Super-transport of Excitons in Atomically Thin Organic Semiconductors at the 2D Quantum Limit
Ankur Sharma, Linglong Zhang, Jonathan O. Tollerud, Miheng Dong, Yi Zhu, Robert Halbich, Tobias Vogl, Kun Liang, Hieu T. Nguyen, Fan Wang, Shilpa Sanwlani, Stua… 展开作者
Ankur Sharma, Linglong Zhang, Jonathan O. Tollerud, Miheng Dong, Yi Zhu, Robert Halbich, Tobias Vogl, Kun Liang, Hieu T. Nguyen, Fan Wang, Shilpa Sanwlani, Stuart K. Earl, Daniel Macdonald, Ping Koy Lam, Jeff A. Davis, Yuerui Lu
Long-range and fast transport of coherent excitons is important for development of high-speed excitonic circuits and quantum computing applications. However, most of these coherent excitons have only been observed in some low-dimensional semiconductors when coupled with cavities, as there are large inhomogeneous broadening and dephasing effects on the exciton transport in their native states of the materials. Here, by confining coherent excitons at the 2D quantum limit, we firstly observed molecular aggregation enabled super-transport of excitons in atomically thin two-dimensional (2D) organic semiconductors between coherent states, with a measured a high effective exciton diffusion coefficient of 346.9 cm2/sec at room temperature. This value is one to several orders of magnitude higher than the reported values from other organic molecular aggregates and low-dimensional inorganic materials. Without coupling to any optical cavities, the monolayer pentacene sample, a very clean 2D quantum system (1.2 nm thick) with high crystallinity (J type aggregation) and minimal interfacial states, showed superradiant emissions from the Frenkel excitons, which was experimentally confirmed by the temperature-dependent photoluminescence (PL) emission, highly enhanced radiative decay rate, significantly narrowed PL peak width and strongly directional in-plane emission. The coherence in monolayer pentacene samples was observed to be delocalized over 135 molecules, which is significantly larger than the values (a few molecules) observed from other organic thin films. In addition, the super-transport of excitons in monolayer pentacene samples showed highly anisotropic behaviour. Our results pave the way for the development of future high-speed excitonic circuits, fast OLEDs, and other opto-electronic devices.
Resolving the momentum degree of freedom of excitons - electron-hole pairs bound by the Coulomb attraction in a photoexcited semiconductor, has remained a largely elusive goal for decades. In atomically thin semiconductors, such a capability could probe the momentum forbidden dark excitons, which critically impact proposed opto-electronic technologies, but are not directly accessible via optical techniques. Here, we probe the momentum-state of excitons in a WSe2 monolayer by photoemitting their constituent electrons, and resolving them in time, momentum and energy. We obtain a direct visual of…
Atomically thin layers of transition metal dichalcogenides (TMDCs) exhibit exceptionally strong Coulomb interaction between charge carriers due to the two-dimensional carrier confinement in connection with weak dielectric screening. The van der Waals nature of interlayer coupling makes it easy to integrate TMDC layers into heterostructures with different dielectric or metallic substrates. This allows to tailor electronic and optical properties of these materials, as Coulomb interaction inside atomically thin layers is very susceptible to screening by the environment. Here we theoretically inve…
As hosts for tightly-bound electron-hole pairs carrying quantized angular momentum, atomically-thin semiconductors of transition metal dichalcogenides provide an appealing platform for optically addressing the valley degree of freedom. In particular, the valleytronic properties of neutral and charged excitons in these systems have been widely investigated. Meanwhile, correlated quantum states involving more particles are so far elusive and controversial. Here we present experimental evidence for valleytronic four-particle biexcitons and five-particle exciton-trions in high-quality monolayer tu…
