Restricting Conformational Space: A New Blueprint for Electrically Switchable Self-Assembled Monolayers.

Tunnel junctions comprising self-assembled monolayers (SAMs) from liquid crystal-inspired molecules show a pronounced hysteretic current-voltage response, due to electric field-driven dipole reorientation in the SAM. This renders these junctions attractive device candidates for emerging technologies such as in-memory and neuromorphic computing. Here, the novel molecular design, device fabrication, and characterization of such resistive switching devices with a largely improved performance, compared to the previously published work are reported. Those former devices suffer from a stochastic switching behavior limiting reliability, as well as from critically small read-out currents. The present progress is based on replacing Al/AlOx with TiN as a new electrode material and as a key point, on redesigning the active molecular material making up the SAM: a previously present, flexible aliphatic moiety has been replaced by a rigid aromatic linker, thereby introducing a molecular "ratchet". This restricts the possible molecular conformations to only two major states of opposite polarity. The above measures have resulted in an increase of the current density by five orders of magnitude as well as in an ON/OFF conductance ratio which is more than ten times higher than the individual scattering ranges of the high and low resistance states.

Location-Selective Work Function Engineering by Self-Assembled Monolayers.

Control over specific interfaces in devices represents a key challenge for modern organic electronics and photovoltaics. Such control is frequently gained by the use of self-assembled monolayers (SAMs), which, by selection of a proper anchoring group, are generally discriminative with respect to different materials but are not selective between different areas of the same material. In particular, selective tailoring of the work function may be useful for different functional devices in a circuit. Here we demonstrate an approach for solving this problem, opening a way to function-selective electrostatic engineering of chemically identical areas, such as source and drain electrodes in a specific type of organic transistor and, more importantly, the electrodes in different types of organic devices, such as p- and n-channel transistors, located on the same circuitry board. The approach is based on the ultraviolet-light-promoted exchange reaction of SAMs on gold, a standard electrode material in organic electronics.

Phosphonic acid anchored tripodal molecular films on indium tin oxide.

Whereas monopodal self-assembling monolayers (SAMs) are most frequently used for surface and interface engineering, tripodal SAMs are less popular due to the difficulty in achieving a reliable and homogeneous bonding configuration. In this context, in the present study, the potential of phosphonic acid (PA) decorated triptycene (TripPA) for formation of SAMs on oxide substrates was studied, using indium tin oxide (ITO) as a representative and application-relevant test support. A combination of several complementary experimental techniques was applied and a suitable monopodal reference system, benzylphosphonic acid (PPA), was used. The resulting data consistently show that TripPA forms well-defined, densely packed, and nearly contamination-free tripodal SAMs on ITO, with the similar parameters and properties as the monopodal reference system. Modification of wetting properties and work function of ITO by non-substituted and cyano-decorated TripPA SAMs was demonstrated, showing a potential of this tripodal system for surface engineering of oxide substrates.

Odd-even effects in aryl-substituted alkanethiolate SAMs: nonsymmetrical attachment of aryl unit and its impact on the SAM structure.

Aryl-substituted alkanethiolate (AT) self-assembled monolayers (SAMs) exhibit typically so-called odd-even effects, viz. systematic variations in the film structure, packing density, and molecular inclination depending on the parity of the number of the methylene units in the alkyl linker, n. As an exception to this rule, ATs carrying an anthracen-2-yl group (Ant-n) as tail group were reported to have different behavior due the non-symmetric attachment of the anthracene unit to the AT linker, providing additional degree of freedom for the molecular organization and allowing for partial compensation of the odd-even effects. In this context, the structure of SAMs formed by adsorption of anthracene-substituted ATs (Ant-n; n = 1-6) at room temperature on Au(111) substrate was investigated by high-resolution scanning tunnelling microscopy (STM). Most of these SAMs exhibit a coexistence of two different ordered phases, some of which are common for either n = odd or n = even while other vary over the series, showing a broad variety of different structures. The average packing density of the Ant-n SAMs, derived from the analysis of the STM data, varies by 7.5-10% depending on the parity of n, being, as expected, higher for n = odd. The respective extent of the odd-even effects is noticeably lower than that usually observed for other aryl-substituted monolayers (∼25%), which goes in line with the previous findings and emphasizes the impact of the non-symmetric attachment of the aromatic unit.

