Fullerene Aggregates Research Articles

Concurrent Effects of Delocalization and Internal Conversion Tune Charge Separation at Regioregular Polythiophene-Fullerene Heterojunctions.

Quantum-dynamical simulations are used to investigate the interplay of exciton delocalization and vibronically induced internal conversion processes in the elementary charge separation steps at regioregular donor-acceptor heterojunctions. Ultrafast internal conversion leads to efficient deexcitation within the excitonic and charge transfer manifolds, thus modifying the charge separation dynamics. We address a model donor-acceptor junction representative of regioregular P3HT-PCBM, using high-dimensional quantum dynamics simulations by multiconfigurational methods. While partial trapping into an interfacial charge separated state occurs, long-range charge-separated states are accessed as previously demonstrated in the work of Tamura and Burghardt [J. Am. Chem. Soc. 2013, 135, 16364]. For an H-aggregate type, stacked donor species, the initial bright state undergoes ultrafast internal conversion within the excitonic manifold, creating multiple charge transfer pathways before reaching the lowest-energy dark exciton, which is uncoupled from the charge transfer manifold. This process profoundly affects the charge separation mechanism and efficiency. For small energetic offsets between the interfacial excitonic and charge transfer states, a delocalized initial bright state proves less prone to electron-hole capture by the interfacial trap than a localized, vibronic wavepacket close to the interface. For both delocalized and localized initial states, a comparable yield of free carriers is obtained, which is found to be optimal for energetic offsets of the order of the Coulomb barrier to charge separation. Interfacial trapping is significantly reduced as the barrier height decreases with fullerene aggregation. Despite the high-dimensional nature of the system, charge separation is an ultrafast coherent quantum process exhibiting oscillatory features as observed in recent experiments.

Polymer solar cells based on poly(3-hexylthiophene) and fullerene: Pyrene acceptor systems

The replacement of widely used fullerene derivatives, e.g. [6,6]-phenyl-C61-butyric acid methyl ester (PCBM), with unfunctionalized C60 and C70 is an effective approach to reduce the costs of organic photovoltaics. However, solubility issues of these compounds have always represented an obstacle to their use. In this study, bulk-heterojunction solar cells made of poly(3-hexylthiophene) donor polymer, C60 or C70 acceptors and a pyrene derivative (1-pyrenebutiric acid butyl ester) are reported. Butyl 1-pyrenebutirate limits the aggregation of fullerenes and improves the active layer morphology, plausibly due to the formation of pyrene-fullerene complexes which, in the case of pyrene-C70, were also obtained in a crystalline form. Maximum power conversion efficiencies of 1.54% and 2.50% have been obtained using, respectively, C60 or C70 as acceptor. Quantum mechanical modeling provides additional insight into the formation of plausible supermolecular structures via π-π interactions and on the redox behaviour of pyrene-fullerene systems.

Effect of Solvent Additive on Generation, Recombination, and Extraction in PTB7:PCBM Solar Cells: A Conclusive Experimental and Numerical Simulation Study

Time-delayed collection field (TDCF), bias-assisted charge extraction (BACE), and space charge-limited current (SCLC) measurements are combined with complete numerical device simulations to unveil the effect of the solvent additive 1,8-diiodooctane (DIO) on the performance of PTB7:PCBM bulk heterojunction solar cells. DIO is shown to increase the charge generation rate, reduce geminate and bimolecular recombination, and increase the electron mobility. In total, the reduction of loss currents by processing with the additive raises the power conversion efficiency of the PTB7:PCBM blend by a factor of almost three. The lower generation rates and higher geminate recombination losses in devices without DIO are consistent with a blend morphology comprising large fullerene clusters embedded within a PTB7-rich matrix, while the low electron mobility suggests that these fullerene clusters are themselves composed of smaller pure fullerene aggregates separated by disordered areas. Our device simulations show unambiguously that the effect of the additive on the shape of the currentvoltage curve (J-V) cannot be ascribed to the variation of only the mobility, the recombination, or the field dependence of generation. It is only when the changes of all three parameters are taken into account that the simulation matches the experimental J-V characteristics under all illumination conditions and for a wide range of voltages.

