Structure-Property Relationships for the Electronic Applications of Bis-Adduct Isomers of Phenyl-C61 Butyric Acid Methyl Ester.

Higher adducts of a fullerene, such as the bis-adduct of PCBM (bis-PCBM), can be used to achieve shallower molecular orbital energy levels than, for example, PCBM or C60. Substituting the bis-adduct for the parent fullerene is useful to increase the open-circuit voltage of organic solar cells or achieve better energy alignment as electron transport layers in, for example, perovskite solar cells. However, bis-PCBM is usually synthesized as a mixture of structural isomers, which can lead to both energetic and morphological disorder, negatively affecting device performance. Here, we present a comprehensive study on the molecular properties of 19 pure bis-isomers of PCBM using a variety of characterization methods, including ultraviolet photoelectron spectroscopy, thermal gravimetric analysis, differential scanning calorimetry, single crystal structure, and (time-dependent) density functional theory calculation. We find that the lowest unoccupied molecular orbital of such bis-isomers can be tuned to be up to 170 meV shallower than PCBM and up to 100 meV shallower than the mixture of unseparated isomers. The isolated bis-isomers also show an electron mobility in organic field-effect transistors of up to 4.5 × 10-2 cm2/(V s), which is an order of magnitude higher than that of the mixture of bis-isomers. These properties enable the fabrication of the highest performing bis-PCBM organic solar cell to date, with the best device showing a power conversion efficiency of 7.2%. Interestingly, we find that the crystallinity of bis-isomers correlates negatively with electron mobility and organic solar cell device performance, which we relate to their molecular symmetry, with a lower symmetry leading to more amorphous bis-isomers, less energetic disorder, and higher dimensional electron transport. This work demonstrates the potential of side chain engineering for optimizing the performance of fullerene-based organic electronic devices.

Charge-Transfer State Dissociation Efficiency Can Limit Free Charge Generation in Low-Offset Organic Solar Cells.

We investigate the charge-generation processes limiting the performance of low-offset organic bulk-heterojunction solar cells by studying a series of newly synthesized PBDB-T-derivative donor polymers whose ionisation energy (IE) is tuned via functional group (difluorination or cyanation) and backbone (thiophene or selenophene bridge) modifications. When blended with the acceptor Y6, the series present heterojunction donor-acceptor IE offsets (ΔEIE) ranging from 0.22 to 0.59 eV. As expected, small ΔEIE decrease nonradiative voltage losses but severely suppresses photocurrent generation. We explore the origin of this reduced charge-generation efficiency at low ΔEIE through a combination of opto-electronic and spectroscopic measurements and molecular and device-level modeling. We find that, in addition to the expected decrease in local exciton dissociation efficiency, reducing ΔEIE also strongly reduces the charge transfer (CT) state dissociation efficiency, demonstrating that poor CT-state dissociation can limit the performance of low-offset heterojunction solar cells.

Cobalt Impregnation on Titania Photocatalysts Enhances Vis Phenol Photodegradation.

One of the main challenges of photocatalysis is to find a stable and effective photocatalyst, that is active and effective under sunlight. Here, we discuss the photocatalytic degradation of phenol as a model pollutant in aqueous solution using NUV-Vis (>366 nm) and UV (254 nm) in the presence of TiO2-P25 impregnated with different concentrations of Co (0.1%, 0.3%, 0.5%, and 1%). The modification of the surface of the photocatalyst was performed by wet impregnation, and the obtained solids were characterized using X-ray diffraction, XPS, SEM, EDS, TEM, N2 physisorption, Raman and UV-Vis DRS, which revealed the structural and morphological stability of the modified material. BET isotherms are type IV, with slit-shaped pores formed by nonrigid aggregate particles and no pore networks and a small H3 loop near the maximum relative pressure. The doped samples show increased crystallite sizes and a lower band gap, extending visible light harvesting. All prepared catalysts showed band gaps in the interval 2.3-2.5 eV. The photocatalytic degradation of aqueous phenol over TiO2-P25 and Co(X%)/TiO2 was monitored using UV-Vis spectrophotometry: Co(0.1%)/TiO2 being the most effective with NUV-Vis irradiation. TOC analysis showed ca. 96% TOC removal with NUV-Vis radiation, while only 23% removal under UV radiation.

