Photosystem I complexes form remarkably stable self-assembled tunneling junctions.

This paper describes large-area molecular tunneling junctions comprising self-assembled monolayers (SAMs) of light-harvesting protein complexes using eutectic Ga-In (EGaIn) as a top contact. The complexes, which are readily isolable in large quantities from spinach leaves, self-assemble on top of SAMs of [6,6]-phenyl-C-butyric acid (PCBA) on gold (Au) supported by mica substrates (Au), which induces them to adopt a preferred orientation with respect to the electron transport chain that runs across the short axis of each complex, leading to temperature-independent rectification. We compared trimeric protein complexes isolated from thermophilic cyanobacteria to monomeric complexes extracted from spinach leaves by measuring charge-transport at variable temperatures and over the course of at least three months.

Carrier-Carrier Repulsion Limits the Conductivity of N-Doped Organic Semiconductors.

Molecular doping is a key strategy to enhance the electrical conductivity of organic semiconductors. Typically, the electrical conductivity shows a maximum value upon increased doping, after which the conductivity decreases. This decrease in conductivity is commonly attributed to unfavorable changes in the morphology.

Self-Assembly Determines Sign of Seebeck Coefficient in Tunneling Junctions Comprising Monolayers and Bilayers of Fullerenes.

We measured the Seebeck coefficient for junctions comprising self-assembled monolayers and bilayers of the fullerene moiety PTEG-1 on Au using eutectic Ga-In in a controlled anhydrous atmosphere by varying the temperature gradient from -12 to 12 °C, observing a linear response in thermovoltage across the range. The sign of the coefficient was positive for monolayers of PTEG-1, (195 ± 8) μV K and negative for bilayers of PTEG-1, (-209 ± 14) μV K, indicating a change from HOMO-mediated to LUMO-mediated charge-transport. Charge-transport is nonresonant tunneling for both monolayers and bilayers, but the former self-assembles with the fullerene cage at the chemisorbed interface while the latter includes a fullerene cage at the physisorbed interface, demonstrating that the physical position of the fullerene cage determines the energetic position of the frontier molecular orbitals of PTEG-1.

Addressing spatiotemporal signal variations in pair correlation function analysis.

Fluorescence correlation spectroscopy (FCS) is a cornerstone technique in optical microscopy to measure, for example, the concentration and diffusivity of fluorescent emitters and biomolecules in solution. The application of FCS to complex biological systems, however, is fraught with inherent intricacies that impair the interpretation of correlation patterns. Critical among these intricacies are temporal variations beyond diffusion in the quantity, intensity, and spatial distribution of fluorescent emitters.

Over 60 h of Stable Water-Operation for N-Type Organic Electrochemical Transistors with Fast Response and Ambipolarity.

Organic electrochemical transistors (OECTs) are of great interest in low-power bioelectronics and neuromorphic computing, as they utilize organic mixed ionic-electronic conductors (OMIECs) to transduce ionic signals into electrical signals. However, the poor environmental stability of OMIEC materials significantly restricts the practical application of OECTs. Therefore, the non-fused planar naphthalenediimide (NDI)-dialkoxybithiazole (2Tz) copolymers are fine-tuned through varying ethylene glycol (EG) side chain lengths from tri(ethylene glycol) to hexa(ethylene glycol) (namely P-XO, X = 3-6) to achieve OECTs with high-stability and low threshold voltage.

A method for identifying the cause of inefficient salt-doping in organic semiconductors.

Doping to enhance the electrical conductivity of organic semiconductors is not without its challenges: The efficacy of this process depends on many factors and it is not always clear how to remedy poor doping. In the case of doping with salts, one of the possible causes of poor doping is a limited yield of integer charge transfer resulting in the presence of both cations and anions in the film. The charge of such ions can severely limit the electrical conductivity, but their presence is not easily determined.

Efficient Selective Sorting of Semiconducting Carbon Nanotubes Using Ultra-Narrow-Band-Gap Polymers.

Conjugated polymers with narrow band gaps are particularly useful for sorting and discriminating semiconducting single-walled carbon nanotubes (s-SWCNT) due to the low charge carrier injection barrier for transport. In this paper, we report two newly synthesized narrow-band-gap conjugated polymers ( and ) based on naphthalene diimide (NDI) and thienylennevinylene (TVT) building blocks, decorated with different polar side chains that can be used for dispersing and discriminating s-SWCNT. Compared with the mid-band-gap conjugated polymer , which is composed of naphthalene diimide (NDI) and head-to-head bithiophene building blocks, the addition of a vinylene linker eliminates the steric congestion present in head-to-head bithiophene, which promotes backbone planarity, extending the π-conjugation length and narrowing the band gap.

Empirical Parameter to Compare Molecule-Electrode Interfaces in Large-Area Molecular Junctions.