Metal-organic Frameworks in Semiconductor Devices.

Metal-organic frameworks (MOFs) are a specific class of hybrid, crystalline, nano-porous materials made of metal-ion-based 'nodes' and organic linkers. Most of the studies on MOFs largely focused on porosity, chemical and structural diversity, gas sorption, sensing, drug delivery, catalysis, and separation applications. In contrast, much less reports paid attention to understanding and tuning the electrical properties of MOFs. Poor electrical conductivity of MOFs (~10-7-10-10 S cm-1), reported in earlier studies, impeded their applications in electronics, optoelectronics, and renewable energy storage. To overcome this drawback, the MOF community has adopted several intriguing strategies for electronic applications. The present review focuses on creatively designed bulk MOFs and surface-anchored MOFs (SURMOFs) with different metal nodes (from transition metals to lanthanides), ligand functionalities, and doping entities, allowing tuning and enhancement of electrical conductivity. Diverse platforms for MOFs-based electronic device fabrications, conductivity measurements, and underlying charge transport mechanisms are also addressed. Overall, the review highlights the pros and cons of MOFs-based electronics (MOFtronics), followed by an analysis of the future directions of research, including optimization of the MOF compositions, heterostructures, electrical contacts, device stacking, and further relevant options which can be of interest for MOF researchers and result in improved devices performance.

Gold Nanoparticle-Loaded Porous Poly(ethylene glycol) Nanosheets for Electrochemical Detection of H2O2.

The effective detection of hydrogen peroxide (H2O2) in different environments and, above all, in biological media, is an important practical issue. To this end, we designed a novel electrochemical sensor for H2O2 detection by introducing gold nanoparticles (AuNPs) into the porous poly(ethylene glycol) (PEG) matrix formed by the thermally activated crosslinking of amino- and epoxy-decorated STAR-PEG precursors. The respective composite PEG-AuNP films could be readily prepared on oxidized Si substrates, separated from them as free-standing nanosheets, and transferred as H2O2 sensing elements onto the working electrode of the electrochemical cell, with the performance of the sensing element relied on the established catalytic activity of AuNPs with respect to H2O2 decomposition. The sensitivity, detection limit, and the operation range of the composite PEG-AuNP sensors were estimated at ~3.4 × 102 µA mM-1 cm-2, 0.17 µM of H2O2, and 20 µM-3.5 mM of H2O2, respectively, which are well comparable with the best values for other types of H2O2 sensors reported recently in literature. The particular advantages of the composite PEG-AuNP sensors are commercial source materials, a simple fabrication procedure, the bioinert character of the PEG matrix, the 3D character of the AuNP assembly, and the possibility of transferring the nanosheet sensing element to any secondary substrate, including the glassy carbon electrode of the electrochemical cell. In particular, the bioinert character of the PEG matrix can be of importance for potential biological and biomedical applications of the designed sensing platform.

Exploiting epoxy-rich poly(ethylene glycol) films for highly selective ssDNA sensing via electrochemical impedance spectroscopy.

This study introduces an alternative approach to immobilize thiolated single-stranded DNA (ssDNA) for the DNA sensing. In contrast to the standard, monomolecular assembly of such moieties on gold substrate, over the thiolate-gold anchors, we propose to use bioinert, porous polyethylene glycol (PEG) films as a 3D template for ssDNA immobilization. The latter process relies on the reaction between the thiol group of the respectively decorated ssDNA and the epoxy groups in the epoxy-rich PEG matrix. The immobilization process and subsequent hybridization ability of the resulting sensing assembly were monitored using cyclic voltammetry and electrochemical impedance spectroscopy, with the latter tool proving itself as the most suitable transduction technique. Electrochemical data confirmed the successful immobilization of thiol-decorated ssDNA probes into the PEG matrix over the thiol-epoxy linkage as well as high hybridization efficiency, selectivity, and sensitivity of the resulting DNA sensor. Whereas this sensor was equivalent to the direct ssDNA assembly in terms of the efficiency, it exhibited a better selectivity and bioinert properties in view of the bioinert character of the PEG matrix. The above findings place PEG films as a promising platform for highly selective ssDNA sensing, leveraging their flexible chemistry, 3D character, and bioinert properties.

Nanoscale molecular rectifiers.

