Thin Film Resistance Gating by Redox Charge Exchange: Evidence for a Quantum Transition State.

Field effect transistors (FETs) and related devices have enabled tremendous advances in electronics, as well as studies of fundamental phenomena. FETs are classically actuated as fields charge/discharge materials, thereby modifying their resistance. Here, we develop charge exchange transistors (CETs) that comprise thin films whose resistance is modified by quantum charge exchange processes, e.g., redox and bonding. We first use CETs to probe the metallocene-thin film interaction during cyclic voltammetry. Remarkably, CETs reveal transient resistance peaks associated with charge transfer during both oxidation and reduction. Our data combined with kinetics and density functional theory modeling are consistent with a multistep redox pathway, including the formation/destruction of a quantum transition state that overlaps molecule + thin film band states. As a further proof-of-principle demonstration, we also use CETs to monitor n-alkanethiol self-assembly on thin Au films in real-time. CETs exhibit monotonic resistance increase consistent with previously reported fast-then-slow kinetics attributed to thiol-thin film bond formation (charge localization) and etching and/or molecule reorganization.

Widely Varying Kondo and Magnetic Interactions in Molecule Gold Nanostructured Materials by Changing the Gold Nanoarchitecture.

Delocalized-localized electron interactions are central to strongly correlated electron phenomena. Here, we study the Kondo effect, a prototypical strongly correlated phenomena, in a tunable fashion using gold nanostructures (nanoparticle, NP, and nanoshell, NS) + molecule cross-linkers (butanedithiol, BDT). NP films exhibit hallmark signatures of the Kondo effect, including (1) a log temperature resistance upturn as temperature decreases in a metallic regime, and (2) zero-bias conductance peaks (ZBCPs) that are well fit by a Frota function near a percolation insulator transition, previously used to model Kondo peaks observed using tunnel junctions. Remarkably, NP + NS films exhibit ZBCPs that persist to >220 K, i.e., >10-fold higher than that in NP films. Magnetic measurements reveal that moments in NP powders align, and in NS powders, they antialign at low temperatures. Based on these observations, we propose a mechanism in which varying such material nanobuilding blocks can modify electron-electron interactions to such a large degree.

Large emergent optoelectronic enhancement in molecularly cross-linked gold nanoparticle nanosheets.

A central goal in molecular electronics and optoelectronics is to translate tailorable molecular properties to larger materials and to the device level. Here, we present a method to fabricate molecularly cross-linked, self-assembled 2D nanoparticle sheets (X-NS). Our method extends a Langmuir approach of self-assembling gold nanoparticle (NP) arrays at an air-water interface by replacing the liquid sub-phase to an organic solvent to enable cross-linking with organic molecules, and then draining the sub-phase to deposit films. Remarkably, X-NS comprising conjugated oligophenylene dithiol cross-linkers (HS-(C6H4)n-SH, 1 ≤ n ≤ 3) exhibit increasing conductance with molecule length, ~6 orders of magnitude enhancement in UV-Vis extinction coefficients, and photoconductivity with molecule vs. NP contributions varying depending on the excitation wavelength. Finite difference time domain (FDTD) analyses and control measurements indicate that these effects can be modeled provided the local complex dielectric constant is strongly modified upon cross-linking. This suggests quantum hybridization at a molecule-band (q-MB) level. Given the vast number of molecules and nano-building blocks available, X-NS have potential to significantly increase the range of available 2D nanosheets and associated quantum properties.

Glucose oxidase kinetics using MnO2 nanosheets: confirming Michaelis-Menten kinetics and quantifying decreasing enzyme performance with increasing buffer concentration.

MnO2 nanosheets and ultraviolet-visible (UV-Vis) absorbance spectroscopy are used to study glucose oxidase (GOx) kinetics. Glucose oxidation by GOx produces H2O2, which rapidly decomposes the nanosheets and reduces their absorption. This direct approach for monitoring glucose oxidation enables simpler, real time kinetics analysis compared to methods that employ additional enzymes. Using this approach, the present study confirms that GOx kinetics is consistent with the Michaelis-Menten (MM) model, and reveals that the MM constant increases by an order of magnitude with increasing buffer concentration. Since larger MM constants imply higher enzyme substrate concentrations are required to achieve the same rate of product formation, increasing MM constants imply decreasing enzyme performance. These results demonstrate the facility of using MnO2 nanosheets to study GOx kinetics and, given the widespread applications of enzymes with buffers, the important sensitivity of enzyme-buffer systems on buffer concentration.

A Scalable, Solution-Based Approach to Tuning the Solubility and Improving the Photoluminescence of Chemically Exfoliated MoS2.

