Thickness Dependent Structural Transition in Ph-BTBT-10 Thin Films and Stabilization of the Ubiquitous Interface Bilayer.

The influence of the film/substrate interface and the role of film thickness on the structural transition temperature for thin films of the asymmetric BTBT derivative 7-decyl-2-phenyl[1]benzothieno[3,2-][1]-benzothiophene (Ph-BTBT-10) have been addressed by using Kelvin probe force microscopy (KPFM) and synchrotron grazing incidence wide angle X-ray scattering (GIWAXS). Our data strongly suggest that the structural transformation from a single-layer phase to the thermodynamically stable bilayer structure develops from the bottom of the film to its surface. Contrary to observations in other organic semiconductor films, notably, the thinner the Ph-BTBT-10 film, the lower is the transition temperature.

Chiral and Catalytic Effects of Site-Specific Molecular Adsorption.

The changes of properties and preferential interactions based on subtle energetic differences are important characteristics of organic molecules, particularly for their functionalities in biological systems. Only slightly energetically favored interactions are important for the molecular adsorption and bonding to surfaces, which define their properties for further technological applications. Here, prochiral tetracenothiophene molecules are adsorbed on the Cu(111) surface.

High-gain, low-voltage unipolar logic circuits based on nanoscale flexible organic thin-film transistors with small signal delays.

One of the circuit topologies for the implementation of unipolar integrated circuits (circuits that use either p-channel or n-channel transistors, but not both) is the zero- architecture. Zero- circuits often provide excellent static performance (large small-signal gain and large noise margins), but they suffer from the large signal delay imposed by the load transistor. To address this limitation, we have used electron-beam lithography to fabricate zero- circuits based on organic transistors with channel lengths as small as 120 nm on flexible polymeric substrates.

Experimental determination of the lateral resolution of surface electric potential measurements by Kelvin probe force microscopy using biased electrodes separated by a nanoscale gap and application to thin-film transistors.

A method is proposed to estimate the lateral resolution of surface potential profile measurements using Kelvin probe force microscopy (KPFM) on operating electronic devices. De-embedding the measured profile from the system response is required for various applications, such as contact characterization of thin-film transistors, or local longitudinal electric field measurements. A method is developed based on the measurement of the electric potential profile of two metallic electrodes separated by a nano-gap, providing a quasi-planar configuration.

Nanoscale flexible organic thin-film transistors.

Direct-write electron-beam lithography has been used to fabricate low-voltage p-channel and n-channel organic thin-film transistors with channel lengths as small as 200 nm and gate-to-contact overlaps as small as 100 nm on glass and on flexible transparent polymeric substrates. The p-channel transistors have on/off current ratios as large as 4 × 10 and subthreshold swings as small as 70 mV/decade, and the n-channel transistors have on/off ratios up to 10 and subthreshold swings as low as 80 mV/decade. These are the largest on/off current ratios reported to date for nanoscale organic transistors.

A Critical Outlook for the Pursuit of Lower Contact Resistance in Organic Transistors.

To take full advantage of recent and anticipated improvements in the performance of organic semiconductors employed in organic transistors, the high contact resistance arising at the interfaces between the organic semiconductor and the source and drain contacts must be reduced significantly. To date, only a small portion of the accumulated research on organic thin-film transistors (TFTs) has reported channel-width-normalized contact resistances below 100 Ωcm, well above what is regularly demonstrated in transistors based on inorganic semiconductors. A closer look at these cases and the relevant literature strongly suggests that the most significant factor leading to the lowest contact resistances in organic TFTs so far has been the control of the thin-film morphology of the organic semiconductor.

"Golden" Cascade Cyclization to Benzo[c]-Phenanthridines.

Herein, we describe a gold-catalyzed cascade cyclization of Boc-protected benzylamines bearing two tethered alkyne moieties in a domino reaction initiated by a 6-endo-dig cyclization. The reaction was screened intensively, and the scope was explored, resulting in nine new Boc-protected dihydrobenzo[c]phenanthridines with yields of up to 98 %; even a π-extension and two bidirectional approaches were successful. Furthermore, thermal cleavage of the Boc group and subsequent oxidation gave substituted benzo[c]phenanthridines in up to quantitative yields.

Optimizing the plasma oxidation of aluminum gate electrodes for ultrathin gate oxides in organic transistors.

A critical requirement for the application of organic thin-film transistors (TFTs) in mobile or wearable applications is low-voltage operation, which can be achieved by employing ultrathin, high-capacitance gate dielectrics. One option is a hybrid dielectric composed of a thin film of aluminum oxide and a molecular self-assembled monolayer in which the aluminum oxide is formed by exposure of the surface of the aluminum gate electrode to a radio-frequency-generated oxygen plasma. This work investigates how the properties of such dielectrics are affected by the plasma power and the duration of the plasma exposure.

Flexible low-voltage high-frequency organic thin-film transistors.