The use of molecules bridged between two electrodes as a stable rectifier is an important goal in molecular electronics. Until recently, however, and despite extensive experimental and theoretical work, many aspects of our fundamental understanding and practical challenges have remained unresolved and prevented the realization of such devices. Recent advances in custom-designed molecular systems with rectification ratios exceeding 105 have now made these systems potentially competitive with existing silicon-based devices. Here, we provide an overview and critical analysis of recent progress in molecular rectification within single molecules, self-assembled monolayers, molecular multilayers, heterostructures, and metal-organic frameworks and coordination polymers. Examples of conceptually important and best-performing systems are discussed, alongside their rectification mechanisms. We present an outlook for the field, as well as prospects for the commercialization of molecular rectifiers.

Effect of the crosslinking agent on the biorepulsive and mechanical properties of polyglycerol membranes.

Polyglycerol (PG) based surfaces materials and surfaces are well-established bio-compatible materials. Crosslinking of the dendrimeric molecules via their OH groups improves their mechanical stability up to the point that free-standing materials can be attained. Here, we investigate the effect of different crosslinkers on PG films regarding their biorepulsivity and mechanical properties. For this purpose, PG films with different thicknesses (15, 50 and 100 nm) were prepared by polymerizing glycidol in a ring-opening polymerization onto hydroxyl-terminated Si substrates. These films were then crosslinked using ethylene glycol diglycidyl ether (EGDGE), divinyl sulfone (DVS), glutaraldehyde (GA), 1,11-di(mesyloxy)-3,6,9-trioxaundecane (TEG-Ms2) or 1,11-dibromo-3,6,9-trioxaundecane (TEG-Br2), respectively. While DVS, TEG-Ms2, and TEG-Br2 resulted in slightly thinned films, presumably due to loss of unbound material, increase of film thickness was observed with GA and, in particular, EDGDE, what can be explained by the different crosslinking mechanisms. The biorepulsive properties of the crosslinked PG films were characterized by water contact angle (WCA) goniometry and various adsorption assays involving proteins (serum albumine, fibrinogen, γ-globulin) and bacteria (E. coli), showing that some crosslinkers (EGDGE, DVS) improved the biorepulsive properties, while others deteriorated them (TEG-Ms2, TEG-Br2, GA). As the crosslinking stabilized the films, it was possible to use a lift-off procedure to obtain free-standing membranes if the thickness of the films was 50 nm or larger. Their mechanical properties were examined with a bulge test showing high elasticities, with the Young's moduli increasing in the order GA ≈ EDGDE < TEG-Br2 ≈ TEG-Ms2 < DVS.

Modular Approach to Creating Functionalized Surface Arrays of Molecular Qubits.

The quest for developing quantum technologies is driven by the promise of exponentially faster computations, ultrahigh performance sensing, and achieving thorough understanding of many-particle quantum systems. Molecular spins are excellent qubit candidates because they feature long coherence times, are widely tunable through chemical synthesis, and can be interfaced with other quantum platforms such as superconducting qubits. A present challenge for molecular spin qubits is their integration in quantum devices, which requires arranging them in thin films or monolayers on surfaces. However, clear proof of the survival of quantum properties of molecular qubits on surfaces has not been reported so far. Furthermore, little is known about the change in spin dynamics of molecular qubits going from the bulk to monolayers. Here, a versatile bottom-up method is reported to arrange molecular qubits as functional groups of self-assembled monolayers (SAMs) on surfaces, combining molecular self-organization and click chemistry. Coherence times of up to 13 µs demonstrate that qubit properties are maintained or even enhanced in the monolayer.

Sweep-Character-Dependent Switching of the Conductance State in Ferrocene-Substituted Thiofluorene Self-Assembled Monolayers.

Self-assembled monolayers (SAMs) of ferrocene-substituted thiofluorene on Au(111) exhibit two distinct conductance states (CSs) in two-terminal junctions featuring a sharp tip of eutectic GaIn as the top electrode. The occurrence of these states and the resulting effective rectification by the SAM depend on the way the bias voltage is swept; when the junction is only negatively biased, the original, high CS is preserved, whereas the junction is switched to a low CS when applying only positive biases. This results in an exceptionally high effective rectification ratio (RR) of ∼2100 already at voltages as low as 0.1 V. In contrast, when sweeping the junction alternatingly to the maximum positive and negative bias voltages (as usually performed in the literature), fully symmetric J-V curves are observed. That is, for the present SAM, rectification disappears, and the effective RR is ≈1. It is noteworthy that whether the junction in these symmetric sweeps is in the high or low CS depends on the polarity of the first sweep. We attribute the occurrence of the two CSs to a (quasi) non-reversible oxidation of the ferrocenes in combination with structural changes in the monolayer geometry. The observed sweeping dependence of the conductivity switching is an additional parameter that needs to be considered when interpreting experimental J-V curves, especially when dealing with redox-active systems.

