Elucidating Operating Modes of Bulk-Heterojunction Solar Cells from Impedance Spectroscopy Analysis

We discuss the progress and challenges in the application of impedance spectroscopy analysis to determine key processes and parameters in organic bulk-heterojunction solar cells. When carrier transport or outer interface extraction do not severely influence the solar cell performance, a simple method to quantify the open-circuit voltage loss caused by the kinetics of charge carrier recombination is provided, based on the determination of chemical capacitance and recombination resistance. This easily allows distinguishing between energetic and kinetic effects on photovoltage, and establishes a benchmark for the performance comparison of a set of different cells. A brief discussion of impedance analysis in the much less studied case of collection-limited solar cells is introduced

Additional file 1: Table S1. of Amyotrophic lateral sclerosis modifies progenitor neural proliferation in adult classic neurogenic brain niches

Antibodies used in the immunohistochemical study. Table S2. Summary of patient characteristics. Table S3. Immunohistochemical studies used in ALS diagnosis. Values for TDP-43 and ubiquitin are expressed in inclusions per field; %pTDP-43 represents the percentage of phosphorylated TDP inclusions out of the total. Table S4. Description of neurogenesis patient to patient. Table S5. Neurogenesis findings in the subgranular zone of the hippocampal dentate gyrus, by patient. Table S6. Summary of results in the SVZ. Table S7. Summary of results in the hippocampus. (DOC 302 kb

Recombination in Organic Bulk Heterojunction Solar Cells: Small Dependence of Interfacial Charge Transfer Kinetics on Fullerene Affinity

We investigate the causes for obtaining higher open-circuit voltage in solar cells that use a fullerene with a smaller electron affinity. Using impedance spectroscopy technique, we show that the change of fullerene LUMO energy has very little influence on the kinetic rate of charge transfer across the interface. In terms of the Marcus theory, large reorganization energy values govern the recombination kinetic rate, which is only slightly dependent on the fullerene LUMO energy, and also depends weakly on the energy location of recombining carriers within the broad density of states. Since the recombination rate is very similar in the different devices, we conclude that the larger open-circuit voltage is due to the larger donor HOMO/acceptor LUMO offset

Toward Stable Solar Hydrogen Generation Using Organic Photoelectrochemical Cells

Organic photoactive materials are promising candidates for the generation of solar fuels in terms of efficiency and cost. However, their low stability in aqueous media constitutes a serious problem for technological deployment. Here we present organic photocathodes for the generation of hydrogen in aqueous media with outstanding stability. The device design relies on the use of water-resistant selective contacts, which protect a P3HT:PCBM photoactive layer. An insoluble cross-linked PEDOT:PSS hole-selective layer avoids delamination of the film, and an electron-selective TiO_<i>x</i> layer in contact with the aqueous solution electrically communicates the organic layer with the hydrogen-evolving catalyst (Pt). We developed a novel method for the synthesis of the TiO_<i>x</i> layer compatible with low-temperature conditions. Tuning the thickness of the TiO_<i>x</i>/Pt layer leads to a trade-off between the achievable photocurrent (∼1 mAcm^–2) and the stability of the photocathode (stable hydrogen generation of 1.5 μmol h^–1 cm^–2 for >3 h)

Interplay between Fullerene Surface Coverage and Contact Selectivity of Cathode Interfaces in Organic Solar Cells

Interfaces play a determining role in establishing the degree of carrier selectivity at outer contacts in organic solar cells. Considering that the bulk heterojunction consists of a blend of electron donor and acceptor materials, the specific relative surface coverage at the electrode interfaces has an impact on the carrier selectivity. This work unravels how fullerene surface coverage at cathode contacts lies behind the carrier selectivity of the electrodes. A variety of techniques such as variable-angle spectroscopic ellipsometry and capacitance–voltage measurements have been used to determine the degree of fullerene surface coverage in a set of PCPDTBT-based solar cells processed with different additives. A full screening from highly fullerene-rich to polymer-rich phases attaching the cathode interface has enabled the overall correlation between surface morphology (relative coverage) and device performance (operating parameters). The general validity of the measurements is further discussed in three additional donor/acceptor systems: PCPDTBT, P3HT, PCDTBT, and PTB7 blended with fullerene derivatives. It is demonstrated that a fullerene-rich interface at the cathode is a prerequisite to enhance contact selectivity and consequently power conversion efficiency

