Molecular Junctions for Terahertz Switches and Detectors.

Molecular electronics targets tiny devices exploiting the electronic properties of the molecular orbitals, which can be tailored and controlled by the chemical structure and configuration 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, although molecular devices working in the THz regime have been 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 nonconjugated 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 and frequency), and we benchmark that these molecular devices would outperform actual THz detectors.

Probing Frontier Orbital Energies of {Co9(P2W15)3} Polyoxometalate Clusters at Molecule-Metal and Molecule-Water Interfaces.

Functionalization of polyoxotungstates with organoarsonate coligands enabling surface decoration was explored for the triangular cluster architectures of the composition [CoII9(H2O)6(OH)3(p-RC6H4AsVO3)2(α-PV2WVI15O56)3]25- ({Co9(P2W15)3}, R = H or NH2), isolated as Na25[Co9(OH)3(H2O)6(C6H5AsO3)2(P2W15O56)3]·86H2O (Na-1; triclinic, P1̅, a = 25.8088(3) Å, b = 25.8336(3) Å, c = 27.1598(3) Å, α = 78.1282(11)°, ß = 61.7276(14)°, γ = 60.6220(14)°, V = 13888.9(3) Å3, Z = 2) and Na25[Co9(OH)3(H2O)6(H2NC6H4AsO3)2(P2W15O56)3]·86H2O (Na-2; triclinic, P1̅, a = 14.2262(2) Å, b = 24.8597(4) Å, c = 37.9388(4) Å, α = 81.9672(10)°, ß = 87.8161(10)°, γ = 76.5409(12)°, V = 12920.6(3) Å3, Z = 2). The axially oriented para-aminophenyl groups in 2 facilitate the formation of self-assembled monolayers on gold surfaces and thus provide a viable molecular platform for charge transport studies of magnetically functionalized polyoxometalates. The title systems were isolated and characterized in the solid state, in aqueous solutions, and on metal surfaces. Using conducting tip atomic force microscopy, the energies of {Co9(P2W15)3} frontier molecular orbitals in the surface-bound state were found to directly correlate with cyclic voltammetry data in aqueous solution.

Concentric-Electrode Organic Electrochemical Transistors: Case Study for Selective Hydrazine Sensing.

We report on hydrazine-sensing organic electrochemical transistors (OECTs) with a design consisting of concentric annular electrodes. The design engineering of these OECTs was motivated by the great potential of using OECT sensing arrays in fields such as bioelectronics. In this work, poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS)-based OECTs have been studied as aqueous sensors that are specifically sensitive to the lethal hydrazine molecule. These amperometric sensors have many relevant features for the development of hydrazine sensors, such as a sensitivity down to 10-5 M of hydrazine in water, an order of magnitude higher selectivity for hydrazine than for nine other water-soluble common analytes, the capability to entirely recover its base signal after water flushing, and a very low operation voltage. The specificity for hydrazine to be sensed by our OECTs is caused by its catalytic oxidation at the gate electrode, and enables an increase in the output current modulation of the devices. This has permitted the device-geometry study of the whole series of 80 micrometric OECT devices with sub-20-nm PEDOT:PSS layers, channel lengths down to 1 µm, and a specific device geometry of coplanar and concentric electrodes. The numerous geometries unravel new aspects of the OECT mechanisms governing the electrochemical sensing behaviours of the device-more particularly the effect of the contacts which are inherent at the micro-scale. By lowering the device cross-talk, micrometric gate-integrated radial OECTs shall contribute to the diminishing of the readout invasiveness and therefore further promote the development of OECT biosensors.

Establishment of a derivatization method to quantify thiol function in sulfur-containing plasma polymer films.

