The Exciton Model for Molecular Materials:Past, Present and Future?

In assemblies of identical molecules or chromophores, electronic excitations can be described as excitons, bound electron-hole pairs that can move from site to site as a pair in a coherent manner. The understanding of excitons is crucial when trying to engineer favorable photophysical properties through structuring organic molecular matter. In recent decades, limitations of the concept of an exciton have become clear. The exciton can hybridize with phonon and photons. To clarify these issues, the exciton is discussed within the broader context of the gauge properties of the electromagnetic force.</p

Programming and Dynamic Control of the Circular Polarization of Luminescence from an Achiral Fluorescent Dye in a Liquid Crystal Host by Molecular Motors

Circular polarized light is utilized in communication and display technologies and a major challenge is to develop systems that can be switched between left and right circular polarized luminescence with high degrees of polarization and enable multiple addressable stable states. Luminescent dyes in Liquid Crystal (LC) cholesteric phases are attractive systems to generate, amplify and modulate circularly polarized luminescence (CPL). In the present study, we employ light‐driven molecular motors as photo‐controlled chiral dopants in LCs to switch the handedness of the LC and the circular polarization of luminescence from an achiral dye embedded in the mesogenic material. Tuning of the color of the CPL and the retention time of the photoprogrammed helicity is demonstrated making use of a variety of motors and dyes. The flexibility offered by the design based on inherently chiral unidirectional rotary motors provides full control over CPL non‐invasively by light, opening possibilities for pixilated displays with externally addressable polarization

Resistive Switching in Metal Oxide/Organic Semiconductor Nonvolatile Memories

Diodes incorporating a bilayer of a metal oxide and an organic semiconductor can show unipolar, nonvolatile memory behavior after electroforming. Electroforming involves dielectric breakdown induced by prolonged bias voltage stress. When the power dissipated during breakdown is limited, electroforming is reversible and involves formation of defects at the organic-oxide interface that can heal spontaneously. When the power dissipation during breakdown exceeds a certain threshold, electroforming becomes irreversible. The fully electroformed diodes show electrical bistability, featuring (meta)stable states with low and high conduction that can be programmed by voltage pulses. The high conduction results from current flowing via filamentary paths. The bistability is explained by the coexistence of two thermodynamically stable phases at the interface between semiconductor and oxide. One phase contains mainly ionized defects and has a low work function, while the other phase has mainly neutral defects and a high work function. In the diodes, domains of the phase with low work function give rise to current filaments. In the filaments, Joule heating will raise temperature locally. When the temperature exceeds the critical temperature, the filament will switch off. The switching involves a collective recombination of charge carriers trapped at the defects as evidenced by bursts of electroluminescence

Stimuli-Responsive Nanostructured Viologen-Siloxane Materials for Controllable Conductivity

Spontaneous phase separation is a promising strategy for the development of novel electronic materials, as the resulting well-defined morphologies generally exhibit enhanced conductivity. Making these structures adaptive to external stimuli is challenging, yet crucial as multistate reconfigurable switching is essential for neuromorphic materials. Here, a modular and scalable approach is presented to obtain switchable phase-separated viologen-siloxane nanostructures with sub-5 nm features. The domain spacing, morphology, and conductivity of these materials can be tuned by ion exchange, repeated pulsed photoirradiation and electric stimulation. Counterion exchange triggers a postsynthetic modification in domain spacing of up to 10%. Additionally, in some cases, 2D to 1D order–order transitions are observed with the latter exhibiting a sevenfold decrease in conductivity with respect to their 2D lamellar counterparts. Moreover, the combination of the viologen core with tetraphenylborate counterions enables reversible and in situ reduction upon light irradiation. This light-driven reduction provides access to a continuum of conducting states, reminiscent of long-term potentiation. The repeated voltage sweeps improve the nanostructures alignment, leading to increased conductivity in a learning effect. Overall, these results highlight the adaptivity of phase-separated nanostructures for the next generation of organic electronics, with exciting applications in smart sensors and neuromorphic devices.</p

Circular Polarization of Luminescence as a Tool To Study Molecular Dynamical Processes

