Non-equilibrium transport in polymer mixed ionic-electronic conductors at ultrahigh charge densities.

Conducting polymers are mixed ionic-electronic conductors that are emerging candidates for neuromorphic computing, bioelectronics and thermoelectrics. However, fundamental aspects of their many-body correlated electron-ion transport physics remain poorly understood. Here we show that in p-type organic electrochemical transistors it is possible to remove all of the electrons from the valence band and even access deeper bands without degradation. By adding a second, field-effect gate electrode, additional electrons or holes can be injected at set doping states. Under conditions where the counterions are unable to equilibrate in response to field-induced changes in the electronic carrier density, we observe surprising, non-equilibrium transport signatures that provide unique insights into the interaction-driven formation of a frozen, soft Coulomb gap in the density of states. Our work identifies new strategies for substantially enhancing the transport properties of conducting polymers by exploiting non-equilibrium states in the coupled system of electronic charges and counterions.

Structural and Dynamic Disorder, Not Ionic Trapping, Controls Charge Transport in Highly Doped Conducting Polymers.

Doped organic semiconductors are critical to emerging device applications, including thermoelectrics, bioelectronics, and neuromorphic computing devices. It is commonly assumed that low conductivities in these materials result primarily from charge trapping by the Coulomb potentials of the dopant counterions. Here, we present a combined experimental and theoretical study rebutting this belief. Using a newly developed doping technique based on ion exchange, we prepare highly doped films with several counterions of varying size and shape and characterize their carrier density, electrical conductivity, and paracrystalline disorder. In this uniquely large data set composed of several classes of high-mobility conjugated polymers, each doped with at least five different ions, we find electrical conductivity to be strongly correlated with paracrystalline disorder but poorly correlated with ionic size, suggesting that Coulomb traps do not limit transport. A general model for interacting electrons in highly doped polymers is proposed and carefully parametrized against atomistic calculations, enabling the calculation of electrical conductivity within the framework of transient localization theory. Theoretical calculations are in excellent agreement with experimental data, providing insights into the disorder-limited nature of charge transport and suggesting new strategies to further improve conductivities.

Comprehensive modelling study of singlet exciton diffusion in donor-acceptor dyads: when small changes in chemical structure matter.

We compare two small π-conjugated donor-bridge-acceptor organic molecules differing mainly in the number of thiophene rings in their bridging motifs (1 ring in 1; 2 rings in 2) with the aim of rationalizing the origin of the enhancement in the singlet exciton diffusion coefficient and length of 1 with respect to 2. By combining force field molecular dynamics and micro electrostatic schemes with time-dependent density functional theory and kinetic Monte Carlo simulations, we dissect the nature of the lowest electronic excitations in amorphous thin films of these molecules and model the transport of singlet excitons across their broadly disordered energy landscapes. In addition to a longer excited-state lifetime associated with a more pronounced intramolecular charge-transfer character, our calculations reveal that singlet excitons in 1 are capable of funneling through long-distance hopping percolation pathways, presumably as a result of the less anisotropic shape of the molecule, which favours long-range 3D transport.

Singlet exciton fission via an intermolecular charge transfer state in coevaporated pentacene-perfluoropentacene thin films.

Singlet exciton fission is a spin-allowed process in organic semiconductors by which one absorbed photon generates two triplet excitons. Theory predicts that singlet fission is mediated by intermolecular charge-transfer states in solid-state materials with appropriate singlet-triplet energy spacing, but direct evidence for the involvement of such states in the process has not been provided yet. Here, we report on the observation of subpicosecond singlet fission in mixed films of pentacene and perfluoropentacene. By combining transient spectroscopy measurements to nonadiabatic quantum-dynamics simulations, we show that direct excitation in the charge-transfer absorption band of the mixed films leads to the formation of triplet excitons, unambiguously proving that they act as intermediate states in the fission process.

Energetic fluctuations in amorphous semiconducting polymers: Impact on charge-carrier mobility.

We present a computational approach to model hole transport in an amorphous semiconducting fluorene-triphenylamine copolymer (TFB), which is based on the combination of molecular dynamics to predict the morphology of the oligomeric system and Kinetic Monte Carlo (KMC), parameterized with quantum chemistry calculations, to simulate hole transport. Carrying out a systematic comparison with available experimental results, we discuss the role that different transport parameters play in the KMC simulation and in particular the dynamic nature of positional and energetic disorder on the temperature and electric field dependence of charge mobility. It emerges that a semi-quantitative agreement with experiments is found only when the dynamic nature of the disorder is taken into account. This study establishes a clear link between microscopic quantities and macroscopic hole mobility for TFB and provides substantial evidence of the importance of incorporating fluctuations, at the molecular level, to obtain results that are in good agreement with temperature and electric field-dependent experimental mobilities. Our work makes a step forward towards the application of nanoscale theoretical schemes as a tool for predictive material screening.