Resonant Inelastic Soft X-ray Scattering and X-ray Emission Spectroscopy of Solid Proline and Proline Solutions.

The amino group of proline is part of a pyrrolidine ring, which makes it unique among the proteinogenic amino acids. To unravel its full electronic structure, proline in solid state and aqueous solution is investigated using X-ray emission spectroscopy and resonant inelastic soft X-ray scattering. By controlling the pH value of the solution, proline is studied in its cationic, zwitterionic, and anionic configurations. The spectra are analyzed within a "building-block principle" by comparing with suitable reference molecules, i.e., acetic acid, cysteine, and pyrrolidine, as well as with spectral calculations based on density functional theory. We find that the electronic structure of the carboxyl group of proline is very similar to that of other amino acids as well as acetic acid. In contrast, the electronic structure of the amino group is significantly different and strongly influenced by the ring structure of proline.

Effect of substitution on the charge transport properties of oligophenylenethiolate self-assembled monolayers.

Electrostatic effects in charge transport across the molecular framework, including those imposed by halogen atoms, have recently attracted noticeable attention of the molecular-electronics community. In this context, in the present work, we studied the effect of tail group (R) substitution on the charge transport properties of oligophenylenethiolate self-assembled monolayers (SAMs) on Au(111), with R = H, F, CH3, and CF3. The length of the molecular backbone was varied from one to three rings and the quality, basic parameters, and electrostatic properties of the SAMs were monitored. For a given length of the molecular backbone, the current density showed a strong dependence on R, being the highest for R = CH3, and then successively lower for R = H, R = CF3, and R = F. This tendency correlated neither with the molecular length of the precursors nor with the work function of the SAMs and was, therefore, exclusively ascribed to the identity of the tail group. In contrast to the current density, the tunneling decay coefficient, describing its dependence on the molecular length, was found to be independent of the identity of the tail group. The reasons behind the observed behavior are discussed and rationalized within the available experimental data and reasonable assumptions.

Rational Design of Porous Poly(ethylene glycol) Films as a Matrix for ssDNA Immobilization and Hybridization.

Poly(ethylene glycol) (PEG) films, fabricated by thermally induced crosslinking of amine- and epoxy-terminated four-arm STAR-PEG precursors, were used as porous and bioinert matrix for single-stranded DNA (ssDNA) immobilization and hybridization. The immobilization relied on the reaction between the amine groups in the films and N-hydroxy succinimide (NHS) ester groups of the NHS-ester-decorated ssDNA. Whereas the amount of reactive amine groups in the films with the standard 1:1 composition of the precursors turned out to be too low for efficient immobilization, it could be increased noticeably using an excess (2:1) concentration of the amine-terminated precursor. The respective films retained the bioinertness of the 1:1 prototype and could be successfully decorated with probe ssDNA, resulting in porous, 3D PEG-ssDNA sensing assemblies. These assemblies exhibited high selectivity with respect to the target ssDNA strands, with a hybridization efficiency of 78-89% for the matching sequences and full inertness for non-complementary strands. The respective strategy can be applied to the fabrication of DNA microarrays and DNA sensors. As a suitable transduction technique, requiring no ssDNA labeling and showing high sensitivity in the PEG-ssDNA case, electrochemical impedance spectroscopy is suggested.

Polymorphism and Building-Block-Resolved STM Imaging of Self-Assembled Monolayers of 4-Fluorobenzenemethanethiol on Au(111).

