High-Brightness Blue Polariton Organic Light-Emitting Diodes.

Polariton organic light-emitting diodes (POLEDs) use strong light-matter coupling as an additional degree of freedom to tailor device characteristics, thus making them ideal candidates for many applications, such as room temperature laser diodes and high-color purity displays. However, achieving efficient formation of and emission from exciton-polaritons in an electrically driven device remains challenging due to the need for strong absorption, which often induces significant nonradiative recombination. Here, we investigate a novel POLED architecture to achieve polariton formation and high-brightness light emission. We utilize the blue-fluorescent emitter material 4,4'-Bis(4-(9H-carbazol-9-yl)styryl)biphenyl (BSBCz), which exhibits strong absorption and a highly horizontal transition-dipole orientation as well as a high photoluminescence quantum efficiency, even at high doping concentrations. We achieve a peak luminance of over 20,000 cd/m2 and external quantum efficiencies of more than 2%. To the best of our knowledge, these values represent the highest reported so far for electrically driven polariton emission from an organic semiconductor emitting in the blue region of the spectrum. Our work therefore paves the way for a new generation of efficient and powerful optoelectronic devices based on POLEDs.

Wireless magnetoelectrically powered organic light-emitting diodes.

Compact wireless light sources are a fundamental building block for applications ranging from wireless displays to optical implants. However, their realization remains challenging because of constraints in miniaturization and the integration of power harvesting and light-emission technologies. Here, we introduce a strategy for a compact wirelessly powered light-source that consists of a magnetoelectric transducer serving as power source and substrate and an antiparallel pair of custom-designed organic light-emitting diodes. The devices operate at low-frequency ac magnetic fields (~100 kHz), which has the added benefit of allowing operation multiple centimeters deep inside watery environments. By tuning the device resonance frequency, it is possible to separately address multiple devices, e.g., to produce light of distinct colors, to address individual display pixels, or for clustered operation. By simultaneously offering small size, individual addressing, and compatibility with challenging environments, our devices pave the way for a multitude of applications in wireless displays, deep tissue treatment, sensing, and imaging.

Orientation distributions of vacuum-deposited organic emitters revealed by single-molecule microscopy.

The orientation of luminescent molecules in organic light-emitting diodes strongly influences device performance. However, our understanding of the factors controlling emitter orientation is limited as current measurements only provide ensemble-averaged orientation values. Here, we use single-molecule imaging to measure the transition dipole orientation of individual emitter molecules in a state-of-the-art thermally evaporated host and thereby obtain complete orientation distributions of the hyperfluorescence-terminal emitter C545T. We achieve this by realizing ultra-low doping concentrations (10-6 wt%) of C545T and minimising background levels to reliably measure its photoluminescence. This approach yields the orientation distributions of >1000 individual emitter molecules in a system relevant to vacuum-processed devices. Analysis of solution- and vacuum-processed systems reveals that the orientation distributions strongly depend on the nanoscale environment of the emitter. This work opens the door to attaining unprecedented information on the factors that determine emitter orientation in current and future material systems for organic light-emitting devices.

High-Density Integration of Ultrabright OLEDs on a Miniaturized Needle-Shaped CMOS Backplane.

Direct deposition of organic light-emitting diodes (OLEDs) on silicon-based complementary metal-oxide-semiconductor (CMOS) chips has enabled self-emissive microdisplays with high resolution and fill-factor. Emerging applications of OLEDs in augmented and virtual reality (AR/VR) displays and in biomedical applications, e.g., as brain implants for cell-specific light delivery in optogenetics, require light intensities orders of magnitude above those found in traditional displays. Further requirements often include a microscopic device footprint, a specific shape and ultrastable passivation, e.g., to ensure biocompatibility and minimal invasiveness of OLED-based implants. In this work, up to 1024 ultrabright, microscopic OLEDs are deposited directly on needle-shaped CMOS chips. Transmission electron microscopy and energy-dispersive X-ray spectroscopy are performed on the foundry-provided aluminum contact pads of the CMOS chips to guide a systematic optimization of the contacts. Plasma treatment and implementation of silver interlayers lead to ohmic contact conditions and thus facilitate direct vacuum deposition of orange- and blue-emitting OLED stacks leading to micrometer-sized pixels on the chips. The electronics in each needle allow each pixel to switch individually. The OLED pixels generate a mean optical power density of 0.25 mW mm-2 , corresponding to >40 000 cd m-2 , well above the requirement for daylight AR applications and optogenetic single-unit activation in the brain.

