Effect of Molecular Side Groups and Local Nanoenvironment on Photodegradation and Its Reversibility

Degradation of organic semiconductors in the presence of oxygen is one of the bottlenecks preventing their wide-spread use in optoelectronic devices. The first step towards such degradation in functionalized pentacene (Pn) derivatives is formation of endoperoxide (EPO), which can either revert back to the parent molecule or proceed to molecule decomposition. We present the study of reversibility of EPO formation through probing the photophysical properties of functionalized fluorinated pentacene (Pn-R-F8) derivatives. Experiments are done in solutions and in films both at the single molecule level and in the bulk. In solutions, degradation of optical absorption and its partial recovery after thermolysis were quantified for various derivatives depending on the solvent. At the single molecule level, low concentrations of each type of molecules were imaged in a variety of polymer matrices at 633 nm excitation at room temperature in air using wide-field fluorescence microscopy. Fluorescence time trajectories were collected and statistically analyzed to quantify blinking due to reversible EPO formation depending on the host matrix. To understand the physical changes of the molecular system, a Monte Carlo method was used to create a multi-level simulation, which enabled us to relate the change in the molecular transition rates to the experimentally measured parameters. At the bulk level, photoluminescence decay due to photobleaching and recovery due to EPO reconversion were measured for the same derivatives incorporated into various matrices. These studies provide insight into the synergistic effect of the local nanoenvironment and molecular side groups on the oxygen-related degradation and subsequent recovery which is important for development of organic electronic devices

Charge carrier dynamics in organic semiconductors and their donor-acceptor composites: Numerical modeling of time-resolved photocurrent

We present a model that describes nanosecond (ns) time-scale photocurrent dynamics in functionalized anthradithiophene (ADT) films and ADT-based donor-acceptor (D/A) composites. By fitting numerically simulated photocurrents to experimental data, we quantify contributions of multiple pathways of charge carrier photogeneration to the photocurrent, as well as extract parameters that characterize charge transport (CT) in organic films including charge carrier mobilities, trap densities, hole trap depth, and trapping and recombination rates. In pristine ADT films, simulations revealed two competing charge photogeneration pathways: fast, occurring on picosecond (ps) or sub-ps time scales with efficiencies below 10%, and slow, which proceeds at the time scale of tens of nanoseconds, with efficiencies of about 11%-12%, at the applied electric fields of 40-80 kV/cm. The relative contribution of these pathways to the photocurrent was electric field dependent, with the contribution of the fast process increasing with applied electric field. However, the total charge photogeneration efficiency was weakly electric field dependent exhibiting values of 14%-20% of the absorbed photons. The remaining 80%-86% of the photoexcitation did not contribute to charge carrier generation at these time scales. In ADT-based D/A composites with 2 wt.% acceptor concentration, an additional pathway of charge photogeneration that proceeds via CT exciton dissociation contributed to the total charge photogeneration. In the composite with the functionalized pentacene (Pn) acceptor, which exhibits strong exciplex emission from a tightly bound D/A CT exciton, the contribution of the CT state to charge generation was small, similar to ~8%-12% of the total number of photogenerated charge carriers, dependent on the electric field. In contrast, in the composite with PCBM acceptor, the CT state contributed about a half of all photogenerated charge carriers. In both D/A composites, the charge carrier mobilities were reduced and trap densities and average trap depths were increased, as compared to a pristine ADT donor film. A considerably slower recombination of free holes with trapped electrons was found in the composite with the PCBM acceptor, which led to slower decays of the transient photocurrent and considerably higher charge retention, as compared to a pristine ADT donor film and the composite with the functionalized Pn acceptor. (C) 2013 AIP Publishing LLC.Keywords: Blends, Recombination, Solar cells, Transfer state, Polymer, Performance, Separation, Exciton dissociation, Photovoltaic devices, PhotogenerationKeywords: Blends, Recombination, Solar cells, Transfer state, Polymer, Performance, Separation, Exciton dissociation, Photovoltaic devices, Photogeneratio

