By comparing photoemission spectroscopy with a non-perturbative dynamical mean field theory extension to many-body ab initio calculations, we show in the prominent case of pentacene crystals that an excellent agreement with experiment for the bandwidth, dispersion and lifetime of the hole carrier bands can be achieved in organic semiconductors provided that one properly accounts for the coupling to molecular vibrational modes and the presence of disorder. Our findings rationalize the growing experimental evidence that even the best band structure theories based on a many-body treatment of electronic interactions cannot reproduce the experimental photoemission data in this important class of materials.
We elucidate the crystalline nature and the three-dimensional orientation of isolated organic nanocrystals embedded in a sol-gel matrix, using a polarized nonlinear microscopy technique that combines two-photon fluorescence and second harmonic generation. This technique allows the distinction between mono-crystalline structures and nano-scale poly-crystalline aggregates responsible for incoherent second harmonic signals.
Molecular organic materials offer the promise of novel electronic devices but also present challenges for understanding charge transport in narrow band systems. Low temperature studies elucidate fundamental transport processes. We report the lowest temperature field effect transport results on a crystalline oligomeric organic material, rubrene. We find field effect switching with on-off ratio up to 10^7 at temperatures down to 10 K. Gated transport shows a factor of ~10 suppression of the thermal activation energy in 10-50 K range and nearly temperature independent resistivity below 10 K.
We consider different structures, which can be obtained by polymerization of aromatic organic molecules under high pressures. These 2D and 3D covalently bonded organic polymers and their functionalization can pave the way to production of energy storage and conversion devices. High-pressure synthesis might serve as a useful hint for production of these structures and their functionalized analogs by means of wet chemical synthesis.
We introduce a new fingerprint that allows distinguishing between liquid-like and solid-like atomic environments. This fingerprint is based on an approximate expression for the entropy projected on individual atoms. When combined with a local enthalpy, this fingerprint acquires an even finer resolution and it is capable of discriminating between different crystal structures.
The consequences of several microscopic interactions on the photoemission spectra of crystalline organic semiconductors (OSC) are studied theoretically. It is argued that their relative roles can be disentangled by analyzing both their temperature and their momentum/energy dependence. Our analysis shows that the polaronic thermal band narrowing, that is the foundation of most theories of electrical transport in OSC, is inconsistent in the range of microscopic parameters appropriate for these materials. An alternative scenario is proposed to explain the experimental trends.
We show that the thermal stability of thin films of the organic semiconductor diindenoperylene (DIP) can be strongly enhanced by aluminum oxide capping layers. By thermal desorption spectroscopy and in-situ X-ray diffraction we demonstrate that organic films do not only stay on the substrate, but even remain crystalline up to 460C, i.e. 270 deg. above their desorption point for uncapped films (190C). We argue that this strong enhancement of the thermal stability compared to uncapped and also metal-capped organic layers is related to the very weak diffusion of aluminum oxide and the structurall…
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…
Although physisorption is a widely occurring mechanism of bonding at the organic/metal interface, contradictory interpretations of this phenomenon are often reported. Photoemission and X-ray absorption spectroscopy investigations of nanorods of a substituted pentacene, 2,3,9,10-tetrafluoropentacene, deposited on gold single crystals reveal to be fundamental to identify the bonding mechanisms. We find fingerprints of a fractional charge transfer from the clean metal substrate to the physisorbed molecules. This phenomenon is unambiguously recognizable by a non-rigid shift of the core-level main …
Covalent-organic frameworks (COFs) are intriguing platforms for designing functional molecular materials. Here, we present a computational study based on van der Waals dispersion-corrected hybrid density functional theory calculations to analyze the material properties of boroxine-linked and triazine-linked intercalated-COFs. The effect of Fe atoms on the electronic band structures near the Fermi energy level of the intercalated-COFs have been investigated. The density of states (DOSs) computations have been performed to analyze the material properties of these kind of intercalated-COFs. We pr…
The alkali hyperoxide KO$_2$ is a molecular analog of strongly-correlated systems, comprising of orbitally degenerate magnetic O$_2^-$ ions. Using first-principles electronic structure calculations, we set up an effective spin-orbital model for the low-energy \textit{molecular} orbitals and argue that many anomalous properties of KO$_2$ replicate the status of its orbital system in various temperature regimes.