Spectroscopic near-infrared photodetectors enabled by strong light-matter coupling in (6,5) single-walled carbon nanotubes.

Strong light-matter coupling leads to the formation of mixed exciton-polariton states, allowing for a rigorous manipulation of the absorption and emission of excitonic materials. Here, we demonstrate the realization of this promising concept in organic photodetectors. By hybridizing the E11 exciton of semiconducting (6,5) single-walled carbon nanotubes (SWNTs) with near-infrared cavity photons, we create spectrally tunable polariton states within a photodiode. In turn, we are able to red-shift the detection peak that coincides with the lower polariton band. Our photodiodes comprise a metal cavity to mediate strong coupling between light and SWNTs and utilize P3HT and PC70BM as the electron donor and acceptor, respectively. The diodes are formed either via mixing of SWNTs, P3HT, and PC70BM to create a bulk heterojunction or by sequential processing of layers to form flat heterojunctions. The resulting near-infrared sensors show tunable, efficient exciton harvesting in an application-relevant wavelength range between 1000 nm and 1300 nm, with optical simulations showing a possible extension beyond 1500 nm.

Tetrapodal Diazatriptycene Enforces Orthogonal Orientation in Self-Assembled Monolayers.

Conformationally rigid multipodal molecules should control the orientation and packing density of functional head groups upon self-assembly on solid supports. Common tripods frequently fail in this regard because of inhomogeneous bonding configuration and stochastic orientation. These issues are circumvented by a suitable tetrapodal diazatriptycene moiety, bearing four thiol-anchoring groups, as demonstrated in the present study. Such molecules form well-defined self-assembled monolayers (SAMs) on Au(111) substrates, whereby the tetrapodal scaffold enforces a nearly upright orientation of the terminal head group with respect to the substrate, with at least three of the four anchoring groups providing thiolate-like covalent attachment to the surface. Functionalization by condensation chemistry allows a large variety of functional head groups to be introduced to the tetrapod, paving the path toward advanced surface engineering and sensor fabrication.

Structure-Property Relationship of Phenylene-Based Self-Assembled Monolayers for Record Low Work Function of Indium Tin Oxide.

Studying the structure-property relations of tailored dipolar phenyl and biphenylphosphonic acids, we report self-assembled monolayers with a significant decrease in the work function (WF) of indium-tin oxide (ITO) electrodes. Whereas the strengths of the dipoles are varied through the different molecular lengths and the introduction of electron-withdrawing fluorine atoms, the surface energy is kept constant through the electron-donating N, N-dimethylamine head groups. The self-assembled monolayer formation and its modification of the electrodes are investigated via infrared reflection absorption spectroscopy, contact angle measurements, and photoelectron spectroscopy. The WF decrease in ITO correlates with increasing molecular dipoles. The lowest ever recorded WF of 3.7 eV is achieved with the fluorinated biphenylphosphonic acid.

Functionalized Nickel Oxide Hole Contact Layers: Work Function versus Conductivity.

Nickel oxide (NiO) is a widely used material for efficient hole extraction in optoelectronic devices. However, its surface characteristics strongly depend on the processing history and exposure to adsorbates. To achieve controllability of the electronic and chemical properties of solution-processed nickel oxide (sNiO), we functionalize its surface with a self-assembled monolayer (SAM) of 4-cyanophenylphosphonic acid. A detailed analysis of infrared and photoelectron spectroscopy shows the chemisorption of the molecules with a nominal layer thickness of around one monolayer and gives an insight into the chemical composition of the SAM. Density functional theory calculations reveal the possible binding configurations. By the application of the SAM, we increase the sNiO work function by up to 0.8 eV. When incorporated in organic solar cells, the increase in work function and improved energy level alignment to the donor does not lead to a higher fill factor of these cells. Instead, we observe the formation of a transport barrier, which can be reduced by increasing the conductivity of the sNiO through doping with copper oxide. We conclude that the widespread assumption of maximizing the fill factor by only matching the work function of the oxide charge extraction layer with the energy levels in the active material is a too narrow approach. Successful implementation of interface modifiers is only possible with a sufficiently high charge carrier concentration in the oxide interlayer to support efficient charge transfer across the interface.

Naphthalene Tetracarboxydiimide-Based n-Type Polymers with Removable Solubility via Thermally Cleavable Side Chains.