Sub-10-fs observation of bound exciton formation in organic optoelectronic devices.

Fundamental mechanisms underlying exciton formation in organic semiconductors are complex and elusive as it occurs on ultrashort sub-100-fs timescales. Some fundamental aspects of this process, such as the evolution of exciton binding energy, have not been resolved in time experimentally. Here, we apply a combination of sub-10-fs Pump-Push-Photocurrent, Pump-Push-Photoluminescence, and Pump-Probe spectroscopies to polyfluorene devices to track the ultrafast formation of excitons. While Pump-Probe is sensitive to the total concentration of excited states, Pump-Push-Photocurrent and Pump-Push-Photoluminescence are sensitive to bound states only, providing access to exciton binding dynamics. We find that excitons created by near-absorption-edge photons are intrinsically bound states, or become such within 10 fs after excitation. Meanwhile, excitons with a modest >0.3 eV excess energy can dissociate spontaneously within 50 fs before acquiring bound character. These conclusions are supported by excited-state molecular dynamics simulations and a global kinetic model which quantitatively reproduce experimental data.

Identifying structure-absorption relationships and predicting absorption strength of non-fullerene acceptors for organic photovoltaics.

Non-fullerene acceptors (NFAs) are excellent light harvesters, yet the origin of their high optical extinction is not well understood. In this work, we investigate the absorption strength of NFAs by building a database of time-dependent density functional theory (TDDFT) calculations of ∼500 π-conjugated molecules. The calculations are first validated by comparison with experimental measurements in solution and solid state using common fullerene and non-fullerene acceptors. We find that the molar extinction coefficient (ε d,max) shows reasonable agreement between calculation in vacuum and experiment for molecules in solution, highlighting the effectiveness of TDDFT for predicting optical properties of organic π-conjugated molecules. We then perform a statistical analysis based on molecular descriptors to identify which features are important in defining the absorption strength. This allows us to identify structural features that are correlated with high absorption strength in NFAs and could be used to guide molecular design: highly absorbing NFAs should possess a planar, linear, and fully conjugated molecular backbone with highly polarisable heteroatoms. We then exploit a random decision forest algorithm to draw predictions for ε d,max using a computational framework based on extended tight-binding Hamiltonians, which shows reasonable predicting accuracy with lower computational cost than TDDFT. This work provides a general understanding of the relationship between molecular structure and absorption strength in π-conjugated organic molecules, including NFAs, while introducing predictive machine-learning models of low computational cost.

Relationship between molecular properties and degradation mechanisms of organic solar cells based on bis-adducts of phenyl-C61 butyric acid methyl ester.

Environmental stability remains a major challenge for the commercialisation of organic solar cells and degradation pathways remain poorly understood. Designing materials for improved device stability requires an understanding of the relationship between the properties of the donor or acceptor molecule and different degradation mechanisms. Here we study the correlations between various molecular parameters of the fullerene derivative bis-PCBM and the degradation rate of polymer:bis-PCBM organic solar cells, based on the same carbazole-alt-benzothiadiazole polymer, in aerobic and anaerobic conditions. We compare eight high purity bis-PCBM isomers with different electronic, chemical and packing properties along with PCBM and the mixture of bis isomers. In the case of aerobic photodegradation, we find that device degradation rate is positively correlated to the LUMO energy of the bis-PCBM isomer and to the degree of crystallinity of the isomer, while the correlation of degradation with driving force for epoxide formation is unclear. These results support the idea that in these samples, aerobic photodegradation proceeds via superoxide formation by the photogenerated polaron on the fullerene, followed by further chemical reaction. In the absence of air, photodegradation rate is correlated with molecular structure, supporting the mechanism of microstructural degradation via fullerene dimerization. The approach and findings presented here show how control of specific molecular parameters through chemical design can serve as a strategy to enhance stability of organic solar cells.

