Influences of Non-fullerene Acceptor Fluorination on Three-Dimensional Morphology and Photovoltaic Properties of Organic Solar Cells.

Fluorination of conjugated molecules has been established as an effective structural modification strategy to influence properties and has attracted extensive attention in organic solar cells (OSCs). Here, we have investigated optoelectronic and photovoltaic property changes of OSCs made of polymer donors with the non-fullerene acceptors (NFAs) ITIC and IEICO and their fluorinated counterparts IT-4F and IEICO-4F. Device studies show that fluorinated NFAs lead to reduced Voc but increased Jsc and fill-factor (FF), and therefore, the ultimate influence to efficiency depends on the compensation of Voc loss and gains of Jsc and FF. Fluorination lowers energy levels of NFAs, reduces their electronic band gaps, and red-shifts the absorption spectra. The impact of fluorination on the molecular order depends on the specific NFA, and the conversion of ITIC to IT-4F reduces the structural order, which can be reversed after blending with the donor PBDB-T. Contrastingly, IEICO-4F presents stronger π-π stacking after fluorination from IEICO, and this is further strengthened after blending with the donor PTB7-Th. The photovoltaic blends universally present a donor-rich surface region which can promote charge transport and collection toward the anode in inverted OSCs. The fluorination of NFAs, however, reduces the fraction of donors in this donor-rich region, consequently encouraging the intermixing of donor/acceptor for efficient charge generation.

A review of non-fullerene polymer solar cells: from device physics to morphology control.

The rise in power conversion efficiency of organic photovoltaic (OPV) devices over the last few years has been driven by the emergence of new organic semiconductors and the growing understanding of morphological control at both the molecular and aggregation scales. Non-fullerene OPVs adopting p-type conjugated polymers as the donor and n-type small molecules as the acceptor have exhibited steady progress, outperforming PCBM-based solar cells and reaching efficiencies of over 15% in 2019. This review starts with a refreshed discussion of charge separation, recombination, and V OC loss in non-fullerene OPVs, followed by a review of work undertaken to develop favorable molecular configurations required for high device performance. We summarize several key approaches that have been employed to tune the nanoscale morphology in non-fullerene photovoltaic blends, comparing them (where appropriate) to their PCBM-based counterparts. In particular, we discuss issues ranging from materials chemistry to solution processing and post-treatments, showing how this can lead to enhanced photovoltaic properties. Particular attention is given to the control of molecular configuration through solution processing, which can have a pronounced impact on the structure of the solid-state photoactive layer. Key challenges, including green solvent processing, stability and lifetime, burn-in, and thickness-dependence in non-fullerene OPVs are briefly discussed.

TDI/TiO2 Hybrid Networks for Superhydrophobic Coatings with Superior UV Durability and Cation Adsorption Functionality.

Durability under UV illumination remains a big challenge of TiO2-based superhydrophobic coatings, with the photocatalytic effect causing degradation of low-surface-energy material over time, resulting in the surfaces losing their hydrophobicity. We report surfaces made from tolylene-2,4-diisocyanate (TDI)/TiO2 hybrid networks that demonstrate superhydrophobicity and superior UV durability. Structural and morphological studies reveal that the TDI/TiO2 hybrid networks are composed of TiO2 nanoparticles interconnected with TDI bridges and then encapsulated by a TDI layer. Through controlling the fraction of TDI in the synthesis process, the thickness of the TDI encapsulation layer around the TDI/TiO2 hybrid networks can be varied. When the weight ratio of TDI/TiO2 is 5:1, the superhydrophobicity of the hybrid network surface remains almost unchanged after a month of continuous UV illumination. This hybrid network surface can also clean methylene blue solution through the synergistic effects of cation adsorption and photocatalysis, holding promising potential for applications toward reducing cation pollutions in both liquid and air environments.

Eliminating Light-Soaking Instability in Planar Heterojunction Perovskite Solar Cells by Interfacial Modifications.

Stability remains as a challenge of perovskite solar cells although encouraging progress has been made toward their maximum achievable power conversion efficiency in recent years. Light-soaking issue, where the device performance improves upon continuous light illumination and reduces upon storage in dark, is widely observed and marked as the early-stage instability during device operation. In this work, we have employed conjugated polymer PCDTBT as the dopant-free hole-transport layer to fabricate devices without hysteresis but with reversible light-soaking instability. The introduction of n-type molecules, either organic molecule PDI2 or fullerene derivative PC61BM, as the interfacial layer between TiO2 and perovskite layers can effectively reduce or eliminate this instability owing to the efficient charge transport and defect passivation at the electron-transport layer interface, accompanied with an efficiency of 15.7 and 17.7%, respectively. We conclude that the light-soaking instability of these perovskite solar cells is mainly originated from the charge accumulation at the TiO2/perovskite interface and can be eliminated once the interfacial charge can be suppressed by interfacial modifications to improve charge transport at the interface.

