Ultrafast exciton dissociation followed by nongeminate charge recombination in PCDTBT:PCBM photovoltaic blends

The precise mechanism and dynamics of charge generation and recombination in bulk heterojunction polymer:fullerene blend films typically used in organic photovoltaic devices have been intensively studied by many research groups, but nonetheless remain debated. In particular the role of interfacial charge-transfer (CT) states in the generation of free charge carriers, an important step for the understanding of device function, is still under active discussion. In this article we present direct optical probes of the exciton dynamics in pristine films of a prototypic polycarbazole-based photovoltaic donor polymer, namely poly[N-11'-henicosanyl-2,7-carbazole-alt-5,5-(4',7'-di-2-thienyl-2',1',3'-benzothiadiazole)] (PCDTBT), as well as the charge generation and recombination dynamics in as-cast and annealed photovoltaic blend films using methanofullerene (PC(61)BM) as electron acceptor. In contrast to earlier studies we use broadband (500-1100 nm) transient absorption spectroscopy including the previously unobserved but very important time range between 2 ns and 1 ms, which allows us not only to observe the entire charge carrier recombination dynamics but also to quantify the existing decay channels. We determine that ultrafast exciton dissociation occurs in blends and leads to two separate pools of products, namely Coulombically bound charge-transfer (CT) states and unbound (free) charge carriers. The recombination dynamics are analyzed within the framework of a previously reported model for poly(3-hexylthiophene):PCBM (Howard, I. A. J. Am. Chem. Soc. 2010, 132, 14866) based on concomitant geminate recombination of CT states and nongeminate recombination of free charge carriers. The results reveal that only ~11% of the initial photoexcitations generate interfacial CT states that recombine exclusively by fast nanosecond geminate recombination and thus do not contribute to the photocurrent, whereas ~89% of excitons create free charge carriers on an ultrafast time scale that then contribute to the extracted photocurrent. Despite the high yield of free charges the power conversion efficiency of devices remains moderate at about 3.0%. This is largely a consequence of the low fill factor of devices. We relate the low fill factor to significant energetic disorder present in the pristine polymer and in the polymer:fullerene blends. In the former we observed a significant spectral relaxation of exciton emission (fluorescence) and in the latter of the polaron-induced ground-state bleaching, implying that the density of states (DOS) for both excitons and charge carriers is significantly broadened by energetic disorder in pristine PCDTBT and in its blend with PCBM. This disorder leads to charge trapping in solar cells, which in turn causes higher carrier concentrations and more significant nongeminate recombination. The nongeminate recombination has a significant impact on the IV curves of devices, namely its competition with charge carrier extraction causes a stronger bias dependence of the photocurrent of devices, in turn leading to the poor device fill factor. In addition our results demonstrate the importance of ultrafast free carrier generation and suppression of interfacial CT-state formation and question the applicability of the often used Braun-Onsager model to describe the bias dependence of the photocurrent in polymer:fullerene organic photovoltaic devices.     

Factors controlling the efficiencies of photoinduced electron-transfer reactions

The overall efficiencies of photoinduced electron transfer reactions in polar solvents are usually determined by the efficiency with which separated radical ions are formed from the initially formed geminate radical-ion pairs. These separation efficiencies are determined by the competition between retum electron transfer and separation within the geminate pairs. A method is described for determining whether variations in the quantum yields for formation of separated radical ions are due to changes in the reorganization parameters for the return electron transfer reactions, or to other factors. The use of the method is illustrated in studies of the effects of varying steric bulk and molecular size of the donors, and also in studies of the effect of using a charged sensitizer.     

Critical Role of Molecular Electrostatic Potential on Charge Generation in Organic Solar Cells

Revealing the charge generation is a crucial step to understand the organic photovoltaics. Recent development in non‐fullerene organic solar cells (OSCs) indicates efficient charge separation even with negligible energetic offset between the donor and acceptor materials. These new findings trigger a critical question concerning the charge separation mechanism in OSCs, traditionally believed to result from sufficient energetic offset between the polymer donor and fullerene acceptor. We propose a new mechanism, which involves the molecular electrostatic potential, to explain efficient charge separation in non‐fullerene OSCs. Together with the new mechanism, we demonstrate a record efficiency of ~12% for systems with negligible energetic offset between donor and acceptor materials. Our analysis also rationalizes different requirement of the energetic offset between fullerene‐based and non‐fullerene OSCs, and paves the way for further design of OSC materials with both high photocurrent and high photovoltage at the same time.     

