Donor Components Research Articles

Enhanced Stability and Optimized Morphology Induced by Electric‐Field‐Assisted Annealing of Bulk Heterojunction Solar Cells

The utility of electric fields during the bulk heterojunction (BHJ) film drying process for tuning the morphology and stability of the device is demonstrated. An external electric‐field‐assisted annealing (EFTA) treatment is used to engineer the stability of amorphous donor polymer‐based BHJs without compromising device performance. Residual additive in the device post fabrication is a major source of degradation. Thermal annealing of an active layer effectively removes residual additive, which in case of amorphous polymer donor‐based BHJs, however, leads to unfavorable changes in the morphology. The detrimental effect of thermal annealing in amorphous donor polymer‐based solar cells is mitigated by the presence of an electric field during the drying stage. The complete removal of additive is ensured by this treatment procedure and leads to improved packing and a rigid morphology. The structural stability is reflected in the performance parameters monitored over the long term and electrical noise measurements. The magnitude and polarity of the applied electric field are observed to control the vertical distribution of donor and acceptor components.

Ternary organic solar cells based on polymer donor, polymer acceptor and PCBM components

In this work, ternary organic solar cells (OSCs) combining a fullerene derivative PC71BM with a non-fullerene acceptor N2200-F blended with a polymer donor PM6 were reported. Compared with the binary systems, the highest power conversion efficiency (PCE) of 8.11% was achieved in ternary solar cells with 30 wt% N2200-F content, mainly due to the improved short-circuit current density (Jsc) and fill factor (FF). Further studies showed that the improved Jsc could attribute to the complementary absorption of the two acceptors and the enhanced FF was originated from the higher hole mobility and the fine-tuned morphology in the ternary system. These results demonstrate that the combination of fullerene and non-fullerene acceptors in ternary organic solar cells is a promising approach to achieve high-performance OSCs.

A Study of the Influence Exerted by Structural Defects on Photoluminescence Spectra in n-3C-SiC

Photoluminescence (PL) spectra have been studied in 3C-SiC/4H-SiC heterostructures and 3C‑SiC single crystals. It was shown that epitaxial 3C-SiC layers grown on 4H-SiC substrates have a markedly poorer crystal perfection than do 3C-SiC single crystals. It was found that doping with aluminum gives rise to a characteristic PL both in epitaxial layers and in 3C-SiC single crystals. At the same time, the electron irradiation of epitaxial layers does not give rise to defect-related PL, in contrast to what is observed for single crystals. An assumption is made that the twin boundaries existing in epitaxial 3C-SiC layers can serve as getters of radiation defects that are components of donor–acceptor pairs responsible for the “defect-related” PL.

Computing solubility parameters of deep eutectic solvents from Molecular Dynamics simulations

The solubility parameter (SP) of a solvent is a key property that measures the polarity and quantifies the ‘like-dissolves-like’ principle, which is an important rule in chemistry for screening solvents for separation processes. It is challenging to experimentally obtain solubility parameters of non-volatile solvents like ionic liquids (ILs), deep eutectic solvents (DESs), and polymers. Here, Molecular Dynamics (MD) simulations have been used to compute the Hildebrand and Hansen solubility parameters of DESs, which are green solvents with potential applications in many different fields. The results from MD simulations are compared with limited available experimental data and commonly used SP correlations for non-volatile solvents. Very limited information is available in literature for the vapor phase composition of DESs. Solubility parameters are computed based on the vaporization of hydrogen bond donor (HBD) and hydrogen bond acceptor (HBA) components of the DESs as well as clusters, consisting of HBD and HBA components. The relatively large SPs computed from MD indicate that the investigated choline chloride-based DESs are polar solvents. The values of SPs are not significantly affected by temperature. A comparison of vaporization enthalpies of HBD, HBA and clusters from the DES mixture suggests that it is more likely for HBD molecules to vaporize from the DES mixture and dominate the vapor phase.

Nanoscale Photoinduced Charge Transfer with Individual Quantum Dots: Tunability through Synthesis, Interface Design, and Interaction with Charge Traps.