Environmentally durable superhydrophobic surfaces with robust photocatalytic self-cleaning and self-healing properties prepared via versatile film deposition methods.

Superhydrophobic (SH) surfaces with self-cleaning photocatalytic properties have become an important research focus in recent years. In this work, we fabricated multifunctional and environmentally durable SH surfaces via a facile one-step reaction of octadecyl isocyanate (ODI) with TiO2 particles. The resulting films possess SH properties, facilitated by a combination of hydrophobic long alkyl chains and the hierarchical crystalline structure. Films can be prepared via spray or blade coating on a variety of hard and soft substrates, and function well when exposed to either air or oil. The coating retains its SH properties for at least 6 months in ambient conditions, and after organic pollution it can recover its SH properties using UV or sun light illumination. After water impalement, the SH properties can self-heal via the self-assembly of long alkyl chains to their original state within several hours at ambient conditions, or within minutes on a heating stage. The covalent bonds between alkyl chains and TiO2, together with hydrogen bonds between adjacent alkyl chains, greatly increased the surface durability of the SH films. This multifunctional SH coating is a very promising material for commercial and industrial coating applications.

Versatile Device Architectures for High-Performing Light-Soaking-Free Inverted Polymer Solar Cells.

Metal oxide charge transport layers have been widely employed to prepare inverted polymer solar cells with high efficiency and long lifetime. However, the intrinsic defects in the metal oxide layers, especially those prepared from low-temperature routes, overshadow the high efficiency that can be achieved and also introduce "light-soaking" issues to these devices. In this work, we have employed polyethyleneimine (PEI) and poly(9,9-bis(6'-(N,N-diethylamino)propyl)-fluorene-alt-9,9-bis-(3-ethyl(oxetane-3-ethyloxy)-hexyl)-fluorene] (PFN-OX) to modify our low-temperature-processed TiO2 electron transport layer (ETL) and demonstrated that the light-soaking issue can be effectively eliminated by PEI modifications because of the formation of abundant dipole moments, whereas PFN-OX was ineffective as a result of deficient dipole moments at the interface. Excitingly, PEI modifications enable versatile device architectures to obtain light-soaking-free, inverted PTB7-Th:PC71BM solar cells with efficiencies of over 10%, by adding PEI either in the bulk or as an adjacent layer below or above the TiO2 ETL.

Molecular Weight Dependence of Interdiffusion and Adhesion of Polymers at Short Contact Times.

The autohesion and subsequent debonding of thin layers of three linear and monodisperse random copolymers of styrene-butadiene (SBR) with molecular weights varying between 30 and 75 times the average molecular weight between entanglements Me were investigated using a carefully controlled tack adhesion testing device in conjunction with a fast camera setup over a range of contact times tc (10 ms to 10 s) much shorter in comparison to the terminal relaxation times of the polymers. The evolution of the stress-strain curves and debonding mechanisms with increasing contact time was examined, and the work required to debond the layers was found to be strongly dependent on molecular weight at long contact times, but not at short contact times. We propose a cutoff contact time of 300 ms, corresponding to 104 times the entanglement time τe after which molecular weight becomes important in controlling the interdiffusion process and the debonding mechanisms of the tack test. For contact times over 300 ms, the debonding energy plotted as a function of tc normalized by the reptation time τrep, collapses onto a master curve. Below this threshold tc, by comparing the adhesion of SBR on itself with the adhesion of SBR on glass, we also show that interdiffusion plays a part in adhesion of two identical polymer layers even at the shortest contact times, where the interdiffusion is controlled by the number of entanglements formed which scales with 1/√N.

Constructing professional and organisational fields.

Purpose - The purpose of this paper is to fill an apparent gap in the literature addressing issues of leadership and change - the development and activities of constructing and leading sports sciences and medicine professions, and similarly, the construction and leadership of multidisciplinary/inter-disciplinary organisations that practice sports sciences and medicine. Design/methodology/approach - This study incorporated explorations through conducting both interviews and survey questionnaires with members of Sports Medicine Australia (SMA). The interviews (qualitative) were semi-structured and asked questions addressing what changed, why change and how change was implemented. Findings - The health sciences and medicine professions moving to specialised sports sciences and medicine disciplines and SMA, evolved through forces driving the need for change (legitimacy, resource dependency, positioning and core competencies). Practical implications - The knowledge developed from understanding activities of change that traditional professions conducted to become specialised Disciplines and parallel changes in a single Discipline organisation evolving to an umbrella organisation (SMA), comprised a membership of specialised Disciplines, can act as a catalyst for inquiry by other professional and organisational groups. Originality/value - The findings of this study contributes to the literature investigating change in professional and organisations fields. More specifically, this study promotes inquiry into leadership practices of sports sciences and medicine, as contributors to the field of health services.