Monte-Carlo simulations of geminate electron–hole pair dissociation in a molecular heterojunction: a two-step dissociation mechanism

The Monte-Carlo simulations are used to investigate the dissociation of a Coulomb correlated charge pair at an idealized interface between an electron accepting and an electron donating molecular material. In the simulations the materials are represented by cubic lattices of sites, with site the energies spread according to Gaussian distributions. The influence of temperature, applied external fields, and the width of the Gaussian densities of states distribution for both the electron and the hole transporting material are investigated. The results show that the dissociation of geminate charge pairs is assisted by disorder and the results can be understood in terms of a two-step model. In the first step, the slow carrier in the most disordered material jumps away from the interface. In the following, second step, the reduced Coulombic attraction allows the faster carrier in the less disordered material to escape from the interface by thermally activated hopping. When the rate for geminate recombination at the interface is very low (<1 ns⁻¹) the simulations predict a high yield for carrier collection, as observed experimentally. Comparison of the simulated and experimentally observed temperature dependence of the collection efficiency indicates that at low temperature dissociation of the geminate charge pairs may be one of the factors limiting the device performance.     

Picosecond kinetic study of the photoinduced homolysis of benzhydryl acetates: the nature of the conversion of radical pairs into ion pairs

The conversion of benzhydryl acetate geminate radical pairs to contact ion pairs following photoinduced homolysis in solution is studied using picosecond pump-probe spectroscopy. The dynamics for the decay of the geminate radical pairs into contact ion pairs is modeled within a Marcus-like theory for nonadiabatic electron transfer. A second decay channel for the geminate radical pairs is diffusional separation to free radicals. The kinetics of this latter process reveals an energy of interaction between the two radicals in the geminate pair.     

Photophysics of an electrophosphorescent platinum (II) porphyrin in solid films

We examine electronic processes in platinum (II) octaethyl porphyrin (PtOEP) embedded in an organic solid state matrix and in the form of vacuum-evaporated neat films in conjunction with potential applications of this compound to organic photovoltaic and electrophosphorescent devices. Absorption, photoexcitation, and luminescence spectra indicate the excitonic dimers to be dominant excited states, and their dissociation underlies the charge photogeneration process. Different charge separation distance (1.5 nm and 2.6 nm) in opposite charge carrier pairs preceding dissociation can be distinguished based on the fit of the three-dimensional Onsager theory of geminate recombination to electromodulated luminescence and photoconduction measurements. The near-positive electrode concentrated triplet dimer excitons, produced by strongly 370 nm absorbed light in neat PtOEP films, are efficiently quenched by electron transfer to the metal (Al), generating the positive charge with an efficiency eta+ exceeding 0.15 at high electric fields and dominating the measured photocurrent. Their dissociation efficiency in the bulk, eta- (negatively biased illuminated electrode), is more than one order of magnitude lower than eta+. The dissociation of singlet dimer states dominates the bulk photogeneration process induced by the weakly-absorbed light at 450 nm, with comparable eta+ and eta-. The "hot excited state" underlying the temperature-increasing emission at 540 nm has been attributed to the upper excitonic component Q+ of the first absorption band Q consistent with the exciton concept applied successfully to the interpretation of all dimer-underlain spectroscopic features of PtOEP samples studied.     

基于苝二酰亚胺类非富勒烯受体共混体系凝聚态结构调控

非富勒烯太阳能电池具有给受体能级可调、吸收范围宽及可溶液加工等优势,已经成为太阳能电池领域发展趋势。在高性能材料开发及器件结构优化的推动下,能量转换效率已经突破11%。其中,苝二酰亚胺(PDI)类分子价格低廉且具有良好的稳定性及较高的电子迁移率,已经发展成为重要的非富勒烯受体材料。然而,PDI类材料刚性稠环结构使得分子间具有强烈的π-π相互作用(受体-受体分子间及给体-受体分子间),导致共混体系相分离尺寸可控性差,给受体分子间共混程度难于调控,从而发生严重的成对以及非成对电荷复合。本文从分子间作用力入手(溶剂-溶质、给体-受体分子间作用力)详述了非富勒烯共混体系相分离结构、相区尺寸及共混相含量调节的相关原理及方法。研究表明基于PDI共混体系,固-液相分离及分子扩散能力是决定相分离结构的本质因素,通过调控给受体比例及热退火温度实现了孤岛及互穿网络结构的构筑。同时,通过平衡受体分子间π-π作用及给受体间电荷转移,实现了低相容性及高相容性共混体系相区尺寸的可控调节。在此基础上,利用添加剂手段通过调节溶剂与溶质分子间的溶度参数差值,实现了薄膜内共混相的可控调节,并针对具有不同相容性共混体系给出了添加剂的选择原则。     

