Surface Engineering for Molecular Electronics

Molecular electronics studies charge transport through molecules and the applications in electronic devices where molecules serve as the ultimate nanosized building blocks. Controllable charge transport properties and stable electrical junctions lie at the heart of molecular electronics because of their crucial impact on practical devices, and both of them concern engineering at the surface and interface, e.g., anchoring functional molecules onto electrodes and forming densely packed monolayers resistive against electrostatic pressure. This thesis aims to unite the synthesis and characterization of functional (bio)organic semiconductive molecular self-assemblies and the fabrication of electronic devices comprising these ensembles for paradigm-shifting applications from a surface engineering perspective

Large-Area Molecular Junctions:Synthesizing Integrated Circuits for Next-Generation Nonvolatile Memory

The development of high-speed, nonvolatile memory devices with low power consumption remains a significant challenge for next-generation computing. A recent study reported molecular switches operating at low voltages in large-area junctions by coupling supramolecular structural changes and counterion migration to bias-dependent redox, culminating in proof-of-concept memory comprising self-assembled monolayers

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. Memory bits are fabricated from crossbar junctions prepared by injecting eutectic Ga-In (EGaIn) into microfluidic channels. The states of two 8-bit registers were set by trains of droplets such that they are able to perform logical AND operations on bit strings encoded into chemical packets that alter the composition of the crossbar junctions through self-assembly to effect memristor-like properties. This proof-of-concept work demonstrates the potential for fieldable devices based on molecular tunneling junctions comprising self-assembled monolayers and bilayers

Conformation-driven quantum interference effects mediated by through-space conjugation in self-assembled monolayers

Tunnelling currents through tunnelling junctions comprising molecules with cross-conjugation are markedly lower than for their linearly conjugated analogues. This effect has been shown experimentally and theoretically to arise from destructive quantum interference, which is understood to be an intrinsic, electronic property of molecules. Here we show experimental evidence of conformation-driven interference effects by examining through-space conjugation in which π-conjugated fragments are arranged face-on or edge-on in sufficiently close proximity to interact through space. Observing these effects in the latter requires trapping molecules in a non-equilibrium conformation closely resembling the X-ray crystal structure, which we accomplish using self-assembled monolayers to construct bottom-up, large-area tunnelling junctions. In contrast, interference effects are completely absent in zero-bias simulations on the equilibrium, gas-phase conformation, establishing through-space conjugation as both of fundamental interest and as a potential tool for tuning tunnelling charge-transport in large-area, solid-state molecular-electronic devices.</p

Systematic experimental study of quantum interference effects in anthraquinoid molecular wires

In order to translate molecular properties in molecular-electronic devices, it is necessary to create design principles that can be used to achieve better structure-function control oriented toward device fabrication. In molecular tunneling junctions, cross-conjugation tends to give rise to destructive quantum interference effects that can be tuned by changing the electronic properties of the molecules. We performed a systematic study of the tunneling charge-transport properties of a series of compounds characterized by an identical cross-conjugated anthraquinoid molecular skeleton but bearing different substituents at the 9 and 10 positions that affect the energies and localization of their frontier orbitals. We compared the experimental results across three different experimental platforms in both single-molecule and large-area junctions and found a general agreement. Combined with theoretical models, these results separate the intrinsic properties of the molecules from platform-specific effects. This work is a step towards explicit synthetic control over tunneling charge transport targeted at specific functionality in (proto-) devices

Engineering the Thermoelectrical Properties of PEDOT:PSS by Alkali Metal Ion Effect

Engineering the electrical properties of poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) holds great potential for various applications such as sensors, thermoelectric (TE) generators, and hole transport layers in solar cells. Various strategies have been applied to achieve optimal electrical properties, including base solution post-treatments. However, the working mechanism and the exact details of the structural transformations induced by base post-treatments are still unclear. In this work, we present a comparative study on the post-treatment effects of using three common and green alkali base solutions: namely LiOH, NaOH, and KOH. The structural modifications induced in the film by the base post-treatments are studied by techniques including atomic force microscopy, grazing-incidence wide-angle X-ray scattering, ultraviolet–visible–near-infrared spectroscopy, and attenuated total reflectance Fourier-transform infrared spectroscopy. Base-induced structural modifications are responsible for an improvement in the TE power factor of the films, which depends on the basic solution used. The results are explained on the basis of the different affinity between the alkali cations and the PSS chains, which determines PEDOT dedoping. The results presented here shed light on the structural reorganization occurring in PEDOT:PSS when exposed to high-pH solutions and may serve as inspiration to create future pH-/ion-responsive devices for various applications

Protonic acid doping of low band-gap conjugated polyions

This paper describes the design and synthesis of a series of conjugated polyions (CPIZ-T, CPIZ-TT and CPIZ-TT-DEG) that incorporate a formal positive charge into their conjugated backbones, balanced by anionic pendant groups with increasing electron-donating ability. The energy levels and the bandgap of these conjugated polyions were determined by using optical absorption spectroscopy and cyclic voltammetry (CV) and were easily modulated by varying the electron donating group. The energies of the occupied states increase with increasing electron-donating ability, while the energies of the unoccupied states are almost unchanged due to the presence of tritylium ions in the conjugated backbone. All conjugated polyions exhibit pristine semiconducting properties in weak protonic acids, but with sufficiently strong acids, the polymers exhibit spontaneous spin unpairing and convert to a metallic state. The required strength of the acids varies with the electron-donating ability, with higher HOMO levels leading to more facile proton acid doping and higher electrical conductivities. The mechanism of protonic acid doping of conjugated polyions involves a spinless doping process (dehydration) followed by a spontaneous spin unpairing leading to the formation of polarons. While protonic acid doping occurs in polyaniline, conjugated polyions offer synthetic tunability and selective processing into insulating, semiconducting and metallic states simply by controlling acidity

Controlling n-Type Molecular Doping via 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 0.08 S cm(-1) and power factor (PF) of 0.24 mu W m(-1) K-2 in the doped copolymer with the polar pendant groups on both the D and A moieties. We used spatially resolved absorption spectroscopy to relate commensurate morphological changes to the dispersion of dopants and to the relative local doping efficiency, demonstrating a direct relationship between the morphology of the polymer phase, the solvation of the molecular dopant, and the electrical properties of doped films. Our work offers fundamental new insights into the influence of the physical properties of pendant chains on the molecular doping process, which should be generalizable to any molecularly doped polymer films

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-C61-butyric acid and a custom peptide on nanostructured gold electrodes. Biophotovoltaic devices fabricated with the C61 fulleroid exhibit significantly improved performance and reproducibility compared to those utilizing the peptide, yielding a 1.6-fold increase in efficiency. In addition, the C61-based devices were more stable under continuous illumination. Our findings show that fulleroids, which are well-known acceptor materials in organic photovoltaic devices, facilitate the extraction of electrons from PSI complexes without sacrificing control over the orientation of the complexes, highlighting this combination of traditional organic semiconductors with biomolecules as a viable approach to coopting natural photosynthetic systems for use in solar cells

Self-assembled monolayers of polyoxovanadates with phthalocyaninato lanthanide moieties on gold surfaces

The two first representatives of phthalocyaninato (Pc) lanthanide-ligated polyoxovanadate cages {[V12O32(Cl)](LnPc)n}n-5 (n = 1 or 2, Ln = Yb3+) were synthesised and fully characterised. These magnetic complexes form two-dimensional self-assembled monolayers exhibiting electrical conductivity on gold substrate surfaces, as assessed by using an EGaIn tip