Dielectric properties of crystalline organic molecular films in the limit of zero overlap.

We present the calculation of the static dielectric susceptibility tensor and dipole field sums in thin molecular films in the well-defined limit of zero intermolecular overlap. Microelectrostatic and charge redistribution approaches are applied to study the evolution of dielectric properties from one to a few molecular layers in films of different conjugated molecules with organic electronics applications. Because of the conditional convergence of dipolar interactions, dipole fields depend on the shape of the sample and different values are found in the middle layer of a thick film and in the bulk. The shape dependence is eliminated when depolarization is taken into account, and the dielectric tensor of molecular films converges to the bulk limit within a few molecular layers. We quantify the magnitude of surface effects and interpret general trends among different systems in terms of molecular properties, such as shape, polarizability anisotropy, and supramolecular organization. A connection between atomistic models for molecular dielectrics and simpler theories for polarizable atomic lattices is also provided.

Charge dissociation at interfaces between discotic liquid crystals: the surprising role of column mismatch.

The semiconducting and self-assembling properties of columnar discotic liquid crystals have stimulated intense research toward their application in organic solar cells, although with a rather disappointing outcome to date in terms of efficiencies. These failures call for a rational strategy to choose those molecular design features (e.g., lattice parameter, length and nature of peripheral chains) that could optimize solar cell performance. With this purpose, in this work we address for the first time the construction of a realistic planar heterojunction between a columnar donor and acceptor as well as a quantitative measurement of charge separation and recombination rates using state of the art computational techniques. In particular, choosing as a case study the interface between a perylene donor and a benzoperylene diimide acceptor, we attempt to answer the largely overlooked question of whether having well-matching donor and acceptor columns at the interface is really beneficial for optimal charge separation. Surprisingly, it turns out that achieving a system with contiguous columns is detrimental to the solar cell efficiency and that engineering the mismatch is the key to optimal performance.

Supramolecular organization of functional organic materials in the bulk and at organic/organic interfaces: a modeling and computer simulation approach.

The molecular organization of functional organic materials is one of the research areas where the combination of theoretical modeling and experimental determinations is most fruitful. Here we present a brief summary of the simulation approaches used to investigate the inner structure of organic materials with semiconducting behavior, paying special attention to applications in organic photovoltaics and clarifying the often obscure jargon hindering the access of newcomers to the literature of the field. Special attention is paid to the choice of the computational "engine" (Monte Carlo or Molecular Dynamics) used to generate equilibrium configurations of the molecular system under investigation and, more importantly, to the choice of the chemical details in describing the molecular interactions. Recent literature dealing with the simulation of organic semiconductors is critically reviewed in order of increasing complexity of the system studied, from low molecular weight molecules to semiflexible polymers, including the challenging problem of determining the morphology of heterojunctions between two different materials.

Are hydrogen-bonded charge transfer crystals room temperature ferroelectrics?

We present a theoretical investigation of the anomalous ferroelectricity of mixed-stack charge transfer molecular crystals, based on the Peierls-Hubbard model, and first-principles calculations for its parametrization. This approach is first validated by reproducing the temperature-induced transition and the electronic polarization of TTF-CA, and then applied to a novel series of hydrogen-bonded crystals, for which room temperature ferroelectricity has recently been claimed. Our analysis shows that the hydrogen-bonded systems present a very low degree of charge transfer and hence support a very small polarization. A critical reexamination of experimental data supports our findings, shedding doubts on the ferroelectricity of these systems. More generally, our modeling allows the rationalization of general features of the ferroelectric transition in charge transfer crystals and suggests design principles for materials optimization.

Charge separation energetics at organic heterojunctions: on the role of structural and electrostatic disorder.

Improving the performance of organic photovoltaic cells requires the individuation of the specific factors limiting their efficiency, by rationalizing the relationship between the chemical nature of the materials, their morphology, and the electronic processes taking place at their interface. In this contribution, we present recent theoretical advances regarding the determination of the energetics and dynamics of charge carriers at organic-organic interfaces, highlighting the role of structural and electrostatic disorder in the separation of electron-hole pairs. The influence of interfacial electrostatic interactions on charge carrier energetics is first illustrated in model aggregates. Then, we review some of our recent theoretical studies in which we combined molecular dynamics, quantum-chemical and classical micro-electrostatic methods to evaluate the energy landscape explored by the mobile charges in the vicinity of donor-acceptor interfaces with realistic morphologies. Finally, we describe the theoretical challenges that still need to be overcome in order to gain a complete overview of the charge separation processes at the molecular level.