Effect of morphology on ultrafast free carrier generation in polythiophene:fullerene organic solar cells

Despite significant study, the precise mechanisms that dictate the efficiency of organic photovoltaic cells, such as charge separation and recombination, are still debated. Here, we directly observe efficient ultrafast free charge generation in the absence of field in annealed poly(3-hexylthiophene):methanofullerene (P3HT:PCBM). However, we find this process is much less efficient in unannealed and amorphous regiorandom blends, explaining the superior short-circuit current and fill-factor of annealed RR-P3HT:PCBM solar cells. We use transient optical spectroscopy in the visible and near-infrared spectral region covering, but not limited to, the previously unobserved and highly relevant time scale spanning 1 to 100 ns, to directly observe both geminate and nongeminate charge recombination. We find that exciton quenching leads directly (time scale less than 100 fs) to two populations: bound charges and free charges. The former do not lead to photocurrent in a photovoltaic cell; they recombine geminately within 2 ns and are a loss channel. However, the latter can be efficiently extracted in photovoltaic cells. Therefore, we find that the probability of ultrafast free charge formation after exciton quenching directly limits solar cell efficiency. This probability is low in disordered P3HT:PCBM blends but approaches unity in annealed blends.     

The effect of chromatographic conditions on the separation of selected alkaloids in RP-HPTLC

Selected alkaloid standards were chromatographed on C18 W layers using various aqueous eluents containing an organic modifier and pH 3 buffer to suppress silanol ionization or an organic modifier and pH 8 buffer to suppress alkaloid ionization. Anionic ion pairs such as sodium dodecyl sulfate, octane-1-sulfonic acid sodium salt, pentane-1-sulfonic acid sodium salt, and bis(2-ethylhexyl)ortho-phosphoric acid are used to improve peak shape, efficiency, and selectivity. Amines (e.g., diethylamine, triethylamine, and tetrabutylamonium chloride) are incorporated into mobile phases to block surface silanols. The effect of chromatographic conditions on the separation of the investigated alkaloids is analyzed by the comparison of particular densitograms, asymmetry factor, or theoretical plate number. The best efficiency, peak symmetry, and separation selectivity of the investigated compounds is obtained through the addition of amine (especially diethylamine) to the mobile phases.     

The influence of organic sample solvents on the separation efficiency of basic compounds under strong cation exchange mode

This study investigated the influence of organic sample solvents on separation efficiency of basic compounds under strong cation exchange (SCX) mode. The mixtures of acidic aqueous solution and organic solvent such as acetonitrile, ethanol, methanol and dimethyl sulfoxide (DMSO) were tested as sample solvents. For later-eluting analytes, the increase of sample solvent elution strength was responsible for the decrease of separation efficiency. Thus, sample solvents with weak elution strength could provide high separation efficiencies. For earlier-eluting analytes, the retention of organic sample solvents was the main factor affecting separation efficiency. Weakly retained solvents could provide high separation efficiency. In addition, an optimized approach was proposed to reduce the effect of organic sample solvent, in which low ionic solvent was employed as initial mobile phase in the gradient. At last, the analysis of impurities in hydrophobic drug berberine was performed. The results showed that using acidic aqueous methanol as sample solvents could provide high separation efficiency and good resolution (R > 1.5).     

Comparison of the performance of conventional microparticulates and monolithic reversed-phase columns for liquid chromatography separation of eleven pollutant phenols

The performance of isocratic separations of 11 pollutant phenols (PP) using monolithic (Chromolith RP-18e) and conventional reversed-phase 5 microm (Luna and Purospher C18) and 4 microm (Synergi C12) particulate size columns, selected from high purity silica materials, has been compared. The separations have been optimized based on a previously optimized separation in which a reversed-phase C18 Luna column and acetonitrile as organic modifier were used, allowing the separation of all phenols tested in 23 min. The optimization process was carried out for each column by studying the effect of the mobile phase (acetonitrile as organic modifier, pH, flow-rate) on phenols separation. Under the optimized separation conditions, all phenols were separated in less than 23 min for all columns tested. Asymmetry factors were further evaluated and used to estimate column efficiency using the Dorsey-Foley equation. The efficiency and asymmetry factors were lower for Chromolith than for Purospher and Luna columns respectively. The Chromolith column was finally selected, due to its lower flow resistance, analysis time and good efficiency and asymmetry factors. The PPs separation was achieved in 3 min. The asymmetry factors were in the range 0.9-1.5 using 50mM acetate buffer (pH = 5.25)-ACN (64:36, v/v) as mobile phase, T=45 degrees C and 4.0 ml min(-1) flow-rate.     