MoS2 are two-dimensional (2D) materials that exhibit emerging photoluminescence (PL) at the monolayer level and have potential optoelectronic applications. Monolayers of MoS2 typically achieved by mechanical exfoliation (Me), chemical vapor deposition (CVD), and chemical exfoliation (Ce) via lithium intercalation contain numerous defects that significantly reduce their PL efficiency. Several studies have reported overcoming poor PL in mechanically exfoliated and CVD-grown MoS2, but such studies for chemically exfoliated MoS2 (Ce-MoS2) have not been reported. Here, we report a solution-based method of enhancing the PL of Ce-MoS2 by reacting with molecules with suitable functional groups at high temperatures. Reaction with dodecanethiol (DDT) generates PL that is more intense than mechanically exfoliated MoS2 (Me-MoS2) with high crystallinity and has a significantly broader range of wavelengths. Based on ultraviolet-visible, Fourier transform infrared, X-ray photoemission, and PL spectroscopy as well as transmission electron and PL imaging, we propose that the present method modifies PL properties of Ce-MoS2 by simultaneously annealing, replacing molybdenum-oxygen with molybdenum-sulfur bonds, inducing strain, and generating a nanopolycrystalline structure. This work points to such defect engineering using molecules as an effective means to modify the properties of Ce-MoS2 and layered transition-metal dichalcogenides more generally.

Large Kondo effect in assemblies of Au nanoparticles linked with alkanedithiol electron bridges.

Using a prototypical nanoparticle-molecule assembly, namely alkanedithiol-linked gold nanoparticle films, we observe hallmark signatures of the Kondo effect in conductance vs. voltage as well as temperature measurements. Its contribution to temperature dependence of conductance is much larger than those from all other temperature-dependant effects up to 300 K by >20-fold - much larger than previous reports of the Kondo effect using other platforms. We find that previous models of the Kondo effect describe our data even in this regime. Given the synthetic control available over nanoparticle properties such as surface area, shape, and chemical composition, our work points to combining flexibility afforded by molecule + nanoparticle assemblies as a powerful way to generate materials exhibiting strong spin-electron interactions.

Controlled hierarchical assembly of gold nanoparticles in macroscopic films: from densely packed monolayers to networks of micropores and nanobundles.

The present study demonstrates the ability of excess, weakly amphiphilic n-alkanethiols (n = 4, 12, 18) and solvent composition to tune through a wide range of large-scale, macroscopic architectures formed by alkanethiol-capped Au nanoparticles (NPs). Both the alkanethiols and NPs are significantly hydrophobic species and compete for surface area at an air-water interface. When solutions of the two species are spread on a large (50 cm2) water surface in a Teflon well, a thin film forms and exhibits co-existing macroscopic regions with various distinct NP self-assembled architectures, namely a close packed monolayer, a network phase characterized by micron-sized pores (micropores) surrounded by quasi-linear bundles of nanoparticles, and finally aggregates. We hypothesize that the co-existence of various NP architectures results from fast, non-uniform evaporation across the large water surface. When solutions are instead deposited on a smaller (5 cm2) water surface contained within a Teflon ring to control the water surface curvature and the evaporation rate is slowed, we show for the first time that NPs form macroscopically uniform self-assemblies whose architectures can be tuned from monolayers → monolayers with micropores → extended micropore/NP bundle networks by varying excess alkanethiol concentration and solvent composition. We propose that competition between NPs and excess alkanethiols for water surface area, and alkanethiol self-assembly as well as solvent dewetting play important roles in the formation of the network phase, and discuss a potential mechanism for its formation.

Influence of low energy barrier contact resistance in charge transport measurements of gold nanoparticle+dithiol-based self-assembled films.

Gold-thiol self-assembly is a widely employed strategy for engineering electronic devices using molecules and other nanostructures as building blocks. However, device behavior is expected to be governed by both building block architecture and contact effects. In order to elucidate the role of the latter in such devices, we have studied conductance of n-butanedithiol-linked Au nanoparticle (NP) films using different types of electrode configurations, namely, four-probe versus two-probe and break junctions before versus after dielectric break down of contact resistance. We find that contact resistance is governed by transport across a small barrier which can dominate device behavior when temperatures and resistances of the self-assembled devices are low. Accounting for such contact resistance reveals a more precise picture of device behavior in these regimes, including in the present system film properties near the onset of the percolation insulator-to-metal transition and beyond.

Conductance oscillations in molecularly linked Au nanoparticle film-superconductor systems.

Charge transport across a disordered normal-superconductor (DN-S) interface was studied using a macroscopic, molecularly linked Au nanoparticle film as the DN component. Low-temperature conductance versus voltage and magnetic field exhibit zero-bias and zero-field peaks, respectively. Importantly, the latter typically exhibit superimposed oscillations. Such oscillations are rarely seen in other DN-S systems and are remarkable given their robustness in these macroscopic films and interfaces. A number of observations indicate that conductance peaks and oscillations arise due to a 'reflectionless tunnelling' process. Scattering length scales extracted from the data using a reflectionless tunnelling picture are consistent with literature values. Factors resulting in the observation of oscillations in this system are discussed.