Mechanical properties of a waterborne pressure-sensitive adhesive with a percolating poly(acrylic acid)-based diblock copolymer network: effect of pH.

Copolymerizing an acrylic acid comonomer is often beneficial for the adhesive properties of waterborne pressure-sensitive adhesives (PSAs). Here, we demonstrate a new strategy in which poly(acrylic acid) (PAA) is distributed as a percolating network within a PSA film formed from a polymer colloid. A diblock copolymer composed of PAA and poly(n-butyl acrylate) (PBA) blocks was synthesized using reversible addition-fragmentation chain transfer (RAFT) polymerization and adsorbed onto soft acrylic latex particles prior to their film formation. The thin adsorbed shells on the particles create a percolating network that raises the elastic modulus, creep resistance and tensile strength of the final film. When the film formation occurs at pH 10, ionomeric crosslinking occurs, and high tack adhesion is obtained in combination with high creep resistance. The results show that the addition of an amphiphilic PAA-b-PBA diblock copolymer (2.0 wt.%) to a soft latex provides a simple yet effective means of adjusting the mechanical and adhesive properties of the resulting composite film.

Building successful student-athlete coach relationships: examining coaching practices and commitment to the coach.

In this study we utilized the concept of commitment to explain the impact of coaching practices on student-athlete's behaviour. We examined the impact of commitment to the coach on the coaching outcome of in-role behaviour, and the influence of coaching practices, of information sharing, training, and encouraging teamwork, on the formation of relationships. We adopted measures from the organizational behaviour literature and surveyed student-athletes at two universities in Canada. The sample included data from 165 student-athletes from two universities. Results from structural equation modeling indicate support for the effect of coaching practices on commitment to the coach. Results also support the effect of commitment to the coach on the student-athletes' role behaviour and performance. By showing that coaching practices impact commitment to the coach, and that commitment to the coach impacts student-athlete role behaviour and performance, the findings have important implications for a better understanding of the determinants of coaches' and athletes' performance. The managerial significance of this research rests in the insight provided into how coaching practices influence athlete's behaviour through commitment to the coach. This study contributes to the literature on coach-athlete relationship within universities and colleges by applying the concept of commitment to the coach. This helps diversity research approaches to understanding coach-athlete relationships and extends prior research on commitment by looking at the context of the relationship between the student-athlete and their coach.

Large-area patterning of the tackiness of a nanocomposite adhesive by sintering of nanoparticles under IR radiation.

We present a simple technique to switch off the tack adhesion in selected areas of a colloidal nanocomposite adhesive. It is made from a blend of soft colloidal polymer particles and hard copolymer nanoparticles. In regions that are exposed to IR radiation, the nanoparticles sinter together to form a percolating skeleton, which hardens and stiffens the adhesive. The tack adhesion is lost locally. Masks can be made from silicone-coated disks, such as coins. Under the masks, adhesive island regions are defined with the surrounding regions being a nontacky coating. When optimizing the nanocomposite's adhesive properties, the addition of the hard nanoparticles raises the elastic modulus of the adhesive significantly, but adhesion is not lost because the yield point remains relatively low. During probe-tack testing, the soft polymer phases yield and enable fibrillation. After heating under IR radiation, the storage modulus increases by a factor of 5, and the yield point increases nearly by a factor of 6, such that yielding and fibrillation do not occur in the probe-tack testing. Hence, the adhesion is lost. Loading and unloading experiments indicate that a rigid skeleton is created when the nanoparticles sinter together, and it fractures under moderate strains. This patterning method is relatively simple and fast to execute. It is widely applicable to other blends of thermoplastic hard nanoparticles and larger soft particles.

Evaluation of growth, nutrient utilization and production of bioproducts by a wastewater-isolated microalga.

Treatment of wastewater while producing microalgal biomass is receiving ever-increasing attention, particularly in the biofuels arena. In this study, a wastewater chlorophyte isolate, Kirchneriella sp., was tested for its ability to be mass cultivated, utilize nutrients from defined media and wastewater, and produce bioproducts of commercial interest. Growth studies were carried out in various systems at scales up to 60L, with Kirchneriella sp. showing an excellent amenability to being cultured. Biomass concentrations of greater than 1gL(-1) were consistently achieved, nitrogen and phosphorus uptake was rapid, and stable medium-term cultures were maintained. Nitrogen limitation affected biomass yield, fatty acid methyl ester (FAME) yield, and cetane index. In contrast, a low phosphorus condition had no effect. Kirchneriella sp. showed an ability to produce several products of commercial value, including carbohydrate-rich biomass, FAME/biodiesel and the pigments ß,ß-carotene and lutein.