Raman scattering and photoluminescence spectroscopy are used to investigate the optical properties of single layer black phosphorus obtained by mechanical exfoliation of bulk crystals under an argon atmosphere. The Raman spectroscopy, performed in situ on the same flake as the photoluminescence measurements, demonstrates the single layer character of the investigated samples. The emission spectra, dominated by excitonic effects, display the expected in plane anisotropy. The emission energy depends on the type of substrate on which the flake is placed due to the different dielectric screening. …
We demonstrate a new approach for dynamically manipulating the optical response of an atomically thin semiconductor, a monolayer of MoSe2, by suspending it over a metallic mirror. First, we show that suspended van der Waals heterostructures incorporating a MoSe2 monolayer host spatially homogeneous, lifetime-broadened excitons. Then, we interface this nearly ideal excitonic system with a metallic mirror and demonstrate control over the exciton-photon coupling. Specifically, by electromechanically changing the distance between the heterostructure and the mirror, thereby changing the local photo…
The realization of mixtures of excitons and charge carriers in van-der-Waals materials presents a new frontier for the study of the many-body physics of strongly interacting Bose-Fermi mixtures. In order to derive an effective low-energy model for such systems, we develop an exact diagonalization approach based on a discrete variable representation that predicts the scattering and bound state properties of three charges in two-dimensional transition metal dichalcogenides. From the solution of the quantum mechanical three-body problem we thus obtain the bound state energies of excitons and trio…
The emergence of two-dimensional crystals has revolutionized modern solid-state physics. From a fundamental point of view, the enhancement of charge carrier correlations has sparked enormous research activities in the transport- and quantum optics communities. One of the most intriguing effects, in this regard, is the bosonic condensation and spontaneous coherence of many-particle complexes. Here, we find compelling evidence of bosonic condensation of exciton-polaritons emerging from an atomically thin crystal of MoSe2 embedded in a dielectric microcavity under optical pumping. The formation o…
We propose a new model to implement organic exciton-semiconductor exciton hybridization by embedding a semiconductor quantum dot array into an organic medium. A Wannier-Mott transfer exciton is formed when the exciton in each semiconductor dot interacts via the multipole-multipole coupling with other excitons in the different dtos of the array. A new hybrid exciton appears in the system owing to strong dipole-dipole interaction of the Frenkel exciton of the organic molecules with the Wannier Mott transfer exciton of the quantum dot array. This hybrid exciton has both a large oscillator strengt…
Monolayer materials are strongly affected by their potential fluctuations, which are induced by an intrinsic corrugation or the surface roughness of the substrate. We compare the effective exciton-exciton annihilation (EEA) rate constants of monolayer WS2 on substrates with different surface topographies. We show that monolayer WS2 on the substrate with atomically flat terraces displays small effective EEA rate constant deviating from the overall tendency and multiple exciton decay components, which cannot be accounted for by a conventional EEA model. To obtain a correct description, we use a …
Atomically thin materials such as graphene and monolayer transition metal dichalcogenides (TMDs) exhibit remarkable physical properties resulting from their reduced dimensionality and crystal symmetry. The family of semiconducting transition metal dichalcogenides is an especially promising platform for fundamental studies of two-dimensional (2D) systems, with potential applications in optoelectronics and valleytronics due to their direct band gap in the monolayer limit and highly efficient light-matter coupling. A crystal lattice with broken inversion symmetry combined with strong spin-orbit i…
Interfaces of dye molecules and two-dimensional transition metal dichalcogenides (TMDCs) combine strong molecular dipole excitations with high carrier mobilities in semiconductors. Förster type energy transfer is one key mechanism for the coupling between both constituents. We report microscopic calculations of a spectrally resolved Förster induced transition rate from dye molecules to a TMDC layer. Our approach is based on microscopic Bloch equations which are solved self-consistently together with Maxwells equations. This approach allows to incorporate the dielectric environment of a TMDC se…
