We present a molecular study combining Raman, infrared, and UV-visible absorption spectroscopy with density functional theory (DFT) calculations to investigate triphenylene and its iodinated derivative, 1,5,9-triiodotriphe-nylene. The results provide a detailed comparison of their vibrational and electronic properties, revealing how iodine substitution affects molecular geometry and electronic structure. Iodination induces nonplanarity in the molecular backbone, leading to shifts in vibrational frequencies as well as modifications of pi-pi* transitions in the UV-visible spectra. Complementary analyses of natural bond orbitals, polarizabilities, and Hirshfeld surfaces further elucidate electronic delocalization and intermolecular interactions. These findings could enable the rational design of triphenylene-based precursors optimized for on-surface reactions, facilitating controlled formation of nanocarbon architectures with tailored structural and electronic properties.

The electronic and thermoelectric properties of molecular junctions formed from iron and ruthenium metal acetylide were studied by using complementary experimental techniques and quantum chemical simulations. We performed physical characterizations of single-molecule and self-assembled monolayer junctions of the same molecules that allowed meaningful comparisons between the Ru and Fe adducts. In the case of the Fe-containing junctions, two distinct oxidation states are present. These junctions exhibit one of the highest Seebeck coefficients (S similar to 130 mu V/K) reported to date for similar systems paired with broad electric conductance distribution and limited thermal conductance. As a result, the experimental thermoelectric figure of merit ZT for Fe-containing junctions reaches up to 0.4 for junctions with a relatively high conductance. This is one of the highest ZT values reported for molecular systems at room temperature.

Conducting polymer dendrite (CPD) morphogenesis is an electrochemical process that enables in materio evolving intelligence in wetware devices. During CPD morphogenesis, voltage transients drive the physical evolution of electrically conductive structures, thereby programming their filtering properties as nonlinear analog devices. Whether studied in an electrochemical experiment or in neuromorphic devices, the dependence of the electrical properties of the electrogenerated structures on the chemical composition of their growth environment is still unreported. In this study, we report the existing interconnection between the nature and concentration of the electrolytes, electroactive compounds and co-solvents and the electrical and electrochemical properties of CPDs in an aqueous electrolyte. CPDs exhibit various chemical sensitivities in water: their morphology is highly dependent on the nature of the chemical resources available in their environment. The selection of these resources therefore critically influences morphogenesis. In addition, the concentrations of the different electrochemical species have varying impacts on growth dynamics, modulating the balance between thermodynamic and kinetic control over polymer electrosynthesis. By correlating the dependencies of these evolving objects with the availability of the chemical resources in an aqueous environment, this study offers guidelines to tune the degree of evolution of electronic materials in water and highlights potential avenues for their application. Such evolving hardware is envisioned to exploit the chemical complexity of real-world environments as part of information processing technologies.

We report here the reversibility and bistability of the switching behavior in an azobenzene derivative induced by the bias applied by a scanning-tunneling microscopy (STM) tip, at low temperature and in ultra-high vacuum environment. Thiscis-to-transandtrans-to-cisswitching were observed during STM imaging in either polarity at +2 V or -2 V, on a sub-second time scale. This results in a blinking effect visible on STM images, corresponding to the reversible switching of the azobenzene molecule under the applied STM bias through an electric field induced process.

We report the temperature-dependent (4.2-300 K) electron transport properties (current-voltage) of photo-switchable two-dimensional arrays of gold nanoparticles (10 nm in diameter) functionalized by azobenzene derivatives. Under UV-light irradiation at 4.2 K, the azobenzene moieties are switched from the trans-to-cis isomers, leading to an increase of the current. In both conformations, at low temperature (<77 K) and low voltage (<1 V), the voltage- and temperature-dependent current behaviors show that electron cotunneling is the dominant transport mechanism. The number of cotunneling events N-cot slightly increases from approximate to 1.4 to 1.7 upon trans-to-cis isomerization of the azobenzenes. The nanoparticle Coulomb charging energy is not significantly modified (approximate to 15 meV) by the azobenzene isomerization. This weak increase of N-cot is explained by the modest cis/trans current ratio (<= 10) and the limited numbers of nanoparticle-molecule-nanoparticle junctions inserted between the two nanoscale electrodes (<50 nm apart) connecting the network. (c) 2025 Author(s). All article content, except where otherwise noted, is licensed under a Creative Commons Attribution-NonCommercial-NoDerivs 4.0 International (CC BY-NC-ND) license (https://creativecommons.org/licenses/by-nc-nd/4.0/).