Size and concentration determination of (functionalised) fullerenes in surface and sewage water matrices using field flow fractionation coupled to an online accurate mass spectrometer: Method development and validation

In order to assess the environmental risks of a compound it is imperative to have suitable and reliable techniques for its determination in environmental matrices. In this paper, we focused on a method development for the recently introduced online coupling of a field flow fractionation (FFF) system to an Orbitrap-HRMS, that allows the simultaneous size and concentration determination of different aqueous fullerene aggregates and their concentrations in different size fractions. A 0.05% NH4OH solution in water was identified as the best carrier liquid for the analysis of the three different aqueous fullerene suspensions (C60 [60], [6,6]-phenyl-C61 butyric acid methyl ester ([60]PCBM) and [6,6]-(bis)phenyl-C61 butyric acid methyl ester ([60]bisPCBM)). The multi-angle light scattering (MALS) data received after employing the ammonia solution was consistent with both the theory and calibration using well defined Au and latex particles. The LODs obtained using Orbitrap HRMS detection were 0.1μgL−1 for an injection volume of 100μL which are significantly better than the LODs obtained by using UV (20μgL−1) and MALS detectors (5μgL−1). However, these LODs can be further improved as in theory there is no limit to the amount of sample that can be injected into the FFF. Environmental samples (river and sewage water) were spiked with fullerenes and the fractograms obtained for these samples revealed that the matrix does affect the size of fullerene aggregates. Information on the size distribution can be useful for the risk assessment of these particles.

Dual Function Additives: A Small Molecule Crosslinker for Enhanced Efficiency and Stability in Organic Solar Cells

A bis-azide-based small molecule cross­linker is synthesized and evaluated as both a stabilizing and efficiency-boosting additive in bulk heterojunction organic photovoltaic cells. Activated by a non­invasive and scalable solution processing technique, polymer:fullerene blends exhibit improved thermal stability with suppressed polymer skin formation at the cathode and frustrated fullerene aggregation on ageing, with initial efficiency increased from 6% to 7%.

Functionalized fullerenes in water: a closer look.

The excellent photophysical properties of C60 fullerenes have spurred much research on their application to aqueous systems for biological and environmental applications. Spontaneous aggregation of C60 in water and the consequent diminution of photoactivity present a significant challenge to aqueous applications. The mechanisms driving the reduction of photoactivity in fullerene aggregates and the effects of functionalization on these processes, however, are not well understood. Here, we take a closer look at the molecular phenomena of functionalized fullerene interactions in water utilizing simulation and experimental tools. Molecular dynamic simulations were performed to investigate time-evolved molecular interactions in systems containing fullerenes with water, oxygen, and/or neighboring fullerene molecules, complimented by physical and chemical characterizations of the fullerenes pre- and postaggregation. Aggregates with widely different photoactivities exhibit similar fullerene-water interactions as well as surface and aggregation characteristics. Photoactive fullerene aggregates had weaker fullerene-fullerene and fullerene-O2 interactions, suggesting the importance of molecular interactions in the sensitization route.

Interaction of C60 with Water: First-Principles Modeling and Environmental Implications

The nature of fullerene-water interactions has been the subject of much research and debate. Specifically, the presence of a stabilizing, negative surface potential on colloidal aggregates of C60 in water is unexpected, given the neutral nature of pure carbon, and is not well understood. Previous simulation efforts have focused on the C60-water interaction using molecular dynamics simulations that lacked the ability to account for charge transfer and distribution interactions. In this study, first-principles density functional theory was used to analyze the fundamental electronic interactions to elucidate the polarization and charge transfer between water and C60. Simulations show that charge is inductively transferred to the C60 from water molecules, with subsequent polarization of the C60 molecule. In a case with two neighboring C60 molecules, the charge polarization induces a charge onto the second C60. Simulation suggests that this charge transfer and polarization may contribute at least partly to the observed negative surface potential of fullerene aggregates and, combined with hydrogen bonding network formation around C60, provides a fundamental driving force for aggregate formation in water.

