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The creation of ordered structures of molecules assembled from solution onto a substrate is a fundamental technological necessity across various disciplines, spanning from crystallography to organic electronics. However, achieving macroscopic order poses significant challenges, since the process of deposition is inherently impacted by factors like solvent evaporation and dewetting flows, which hinder the formation of well‐organized structures.Traditional methods like drop casting or spin coating encounter limitations due to the rapid kinetics of solvent evaporation, leading to limited control over final uniformity and order.In response to these challenges, Solvent Vapour Annealing (SVA) has emerged as a promising solution for realizing ordered molecular structures at scales ranging from nano‐ to milli‐ meters. SVA decouples the self‐assembly stage from the deposition stage by utilizing solvent vapours which can enable rearrangement, movement, and diffusion of large molecules on the surface even on a macroscopic scale. Essentially acting as “molecular lubricants,” solvent vapours enable the formation of well‐ordered molecular films. This review discusses the advancements, obstacles, and promising strategies associated with utilizing SVA for the development of innovative nanostructured thin films, and emphasizes the originality and effectiveness of molecular assembly on substrates achieved through this approach. [ABSTRACT FROM AUTHOR]

The patterning of composites with carbon-based additives of nanometer or micrometer size was studied by the precise modification of material surfaces using laser technology. Initially, the composites are electrical insulators, but we can make them conductive by selective patterning; this process allows us to create conductive tracks within seconds, with a sheet resistance that can be adjusted over a wide range, from 108 Ω/sq down to 2.5 Ω/sq. The additives used include graphene nanoplatelets, graphene oxide nanosheets, and aramid fibers. By conducting microscopic and spectroscopic characterizations before and after laser treatment, we can distinguish between two different processes that lead to electrical conduction: (a) localized increase in the concentration of conductive additives or (b) localized reduction and pyrolysis of insulating additives. To demonstrate the versatility and usefulness of this technique in different fields of application, such as automotive, we fabricate three different devices on polyurethane: a heater, a proximity sensor, and an amperometric sensor for detecting biological analytes. [ABSTRACT FROM AUTHOR]

Fluorescent nanodiamonds (FNDs) containing quantum defects enable the optical measurement of electromagnetic fields and temperature and are among the most developed nanoscale quantum sensors today. Yet, for many applications in biomedicine and beyond, FNDs must be integrated into biocompatible substrates that preserve FND sensitivity and bring FNDs within nanoscale distance of their sensing target. At the same time, the high excitation light intensity required for most quantum sensing protocols remains a major challenge for applications in biomedicine. Here, it is shown that FNDs embedded in polyvinyl‐alcohol (PVA) fibers are a powerful 3D platform for nanoscale quantum sensing via light guiding. First, it is demonstrated that biocompatible PVA fibers can guide light to excite FNDs >10 µm from the excitation beam. Using this light‐guiding‐enabled excitation, optically detected magnetic resonance (ODMR) and T1 spin relaxometry measurements are performed using the nitrogen‐vacancy (NV) center in FNDs. Through ODMR thermometry, it is shown that light‐guiding‐enabled excitation mitigates light‐induced heating. Finally, the quantum sensing capability of the platform is established by detecting paramagnetic gadolinium in a dry and aqueous environment using T1 relaxometry of the NV center in FNDs. These results pave the way for light‐guiding‐enabled optical quantum sensing in biomedicine using nanodiamond‐doped biosubstrates. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

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 ~ 1010 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. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

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 Δ 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. [ABSTRACT FROM AUTHOR]

The article discusses a study that investigates the hysteretic behavior in vacuum deposited submonolayer of single ion magnets sublimated on pyrolytic graphite with the help of X-ray absorption spectroscopy and X-ray magnetic circular dichroism. Topics discussed include field dependence of the magnetization in central lanthanide ion at low temperature, integration of organic materials into spintronic devices and remanent magnetization of single ion magnets.

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. [ABSTRACT FROM AUTHOR]

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

Abstract: We report on the magnetic and thermal properties of the Fe14 molecular nanocluster. We find a huge magnetocaloric response in the temperature range below 10K. 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 T N =1.87K. [Copyright &y& Elsevier]

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 TN=1.87 K. [ABSTRACT FROM AUTHOR]

The article focuses on the study of ultrafast dynamics and conductivity related to photoexcited graphene at Fermi energies. It focuses on understanding subpicosecond carrier dynamics following photoexcitation and the effect of photoexcitation on the electrical conductivity called the photoconductivity.

The syntheses and structures of two decametallic mixed-valent Mn supertetrahedra using 2-amino- 2-methyl-1,3-propanediol (ampH2), two decametallic mixed-valent Mn planar discs using 2-amino-2-methyl-1,3-propanediol (ampH2) and 2-amino-2-ethyl-1,3-propanediol (aepH2), and a tetradecametallic mixed- valent Mn planar disc using pentaerythritol (H4peol) are reported. The decametallic complexes display dominant ferromagnetic exchange and spin ground states of S = 22, and the tetradecametallic complex displays dominant antiferromagnetic exchange and a spin ground state of S = 7 ± 1. All display large (the former) and enormous (the latter) magnetocaloric effect—the former as a result of negligible zero-field splitting of the ground state, and the latter as a result of possessing a high spin-degeneracy at finite low temperatures-making them the very best cooling refrigerants for low-temperature applications. [ABSTRACT FROM AUTHOR]

Abstract: 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/k B ∼13K at zero magnetic field) from the first excited multiplet. This relatively large value of Δ 0, 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 ⩽1K 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. [Copyright &y& Elsevier]

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 2 BaCo(PO 4 ) 2 , which can be described by a spin-1/2 easy axis XXZ model. The zero-field neutron diffraction experiment reveals an incommensurate antiferromagnetic ground state with a significantly reduced ordered moment of about 0.54(2) μ B /Co. Different magnetic phase diagrams with magnetic fields in the a b plane and along the easy c -axis were extracted based on the magnetic susceptibility, specific heat, and elastic neutron-scattering results. In addition, two-dimensional (2D) spin dispersion in the triangular plane was observed in the high-field polarized state, and microscopic exchange parameters of the spin Hamiltonian have been determined through the linear spin wave theory. Consistently, quantum critical behaviors with the universality class of d  = 2 and ν z = 1 were established in the vicinity of the saturation field, where a Bose-Einstein condensation (BEC) of diluted magnons occurs. The newly discovered quantum criticality and fractional magnetization phase in this ideal spin-1/2 TAF present exciting opportunities for exploring exotic quantum phenomena.

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 sp 2 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.

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.

We investigate the electronic and magnetic properties of TbPc 2 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.

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 ∼ 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.

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.

The magnetic and electronic properties of single-molecule magnets are studied by X-ray absorption spectroscopy and X-ray magnetic circular dichroism. We study the magnetic coupling of ultrathin Co and Ni films that are epitaxially grown onto a Cu(100) substrate, to an in situ deposited submonolayer of TbPc2 molecules. Because of the element specificity of the X-ray absorption spectroscopy we are able to individually determine the field dependence of the magnetization of the Tb ions and the Ni or Co film. On both substrates the TbPc2 molecules couple antiferromagnetically to the ferromagnetic films, which is possibly due to a superexchange interaction via the phthalocyanine ligand that contacts the magnetic surface.