Alternating oligo(p-phenylene vinylene)--perylene bisimide copolymers: synthesis,photophysics, and photovoltaic properties of a new class of donor--acceptor materials

A Suzuki polycondensation reaction has been used to synthesize two copolymers consisting of alternating oligo(p-phenylene vinylene) (OPV) donor and perylene bisimide (PERY) acceptor chromophores. The copolymers differ by the length of the saturated spacer that connects the OPV and PERY units. Photoinduced singlet energy transfer and photoinduced charge separation in these polychromophores have been studied in solution and in the solid state via photoluminescence and femtosecond pump-probe spectroscopy. In both polymers a photoinduced electron transfer occurs within a few picoseconds after excitation of the OPV or the PERY chromophore. The electron transfer from OPV excited state competes with a singlet energy transfer state to the PERY chromophore. The differences in rate constants for the electron- and energy-transfer processes are discussed on the basis of correlated quantum-chemical calculations and in terms of conformational preferences and folding of the two polymers. In solution, the lifetime of the charge-separated state is longer than in the films where geminate recombination is much faster. However, in the films some charges are able to escape from geminate recombination and diffuse away and can be collected at the electrodes when the polymers are incorporated in a photovoltaic device.     

Are the asserted advantages of organic solvents in capillary electrophoresis real? A critical discussion

Background electrolytes (BGEs) prepared in pure organic solvents are common alternatives to aqueous BGEs in capillary electrophoresis. Several general advantages of organic solvents over water have been asserted in the literature, namely (i) organic solvents increase the separation selectivity; (ii) organic solvents increase the separation efficiency; (iii) high separation voltages and/or high BGE ionic strengths can be used in organic solvents due to lower electric current compared to water. Related assumptions are that (iv) due to higher field strengths applicable in organic solvents the analysis time is shorter than in aqueous BGEs, and (v) the solubility and/or stability of components (either analytes or BGE chemicals) is higher/better in organic solvents. In the present work, these asserted advantages were critically evaluated based on the physical principles of ion transport and zone dispersion in solution. The result was that many of the above-mentioned general advantages are overestimated or even inexistent; often they have no fundamental basis.     

A quantitative analytical model for static dipolar disorder broadening of the density of states at organic heterointerfaces

Understanding the electronic structure of organic-organic heterointerfaces is crucial for many device applications of organic semiconductors. Here we have developed a simple analytical model to describe the effect of static dipolar disorder in a polymer dielectric on the density of states of an adjacent organic semiconductor. The degree of energetic disorder varies strongly with distance from the interface. Using a simple mobility model, we have been able to explain quantitatively both the magnitude as well as the gate voltage dependence of the field-effect mobility for polymer gate dielectrics with different dielectric constants.     

Solid film versus solution-phase charge-recombination dynamics of exTTF-bridge-C60 dyads

The charge-recombination dynamics of two exTTF-C60 dyads (exTTF = 9,10-bis(1,3-dithiol-2-ylidene)-9,10-dihydroanthracene), observed after photoinduced charge separation, are compared in solution and in the solid state. The dyads differ only in the degree of conjugation of the bridge between the donor (exTTF) and the acceptor (C60) moieties. In solution, photoexcitation of the nonconjugated dyad C60-BN-exTTF (1) (BN = 1,1'-binaphthyl) shows slower charge-recombination dynamics compared with the conjugated dyad C60-TVB-exTTF (2) (TVB = bisthienylvinylenebenzene) (lifetimes of 24 and 0.6 micros, respectively), consistent with the expected stronger electronic coupling in the conjugated dyad. However, in solid films, the dynamics are remarkably different, with dyad 2 showing slower recombination dynamics than 1. For dyad 1, recombination dynamics for the solid films are observed to be tenfold faster than in solution, with this acceleration attributed to enhanced electronic coupling between the geminate radical pair in the solid film. In contrast, for dyad 2, the recombination dynamics in the solid film exhibit a lifetime of 7 micros, tenfold slower than that observed for this dyad in solution. These slow recombination dynamics are assigned to the dissociation of the initially formed geminate radical pair to free carriers. Subsequent trapping of the free carriers at film defects results in the observed slow recombination dynamics. It is thus apparent that consideration of solution-phase recombination data is of only limited value in predicting the solid-film behaviour. These results are discussed with reference to the development of organic solar cells based upon molecular donor-acceptor structures.     