Thiol-supported surfaces draw more and more interest in numerous fields of applications from biotechnology to catalysis. Among the various strategies to generate such surfaces, the plasma polymerization of a thiol-containing molecule appears to be one of the ideal candidates. Nevertheless, considering such an approach, a careful characterization of the material surface chemistry is necessary. In this work, an original chemical derivatization method aiming to quantitatively probe the -SH functions in plasma polymers was established using N-ethylmaleimide as a labeling molecule. The method was qualitatively and quantitatively validated on self-assembled monolayers of 3-mercaptopropyltrimethoxysilane exhibiting a -SH-terminated group used as "model" surface. For a quantitative determination of the -SH content in propanethiol plasma polymers, the kinetics of the reaction was investigated. The latter is described as a two-step mechanism, namely a fast surface reaction followed by a diffusion-limited one. The density of -SH groups deduced from the derivatization method (~4%) is in good agreement with typical values measured in some other plasma polymer families. The whole set of our data opens up new possibilities for optimizing the -SH content in thiol-based plasma polymer films.

The Effect of C60 and Pentacene Adsorbates on the Electrical Properties of CVD Graphene on SiO2.

Graphene is an excellent 2D material for vertical organic transistors electrodes due to its weak electrostatic screening and field-tunable work function, in addition to its high conductivity, flexibility and optical transparency. Nevertheless, the interaction between graphene and other carbon-based materials, including small organic molecules, can affect the graphene electrical properties and therefore, the device performances. This work investigates the effects of thermally evaporated C60 (n-type) and Pentacene (p-type) thin films on the in-plane charge transport properties of large area CVD graphene under vacuum. This study was performed on a population of 300 graphene field effect transistors. The output characteristic of the transistors revealed that a C60 thin film adsorbate increased the graphene hole density by (1.65 ± 0.36) × 1012 cm-2, whereas a Pentacene thin film increased the graphene electron density by (0.55 ± 0.54) × 1012 cm-2. Hence, C60 induced a graphene Fermi energy downshift of about 100 meV, while Pentacene induced a Fermi energy upshift of about 120 meV. In both cases, the increase in charge carriers was accompanied by a reduced charge mobility, which resulted in a larger graphene sheet resistance of about 3 kΩ at the Dirac point. Interestingly, the contact resistance, which varied in the range 200 Ω-1 kΩ, was not significantly affected by the deposition of the organic molecules.

Experimental observation of the role of countercations in modulating the electrical conductance of Preyssler-type polyoxometalate nanodevices.

Polyoxometalates are nanoscale molecular oxides with promising properties that are currently explored for molecule-based memory devices. In this work, we synthesize a series of Preyssler polyoxometalates (POMs), [Na⊂P5W30O110]14-, stabilized with four different counterions, H+, K+, NH4+, and tetrabutylammonium (TBA+). We study the electron transport properties at the nanoscale (conductive atomic force microscopy, C-AFM) of molecular junctions formed by self-assembled monolayers (SAMs) of POMs electrostatically deposited on the ultraflat gold surface prefunctionalized with a positively charged SAM of amine-terminated alkylthiol chains. We report that the electron transport properties of P5W30-based molecular junctions depend on the nature of the counterions; the low-bias current (in the voltage range [-0.6 V; 0.6 V]) gradually increases by a factor of ∼100 by changing the counterion in the order: K+, NH4+, H+ and TBA+. From a statistical study (hundreds of current-voltage traces) using a simple analytical model for charge transport in nanoscale devices, we show that the energy position of the lowest unoccupied molecular orbital (LUMO) of P5W30 with respect to the Fermi energy of the electrodes increases from ∼0.4 eV to ∼0.7 eV and that the electrode coupling energy also increases from ∼0.05 to 1 meV in the same order from K+, NH4+, H+ to TBA+. We discuss several hypotheses on the possible origin of these features, such as a counterion-dependent dipole at the POM/electrode interface and counterion-modulated molecule/electrode hybridization, with, in both cases, the largest effect in the case of TBA+ counterions.

Field and Thermal Emission Limited Charge Injection in Au-C60-Graphene van der Waals Vertical Heterostructures for Organic Electronics.

