The classical and quantum dynamics of molecular spins on graphene

PMCID: PMC4800001.-- et al.Controlling the dynamics of spins on surfaces is pivotal to the design of spintronic and quantum computing devices. Proposed schemes involve the interaction of spins with graphene to enable surface-state spintronics and electrical spin manipulation. However, the influence of the graphene environment on the spin systems has yet to be unravelled. Here we explore the spin-graphene interaction by studying the classical and quantum dynamics of molecular magnets on graphene. Whereas the static spin response remains unaltered, the quantum spin dynamics and associated selection rules are profoundly modulated. The couplings to graphene phonons, to other spins, and to Dirac fermions are quantified using a newly developed model. Coupling to Dirac electrons introduces a dominant quantum relaxation channel that, by driving the spins over Villain's threshold, gives rise to fully coherent, resonant spin tunnelling. Our findings provide fundamental insight into the interaction between spins and graphene, establishing the basis for electrical spin manipulation in graphene nanodevices.Financial support from Italian MIUR, Spanish MINECO (MAT2012-38318-C03-01), BW-Stiftung (Kompetenznetz Funktionelle Nanostrukturen), ERC StG-338258 “OptoQMol”, the Royal Society (URF fellowship and grant) and the AvH Stiftung (Sofja Kovalevskaja award).Peer Reviewe

Towards automated and objective assessment of fabric pilling

Pilling is a complex property of textile fabrics, representing, for the final user, a non-desired feature to be controlled and measured by companies working in the textile industry. Traditionally, pilling is assessed by visually comparing fabrics with reference to a set of standard images, thus often resulting in inconsistent quality control. A number of methods using machine vision have been proposed all over the world, with almost all sharing the idea that pilling can be assessed by determining the number of pills or the area occupied by the pills on the fabric surface. In the present work a different approach is proposed: instead of determining the number of pills, a machine vision-based procedure is devised with the aim of extracting a number of parameters characterizing the fabric. These are then used to train an artificial neural network to automatically grade the fabrics in terms of pilling. Tested against a set of differently pilled fabrics, the method shows its effectiveness

Emissive brightening in molecular graphene nanoribbons by twilight states

Carbon nanomaterials are expected to be bright and efficient emitters, but structural disorder, intermolecular interactions and the intrinsic presence of dark states suppress their photoluminescence. Here, we study synthetically-made graphene nanoribbons with atomically precise edges and which are designed to suppress intermolecular interactions to demonstrate strong photoluminescence in both solutions and thin films. The resulting high spectral resolution reveals strong vibron-electron coupling from the radial-breathing-like mode of the ribbons. In addition, their cove-edge structure produces inter-valley mixing, which brightens conventionally-dark states to generate hitherto-unrecognised twilight states as predicted by theory. The coupling of these states to the nanoribbon phonon modes affects absorption and emission differently, suggesting a complex interaction with both Herzberg–Teller and Franck– Condon coupling present. Detailed understanding of the fundamental electronic processes governing the optical response will help the tailored chemical design of nanocarbon optical devices, via gap tuning and side-chain functionalisation

Quantum Interference Enhances the Performance of Single-Molecule Transistors

An unresolved challenge facing electronics at a few-nm scale is that resistive channels start leaking due to quantum tunneling. This affects the performance of nanoscale transistors, with single-molecule devices displaying particularly low switching ratios and operating frequencies, combined with large subthreshold swings.1 The usual strategy to mitigate quantum effects has been to increase device complexity, but theory shows that if quantum effects are exploited correctly, they can simultaneously lower energy consumption and boost device performance.2-6 Here, we demonstrate experimentally how the performance of molecular transistors can be improved when the resistive channel contains two destructively-interfering waves. We use a zinc-porphyrin coupled to graphene electrodes in a three-terminal transistor device to demonstrate a >104 conductance-switching ratio, a subthreshold swing at the thermionic limit, a > 7 kHz operating frequency, and stability over >105 cycles. This performance is competitive with the best nanoelectronic transistors. We fully map the antiresonance interference features in conductance, reproduce the behaviour by density functional theory calculations, and trace back this high performance to the coupling between molecular orbitals and graphene edge states. These results demonstrate how the quantum nature of electron transmission at the nanoscale can enhance, rather than degrade, device performance, and highlight directions for future development of miniaturised electronics.Comment: 11 pages, 4 figure

Efficient heating of single-molecule junctions for thermoelectric studies at cryogenic temperatures

The energy dependent thermoelectric response of a single molecule contains valuable information about its transmission function and its excited states. However, measuring it requires devices that can efficiently heat up one side of the molecule while being able to tune its electrochemical potential over a wide energy range. Furthermore, to increase junction stability, devices need to operate at cryogenic temperatures. In this work, we report on a device architecture to study the thermoelectric properties and the conductance of single molecules simultaneously over a wide energy range. We employ a sample heater in direct contact with the metallic electrodes contacting the single molecule which allows us to apply temperature biases up to ΔT = 60 K with minimal heating of the molecular junction. This makes these devices compatible with base temperatures Tbath < 2 K and enables studies in the linear (Δ T ≪ T molecule) and nonlinear (Δ T ≫ T molecule) thermoelectric transport regimes

