Electronic Structure of Organic Semiconductor Multi-Heterojunctions

Master'sMASTER OF SCIENC

Proximity control of interlayer exciton-phonon hybridization in van der Waals heterostructures

Van der Waals stacking has provided unprecedented flexibility in shaping many-body interactions by controlling electronic quantum confinement and orbital overlap. Theory has predicted that also electron-phonon coupling critically influences the quantum ground state of low-dimensional systems. Here we introduce proximity-controlled strong-coupling between Coulomb correlations and lattice dynamics in neighbouring van der Waals materials, creating new electrically neutral hybrid eigenmodes. Specifically, we explore how the internal orbital 1s-2p transition of Coulomb-bound electron-hole pairs in monolayer tungsten diselenide resonantly hybridizes with lattice vibrations of a polar capping layer of gypsum, giving rise to exciton-phonon mixed eigenmodes, called excitonic Lyman polarons. Tuning orbital exciton resonances across the vibrational resonances, we observe distinct anticrossing and polarons with adjustable exciton and phonon compositions. Such proximity-induced hybridization can be further controlled by quantum designing the spatial wavefunction overlap of excitons and phonons, providing a promising new strategy to engineer novel ground states of two-dimensional systems. Here, the authors demonstrate proximity-controlled strong-coupling between Coulomb correlations and lattice dynamics in neighbouring van der Waals materials (WSe2 and a gypsum layer), creating electrically neutral hybrid exciton-phonon eigenmodes called excitonic Lyman polarons

Twist-tailoring Coulomb correlations in van der Waals homobilayers

The recent discovery of artificial phase transitions induced by stacking monolayer materials at magic twist angles represents a paradigm shift for solid state physics. Twist-induced changes of the single-particle band structure have been studied extensively, yet a precise understanding of the underlying Coulomb correlations has remained challenging. Here we reveal in experiment and theory, how the twist angle alone affects the Coulomb-induced internal structure and mutual interactions of excitons. In homobilayers of WSe2, we trace the internal 1s-2p resonance of excitons with phase-locked mid-infrared pulses as a function of the twist angle. Remarkably, the exciton binding energy is renormalized by up to a factor of two, their lifetime exhibits an enhancement by more than an order of magnitude, and the exciton-exciton interaction is widely tunable. Our work opens the possibility of tailoring quasiparticles in search of unexplored phases of matter in a broad range of van der Waals heterostructures. The crystallographic orientation of monolayers in van der Waals multi-layers controls their electronic and optical properties. Here the authors show how the twist angle affects Coulomb correlations governing the internal structure and the mutual interaction of excitons in homobilayers of WSe2

Decoupling Charge Transport and Electroluminescence in a High Mobility Polymer Semiconductor.

Fluorescence enhancement of a high-mobility polymer semiconductor is achieved via energy transfer to a higher fluorescence quantum yield squaraine dye molecule on 50 ps timescales. In organic light-emitting diodes, an order of magnitude enhancement of the external quantum efficiency is observed without reduction in the charge-carrier mobility resulting in radiances of up to 5 W str(-1) m(-2) at 800 nm.We gratefully acknowledge funding from the Engineering and Physical Sciences Research Council (EPSRC) through a programme grant EP/M005143/1. We would like to thank the Doctoral Training Centre in Plastic Electronics EP/G037515/1. K. B. acknowledges financial support by the Deutsche Forschungsgemeinschaft (BR-4869/1-1). The group at Würzburg would like to acknowledge support from the Deutsche Forschungsgemeinschaft (DFG Research Unit FOR 1809) and from the SolTech Initiative of the Bavarian State Ministry of Science, Research and the Arts. D. H. and K.B. would like to thank Dr. Jiři Novak and Jakub Rozbořil (Central European Institute of Technology, Masaryk University, Czech Republic) and Dr. Tom Arnold (Diamond Light Source, Didcot, UK) for assistance during the synchrotron experiment and Diamond Light Source, Didcot, UK for financial support

Valley-dependent Exciton Fine Structure and Autler-Townes Doublets from Berry Phases in Monolayer Molybdenum Diselenide