Reconciling models of interfacial state kinetics and device performance in organic solar cells: impact of the energy offsets on the power conversion efficiency.

Achieving the simultaneous increases in the open circuit voltage (V oc), short circuit current (J sc) and fill factor (FF) necessary to further increase the power conversion efficiency (PCE) of organic photovoltaics (OPV) requires a unified understanding of how molecular and device parameters affect all three characteristics. In this contribution, we introduce a framework that for the first time combines different models that have been used separately to describe the different steps of the charge generation and collection processes in OPV devices: a semi-classical rate model for charge recombination processes in OPV devices, zero-dimensional kinetic models for the photogeneration process and exciton dissociation and one-dimensional semiconductor device models. Using this unified multi-scale model in conjunction with experimental techniques (time-resolved absorption spectroscopy, steady-state and transient optoelectronic measurements) that probe the various steps involved in charge generation we can shed light on how the energy offsets in a series of polymer: non-fullerene devices affect the charge carrier generation, collection, and recombination properties of the devices. We find that changing the energy levels of the donor significantly affects not only the transition rates between local-exciton (LE) and charge-transfer (CT) states, but also significantly changes the transition rates between CT and charge-separated (CS) states, challenging the commonly accepted picture of charge generation and recombination. These results show that in order to obtain an accurate picture of charge generation in OPV devices, a variety of different experimental techniques under different conditions in conjunction with a comprehensive model of processes occurring at different time-scales are required.

Emissive Charge-Transfer States at Hybrid Inorganic/Organic Heterojunctions Enable Low Non-Radiative Recombination and High-Performance Photodetectors.

Hybrid devices based on a heterojunction between inorganic and organic semiconductors have offered a means to combine the advantages of both classes of materials in optoelectronic devices, but, in practice, the performance of such devices has often been disappointing. Here, it is demonstrated that charge generation in hybrid inorganic-organic heterojunctions consisting of copper thiocyanate (CuSCN) and a variety of molecular acceptors (ITIC, IT-4F, Y6, PC70 BM, C70 , C60 ) proceeds via emissive charge-transfer (CT) states analogous to those found at all-organic heterojunctions. Importantly, contrary to what has been observed at previous organic-inorganic heterojunctions, the dissociation of the CT-exciton and subsequent charge separation is efficient, allowing the fabrication of planar photovoltaic devices with very low non-radiative voltage losses (0.21 ±  0.02 V). It is shown that such low non-radiative recombination enables the fabrication of simple and cost-effective near-IR (NIR) detectors with extremely low dark current (4 pA cm-2 ) and noise spectral density (3 fA Hz-1/2 ) at no external bias, leading to specific detectivities at NIR wavelengths of just under 1013 Jones, close to the performance of commercial silicon photodetectors. It is believed that this work demonstrates the possibility for hybrid heterojunctions to exploit the unique properties of both inorganic and organic semiconductors for high-performance opto-electronic devices.

Effect of heat treatment on the photocatalytic activity of α-Fe2O3 nanoparticles: towards diclofenac elimination.

α-Fe2O3 nanoparticles were synthesized via a straightforward method. XRD, FTIR, SEM, ESR, and DRS techniques investigated the influence of various calcination temperatures on the crystal structure, optical, and photocatalytic properties of the samples. The obtained results demonstrated that the average crystallite size increased with the increase in the calcination temperature. Measured and computed optical properties were in accordance and the bandgap energy decreased with the increase in the calcination temperature. The highest photocatalytic degradation efficiency for diclofenac (DCF) was obtained with the sample calcinated at 300 °C (96%). The photocatalytic process occurs because of the presence of OH• radicals. The addition of H2O2 led to the inhibition of OH• radicals that H2O2 scavenged.

Influence of static disorder of charge transfer state on voltage loss in organic photovoltaics.