Semiconducting colloidal quantum dots (QDs) provide an excellent platform for nanoscale charge-transfer studies. Because of their size-dependent optoelectronic properties, which can be tuned via chemical synthesis and of their versatility in surface ligand exchange, QDs can be coupled with various types of acceptors to create hybrids with controlled type (electron or hole), direction, and rate of charge flow, depending on the foreseen application, either solar harvesting, light emitting, or biosensing. This perspective highlights several examples of QD-based hybrids with controllable (tunable) rate of charge transfer obtained by various approaches, including by changing the QD core size and shell thickness by colloidal synthesis, by the insertion of molecular linkers or dielectric spacers between donor and acceptor components. We also show that subjecting QDs to external factors such as electric fields and alternate optical excitation energy is another approach to bias the internal charge transfer between charges photogenerated in the QD core and QD’s surface charge traps. The perspective also provides the reader with various examples of how single nanoparticle spectroscopic studies can help in understanding and quantifying nanoscale charge transfer with QDs.

Fate of NaClO and membrane foulants during in-situ cleaning of membrane bioreactors: Combined effect on thermodynamic properties of sludge

In this study, the fate of sodium hypochlorite (NaClO) and detached membrane foulants and their impacts on the thermodynamic properties of raw sludge were investigated in a membrane bioreactor (MBR). It was found that about 20.3% of the total NaClO was potentially released into the bulk sludge, which significantly altered the raw sludge surface properties, such as a reduction in the number of surface electron donor components (γ−) and an increase in surface hydrophobicity. After exposure to NaClO, the treated sludge had a higher adhesive and cohesive propensity compared to the raw sludge. Based on the extended Derjaguin-Landau-Verwey- Overbeek (XDLVO) theory and the batch filtration test results, the detached foulants potentially aggregated with the treated sludge and form the reconstructed sludge. The reconstructed sludge had a high protein (PN) level in the extracellular polymeric substances (EPS), with a higher membrane fouling potential compared with the raw sludge.

Homocoupling defects in porphyrinoid small molecules and their effect on organic solar cell performance

Abstract Porphyrinoid small molecules can be used as electron donor or acceptor components in bulk heterojunction organic solar cells, which has resulted in steadily improving power conversion efficiencies. However, the effect of material purity is often neglected. In this work, a series of D1-A-π-D2-π-A-D1 conjugated chromophores based on the A2B2-meso-ethynylporphyrin core is synthesized. Different electron-donating (D1) end groups are chosen to investigate their influence on the material properties and optoelectronic characteristics. The porphyrin small molecules are tested as electron donor materials in bulk heterojunction organic solar cells in combination with PC71BM, affording an efficiency up to 4.6% under standard illumination. Furthermore, it is shown that (Glaser type) homocoupled side products are generated during the final Sonogashira cross-coupling reactions, which can be very challenging to remove. Their presence reduces solar cell performance by affecting the open-circuit voltage and fill factor.

Role of the hydrogen bond donor component for a proper development of novel hydrophobic deep eutectic solvents

The environmental impact of chemical applications can be reduced by using novel solvents with green properties. In this field, Deep Eutectic Solvents (DESs) are promising liquids thanks to their low toxicity, high eco-compatibility and high easiness and “greenness” of preparation. DESs are mixtures of a hydrogen bond donor molecule (HBD) and a hydrogen bond acceptor molecule (HBA) at the proper molar ratio. In this paper, we present the preparation of novel hydrophobic deep eutectic solvents and the studies of their properties: density, eutectic profiles, ranges of water separation, contamination of the separated phases, extraction capabilities of phenol model polluting molecules, capabilities of extraction at acidic and basic conditions. Interesting results emerged about the role of the components of the DESs because of the use of a properly-chosen set of liquids. Their capabilities were dependent on the nature of the HBD molecule, and in particular on its hydrophobicity. Even the DESs with highly water-soluble HBA showed to be easily separable from water and really efficacious as extracting agents when prepared with hydrophobic HBDs. The results of the extractions of pollutants in acid and basic conditions showed the capability of water separation and extraction efficiency of these mixtures even with water at pH = 2 and pH = 9; therefore, the phenols could interact with these liquids without involvement of any acid/base-type of interactions.