Magnetoconductance oscillations at a nanoparticle film-superconductor interface: a means for probing flux penetration depth.

Interfaces between disordered normal materials and superconductors (S) can exhibit 'reflectionless tunnelling' (RT)-a phenomenon that arises from repeated disorder-driven elastic scattering, multiple Andreev reflections, and electron/hole interference. RT has been used to explain zero-bias conductance peaks (ZBCPs) observed using doped semiconductors and evaporated granular metal films as the disordered normal materials. Recently, in addition to ZBCPs, magnetoconductance oscillations predicted by RT theory have been observed using a novel normal disordered material: self-assembled nanoparticle films. In the present study, we find that the period of these oscillations decreases as temperature (T) increases. This suggests that the magnetic flux associated with interfering pathways increases accordingly. We propose that the increasing flux can be attributed to magnetic field penetration into S as [Formula: see text]. This model agrees remarkably well with known T dependence of penetration depth predicted by Bardeen-Cooper-Schrieffer theory. Our study shows that this additional region of flux is significant and must be considered in experimental and theoretical studies of RT.

Metal to insulator transition in films of molecularly linked gold nanoparticles.

We report a metal to insulator transition (MIT) in disordered films of molecularly linked gold nanoparticles (NPs). As the number of carbons (n) of alkanedithiol linker molecules (C(n)S2) is varied, resistance (R) at low temperature (T = 2 K) and at 200 K, as well as trends in R vs T data at intermediate temperatures, all point to an MIT occurring at n = 5. We describe these results in a context of a Mott-Hubbard MIT. We find that all insulating samples (n > or = 5) exhibit a universal scaling behavior R approximately exp[(T0/T)nu] with nu = 0.65, and all metallic samples (n < or = 5) exhibit weaker R-T dependencies than bulk gold. We discuss these observations in terms of competitive thermally activated processes and strong, T-independent elastic scattering, respectively.

Influence of linker molecules on charge transport through self-assembled single-nanoparticle devices.

We investigate electrical characteristics of single-electron electrode/nanoisland/electrode devices formed by alkanedithiol assisted self-assembly. Contrary to predictions of the orthodox model for double tunnel junction devices, we find a significant ( approximately fivefold) discrepancy in single-electron charging energies determined by Coulomb blockade (CB) voltage thresholds in current-voltage measurements versus those determined by an Arrhenius analysis of conductance in the CB region. The energies do, however, scale with particle sizes, consistent with single-electron charging phenomena. We propose that the discrepancy is caused by a multibarrier junction potential that leads to a voltage divider effect. Temperature and voltage dependent conductance measurements performed outside the blockade region are consistent with this picture. We simulated our data using a suitably modified orthodox model.

Gating of enhanced electron-charging thresholds in self-assembled nanoparticle films.

Films of butanedithiol interconnected nanoparticles can exhibit a percolation-driven insulating to metal transition. To explore properties of materials with interpolating behavior, we have measured conductance of these films with systematically varying thickness. Films below a certain threshold coverage exhibit thermally assisted conductance and conductance suppression near zero bias indicative of single-electron-charging barriers. In analogy with semiconductors, we show that these films permit transistor-type gating of film conductivity.

Differential conductance switching of planar tunnel junctions mediated by oxidation/reduction of functionally protected ferrocene.

Planar tunnel junctions were fabricated by self-assembling 1,1'- ferrocenedicarboxylic acid (FDCA) onto native oxides of thermally deposited aluminum films and subsequently depositing a second aluminum film. Junctions were characterized using Reflection-Absorption Fourier Transform Infrared Spectroscopy (RAIRS) and current-voltage (I-V) spectroscopy. Before deposition of the second aluminum film, RAIRS of FDCA and ferrocenecarboxylic acid (FCA) films revealed COO(-), C=O, and Fc ring stretching modes, indicating that both types of molecules can interact strongly with the oxide and remain intact. After deposition, systems exhibited prominent COO(-) modes and weakened C=O modes, indicating further reaction with aluminum/aluminum oxide. Fc ring modes persisted in FDCA systems but disappeared in FCA systems, suggesting that the second COOH group in the FDCA molecule can act as a protecting group for the ferrocene moiety. Cyclic I-V measurements of FDCA tunnel junction systems revealed very strong ( approximately 10-fold) hysteretic differential conductance switching that was both reversible and stable. Control measurements using as prepared junctions, as well as junctions containing 1,6-hexanedioic acid, 1,9-nonanedioic acid, 1,4-dibenzoic acid, or FCA revealed only very weak ( approximately 10%) differential conductance changes. We attribute FDCA junction switching to barrier profile modifications induced by oxidation/reduction of the functionally protected ferrocene moieties.