Among the family of 2D materials, graphene is the ideal candidate as top or interlayer electrode for hybrid van der Waals heterostructures made of organic thin films and 2D materials due to its high conductivity and mobility and its inherent ability of forming neat interfaces without diffusing in the adjacent organic layer. Understanding the charge injection mechanism at graphene/organic semiconductor interfaces is therefore crucial to develop organic electronic devices. In particular, Gr/C60 interfaces are promising building blocks for future n-type vertical organic transistors exploiting graphene as tunneling base electrode in a two back-to-back Gr/C60 Schottky diode configuration. This work delves into the charge transport mechanism across Au/C60/Gr vertical heterostructures fabricated on Si/SiO2 using a combination of techniques commonly used in the semiconductor industry, where a resist-free CVD graphene layer functions as a top electrode. Temperature-dependent electrical measurements show that the transport mechanism is injection limited and occurs via Fowler-Nordheim tunneling at low temperature, while it is dominated by a nonideal thermionic emission at room and high temperatures, with energy barriers at room temperature of ca. 0.58 and 0.65 eV at the Gr/C60 and Au/C60 interfaces, respectively. Impedance spectroscopy confirms that the organic semiconductor is depleted, and the energy band diagram results in two electron blocking interfaces. The resulting rectifying nature of the Gr/C60 interface could be exploited in organic hot electron transistors and vertical organic permeable-base transistors.

Nanoscale electronic transport at graphene/pentacene van der Waals interfaces.

We report a study on the relationship between the structure and electron transport properties of nanoscale graphene/pentacene interfaces. We fabricated graphene/pentacene interfaces from 10 to 30 nm thick needle-like pentacene nanostructures down to two-three layer (2L-3L) dendritic pentacene islands, and we measured their electron transport properties by conductive atomic force microscopy (C-AFM). The energy barrier at the interfaces, i.e., the energy position of the pentacene highest occupied molecular orbital (HOMO) with respect to the Fermi energy of graphene and the C-AFM metal tip was determined and discussed with an appropriate electron transport model (a double Schottky diode model and a Landauer-Buttiker model, respectively) taking into account the voltage-dependent charge doping of graphene. In both types of samples, the energy barrier at the graphene/pentacene interface is slightly larger than that at the pentacene/metal tip interface, resulting in 0.47-0.55 eV and 0.21-0.34 eV, respectively, for the 10-30 nm thick needle-like pentacene islands, and 0.92-1.44 eV and 0.67-1.05 eV, respectively, for the 2L-3L thick dendritic pentacene nanostructures. We attribute this difference to the molecular organization details of the pentacene/graphene heterostructures, with pentacene molecules lying flat on graphene in the needle-like pentacene nanostructures, while standing upright in the 2L-3L dendritic islands, as observed from Raman spectroscopy.

Electronic properties of single Prussian Blue Analog nanocrystals determined by conductive-AFM.

We report a study of the electron transport (ET) properties at the nanoscale (conductive-AFM denoted as C-AFM hereafter) of individual Prussian Blue Analog (PBA) cubic nanocrystals (NCs) of CsCoIIIFeII, with a size between 15 and 50 nm deposited on HOPG. We demonstrate that these PBA NCs feature an almost size-independent electron injection barrier of 0.41 ± 0.02 eV and 0.27 ± 0.03 eV at the CsCoIIIFeII/HOPG and CsCoIIIFeII/C-AFM tip, respectively, and an intrinsic electron conductivity evolving from a large dispersion between ∼5 × 10-4 and 2 × 10-2 S cm-1 without a clear correlation with the nanocrystal size. The conductivity values measured on individual nanocrystals are up to fifty times higher than those reported on PBA films.

Thermal and electrical cross-plane conductivity at the nanoscale in poly(3,4-ethylenedioxythiophene):trifluoromethanesulfonate 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 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.

Terphenylthiazole-based self-assembled monolayers on cobalt with high conductance photo-switching ratio for spintronics.

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.

Correction: Redox-controlled conductance of polyoxometalate molecular junctions.

Correction for 'Redox-controlled conductance of polyoxometalate molecular junctions' by Cécile Huez et al., Nanoscale, 2022, 14, 13790-13800, https://doi.org/10.1039/D2NR03457C.

Charge Transport Across Au-P3HT-Graphene van der Waals Vertical Heterostructures.