The Berry phase of Bloch states can have profound effects on electron dynamics lead to novel transport phenomena, such as the anomalous Hall effect and the valley Hall effect. Recently, it was predicted that the Berry phase effect can also modify the exciton states in transition metal dichalcogenide monolayers, and lift the energy degeneracy of exciton states with opposite angular momentum through an effective valley-orbital coupling. Here, we report the first observation and control of the Berry-phase induced splitting of the 2p-exciton states in monolayer molybdenum diselenide using the intraexciton optical Stark spectroscopy. We observe the time-reversal-symmetric analog of the orbital Zeeman effect resulting from the valley-dependent Berry phase, which leads to energy difference of +14 (-14) meV between the $2p^+$ and $2p^-$ exciton states in +K (-K) valley, consistent with the ordering from our ab initio GW-BSE results. In addition, we show that the light-matter coupling between intraexciton states are remarkably strong, leading to prominent valley-dependent Autler-Townes doublet under resonant driving. Our study opens up new pathways to coherently manipulate the quantum states and excitonic excitation with infrared radiation in two-dimensional semiconductors

Ultrafast carrier dynamics in organic-inorganic semiconductor nanostructures

This thesis is concerned with the influence of nanoscale boundaries and interfaces upon the electronic processes that occur within the inorganic semiconductors. Inorganic semiconductor nanowires and their blends with semiconducting polymers have been investigated using state-of-the-art ultrafast optical techniques to provide information on the sub-picosecond to nanosecond photoexcitation dynamics in these systems. Chapters 1 and 2 introduce the theory and background behind the work and present a literature review of previous work utilising nanowires in hybrid organic photovoltaic devices, revealing the performances to date. The experimental methods used during the thesis are detailed in Chapter 3. Chapter 4 describes the crucial roles of surface passivation on the ultrafast dynamics of exciton formation in gallium arsenide (GaAs) nanowires. By passivating the surface states of nanowires, exciton formation via the bimolecular conversion of electron-hole plasma can observed over few hundred picoseconds, in-contrast to the fast carrier trapping in 10 ps observed in the uncoated nanowires. Chapter 5 presents a novel method to passivate the surface-states of GaAs nanowires using semiconducting polymer. The carrier lifetime in the nanowires can be strongly enhanced when the ionization potential of the overcoated semiconducting polymer is smaller than the work function of the nanowires and the surface native oxide layers of nanowires are removed. Finally, Chapter 6 shows that the carrier cooling in the type-II wurtzite-zincblend InP nanowires is reduced by order-of magnitude during the spatial charge-transfer across the type-II heterojunction. The works decribed in this thesis reveals the crucial role of surface-states and bulk defects on the carrier dynamics of semiconductor nanowires. In-addition, a novel approach to passivate the surface defect states of nanowires using semiconducting polymers was developed.</p

Ultrafast carrier dynamics in organic-inorganic semiconductor nanostructures

This thesis is concerned with the influence of nanoscale boundaries and interfaces upon the electronic processes that occur within the inorganic semiconductors. Inorganic semiconductor nanowires and their blends with semiconducting polymers have been investigated using state-of-the-art ultrafast optical techniques to provide information on the sub-picosecond to nanosecond photoexcitation dynamics in these systems. Chapters 1 and 2 introduce the theory and background behind the work and present a literature review of previous work utilising nanowires in hybrid organic photovoltaic devices, revealing the performances to date. The experimental methods used during the thesis are detailed in Chapter 3. Chapter 4 describes the crucial roles of surface passivation on the ultrafast dynamics of exciton formation in gallium arsenide (GaAs) nanowires. By passivating the surface states of nanowires, exciton formation via the bimolecular conversion of electron-hole plasma can observed over few hundred picoseconds, in-contrast to the fast carrier trapping in 10 ps observed in the uncoated nanowires. Chapter 5 presents a novel method to passivate the surface-states of GaAs nanowires using semiconducting polymer. The carrier lifetime in the nanowires can be strongly enhanced when the ionization potential of the overcoated semiconducting polymer is smaller than the work function of the nanowires and the surface native oxide layers of nanowires are removed. Finally, Chapter 6 shows that the carrier cooling in the type-II wurtzite-zincblend InP nanowires is reduced by order-of magnitude during the spatial charge-transfer across the type-II heterojunction. The works decribed in this thesis reveals the crucial role of surface-states and bulk defects on the carrier dynamics of semiconductor nanowires. In-addition, a novel approach to passivate the surface defect states of nanowires using semiconducting polymers was developed.This thesis is not currently available in ORA