Mitigation of Soot Deposition on Modified Surfaces of Exhaust Gas Recirculation Coolers

A common approach for lower emission of NOx from diesel engines is to use exhaust gas recirculation (EGR) coolers where part of the exhaust gas is returned to the cylinder to reduce the combustion temperature. Nonetheless, the deposition of various species, i.e. soot particles, on surfaces deteriorates the thermal efficiency of EGR coolers. This study investigated the impact of surface treatment on particulate fouling of a rectangular EGR cooler. An experimental setup was assembled through which the uncoated and coated plates were exposed to the flow of exhaust flue gases. The cooler surfaces were coated by ceramic-based materials with resistance to high temperatures by spraying. The results showed that surface modification abated soot deposition to some extent and the deposit layer was easily flaked off with a force of 0.8 N when it was scratched with a nano-intender. Contrariwise, the deposit formed on the uncoated surface did not result in similar propensity and instead it required a larger force of 2.25 N. This implies weaker stickiness of soot deposit on the investigated coatings compared to baseline stainless steel surface. It was also found that the electron donor component of surface energy would determine the tendency of a surface to foul or not.

Dual Sensitizer and Processing-Aid Behavior of Donor Enables Efficient Ternary Organic Solar Cells

Summary Herein, we report ternary organic solar cells with a power conversion efficiency (PCE) of 14.0%. By incorporating 10 wt % of BIT-4F-T in the PTB7-Th:IEICO-4F blend, we obtain an enhancement of all photovoltaic parameters compared to the binary devices, leading to a 15% performance improvement in ternary blend. The high photocurrent in 10% BIT-4F-T blend results from a complementary absorption profile of donor components and a hole transfer from BIT-4F-T to PTB7-Th. Morphological and device characterizations reveal that the addition of 10% BIT-4F-T acts not only as a sensitizer but also as a solid processing aid, which is beneficial for charge generation and transport. The effect of the third component is observed in different non-fullerene and fullerene OSCs. Our study demonstrates that careful selection of a third component, where dual sensitizing and processing-aid effects are observed, can be a design strategy to achieve a concomitant improvement in all photovoltaic parameters.

Superhydrophilic and oleophobic membrane functionalized with heterogeneously tailored two-dimensional layered double hydroxide nanosheets for antifouling

Fouling is a common challenge to all membrane-based separation technologies. The current study demonstrated an antifouling membrane with a superhydrophilic but oleophobic (in air) characteristic, which was achieved through covalently tethering heterogeneously tailored two-dimensional layered double hydroxide (LDH) nanosheets to a polyvinylidene fluoride membrane surface. The nanosheets were in situ grafted with alternately arranged sodium 1-dodecanesulfonate (SDS) and 3-aminopropyltriethoxysilane (APTS) chains during preparation. Poly(methacrylic acid) (PMAA) was previously grafted on the membrane via plasma induced graft copolymerization as anchor sites for nanosheet binding. With a simple dip-coating operation, the surface-tailored LDH nanosheets could be bound to the membrane via cross-linking between the amine groups of APTS and carboxyl groups of PMAA. Ultimately, the long hydrophobic SDS and short hydrophilic APTS chains on the nanosheets formed a heterogeneous and infiltration selective (due to steric exclusion) surface on the membrane. As a result, the hydrophilic moieties on the membrane surface were much more accessible to water than to liquids of larger molecular size, thereby bringing about the superhydrophilic but oleophobic characteristic. The functionalization gave rise to both significantly enhanced wettability and hydrophilicity of the membrane, mainly owing to the increase of the electron donor component of surface energy (γAB−). Additionally, the functionalized membrane obtained a greater permeability without compromising its selectivity. Furthermore, as verified in both filtration tests with synthetic and practical foulant solutions, the superhydrophilic and oleophobic characteristic endowed the functionalized membrane with conspicuously greater cleaning efficiency and excellent capability in resisting irreversible fouling, suggesting promising applications in various fields.

Innovative non-metal heat transfer surfaces to mitigate crystallization fouling

In this study, non-metal silicon carbide (SiC) substrates were used as non-adhesive heat transfer surfaces to eliminate the negative impacts of crystallization fouling of CaSO4 solutions. The experimental results showed that the SiC substrates, to large extent, were able to mitigate scaling in terms of lower initial fouling rates by as much as four-fold to that of baseline stainless steel (SS) substrates. The superiority can be related to the unique surface characteristic of SiC substrates in terms of higher value of the electron donor component which was 8 times higher than SS surfaces. The post-fouling examination of deposit layers revealed that the layers were very porous where only few number of crystal clusters formed on the surfaces. The deposited crystal clusters, to some extent, were also non-stickable as such that they dropped off the surface completely after each dismantling from the test rig. Larger porous deposit layer on SiC substrates showed also better thermal performance compared to similar tests for the SS substrates. The fouling runs of SiC surfaces showed similar propensity for different surface temperatures, where a reduction of surface temperature by 10 °C resulted in 89% lower initial fouling rate which is noticeable for implementation in industry. The low stickability of the deposit layer on SiC surfaces would implicitly indicate much less hazardous chemical inhibitors and/or cleaning agents would be required to clean the surface from formed deposits.