Design of Organic Ternary Blends and Small-Molecule Bulk Heterojunctions: Photophysical Considerations

We explored relationships between photophysical processes and solar cell characteristics in solution-processable bulk heterojunctions (BHJs), in particular: (1) polymer donor:fullerene acceptor:small-molecule (SM) nonfullerene acceptor, (2) polymer donor:SM donor:SM nonfullerene acceptor, and (3) SM donor:SM nonfullerene or fullerene acceptor. Addition of a nonfullerene SM acceptor to “efficient” polymer:fullerene BHJs led to a reduction in power conversion efficiency (PCE), mostly due to decreased charge photogeneration efficiency and increased disorder. By contrast, addition of an SM donor to “inefficient” polymer:SM nonfullerene acceptor BHJs led to a factor of two to three improvement in the PCE, due to improved charge photogeneration efficiency and transport. In most blends, exciplex formation was observed and correlated with a reduced short-circuit current (Jsc) without negatively impacting the open-circuit voltage (Voc). A factor of ∼5 higher PCE was observed in SM donor:fullerene acceptor BHJs as compared to SMBHJs with the same SM donor but nonfullerene acceptor, due to enhanced charge carrier photogeneration in the blend with fullerene. Our study revealed that the HOMO and LUMO energies of molecules comprising a blend are not reliable parameters for predicting Voc of the blend, and an understanding of the photophysics is necessary for interpreting solar cell characteristics and improving the molecular design of BHJs

Single Molecule-Level Study of Donor-Acceptor Interactions and Nanoscale Environment in Blends

Organic semiconductors have attracted considerable attention due to their applications in low-cost (opto)electronic devices. The most successful organic materials for applications that rely on charge carrier generation, such as solar cells, utilize blends of several types of molecules. In blends, the local environment strongly influences exciton and charge carrier dynamics. However, relationship between nanoscale features and photophysics is difficult to establish due to the lack of necessary spatial resolution. We use functionalized fluorinated pentacene (Pn) molecule as single molecule probes of intermolecular interactions and of the nanoscale environment in blends containing donor and acceptor molecules. Single Pn donor (D) molecules were imaged in PMMA in the presence of acceptor (A) molecules using wide-field fluorescence microscopy. Two sample configurations were realized: (i) a fixed concentration of Pn donor molecules, with increasing concentration of acceptor molecules (functionalized indenflouorene or PCBM) and (ii) a fixed concentration of acceptor molecules with an increased concentration of the Pn donor. The D-A energy transfer and changes in the donor emission due to those in the acceptor- modified polymer morphology were quantified. The increase in the acceptor concentration was accompanied by enhanced photobleaching and blinking of the Pn donor molecules. To better understand the underlying physics of these processes, we modeled photoexcited electron dynamics using Monte Carlo simulations. The simulated blinking dynamics were then compared to our experimental data, and the changes in the transition rates were related to the changes in the nanoscale environment. Our study provides insight into evolution of nanoscale environment during the formation of bulk heterojunctions

Photophysics of Organic Semiconductors: From Ensemble to the Single-Molecule Level

We present photophysical properties of functionalized anthradithiophene (ADT) and pentacene (Pn) derivatives, as well as charge and energy transfer properties of donor-acceptor (D/A) pairs of these derivatives. All molecules studied were fluorescent and photostable enough to be imaged on the single-molecule level in a variety of polymeric and in a functionalized benzothiophene (BTBTB) crystalline host using room-temperature wide- field epifluorescence microscopy. Flexibility of functionalization of both guest (ADT, Pn) and host (BTBTB or polymer) molecules can be used for systematic studies of nanoscale morphology and photophysics of D/A organic semiconductor bulk heterojunctions, as well as in applications relying on FRET, using single-molecule fluorescence microscopy

