对非晶有机材料中的激子和电荷跳跃进行模拟涉及大量物理参数。在模拟开始之前，每个参数都必须通过成本高昂的从头算计算获得，这给研究激子扩散带来了显著的计算开销，尤其是在大型且复杂的材料数据集中。尽管此前已经探索过利用机器学习快速预测这些参数的想法，但典型的机器学习模型需要较长的训练时间，最终也会增加模拟开销。本文提出了一种新的机器学习架构，用于构建分子间激子耦合参数的预测模型。该架构的设计使其总训练时间相较于普通的 Gaussian process regression（高斯过程回归）或 kernel ridge regression（核岭回归）模型有所减少。基于这一架构，我们构建了一个预测模型，并用它来估算进入非晶并五苯中激子跳跃模拟的耦合参数。我们表明，与完全使用由 density functional theory（密度泛函理论）计算得到的耦合参数所进行的模拟相比，这种跳跃模拟能够对激子扩散张量元素及其他性质作出极好的预测。这一结果，连同我们架构所带来的较短训练时间，因此展示了如何利用机器学习来降低与非晶有机材料中激子和电荷扩散模拟相关的高昂计算开销。
英文摘要：
Simulations of exciton and charge hopping in amorphous organic materials involve numerous physical parameters. Each of these parameters must be computed from costly ab initio calculations before the simulation can commence, resulting in a significant computational overhead for studying exciton diffusion, especially in large and complex material datasets. While the idea of using machine learning to quickly predict these parameters has been explored previously, typical machine learning models require long training times which ultimately contribute to simulation overheads. In this paper, we present a new machine learning architecture for building predictive models for intermolecular exciton coupling parameters. Our architecture is designed in such a way that the total training time is reduced compared to ordinary Gaussian process regression or kernel ridge regression models. Based on this architecture, we build a predictive model and use it to estimate the coupling parameters which enter into an exciton hopping simulation in amorphous pentacene. We show that this hopping simulation is able to achieve excellent predictions for exciton diffusion tensor elements and other properties as compared to a simulation using coupling parameters computed entirely from density functional theory. This result, along with the short training times afforded by our architecture, therefore shows how machine learning can be used to reduce the high computational overheads associated with exciton and charge diffusion simulations in amorphous organic materials.
We report a detailed comparison on the role of a self-assembled monolayer (SAM) of dipolar molecules on the threshold voltage and charge carrier mobility of organic field-effect transistor (OFET) made of both amorphous and polycrystalline organic semiconductors. We show that the same relationship between the threshold voltage and the dipole-induced charges in the SAM holds when both types of devices are fabricated on strictly identical base substrates. Charge carrier mobilities, almost constant for amorphous OFET, are not affected by the dipole in the SAMs, while for polycrystalline OFET (pent…
There is an increasing interest in the amorphous states of metal-organic frameworks (MOFs) and porous coordination polymers, which can be produced by pressure-induced amorphization, temperature-induced amorphization, melt-quenching, ball-milling, irradiation, etc. They can exhibit useful physical and chemical properties, distinct from those achievable in the crystalline states, along with greater ease of processing, and intrinsic advantages over crystals and powders, such as high transparency and mechanical robustness. However, these amorphous states are particularly challenging to characteriz…
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-…
The excited state dynamics in organic semiconductors plays an important role for many processes associated with light absorption and emission. We have studied the momentum dependence of the lowest singlet excitons in tetracene molecular solids, an archetype system for other organic semiconductors. Our results reveal an anisotropic bandstructure of these excitons with an energy minimum at finite momentum, i. e., a low energy exciton pocket. The existence of such low energy states might have important consequences for the photophysical behavior, also in view of applications in, e. g., organic so…
Excitonic insulators are long-sought-after quantum materials predicted to spontaneously open a gap by the Bose condensation of bound electron-hole pairs, namely, excitons, in their ground state. Since the theoretical conjecture, extensive efforts have been devoted to pursuing excitonic insulator platforms for exploring macroscopic quantum phenomena in real materials. Reliable evidences of excitonic character have been obtained in layered chalcogenides as promising candidates. However, owing to the interference of intrinsic lattice instabilities, it is still debatable whether those features, su…
We present a simple model of the bimolecular charge carrier recombination in polar amorphous organic semiconductors where the dominant part of the energetic disorder is provided by permanent dipoles and show that the recombination rate constant could be much smaller than the corresponding Langevin rate constant. The reason for the strong decrease of the rate constant is the long range spatial correlation of the random energy landscape in amorphous dipolar materials, without spatial correlation even strong disorder does not modify the Langevin rate constant. Our study shows that the significant…
We consider the bimolecular charge carrier recombination in amorphous organic semiconductors having a special kind of energetic disorder where energy levels for electrons and holes at a given transport site move in the same direction with the variation of some disorder governing parameter (the parallel disorder). This particular kind of disorder could be found in materials where the dominant part of the energetic disorder is provided by the conformational disorder. Contrary to the recently studied case of electrostatic disorder, the conformational disorder, if spatially correlated, leads to th…
In a combined theoretical and experimental work, we investigate X-ray Absorption Near-Edge Structure (XANES) spectroscopy of the I $L_3$ and the Pb $M_5$ edges of the methylammonium lead iodide ($\textrm{MAPbI}_3$) hybrid inorganic-organic perovskite and its binary phase $\textrm{PbI}_2$. The absorption onsets are dominated by bound excitons with sizable binding energies of a few hundred meV and pronounced anisotropy. The spectra of both materials exhibit remarkable similarities, suggesting that the fingerprints of core excitations in $\textrm{MAPbI}_3$ are essentially given by its inorganic c…
We consider the two-dimensional bimolecular recombination of charge carriers in amorphous organic semiconductors having the lamellar structure. We calculate the dependence of the effective recombination rate constant on the carrier density taking into account the correlated nature of the energetic disorder typical for organic semiconductors. Resulting recombination kinetics demonstrates a very rich variety of behaviors depending on the correlation properties of the particular semiconductor and relevant charge density range.