New insights into the rapid formation of initial membrane fouling after in-situ cleaning in a membrane bioreactor

Abstract In-situ chemical cleaning with sodium hypochlorite (NaClO) is often employed for maintaining constant permeability in a membrane bioreactor (MBR). In this study, the effect of NaClO shock on the rapid formation of initial membrane fouling was investigated over the course of the in-situ cleaning of a MBR. Variations of trans-membrane pressure (TMP) in the different runs indicated that the bulk sludge after NaClO-shock promotes the rapid formation of initial membrane fouling. After in-situ cleaning, the sludge had a high protein content in different extracellular polymeric substance layers and a substantial deterioration in sludge filterability compared to raw sludge. Based on the extended Derjaguin-Landau-Verwey-Overbeek (XDLVO) theory, NaClO shock significantly changes the surface properties of raw sludge. It reduces the surface electron donor component ( γ − ) and increases surface hydrophobicity. The sludge after NaClO-shock exhibited a stronger adhesive energy with the membrane and higher self-cohesive ability, resulting in severe membrane fouling.

Ternary organic solar cells: using molecular donor or acceptor third components to increase open circuit voltage

The addition of donor or acceptor type molecular semiconductors to PBDB-T:PC60BM based organic photovoltaics leads to increases in open circuit-voltages and overall power conversion efficiencies.

Исследование влияния структурных дефектов на спектры фотолюминесценции в n-3C-SiC

AbstractPhotoluminescence (PL) spectra have been studied in 3 C -SiC/4 H -SiC heterostructures and 3 C ‑SiC single crystals. It was shown that epitaxial 3 C -SiC layers grown on 4 H -SiC substrates have a markedly poorer crystal perfection than do 3 C -SiC single crystals. It was found that doping with aluminum gives rise to a characteristic PL both in epitaxial layers and in 3 C -SiC single crystals. At the same time, the electron irradiation of epitaxial layers does not give rise to defect-related PL, in contrast to what is observed for single crystals. An assumption is made that the twin boundaries existing in epitaxial 3 C -SiC layers can serve as getters of radiation defects that are components of donor–acceptor pairs responsible for the “defect-related” PL.

Synthesis and Properties of Alternating Copolymers Based on 4H-Cyclopenta[2,1-b:3,4-b']dithiophene and 4H-Dithieno[3,2-b:2',3'-d]silol

A number of copolymers based on 4H-cyclopenta[2,1-b:3,4-b']dithiophene and 4H-dithieno[3,2-b:2',3'-d]silol are synthesized via direct С–Н arylation and Suzuki cross-coupling, and their properties are compared. The chemical structure of the copolymers is investigated by 1Н and 13С NMR spectroscopy, and their molecular-mass characteristics are determined by GPC. The study of absorption spectra of the copolymers in dilute solutions and thin films shows that they absorb light in a wide visible spectral range (300–800 nm). On the basis of the cyclic voltammetry data, the levels of boundary molecular orbitals—the highest occupied and the lowest unoccupied—are estimated and the width of the energy gap is shown to be in the range of 1.4–1.9 eV. Using the copolymers as donor components of the active layer, the samples of solar photocells are manufactured and their photovoltaic properties are investigated.

Zn Phthalocyanine Derivatives for Solution‐Processed Small Molecule Organic Solar Cells

AbstractZinc phthalocyanine derivatives, 1 and 2, having either electron donating octyl‐thiol group or electron accepting octyl‐sulfonyl groups have been synthesized to serve as new electron donor components for bulk heterojunction (BHJ) solar cells. BHJ solar cells, in which the active layer consist of zinc phthalocyanine (ZnPc) as an electron donor and a soluble fullerene derivative, namely PCBM, as an electron acceptor component were produced and characterized. The device consisting of octylthiol‐ZnPc:PCBM (1:4) gave power‐conversion efficiencies of 0.42%. On the other hand, the device having octyl‐sulfonyl substituted ZnPc gave very low efficiency due to both low Voc and Jsc values.

