Christof M. Jäger

Improving the charge transport in self-assembled monolayer field-effect transistors:from theory to devices

A three-pronged approach has been used to design rational improvements in self-assembled monolayer field-effect transistors: classical molecular dynamics (MD) simulations to investigate atomistic structure, large-scale quantum mechanical (QM) calculations for electronic properties, and device fabrication and characterization as the ultimate goal. The MD simulations reveal the effect of using two-component monolayers to achieve intact dielectric insulating layers and a well-defined semiconductor channel. The QM calculations identify improved conduction paths in the monolayers that consist of an optimum mixing ratio of the components. These results have been used both to confirm the predictions of the calculations and to optimize real devices. Monolayers were characterized with X-ray reflectivity measurements and by electronic characterization of complete devices.

Amphiphilic Perylene–Calix[4]arene Hybrids: Synthesis and Tunable Self-Assembly

The first highly water-soluble perylene-calix[4]arene hybrid with the calixarene scaffold acting as a structure-determining central platform is presented. In this tetrahedrally shaped amphiphilic architecture the hydrophilic and hydrophobic subunits are oriented at the opposite side of the calixarene platform. The hydrophobic part contains the two perylene diimide moieties, which enable strong π-π interactions in self-assembly processes. Two hydrophilic Newkome-type dendrons provide sufficient water solubility at slightly basic conditions. The tetrahedrally shaped amphiphile displays an unprecedented aggregation behavior down to concentrations as low as 10(-7) mol L(-1). The intriguing self-assembly process of the compound in water as well as under changed polarity conditions, achieved by addition of THF, could be monitored by the complemented use of cryogenic transmission electron microscopy (cryo-TEM), UV-vis spectroscopy, and fluorescence spectroscopy. Molecular-dynamics and molecular modeling simulations helped in understanding the interplay of supramolecular and optical behavior.

Self-assembly of structurally persistent micelles is controlled by specific-ion effects and hydrophobic guests

A combined study using cryo-TEM experiments and molecular dynamics simulations reveals remarkable details of the factors that affect the self-organization of specifically designed T-shaped amphiphilic dendrimers upon treatment of an aqueous solution with ultrasound under a layer of hexane. This treatment leads to dodecameric, structured micelles rather than the heptameric ones observed without hexane. Three-dimensional reconstruction of the cryo-TEM images provides very detailed structures of the micelles, and molecular dynamics simulations suggest that approximately 36 hexane molecules are needed to stabilize the dodecameric micelles. Sodium counterions are found to exert a significant stabilizing effect that results in an apparent attraction between the highly negatively charged polycarboxylate headgroups. DFT calculations support the observation that the formation of ion multiplets is especially crucial for this stabilizing counterion effect, which reduces headgroup repulsion. This and the increased hydrophobic stabilization that results from the hexane-enlarged core of the micelle lead to stable dodecameric micelles. The specific effects found for sodium counterions are largely absent for potassium.

Mixed self-assembled monolayer of molecules with dipolar and acceptor character—Influence on hysteresis and threshold voltage in organic thin-film transistors

In this report, we investigate the impact of the molecular dipole moment and redox active head groups (C60) in pure and mixed self-assembled monolayers (SAMs), which serve as an ultra-thin hybrid dielectric layer in low-voltage operating organic thin-film transistors. We show that the dipole of the SAM-forming molecules affects the threshold voltage, while the concentration of redox-active C60 moieties determines the hysteresis in devices with α,α′-dihexyl-sexithiophene and pentacene as organic semiconductors.

Molecular Dynamics Simulations of Liquid Phase Interfaces: Understanding the Structure of the Glycerol/Water−Dodecane System

Modern spectroscopic techniques such as time-resolved second-harmonic-generation spectroscopy allow molecules to be examined selectively directly at phase interfaces. Two-phase systems formed by glycerol/water and alkane layers have previously been studied by time-resolved second-harmonic-generation spectroscopic measurements. In this molecular dynamics study, a triphenylmethane dye was inserted at the glycerol/water-alkane interface and was used as a probe for local properties such as viscosity. We now show how extensive simulations over a wide range of concentrations can be used to obtain a detailed view of the molecular structure at the glycerol/water-alkane interface. Glycerol is accumulated in a double layer adjacent to the alkane interface, which results in increased viscosity of the glycerol/water phase in the direct vicinity of the interface. We also show that conformational ensembles created by classical molecular-dynamics simulations can serve as input for QM/MM calculations, yielding further information such as transition dipoles, which can be compared with spectroscopic measurements.

