Effects of Processing-Induced Contamination on Organic Electronic Devices.

Organic semiconductors are a family of pi-conjugated compounds used in many applications, such as displays, bioelectronics, and thermoelectrics. However, their susceptibility to processing-induced contamination is not well understood. Here, it is shown that many organic electronic devices reported so far may have been unintentionally contaminated, thus affecting their performance, water uptake, and thin film properties. Nuclear magnetic resonance spectroscopy is used to detect and quantify contaminants originating from the glovebox atmosphere and common laboratory consumables used during device fabrication. Importantly, this in-depth understanding of the sources of contamination allows the establishment of clean fabrication protocols, and the fabrication of organic field effect transistors (OFETs) with improved performance and stability. This study highlights the role of unintentional contaminants in organic electronic devices, and demonstrates that certain stringent processing conditions need to be met to avoid scientific misinterpretation, ensure device reproducibility, and facilitate performance stability. The experimental procedures and conditions used herein are typical of those used by many groups in the field of solution-processed organic semiconductors. Therefore, the insights gained into the effects of contamination are likely to be broadly applicable to studies, not just of OFETs, but also of other devices based on these materials.

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. The chiral adsorption configurations are determined by Scanning Tunneling Microscopy studies and confirmed by first-principles calculations. Remarkably, the selection of the adsorption sites by chemically different moieties of the molecules is dictated by the arrangement of the atoms in the first and second surface layers. Furthermore, we have investigated the thermal effects on the direct desulfurization reaction that occurs under the catalytic activity of the Cu substrate. This reaction leads to a product that is covalently bound to the surface in chiral configurations.

Improving OFF-State Bias-Stress Stability in High-Mobility Conjugated Polymer Transistors with an Antisolvent Treatment.

Conjugated polymer field-effect transistors are emerging as an enabling technology for flexible electronics due to their excellent mechanical properties combined with sufficiently high charge-carrier mobilities and compatibility with large-area, low-temperature processing. However, their electrical stability remains a concern. ON-state (accumulation mode) bias-stress instabilities in organic semiconductors have been widely studied, and multiple mitigation strategies have been suggested. In contrast, OFF-state (depletion mode) bias-stress instabilities remain poorly understood despite being crucial for many applications in which the transistors are held in their OFF-state for most of the time. Here, a simple method of using an antisolvent treatment is presented to achieve significant improvements in OFF-state bias-stress and environmental stability as well as general device performance for one of the best performing polymers, solution-processable indacenodithiophene-co-benzothiadiazole (IDT-BT). IDT-BT is weakly crystalline, and the notable improvements to an antisolvent-induced, increased degree of crystallinity, resulting in a lower probability of electron trapping and the removal of charge traps is attributed. The work highlights the importance of the microstructure in weakly crystalline polymer films and offers a simple processing strategy for achieving the reliability required for applications in flexible electronics.

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. The parameters affecting the conductance are mainly related to their electronic structure and to the coupling to the metallic electrodes. Here, the experimental and theoretical analyses are focused on single tetracenothiophene molecules and demonstrate that an in situ-induced direct desulfurization reaction of the thiophene moiety strongly improves the molecular anchoring by forming covalent bonds between molecular carbon and copper surface atoms. This bond formation leads to an increase of the conductance by about 50 % compared to the initial state.

An integrated self-healable electronic skin system fabricated via dynamic reconstruction of a nanostructured conducting network.

Electronic skin devices capable of monitoring physiological signals and displaying feedback information through closed-loop communication between the user and electronics are being considered for next-generation wearables and the 'Internet of Things'. Such devices need to be ultrathin to achieve seamless and conformal contact with the human body, to accommodate strains from repeated movement and to be comfortable to wear. Recently, self-healing chemistry has driven important advances in deformable and reconfigurable electronics, particularly with self-healable electrodes as the key enabler. Unlike polymer substrates with self-healable dynamic nature, the disrupted conducting network is unable to recover its stretchability after damage. Here, we report the observation of self-reconstruction of conducting nanostructures when in contact with a dynamically crosslinked polymer network. This, combined with the self-bonding property of self-healing polymer, allowed subsequent heterogeneous multi-component device integration of interconnects, sensors and light-emitting devices into a single multi-functional system. This first autonomous self-healable and stretchable multi-component electronic skin paves the way for future robust electronics.