Circular polarization of luminescence is a phenomenon that can be observed for chiral molecules in isotropic solution, for molecular aggregates and molecular materials. Also, the electroluminescence from chiral molecular materials in organic light emitting diodes can be nearly completely circularly polarized. In this review we focus on the latest developments in experimental results for the categories listed above. A unifying description of the origin of the circular polarization is still missing. We revisit the very earliest efforts to measure and understand circular polarization in light emission in order to better understand the present day confusion on the origins of the polarization. It seems that quantum field theory of electromagnetic interactions could provide leads for a comprehensive description of the circular polarization including contributions from helicity at all possible length scales from the molecular to the macroscopic

Consequences of chirality on the response of materials

Chirality refers to the absence of a mirror image related symmetry in objects, materials and molecules. As a consequence of the absence of these symmetry elements, chiral materials show a number of properties and effects which are forbidden in achiral materials. Here we review new optical, optoelectronic and mechanical properties that chiral materials can have but are not allowed in mirror symmetric compounds. In particular, we investigate out-of-equilibrium systems where spatial and time-inversion symmetry provides a framework to understand and control electronic transport and molecular rotational motion

Polaritons in a Polycrystalline Layer of Non-fullerene Acceptor

Non-fullerene acceptor molecules developed for organic solar cells feature a very intense absorption band in the near-infrared. In the solid phase, the strong interaction between light and the transition dipole moment for molecular excitation should induce formation of polaritons. The reflection spectra for polycrystalline films of a non-fullerene acceptor with a thienothienopyrrolo-thienothienoindole core of the so-called Y6 type indeed show a signature of polaritons. A local minimum in the middle of the reflection band is associated with the allowed molecular transition. The minimum in reflection allows efficient entry of light into the solid, resulting in a local maximum in external quantum efficiency of a photovoltaic cell made of the pure acceptor

Semi-Transparent, Chiral Organic Photodiodes with Incident Direction-Dependent Selectivity for Circularly Polarized Light

Detection of the circular polarization of light is possible using chiral semiconductors, yet the mechanisms remain poorly understood. Semi-transparent chiral photodiodes allow for a simple experiment to investigate the basis of their selectivity: changing the side from which the diode is illuminated. A reversal of circular selectivity is observed in photocurrent generation when changing the direction of illumination on organic, bulk-heterojunction cells. The change in selectivity can be explained by a space-charge limitation on the collection of photocarriers in combination with preferential absorption of one of the circular polarizations of near-infrared light by the chiral non-fullerene acceptor. The space-charge limitation is supported by detailed measurements of frequency and intensity dependence of dc and ac photocurrents

Electronic memory effects in zinc oxide nanoparticle -polystyrene devices with a calcium top electrode

Diodes with an active layer of solution processed zinc oxide (ZnO) nanoparticles and polystyrene are studied. Poly(3,4-ethylenedioxythiophene)- polystyrenesulfonate (PEDOT:PSS) on indium doped tin oxide (ITO) is used as the bottom electrode and aluminum or calcium are used as top electrode. Pristine devices show diode behavior in their current-voltage characteristics. The conductivity of the device in reverse bias can be raised three orders of magnitude by applying a positive voltage or by illumination with UV light. In this high conductivity state we observe reversible electronic memory effects. The electronic memory effects are attributed to a reversible electrochemical process at the PEDOT:PSS/ZnO interface. Memory effects in diodes with Al and Ca metal electrode are found to be very similar, consistent with the view that the memory effects arise at the PEDOT:PSS/ZnO interface.</p

Application of circularly polarized luminescence spectroscopy to the solution structure of racemic polyaminocarboxylate lanthanide (III) complexes

Circularly polarized luminescence from 1:1 complexes of Eu(III) with triethylenetetra-aminehexaacetic acid (TTHA) following excitation with circularly polarized light is reported. This observation is consistent with a solution structure for this complex that is chiral, and stable on the emission time scale of Eu(III) (approximately 1.2ms). Additional measurements show only a slight dependence on temperature, and an estimate for the activation energy for racemization (23 kcal/mol) may be obtained. Attempts at detecting enantio-selective quenching of Tb(TTHA)3- by optically active Ru(phen)2+3 are also reported. Although significant quenching was observed, and the time-decay of the Tb(III) emission was not mono-exponential, no enantio-selectivity was found. This latter result may be interpreted in terms of the lack of discriminating short-range diastereomeric interactions between the chiral ion pairs. © 1994