Switching off the tackiness of a nanocomposite adhesive in 30 s via infrared sintering.

Soft adhesives require an optimum balance of viscous and elastic properties. Adhesion is poor when the material is either too solidlike or too liquidlike. The ability to switch tack adhesion off at a desired time has many applications, such as in recycling, disassembly of electronics, and painless removal of wound dressings. Here, we describe a new strategy to switch off the tack adhesion in a model nanocomposite adhesive in which temperature is the trigger. The nanocomposite comprises hard methacrylic nanoparticles blended with a colloidal dispersion of soft copolymer particles. At relatively low volume fractions, the nanoparticles (50 nm diameter) accumulate near the film surface, where they pack around the larger soft particles (270 nm). The viscoelasticity of the nanocomposite is adjusted via the nanoparticle concentration. When the nanocomposite is heated above the glass transition temperature of the nanoparticles (T(g) = 130 °C), they sinter together to create a rigid network that raises the elastic modulus at room temperature. The tackiness is switched off. Intense infrared radiation is used to heat the nanocomposites, leading to a fast temperature rise. Tack adhesion is switched off within 30 s in optimized compositions. These one-way switchable adhesives have the potential to be patterned through localized heating.

Effects of lifetime chemical inhibition of aromatase on the sexual differentiation, sperm characteristics and fertility of medaka (Oryzias latipes) and zebrafish (Danio rerio).

The deleterious effects of tributyltin (TBT) on spermiation in fish have been attributed to its role in inhibiting aromatisation of androgens to estrogens, and the critical role of the latter in sperm development. We test this hypothesis by examining sperm parameters, fertilisation and hatching success in males of two fish species exposed throughout life to doses of Fadrozole, a non-steroidal aromatase inhibitor (AI), provided in their diets. AI-treatment caused 100% male development in zebrafish, but only partial masculinisation in medaka, in both cases supporting previous studies and suggesting different roles of estrogen in sexual differentiation in the two species. Milt volume, initial sperm motility, maximum sperm swimming duration and sperm morphology did not differ significantly between Control and AI-dosed fish in either species, after excluding low milt volumes in sex-changed females in medaka. Fertilisation rates were also unaffected by the aromatase inhibition, but hatching success in medaka was 31% lower than in Control males, suggesting a previously unreported effect of aromatase on sperm quality. The slight effect of aromatase inhibition on sperm parameters in general contrasts with the marked effect of TBT on fish sperm, and suggests that a mechanism other than depressed estrogen levels is involved.

Land surface anomaly simulations and predictions with a climate model: an El Niño Southern Oscillation case study.

The ability of climate models to reproduce and predict land surface anomalies is an important but little-studied topic. In this study, an atmosphere and ocean assimilation scheme is used to determine whether HadCM3 can reproduce and predict snow water equivalent and soil moisture during the 1997-1998 El Niño Southern Oscillation event. Soil moisture is reproduced more successfully, though both snow and soil moisture show some predictability at 1- and 4-month lead times. This result suggests that land surface anomalies may be reasonably well initialized for climate model predictions and hydrological applications using atmospheric assimilation methods over a period of time.

An experimental evaluation of host specificity: the role of encounter and compatibility filters for a rhizocephalan parasite of crabs.

The encounter/compatibility paradigm of host specificity provides three qualitative pathways to the success or failure of a potential host-parasite interaction. It is usually impossible to distinguish between two of these (encounter and compatibility filters closed versus encounter filter open and compatibility filter closed) because unsuccessful infection attempts are difficult to observe in nature. We were able to open the encounter filter under experimental laboratory conditions. Our analytical system used the rhizocephalan barnacle, Sacculina carcini, a parasitic castrator of the European green crab, Carcinus maenas, and Pachygrapsus marmoratus, a native European crab that occurs with C. maenas but is not parasitized by S. carcini in nature. Penetration followed by unsuccessful infection of P. marmoratus crabs by parasitic barnacle larvae leaves a uniquely permanent record in the thoracic ganglion of the crabs. This provided us with a novel tool to quantify the encounter filter in a host-parasite system in nature. We demonstrated, in the laboratory, that the compatibility filter was closed and that, in nature, even where barnacle larvae were present, the encounter filter was also effectively closed. The closure of both filters in nature explains the failure of this potential host-parasite interaction, an outcome favored by selection in both host and parasite.