Tuning Charge-Transfer States by Interface Electric Fields.

Intermolecular charge-transfer (CT) states are extended excitons with a charge separation on the nanometer scale. Through absorption and emission processes, they couple to the ground state. This property is employed both in light-emitting and light-absorbing devices. Their conception often relies on donor-acceptor (D-A) interfaces, so-called type-II heterojunctions, which usually generate significant electric fields. Several recent studies claim that these fields alter the energetic configuration of the CT states at the interface, an idea holding prospects like multicolor emission from a single emissive interface or shifting the absorption characteristics of a photodetector. Here, we test this hypothesis and contribute to the discussion by presenting a new model system. Through the fabrication of planar organic p-(i-)n junctions, we generate an ensemble of oriented CT states that allows the systematic assessment of electric field impacts. By increasing the thickness of the intrinsic layer at the D-A interface from 0 to 20 nm and by applying external voltages up to 6 V, we realize two different scenarios that controllably tune the intrinsic and extrinsic electric interface fields. By this, we obtain significant shifts of the CT-state peak emission of about 0.5 eV (170 nm from red to green color) from the same D-A material combination. This effect can be explained in a classical electrostatic picture, as the interface electric field alters the potential energy of the electric CT-state dipole. This study illustrates that CT-state energies can be tuned significantly if their electric dipoles are aligned to the interface electric field.

In-plane oxygen diffusion measurements in polymer films using time-resolved imaging of programmable luminescent tags.

Oxygen diffusion properties in thin polymer films are key parameters in industrial applications from food packaging, over medical encapsulation to organic semiconductor devices and have been continuously investigated in recent decades. The established methods have in common that they require complex pressure-sensitive setups or vacuum technology and usually do not come without surface effects. In contrast, this work provides a low-cost, precise and reliable method to determine the oxygen diffusion coefficient D in bulk polymer films based on tracking the phosphorescent pattern of a programmable luminescent tag over time. Our method exploits two-dimensional image analysis of oxygen-quenched organic room-temperature phosphors in a host polymer with high spatial accuracy. It avoids interface effects and accounts for the photoconsumption of oxygen. As a role model, the diffusion coefficients of polystyrene glasses with molecular weights between 13k and 350k g/mol are determined to be in the range of (0.8-1.5) × 10-7 cm2/s, which is in good agreement with previously reported values. We finally demonstrate the reduction of the oxygen diffusion coefficient in polystyrene by one quarter upon annealing above its glass transition temperature.

Accurate Wavelength Tracking by Exciton Spin Mixing.

Wavelength-discriminating systems typically consist of heavy benchtop-based instruments, comprising diffractive optics, moving parts, and adjacent detectors. For simple wavelength measurements, such as lab-on-chip light source calibration or laser wavelength tracking, which do not require polychromatic analysis and cannot handle bulky spectroscopy instruments, lightweight, easy-to-process, and flexible single-pixel devices are attracting increasing attention. Here, a device is proposed for monotonously transforming wavelength information into the time domain with room-temperature phosphorescence at the heart of its functionality, which demonstrates a resolution down to 1 nm and below. It is solution-processed from a single host-guest system comprising organic room-temperature phosphors and colloidal quantum dots. The share of excited triplet states within the photoluminescent layer is dependent on the excitation wavelength and determines the afterglow intensity of the film, which is tracked by a simple photodetector. Finally, an all-organic thin-film wavelength sensor and two applications are demonstrated where this novel measurement concept successfully replaces a full spectrometer.

Experimental proof of Joule heating-induced switched-back regions in OLEDs.