The primary driver for the development of organic thin-film transistors (TFTs) over the past few decades has been the prospect of electronics applications on unconventional substrates requiring low-temperature processing. A key requirement for many such applications is high-frequency switching or amplification at the low operating voltages provided by lithium-ion batteries (~3 V). To date, however, most organic-TFT technologies show limited dynamic performance unless high operating voltages are applied to mitigate high contact resistances and large parasitic capacitances.

2,7,11,16-Tetra-tert-Butyl Tetraindenopyrene Revisited by an "Inverse" Synthetic Approach.

A new synthetic route to tetraindenopyrene (TIP)-a bowl-shaped cut-out structure of C -is reported. The key step in this approach is a fourfold palladium-catalyzed C-H activation that increases the yield more than 50 times in comparison to the approach originally described by Scott and co-workers. Besides examination of its optoelectronic properties and study of its aggregation in solution, TIP was also re-investigated by dispersion-corrected DFT methods, which showed that dispersion interactions significantly increase the bowl-to-bowl inversion barrier.

Perhalogenated Tetraazaperopyrenes and Their Corresponding Mono- and Dianions.

Chlorination and bromination of 2,9-perfluoropropyl-substituted tetraazaperopyrenes (TAPPs) under forcing conditions resulted in fully core-halogenated TAPP derivatives, devoid of hydrogen atoms at the polycyclic aromatic core. The octahalogenation stabilized the reduced mono- and dianionic compounds sufficiently to allow for their characterization. The additional ortho-chlorination led to an improvement of the electron mobility compared to the bay-substituted tetrachloro-TAPP when employed as an n-channel semiconductor in thin-film transistors.

Controlling Single Molecule Conductance by a Locally Induced Chemical Reaction on Individual Thiophene Units.

Among the prerequisites for the progress of single-molecule-based electronic devices are a better understanding of the electronic properties at the individual molecular level and the development of methods to tune the charge transport through molecular junctions. Scanning tunneling microscopy (STM) is an ideal tool not only for the characterization, but also for the manipulation of single atoms and molecules on surfaces. The conductance through a single molecule can be measured by contacting the molecule with atomic precision and forming a molecular bridge between the metallic STM tip electrode and the metallic surface electrode.

Extracting the shape of nanometric field emitters.

The high resolution nanoanalysis by atom probe tomography is based on needle-shaped samples that represent nanometric field emitters with typical curvature radii of 50 nm. After field desorption and detection of a large set of atoms, the sample volume has to be numerically reconstructed. Conventionally, this reconstruction is performed with the assumption of a hemispherical apex.

Twisting the TAPPs: Bay-Substituted Non-planar Tetraazapero-pyrenes and their Reduced Anions.

A new synthesis of tetraazaperopyrenes (TAPPs) starting from a halogenated perylene derivative 3,4,9,10- tetrabromo-1,6,7,12-tetrachloroperylene (1) gave access to bay-substituted TAPPs for the first time. Selective lithiation of the bromine-positions and subsequent addition of tosyl azide led to the formation of the tetraazidotetrachloroperylene (2), which was subsequently reduced by addition of sodium borohydride to the corresponding tetraaminotetrachloroperylene (3). Oxidation to its semiquinoidal form 4 and subsequent cyclization with acid chlorides gave rise to a series of bay-chlorinated TAPPs.

Achieving Ultralow Turn-On Voltages in Organic Thin-Film Transistors: Investigating Fluoroalkylphosphonic Acid Self-Assembled Monolayer Hybrid Dielectrics.

The properties of organic thin-film transistors (TFTs) and thus their ability to address specific circuit design requirements depend greatly on the choice of the materials, particularly the organic semiconductor and the gate dielectric. For a particular organic semiconductor, the TFT performance must be reviewed for different combinations of substrates, fabrication conditions, and the choice of the gate dielectric in order to achieve the optimum TFT and circuit characteristics. We have fabricated and characterized organic TFTs based on the small-molecule organic semiconductor 2,7-diphenyl[1]benzothieno[3,2-][1]benzothiophene in combination with an ultrathin hybrid gate dielectric consisting of aluminum oxide and a self-assembled monolayer.

Small contact resistance and high-frequency operation of flexible low-voltage inverted coplanar organic transistors.

The contact resistance in organic thin-film transistors (TFTs) is the limiting factor in the development of high-frequency organic TFTs. In devices fabricated in the inverted (bottom-gate) device architecture, staggered (top-contact) organic TFTs have usually shown or are predicted to show lower contact resistance than coplanar (bottom-contact) organic TFTs. However, through comparison of organic TFTs with different gate-dielectric thicknesses based on the small-molecule organic semiconductor 2,9-diphenyl-dinaphtho[2,3-b:2',3'-f]thieno[3,2-b]thiophene, we show the potential for bottom-contact TFTs to have lower contact resistance than top-contact TFTs, provided the gate dielectric is sufficiently thin and an interface layer such as pentafluorobenzenethiol is used to treat the surface of the source and drain contacts.