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…
Measuring similarities/dissimilarities between atomic structures is important for the exploration of potential energy landscapes. However, the cell vectors together with the coordinates of the atoms, which are generally used to describe periodic systems, are quantities not suitable as fingerprints to distinguish structures. Based on a characterization of the local environment of all atoms in a cell we introduce crystal fingerprints that can be calculated easily and allow to define configurational distances between crystalline structures that satisfy the mathematical properties of a metric. Thi…
Rapid, non-destructive characterization of molecular level chemistry for organic matter (OM) is experimentally challenging. Raman spectroscopy is one of the most widely used techniques for non-destructive chemical characterization, although it currently does not provide detailed identification of molecular components in OM, due to the combination of diffraction-limited spatial resolution and poor applicability of peak-fitting algorithms. Here, we develop a genome-inspired collective molecular structure fingerprinting approach, which utilizes ab initio calculations and data mining techniques to…
We investigate the direct-current response of crystalline organic semiconductors in the presence of finite external electric fields by the quantum-classical Ehrenfest dynamics complemented with instantaneous decoherence corrections (IDC). The IDC is carried out in the real-space representation with the energy-dependent reweighing factors to account for both intermolecular decoherence and energy relaxation by which conduction occurs. In this way, both the diffusion and drift motion of charge carriers are described in a unified framework. Based on an off-diagonal electron-phonon coupling model f…
Terahertz Time-Domain Spectroscopy as a Universal Defect Fingerprinting Tool for Organic Halide Perovskite Solar Cells
YUHS-KRIBB Medical Convergence Research Institute, College of Medicine, Yonsei University（延世大学医学院YUHS-KRIBB医学融合研究所）；Beamline Department, Pohang Accelerator Laboratory, POSTECH（韩国科学技术院浦项加速器实验室光束线部门）；Department of Physics, University of Seoul（首尔大学物理系）；Global Institute of Future Technology, Shanghai Jiao Tong University（上海交通大学全球未来技术研究院）
In addition to electronic polarization or charge redistribution, the shape of neutral conjugated molecules yields position-dependent ionization potentials and electron affinities in organic thin films. Self-consistent I(n) and A(n) are computed in each layer n of 10-layer films of prototypical organics on a metal. The depth dependence of I(n) is discussed at surfaces of anthracene, C60 and PTCDA. The shape contribution can be substantial, up to 0.5 eV, and comes primarily from charge-quadrupole interactions.
The effect of thermal structural fluctuations on the modulation of the transfer integrals between close molecules is studied using a combination of molecular dynamics simulations and quantum chemical calculations of the transfer integral. We have found that the fluctuations of the transfer integrals are of the same order of magnitude of their average value for two common organic semiconductors an observation that puts into question the currently adopted models for charge transport in organic semiconductors and identifies in the dynamic electronic disorder the limiting factor for the charge car…
Charge transport in crystalline organic semiconductors is intrinsically limited by the presence of large thermal molecular motions, which are a direct consequence of the weak van der Waals inter-molecular interactions. These lead to an original regime of transport called \textit{transient localization}, sharing features of both localized and itinerant electron systems. After a brief review of experimental observations that pose a challenge to the theory, we concentrate on a commonly studied model which describes the interaction of the charge carriers with inter-molecular vibrations. We present…
Southern University of Science and Technology（南方科技大学）；Shanghai University（上海大学）；Zhejiang Laboratory（之江实验室）
In the process of finding high-performance organic semiconductors (OSCs), it is of paramount importance in material development to identify important functional units that play key roles in material performance and subsequently establish substructure-property relationships. Herein, we describe a polymer-unit fingerprint (PUFp) generation framework. Machine learning (ML) models can be used to determine structure-mobility relationships by using PUFp information as structural input with 678 pieces of collected OSC data. A polymer-unit library consisting of 445 units is constructed, and the key po…
We consider the non-radiative resonant energy transfer from a two-dimensional Wannier exciton (donor) to a Frenkel exciton of a molecular crystal overlayer (acceptor). We characterize the effect of the optical anisotropy of the organic subsystem on this process. Using realistic values of material parameters, we show that it is possible to change the transfer rate within typically a factor of two depending on the orientation of the crystalline overlayer. The resonant matching of donor and acceptor energies is also partly tunable via the organic crystal orientation.