Spectroscopic measurements of charge transfer (CT) states provide valuable insight into the voltage losses in organic photovoltaics (OPVs). Correct interpretation of CT-state spectra depends on knowledge of the underlying broadening mechanisms, and the relative importance of molecular vibrational broadening and variations in the CT-state energy (static disorder). Here, we present a physical model, that obeys the principle of detailed balance between photon absorption and emission, of the impact of CT-state static disorder on voltage losses in OPVs. We demonstrate that neglect of CT-state disorder in the analysis of spectra may lead to incorrect estimation of voltage losses in OPV devices. We show, using measurements of polymer:non-fullerene blends of different composition, how our model can be used to infer variations in CT-state energy distribution that result from variations in film microstructure. This work highlights the potential impact of static disorder on the characteristics of disordered organic blend devices.

New insights into the efficient removal of emerging contaminants by biochars and hydrochars derived from olive oil wastes.

The removal of emerging contaminants (ECs) for water source reclamation, minimizing energy and chemical use, is an environmental concern worldwide. In this study, we used the technologically cleaner pyrolysis and hydrothermal carbonization (HTC) processes to convert olive oil production wastes into chars in order to simultaneously remove triclosan (TCS), ibuprofen (IBP) and diclofenac (DCF) from water. The chars prepared from olive stone (S), olive tree pruning (P) and pitted and reprocessed wet olive mill waste (H), as well as commercial biochars and a commercial active carbon (CAC), were characterized using different techniques and assayed as adsorbents. Pyrolysis temperatures had only a slight effect on the adsorption capacity of chars. The pseudo second-order reaction kinetic and the Freundlich equation provided the best fit for experimental data. The pH values of char suspensions were negatively correlated with their maximum adsorption capacities. The hydrochars synthetized at the lowest temperatures (≤ 240 °C), which had an acidic pH and were rich in oxygenated functional groups, recorded the highest adsorption rates (64% for DCF, 43% for IBP) and especially for TCS, with a rate of 98%, despite of a low surface area of 7.5 m2/ g. This study demonstrates for the first time that unmodified hydrochars from pitted and reprocessed wet olive mill waste are inexpensive, sustainable and environmentally friendly adsorbents which can be used to remove ECs and other similar compounds in water treatments.

Structure Dependence of Kinetic and Thermodynamic Parameters in Singlet Fission Processes.

Singlet fission-whereby one absorbed photon generates two coupled triplet excitons-is a key process for increasing the efficiency of optoelectronic devices by overcoming the Shockley-Queisser limit. A crucial parameter is the rate of dissociation of the coupled triplets, as this limits the number of free triplets subsequently available for harvesting and ultimately the overall efficiency of the device. Here we present an analysis of the thermodynamic and kinetic parameters for this process in parallel and herringbone dimers measured by electron paramagnetic resonance spectroscopy in coevaporated films of pentacene in p-terphenyl. The rate of dissociation is higher for parallel dimers than for their herringbone counterparts, as is the rate of recombination to the ground state. DFT calculations, which provide the magnitude of the electronic coupling as well as the distribution of molecular orbitals for each geometry, suggest that weaker triplet coupling in the parallel dimer is the driving force for faster dissociation. Conversely, localization of the molecular orbitals and a stronger triplet-triplet interaction result in slower dissociation and recombination. The identification and understanding of how the intermolecular geometry promotes efficient triplet dissociation provide the basis for control of triplet coupling and thereby the optimization of one important parameter of device performance.

Influence of Polymer Aggregation and Liquid Immiscibility on Morphology Tuning by Varying Composition in PffBT4T-2DT/Non-Fullerene Organic Solar Cells.

The temperature dependent aggregation behavior of PffBT4T polymers used in organic solar cells plays a critical role in the formation of a favorable morphology in fullerene-based devices. However, there has been little investigation into the impact of donor/acceptor ratio on morphology tuning, especially for non-fullerene acceptors (NFAs). Herein, the influence of composition on morphology is reported for blends of PffBT4T-2DT with two NFAs, O-IDTBR and O-IDFBR. The monotectic phase behavior inferred from differential scanning calorimetry provides qualitative insight into the interplay between solid-liquid and liquid-liquid demixing. Transient absorption spectroscopy suggests that geminate recombination dominates charge decay and that the decay rate is insensitive to composition, corroborated by negligible changes in open-circuit voltage. Exciton lifetimes are also insensitive to composition, which is attributed to the signal being dominated by acceptor excitons which are formed and decay in domains of similar size and purity irrespective of composition. A hierarchical morphology is observed, where the composition dependence of size scales and scattering intensity from resonant soft X-ray scattering (R-SoXS) is dominated by variations in volume fractions of polymer/polymer rich domains. Results suggest an optimal morphology where polymer crystallite size and connectivity are balanced, ensuring a high probability of hole extraction via such domains.

