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E. W. Meijer

Publications and source records attributed to E. W. Meijer.

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Dispersion Control of Chiral Exciton-Polariton Transport with Dielectric Metasurfaces

Exciton-polaritons provide a powerful platform for manipulating hybrid light-matter states with low effective masses and strong nonlinearities. Introducing chirality into these quasiparticles enables selective control over their spin and propagation, opening new opportunities for chiral transport and spin-selective polaritonic devices. We exploit the strong chiral light-matter coupling in silicon metasurfaces composed of tilted nanorod dimers to demonstrate selective transport of organic chiral exciton-polaritons. The metasurface supports surface lattice resonances and quasi-bound states in the continuum that simultaneously provide high photonic confinement and extrinsic chirality, giving rise to chiral exciton-polaritons in the achiral molecules. These exciton-polaritons exhibit a large magnitude of the dissymmetry factor, reaching a value of 0.93. Using photoluminescence Fourier microscopy and real-space imaging, we show that chiral exciton-polaritons propagate over distances exceeding 50 um without significant degradation of their dissymmetry, with characteristic propagation lengths of approximately 6-13 um. These propagation lengths correspond to an enhancement of 3 orders of magnitude compared to bare excitons. This work constitutes the first demonstration of enhanced and selective chiral transport of organic exciton-polaritons, driven by strong light-matter coupling, in achiral metasurfaces, paving the way for spin-selective polaritonic technologies using simple metasurfaces.

physics.optics

Control of Electrons Spin Eliminates Hydrogen Peroxide Formation During Water Splitting

The production of hydrogen through water splitting in a photoelectrochemical cell suffers from an overpotential that limits the efficiencies. In addition, hydrogen-peroxide formation is identified as a competing process affecting the oxidative stability of photoelectrodes. We impose spin-selectivity by coating the anode with chiral organic semiconductors from helically-aggregated dyes as sensitizers; Zn-porphyrins and triarylamines. Hydrogen peroxide formation is dramatically suppressed, while the overall current through the cell, correlating with the water splitting process, is enhanced. Evidence for a strong spin-selection in the chiral semiconductors is presented by magnetic conducting (mc-)AFM measurements, where chiral and achiral Zn-porphyrins are compared. These findings contribute to our understanding of the underlying mechanism of spin selectivity in multiple electron-transfer reactions and pave the way towards better chiral dye-sensitized photoelectrochemical cells.

physics.chem-ph

Circularly polarised electroluminescence from chiral excitons in vacuum-sublimed supramolecular semiconductor thin films

Materials with chiral electronic structures are of great interest. We report a triazatruxene, TAT, molecular semiconductor with chiral alkyl side chains that crystallises from solution to form chirally-stacked columns with a helical pitch of 6 TATs (2.3 nm). These crystals show strong circularly polarised, CP, green photoluminescence, with dissymmetry of 24%. Electronic structure calculations using the full crystal structure, show that this chiral stacking associates angular momentum to the valence and conduction states and thus gives rise to the observed CP luminescence. Free-standing crystals are not useful for active semiconductor devices, but we have discovered that co-sublimation of TAT as the guest in a structurally mismatched host enables the fabrication of thin films where the chiral crystallization is achieved in-situ by thermally-triggered nano-phase segregation of dopant and host whilst preserving the integrity of the film. This enables fabrication of bright (green) organic light-emitting diodes with unexpectedly high external quantum efficiencies of up to 16% and electroluminescence dissymmetries above 10%. These materials and this process method offer significant application potential in spintronics, optical displays and multidimensional optoelectronics.

cond-mat.mtrl-sci

Polaritonic Chemistry Enabled by Non-Local Metasurfaces

Vibrational strong coupling can modify chemical reaction pathways in unconventional ways. Thus far, Fabry-Perot cavities formed by pairs of facing mirrors have been mostly utilized to achieve vibrational strong coupling. In this study, we demonstrate the application of plasmonic microparticle arrays defining non-local metasurfaces that can sustain surface lattice resonances as a novel tool to enable chemical reactions under vibrational strong coupling. We show that the solvolysis kinetics of \textit{para}-nitrophenyl acetate can be accelerated by a factor of 2.7 by strong coupling to the carbonyl bond of the solvent and the solute with a surface lattice resonance. Our work introduces a new platform to investigate and control polaritonic chemical reactions. In contrast to Fabry-Perot cavities, metasurfaces define open optical cavities with single surfaces, which removes alignment hurdles, facilitating polaritonic chemistry across large areas.