Investigating Limiting Factors in Stretchable All-Carbon Transistors for Reliable Stretchable Electronics.

Stretchable form factors enable electronic devices to conform to irregular 3D structures, including soft and moving entities. Intrinsically stretchable devices have potential advantages of high surface coverage of active devices, improved durability, and reduced processing costs. This work describes intrinsically stretchable transistors composed of single-walled carbon nanotube (SWNT) electrodes and semiconductors and a dielectric that consists of a nonpolar elastomer. The use of a nonpolar elastomer dielectric enabled hysteresis-free device characteristics. Compared to devices on SiO2 dielectrics, stretchable devices with nonpolar dielectrics showed lower mobility in ambient conditions because of the absence of doping from water. The effect of a SWNT band gap on device characteristics was investigated by using different SWNT sources as the semiconductor. Large-band-gap SWNTs exhibited trap-limited behavior caused by the low capacitance of the dielectric. In contrast, high-current devices based on SWNTs with smaller band gaps were more limited by contact resistance. Of the tested SWNT sources, SWNTs with a maximum diameter of 1.5 nm performed the best, with a mobility of 15.4 cm2/Vs and an on/off ratio >103 for stretchable transistors. Large-band-gap devices showed increased sensitivity to strain because of a pronounced dependence on the dielectric thickness, whereas contact-limited devices showed substantially less strain dependence.

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. Comparison of spatially mapped molecular states close to the Fermi level of the metallic substrate acquired at each reaction step with density functional theory calculations reveals the two elementary steps of this reaction mechanism. The first reaction step is activated by an electric field larger than 2 V nm-1, practically in absence of tunneling electrons, opening the thiophene ring and leading to a transient intermediate. Subsequently, at the same threshold electric field and with simultaneous injection of electrons into the molecule, the exergonic detachment of the sulfur atom is triggered. Thus, a stable molecule with a bifurcated end is obtained, which is covalently bound to the metallic surface. The sulfur atom is expelled from the vicinity of the molecule.

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). The carriers propagate laterally and trigger the switch in molecules at distances as far as 100 nm from the tip location. The switching process is shown to be long-ranged, fully reversible, and isomer selective, discriminating between cis and trans diastereomers, enabling maximum control.

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 . The switching induces changes between bistable orbital structures and energy level alignment at the interface. The most stable geometry, the "off" state, which all molecules adopt upon evaporation, corresponds to a short adsorption distance at which the electronic interactions of the acene rings bend the central part of the molecule toward the surface accompanied by a significant charge transfer from the metallic surface to the ADT molecules. This leads to a shift of the lowest unoccupied molecular orbital down to the Fermi level (EF). In the "on" state the molecule has a flat geometry at a larger distance from the surface; consequently the interaction is weaker, resulting in a negligible charge transfer with an orbital structure resembling the highest occupied molecular orbital when imaged close to EF. The potential barrier between these two states can be overcome reversibly by injecting charge carriers locally into individual molecules. Voltage-controlled current traces show a hysteresis characteristic of a bipolar switching behavior. The interpretation is supported by first-principles calculations.

Flexible low-voltage organic complementary circuits: finding the optimum combination of semiconductors and monolayer gate dielectrics.

Low-voltage p-channel and n-channel organic transistors with channel lengths down to 0.5 µm using four small-molecule semiconductors and ultra-thin dielectrics based on two different phosphonic acid monolayers are fabricated on plastic substrates and studied in terms of effective mobility, intrinsic mobility and contact resistance. For the optimum materials combination, flexible complementary circuits have signal delays of 3.1 µs at 5 V.