Comparative studies of optical limiting in fullerene and shungite nanocarbon aqueous dispersions

Optical limiting properties of natural carbon nanoparticles (Shungite carbon) and fullerene aggregates in aqueous dispersions were for the first time studied and juxtaposed. For the picosecond laser pulses both dispersions exhibited comparable optical limiting property, apparently due to nonlinear absorption (mainly TPA). In the domain of the nanosecond laser pulses, nonlinear scattering NLS is thought to be main optical limiting mechanism in the dispersions under study. Shungite carbon dispersion showed stronger optical limiting (being similar to CBS) in visible and IR, which we ascribe to its structure more favorable to the thermal relaxation processes responsible for the NLS mechanism.

Liquid chromatography–atmospheric pressure photoionization–Orbitrap analysis of fullerene aggregates on surface soils and river sediments from Santa Catarina (Brazil)

In the present work, a new analytical approach is proposed for the analysis of seven fullerenes (C60, C70, N-methylfulleropyrrolidine, [6,6]-phenyl C61 butyric acid methyl ester, [6,6]-thienyl C61 butyric acid methyl ester, C60 pyrrolidine tris-acid ethyl ester and [6,6]-phenyl C71 butyric acid methyl ester fullerenes) in soils and sediments.This procedure combines an ultrasound-assisted solvent extraction (UAE) with toluene followed by liquid chromatography (LC), using a pyrenylpropyl group bonded silica based column, coupled to a high-resolution mass spectrometer (HRMS) using atmospheric pressure photoionisation (APPI) in negative ion mode. The analytical performance for fullerene separation of the pyrenylpropyl group bonded silica column was compared to the C18 column. For the ultra-trace analysis of fullerenes in complex environmental samples, the use of the APPI source and the use of the electrospray ionisation (ESI) source were compared.Using this approach for the analysis of fullerenes in complex matrices, a series of advantages, in terms of sensitivity and specificity, have been demonstrated. The method limits of detection (MLOD) and the method limits of quantification (MLOQ) in soils and sediments ranged from 0.022 to 0.39pg/g and from 0.072 to 1.3pg/g, respectively. Recoveries were between 68 and 106%.The analytical method was applied in order to assess the occurrence of selected fullerenes in 45 soils of Sul Catarinense (Santa Catalina State, Brazil) and 15 sediments from the Tubarão River, presenting different pressures of contamination: a coal-combustion power plant, car exhaust, coal mining industry and wastewater effluents. C60 and C70 fullerenes have been detected at concentrations ranging from the MLOD to 0.150ng/g. None of the functionalised fullerenes were detected in any of the samples.Combustion processes, in particular car exhaust, were identified as the main source of fullerenes. However, the potential degradation of residual concentrations of engineered fullerenes to more stable forms, such as C60 and C70, should also be considered.

C₆₀-dyad aggregates: self-organized structures in aqueous solutions.

Extensive full-atomistic molecular dynamics simulations are performed to study the self-organization of C60-fullerene dyad molecules in water, namely phenyl-C61-butyric acid methyl ester and fulleropyrrolidines, which have two elements of ordering, the hydrophobic fullerene cage and the hydrophilic/ionic group. While pristine fullerene or phenyl-C61-butyric acid methyl ester forms spherical droplets in order to minimize the surface tension, the amphiphilic nature of charged solute molecules leads to the formation of supramolecular assemblies having cylindrical shape driven by charge repulsion between the ionic groups located on the surface of the aggregates. We show that formation of non-spherical micelles is the geometrical consequence if the fullerene derivatives are considered as surfactants where the ionized groups are only hydrophilic unit. The agglomeration behavior of fullerenes is evaluated by determining sizes of the clusters, solvent accessible surface areas, and shape parameters. By changing the size of the counterions from chloride over iodide to perchlorate we find a thickening of the cylinder-like structures which can be explained by stronger condensation of larger ions and thus partial screening of the charge repulsion on the cluster surface. The reason for the size dependence of counterion condensation is the formation of a stronger hydration shell in case of small ions which in turn are repelled from the fullerene aggregates. Simulations are also in good agreement with the experimentally observed morphologies of decorated C60-nanoparticles.

