystallographic c axis of the molecular spins, as determined by the neutron diffraction experiments, is in agreement with ground-state dipolar energy calculations.

Lisnard, Laurent Tuna, Floriana Candini, Andrea Affronte, Marco Winpenny, Richard E. P. McInnes, Eric J. L. EPSRC (UK) ; EC "Network of Excellence" MAGMANet ; EC-TMR Network "QuEMolNa" This work was supported by the EPSRC (UK), the EC "Network of Excellence" MAGMANet, and the EC-TMR Network "QuEMolNa". 31 WILEY-V C H VERLAG GMBH WEINHEIM 384EP

We report on a family of molecular crystals containing non-interacting Ni10 magnetic molecules. These crystals display slow relaxation of the magnetization below a temperature as high as 17 K. This behavior is not associated with an anisotropy energy barrier. The magnetic energy spectrum of a Ni10 molecule is structured in dense well-separated bands, the lowest of which makes the crystal nearly opaque to phonons of energy below about 1 meV. We interpret the observed non-equilibrium behavior as due to resonant trapping of these low-energy phonons.

We have fabricated and characterized Hall probes on an In0.75Al0.25As/In0.75Ga0.25As two-dimensional electron gas with lateral sizes down to 100 nm. We studied the dependence of the low temperature (4 K) magnetic field sensitivity on the probe size, showing that the best flux sensitivity is achieved by devices of ≈ 200 nm, employing highly doped systems ( n ∼ 1 0 12 cm−2). Hall bars with sizes down to the range of 200–250 nm show a magnetic field sensitivity of a few Gauss, corresponding to a flux sensitivity equal to ≈ 1 0 − 2 Φ 0 .

We have developed a novel strategy to build arrays of magnetic nanodots on the 100 nm scale, which exploits the potentialities of both bottom-up and top-down approaches, by self-assembling sulfur-functionalized Mn12 single molecule magnets (SMMs) on patterned An dot matrices nanofabricated by FIB (focus ion beam). In this way, we demonstrate the capability to assemble SMMs in ordered arrays, where the magnetic information can be easily addressed, being the single bit represented by a 2D distribution of few hundred Mn12 clusters, grafted on top of each 100 x 100 nm(2) Au dot. Moreover, the chosen Mn12 functionalization is expected to favour a preferential orientation of the grafted molecule with the easy magnetization axis normal to the surface. (C) 2006 Elsevier B.V. All rights reserved.

We report on the Fe17 high-spin molecular cluster and show that this system is an exemplification of nanostructured dipolar magnetism. Each Fe17 molecule, with spin S=35/2 and axial anisotropy as small as D=-0.02K, is the magnetic unit that can be chemically arranged in different packing crystals whilst preserving both spin ground-state and anisotropy. For every configuration, molecular spins are correlated only by dipolar interactions. The ensuing interplay between dipolar energy and anisotropy gives rise to macroscopic behaviors ranging from superparamagnetism to long-range magnetic order at temperatures below 1K., Replaced with version accepted for publication in Physical Review Letters

Hall magnetometers with active areas down to 100 x 100 nm(2) were fabricated patterning gold and Si-doped GaAs films by focused ion beam. For GaAs probes, electrical characterization shows that the magnetic flux sensitivity is better than 10(-2)Phi(0) at room temperature. Hall nano-probes made of gold can work down to liquid helium temperature with magnetic flux sensitivity 10(-1)Phi(0).

An unusually large magnetocaloric effect for the temperature region below 10 K is found for the Fe14 molecular nanomagnet. This is to large extent caused by its extremely large spin S ground-state combined with an excess of entropy arising from the presence of low-lying excited S states. We also show that the highly symmetric Fe14 cluster core, resulting in small cluster magnetic anisotropy, enables the occurrence of long-range antiferromagnetic order below T_N=1.87 K., Comment: 4 pages, 3 figures, accepted for publication in Applied Physics Letters

We report on the magnetic and thermal properties of the Fe14 molecular nanocluster. We find a huge magnetocaloric response in the temperature range below 10 K. This is to large extent caused by its very large spin ground-state combined with an excess of entropy arising from the admixture of low-lying excited S states. We also show that the high degree of symmetry of the Fe14 cluster core, resulting in a very small cluster magnetic anisotropy, enables the occurrence of long-range antiferromagnetic order below TN = 1.87 K.

We used inelastic neutron scattering to determine the microscopic spin Hamiltonian of a tetrairon(III) molecular cluster with trigonal symmetry, $[{\mathrm{Fe}}_{4}{(\mathrm{thme})}_{2}{(\mathrm{dpm})}_{6}]$, obtained from a parent compound with ${C}_{2}$ symmetry by site-specific ligand substitution. Intra-multiplet excitations within the anisotropy split $S=5$ ground spin state, and inter-multiplet transitions toward the first $S=4$ excited states have been observed. The model spin Hamiltonian used to interpret the experimental data evidences an enhancement of the anisotropy barrier due to the chemical modification of the parent molecular cluster. A rhombic anisotropy term, forbidden in ${D}_{3}$ symmetry, is necessary to reproduce experimental data. The determination of this term is crucial for the understanding of quantum tunneling of the magnetization in this model compound. The calculated temperature dependence of heat capacity for different applied magnetic field values is in good agreement with experimental measurements. Within this model, the estimated temperature dependence of the relaxation time agrees with available experimental data.