We present a detailed investigation of the exciton and trion dynamics in naturally doped MoSe2 and WSe2 single atomic layers as a function of temperature in the range 10-300K under above band-gap laser excitation. By combining time-integrated and time-resolved photoluminescence (PL) spectroscopy we show the importance of exciton and trion localization in both materials at low temperatures. We also reveal the transition to delocalized exciton complexes at higher temperatures where the exciton and trion thermal energy exceeds the typical localization energy. This is accompanied with strong chang…
Metal-organic species can be designed to self-assemble in large-scale, atomically defined, supramolecular architectures. Hybrid quantum wells, where inorganic two-dimensional (2D) planes are separated by organic ligands, are a particular example. The ligands effectively provide an intralayer confinement for charge carriers resulting in a 2D electronic structure, even in multilayered assemblies. Air-stable metal organic chalcogenides hybrid quantum wells have recently been found to host tightly bound 2D excitons with strong optical anisotropy in a bulk matrix. Here, we investigate the excited c…
Tuning the electronic properties of a material by subjecting it to strain constitutes an important strategy to enhance the performance of semiconducting electronic devices. Using local strain, confinement potentials for excitons can be engineered, with exciting possibilities for trapping excitons for quantum optics and for efficient collection of solar energy. Two-dimensional materials are able to withstand large strains before rupture, offering a unique opportunity to introduce large local strains. Here, we study atomically thin MoS2 layers with large local strains of up to 2.5% induced by co…
A novel type of exciton-phonon bound state -- interlayer polaron -- in a double-layer two-dimensional semiconductor with transition metal dichalcogenides as an example, is predicted. In these systems the interaction of the interlayer exciton with the soft modes of out-of-plane lattice vibrations caused by van der Waals forces and flexural rigidity gives rise to a bound quasiparticle. The energy and effective mass of the formed polaron for weak and strong exciton-phonon coupling regimes are calculated and analyzed. Possible manifestations of these effects in transport- and spectroscopy-related …
We systematically measure the dielectric function of atomically thin MoS2 films with different layer numbers and demonstrate that excitonic effects play a dominant role in the dielectric function when the films are less than 5-7 layers thick. The dielectric function shows an anomalous dependence on the layer number. It decreases with the layer number increasing when the films are less than 5-7 layers thick but turns to increase with the layer number for thicker films. We show that this is because the excitonic effect is very strong in the thin MoS2 films and its contribution to the dielectric …
We present an investigation of the microscopic interplay between excitons and charge carriers by means of combined photoluminescence (PL) and charge carrier transport measurements on organic thin film transistors (OTFT). For this purpose, the prototypical organic semiconductor Diindenoperylene (DIP) was utilized as active material. The OTFT accumulation layer provides a spatially defined interaction zone for charges and photo-generated excitons leading to a PL intensity reduction of up to 4.5%. This effect correlates with the accumulated hole carrier density and provides a lower estimate of ab…
Time-resolved and temperature-dependent photoluminescence measurements on one-dimensional sexithiophene lattices reveal intrinsic branching of photoexcitations to two distinct species: self-trapped excitons and dark charge-transfer excitons (CTX; > 5% yield), with radii spanning 2-3 sites. The significant CTX yield results from the strong charge-transfer character of the Frenkel exciton band due to the large free exciton bandwidth (~400 meV) in these supramolecular nanostructures.