Characterizing reactive oxygen generation and bacterial inactivation by a zerovalent iron-fullerene nano-composite device at neutral pH under UV-A illumination

A nano-composite device composed of nano-scale zerovalent iron (ZVI) and C60 fullerene aggregates (ZVI/nC60) was produced via a rapid nucleation method. The device was conceived to deliver reactive oxygen species (ROS) generated by photosensitization and/or electron transfer to targeted contaminants, including waterborne pathogens under neutral pH conditions. Certain variations of the nano-composite were fabricated differing in the amounts of (1) ZVI (0.1mM and 2mM) but not nC60 (2.5mg-C/L), and (2) nC60 (0–25mg-C/L) but not ZVI (0.1mM). The generation of ROS by the ZVI/nC60 nano-composites and ZVI nanoparticles was quantified using organic probe compounds. 0.1mM ZVI/2.5mg-C/L C60 generated 3.74-fold higher O2− concentration and also resulted in an additional 2-log inactivation of Pseudomonas aeruginosa when compared to 0.1mM ZVI (3-log inactivation). 2mM ZVI/2.5mg-C/L nC60 showed negligible improvement over 2mM ZVI in terms of O2− generation or inactivation. Further, incremental amounts of nC60 in the range of 0–25mg-C/L in 0.1mM ZVI/nC60 led to increased O2− concentration, independent of UV-A. This study demonstrates that ZVI/nC60 device delivers (1) enhanced O2− with nC60 as a mediator for electron transfer, and (2) 1O2 (only under UV-A illumination) at neutral pH conditions.

Spectroscopic Evaluation of Mixing and Crystallinity of Fullerenes in Bulk Heterojunctions

The microstructure of blend films of conjugated polymer and fullerene, especially the degree of mixing and crystallization, impacts the performance of organic photovoltaic devices considerably. Mixing and crystallization affect device performance in different ways. These phenomena are not easy to screen using traditional methods such as imaging. In this paper, the amorphous regiorandom poly(3-hexylthiophene) is blended with the potentially crystalline fullerene [6,6]-phenyl-C61-butyric acid methyl ester PCBM and the amorphous bis-adduct. First, the degree of mixing of polymer: fullerene blends is evaluated using UV–Vis absorption, steady-state and ultra-fast photoluminescence spectroscopy. The blue-shift of the polymer emission and absorption onset are used in combination with the saturation of the polymer emission decay time upon fullerene addition in order to infer the onset of aggregation of the blends. Second, the crystallinity of the fullerene is probed using variable angle spectroscopic ellipsometry (VASE), electroluminescence and photoluminescence spectroscopy. It is shown that the red-shift of charge transfer emission in the case of PCBM based blends cannot be explained solely by a variation of optical dielectric constant as probed by VASE. A combination of optical spectroscopy techniques, therefore, allows to probe the degree of mixing and can also distinguish between aggregation and crystallization of fullerenes.

Conformation and Interactions of Polystyrene and Fullerenes in Dilute to Semidilute Solutions

We report the polymer conformation and fullerene aggregation in a ternary system containing polystyrene, C60, and toluene measured by small angle neutron, static, and dynamic light scattering. We investigate polymer concentrations across the dilute and semidilute regime for five polymer molecular weights (Mw = 20 kg/mol to 1 Mg/mol), and fullerene concentrations below and above its miscibility threshold in toluene. We find that the polymer radius of gyration (Rgpoly), hydrodynamic radius (Rh), and the mixture correlation length (ξ) remain unchanged upon addition of C60. The miscibility of C60 in toluene, however, decreases upon addition of polystyrene forming aggregates with a time-dependent radius on the order of 100 nm, and this effect is amplified with increasing polymer Mw. Our findings are relevant to the solution processing of organic photovoltaics, which generally require the effective solubilization of fullerene derivatives and polymer pairs in this concentration range.