physics.chem-ph

Charge transport modulation by a redox supramolecular spin-filtering chiral crystal

The chirality induced spin selectivity (CISS) effect is a fascinating phenomena correlating molecular structure with electron spin-polarisation in excited state measurements. Experimental procedures to quantify the spin-filtering magnitude relies generally on averaging data sets, especially those from magnetic field dependent conductive-AFM. We investigate the underlying observed disorder in the IV spectra and the origin of spikes superimposed. We demonstrate and explain that a dynamic, voltage sweep rate dependent, phenomena can give rise to complex IV curves for chiral crystals of coronene bisimide. The redox group, able to capture localized charge states, acts as an impurity state interfering with a continuum, giving rise to Fano resonances. We introduce a novel mechanism for the dynamic transport which might also provide insight into the role of spin-polarization. Crucially, interference between charge localisation and delocalisation during transport may be important properties into understanding the CISS phenomena.

cond-mat.mtrl-sci

Mesoscopic order and the dimentionality of long-range resonance energy transfer in supramolecular semiconductors

We present time-resolved photoluminescence measurements on two series of oligo-p-phenylenevinylene materials that self-assemble into supramolecular nanostructures with thermotropic reversibility in dodecane. One set of derivatives form chiral, helical stacks while the second set form less organised, frustrated stacks. Here we study the effects of supramolecular organisation on the resonance energy transfer rates. We measure these rates in nanoassemblies formed with mixed blends of oligomers and compare them with the rates predicted by Foerster theory. Our results and analysis show that control of supramolecular order in the nanometre lengthscale has a dominant effect on the efficiency and dimentionality of resonance energy transfer.

cond-mat.mtrl-sci

Anharmonic magnetic deformation of self-assembled molecular nanocapsules

High magnetic fields were used to deform spherical nanocapsules, self-assembled from bola-amphiphilic sexithiophene molecules. At low fields the deformation -- measured through linear birefringence -- scales quadratically with the capsule radius and with the magnetic field strength. These data confirm a long standing theoretical prediction (W. Helfrich, Phys. Lett. {\bf 43A}, 409 (1973)), and permits the determination of the bending rigidity of the capsules as (2.6$\pm$0.8)$\times 10^{-21}$ J. At high fields, an enhanced rigidity is found which cannot be explained within the Helfrich model. We propose a complete form of the free energy functional that accounts for this behaviour, and allows discussion of the formation and stability of nanocapsules in solution.

cond-mat.soft

Exciton bimolecular annihilation dynamics in supramolecular nanostructures of conjugated oligomers

We present femtosecond transient absorption measurements on $π$-conjugated supramolecular assemblies in a high pump fluence regime. Oligo(\emph{p}-phenylenevinylene) monofunctionalized with ureido-\emph{s}-triazine (MOPV) self-assembles into chiral stacks in dodecane solution below 75$^{\circ}$C at a concentration of $4\times 10^{-4}$ M. We observe exciton bimolecular annihilation in MOPV stacks at high excitation fluence, indicated by the fluence-dependent decay of $1^1$B$_{u}$-exciton spectral signatures, and by the sub-linear fluence dependence of time- and wavelength-integrated photoluminescence (PL) intensity. These two characteristics are much less pronounced in MOPV solution where the phase equilibrium is shifted significantly away from supramolecular assembly, slightly below the transition temperature. A mesoscopic rate-equation model is applied to extract the bimolecular annihilation rate constant from the excitation fluence dependence of transient absorption and PL signals. The results demonstrate that the bimolecular annihilation rate is very high with a square-root dependence in time. The exciton annihilation results from a combination of fast exciton diffusion and resonance energy transfer. The supramolecular nanostructures studied here have electronic properties that are intermediate between molecular aggregates and polymeric semiconductors.

cond-mat.soft