Bimolecular Crystals of Fullerenes in Conjugated Polymers and the Implications of Molecular Mixing for Solar Cells

The performance of polymer:fullerene bulk heterojunction solar cells is heavily influenced by the interpenetrating nanostructure formed by the two semiconductors because the size of the phases, the nature of the interface, and molecular packing affect exciton dissociation, recombination, and charge transport. Here, X‐ray diffraction is used to demonstrate the formation of stable, well‐ordered bimolecular crystals of fullerene intercalated between the side‐chains of the semiconducting polymer poly(2,5‐bis(3‐tetradecylthiophen‐2‐yl)thieno[3,2‐b]thiophene. It is shown that fullerene intercalation is general and is likely to occur in blends with both amorphous and semicrystalline polymers when there is enough free volume between the side‐chains to accommodate the fullerene molecule. These findings offer explanations for why luminescence is completely quenched in crystals much larger than exciton diffusion lengths, how the hole mobility of poly(2‐methoxy‐5‐(3′,7′‐dimethyloxy)‐p‐phylene vinylene) increases by over 2 orders of magnitude when blended with fullerene derivatives, and why large‐scale phase separation occurs in some polymer:fullerene blend ratios while thermodynamically stable mixing on the molecular scale occurs for others. Furthermore, it is shown that intercalation of fullerenes between side chains mostly determines the optimum polymer:fullerene blending ratios. These discoveries suggest a method of intentionally designing bimolecular crystals and tuning their properties to create novel materials for photovoltaic and other applications.     

Method for ultra-low-level analysis of gold in rocks

A new method for analyzing gold at ultralow concentrations (<10 pg/g) in geological samples has been developed involving HF-aqua regia acid digestion, chromatographic separation of Au from matrix elements using DIBK supported on an inert resin, and analysis by inductively coupled plasma-mass spectrometry (ICPMS). This method has an analytical detection limit of 2 parts per trillion (pg/g), significantly lower than most routinely used methods developed for analysis of ore samples with Au concentrations considerably higher than average crustal abundance ( approximately 2 ng/g). Such methods commonly have detection limits in the low nanogram per gram range. Many areas of geological research including ore genesis, crustal mobility and redistribution, planetary differentiation, and plume volcanism require quantitative analysis of geological materials with much lower Au concentrations. We present a rapid, easy to use method where Au is separated from matrix elements onto extractant primed chromatographic resin and analyzed by quadrupole ICPMS. The method is suitable for the relatively rapid analysis of a large number of samples and is reliable over a wide range of concentrations from picogram to microgram per gram level. Analysis of four different geostandards, GXR1, GXR4, CH-3, and SARM 7, yields concentrations within error of the published concentrations with accuracies of >95%.     

Regulating the geological sequestration of CO2

Governments worldwide should provide incentives for initial large-scale GS projects to help build the knowledge base for a mature, internationally harmonized GS regulatory framework. Health, safety, and environmental risks of these early projects can be managed through modifications of existing regulations in the EU, Australia, Canada, and the U.S. An institutional mechanism, such as the proposed Federal Carbon Sequestration Commission in the U.S., should gather data from these early projects and combine them with factors such as GS industrial organization and climate regime requirements to create an efficient and adaptive regulatory framework suited to large-scale deployment. Mechanisms to structure long-term liability and fund long-term postclosure care must be developed, most likely at the national level, to equitably balance the risks and benefits of this important climate change mitigation technology. We need to do this right. During the initial field experiences, a single major accident, resulting from inadequate regulatory oversight, anywhere in the world, could seriously endanger the future viability of GS. That, in turn, could make it next to impossible to achieve the needed dramatic global reductions in CO2 emissions over the next several decades. We also need to do it quickly. Emissions are going up, the climate is changing, and impacts are growing. The need for safe and effective CO2 capture with deep GS is urgent.     