We report on the optical characterization of non-polar a-plane InGaN quantum dots (QDs) grown by metal-organic vapor phase epitaxy using a short nitrogen anneal treatment at the growth temperature. Spatial and spectral mapping of sub-surface QDs have been achieved by cathodoluminescence at 8 K. Microphotoluminescence studies of the QDs reveal resolution limited sharp peaks with typical linewidth of 1 meV at 4.2 K. Time-resolved photoluminescence studies suggest the excitons in these QDs have a typical lifetime of 538 ps, much shorter than that of the c-plane QDs, which is strong evidence of th…
This work reports our effort on understanding the efficiency roll-off in blue phosphorescent organic light-emitting diodes (OLEDs), based on a blue phosphorescence from bis(3,5-difluoro-2-(2-pyridyl)phenyl-(2-carboxypyridyl)- iridium (FIrpic) doped in 4,4-N,N-dicarbazole-biphenyl (CBP) host. The performance of a set of blue phosphorescent OLEDs with different FIrpic dopant concentrations was analyzed. Phosphorescent OLEDs, having a 30 nm thick pure FIrpic emissive layer, with a high luminous efficiency of 7.76 cd/A at 100 mA/cm2 was obtained. Theoretical calculation, based on the density funct…
Frenkel excitons are the primary photoexcitations in organic semiconductors and are ultimately responsible for the optical properties of such materials. They are also predicted to form \emph{bound} exciton pairs, termed biexcitons, which are consequential intermediates in a wide range of photophysical processes. Generally, we think of bound states as arising from an attractive interaction. However, here we report on our recent theoretical analysis predicting the formation of stable biexciton states in a conjugated polymer material arising from both attractive and repulsive interactions. We sho…
Efficient energy transport is highly desirable for organic semiconductor (OSC) devices such as photovoltaics, photodetectors, and photocatalytic systems. However, photo-generated excitons in OSC films mostly occupy highly localized states over their lifetime. Energy transport is hence thought to be mainly mediated by the site-to-site hopping of localized excitons, limiting exciton diffusion coefficients to below ~10^{-2} cm^2/s with corresponding diffusion lengths below ~50 nm. Here, using ultrafast optical microscopy combined with non-adiabatic molecular dynamics simulations, we present evide…
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.
Understanding the transport mechanism of electronic excitations in conjugated polymers is key to advancing organic optoelectronic applications, such as solar cells, OLEDs and flexible electronics. While crystalline polymers can be studied using solid-state techniques based on lattice periodicity, the characterisation of amorphous polymers is hindered by an intermediate regime of disorder and the associated lack of symmetries. To overcome these hurdles we use a reduced state quantum master equation approach based on the Merrifield exciton formalism. Using this model we study exciton transport i…
General properties of the hopping transport of charge carriers in amorphous organic and inorganic materials are discussed. We consider the case where the random energy landscape in the materials is strongly spatially correlated. This is a very typical situation in the organic materials having the Gaussian density of states (DOS) and may be realized in some materials with the exponential DOS. We demonstrate that the different type of DOS leads to a very different functional form of the mobility field dependence even in the case of the identical correlation function of random energy. We provide …
We present a simple model of the local order in amorphous organic semiconductors which naturally produces a spatially correlated exponential density of states (DOS). The dominant contribution to the random energy landscape is provided by electrostatic contributions from dipoles or quadrupoles. An assumption of the preferable parallel orientation of neighbor quadrupoles or antiparallel orientation of dipoles directly leads to the formation of the exponential tails of the DOS even for a moderate size of the ordered domains. The insensitivity of the exponential tail formation to the details of th…
We present an exciton/lattice model of the electronic dynamics of primary photoexcitations in a polymeric semiconductor heterojunction which includes both polymer pi-stacking, energetic disorder, and phonon relaxation. Results from our model are consistent with a wide range of recent experimental evidence that excitons decay directly to well-defined polarons on a sub-100 fs timescale, which is substantially faster than exciton relaxation processes. Averaging over multiple samples, we find that as the interfacial offset is increased, a substantial fraction of the density of electronic states in…
Excitons are widely found in semiconductors. In contrast to inorganic-based semiconductors, where the presence of excitons may need special morphonology, like low-dimensional layer structure, the excitons prevailingly exist in molecular organic semiconductors in a three-dimension solid state. The excitons can undergo a charging process to yield another kind of quasiparticles originating from the coupling of excitons and free charges. Herein, we investigated the interaction between excitons and free charges in a representative arylamine-derivative organic semiconductor(NPB), by the time-of-flig…
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…