Fabricating electronic devices spoiling the least resources is of an increasingly high importance. Also, micro-electronics hardly embeds chemical functionalities on silicon, as soft materials suffer from harsh conditions of conventional processes. In this study, electrochemistry on a chip is investigated to pattern conductivity-based measurement devices at small scale via electropolymerization. To comply with additive manufacturing, a dewetting coating and local quasi-reference/counter micro-electrodes shall be integrated on each chip. The process reliability is challenged using minimalist chemical and energy resources, such that a μL droplet of an electro-active solution composed mostly of a non-toxic and affordable solvent suffices to coat 16 elements on a 3×3 mm2 chip. Despite the complexity of electrochemistry at such scales, the coatings variability is dominated by the chemical composition of the droplet. Avoiding a vessel to confine large volumes of solutions and integrating all electrodes is required to reduce drastically the electrochemical signal noise. This demonstrates its sufficient stability to screen conducting polymer materials when their precursors are not available in large amount to be coated with conventional techniques. It also demonstrates its compliance for chips microfabrication using conducting polymers as functional materials for electrochemically-assisted additive manufacturing production.

Molecular electronics targets tiny devices exploiting the electronic properties of the molecular orbitals, which can be tailored and controlled by the chemical structure/conformation of the molecules. Many functional devices have been experimentally demonstrated; however, these devices were operated in the low frequency domain (mainly, dc to MHz). This represents a serious limitation for electronic applications, albeit molecular devices working in the THz regime were theoretically predicted. Here, we experimentally demonstrate molecular THz switches at room temperature. The devices consist of self-assembled monolayers of molecules bearing two conjugated moieties coupled through a non-conjugated linker. These devices exhibit clear negative differential conductance behaviors (peaks in the current-voltage curves), as confirmed by ab initio simulations, which were reversibly suppressed under illumination with a 30 THz wave. We analyze how the THz switching behavior depends on the THz wave properties (power, frequency), and we benchmark that these molecular devices would outperform actual THz detectors.

We studied the low-frequency noise, i.e. flicker noise, also referred to as 1/f noise, in 2D networks of molecularly functionalized gold nanoparticles (NMN: nanoparticle-molecule network). We examined the noise behaviors of the NMN hosting alkyl chains (octanethiol), fatty acid oleic acids (oleylamine), redox molecule switches (polyoxometalate derivatives) or photo-isomerizable molecules (azobenzene derivatives) and we compared their 1/f noise behaviors. These noise metrics are used to evaluate which molecules are the best candidates to build in materio reservoir computing molecular devices based on the NMNs.

Microelectrode Arrays (MEAs) are popular tools for in vitro extracellular recording. They are often optimized by surface engineering to improve affinity with neurons and guarantee higher recording quality and stability. Recently, PEDOT:PSS has been used to coat microelectrodes due to its good biocompatibility and low impedance, which enhances neural coupling. Herein, we investigate on electro-co-polymerization of EDOT with its triglymated derivative to control valence between monomer units and hydrophilic functions on a conducting polymer. Molecular packing, cation complexation, dopant stoichiometry are governed by the glycolation degree of the electro-active coating of the microelectrodes. Optimal monomer ratio allows fine-tuning the material hydrophilicity and biocompatibility without compromising the electrochemical impedance of microelectrodes nor their stability while interfaced with a neural cell culture. After incubation, sensing readout on the modified electrodes shows higher performances with respect to unmodified electropolymerized PEDOT, with higher signal-to-noise ratio (SNR) and higher spike counts on the same neural culture. Reported SNR values are superior to that of state-of-the-art PEDOT microelectrodes and close to that of state-of-the-art 3D microelectrodes, with a reduced fabrication complexity. Thanks to this versatile technique and its impact on the surface chemistry of the microelectrode, we show that electro-co-polymerization trades with many-compound properties to easily gather them into single macromolecular structures. Applied on sensor arrays, it holds great potential for the customization of neurosensors to adapt to environmental boundaries and to optimize extracted sensing features.