Enhanced Charge Photogeneration Promoted by Crystallinity in Small-Molecule Donor-Acceptor Bulk Heterojunctions

We examined sub-nanosecond time-scale charge carrier dynamics in crystalline films of a functionalized anthradithiophene (ADT) donor (D) with three different acceptor (A) molecules. A four-fold enhancement in ultrafast charge carrier separation efficiency was observed in D/A blends with a fullerene acceptor added at 7–10 wt. % concentrations, whereas a gradual decrease in peak photocurrent amplitude with acceptor concentration was observed with functionalized pentacene and indenofluorene acceptors. The results were directly correlated with the ADT-tri(ethylsilyl)ethynyl-F donor crystallinity. In the best-performing blends, the presence of crystalline acceptor domains was also established

Fungi-Derived Pigments for Sustainable Organic (Opto)Electronics

We present on the optical and electronic properties of a fungi-derived pigment xylindein for potential use in (opto)electronic applications. Optical absorption spectra in solutions of various concentrations and in film are compared and are consistent with aggregate formation in concentrated solutions and films. In order to improve film morphology obtained by solution deposition techniques, an amorphous polymer PMMA was introduced to xylindein to form xylindein:PMMA blends. Current-voltage characteristics and hole mobilities extracted from space-charge limited currents were found to be comparable between pristine xylindein and xylindein:PMMA films. Side by side comparison of the photoresponse of pristine xylindein and xylindein:PMMA films at 633 nm revealed an increase in the photosensitivity in xylindein:PMMA films due to the improved morphology favouring enhanced charge generation

Organic semiconductor composites: influence of additives on the transient photocurrent

We report on the effect of various guest molecules added to a functionalized anthradithiophene (ADT) host on photoexcited charge carrier dynamics in solution-deposited thin films, from ~100 ps to >100 μs after photoexcitation with 100 fs laser pulses. An addition of 2 and 5 wt % of C60 to a fluorinated ADT derivative, ADT-TES-F, resulted in transient photocurrent amplitude enhancement by a factor of ~3 and 10, respectively. In contrast, an addition of 10 wt % of another ADT derivative, ADT-TIPS-CN, or a functionalized pentacene derivative (TIPS pentacene) to ADT-TES-F led to a decrease in the amplitude by a factor of ~3–4 and dramatically different photocurrent dynamics

Bioreplicated coatings for photovoltaic solar panels nearly eliminate light pollution that harms polarotactic insects

Many insect species rely on the polarization properties of object-reflected light for vital tasks like water or host detection. Unfortunately, typical glass-encapsulated photovoltaic modules, which are expected to cover increasingly large surfaces in the coming years, inadvertently attract various species of water-seeking aquatic insects by the horizontally polarized light they reflect. Such polarized light pollution can be extremely harmful to the entomofauna if polarotactic aquatic insects are trapped by this attractive light signal and perish before reproduction, or if they lay their eggs in unsuitable locations. Textured photovoltaic cover layers are usually engineered to maximize sunlight-harvesting, without taking into consideration their impact on polarized light pollution. The goal of the present study is therefore to experimentally and computationally assess the influence of the cover layer topography on polarized light pollution. By conducting field experiments with polarotactic horseflies (Diptera: Tabanidae) and a mayfly species (Ephemeroptera: Ephemera danica), we demonstrate that bioreplicated cover layers (here obtained by directly copying the surface microtexture of rose petals) were almost unattractive to these species, which is indicative of reduced polarized light pollution. Relative to a planar cover layer, we find that, for the examined aquatic species, the bioreplicated texture can greatly reduce the numbers of landings. This observation is further analyzed and explained by means of imaging polarimetry and ray-tracing simulations. The results pave the way to novel photovoltaic cover layers, the interface of which can be designed to improve sunlight conversion efficiency while minimizing their detrimental influence on the ecology and conservation of polarotactic aquatic insects