Molecularly induced order promotes charge separation through delocalized charge-transfer states at donor-acceptor heterojunctions.

The energetic landscape at the interface between electron donating and accepting molecular materials favors efficient conversion of intermolecular charge-transfer (CT) states into free charge carriers (FCC) in high-performance organic solar cells. Here, we elucidate how interfacial energetics, charge generation and radiative recombination are affected by molecular arrangement. We experimentally determine the CT dissociation properties of a series of model, small molecule donor-acceptor blends, where the used acceptors (B2PYMPM, B3PYMPM and B4PYMPM) differ only in the nitrogen position of their lateral pyridine rings. We find that the formation of an ordered, face-on molecular packing in B4PYMPM is beneficial to efficient, field-independent charge separation, leading to fill factors above 70% in photovoltaic devices. This is rationalized by a comprehensive computational protocol showing that, compared to the more amorphous and isotropically oriented B2PYMPM, the higher structural order of B4PYMPM molecules leads to more delocalized CT states. Furthermore, we find no correlation between the quantum efficiency of FCC radiative recombination and the bound or unbound nature of the CT states. This work highlights the importance of structural ordering at donor-acceptor interfaces for efficient FCC generation and shows that less bound CT states do not preclude efficient radiative recombination.

Peak Broadening in Photoelectron Spectroscopy of Amorphous Polymers: The Leading Role of the Electrostatic Landscape.

The broadening in photoelectron spectra of polymers can be attributed to several factors, such as light source spread, spectrometer resolution, the finite lifetime of the hole state, and solid-state effects. Here, for the first time, we set up a computational protocol to assess the peak broadening induced for both core and valence levels by solid-state effects in four amorphous polymers by using a combination of density functional theory, many-body perturbation theory, and classical polarizable embedding. We show that intrinsic local inhomogeneities in the electrostatic environment induce a Gaussian broadening of 0.2-0.7 eV in the binding energies of both core and semivalence electrons, corresponding to a full width at half-maximum (FWHM) of 0.5-1.7 eV for the investigated systems. The induced broadening is larger in acrylate-based than in styrene-based polymers, revealing the crucial role of polar groups in controlling the roughness of the electrostatic landscape in the solid matrix.

Disentangling the multiorbital contributions of excitons by photoemission exciton tomography.

Excitons are realizations of a correlated many-particle wave function, specifically consisting of electrons and holes in an entangled state. Excitons occur widely in semiconductors and are dominant excitations in semiconducting organic and low-dimensional quantum materials. To efficiently harness the strong optical response and high tuneability of excitons in optoelectronics and in energy-transformation processes, access to the full wavefunction of the entangled state is critical, but has so far not been feasible. Here, we show how time-resolved photoemission momentum microscopy can be used to gain access to the entangled wavefunction and to unravel the exciton's multiorbital electron and hole contributions. For the prototypical organic semiconductor buckminsterfullerene (C60), we exemplify the capabilities of exciton tomography and achieve unprecedented access to key properties of the entangled exciton state including localization, charge-transfer character, and ultrafast exciton formation and relaxation dynamics.

Doping-Induced Dielectric Catastrophe Prompts Free-Carrier Release in Organic Semiconductors.

The control over material properties attainable through molecular doping is essential to many technological applications of organic semiconductors, such as organic light-emitting diodes or thermoelectrics. These excitonic semiconductors typically reach the degenerate limit only at impurity concentrations of 5-10%, a phenomenon that has been put in relation with the strong Coulomb binding between charge carriers and ionized dopants, and whose comprehension remained elusive so far. This study proposes a general mechanism for the release of carriers at finite doping in terms of collective screening phenomena. A multiscale model for the dielectric properties of doped organic semiconductor is set up by combining first principles and microelectrostatic calculations. The results predict a large nonlinear enhancement of the dielectric constant (tenfold at 8% load) as the system approaches a dielectric instability (catastrophe) upon increasing doping. This can be attributed to the presence of highly polarizable host-dopant complexes, plus a nontrivial leading contribution from dipolar interactions in the disordered and heterogeneous system. The enhanced screening in the material drastically reduces the (free) energy barriers for electron-hole separation, rationalizing the possibility for thermal charge release. The proposed mechanism is consistent with conductivity data and sets the basis for achieving higher conductivities at lower doping loads.