Quantum confinement profoundly affects the properties and interactions of electrons, holes, and excitons in nanomaterials. We apply first-principles calculations to study the effects of extreme quantum confinement on the electronic, excitonic, and radiative properties of atomically thin GaN quantum wells with a thickness of 1 to 4 atomic monolayers embedded in AlN. We determine the quasiparticle band gaps, exciton energies and wave functions, radiative lifetimes, and Mott critical densities as a function of well and barrier thickness. Our results show that quantum confinement in GaN monolayers…
Quantifying the spin-spin interactions which influence electronic transitions in organic semiconductors is crucial for understanding their magneto-optoelectronic properties. By combining a theoretical model for three spin interactions in the coherent regime with pulsed electrically detected magnetic resonance experiments on MEH-PPV diodes, we quantify the spin-coupling within complexes comprising three spin-half particles. We determine that these particles form triplet-exciton:polaron pairs, where the polaron:exciton exchange is over 5 orders of magnitude weaker (less than 170 MHz) than that w…
In monolayers of transition metal dichalcogenides the nonlocal nature of the effective dielectric screening leads to large binding energies of excitons. Additional lateral confinement gives rise to exciton localization in quantum dots. By assuming parabolic confinement for both the electron and the hole, we derive model wave functions for the relative and the center-of-mass motions of electron-hole pairs, and investigate theoretically resonant energy transfer among excitons localized in two neighboring quantum dots. We quantify the probability of energy transfer for a direct-gap transition by …
Low-dimensional organic-inorganic perovskites synergize the virtues of two unique classes of materials featuring intriguing possibilities for next-generation optoelectronics: they offer tailorable building blocks for atomically thin, layered materials while providing the enhanced light harvesting and emitting capabilities of hybrid perovskites. Here, we go beyond the paradigm that atomically thin materials require in-plane covalent bonding and report single layers of the one-dimensional organic-inorganic perovskite [C$_7$H$_{10}$N]$_3$[BiCl$_5$]Cl. Its unique 1D-2D structure enables single lay…
Exciton-polaritons are quasiparticles with mixed photon and exciton character that demonstrate rich quantum phenomena, novel optoelectronic devices and the potential to modify chemical properties of materials. Organic semiconductors are of current interest for their room-temperature polariton formation. However, within organic optoelectronic devices, it is often the 'dark' spin-1 triplet excitons that dominate operation. These triplets have been largely ignored in treatments of polariton physics. Here we demonstrate polariton population from the triplet manifold via triplet-triplet annihilatio…
In the strong light-matter coupling regime realized e.g. by integrating semiconductors into optical microcavities, polaritons as new hybrid light-matter quasi-particles are formed. The corresponding change in the dispersion relation has a large impact on optics, dynamics and transport behaviour of semiconductors. In this work, we investigate the strong-coupling regime in hBN-encapsulated MoSe$_2$ monolayers focusing on exciton-polariton diffusion. Applying a microscopic approach based on the exciton density matrix formalism combined with the Hopfield approach, we predict a drastic increase of …
We probe the room temperature photoluminescence of $N$-layer molybdenum ditelluride (MoTe$_2$) in the continuous wave (cw) regime. The photoluminescence quantum yield of monolayer MoTe$_2$ is three times larger than in bilayer MoTe$_2$ and forty times greater than in the bulk limit. Mono- and bilayer MoTe$_2$ display almost symmetric emission lines at $1.10~\rm eV$ and $1.07~\rm eV$, respectively, which predominantly arise from direct radiative recombination of the A exciton. In contrast, $N\geq3-$layer MoTe$_2$ exhibits a much reduced photoluminescence quantum yield and a broader, redshifted …
Metasurfaces enable flat optical elements by leveraging optical resonances in metallic or dielectric nanoparticles to obtain accurate control over the amplitude and phase of the scattered light. While highly efficient, these resonances are static and difficult to tune actively. Exciton resonances in atomically thin 2D semiconductors provide a novel and uniquely strong resonant light-matter interaction, which presents a new opportunity for optical metasurfaces. Their resonant properties are intrinsic to the band structure of the material and do not rely on nanoscale patterns and are highly tuna…
Magnetoelectroluminescence (MEL) of organic semiconductor has been experimentally tuned by adopting blended emitting layer consisting of both hole and electron transporting materials. A theoretical model considering intermolecular quantum correlation is proposed to demonstrate two fundamental issues: (1) two mechanisms, spin scattering and spin mixing, dominate the two different steps respectively in the process of the magnetic field modulated generation of exciton; (2) the hopping rate of carriers determines the intensity of MEL. Calculation successfully predicts the increase of singlet excit…