Self-assembled monolayers (SAMs) of 4-fluorobenzenemethanethiol (p-FBMT) on Au(111), prepared by immersion procedure (1 mM ethanolic solution; 60 °C; 18 h), were characterized by scanning tunneling microscopy (STM). The data suggest the formation of highly ordered monolayer with a commensurate structure, described by the 2 3 × 13 R 13 ∘ unit cell. The STM appearance of this cell occurs, however, in two different forms, with either well-localized individual spots or splitting of these spots in two components. These components are assigned to the tunneling through the entire molecule or sulfur docking group only. The respective spots correspond then to the terminal fluorine atom and sulfur docking group, manifesting, thus, building-block-resolving STM imaging. The accessibility of the docking group for direct tunneling is most likely related to a specific molecular organization for one of the two possible internal structures of the unit cell. The above results represent a showcase for potential of STM for imaging of upright-arranged and densely packed molecular assemblies, such as SAMs.

Concept of Embedded Dipoles as a Versatile Tool for Surface Engineering.

Controlling the physical and chemical properties of surfaces and interfaces is of fundamental relevance in various areas of physical chemistry and a key issue of modern nanotechnology. A highly promising strategy for achieving that control is the use of self-assembled monolayers (SAMs), which are ordered arrays of rodlike molecules bound to the substrate by a suitable anchoring group and carrying a functional tail group at the other end of the molecular backbone. Besides various other applications, SAMs are frequently used in organic electronics for the electrostatic engineering of interfaces by controlling the interfacial level alignment. This is usually achieved by introducing a dipolar tail group at the SAM-semiconductor interface. Such an approach, however, also changes the chemical character of that interface, for example, affecting the growth of subsequent layers. A strategy for avoiding this complication is to embed polar groups into the backbones of the SAM-forming molecules. This allows disentangling electronic interface engineering and the nucleation of further layers, such that both can be optimized independently. This novel concept was successfully demonstrated for both aliphatic and aromatic SAMs on different application-relevant substrates, such as gold, silver, and indium tin oxide. Embedding, for example, ester and pyrimidine groups in different orientations into the backbones of the SAM-forming molecules results in significant work-function changes. These can then be fine-tuned over a wide energy range by growing mixed monolayers consisting of molecules with oppositely oriented polar groups. In such systems, the variation of the work function is accompanied by pronounced shifts of the peaks in X-ray photoelectron spectra, which demonstrates that electrostatically triggered core-level shifts can be as important as the well-established chemical shifts. This illustrates the potential of X-ray photoelectron spectroscopy (XPS) as a tool for probing the local electrostatic energy within monolayers and, in systems like the ones studied here, makes XPS a powerful tool for studying the composition and morphology of binary SAMs. All these experimental observations can be rationalized through simulations, which show that the assemblies of embedded dipolar groups introduce a potential discontinuity within the monolayer, shifting the energy levels above and below the dipoles relative to each other. In molecular and monolayer electronics, embedded-dipole SAMs can be used to control transition voltages and current rectification. In devices based on organic and 2D semiconductors, such as MoS2, they can reduce contact resistances by several orders of magnitude without adversely affecting film growth even on flexible substrates. By varying the orientation of the embedded dipolar moieties, it is also possible to build p- and n-type organic transistors using the same electrode materials (Au). The extensions of the embedded-dipole concept from hybrid interfaces to systems such as metal-organic frameworks is currently underway, which further underlines the high potential of this approach.

Elastic Properties of Poly(ethylene glycol) Nanomembranes and Respective Implications.

Free-standing poly(ethylene glycol) (PEG) membranes were prepared from amine- and epoxy-terminated four-arm STAR-PEG precursors in a thickness range of 40-320 nm. The membranes feature high stability and an extreme elasticity, as emphasized by the very low values of Young's modulus, varying from 2.08 MPa to 2.6 MPa over the studied thickness range. The extreme elasticity of the membranes stems from the elastomer-like character of the PEG network, consisting of the STAR-PEG cores interconnected by crosslinked PEG chains. This elasticity is only slightly affected by a moderate reduction in the interconnections at a deviation from the standard 1:1 composition of the precursors. However, both the elasticity and stability of the membranes are strongly deteriorated by a strong distortion of the network imposed by electron irradiation of the membranes. In contrast, exposure of the membranes to ultraviolet (UV) light (254 nm) does not affect their elastic properties, supporting the assumption that the only effect of such treatment is the decomposition of the PEG material with subsequent desorption of the released fragments. An analysis of the data allowed for the exclusion of so called "hot electrons" as a possible mechanism behind the modification of the PEG membranes by UV light.