Hybrid van der Waals heterostructures based on 2D materials and/or organic thin films are being evaluated as potential functional devices for a variety of applications. In this context, the graphene/organic semiconductor (Gr/OSC) heterostructure could represent the core element to build future vertical organic transistors based on two back-to-back Gr/OSC diodes sharing a common graphene sheet, which functions as the base electrode. However, the assessment of the Gr/OSC potential still requires a deeper understanding of the charge carrier transport across the interface as well as the development of wafer-scale fabrication methods. This work investigates the charge injection and transport across Au/OSC/Gr vertical heterostructures, focusing on poly(3-hexylthiophen-2,5-diyl) as the OSC, where the PMMA-free graphene layer functions as the top electrode. The structures are fabricated using a combination of processes widely exploited in semiconductor manufacturing and therefore are suited for industrial upscaling. Temperature-dependent current-voltage measurements and impedance spectroscopy show that the charge transport across both device interfaces is injection-limited by thermionic emission at high bias, while it is space charge limited at low bias, and that the P3HT can be assumed fully depleted in the high bias regime. From the space charge limited model, the out-of-plane charge carrier mobility in P3HT is found to be equal to µ ≈ 2.8 × 10-4 cm2 V-1 s-1, similar to the in-plane mobility reported in previous works, while the charge carrier density is N0 ≈ 1.16 × 1015 cm-3, also in agreement with previously reported values. From the thermionic emission model, the energy barriers at the Gr/P3HT and Au/P3HT interfaces result in 0.30 eV and 0.25 eV, respectively. Based on the measured barriers heights, the energy band diagram of the vertical heterostructure is proposed under the hypothesis that P3HT is fully depleted.

Redox-controlled conductance of polyoxometalate molecular junctions.

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.

Large array of sub-10-nm single-grain Au nanodots for use in nanotechnology.

A uniform array of single-grain Au nanodots, as small as 5-8 nm, can be formed on silicon using e-beam lithography. The as-fabricated nanodots are amorphous, and thermal annealing converts them to pure Au single crystals covered with a thin SiO(2) layer. These findings are based on physical measurements, such as atomic force microscopy (AFM), atomic-resolution scanning transmission electron microscopy, and chemical techniques using energy dispersive X-ray spectroscopy. A self-assembled organic monolayer is grafted on the nanodots and characterized chemically with nanometric lateral resolution. The extended uniform array of nanodots is used as a new test-bed for molecular electronic devices.

Thiolate chemistry: a powerful and versatile synthetic tool for immobilization/functionalization of oligothiophenes on a gold surface.

The synthesis and characterization of a series of quaterthiophenes (4Ts) with thiolate groups protected with 2-cyanoethyl (CNE), 2-trimethylsilylethyl (TMSE), and acetyl (Ac) groups are described. Sequential cleavage of these different protecting groups allows for the preparation of 4Ts derivatized with ferrocene and/or alkanethiol chains. The electrochemical behavior of these compounds has been analyzed in solution by cyclic voltammetry (CV). A ferrocene-derivatized dithiol 4T 14 and a dithiol 4T 15 with two TMSE-protected thiolate groups have been immobilized on a gold surface as monolayers that have been characterized by CV, ellipsometry, contact-angle measurement, and X-ray photoelectron spectroscopy (XPS). The results show that molecules 14 and 15 are doubly grafted with a horizontal orientation of the conjugated system relative to the surface. Furthermore, application of the deprotection/alkylation sequence of the remaining protected thiolate groups on a monolayer of 15 allows for efficient post-functionalization.

Impact of chain length, temperature, and humidity on the growth of long alkyltrichlorosilane self-assembled monolayers.