Strong spin-orbit coupling and inversion symmetry breaking in transition metal dichalcogenide monolayers yield the intriguing effects of valley-dependent optical selection rules. As such, it is possible to substantially polarize valley excitons with chiral light and furthermore create coherent superpositions of K and K- polarized states. Yet, at ambient conditions dephasing usually becomes too dominant, and valley coherence typically is not observable. Here, we demonstrate that valley coherence is, however, clearly observable for a single monolayer of WSe2, if it is strongly coupled to the opt…
Excitonic emission from atomically precise graphene nanoribbons (GNRs) synthesised on a metal surface is probed with atomic-scale spatial resolution using a scanning tunneling microscopy (STM) approach. A STM-based strategy to transfer the GNRs to a partially insulating surface is used to prevent light emission quenching of the ribbons by the metal substrate. Sub-nanometer resolved STM-induced fluorescence spectra reveal emission from localized dark excitons build upon the topological end states of the GNRs. A low frequency vibronic emission comb whose characteristics change with the GNR lengt…
Transition metal dichalcogenide monolayers are promising candidates for exploring new electronic and optical phenomena and for realizing atomically thin optoelectronic devices. They host tightly bound electron-hole pairs (excitons) that can be efficiently excited by resonant light fields. Here, we demonstrate that a single monolayer of molybdenum diselenide (MoSe2) can dramatically modify light transmission near the excitonic resonance, acting as an electrically switchable mirror that reflects up to 85% of incident light at cryogenic temperatures. This high reflectance is a direct consequence …
Atomically thin semiconductors have dimensions that are commensurate with critical feature sizes of future optoelectronic devices defined using electron/ion beam lithography. Robustness of their emergent optical and valleytronic properties is essential for typical exposure doses used during fabrication. Here, we explore how focused helium ion bombardment affects the intrinsic vibrational, luminescence and valleytronic properties of atomically thin MoS$_{2}$. By probing the disorder dependent vibrational response we deduce the interdefect distance by applying a phonon confinement model. We show…
We present a quantitative study of the nonlinear optical response of layered perovskites placed inside planar photonic microcavities in the regime of strong light matter coupling, when excitonic and photonic modes hybridize and give rise to cavity polaritons. Two sources of nonlinearity are specified, the saturation of the excitonic transition with increase of the optical pump and Coulomb interaction between the excitons. It is demonstrated, that peculiar form of the interaction potential, specific to multilayer structure of organic perovskites, is responsible for substantial increase of the e…
In organic semiconductors working under ambient circumstance, there are remarkable quantum effects lack of comprehensive understanding, and an exotic composite particle named charge transfer (CT) exciton is normally regarded as the key ingredient. Another essential substance is the phonons stemming from intra- and inter-molecular vibrations, and the relevant diagonal electron-phonon couplings give rise to spatial localization and the off-diagonal couplings refer to the dispersion of electron wavefunctions. In this work, we first propose a toy model based upon the fracton physics to phenomenolo…
Manipulating strong light-matter interaction in semiconductor microcavities is crucial for developing high-performance exciton polariton devices with great potentials in next-generation all-solid state quantum technologies. In this work, we report surface plasmon enhanced strong exciton-photon interaction in CH3NH3PbBr3 perovskite nanowires. Characteristic anti-crossing behaviors, indicating Rabi splitting energy up to ~ 560 meV, are observed near exciton resonance in hybrid semiconductor-insulator-metallic waveguide cavity at room temperature. An exciton-photon coupling strength enhancement f…
We have experimentally determined the energies of the ground and first four excited excitonic states of the fundamental optical transition in monolayer WS2, a model system for the growing class of atomically thin two-dimensional semiconductor crystals. From the spectra, we establish a large exciton binding energy of 0.32 eV and a pronounced deviation from the usual hydrogenic Rydberg series of energy levels of the excitonic states. We explain both of these results using a microscopic theory in which the non-local nature of the effective dielectric screening modifies the functional form of the …
Optical spectroscopy of ultimately thin materials has significantly enhanced our understanding of collective excitations in low-dimensional semiconductors. This is particularly reflected by the rich physics of excitons in atomically thin crystals which uniquely arises from the interplay of strong Coulomb correlation, spin-orbit coupling (SOC), and lattice geometry. Here we extend the field by reporting the observation of room temperature excitons in a material of non-trivial global topology. We study the fundamental optical excitation spectrum of a single layer of bismuth atoms epitaxially gro…