Molecular Electronic Coupling Controls Charge Recombination Kinetics in Organic Solar Cells of Low Bandgap Diketopyrrolopyrrole, Carbazole, and Thiophene Polymers

Low-bandgap diketopyrrolopyrrole- and carbazole-based polymer bulk-heterojunction solar cells exhibit much faster charge carrier recombination kinetics than that encountered for less-recombining poly­(3-hexylthiophene). Solar cells comprising these polymers exhibit energy losses caused by carrier recombination of approximately 100 mV, expressed as reduction in open-circuit voltage, and consequently photovoltaic conversion efficiency lowers in more than 20%. The analysis presented here unravels the origin of that energy loss by connecting the limiting mechanism governing recombination dynamics to the electronic coupling occurring at the donor polymer and acceptor fullerene interfaces. Previous approaches correlate carrier transport properties and recombination kinetics by means of Langevin-like mechanisms. However, neither carrier mobility nor polymer ionization energy helps understanding the variation of the recombination coefficient among the studied polymers. In the framework of the charge transfer Marcus theory, it is proposed that recombination time scale is linked with charge transfer molecular mechanisms at the polymer/fullerene interfaces. As expected for efficient organic solar cells, small electronic coupling existing between donor polymers and acceptor fullerene (<i>V</i>_if < 1 meV) and large reorganization energy (λ ≈ 0.7 eV) are encountered. Differences in the electronic coupling among polymer/fullerene blends suffice to explain the slowest recombination exhibited by poly­(3-hexylthiophene)-based solar cells. Our approach reveals how to directly connect photovoltaic parameters as open-circuit voltage to molecular properties of blended materials

How the Charge-Neutrality Level of Interface States Controls Energy Level Alignment in Cathode Contacts of Organic Bulk-Heterojunction Solar Cells

Electronic equilibration at the metal–organic interface, leading to equalization of the Fermi levels, is a key process in organic optoelectronic devices. How the energy levels are set across the interface determines carrier extraction at the contact and also limits the achievable open-circuit voltage under illumination. Here, we report an extensive investigation of the cathode energy equilibration of organic bulk-heterojunction solar cells. We show that the potential to balance the mismatch between the cathode metal and the organic layer Fermi levels is divided into two contributions: spatially extended band bending in the organic bulk and voltage drop at the interface dipole layer caused by a net charge transfer. We scan the operation of the cathode under a varied set of conditions, using metals of different work functions in the range of ∼2 eV, different fullerene acceptors, and several cathode interlayers. The measurements allow us to locate the charge-neutrality level within the interface density of sates and calculate the corresponding dipole layer strength. The dipole layer withstands a large part of the total Fermi level mismatch when the polymer:fullerene blend ratio approaches ∼1:1, producing the practical alignment between the metal Fermi level and the charge-neutrality level. Origin of the interface states is linked with fullerene reduced molecules covering the metal contact. The dipole contribution, and consequently the band bending, is highly sensitive to the nature and amount of fullerene molecules forming the interface density of states. Our analysis provides a detailed picture of the evolution of the <i>potentials</i> in the bulk and the interface of the solar cell when forward <i>voltage</i> is applied or when photogeneration takes place

Amorphous Iron Oxyhydroxide Nanosheets: Synthesis, Li Storage, and Conversion Reaction Kinetics

We present a facile approach to synthesize amorphous iron oxyhydroxide nanosheet from the surfactant-assisted oxidation of iron sulfide nanosheet. The amorphous iron oxyhydroxide nanosheet is porous and has a high surface area of 223 m² g^–1. The lithium storage properties of the amorphous iron oxyhydroxide are characterized: it is a conversion-reaction electrode material, and it demonstrates superior rate capabilities (e.g., discharge capacities as high as 642 mAh g^–1 are delivered at a current density of 2 C). The impedance spectroscopy analysis identifies a <i>RC</i> series subcircuit originated by the conversion-reaction process. Investigation of the conversion-reaction kinetics through the <i>RC</i> subcircuit time constant reproduces the hysteresis in the discharge/charge voltage profile. Hysteresis is then connected to underlying thermodynamics of the conversion reaction rather than to a kinetic limitation