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Singlet fission (SF) is a multielectron process in which one singlet exciton S converts into a pair of triplet excitons T+T. SF is widely studied as it may help overcome the Shockley-Queisser efficiency limit for semiconductor photovoltaic cells. To elucidate and control the SF mechanism, great attention has been given to the identification of intermediate states in SF materials, which often appear elusive due to the complexity and fast timescales of the SF process. Here, we apply 10fs-1ms transient absorption techniques to high-purity rubrene single crystals to disentangle the intrinsic fission dynamics from the effects of defects and grain boundaries and to identify reliably the fission intermediates. We show that above-gap excitation directly generates a hybrid vibronically assisted mixture of singlet state and triplet-pair multiexciton [S:TT], which rapidly (<100fs) and coherently branches into pure singlet or triplet excitations. The relaxation of [S:TT] to S is followed by a relatively slow and temperature-activated (48 meV activation energy) incoherent fission process. The SF competing pathways and intermediates revealed here unify the observations and models presented in previous studies of SF in rubrene and propose alternative strategies for the development of SF-enhanced photovoltaic materials.

State-of-the-art Y6-type molecular acceptors exhibit nanosecond excited-state lifetimes despite their low optical gaps (~1.4 eV), thus allowing organic solar cells (OSCs) to achieve highly efficient charge generation with extended near-infrared (NIR) absorption range (up to ~1000 nm). However, the precise molecular-level mechanism that enables low-energy excited states in Y6-type acceptors to achieve nanosecond lifetimes has remained elusive. Here, we demonstrate that the distinct packing of Y6 molecules in film leads to a strong intermolecular charge-transfer (iCT) character of the lowest excited state in Y6 aggregates, which is absent in other low-gap acceptors such as ITIC. Due to strong electronic couplings between the adjacent Y6 molecules, the iCT-exciton energies are greatly reduced by up to ~0.25 eV with respect to excitons formed in separated molecules. Importantly, despite their low energies, the iCT excitons have reduced non-adiabatic electron-vibration couplings with the electronic ground state, thus suppressing non-radiative recombination and allowing Y6 to overcome the well-known energy gap law. Our results reveal the fundamental relationship between molecular packing and nanosecond excited-state lifetimes in NIR-absorbing Y6-type acceptors underlying the outstanding performance of Y6-based OSCs.

Kondo resonances in molecular adsorbates are an important building block for applications in the field of molecular spintronics. Here, we introduce the novel concept of using frontier orbital degeneracy for tailoring the magnetic state, which is demonstrated for the case of the organic semiconductor 1,4,5,8,9,11-Hexaazatriphenylenehexacarbonitrile (HATCN, C18N12) on Ag(111). Low-temperature scanning tunneling microscopy/spectroscopy (LT-STM/STS) measurements reveal the existence of two types of adsorbed HATCN molecules with distinctly different appearances and magnetic states, as evident from the presence or absence of an Abrikosov-Suhl-Kondo resonance. Our DFT results show that HATCN on Ag(111) supports two almost isoenergetic states, both with one excess electron transferred from the Ag surface, but with magnetic moments of either 0 or 0.65 uB. Therefore, even though all molecules undergo charge transfer of one electron from the Ag substrate, they exist in two different molecular magnetic states that resemble a free doublet or an entangled spin state. We explain how the origin of this behavior lies in the twofold degeneracy of the lowest unoccupied molecular orbitals of gas phase HATCN, lifted upon adsorption and charge-transfer from Ag(111). Our combined STM and DFT study introduces a new pathway to tailoring the magnetic state of molecular adsorbates on surfaces, with significant potential for spintronics and quantum information science.

Relative to conventional wet-chemical synthesis techniques, on-surface synthesis of organic networks in ultrahigh vacuum has few control parameters. The molecular deposition rate and substrate temperature are typically the only synthesis variables to be adjusted dynamically. Here we demonstrate that reducing conditions in the vacuum environment can be created and controlled without dedicated sources -- relying only on backfilled hydrogen gas and ion gauge filaments -- and can dramatically influence the Ullmann-like on-surface reaction used for synthesizing two-dimensional covalent organic frameworks (2D COFs). Using tribromo dimethylmethylene-bridged triphenylamine ((Br$_3$)DTPA) as monomer precursors, we find that atomic hydrogen blocks aryl-aryl bond formation. Control of the relative monomer and hydrogen fluxes is used to produce large islands of self-assembled monomers, dimers, or macrocycle hexamers. On-surface synthesis of these oligomers, from a single precursor, circumvents potential challenges with protracted wet-chemical synthesis or low precursor volatility for large molecules. Using scanning tunneling microscopy and spectroscopy (STM/STS), we show that changes in the electronic states through this oligomer sequence provide an insightful view of the 2D-COF (synthesized in the absence of atomic hydrogen) as the endpoint in an evolution of electronic structures from the monomer.

Carbyne, i.e. an infinitely long linear carbon chain (LCC), has been at the focus of a lot of research for quite a while, yet its optical, electronic, and vibrational properties have only recently started to become accessible experimentally thanks to its synthesis inside carbon nanotubes (CNTs). While the role of the host CNT in determining the optical gap of the LCCs has been studied previously, little is known about the excited states of such ultralong LCCs. In this work, we employ the selectivity of wavelength-dependent resonant Raman spectroscopy to investigate the excited states of ultralong LCCs encapsulated inside double-walled CNTs. In addition to the optical gap, the Raman resonance profile shows three additional resonances. Corroborated with DFT calculations on LCCs with up to 100 C-atoms, we assign these resonances to a vibronic series of a different electronic state. Indeed, the calculations predict the existence of two optically allowed electronic states separated by an energy of 0.14-0.22 eV in the limit of an infinite chain, in agreement with the experimental results. Furthermore, among these two states, the one with highest energy is also characterized by the largest electron-vibration couplings, which explains the corresponding vibronic series of overtones.