Enhanced Photocatalytic Degradation of the Imidazolinone Herbicide Imazapyr upon UV/Vis Irradiation in the Presence of CaxMnOy-TiO2 Hetero-Nanostructures: Degradation Pathways and Reaction Intermediates.

The determination of reaction pathways and identification of products of pollutants degradation is central to photocatalytic environmental remediation. This work focuses on the photocatalytic degradation of the herbicide Imazapyr (2-(4-methyl-5-oxo-4-propan-2-yl-1H-imidazol-2-yl) pyridine-3-carboxylic acid) under UV-Vis and visible-only irradiation of aqueous suspensions of CaxMnOy-TiO2, and on the identification of the corresponding degradation pathways and reaction intermediates. CaxMnOy-TiO2 was formed by mixing CaxMnOy and TiO2 by mechanical grinding followed by annealing at 500 °C. A complete structural characterization of CaxMnOy-TiO2 was carried out. The photocatalytic activity of the hetero-nanostructures was determined using phenol and Imazapyr herbicide as model pollutants in a stirred tank reactor under UV-Vis and visible-only irradiation. Using equivalent loadings, CaxMnOy-TiO2 showed a higher rate (10.6 µM·h-1) as compared to unmodified TiO2 (7.4 µM·h-1) for Imazapyr degradation under UV-Vis irradiation. The mineralization rate was 4.07 µM·h-1 for CaxMnOy-TiO2 and 1.21 µM·h-1 for TiO2. In the CaxMnOy-TiO2 system, the concentration of intermediate products reached a maximum at 180 min of irradiation that then decreased to a half in 120 min. For unmodified TiO2, the intermediates continuously increased with irradiation time with no decrease observed in their concentration. The enhanced efficiency of the CaxMnOy-TiO2 for the complete degradation of the Imazapyr and intermediates is attributed to an increased adsorption of polar species on the surface of CaxMnOy. Based on LC-MS, photocatalytic degradation pathways for Imazapyr under UV-Vis irradiation have been proposed. Some photocatalytic degradation was obtained under visible-only irradiation for CaxMnOy-TiO2. Hydroxyl radicals were found to be main reactive oxygen species responsible for the photocatalytic degradation through radical scavenger investigations.

Analysis of the Voltage Losses in CZTSSe Solar Cells of Varying Sn Content.

The performance of kesterite (Cu2ZnSn(S,Se)4, CZTSSe) solar cells is hindered by low open circuit voltage ( Voc). The commonly used metric for Voc-deficit, namely, the difference between the absorber band gap and qVoc, is not well-defined for compositionally complex absorbers like kesterite where the bandgap is hard to determine. Here, nonradiative voltage losses are analyzed by measuring the radiative limit of Voc, using external quantum efficiency (EQE) and electroluminescence (EL) spectra, without relying on precise knowledge of the bandgap. The method is applied to a series of Cu2ZnSn(S,Se)4 devices with Sn content variation from 27.6 to 32.9 at. % and a corresponding Voc range from 423 to 465 mV. Surprisingly, the lowest nonradiative loss, and hence the highest external luminescence efficiency (QELED), were obtained for the device with the lowest Voc. The trend is assigned to better interface quality between absorber and CdS buffer layer at lower Sn content.

Hybridization of Local Exciton and Charge-Transfer States Reduces Nonradiative Voltage Losses in Organic Solar Cells.