High-Efficiency Ion-Exchange Doping of Conducting Polymers.

Molecular doping-the use of redox-active small molecules as dopants for organic semiconductors-has seen a surge in research interest driven by emerging applications in sensing, bioelectronics, and thermoelectrics. However, molecular doping carries with it several intrinsic problems stemming directly from the redox-active character of these materials. A recent breakthrough was a doping technique based on ion-exchange, which separates the redox and charge compensation steps of the doping process. Here, the equilibrium and kinetics of ion exchange doping in a model system, poly(2,5-bis(3-alkylthiophen-2-yl)thieno(3,2-b)thiophene) (PBTTT) doped with FeCl3 and an ionic liquid, is studied, reaching conductivities in excess of 1000 S cm-1 and ion exchange efficiencies above 99%. Several factors that enable such high performance, including the choice of acetonitrile as the doping solvent, which largely eliminates electrolyte association effects and dramatically increases the doping strength of FeCl3 , are demonstrated. In this high ion exchange efficiency regime, a simple connection between electrochemical doping and ion exchange is illustrated, and it is shown that the performance and stability of highly doped PBTTT is ultimately limited by intrinsically poor stability at high redox potential.

Analysis of External and Internal Disorder to Understand Band-Like Transport in n-Type Organic Semiconductors.

Charge transport in organic semiconductors is notoriously extremely sensitive to the presence of disorder, both internal and external (i.e., related to interactions with the dielectric layer), especially for n-type materials. Internal dynamic disorder stems from large thermal fluctuations both in intermolecular transfer integrals and (molecular) site energies in weakly interacting van der Waals solids and sources transient localization of the charge carriers. The molecular vibrations that drive transient localization typically operate at low-frequency (

Accurate Prediction of the S1 Excitation Energy in Solvated Azobenzene Derivatives via Embedded Orbital-Tuned Bethe-Salpeter Calculations.

By employing the Bethe-Salpeter formalism coupled with a nonequilibrium embedding scheme, we demonstrate that the paradigmatic case of S1 band separation between cis and trans in azobenzene derivatives can be computed with excellent accuracy compared to experimental optical spectra. Besides embedding, we show that the choice of the Kohn-Sham exchange correlation functional for DFT is critical, despite the iterative convergence of GW quasiparticle energies. We address this by adopting an orbital-tuning approach via the global hybrid functional, PBEh, yielding an environment-consistent ionization potential. The vertical excitation energy of 20 azo molecules is predicted with a mean absolute error as low as 0.06 eV, up to three times smaller compared to standard functionals such as M06-2X and PBE0, and five times smaller compared to recent TDDFT results.

Fate of Low-Lying Charge-Transfer Excited States in a Donor:Acceptor Blend with a Large Energy Offset.

In an effort to gain a comprehensive picture of the interfacial states in bulk heterojunction solar cells, we provide a combined experimental-theoretical analysis of the energetics and dynamics of low-lying electronic charge-transfer (CT) states in donor:acceptor blends with a large frontier orbital energy offset. By varying the blend composition and temperature, we unravel the static and dynamic contributions to the disordered density of states (DOS) of the CT-state manifold and assess their recombination to the ground state. Namely, we find that static disorder (conformational and electrostatic) shapes the CT DOS and that fast nonradiative recombination crops the low-energy tail of the distribution probed by external quantum efficiency (EQE) measurements (thereby largely contributing to voltage losses). Our results then question the standard practice of extracting microscopic parameters such as exciton energy and energetic disorder from EQE.

Orientation dependent molecular electrostatics drives efficient charge generation in homojunction organic solar cells.

Organic solar cells usually utilise a heterojunction between electron-donating (D) and electron-accepting (A) materials to split excitons into charges. However, the use of D-A blends intrinsically limits the photovoltage and introduces morphological instability. Here, we demonstrate that polycrystalline films of chemically identical molecules offer a promising alternative and show that photoexcitation of α-sexithiophene (α-6T) films results in efficient charge generation. This leads to α-6T based homojunction organic solar cells with an external quantum efficiency reaching up to 44% and an open-circuit voltage of 1.61 V. Morphological, photoemission, and modelling studies show that boundaries between α-6T crystalline domains with different orientations generate an electrostatic landscape with an interfacial energy offset of 0.4 eV, which promotes the formation of hybridised exciton/charge-transfer states at the interface, dissociating efficiently into free charges. Our findings open new avenues for organic solar cell design where material energetics are tuned through molecular electrostatic engineering and mesoscale structural control.