arXiv subjects

D. Guerin

Publications and source records attributed to D. Guerin.

15 recordsLinked to original sources

arXiv2022

Thermal and electrical cross-plane conductivity at the nanoscale in poly(3,4-ethylenedioxythiophene):trifuoromethanesulfonate thin films

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 cross-plane direction is measured with Null-Point scanning thermal microscopy (NP-SThM): PEDOT:OTf indeed demonstrates non-negligible electronic contribution to the thermal transport. We further investigate the correlation between electrical and thermal conductivity by applying posttreatment: chemical reduction (de-doping) for the purpose of lowering 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) Wm-1 K-1. From the linear dependence or the electronic contribution of thermal conductivity vs. the electronic conductivity (Widemann-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. Applying the recently proposed molecular Widemann-Franz law, we deduced a reorganization energy of 0.53 (+/- 0.06) eV.

cond-mat.mtrl-sci↗

arXiv2020

Electrical molecular switch addressed by chemical stimuli

We demonstrate that the conductance switching of benzo-bis(imidazole) molecules upon protonation depends on the lateral functional groups. The protonated H-substituted molecule shows a higher conductance than the neutral one (Gpro>Gneu), while the opposite (Gneu>Gpro) is observed for a molecule laterally functionalized by amino-phenyl groups. These results are demonstrated at various scale lengths : self-assembled monolayer, tiny nanodot-molecule junction and single molecules. From ab-initio theoretical calculations, we conclude that for the H-substituted molecule, the result Gpro>Gneu is correctly explained by a reduction of the LUMO-HOMO gap, while for the amino-phenyl functionnalized molecule, the result Gneu>Gpro is consistent with a shift of HOMO, which reduces the density of states at the Fermi energy.

physics.app-ph↗

arXiv2020

Conductance switching at the nanoscale of diarylethene derivatives self-assembled monolayers on La$_{0.7}$Sr$_{0.3}$MnO$_3$

We report on the phosphonic acid route for the grafting of functional molecules, optical switch (dithienylethene diphosphonic acid, DDA), on La0.7Sr0.3MnO3 (LSMO). Compact self-assembled monolayers (SAMs) of DDA are formed on LSMO as studied by topographic atomic force microscopy (AFM), ellipsometry, water contact angle and X-ray photoemission spectroscopy (XPS). The conducting AFM measurements show that the electrical conductance of LSMO/DDA is about 3 decades below that of the bare LSMO substrate. Moreover, the presence of the DDA SAM suppresses the known conductance switching of the LSMO substrate that is induced by mechanical and/or bias constraints during C-AFM measurements. A partial light-induced conductance switching between the open and closed forms of the DDA is observed for the LSMO/DDA/C-AFM tip molecular junctions (closed/open conductance ratio of about 8). We show that, in the case of long-time exposition to UV light, this feature can be masked by a non-reversible decrease (a factor of about 15) of the conductance of the LSMO electrode.

physics.app-ph↗

arXiv2019

Electron transport through self-assembled monolayers of tripeptides

We report how the electron transport through a solid-state metal/Gly-Gly-His tripeptide (GGH) monolayer/metal junction and the metal/GGH work function are modified by the GGH complexation with Cu2+ ions. Conducting AFM is used to measure the current-voltage histograms. The work function is characterized by combining macroscopic Kelvin probe and Kelvin probe force microscopy at the nanoscale. We observe that the Cu2+ ions complexation with the GGH monolayer is highly dependent on the molecular surface density and results in opposite trends. In the case of a high density monolayer the conformational changes are hindered by the proximity of the neighboring peptides, hence forming an insulating layer in response to copper-complexation. Whereas the slightly lower density monolayers allow for the conformational change to a looped peptide wrapping the Cu-ion, which results in a more conductive monolayer. Copper-ion complexation to the high- and low-density monolayers systematically induces an increase of the work functions. Copper-ion complexation to the low-density monolayer induces an increase of electron transport efficiency, while the copper-ion complexation to the high-density monolayer results in a slight decrease of electron transport. Both of the observed trends are in agreement with first-principle calculations. Complexed copper to low density GGH-monolayer induces a new gap state slightly above the Au Fermi energy that is absent in the high density monolayer.