Two new photo-switchable terphenylthiazole molecules are synthesized and self-assembled as monolayers on Au and on ferromagnetic Co electrodes. The electron transport properties probed by conductive atomic force microscopy in ultra-high vacuum reveal a larger conductance of the light-induced closed (c) form than for the open (o) form. We report an unprecedented conductance ratio of up to 380 between the closed and open forms on Co for the molecule with the anchoring group (thiol) on the side of the two N atoms of the thiazole unit. This result is rationalized by Density Functional Theory (DFT) calculations coupled to the Non-Equilibrium Green's function (NEGF) formalism. These calculations show that the high conductance in the closed form is due to a strong electronic coupling between the terphenylthiazole molecules and the Co electrode that manifests by a resonant transmission peak at the Fermi energy of the Co electrode with a large broadening. This behavior is not observed for the same molecules self-assembled on gold electrodes. These high conductance ratios make these Co-based molecular junctions attractive candidates to develop and study switchable molecular spintronic devices.

Cross-plane electrical and thermal transport in thin films of a conducting polymer (poly(3,4-ethylenedioxythiophene), PEDOT) stabilized with trifluoromethanesulfonate (OTf) is investigated in this study. We explore their electrical properties by conductive atomic force microscopy (C-AFM), which reveals the presence of highly conductive nano-domains. Thermal conductivity in the cross-plane direction is measured by null-point scanning thermal microscopy (NP-SThM). PEDOT:OTf indeed demonstrates a non-negligible electronic contribution to the thermal transport. We further investigate the correlation between electrical and thermal conductivity by applying post-treatment: chemical reduction (de-doping) to lower charge carrier concentration and hence, electrical conductivity and acid treatment (over-doping) to increase the latter. From our measurements, we find a vibrational thermal conductivity of 0.34 ± 0.04 W m-1 K-1. From the linear dependence or the electronic contribution of thermal conductivity vs. the electronic conductivity (Wiedemann-Franz law), we infer a Lorenz number 6 times larger than the classical Sommerfeld value as also observed in many organic materials for in-plane thermal transport. By applying the recently proposed molecular Wiedemann-Franz law, we deduced a reorganization energy of 0.53 ± 0.06 eV.

We demonstrate the reversible in situ photoreduction of molecular junctions of a phosphomolybdate [PMo12O40]3- monolayer self-assembled on flat gold electrodes, connected by the tip of a conductive atomic force microscope. The conductance of the one electron reduced [PMo12O40]4- molecular junction is increased by ∼10, and this open-shell state is stable in the junction in air at room temperature. The analysis of a large current-voltage dataset by unsupervised machine learning and clustering algorithms reveals that the electron transport in the pristine phosphomolybdate junctions leads to symmetric current-voltage curves, controlled by the lowest unoccupied molecular orbital (LUMO) at 0.6-0.7 eV above the Fermi energy with ∼25% of the junctions having a better electronic coupling to the electrodes than the main part of the dataset. This analysis also shows that a small fraction (∼18% of the dataset) of the molecules is already reduced. The UV light in situ photoreduced phosphomolybdate junctions systematically feature slightly asymmetric current-voltage behaviors, which is ascribed to the electron transport mediated by the single occupied molecular orbital (SOMO) nearly at resonance with the Fermi energy of the electrodes and by a closely located single unoccupied molecular orbital (SUMO) at ∼0.3 eV above the SOMO with a weak electronic coupling to the electrodes (∼50% of the dataset) or at ∼0.4 eV but with a better electrode coupling (∼50% of the dataset). These results shed light on the electronic properties of reversible switchable redox polyoxometalates, a key point for potential applications in nanoelectronic devices.

Correction for"Redox-controlled conductance of polyoxometalate molecular junctions'by C & eacute;cile Huezetal.,Nanoscale, 2022,14, 13790-13800,https://doi.org/10.1039/D2NR03457C.