Temperature dependence of charge mobility in model discotic liquid crystals

We address the calculation of charge carrier mobility of liquid-crystalline columnar semiconductors, a very promising class of materials in the field of organic electronics. We employ a simple coarse-grained theoretical approach and study in particular the temperature dependence of the mobility of the well-known triphenylene family of compounds, combining a molecular-level simulation for reproducing the structural changes and the Miller-Abrahams model for the evaluation of the transfer rates within the hopping regime. The effects of electric field, positional and energetic disorder are also considered. Simulations predict a low energetic disorder (~0.05 eV), slightly decreasing with temperature within the crystal, columnar and isotropic phases, and fluctuations of the square transfer integral of the order of 0.003 eV(2). The shape of the temperature-dependent mobility curve is however dominated by the variation of the transfer integral and barely affected by the disorder. Overall, this model reproduces semi-quantitatively all the features of experimentally measured mobilities, on one hand reinforcing the correctness of the hopping transport picture and of its interplay with system morphology, and on the other suggesting future applications for off-lattice modeling of organic electronics devices.     

A tandem mechanism of charge-carrier photogeneration in disordered organic materials

A model of tandem charge-carrier photogeneration in disordered organic materials at low excess photon energies above the absorption edge is formulated. It suggests that relaxed singlet excitons dissociate into strongly bound metastable short off-chain geminate pairs. In parallel, triplet excitons can be generated from both primary singlets and short geminate pairs. Owing to a long intrinsic lifetime of triplets, most of them are quenched by geminate pairs and the latter can gain additional energy that facilitates transformation of short pairs into longer ones. This reduces the Coulomb binding energy such that field-assisted full dissociation into free carriers becomes feasible.     

Comparison of photoinduced electron transfer reactions of aromatic carbonyl vs. cyano compounds with electron donors in condensed phase:the importance

Photoinduced electron transfer reactions in acetonitrile with bensopheneone, anthraquinone, 9-cyanoanthracene and 9,10-dicyanoanthracene as electron acceptors, and with 1,4-diasabicyclo[2,2,2]octane and N,N-dimethylaniline as electron donors have been studied with ns-laser flash photolysis and fluorescence quenching measurements. For these systems the resulting free ion yield depends on the spin state of the geminate ion pair: its separation is very efficient if formed in a triplet state (carbonyl compounds/donors), while it is very inefficient if formed in a singlet state (cyanoanthracenes/donors). In the triplet systems, geminate back electron transfer is limited by the rate of spin flip.     

Dynamic Monte Carlo modeling of exciton dissociation in organic donor-acceptor solar cells

A general dynamic Monte Carlo model for exciton dissociation at a donor-acceptor interface that includes exciton delocalization and hot charge separation is developed to model the experimental behavior observed for the poly(3-hexylthiophene):fullerene system and predict the theoretical performance of future materials systems. The presence of delocalized excitons and the direct formation of separated charge pairs has been recently measured by transient photo-induced absorption experiments and has been proposed to facilitate charge separation. The excess energy of the exciton dissociation process has also been observed to have a strong correlation with the charge separation yield for a series of thiophene based polymer:fullerene systems, suggesting that a hot charge separation process is also occurring. Hot charge separation has been previously theorized as a cause for highly efficient charge separation. However, a detailed model for this process has not been implemented and tested. Here, both conceptual models are implemented into a dynamic Monte Carlo simulation and tested using a simple bilayer donor-acceptor system. We find that exciton delocalization can account for a significant reduction in geminate recombination when compared to the traditional, bound polaron pair model. In addition, the hot charge separation process could further reduce the geminate recombination, but only if the hot charge mobility is several orders of magnitude larger than the standard charge mobility.     

Comparison of microemulsion electrokinetic chromatography and micellar electrokinetic chromatography as methods for the analysis of ten benzophenones

Microemulsion electrokinetic chromatography (MEEKC) and micellar electrokinetic chromatograpy (MEKC) were compared for their abilities to separate and detect ten similar benzophenones, which are commonly used as UV filters in various plastic and cosmetic products. Sodium dodecyl sulfate (SDS) concentration and column temperature rarely affected separation resolution for MEEKC, but separation of benzophenones could be improved by changing the SDS concentration and column temperature for MEKC. Buffer pH and ethanol (organic modifier) were found to markedly influence the separation selectivity for both MEEKC and MEKC systems. In addition, a higher electric voltage improved the separation efficiency without a noticeable reduction in separation resolution for MEEKC, whereas it caused a poor separation resolution for the MEKC system.