Singlet fission (SF), an exciton multiplication process occurring in organic semiconductors, offers a way to break the Shockley-Queisser limit in single-bandgap photovoltaics (PV). If the triplet excitons generated by SF can be transferred to inorganic quantum dots (QDs), where they radiatively recombine, SF based photon multiplication is achieved, converting a single high-energy photon into two low-energy photons. Such a SF photon multiplication film (SF-PMF) could raise the efficiency of the best Si-PV from 26.7% to 32.5%. But a precise nanoscale morphology is required within such a film con…
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…
Far tails of the density of state (DOS) are calculated for the simple models of organic amorphous material, the model of dipolar glass and model of quadrupolar glass. It was found that in both models far tails are non-Gaussian. In the dipolar glass model the DOS is symmetric around zero energy, while for the model of quadrupolar glass the DOS is generally asymmetric and its asymmetry is directly related to the particular geometry of quadrupoles. Far tails of the DOS are relevant for the quasi-equilibrium transport of the charge carriers at low temperature. Asymmetry of DOS in quadrupolar glass…
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…
Two dimensional (2D) van der Waals heterostructures from transition metal dichalcogenide (TMDC) semiconductors show a new class of spatially separate excitons with extraordinary properties. The interlayer excitons (XI) have been studied extensively, yet the mechanisms that modulate XI are still not well understood. Here, we introduce several organic-layer-embedded hybrid heterostructures, MoS2/organic/WSe2, to study the binding energy of XI. We discover that the dielectric screening of the quasi-particle is reduced with organic molecules due to decreased dielectric constant and greater separat…
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…
Organic semiconductors exhibit properties of individual molecules and extended crystals simultaneously. The strongly bound excitons they host are typically described in the molecular limit, but excitons can delocalize over many molecules, raising the question of how important the extended crystalline nature is. Using accurate Green's function based methods for the electronic structure and non-perturbative finite difference methods for exciton-vibration coupling, we describe exciton interactions with molecular and crystal degrees of freedom concurrently. We find that the degree of exciton deloc…
Crystallization is a key for ferroelectricity which is a collective behavior of microscopic electric dipoles. On the other hand, uncontrolled crystallization leads to uneven morphology and random crystal orientations, which undermines the application potential of ferroelectric thin films. In this work, we introduce a film fabrication method of low-temperature physical vapor deposition followed by restrained crystallization, with electrical properties monitored in real-time by in situ measurements. This method was adopted to fabricate films of 2-methylbenzimidazole (MBI), whose molecule crystal…
Surface Exciton Polaritons and Near-Zero Permittivity Surface Waves Supported by Artificial Organic Hyperbolic Metamaterials
CINBIO, Universidade de Vigo（维戈大学）；Centro de Física das Universidades do Minho e do Porto (CF-UM-UP), Universidade do Minho（米尼奥大学与波尔图大学物理中心）；International Iberian Nanotechnology Laboratory (INL)（伊比利亚纳米技术国际实验室）；Instituto de Ciencia de Materiales de Madrid (ICMM), Consejo Superior de Investigaciones Científicas (CSIC)（马德里材料科学研究所，西班牙高等科学研究理事会）；ALBA Synchrotron Light Source（阿尔巴同步辐射光源）
The effectiveness of molecular-based light harvesting relies on transport of optical excitations, excitons, to charg-transfer sites. Measuring exciton migration has, however, been challenging because of the mismatch between nanoscale migration lengths and the diffraction limit. In organic semiconductors, common bulk methods employ a series of films terminated at quenching substrates, altering the spatioenergetic landscape for migration. Here we instead define quenching boundaries all-optically with sub-diffraction resolution, thus characterizing spatiotemporal exciton migration on its native n…
Understanding the role that exciton diffusion plays in organic solar cells is a crucial to understanding the recent rise in power conversion effciencies brought about by non-fullerene acceptors (NFA). Established methods for measuring exciton diffusion lengths in organic solar cells require specialized equipment designed for measuring high-resolution time-resolved photoluminescence (TRPL). Here we introduce a technique, coined pulsed-PLQY, to measure the diffusion length of organic solar cells without any temporal measurements. Using a Monte-Carlo model we simulate the dynamics within a thin f…
On the critical competition between singlet exciton decay and free charge generation in non-fullerene-based organic solar cells with low energetic offsets
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…
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…
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.
In organic photovoltaics, the mechanism by which free electrons and holes are generated overcoming the Coulomb attraction is a currently much debated topic. To elucidate this mechanism at a molecular level, we carried out a combined electronic structure and quantum dynamical analysis that captures the elementary events from the exciton dissociation to the free carrier generation at polymer/fullerene donor-acceptor heterojunctions. Our calculations show that experimentally observed efficient charge separations can be explained by a combination of two effects: First, the delocalization of charge…