Amorphous organic semiconductors based on small molecules and polymers are used in many applications, most prominently organic light emitting diodes (OLEDs) and organic solar cells. Impurities and charge traps are omnipresent in most currently available organic semiconductors and limit charge transport and thus device efficiency. The microscopic cause as well as the chemical nature of these traps are presently not well understood. Using a multiscale model we characterize the influence of impurities on the density of states and charge transport in small-molecule amorphous organic semiconductors. We use the model to quantitatively describe the influence of water molecules and water-oxygen complexes on the electron and hole mobilities. These species are seen to impact the shape of the density of states and to act as explicit charge traps within the energy gap. Our results show that trap states introduced by molecular oxygen can be deep enough to limit the electron mobility in widely used materials., Comment: 13 pages + SI, 7 figures + TOC-graphic + 2 figures in SI

The chemical modification of electrodes with organic materials is a common approach to tune the electronic and electrostatic landscape between interlayers in optoelectronic devices, thus facilitating charge injection at the electrode/semiconductor interfaces and improving their performance. The use of photochromic molecules for the surface modification allows dynamic control of the electronic and electrostatic properties of the electrode and thereby enables additional functionalities in such devices. Here, we show that the electronic properties of a transparent indium tin oxide (ITO) electrode are reversibly and dynamically modified by depositing organic photochromic switches (diarylethenes) in the form of self-assembled monolayers (SAMs). By combining a range of surface characterization and density functional theory calculations, we present a detailed picture of the SAM binding onto ITO, the packing density of molecules, their orientation, as well as the work function modification of the ITO surface due to the SAM deposition. Upon illumination with ultraviolet and green light, we observe a reversible shift of the frontier occupied levels by 0.7 eV, and concomitantly a reversible work function change of ca. 60 meV. Our results prove the viability of dynamic switching of the electronic properties of the electrode with external light stimuli, which could be used to fabricate ITO-based photo-switchable optoelectronic devices.

Two-dimensional (2D) perovskites with general formula $APbX_4$ are attracting increasing interest as solution processable, white-light emissive materials. Recent studies have shown that their broadband emission is related to the formation of intra-gap color centers; however, the nature and dynamics of the emissive species have remained elusive. Here we show that the broadband photoluminescence of the 2D perovskites $(EDBE)PbCl_4$ and $(EDBE)PbBr_4$ stems from the localization of small polarons within the lattice distortion field. Using a combination of spectroscopic techniques and first-principles calculations, we infer the formation of ${Pb_2}^{3+}$, $Pb^{3+}$, and ${X_2}^-$ (where X=Cl or Br) species confined within the inorganic perovskite framework. Due to strong Coulombic interactions, these species retain their original excitonic character and form self-trapped polaron-excitons acting as radiative color centers. These findings are expected to be applicable to a broad class of white-light emitting perovskites with large polaron relaxation energy., Comment: 34 pages, 15 figures, 3 tables

The soft character of organic materials leads to strong coupling between molecular nuclear and electronic dynamics. This coupling opens the way to control charge transport in organic electronic devices by inducing molecular vibrational motions. However, despite encouraging theoretical predictions, experimental realization of such control has remained elusive. Here we demonstrate experimentally that photoconductivity in a model organic optoelectronic device can be controlled by the selective excitation of molecular vibrations. Using an ultrafast infrared laser source to create a coherent superposition of vibrational motions in a pentacene/C60 photoresistor, we observe that excitation of certain modes in the 1500-1700 cm$^{-1}$ region leads to photocurrent enhancement. Excited vibrations affect predominantly trapped carriers. The effect depends on the nature of the vibration and its mode-specific character can be well described by the vibrational modulation of intermolecular electronic couplings. Vibrational control thus presents a new tool for studying electron-phonon coupling and charge dynamics in (bio)molecular materials.

We present a multiscale modeling of the infrared optical properties of the rubrene crystal. The results are in very good agreement with the experimental data that point to nonmonotonic features in the optical conductivity spectrum and small optical effective masses. We find that, in the static-disorder approximation, the nonlocal electron-phonon interactions stemming from low-frequency lattice vibrations can decrease the optical effective masses and lead to lighter quasiparticles. On the other hand, the charge-transport and infrared optical properties of the rubrene crystal at room temperature are demonstrated to be governed by localized carriers driven by inherent thermal disorders. Our findings underline that the presence of apparently light carriers in high-mobility organic semiconductors does not necessarily imply band-like transport.

We report on electronic-structure calculations for the pentacene and rubrene crystals, based on experimental crystal geometries measured at different temperatures. The results are in very good agreement with angle-resolved photoelectron spectroscopy data that indicate that the widths of the valence and conduction bands in both materials become narrower at higher temperatures. Our findings strongly suggest that the thermal bandwidth narrowing in the pentacene and rubrene crystals is primarily caused by the thermal expansion of the lattice rather than by a renormalization of the transfer integrals induced by a polaron effect. The effect of thermal expansion on the charge-transport properties is also discussed., Comment: This paper has been withdrawn by the authors to comply with the publication policy of ACS

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 interactions in reciprocal space. Our findings demonstrate the importance of aspects that are usually missing in current transport models. Importantly, an adequate description of the electronic and charge-transport properties of organic semiconductors requires that the models take into account both antisymmetric and symmetric contributions to the nonlocal electron-phonon coupling mechanism., Comment: Please refer to: PhysRevB.85.245201(2012)