This paper describes a simple model for comparing the degree of electronic coupling between molecules and electrodes across different large-area molecular junctions. The resulting coupling parameter can be obtained directly from current-voltage data or extracted from published data without fitting. We demonstrate the generalizability of this model by comparing over 40 different junctions comprising different molecules and measured by different laboratories.

Investigating the dielectric properties and exciton diffusion in C derivatives.

In recent years, the dielectric constant () of organic semiconductors (OSCs) has been of interest in the organic photovoltaic (OPV) community due to its potential influence on the exciton binding energy. Despite progress in the design of high OSCs and the accurate measurement of the , the effects of the synthetic strategies on specific (opto)electronic properties of the OSCs remain uncertain. In this contribution, the effects of on the optical properties of five new C derivatives and [70]PCBM are investigated.

Printable logic circuits comprising self-assembled protein complexes.

This paper describes the fabrication of digital logic circuits comprising resistors and diodes made from protein complexes and wired together using printed liquid metal electrodes. These resistors and diodes exhibit temperature-independent charge-transport over a distance of approximately 10 nm and require no encapsulation or special handling. The function of the protein complexes is determined entirely by self-assembly.

Graphene oxide decorated with gold enables efficient biophotovolatic cells incorporating photosystem I.

This paper describes the use of reduced graphene oxide decorated with gold nanoparticles as an efficient electron transfer layer for solid-state biophotovoltic cells containing photosystem I as the sole photo-active component. Together with polytyrosine-polyaniline as a hole transfer layer, this device architecture results in an open-circuit voltage of 0.3 V, a fill factor of 38% and a short-circuit current density of 5.

Adaptive Biosensing and Neuromorphic Classification Based on an Ambipolar Organic Mixed Ionic-Electronic Conductor.

Organic mixed ionic-electronic conductors (OMIECs) are central to bioelectronic applications such as biosensors, health-monitoring devices, and neural interfaces, and have facilitated efficient next-generation brain-inspired computing and biohybrid systems. Despite these examples, smart and adaptive circuits that can locally process and optimize biosignals have not yet been realized. Here, a tunable sensing circuit is shown that can locally modulate biologically relevant signals like electromyograms (EMGs) and electrocardiograms (ECGs), that is based on a complementary logic inverter combined with a neuromorphic memory element, and that is constructed from a single polymer mixed conductor.

Fullerenes Enhance Self-Assembly and Electron Injection of Photosystem I in Biophotovoltaic Devices.

This paper describes the fabrication of microfluidic devices with a focus on controlling the orientation of photosystem I (PSI) complexes, which directly affects the performance of biophotovoltaic devices by maximizing the efficiency of the extraction of electron/hole pairs from the complexes. The surface chemistry of the electrode on which the complexes assemble plays a critical role in their orientation. We compared the degree of orientation on self-assembled monolayers of phenyl-C-butyric acid and a custom peptide on nanostructured gold electrodes.

Molecular Doping Directed by a Neutral Radical.

Molecular doping makes possible tunable electronic properties of organic semiconductors, yet a lack of control of the doping process narrows its scope for advancing organic electronics. Here, we demonstrate that the molecular doping process can be improved by introducing a neutral radical molecule, namely nitroxyl radical (2,2,6,6-teramethylpiperidin-i-yl) oxyl (TEMPO). Fullerene derivatives are used as the host and 1,3-dimethyl-2-phenyl-2,3-dihydro-1-benzo[d]imidazoles (DMBI-H) as the n-type dopant.

Controlling n-Type Molecular Doping Regiochemistry and Polarity of Pendant Groups on Low Band Gap Donor-Acceptor Copolymers.

We demonstrate the impact of the type and position of pendant groups on the n-doping of low-band gap donor-acceptor (D-A) copolymers. Polar glycol ether groups simultaneously increase the electron affinities of D-A copolymers and improve the host/dopant miscibility compared to nonpolar alkyl groups, improving the doping efficiency by a factor of over 40. The bulk mobility of the doped films increases with the fraction of polar groups, leading to a best conductivity of 0.

In Operando Modulation of Rectification in Molecular Tunneling Junctions Comprising Reconfigurable Molecular Self-Assemblies.

The reconfiguration of molecular tunneling junctions during operation via the self-assembly of bilayers of glycol ethers is described. Well-established functional groups are used to modulate the magnitude and direction of rectification in assembled tunneling junctions by exposing them to solutions containing different glycol ethers. Variable-temperature measurements confirm that rectification occurs by the expected bias-dependent tunneling-hopping mechanism for these functional groups and that glycol ethers, besides being an unusually efficient tunneling medium, behave similarly to alkanes.

Amphipathic Side Chain of a Conjugated Polymer Optimizes Dopant Location toward Efficient N-Type Organic Thermoelectrics.