Free electron laser-powered pulsed electron paramagnetic resonance (EPR) experiments performed at 240 GHz / 8.56 T on the crystalline organic radical BDPA reveal a tip-angle dependent resonant frequency. Frequency shifts as large as 11 MHz (45 ppm) are observed during a single Rabi oscillation. We attribute the frequency shifts to a "dressing" of the nutation by spin-spin interactions. A nonlinear semi-classical model which includes a temperature- and sample-geometry-dependent demagnetizing field reproduces experimental results. Because experiments are performed without a cavity, radiation dam…
A relation derived from the Kubo formula shows that optical conductivity measurements below the gap frequency in doped semiconductors can be used to probe directly the time-dependent quantum dynamics of charge carriers. This allows to extract fundamental quantities such as the elastic and inelastic scattering rates, as well as the localization length in disordered systems. When applied to crystalline organic semiconductors, an incipient electron localization caused by large dynamical lattice disorder is unveiled, implying a breakdown of semiclassical transport.
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…
The transport properties at finite temperature of crystalline organic semiconductors are investigated, within the Su-Schrieffer-Heeger model, by combining exact diagonalization technique, Monte Carlo approaches, and maximum entropy method. The temperature-dependent mobility data measured in single crystals of rubrene are successfully reproduced: a crossover from super- to sub-diffusive motion occurs in the range $150 \leq T \leq 200$ K, where the mean free path becomes of the order of the lattice parameter and strong memory effects start to appear. We provide an effective model which can succe…
Many crystals in nature exhibit fascinating mechanical, optical, magnetic and other characteristics. One of the reasons for this phenomenon has to do with the presence of specific organic molecules that are tightly associated with the mineral. Over the years, some organic crystals have been found to be located within the lattices of their singlecrystalline biogenic hosts. A number of questions remain unanswered: for example, how do these molecules become incorporated and what is their function? In this review we survey the gradual refinement of the above mentioned finding in biogenic crystals,…
It is textbookly regarded that phonons, i.e., an energy quantum of propagating lattice waves, are the main heat carriers in perfect crystals. As a result, in many crystals, e.g., bulk silicon, the temperature-dependent thermal conductivity shows the classical 1/T relationship because of the dominant Umklapp phonon-phonon scattering in the systems. However, the thermal conductivity of many crystalline metal-organic frameworks is very low and shows no, a weakly negative and even a weakly positive temperature dependence (glass-like thermal conductivity). It has been in debate whether the thermal …
The performance of organic solar cells strongly depends on the bulk heterojunction (BHJ) morphology of the photoactive layer. This BHJ forms during the drying of the wet-deposited solution, because of physical processes such as crystallization and/or liquid liquid phase separation (LLPS). However, the process-structure relationship remains insufficiently understood. In this work, a recently developed, coupled phase field fluid mechanics framework is used to simulate the BHJ formation upon drying. For the first time, this allows to investigate the interplay between all the relevant physical pro…
The nucleation mechanisms during solution deposition of organic semiconductor thin films determine the grain morphology and may influence the crystalline packing in some cases. Here, in-situ optical spectromicroscopy in reflection mode is used to study the growth mechanisms and thermal stability of 6,13-bis(trisopropylsilylethynyl)-pentacene thin films. The results show that the films form in a supersaturated state before transforming to a solid film. Molecular aggregates corresponding to subcritical nuclei in the crystallization process are inferred from optical spectroscopy measurements of t…
Electron-phonon coupling plays a central role in the transport properties and photophysics of organic crystals. Successful models describing charge- and energy-transport in these systems routinely include these effects. Most models for describing photophysics, on the other hand, only incorporate local electron-phonon coupling to intramolecular vibrational modes, while nonlocal electron-phonon coupling is neglected. One might expect nonlocal coupling to have an important effect on the photophysics of organic crystals, because it gives rise to large fluctuation in the charge-transfer couplings, …