Electrochemical Characterization of Redox Probes Confined in 3D Conducting Polymer Networks.

In this manuscript we present a versatile platform for introducing functional redox species into tailor-made 3D redox polymer networks. Electrochemical characterization based on cyclic voltammetry is applied to verify the immobilization of the redox species within the conducting networks. Ultimately this strategy shall be extended to (photo)electrocatalytic applications which will profit from the conducting polymer matrix. Soluble precursor copolymers are synthesized via radical copolymerization of vinyltriphenylamine (VTPA) with chloromethylstyrene (CMS) in different ratios, whereas CMS is subsequently converted into azidomethylstyrene (AMS) to yield poly(VTPA-co-AMS) copolymers. Spin-coating of poly(VTPA-co-AMS) on gold electrodes yields thin films which are converted into stable polymer network structures by electrochemical crosslinking of the polymer chains via their pendant triphenylamine groups to yield N,N,N',N'-tetraphenylbenzidine (TPB) crosslinking points. Finally, the resulting redox-active, TPB-crosslinked films are functionalized with ethynylferrocene (EFc) as a representative redox probe using a click reaction. Main experimental tools are polarization modulation infrared reflection absorption spectroscopy and scan rate dependent cyclic voltammetry. Especially the latter proves the successful conversion and the immobilization of redox probes in the polymer matrix. The results are compared with the reference system of azide-terminated self-assembled monolayers on gold substrates, allowing to distinguish between free and immobilized EFc species.

A Copper(I) Complex with Two Unpaired Electrons, Synthesised by Oxidation of a Copper(II) Complex with Two Redox-Active Ligands.

Two homoleptic copper(II) complexes [Cu(L1)2 ] and [Cu(L2)2 ] with anionic redox-active ligands were synthesised, one with urea azine (L1) and the other with thio-urea azine (L2) ligands. One-electron oxidation of the complexes initiates an unprecedented redox-induced electron transfer process, leading to monocationic copper(I) complexes [Cu(L1)2 ]+ and [Cu(L2)2 ]+ with two oxidised ligands. While [Cu(L1)2 ]+ is best described as a CuI complex with two neutral radical ligands that couple antiferromagnetically, [Cu(L2)2 ]+ is a CuI complex with two clearly different ligand units in the solid state and with a magnetic susceptibility close to a diamagnetic compound. Further one-electron oxidation of the complex with L1 ligands results in a dication [Cu(L1)2 ]2+ , best described as a CuI complex with a twofold oxidised, monocationic ligand and a neutral radical ligand. The stability in at least three redox states, the accumulation of spin density at the ligands and the facile ligand-metal electron transfer make these complexes highly attractive for a variety of applications; here the catalytic aerobic oxidation of alcohols to aldehydes is tested.

Porous Honeycomb Self-Assembled Monolayers: Tripodal Adsorption and Hidden Chirality of Carboxylate Anchored Triptycenes on Ag.

Molecules with tripodal anchoring to substrates represent a versatile platform for the fabrication of robust self-assembled monolayers (SAMs), complementing the conventional monopodal approach. In this context, we studied the adsorption of 1,8,13-tricarboxytriptycene (Trip-CA) on Ag(111), mimicked by a bilayer of silver atoms underpotentially deposited on Au. While tripodal SAMs frequently suffer from poor structural quality and inhomogeneous bonding configurations, the triptycene scaffold featuring three carboxylic acid anchoring groups yields highly crystalline SAM structures. A pronounced polymorphism is observed, with the formation of distinctly different structures depending on preparation conditions. Besides hexagonal molecular arrangements, the occurrence of a honeycomb structure is particularly intriguing as such an open structure is unusual for SAMs consisting of upright-standing molecules. Advanced spectroscopic tools reveal an equivalent bonding of all carboxylic acid anchoring groups. Notably, density functional theory calculations predict a chiral arrangement of the molecules in the honeycomb network, which, surprisingly, is not apparent in experimental scanning tunneling microscopy (STM) images. This seeming discrepancy between theory and experiment can be resolved by considering the details of the actual electronic structure of the adsorbate layer. The presented results represent an exemplary showcase for the intricacy of interpreting STM images of complex molecular films. They are also further evidence for the potential of triptycenes as basic building blocks for generating well-defined layers with unusual structural motifs.