Aging of fullerene C60 nanoparticle suspensions in the presence of microbes

Despite the growing use of carbon nanomaterials in commercial applications, very little is known about the fate of these nanomaterials once they are released into the environment. The carbon–carbon bonding of spherical sp2 hybridized fullerene (C60) forms a strong and resilient material that resists biodegradation. Moreover, C60 is widely reported to be bactericidal. Here however, we observe the changing properties of fullerene nanoparticle aggregates aged in the presence of microbes. C60 aggregates were observed to decrease in size with aging, while hydroxylation and photosensitized reactivity measured by the production of reactive oxygen species (ROS) increased, suggesting that chemically and/or biologically-mediated activity is capable of partially transforming fullerene structure and reactivity in the environment. However, stable-isotope-labeling C60 aggregates incubated with microbial cultures from aged suspensions for 203 days did not produce significant labeled carbon dioxide, despite significant reduction in aggregate radius for biological samples. These results suggest that either the rate of biodegradation of these particles is too slow to quantify or that the biologically-enhanced transformation of these particles does not occur through microbial biodegradation to carbon dioxide.

Mechanical properties of aluminum-based nanocomposite reinforced with fullerenes

The strengthening effect of fullerenes in aluminum matrix composites was investigated. The composites are produced using a two-step ball-milling technique combined with a hot rolling process. First, fullerene aggregates, where fullerene molecules initially come together to form giant particles (∼200 μm in diameter) via van der Waals bonding, are shattered into smaller particles (∼1 μm in diameter) by planetary milling. Second, primarily ball-milled fullerenes are dispersed in aluminum powder via attrition milling. Finally, aluminum/fullerene composite powder is consolidated by hot-rolling at 480 °C. For the composite sheet, grain refinement strengthening and dispersion hardening by fullerenes are accomplished at the same time, thereby exhibiting HV ∼222 of Vickers hardness (e.g., ∼740 MPa of yield strength) with only 2% (volume fraction) of fullerenes.

Asymmetrical flow field-flow fractionation hyphenated to Orbitrap high resolution mass spectrometry for the determination of (functionalised) aqueous fullerene aggregates

In this short communication we report on the technical implementations of coupling an asymmetric flow field-flow fractionation (AF4) instrument to a high resolution mass spectrometer (Orbitrap) using an atmospheric photoionisation interface. This will allow for the first time online identification of different fullerenes in aqueous samples after their aggregates have been fractionated in the FFF channel. Quality parameters such as limits of detection (LODs), limits of quantification (LOQs) or linear range were evaluated and they were in the range of hundreds ng/L for LODs and LOQs and the detector response was linear in the range tested (up to ∼20μg/L). The low detection and quantification limits make this technique useful for future environmental or ecotoxicology studies in which low concentration levels are expected for fullerenes and common on-line detectors such as UV or MALS do not have enough sensitivity and selectivity.

Cationic Fullerene Aggregates with Unprecedented Virus Photoinactivation Efficiencies in Water

Of the many fullerene derivatives that have been examined, cationic functionalization has proven to be most promising for aqueous or biological applications. Until recently, however, no cationic colloidal fullerene aggregates in the nanosize regime have been characterized in the aqueous phase. The results presented here represent the most rapid and efficient, to the best of our knowledge, viral inactivation reported for any colloidal fullerene aggregates. Tris-adducted fulleropyrrolidinium aggregates are prepared and analyzed for concentration-dependent singlet oxygen (1O2) production and MS2 bacteriophage inactivation. Experiments are performed under visible, UVA, and sunlight irradiation with the addition of natural organic matter (NOM) to simulate environmental conditions. Viral inactivation was observed at sensitizer concentrations in the nanomolar range. A 5-log inactivation of MS2 was observed after 4 or 1 min of sunlight exposure with 250 nM fullerenes with or without NOM, respectively. The environmental implications of these results are discussed in the context of previously reported 1O2-mediated MS2 inactivation.