Metal--organic frameworks (MOFs) are a family of chemically diverse materials, with applications in a wide range of fields covering engineering, physics, chemistry, biology and medicine. Research so far has focused almost entirely on crystalline structures, yet a clear trend has emerged shifting the emphasis onto disordered states of MOFs, including "defective by design" crystals, as well as amorphous phases such as glasses and gels. Here we introduce a MOF liquid, a strongly associated liquid obtained by melting a zeolitic imidazolate framework (ZIF), with retention of chemical configuration,…
Since the discovery of the TTF-TCNQ charge transfer complex as the first metallic material composed of molecules, many other molecular metals were reported. It was however only recently that the first metal-free single-component organic metal was characterized by Kobayashi et al. Although the measured properties of a poorly crystalline sample clearly showed metallic behavior, the crystal structure itself could not be solved, so that the conduction mechanism in this material is still unknown. Here, we present the results of theoretical crystal structure prediction calculations for the TED molec…
Crystalline organic semiconductors, bonded by weak van der Waals forces, exhibit macroscopic properties that are very similar to those of inorganic semiconductors. While there are many open questions concerning the microscopic nature of charge transport, minimizing the density of trap states (trap DOS) is crucial to elucidate the intrinsic transport mechanism. We explore the limits of state-of-the-art organic crystals by measuring single crystalline rubrene field-effect transistors that show textbook like transfer characteristics, indicating a very low trap DOS. Particularly, the high purity o…
We combined the group theory and data mining approach within the Organic Materials Database that leads to the prediction of stable Dirac-point nodes within the electronic band structure of 3-dimensional organic crystals. We find a particular space group $P2_12_12_1$ ($\#19$) that is conducive to the Dirac nodes formation. We prove that nodes are a consequence of the orthorhombic crystal structure. Within the electronic band structure, two different kinds of nodes can be distinguished: 8-fold degenerate Dirac nodes protected by the crystalline symmetry and 4-fold degenerate Dirac nodes protecte…
An oligomeric semiconductor containing three bisthiophenediketopyrrolopyrole units (Tri-BTDPP) was synthesized and characterized. Tri-BTDPP has a HOMO level of -5.34 eV, a broad absorption close to the near infrared region and a low band gap of 1.33 eV. Additionally, a promising hole mobility of 1 x 10-3 cm V-1 s-1 was achieved after thermal annealing at 150 C in organic field effect transistors (OFET). Organic photovoltaic (OPV) cells containing Tri-BTDPP and PC71BM as the donor/acceptor couple exhibited a power conversion efficiency (PCE) of 0.72%. Through an intensive study of the active la…
The electronic and electrical properties of crystalline organic semiconductors, such as the dispersions of the electronic bands and the dependence of charge-carrier mobility on temperature, are greatly impacted by the nonlocal electron-phonon interactions associated with intermolecular lattice vibrations. Here, we present a theoretical description that underlines that these properties vary differently as a function of the symmetry of the nonlocal electron-phonon coupling mechanism. The electron-phonon coupling patterns in real space are seen to have a direct and significant impact on the inter…
We propose an experimental method to examine the in-plane anisotropy of electronic structure in layered conductors. In the method, we measure the interlayer magnetoresistance as a function of in-plane magnetic field orientation. We applied it to an organic Dirac fermion system a-(BEDT-TTF)2I3 to experimentally determine the orientation of the anisotropic Dirac cones. It is concluded that the long axis of the elliptic constant-energy contours of the Dirac cone is tilted by approximately -30 deg from the crystalline a-axis to b-axis under hydrostatic pressures. Additionally, we observed a signat…
We have measured the thermal resistances of thin films of the small molecule organic semiconductors bis(triisopropylsilylethynyl) pentacene (TIPS-pn), bis(triethylsilylethynyl) anthradithiophene (TES-ADT) and difluoro bis(triethylsilylethynyl) anthradithiophene (diF-TES-ADT). For each material, several films of different thicknesses have been measured to separate the effects of intrinsic thermal conductivity from interface thermal resistance. For non-crystalline films of all three materials, with thicknesses ranging from < 100 nm to > 4 microns, the thermal conductivities are similar to that o…