Sodium Effect on Self‐Organization of Amphiphilic Carboxylates: Formation of Structured Micelles and Superlattices

Not only the self-aggregation of dendritic polycarboxylates into structurally persistent micelles, but also that of the micelles themselves into superlattices is controlled by alkali-metal counterions and shows a pronounced sodium effect. Our combined experimental and computational work has revealed the formation of superlattices for the first time. The behavior of a variety of amphiphilic carboxylates and the different effects of the alkali cations Li(+), Na(+), and K(+) have been investigated by conductivity measurements, cryogenic transmission electron microscopy (cryo-TEM), and molecular-dynamics (MD) simulations. Together, these show that sodium salts of the amphiphiles give the most stable micelles, followed by lithium and potassium. Our results suggest that ion multiplets in bridging positions, rather than contact ion pairs, are responsible for the enhanced stability and the formation of hexagonally ordered superlattices with sodium counterions. Potassium ions do not form such ion multiplets and cannot therefore induce aggregation of the micelles. This sodium effect has far-reaching consequences for a large number of biological and technical systems and sheds new light on the origin of specific-ion effects.

Indentation and Self-Healing Mechanisms of a Self-Assembled Monolayer—A Combined Experimental and Modeling Study

A combination of in situ vibrational sum-frequency generation (SFG) spectroscopy and molecular-dynamics (MD) simulations has allowed us to study the effects of indentation of self-assembled octadecylphosphonic acid (ODPA) monolayers on α-Al2O3(0001). Stress-induced changes in the vibrational signatures of C-H stretching vibrations in SFG spectra and the results of MD simulations provide clear evidence for an increase in gauche-defect density in the monolayer as a response to indentation. A stress-dependent analysis indicates that the defect density reaches saturation at approximately 155 MPa. After stress is released, the MD simulations show an almost instantaneous healing of pressure-induced defects in good agreement with experimental results. The lateral extent of the contact areas was studied with colocalized SFG spectroscopy and compared to theoretical predictions for pressure gradients from Hertzian contact theory. SFG experiments reveal a gradual increase in gauche-defect density with pressure before saturation close to the contact center. Furthermore, our MD simulations show a spatial anisotropy of pressure-induced effects within ODPA domains: molecules tilted in the direction of the pressure gradient increase in tilt angle while those on the opposite side form gauche-defects.

Counterions Control the Self‐Assembly of Structurally Persistent Micelles: Theoretical Prediction and Experimental Observation of Stabilization by Sodium Ions

We show by molecular-dynamics (MD) simulations and cryo-transmission electron microscopy (cryo-TEM) experiments that the size and form of structurally persistent micelles formed by the T-shaped amphiphile 1 are controlled by the counterions. The two techniques reveal that the micelles are specifically stabilized by sodium counterions relative to potassium ions. Both the simulations and the cryo-TEM experiments suggest that the micelles are stabilized by strongly conserved hydrated contact ion pairs with sodium counterions but not with potassium ions. We suggest that the TEM is observing local high density due to hydrated carboxylate/sodium ion pairs at the surface of the micelle. A high concentration of such structures is found in MD simulations with sodium counterions, but not with potassium.

Dendronizing and Metalating trans‐2 C60 Tetraaryl Porphyrins—A Versatile Approach Toward Water‐Soluble Donor–Acceptor Conjugates

We have realized for the first time a series of truly water-soluble and tightly coupled porphyrin/C(60) electron-donor-acceptor conjugates in which the charge separation and charge recombination dynamics are controlled by modifying the nature of the dendrimer and/or the choice of the central metal atom.

Modeling charge transport in C60-based self-assembled monolayers for applications in field-effect transistors.

We have investigated the conductance properties of C60-containing self-assembled monolayers (SAMs), which are used in organic field-effect transistors, employing a combination of molecular-dynamics simulations, semiempirical electronic structure calculations, and Landauer transport theory. The results reveal the close relation between the transport characteristics and the structural and electronic properties of the SAM. Furthermore, both local pathways of charge transport in the SAMs and the influence of structural fluctuations are analyzed.