Electron Collection as a Limit to Polymer:PCBM Solar Cell Efficiency: Effect of Blend Microstructure on Carrier Mobility and Device Performance in PTB7:PCBM

The poor photovoltaic performance of state‐of‐the‐art blends of poly[4,8‐bis[(2‐ethylhexyl)oxy]benzo[1,2‐b:4,5‐b′]dithiophene‐2,6‐diyl][3‐fluoro‐2‐[(2‐ethylhexyl)carbonyl]thieno[3,4‐b]thiophenediyl] (PTB7) and [6,6]‐phenyl‐C61‐butyric acid (PCBM) at large active layer thicknesses is studied using space‐charge‐limited current mobility and photovoltaic device measurements. The poor performance is found to result from relatively low electron mobility. This is attributed to the low tendency of PTB7 to aggregate, which reduces the ability of the fullerene to form a connected network. Increasing the PCBM content 60–80 wt% increases electron mobility and accordingly improves performance for thicker devices, resulting in a fill factor (FF) close to 0.6 at 300 nm. The result confirms that by improving only the connectivity of the fullerene phase, efficient electron and hole collection is possible for 300 nm‐thick PTB7:PCBM devices. Furthermore, it is shown that solvent additive 1,8‐diiodooctane (DIO), used in the highest efficiency PTB7:PCBM devices, does not improve the thickness dependence and, accordingly, does not lead to an increase in either hole or electron mobility or in the carrier lifetime. A key challenge for researchers is therefore to develop new methods to ensure connectivity in the fullerene phase in blends without relying on either a large excess of fullerene or strong aggregation of the polymer.

Domain Compositions and Fullerene Aggregation Govern Charge Photogeneration in Polymer/Fullerene Solar Cells

The complex microstructure of organic semiconductor mixtures continues to obscure the connection between the active layer morphology and photovoltaic device performance. For example, the ubiquitous presence of mixed phases in the active layer of polymer/fullerene solar cells creates multiple morphologically distinct interfaces which are capable of exciton dissociation or charge recombination. Here, it is shown that domain compositions and fullerene aggregation can strongly modulate charge photogeneration at ultrafast timescales through studies of a model system, mixtures of a low band‐gap polymer, poly[(4,4′‐bis(2‐ethylhexyl)dithieno[3,2‐b:2′,3′‐d]germole)‐2,6‐diyl‐alt‐(2,1,3‐benzothia‐diazole)‐4,7‐diyl], and [6,6]‐phenyl‐C71‐butyric acid methyl ester. Structural characterization using energy‐filtered transmission electron microscopy (EFTEM) and resonant soft X‐ray scattering shows similar microstructures even with changes in the overall film composition. Composition maps generated from EFTEM, however, demonstrate that compositions of mixed domains vary significantly with overall film composition. Furthermore, the amount of polymer in the mixed domains is inversely correlated with device performance. Photoinduced absorption studies using ultrafast infrared spectroscopy demonstrate that polaron concentrations are highest when mixed domains contain the least polymer. Grazing‐incidence X‐ray scattering results show that larger fullerene coherence lengths are correlated to higher polaron yields. Thus, the purity of the mixed domains is critical for efficient charge photogeneration because purity modulates fullerene aggregation and electron delocalization.

Evidence of entropically driven C60 fullerene aggregation in aqueous solution

In the present work, we report the first experimental evidence of entropically driven C60 fullerene aggregation in aqueous solution, occurring with nearly zero enthalpy change.