Design, Electrical, and Optical Modelling of Bulk Heterojunction Polymer Solar Cell

The energy scenario today is focused on the development and usage of solar cells, especially in the paradigm of clean energy. To readily create electron and hole pairs, solar cells utilize either photoactive or photosensitive components. A bulk heterojunction (BHJ) is a nanolayer consisting of donor and acceptor components with a large interpenetrated acceptor and donor contact area. In this context, a mix of P3HT and PCBM offers novelty for its use as an acceptor as well as a donor. In the work presented here, we address the mechanism of modelling and characterization of a BHJ-based polymer solar cell. Here, a new design of BHJ polymer solar cells have been designed, modelled, using Silvaco TCAD in the Organic Solar module, and matched with an already assembled device having similar features. Using this model, we have been able to estimate key parameters for the modelled devices, such as the short-circuit current density, open-circuit voltage, and fill factor with less than 0.25 error index compared to the fabricated counterpart, paving the way for fabless polymer solar cell design and optimization.

Tailoring Photophysical Processes of Perylene-Based Light Harvesting Antenna Systems with Molecular Structure and Solvent Polarity.

The excited-state dynamics of perylene-based bichromophoric light harvesting antenna systems has been tailored by systematic modification of the molecular structure and by using solvents of increasing polarity in the series toluene, chloroform, and benzonitrile. The antenna systems consist of blue light absorbing naphthalene monoimide (NMI) energy donors (D1, D2, and D3) and the perylene derived green light absorbing energy acceptor moieties, 1,7-perylene-3,4,9,10-tetracarboxylic tetrabutylester (A1), 1,7-perylene-3,4,9,10-tetracarboxylic monoimide dibutylester (A2), and 1,7-perylene-3,4,9,10-tetracarboxylic bisimide (A3). The design of these antenna systems is such that all exhibit ultrafast excitation energy transfer (EET) from the excited donor to the acceptor, due to the effective matching of optical properties of the constituent chromophores. At the same time, electron transfer from the donor to the excited acceptor unit has been limited by the use of a rigid and nonconjugated phenoxy bridge to link the donor and acceptor components. The antenna molecules D1A1, D1A2, and D1A3, which bear the least electron-rich energy donor, isopentylthio-substituted NMI D1, exhibited ultrafast EET (τEET ∼ 1 ps) but no charge transfer and, resultantly, emitted a strong yellow-orange acceptor fluorescence upon excitation of the donor. The other antenna molecules D2A2, D2A3, and D3A3, which bear electron-rich energy donors, the amino-substituted NMIs D2 and D3, exhibited ultrafast energy transfer that was followed by a slower (ca. 20–2000 ps) electron transfer from the donor to the excited acceptor. This charge transfer quenched the acceptor fluorescence to an extent determined by molecular structure and solvent polarity. These antenna systems mimic the primary events occurring in the natural photosynthesis, i.e., energy capture, efficient energy funneling toward the central chromophore, and finally charge separation, and are suitable building blocks for achieving artificial photosynthesis, because of their robustness and favorable and tunable photophysical properties.

Preparation and characterization of amine (N-methyl diethanolamine)-based transition temperature mixtures (deep eutectic analogues solvents)

In this study, three mixtures of methylyltriphenylphosphonium bromide (MTPPB) as hydrogen bond acceptor (HBA) and N-methyl diethanolamine (MDEA) as hydrogen bond donor (HBD) component was used to prepare transition temperature mixtures (TTMs) into different mole ratios of 1:7, 1:10 and 1:16 HBA/HBD. Two important physicochemical properties of TTMs such as density and refractive index were investigated at the atmospheric pressure and temperature ranges of (293.15–353.15) K and (293.15–343.15) K, respectively. The experimental density data were used to derive the molar volume, molecular volume, lattice energy and isobaric thermal expansion coefficients. With the help of experimental refractive index data, the electronic polarization, molar refraction, and free volume were calculated at the whole temperatures. Several empirical equations were used to correlate refractive indices such as an empirical equation and one-parameter equations (Dale–Gladstone, Eykman, Lorentz–Lorenz, Newton, Arago–Biot, and Oster). Finally, the response surface methodology (RSM) was applied to evaluate the effects of two main factors such as temperature and mole ratio on the density and refractive index of TTMs. The results revealed that the molar ratio has almost a higher effect on the studied properties than temperature.