Longitudinal micromorphological 15-year results of posterior composite restorations using three-dimensional scanning electron microscopy.

OBJECTIVES: Hybrid composite restorations in posterior teeth were evaluated over 15 years using the semiquantitative Clinical, Photographic and Micromorphologic (CPM) index. It was a further aim to quantitate the surface morphology by three-dimensional scanning electron microscopy (3D-SEM). METHODS: Thirty seven hybrid composite restorations (Ketac-Bond/Visio-Molar X, ESPE, Seefeld/Germany) were longitudinally followed up. Parallel to clinical assessment replicas were taken at baseline, after 1, 5, 10 and 15 years and evaluated by SEM, and profilometrical analyses of 3D-SEM data were computed. The profilometrical results were statistically analysed by ANOVA. The level of significance was set to p<0.05. RESULTS: The semiquantitative micromorphological evaluation exhibited the most considerable deterioration within the first year and up to 5 years of function. Less change was detected during the next 10 years. The profilometrical quantification showed raising depth of the negative marginal ledges with a mean of 27.2µm (range 0.6-94.5µm) after 10 years, with no statistically significant changes from 5 to 10 and 10 to 15 years. The 3D-SEM revealed marginal grooves beneath the level of the ledges (mean 34.5µm after 5 years) within the bonding zone, exposing enamel margins. Leakages, marginal fractures and surface roughness did not seriously deteriorate the quality of restorations. CONCLUSIONS: Hybrid composite restorations of Class I and II cavities surviving the first five years performed well over 15 years of function. Quantitative 3D-SEM profilometrical measurements revealed the dynamics of marginal behaviour over time. CLINICAL SIGNIFICANCE: Long-term parallel clinical and micromorphological evaluation of posterior composite restorations of Class I and Class II cavities documented the clinical safety and acceptable longevity. The longitudinal 3D micromorphologic assessment of the surface changes and of the marginal behaviour revealed deteriorating as well as improving factors hidden in clinical performance.

Bonded resin sealant on smooth surface dental enamel--an in vitro study.

The aim of this study was to in vitro evaluate the micro leakage of a fissure sealant on sound and demineralized enamel using thermo cycling. The effect of the sealing procedure on sound and demineralized enamel were assessed on human premolars that were divided into one Control group and two Test groups. The Control group served as a baseline reference for the subsequent test procedures. The crowns of five teeth were covered with wax leaving three separate windows on the buccal surfaces. The enamel in one window was acid-etched, in the second window demineralized, and in the third window demineralized and subsequently acid-etched. In Test group 1, containing ten teeth, a defined enamel area on the buccal surfaces was acid-etched and sealed. The sealed area and a border of sound enamel around it were subjected to the demineralizing procedure. In Test group 2, a defined enamel window of 13 teeth was demineralized and subsequently etched and sealed. The sealed area and a border of surrounding enamel were subjected to a new cycle of demineralization. The longitudinal, bucco-lingual sections were examined in polarized light. When placed on acid-etched surfaces, the resin adhered firmly to the enamel with no evidence of demineralization or enlargement of previously demineralized areas underneath the sealants.

Influence of cementum on the demineralization and remineralization processes of root surface caries in vitro.

The influence of the nature of the root surface on the demineralization and remineralization processes within artificial fluoride-treated caries lesions was investigated using microscopic and X-ray microanalytical methods. Traces of fluoride were detected in the outer parts (about 25 micrometers) of the lesions after the application of fluorides, and a high mineral content was proved for the same region by means of microanalytical calcium estimation. The location of this mineral-rich band in relation to the root surface was deeper into the root depending on the existence and thickness of a cementum layer. However, within the dentine the location and intensity of the mineral content were unaffected by the cementum. Investigation of artificial caries lesions without fluoride treatment showed the following: The degree of mineralization was kept at a higher level near the root surface in the presence of cementum. Consequently, a cementum layer gives some initial caries resistance of the root surface.