physics.app-ph↗

arXiv2019

Charge transport through redox active [H7P8W48O184]33- polyoxometalates self-assembled onto gold surfaces and gold nanodots

Polyoxometalates (POMs) are redox-active molecular oxides, which attract growing interest for their integration into nano-devices, such as high-density data storage non-volatile memories. In this work, we investigated the electrostatic deposition of the negatively charged [H7P8W48O184]33- POM onto positively charged 8-amino-1-octanethiol self-assembled monolayers (SAMs) preformed onto gold substrates or onto an array of gold nanodots. The ring-shaped [H7P8W48O184]33- POM was selected as an example of large POMs with high charge storage capacity. To avoid the formation of POM aggregates onto the substrates, which would introduce variability in the local electrical properties, special attention has to be paid to the preformed SAM seeding layer, which should itself be deprived of aggregates. Where necessary, rinsing steps were found to be crucial to eliminate these aggregates and to provide uniformly covered substrates for subsequent POM deposition and electrical characterizations. This especially holds for commercially available gold/glass substrates while these rinsing steps were not essential in the case of template stripped gold of very low roughness. Charge transport through the related molecular junctions and nanodot molecule junctions (NMJs) has been probed by conducting-AFM. We analyzed the current-voltage curves with different models: electron tunneling though the SAMs (Simmons model), transition voltage spectroscopy (TVS) method or molecular single energy level mediated transport (Landauer equation) and we discussed the energetics of the molecular junctions. We concluded to an energy level alignment of the alkyl spacer and POM lowest occupied molecular orbitals (LUMOs), probably due to dipolar effects.

physics.app-ph↗

arXiv2018

Light-stimulable molecules/nanoparticles networks for switchable logical functions and reservoir computing

We report the fabrication and electron transport properties of nanoparticles self-assembled networks (NPSAN) of molecular switches (azobenzene derivatives) interconnected by Au nanoparticles, and we demonstrate optically-driven switchable logical operations associated to the light controlled switching of the molecules. The switching yield is up to 74%. We also demonstrate that these NPSANs are prone for light-stimulable reservoir computing. The complex non-linearity of electron transport and dynamics in these highly connected and recurrent networks of molecular junctions exhibit rich high harmonics generation (HHG) required for reservoir computing (RC) approaches. Logical functions and HHG are controlled by the isomerization of the molecules upon light illumination. These results, without direct analogs in semiconductor devices, open new perspectives to molecular electronics in unconventional computing.

physics.app-ph↗

arXiv2017

Negative Differential Resistance, Memory and Reconfigurable Logic Functions based on Monolayer Devices derived from Gold Nanoparticles Functionalized with Electro-polymerizable Thiophene-EDOT Units

We report on hybrid memristive devices made of a network of gold nanoparticles (10 nm diameter) functionalized by tailored 3,4(ethylenedioxy)thiophene (TEDOT) molecules, deposited between two planar electrodes with nanometer and micrometer gaps (100 nm to 10 um apart), and electropolymerized in situ to form a monolayer film of conjugated polymer with embedded gold nanoparticles (AuNPs). Electrical properties of these films exhibit two interesting behaviors: (i) a NDR (negative differential resistance) behavior with a peak/valley ratio up to 17, and (ii) a memory behavior with an ON/OFF current ratio of about 1E3 to 1E4. A careful study of the switching dynamics and programming voltage window is conducted demonstrating a non-volatile memory. The data retention of the ON and OFF states is stable (tested up to 24h), well controlled by the voltage and preserved when repeating the switching cycles (800 in this study). We demonstrate reconfigurable Boolean functions in multiterminal connected NP molecule devices.