The insertion losses of miniature gold/silicon-on-insulator (SOI) coplanar waveguides (CPW) are rendered low, stable, and light insensitive when covered with a thin film (95 nm) fluoropolymer deposited by a trifluoromethane (CHF 3 ) plasma. Microwave characterization (0–50 GHz) of the CPWs indicates that the fluoropolymer stabilizes a hydrogen-passivated silicon surface between the CPW tracks. The hydrophobic nature of the fluoropolymer acts as a humidity barrier, meaning that the underlying intertrack silicon surfaces do not re-oxidize over time—something that is known to increase losses. In addition, the fluoropolymer thin film also renders the CPW insertion losses insensitive to illumination with white light (2400 lx)—something potentially advantageous when using optical microscopy observations during microwave measurements. Capacitance–voltage (CV) measurements of gold/fluoropolymer/silicon metal–insulator-semiconductor (MIS) capacitors indicate that the fluoropolymer is an electret—storing positive charge. The experimental results suggest that the stored positive charge in the fluoropolymer electret and charge trapping influence surface-associated losses in CPW—MIS device modelling supports this. Finally, and on a practical note, the thin fluoropolymer film is easily pierced by commercial microwave probes and does not adhere to them—facilitating the repeatable and reproducible characterization of microwave electronic circuitry passivated by thin fluoropolymer.

We study by scanning thermal microscopy the nanoscale thermal conductance of films (40-400 nm thick) of [1]benzothieno[3,2-b][1]benzothiophene (BTBT) and 2,7-dioctyl[1]benzothieno[3,2-b][1]benzothiophene (C8-BTBT-C8). We demonstrate that the out-of-plane thermal conductivity is significant along the interlayer direction, larger for BTBT (0.63 ± 0.12 W m-1 K-1) compared to C8-BTBT-C8 (0.25 ± 0.13 W m-1 K-1). These results are supported by molecular dynamics calculations (approach to equilibrium molecular dynamics method) performed on the corresponding molecular crystals. The calculations point to significant thermal conductivity (3D-like) values along the 3 crystalline directions, with anisotropy factors between the crystalline directions below 1.8 for BTBT and below 2.8 for C8-BTBT-C8, in deep contrast with the charge transport properties featuring a two-dimensional character for these materials. In agreement with the experiments, the calculations yield larger values in BTBT compared to C8-BTBT-C8 (0.6-1.3 W m-1 K-1versus 0.3-0.7 W m-1 K-1, respectively). The weak thickness dependence of the nanoscale thermal resistance is in agreement with a simple analytical model.

In this work, we demonstrate P3HT (poly 3-hexylthiophene) organic rectifier diode both in rigid and flexible substrate with a rectification ratio up to 106. This performance has been achieved through tuning the work function of gold with a self-assembled monolayer of 2,3,4,5,6-pentafluorobenzenethiol (PFBT). The diode fabricated on flexible paper substrate shows a very good electrical stability under bending tests and the frequency response is estimated at more than 20 MHz which is sufficient for radio frequency identification (RFID) applications. It is also shown that the low operating voltage of this diode can be a real advantage for use in a rectenna for energy harvesting systems. Simulations of the diode structure show that it can be used at GSM and Wi-Fi frequencies if the diode capacitance is reduced to a few pF and its series resistance to a few hundred ohms. Under these conditions, the DC voltages generated by the rectenna can reach a value up to 1 V.

We have adapted a "peel-off" process to structure stacked organic semiconductors (conducting polymers or small molecules) and metal layers for diode microfabrication. The fabricated devices are organic diode rectifier in a coplanar waveguide structure. Unlike conventional lithographic process, this technique does not lead to destroy organic active layers since it does not involve harsh developer or any non-orthogonal solvent that alter the functionality of subsequentially deposited materials. This process also involves recently reported materials, as a p-dopant of an organometallic electron-acceptor Copper (II) trifluoromethanesulfonate, that play the role of hole injection layer in order to enhance the performances of the diode. Comparatively to self-assembled monolayers based optimized structures, the fabricated diodes show higher reproducibility and stability. High rectification ratio for realized pentacene and poly (3-hexylthiophene) diodes up to 106 has been achieved. Their high frequency response has been evaluated by performing theoretical simulations. The results predict operating frequencies of 200 MHz and 50 MHz for pentacene and P3HT diode rectifiers respectively, with an input oscillating voltage of 2 V peak-to-peak, promising for RFID device applications or for GSM band energy harvesting in low-cost IoT objects.