Carbonyl-Functionalized Cyclazines as Colorants and Air-Stable n-Type Semiconductors.

A series of π-extended cycl[3,3,2]azines (3) bearing additional carbonyl groups were synthesized via aldol condensations. Two strong electron acceptor molecules (4 and 5), with low-lying LUMO energy levels of -3.99 and -3.

Few-Layer WSe Schottky Junction-Based Photovoltaic Devices through Site-Selective Dual Doping.

Ultrathin sheets of two-dimensional (2D) materials like transition metal dichalcogenides have attracted strong attention as components of high-performance light-harvesting devices. Here, we report the implementation of Schottky junction-based photovoltaic devices through site-selective surface doping of few-layer WSe in lateral contact configuration. Specifically, whereas the drain region is covered by a strong molecular p-type dopant (NDP-9) to achieve an Ohmic contact, the source region is coated with an AlO layer, which causes local n-type doping and correspondingly an increase of the Schottky barrier at the contact.

(Oligo-)Thiophene Functionalized Tetraazaperopyrenes: Donor-Acceptor Dyes and Ambipolar Organic Semiconductors.

Tetraazaperopyrenes (TAPPs) have been functionalized with thiophene and terthiophene units of different architecture resulting in a variety of organic donor-acceptor (D-A) compounds. The influence of the connection of the thiophenes to the TAPP core on their structural, photophysical and electrochemical properties has been studied in detail by a combination of X-ray crystallography, UV-vis and fluorescence spectroscopy as well as cyclic voltammetry, which allowed the establishment of structure-property relationships. The HOMO-LUMO gap is significantly decreased upon substitution of the TAPP core with electron-donating thiophene units, the extent of which is strongly influenced by the orientation of the thiophene units.

Nanoantenna-Enhanced Infrared Spectroscopic Chemical Imaging.

Spectroscopic infrared chemical imaging is ideally suited for label-free and spatially resolved characterization of molecular species, but often suffers from low infrared absorption cross sections. Here, we overcome this limitation by utilizing confined electromagnetic near-fields of resonantly excited plasmonic nanoantennas, which enhance the molecular absorption by orders of magnitude. In the experiments, we evaporate microstructured chemical patterns of C and pentacene with nanometer thickness on top of homogeneous arrays of tailored nanoantennas.

Electric-Field-Driven Direct Desulfurization.

The ability to elucidate the elementary steps of a chemical reaction at the atomic scale is important for the detailed understanding of the processes involved, which is key to uncover avenues for improved reaction paths. Here, we track the chemical pathway of an irreversible direct desulfurization reaction of tetracenothiophene adsorbed on the Cu(111) closed-packed surface at the submolecular level. Using the precise control of the tip position in a scanning tunneling microscope and the electric field applied across the tunnel junction, the two carbon-sulfur bonds of a thiophene unit are successively cleaved.

Facile Synthetic Approach to a Large Variety of Soluble Diarenoperylenes.

Fused, extended π-systems such as larger acenes and heteroacenes are interesting compounds for organic thin-film transistors (TFTs). The larger the number of linearly cata-fused rings, the lower the stability of the acenes. By peri-fusion of additional rings, the stabilities can significantly be increased.

Remotely Controlled Isomer Selective Molecular Switching.

Nonlocal addressing-the "remote control"-of molecular switches promises more efficient processing for information technology, where fast speed of switching is essential. The surface state of the (111) facets of noble metals, a confined two-dimensional electron gas, provides a medium that enables transport of signals over large distances and hence can be used to address an entire ensemble of molecules simultaneously with a single stimulus. In this study we employ this characteristic to trigger a conformational switch in anthradithiophene (ADT) molecules by injection of hot carriers from a scanning tunneling microscope (STM) tip into the surface state of Cu(111).

Bipolar Conductance Switching of Single Anthradithiophene Molecules.

Single molecular switches are basic device elements in organic electronics. The pentacene analogue anthradithiophene (ADT) shows a fully reversible binary switching between different adsorption conformations on a metallic surface accompanied by a charge transfer. These transitions are activated locally in single molecules in a low-temperature scanning tunneling microscope .

Core Halogenation as a Construction Principle in Tuning the Material Properties of Tetraazaperopyrenes.

A detailed study on the effects of core halogenation of tetraazaperopyrene (TAPP) derivatives is presented. Its impact on the solid structure, as well as the photophysical and electrochemical properties, has been probed by the means of X-ray crystallography, UV/Vis and fluorescence spectroscopy, high-resolution electron energy loss spectroscopy (HREELS), cyclic voltammetry (CV), and DFT modeling. The aim was to assess the potential of this approach as a construction principle for organic electron-conducting materials of the type studied in this work.