physics.app-ph↗

arXiv2016

Physical Study by Surface Characterizations of Sarin Sensor on the Basis of Chemically Functionalized Silicon Nanoribbon Field Effect Transistor

Surface characterizations of an organophosphorus (OP) gas detector based on chemically functionalized silicon nanoribbon field-effect transistor (SiNR-FET) were performed by Kelvin Probe Force Microscopy (KPFM) and ToF-SIMS, and correlated with changes in the current-voltage characteristics of the devices. KPFM measurements on FETs allow (i) to investigate the contact potential difference (CPD) distribution of the polarized device as function of the gate voltage and the exposure to OP traces and, (ii) to analyze the CPD hysteresis associated to the presence of mobile ions on the surface. The CPD measured by KPFM on the silicon nanoribbon was corrected due to side capacitance effects in order to determine the real quantitative surface potential. Comparison with macroscopic Kelvin probe (KP) experiments on larger surfaces was carried out. These two approaches were quantitatively consistent. An important increase of the CPD values (between + 399 mV and + 302 mV) was observed after the OP sensor grafting, corresponding to a decrease of the work function, and a weaker variation after exposure to OP (between - 14 mV and - 61 mV) was measured. Molecular imaging by ToF-SIMS revealed OP presence after SiNR-FET exposure. The OP molecules were essentially localized on the Si-NR confirming effectiveness and selectivity of the OP sensor. A prototype was exposed to Sarin vapors and succeeded in the detection of low vapor concentrations (40 ppm).

cond-mat.mes-hall↗

arXiv2014

Interface Dipole : Effects on Threshold Voltage and Mobility for both Amorphous and Poly-crystalline Organic Field Effect Transistors

We report a detailed comparison on the role of a self-assembled monolayer (SAM) of dipolar molecules on the threshold voltage and charge carrier mobility of organic field-effect transistor (OFET) made of both amorphous and polycrystalline organic semiconductors. We show that the same relationship between the threshold voltage and the dipole-induced charges in the SAM holds when both types of devices are fabricated on strictly identical base substrates. Charge carrier mobilities, almost constant for amorphous OFET, are not affected by the dipole in the SAMs, while for polycrystalline OFET (pentacene) the large variation of charge carrier mobilities is related to change in the organic film structure (mostly grain size).

cond-mat.mtrl-sci↗

arXiv2013

Water Electrolysis and Energy Harvesting with 0D Ion-Sensitive Field-Effect Transistors

The relationship of the gas bubble size to the size distribution critically influences the effectiveness of electrochemical processes. Several optical and acoustical techniques have been used to characterize the size and emission frequency of bubbles. Here, we used zero-dimensional (0D) ion-sensitive field-effect transistors (ISFETs) buried under a microbath to detect the emission of individual bubbles electrically and to generate statistics on the bubble emission time. The bubble size was evaluated via a simple model of the electrolytic current. We suggest that energy lost during water electrolysis could be used to generate electric pulses at an optimal efficiency with an array of 0D ISFETs.

cond-mat.mes-hall↗

arXiv2010

A Silicon Nanowire Ion-Sensitive Field-Effect-Transistor with elementary charge sensitivity

We investigate the mechanisms responsible for the low-frequency noise in liquid-gated nano-scale silicon nanowire field-effect transistors (SiNW-FETs) and show that the charge-noise level is lower than elementary charge. Our measurements also show that ionic strength of the surrounding electrolyte has a minimal effect on the overall noise. Dielectric polarization noise seems to be at the origin of the 1/f noise in our devices. The estimated spectral density of charge noise Sq = 1.6x10-2 e/sqr(Hz) at 10 Hz opens the door to metrological studies with these SiNW-FETs for the electrical detection of a small number of molecules.

cond-mat.mes-hall↗

arXiv2010

Synthesis and electrical properties of fullerene-based molecular junctions on silicon substrate