Organic light-emitting diodes (OLEDs) have become a major pixel technology in the display sector, with products spanning the entire range of current panel sizes. The ability to freely scale the active area to large and random surfaces paired with flexible substrates provides additional application scenarios for OLEDs in the general lighting, automotive, and signage sectors. These applications require higher brightness and, thus, current density operation compared to the specifications needed for general displays. As extended transparent electrodes pose a significant ohmic resistance, OLEDs suffering from Joule self-heating exhibit spatial inhomogeneities in electrical potential, current density, and hence luminance. In this article, we provide experimental proof of the theoretical prediction that OLEDs will display regions of decreasing luminance with increasing driving current. With a two-dimensional OLED model, we can conclude that these regions are switched back locally in voltage as well as current due to insufficient lateral thermal coupling. Experimentally, we demonstrate this effect in lab-scale devices and derive that it becomes more severe with increasing pixel size, which implies its significance for large-area, high-brightness use cases of OLEDs. Equally, these non-linear switching effects cannot be ignored with respect to the long-term operation and stability of OLEDs; in particular, they might be important for the understanding of sudden-death scenarios.

Highly Luminescent and Water-Resistant CsPbBr3-CsPb2Br5 Perovskite Nanocrystals Coordinated with Partially Hydrolyzed Poly(methyl methacrylate) and Polyethylenimine.

All inorganic lead halide perovskite nanocrystals (PNCs) typically suffer from poor stability against moisture and UV radiation as well as degradation during thermal treatment. The stability of PNCs can be significantly enhanced through polymer encapsulation, often accompanied by a decrease of photoluminescence quantum yield (PLQY) due to the loss of highly dynamic oleylamine/oleic acid (OLA/OA) ligands. Herein, we propose a solution for this problem by utilizing partially hydrolyzed poly(methyl methacrylate) (h-PMMA) and highly branched poly(ethylenimine) (b-PEI) as double ligands stabilizing the PNCs already during the mechanochemical synthesis (grinding). The hydrophobic polymer of h-PMMA imparts excellent film-forming properties and water stability to the resulting NC-polymer composite. In its own turn, the b-PEI forms an amino-rich, strongly binding ligand layer on the surface of the PNCs being responsible for the significant improvement of the PLQY and the stability of the resulting material. Moreover, the introduction of b-PEI promotes a partial phase conversion from CsPbBr3 to CsPb2Br5 to obtain CsPbBr3/CsPb2Br5 nanocrystals with a core-shell-like structure. As-prepared PNCs solutions are directly processable as inks, while their PLQY drops only slightly from 75% in colloidal solution to 65% in films. Moreover, the final PNC-polymer film exhibits excellent stability against water, heat, and ultraviolet light irradiation. These superior properties allowed us to fabricate a proof of concept thin film OLED with h-PMMA/b-PEI-stabilized PNCs as an easily processable, narrowly emitting color conversion composite material.

Simultaneous Singlet-Singlet and Triplet-Singlet Förster Resonance Energy Transfer from a Single Donor Material.

For almost 70 years, Förster resonance energy transfer (FRET) has been investigated, implemented into nowadays experimental nanoscience techniques, and considered in a manifold of optics, photonics, and optoelectronics applications. Here, we demonstrate for the first time simultaneous and efficient energy transfer from both donating singlet and triplet states of a single photoluminescent molecular species. Using a biluminescent donor that can emit with high yield from both excited states at room temperature allows application of the FRET framework to such a bimodal system. It serves as an exclusive model system where the spatial origin of energy transfer is exactly the same for both donating spin states involved. Of paramount significance are the facts that both transfers can easily be observed by eye and that Förster theory is successfully applied to state lifetimes spanning over 8 orders of magnitude.

A Silicon-Singlet Fission Tandem Solar Cell Exceeding 100% External Quantum Efficiency with High Spectral Stability.

After 60 years of research, silicon solar cell efficiency saturated close to the theoretical limit, and radically new approaches are needed to further improve the efficiency. The use of tandem systems raises this theoretical power conversion efficiency limit from 34% to 45%. We present the advantageous spectral stability of using voltage-matched tandem solar cells with respect to their traditional series-connected counterparts and experimentally demonstrate how singlet fission can be used to produce simple voltage-matched tandems. Our singlet fission silicon-pentacene tandem solar cell shows efficient photocurrent addition. This allows the tandem system to benefit from carrier multiplication and to produce an external quantum efficiency exceeding 100% at the main absorption peak of pentacene.