Neutral and charged excitons (trions) in atomically-thin materials offer important capabilities for photonics, from ultrafast photodetectors to highly-efficient light-emitting diodes and lasers. Recent studies of van der Waals (vdW) heterostructures comprised of dissimilar monolayer materials have uncovered a wealth of optical phenomena that are predominantly governed by interlayer interactions. Here, we examine the optical properties in NbSe$_2$ - MoSe$_2$ vdW heterostructures, which provide an important model system to study metal-semiconductor interfaces, a common element in optoelectronics…
We determine the zero temeperature phase diagram of excitons in the symmetric transition-metal dichalcogenide tri-layer heterosctructure WSe2/MoSe2/WSe2. First principle calculations reveal two distinct types of interlayer excitonic states, a lower energy symmetric quadrupole and a higher energy asymmetric dipole. While interaction between quadrupolar excitons is always repulsive, anti-parallel dipolar excitons attract at large distances. We find quantum phase transitions between a repulsive quadrupole lattice phase and a staggered (anti-parallel) dipolar lattice phase, driven by the competiti…
Atomically thin semiconductors such as monolayer MoS2 and WS2 exhibit nonlinear exciton-exciton annihilation at notably low excitation densities (below ~10 excitons/um2 in MoS2). Here, we show that the density threshold at which annihilation occurs can be tuned by changing the underlying substrate. When the supporting substrate is changed from SiO2 to Al2O3 or SrTiO3, the rate constant for second-order exciton-exciton annihilation, k_XX [cm2/s], is reduced by one or two orders of magnitude, respectively. Using transient photoluminescence microscopy, we measure the effective room-temperature ex…
For small organic conjugated molecules the exciton binding energy can be calculated treating molecules as conductor, and is given by a simple relation BE \approx e2/(4πε0εR), where ε is the dielectric constant and R is the equivalent radius of the molecule. However, if the molecule deviates from spherical shape, a minor correction factor should be added.
We report on the strong coupling between the Bloch surface wave supported by an inorganic multilayer structure and $J$-aggregate excitons in an organic semiconductor. The dispersion curves of the resulting polariton modes are investigated by means of angle-resolved attenuated total reflection as well as photoluminescence experiments. The measured Rabi splitting is 290 meV. These results are in good agreement with those obtained from our theoretical model.
Optical absorption is one of fundamental light-matter interactions. In most materials, optical absorption is a weak perturbation to the light. In this regime, absorption and emission are irreversible, incoherent processes due to strong damping. Excitons in monolayer transition metal dichalcogenides, however, interact strongly with light, leading to optical absorption in the non-perturbative regime where coherent re-emission of the light has to be considered. Between the incoherent and coherent limits, we show that a robust critical coupling condition exists, leading to perfect optical absorpti…
The exciton transport in the prototypical organic semiconductor Di-Indeno-Perylene (DIP) has been investigated by means of photoluminescence (PL) quenching and interpreted by an advanced exciton diffusion model including interference effects, quencher penetration as well as non-perfect exciton quenching. X-ray difraction revealed a correlation between the exciton diffusion length of about 90 nm and the structural coherence length of the DIP layers. Temperature dependent studies in a range of 5 - 300 K indicated an incoherent exciton transport above 80 K at activation energies of 10 - 20 meV re…
The rise of organic electronics calls for versatile modeling tools. In this context, we develop a semiclassical Boltzmann theory that describes transport and excitonic processes in crystalline organic semiconductors on equal footing. The generation of singlet and triplet excitons out of the ground state, their formation from free electrons and holes, the reverse processes, as well as the fusion and fission of excitons are included. The corresponding scattering integrals respect spin conservation, which requires matrix-valued distribution functions. They also include fermionic and bosonic many-…
In organic semiconductors, bi-excitons are key intermediates in carrier-multiplication and exciton annihilation. Their local geometry governs their electronic properties and yet has been challenging to determine. Here, we access the structure of the recently discovered $S=2$ quintet bi-exciton state in an organic semiconductor using broadband optically detected magnetic resonance. We correlate the experimentally extracted spin structure with the molecular crystal geometry to identify the specific molecular pairings on which bi-exciton states reside.