We report the synthesis and the electrical properties of fullerene-based molecular junctions on silicon substrate in which the highly π-conjugated molecule C60 (πquantum well) is isolated from the electrodes by alkyl chains (σtunnel barriers). Initially, the Si/SiO2/\sigmaC60 architecture was prepared either by sequential synthesis (3 different routes) or by direct grafting of the presynthesized C60-σ-Si(OEt)3 molecule. We described the chemical synthesis of these routes and the physico-chemical properties of the molecular monolayers. Then, the second σtunnel barrier was added on the Si/SiO2/σC60 junction by applying a hanging mercury drop electrode thiolated with an alkanethiol monolayer. We compared the electronic transport properties of the Si/SiO2/σC60//Hg and Si/SiO2/σC60//\sigmaHg molecular junctions, and we demonstrated by transition voltage spectroscopy that the fullerene LUMO - metal Fermi energy offset can be tailored from ~ 0.2 eV to ~ 1 eV by changing the length of the alkyl chain between the C60 core and the Hg metal electrode (i. e. from direct C60//Hg contact to 14 carbon atoms tunnel barrier).

cond-mat.mes-hall↗

arXiv2009

An organic nanoparticle transistor behaving as a biological synapse

Molecule-based devices are envisioned to complement silicon devices by providing new functions or already existing functions at a simpler process level and at a lower cost by virtue of their self-organization capabilities. Moreover, they are not bound to von Neuman architecture and this feature may open the way to other architectural paradigms. Neuromorphic electronics is one of them. Here we demonstrate a device made of molecules and nanoparticles, a nanoparticle organic memory filed-effect transistor (NOMFET), which exhibits the main behavior of a biological spiking synapse. Facilitating and depressing synaptic behaviors can be reproduced by the NOMFET and can be programmed. The synaptic plasticity for real time computing is evidenced and described by a simple model. These results open the way to rate coding utilization of the NOMFET in dynamical neuromorphic computing circuits.

cond-mat.mes-hall↗

arXiv2009

An artificial spiking synapse made of molecules and nanoparticles

Molecule-based devices are envisioned to complement silicon devices by providing new functions or already existing functions at a simpler process level and at a lower cost by virtue of their self-organization capabilities, moreover, they are not bound to von Neuman architecture and this may open the way to other architectural paradigms. Here we demonstrate a device made of conjugated molecules and metal nanoparticles (NPs) which behaves as a spiking synapse suitable for integration in neural network architectures. We demonstrate that this device exhibits the main behavior of a biological synapse. These results open the way to rate coding utilization of the NOMFET in perceptron and Hopfield networks. We can also envision the NOMFET as a building block of neuroelectronics for interfacing neurons or neuronal logic devices made from patterned neuronal cultures with solid-state devices and circuits.

cond-mat.mtrl-sci↗

arXiv2006

Electron transport through rectifying self-assembled monolayer diodes on silicon: Fermi level pinning at the molecule-metal interface

We report the synthesis and characterization of molecular rectifying diodes on silicon using sequential grafting of self-assembled monolayers of alkyl chains bearing a pi group at their outer end (Si/sigma-pi/metal junctions). We investigate the structure-performance relationships of these molecular devices and we examine to what extent the nature of the pi end-group (change in the energy position of their molecular orbitals) drives the properties of these molecular diodes. For all the pi-groups investigated here, we observe rectification behavior. These results extend our preliminary work using phenyl and thiophene groups (S. Lenfant et al., Nano Letters 3, 741 (2003)).The experimental current-voltage curves are analyzed with a simple analytical model, from which we extract the energy position of the molecular orbital of the pi-group in resonance with the Fermi energy of the electrodes. We report the experimental studies of the band lineup in these silicon/alkyl-pi conjugated molecule/metal junctions. We conclude that Fermi level pinning at the pi-group/metal interface is mainly responsible for the observed absence of dependence of the rectification effect on the nature of the pi-groups, even though they were chosen to have significant variations in their electronic molecular orbitals

cond-mat.mtrl-sci↗