Phase-Coherent Charge Transport through a Porphyrin Nanoribbon

Quantum interference in nano-electronic devices could lead to reduced-energy computing and efficient thermoelectric energy harvesting. When devices are shrunk down to the molecular level it is still unclear to what extent electron transmission is phase coherent, as molecules usually act as scattering centres, without the possibility of showing particle-wave duality. Here we show electron transmission remains phase coherent in molecular porphyrin nanoribbons, synthesized with perfectly defined geometry, connected to graphene electrodes. The device acts as a graphene Fabry-P\'erot interferometer, allowing direct probing of the transport mechanisms throughout several regimes, including the Kondo one. Electrostatic gating allows measurement of the molecular conductance in multiple molecular oxidation states, demonstrating a thousand-fold increase of the current by interference, and unravelling molecular and graphene transport pathways. These results demonstrate a platform for the use of interferometric effects in single-molecule junctions, opening up new avenues for studying quantum coherence in molecular electronic and spintronic devices.Comment: 14 pages, 3 figure

Magnetic edge states and coherent manipulation of graphene nanoribbons

Graphene, a single-layer network of carbon atoms, has outstanding electrical and mechanical properties. Graphene ribbons with nanometre-scale widths (nanoribbons) should exhibit half-metallicity and quantum confinement. Magnetic edges in graphene nanoribbons have been studied extensively from a theoretical standpoint because their coherent manipulation would be a milestone for spintronic and quantum computing devices. However, experimental investigations have been hampered because nanoribbon edges cannot be produced with atomic precision and the graphene terminations that have been proposed are chemically unstable. Here we address both of these problems, by using molecular graphene nanoribbons functionalized with stable spin-bearing radical groups. We observe the predicted delocalized magnetic edge states and test theoretical models of the spin dynamics and spin–environment interactions. Comparison with a non-graphitized reference material enables us to clearly identify the characteristic behaviour of the radical-functionalized graphene nanoribbons. We quantify the parameters of spin–orbit coupling, define the interaction patterns and determine the spin decoherence channels. Even without any optimization, the spin coherence time is in the range of microseconds at room temperature, and we perform quantum inversion operations between edge and radical spins. Our approach provides a way of testing the theory of magnetism in graphene nanoribbons experimentally. The coherence times that we observe open up encouraging prospects for the use of magnetic nanoribbons in quantum spintronic devices

Local spin dynamics at low temperature in the slowly relaxing molecular chain [Dy(hfac)3NIT(C6H4OPh)]: A &#956;+ spin relaxation study

The spin dynamics of the molecular magnetic chain [Dy(hfac)3NIT(C6H4OPh)] were investigated by means of the Muon Spin Relaxation (\u3bc+SR) technique. This system consists of a magnetic lattice of alternating Dy(III) ions and radical spins, and exhibits single-chain-magnet behavior. The magnetic properties of [Dy(hfac)3NIT(C6H4OPh)] have been studied by measuring the magnetization vs. temperature at different applied magnetic fields (H = 5, 3500, and 16500 Oe) and by performing \u3bc+SR experiments vs. temperature in zero field and in a longitudinal applied magnetic field H = 3500 Oe. The muon asymmetry P(t) was fitted by the sum of three components, two stretched-exponential decays with fast and intermediate relaxation times, and a third slow exponential decay. The temperature dependence of the spin dynamics has been determined by analyzing the muon longitudinal relaxation rate \u3bbinterm(T), associated with the intermediate relaxing component. The experimental \u3bbinterm(T) data were fitted with a corrected phenomenological Bloembergen-Purcell-Pound law by using a distribution of thermally activated correlation times, which average to \u3c4 = \u3c40 exp(\u394/kBT), corresponding to a distribution of energy barriers \u394. The correlation times can be associated with the spin freezing that occurs when the system condenses in the ground state

Porphyrin-fused graphene nanoribbons

Graphene nanoribbons (GNRs), nanometre-wide strips of graphene, are promising materials for fabricating electronic devices. Many GNRs have been reported, yet no scalable strategies are known for synthesizing GNRs with metal atoms and heteroaromatic units at precisely defined positions in the conjugated backbone, which would be valuable for tuning their optical, electronic and magnetic properties. Here we report the solution-phase synthesis of a porphyrin-fused graphene nanoribbon (PGNR). This PGNR has metalloporphyrins fused into a twisted fjord-edged GNR backbone; it consists of long chains (>100 nm), with a narrow optical bandgap (~1.0 eV) and high local charge mobility (>400 cm2 V–1 s–1 by terahertz spectroscopy). We use this PGNR to fabricate ambipolar field-effect transistors with appealing switching behaviour, and single-electron transistors displaying multiple Coulomb diamonds. These results open an avenue to π-extended nanostructures with engineerable electrical and magnetic properties by transposing the coordination chemistry of porphyrins into graphene nanoribbons