In this work, we have studied the growth of self-assembled monolayers (SAMs) on silicon dioxide (SiO(2)) made of various long alkyltrichlorosilane chains (16, 18, 20, 24, and 30 carbon atoms in the alkyl chain), at several values of temperature (11 and 20 °C in most cases) and relative humidity (18 and 45% RH). Using atomic force microscopy analysis, thickness measurements by ellipsometry, and contact angle measurements, we have built a model of growth behaviour of SAMs of those molecules according to the deposition conditions and the chain length. Particularly, this work brings not only a better knowledge of the less studied growth of triacontyltrichlorosilane (C(30)H(61)SiCl(3)) SAMs but also new results on SAMs of tetracosyltrichlorosilane (C(24)H(49)SiCl(3)) that have not already been studied to our knowledge. We have shown that the SAM growth behaviour of triacontyltrichlorosilane at 20 °C and 45% RH is similar to that obtained at 11 °C and 45% RH for shorter molecules of hexadecyltrichlorosilane (C(16)H(33)SiCl(3)), octadecyltrichlorosilane (C(18)H(37)SiCl(3)), eicosyltrichlorosilane (C(20)H(41)SiCl(3)) and tetracosyltrichlorosilane (C(24)H(49)SiCl(3)). We have also observed that the monolayers grow faster at 45% than at 18% RH, and surprisingly slower at 20 °C than at 11 °C. Another important result is that the growth time constant decreases with the number of carbon atoms in the alkyl chain except for C(24)H(49)SiCl(3) at 11 °C and 18% RH, and for C(30)H(61)SiCl(3). To our knowledge, such a chain length dependence of the growth time constant has never been reported. The latter and all the other results are interpreted by adapting a diffusion limited aggregation growth model.

Conductance switching of azobenzene-based self-assembled monolayers on cobalt probed by UHV conductive-AFM.

We report the formation of self-assembled monolayers of a molecular photoswitch (azobenzene-bithiophene derivative, AzBT) on cobalt via a thiol covalent bond. We study the electrical properties of the molecular junctions formed with the tip of a conductive atomic force microscope under ultra-high vacuum. The statistical analysis of the current-voltage curves shows two distinct states of the molecule conductance, suggesting the coexistence of both the trans and cis azobenzene isomers on the surface. The cis isomer population (trans isomer) increases (decreases) upon UV light irradiation. The situation is reversed under blue light irradiation. The experiments are confronted to first-principle calculations performed on the molecular junctions with the Non-Equilibrium Green's Function formalism combined with Density Functional Theory (NEGF/DFT). The theoretical results consider two different molecular orientations for each isomer. Whereas the orientation does not affect the conductance of the trans isomer, it significantly modulates the conductance of the cis isomer and the resulting conductance ON/OFF ratio of the molecular junction. This helps identifying the molecular orientation at the origin of the observed current differences between the trans and cis forms. The ON state is associated to the trans isomer irrespective of its orientation in the junction, while the OFF state is identified as a cis isomer with its azobenzene moiety folded upward with respect to the bithiophene core. The experimental and calculated ON/OFF conductance ratios have a similar order of magnitude. This conductance ratio seems reasonable to make these Co-AzBT molecular junctions a good test-bed to further explore the relationship between the spin-polarized charge transport, the molecule conformation and the molecule-Co spinterface.

Thermal conductivity of benzothieno-benzothiophene derivatives at the nanoscale.

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.

Long-range electron transport in Prussian blue analog nanocrystals.

We report electron transport measurements through nano-scale devices consisting of 1 to 3 Prussian blue analog (PBA) nanocrystals connected between two electrodes. We compare two types of cubic nanocrystals, CsCoIIIFeII (15 nm) and CsNiIICrIII (6 nm), deposited on highly oriented pyrolytic graphite and contacted by conducting-AFM. The measured currents show an exponential dependence with the length of the PBA nano-device (up to 45 nm), with low decay factors ß, in the range 0.11-0.18 nm-1 and 0.25-0.34 nm-1 for the CsCoFe and the CsNiCr nanocrystals, respectively. From the theoretical analysis of the current-voltage curve for the nano-scale device made of a single nanoparticle, we deduce that the electron transport is mediated by the localized d bands at around 0.5 eV from the electrode Fermi energy in the two cases. By comparison with previously reported ab initio calculations, we tentatively identify the involved orbitals as the filled Fe(ii)-t2g d band (HOMO) for CsCoFe and the half-filled Ni(ii)-eg d band (SOMO) for CsNiCr. Conductance values measured for multi-nanoparticle nano-scale devices (2 and 3 nanocrystals between the electrodes) are consistent with a multi-step coherent tunneling in the off-resonance regime between adjacent PBAs, a simple model gives a strong coupling (around 0.1-0.25 eV) between the adjacent PBA nanocrystals, mediated by electrostatic interactions.