A number of recent studies have shown that the nonradiative voltage losses in organic solar cells can be suppressed in systems with low energetic offsets between donor and acceptor molecular states, but the physical reasons underpinning this remain unclear. Here, we present a systematic study of 18 different donor/acceptor blends to determine the effect that energetic offset has on both radiative and nonradiative recombination of the charge-transfer (CT) state. We find that, for certain blends, low offsets result in hybridization between charge-transfer and lowest donor or acceptor exciton states, which leads to a strong suppression in the nonradiative voltage loss to values as low as 0.23 V associated with an increase in the luminescence of the CT state. Further, we extend a two-state CT-state recombination model to include the interaction between CT and first excited states, which allows us to explain the low nonradiative voltage losses as an increase in the effective CT to ground state oscillator strength due to the intensity borrowing mechanism. We show that low nonradiative voltage losses can be achieved in material combinations with a strong electronic coupling between CT and first excited states and where the lower band gap material has a high oscillator strength for transitions from the excited state to the ground state. Finally, from our model we propose that achieving very low nonradiative voltage losses may come at a cost of higher overall recombination rates, which may help to explain the generally lower FF and EQE of highly hybridized systems.

Factors Influencing Imazapyr Herbicide Removal from Wastewater Using Photocatalytic Ozonation.

This study investigates the degradation of imazapyr herbicide from wastewater by photocatalytic ozonation using TiO2 as a semiconductor. Effects of operational parameters on imazapyr removal efficiency including TiO2 dosing, initial herbicide concentration and pH were also studied. Obtained results showed that more than 90% of removal efficiency representing the disappearance of imazapyr was maintained until 7 µM in the presence of 200 mgL-1of UV100-TiO2. Otherwise, the degradation of imazapyr followed the first-order kinetics with a photocatalytic rate constant of 0.247 min-1, and complete degradation was achieved within 20 min using photocatalytic ozonation for 5 µM of Imazapyr at pH 7.

An Alkylated Indacenodithieno[3,2-b]thiophene-Based Nonfullerene Acceptor with High Crystallinity Exhibiting Single Junction Solar Cell Efficiencies Greater than 13% with Low Voltage Losses.

A new synthetic route, to prepare an alkylated indacenodithieno[3,2-b]thiophene-based nonfullerene acceptor (C8-ITIC), is reported. Compared to the reported ITIC with phenylalkyl side chains, the new acceptor C8-ITIC exhibits a reduction in the optical band gap, higher absorptivity, and an increased propensity to crystallize. Accordingly, blends with the donor polymer PBDB-T exhibit a power conversion efficiency (PCE) up to 12.4%. Further improvements in efficiency are found upon backbone fluorination of the donor polymer to afford the novel material PFBDB-T. The resulting blend with C8-ITIC shows an impressive PCE up to 13.2% as a result of the higher open-circuit voltage. Electroluminescence studies demonstrate that backbone fluorination reduces the energy loss of the blends, with PFBDB-T/C8-ITIC-based cells exhibiting a small energy loss of 0.6 eV combined with a high JSC of 19.6 mA cm-2 .

Chromatography and high-resolution mass spectrometry for the characterization of the degradation products of the photodegradation of amidosulfuron: an analytical approach.

Simulated sunlight irradiation causing degradation of amidosulfuron, a pyrimidinylsulfonylurea herbicide, has been investigated in aqueous solution. The main degradation products were followed up by ultrahigh-pressure liquid chromatography with a UV detector (UHPLC-UV) and identified by combining ultrahigh-pressure liquid chromatography-mass spectrometry (UHPLC-MS) and Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS). On the basis of the retrosynthetic analysis, the most identified degradation products were mainly due to the losses of methylsulfamic acid (CH5NO3S), sulfocarbamic acid (CH3NO5S), carbamic acid (CH3NO2), methyl(methylsulfonyl)sulfamic acid (C2H7NO5S2), N-methylmethanesulfonamide (C2H7NO2S), and sulfonic acid (H2SO4) molecules. Accordingly, O and S-demethylation as well as hydroxylation processes were also observed. Sum formulas of the main degradation products were assigned, and a mechanical pathway is proposed.