Multilayer solution-processed devices in organic electronics show the tendency of intermixing of subsequently deposited layers. Here, we synthesize naphthalene tetracarboxydiimide (NDI)-based n-type semiconducting polymers with thermally cleavable side chains which upon removal render the polymer insoluble. Infrared and photoelectron spectroscopy were performed to investigate the pyrolysis process. Characterization of organic field-effect transistors provides insight into charge transport. After the pyrolysis homogeneous films could be produced which are insoluble in the primary solvent. By varying curing temperature and time we show that these process parameters govern the amount of side chains in the film and influence the device performance.

Dipolar SAMs Reduce Charge Carrier Injection Barriers in n-Channel Organic Field Effect Transistors.

In this work we examine small conjugated molecules bearing a thiol headgroup as self assembled monolayers (SAM). Functional groups in the SAM-active molecule shift the work function of gold to n-channel semiconductor regimes and improve the wettability of the surface. We examine the effect of the presence of methylene linkers on the orientation of the molecule within the SAM. 3,4,5-Trimethoxythiophenol (TMP-SH) and 3,4,5-trimethoxybenzylthiol (TMP-CH2-SH) were first subjected to computational analysis, predicting work function shifts of -430 and -310 meV. Contact angle measurements show an increase in the wetting envelope compared to that of pristine gold. Infrared (IR) measurements show tilt angles of 22 and 63°, with the methylene-linked molecule (TMP-CH2-SH) attaining a flatter orientation. The actual work function shift as measured with photoemission spectroscopy (XPS/UPS) is even larger, -600 and -430 meV, respectively. The contact resistance between gold electrodes and poly[N,N'-bis(2-octyldodecyl)-naphthalene-1,4:5,8-bis(dicarboximide)-2,6-diyl]-alt-5,5'-(2,2'-bithiophene) (Polyera Aktive Ink, N2200) in n-type OFETs is demonstrated to decrease by 3 orders of magnitude due to the use of TMP-SH and TMP-CH2-SH. The effective mobility was enhanced by two orders of magnitude, significantly decreasing the contact resistance to match the mobilities reported for N2200 with optimized electrodes.

Radiation induced chromatin conformation changes analysed by fluorescent localization microscopy, statistical physics, and graph theory.

It has been well established that the architecture of chromatin in cell nuclei is not random but functionally correlated. Chromatin damage caused by ionizing radiation raises complex repair machineries. This is accompanied by local chromatin rearrangements and structural changes which may for instance improve the accessibility of damaged sites for repair protein complexes. Using stably transfected HeLa cells expressing either green fluorescent protein (GFP) labelled histone H2B or yellow fluorescent protein (YFP) labelled histone H2A, we investigated the positioning of individual histone proteins in cell nuclei by means of high resolution localization microscopy (Spectral Position Determination Microscopy = SPDM). The cells were exposed to ionizing radiation of different doses and aliquots were fixed after different repair times for SPDM imaging. In addition to the repair dependent histone protein pattern, the positioning of antibodies specific for heterochromatin and euchromatin was separately recorded by SPDM. The present paper aims to provide a quantitative description of structural changes of chromatin after irradiation and during repair. It introduces a novel approach to analyse SPDM images by means of statistical physics and graph theory. The method is based on the calculation of the radial distribution functions as well as edge length distributions for graphs defined by a triangulation of the marker positions. The obtained results show that through the cell nucleus the different chromatin re-arrangements as detected by the fluorescent nucleosomal pattern average themselves. In contrast heterochromatic regions alone indicate a relaxation after radiation exposure and re-condensation during repair whereas euchromatin seemed to be unaffected or behave contrarily. SPDM in combination with the analysis techniques applied allows the systematic elucidation of chromatin re-arrangements after irradiation and during repair, if selected sub-regions of nuclei are investigated.

Processing follows function: pushing the formation of self-assembled monolayers to high-throughput compatible time scales.

Self-assembled monolayers (SAMs) of organic molecules can be used to tune interface energetics and thereby improve charge carrier injection at metal-semiconductor contacts. We investigate the compatibility of SAM formation with high-throughput processing techniques. Therefore, we examine the quality of SAMs, in terms of work function shift and chemical composition as measured with photoelectron and infrared spectroscopy and in dependency on molecular exposure during SAM formation. The functionality of the SAMs is determined by the performance increase of organic field-effect transistors upon SAM treatment of the source/drain contacts. This combined analytical and device-based approach enables us to minimize the necessary formation times via an optimization of the deposition conditions. Our findings demonstrate that SAMs composed of partially fluorinated alkanethiols can be prepared in ambient atmosphere from ethanol solution using immersion times as short as 5 s and still exhibit almost full charge injection functionality if process parameters are chosen carefully. This renders solution-processed SAMs compatible with high-throughput solution-based deposition techniques.