There is no molecular strategy for selectively increasing the Seebeck coefficient without reducing the electrical conductivity for organic thermoelectrics. Here, it is reported that the use of amphipathic side chains in an n-type donor-acceptor copolymer can selectively increase the Seebeck coefficient and thus increase the power factor by a factor of ≈5. The amphipathic side chain contains an alkyl chain segment as a spacer between the polymer backbone and an ethylene glycol type chain segment.

N-type organic thermoelectrics: demonstration of ZT > 0.3.

The 'phonon-glass electron-crystal' concept has triggered most of the progress that has been achieved in inorganic thermoelectrics in the past two decades. Organic thermoelectric materials, unlike their inorganic counterparts, exhibit molecular diversity, flexible mechanical properties and easy fabrication, and are mostly 'phonon glasses'. However, the thermoelectric performances of these organic materials are largely limited by low molecular order and they are therefore far from being 'electron crystals'.

Intermolecular Effects on Tunneling through Acenes in Large-Area and Single-Molecule Junctions.

This paper describes the conductance of single-molecules and self-assembled monolayers comprising an oligophenyleneethynylene core, functionalized with acenes of increasing length that extend conjugation perpendicular to the path of tunneling electrons. In the Mechanically Controlled Break Junction (MCBJ) experiment, multiple conductance plateaus were identified. The high conductance plateau, which we attribute to the single molecule conformation, shows an increase of conductance as a function of acene length, in good agreement with theoretical predictions.

Correlating the Influence of Disulfides in Monolayers across Photoelectron Spectroscopy Wettability and Tunneling Charge-Transport.

Despite their ubiquity, self-assembled monolayers (SAMs) of thiols on coinage metals are difficult to study and are still not completely understood, particularly with respect to the nature of thiol-metal bonding. Recent advances in molecular electronics have highlighted this deficiency due to the sensitivity of tunneling charge-transport to the subtle differences in the overall composition of SAMs and the chemistry of their attachment to surfaces. These advances have also challenged assumptions about the spontaneous formation of covalent thiol-metal bonds.

Understanding the Role of Parallel Pathways via In-Situ Switching of Quantum Interference in Molecular Tunneling Junctions.

This study describes the modulation of tunneling probabilities in molecular junctions by switching one of two parallel intramolecular pathways. A linearly conjugated molecular wire provides a rigid framework that allows a second, cross-conjugated pathway to be effectively switched on and off by protonation, affecting the total conductance of the junction. This approach works because a traversing electron interacts with the entire quantum-mechanical circuit simultaneously; Kirchhoff's rules do not apply.

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Successful integration of proteins in solid-state electronics requires contacting them in a non-invasive fashion, with a solid conducting surface for immobilization as one such contact. The contacts can affect and even dominate the measured electronic transport. Often substrates, substrate treatments, protein immobilization, and device geometries differ between laboratories.

Synthesis, Optical and Electrochemical Properties of High-Quality Cross-Conjugated Aromatic Polyketones.

This paper describes the synthesis and characterization of three new aromatic polyketones with repeating units based on 2,2'-(2,5-dihexyl-1,4-phenylene) dithiophene (PTK), 2,2'-(9,9-dihexyl-9-fluorene-2,7-diyl)dithiophene (PFTK), and 4,7-bis(3-hexylthiophen-2-yl)benzo[][1,2,5]thiadiazole (PBTK). These polymers were obtained with a one-pot Suzuki-Miyaura cross-coupling-promoted homopolymerization to afford high-quality, defect-free polymers. Experimental and theoretical studies were applied to investigate their optical and electrical properties.

Thiol-free self-assembled oligoethylene glycols enable robust air-stable molecular electronics.

Self-assembled monolayers (SAMs) are widely used to engineer the surface properties of metals. The relatively simple and versatile chemistry of metal-thiolate bonds makes thiolate SAMs the preferred option in a range of applications, yet fragility and a tendency to oxidize in air limit their long-term use. Here, we report the formation of thiol-free self-assembled mono- and bilayers of glycol ethers, which bind to the surface of coinage metals through the spontaneous chemisorption of glycol ether-functionalized fullerenes.

Conductive Self-Assembled Monolayers of Paramagnetic {Co } and { } Coordination Clusters on Gold Surfaces.

Two polynuclear cobalt(II,III) complexes, [Co(N)(--bda)(bza·SMe)] () and [Co(N)(--bda)(bza·SMe)(MeOH)]Cl (), where Hbza·SMe = 4-(methylthio)benzoic acid and --Hbda = --butyldiethanolamine, were synthesized and fully characterized by various techniques. Compound exhibits an unusual, approximately -symmetric {Co } core of two isosceles Co triangles with perpendicularly oriented planes, sharing a central, high-spin Co ion residing in a distorted tetrahedral coordination environment. This central Co ion is connected to four outer, octahedrally coordinated low-spin Co ions oxo bridges.