Carrier multiplication by singlet exciton fission enhances photovoltaic conversion efficiencies in organic solids. This decay of one singlet exciton into two triplet states promises to overcome the Shockley-Queisser limit as up to two electrons may be harvested per absorbed photon. Intermolecular coupling is deemed mandatory for both, singlet exciton fission and a band-like transport. Such a coupling is manifested, $e.g.$, by the Davydov-splitting of the lowest-energy exciton transition in crystalline organic solids. For the model system perfluoropentacene, the corresponding transitions in the…
Charge-transfer excitons (CTX) at organic donor/acceptor interfaces are considered important intermediates for charge separation in photovoltaic devices. Crystalline model systems provide microscopic insights into the nature of such states as they enable microscopic structure-property investigations. Here, we use angular-resolved UV/Vis absorption spectroscopy to characterize the CTX of crystalline pentacene:perfluoro-pentacene (PEN:PFP) films allowing to determine the polarization of this state. This analysis is complemented by first-principles many-body calculations, performed on the three-d…
The heat transfer properties of the organic molecular crystal $α$-RDX were studied using three phonon-based thermal conductivity models. It was found that the widely used Peierls-Boltzmann model for thermal transport in crystalline materials breaks down for $α$-RDX. We show this breakdown is due to a large degree of anharmonicity that leads to a dominance of diffusive-like carriers. Despite being developed for disordered systems, the Allen-Feldman theory for thermal conductivity actually gives the best description of thermal transport. This is likely because diffusive carriers contribute to ov…
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-…
Data-driven methodologies for designing new materials are developing apace, yet advances for organic crystals have been infrequent. For organic crystals, the need to predict solid-state electronic properties from molecular structure alone is an exceedingly difficult task for typical, regression-based design strategies. In this paper, we present a new strategy for designing organic crystals which circumvents the need to regress solid-state physical properties directly. At the core of this strategy is an electronic structure chart, a two-dimensional projection of an organic crystal database in w…
The dynamic disorder model for charge carrier transport in organic semiconductors has been extensively studied in recent years. Although it is successful on determining the value of bandlike mobility in the organic crystalline materials, the incoherent hopping, the typical transport characteristic in organic semiconductors, cannot be described. In this work, the decoherence process is taken into account via a phenomenological parameter, say decoherence time, and the projective and Monte Carlo method is applied for this model to determine the waiting time and thus the diffusion coefficient. We …
We find that the hole mobility of the crystal smectic phases of the liquid crystal 1,4-di-(5-n-tridecylthien-2-yl)-benzene increases exponentially with decreasing temperature. While qualitatively consistent with transport via polaron bands, we find that it is quantitatively difficult to explain the behaviour with physically realistic parameters. In particular, the data demand either quite large typical optical phonon frequencies and/or phonon bandwidths. We also find evidence that an unusually highly ordered smectic-F phase templates the formation of lower temperature highly crystalline smecti…
Organosulfur compounds at the interface to noble metals have proved over the last decades to be extremely versatile systems for both fundamental and applied research. However, the anchoring of thiols to gold remained an object of controversy for long times. The RS-Au-SR linkage, in particular, is a robust bonding configuration that displays interesting properties. It is generated spontaneously at room temperature and can be used for the production of extended molecular nanostructures. In this work we explore the behavior of 1,4-Bis(4-mercaptophenyl)benzene (BMB) on the Au(111) surface, which r…
We explore the charge transport mechanism in organic semiconductors based on a model that accounts for the thermal intermolecular disorder at work in pure crystalline compounds, as well as extrinsic sources of disorder that are present in current experimental devices. Starting from the Kubo formula, we develop a theoretical framework that relates the time-dependent quantum dynamics of electrons to the frequency-dependent conductivity. The electron mobility is then calculated through a relaxation time approximation that accounts for quantum localization corrections beyond Boltzmann theory, and …