Social information use and the evolution of unresponsiveness in collective systems

Animal groups in nature often display an enhanced collective information-processing capacity. It has been speculated that natural selection will tune this response to be optimal, ensuring that the group is reactive while also being robust to noise. Here, we show that this is unlikely to be the case. By using a simple model of decision-making in a dynamic environment, we find that when individuals behave rationally and are subject to selection based on their accuracy, optimality of collective decision-making is not attained. Instead, individuals overly rely on social information and evolve to be too readily influenced by their neighbours. This is due to a classic evolutionary conflict between individual and collective interest. The result is a sub-optimal system that is poised on the cusp of total unresponsiveness. Individuals in the evolved group exhibit delayed reactions to changes in the environment, before responding with rapid, socially reinforced transitions, reminiscent of familiar human and animal social systems (markets, stampedes, fashions, etc.). Our results demonstrate that behaviour of this type may not be pathological, but instead could represent an evolutionary attractor for such collective systems.     

Systematic Control of the Orientation of Organic Phosphorescent Pt Complexes in Thin Films for Increased Optical Outcoupling

Orienting light‐emitting molecules relative to the substrate is an effective method to enhance the optical outcoupling of organic light‐emitting devices. Platinum(II) phosphorescent complexes enable facile control of the molecular alignment due to their planar structures. Here, the orientation of Pt(II) complexes during the growth of emissive layers is controlled by two different methods: modifying the molecular structure and using structural templating. Molecules whose structures are modified by adjusting the diketonate ligand of the Pt complex, dibenzo‐(f,h)quinoxaline Pt dipivaloylmethane, (dbx)Pt(dpm), show an ≈20% increased fraction of horizontally aligned transition dipole moments compared to (dbx)Pt(dpm) doped into a 4,4′‐bis(N‐carbazolyl)‐1,1′‐biphenyl, CBP, host. Alternatively, a template composed of highly ordered 3,4,9,10‐perylenetetracarboxylic dianhydride monolayers is predeposited to drive the alignment of a subsequently deposited emissive layer comprising (2,3,7,8,12,13,17,18‐octaethyl)‐21H,23H‐porphyrinplatinum(II) doped into triindolotriazine. This results in a 60% increase in horizontally aligned transition dipole moments compared to the film deposited in the absence of the template. The findings provide a systematic route for controlling molecular alignment during layer growth, and ultimately to increase the optical outcoupling in organic light‐emitting diodes.     

Role of the Anion on the Transport and Structure of Organic Mixed Conductors

Organic mixed conductors are increasingly employed in electrochemical devices operating in aqueous solutions that leverage simultaneous transport of ions and electrons. Indeed, their mode of operation relies on changing their doping (oxidation) state by the migration of ions to compensate for electronic charges. Nevertheless, the structural and morphological changes that organic mixed conductors experience when ions and water penetrate the material are not fully understood. Through a combination of electrochemical, gravimetric, and structural characterization, the effects of water and anions with a hydrophilic conjugated polymer are elucidated. Using a series of sodium‐ion aqueous salts of varying anion size, hydration shells, and acidity, the links between the nature of the anion and the transport and structural properties of the polymer are systematically studied. Upon doping, ions intercalate in the crystallites, permanently modifying the lattice spacings, and residual water swells the film. The polymer, however, maintains electrochemical reversibility. The performance of electrochemical transistors reveals that doping with larger, less hydrated, anions increases their transconductance but decreases switching speed. This study highlights the complexity of electrolyte‐mixed conductor interactions and advances materials design, emphasizing the coupled role of polymer and electrolyte (solvent and ion) in device performance.     

Towards Efficient Integrated Perovskite/Organic Bulk Heterojunction Solar Cells: Interfacial Energetic Requirement to Reduce Charge Carrier Recombination Losses

Integrated perovskite/organic bulk heterojunction (BHJ) solar cells have the potential to enhance the efficiency of perovskite solar cells by a simple one‐step deposition of an organic BHJ blend photoactive layer on top of the perovskite absorber. It is found that inverted structure integrated solar cells show significantly increased short‐circuit current (J_sc) gained from the complementary absorption of the organic BHJ layer compared to the reference perovskite‐only devices. However, this increase in J_sc is not directly reflected as an increase in power conversion efficiency of the devices due to a loss of fill factor. Herein, the origin of this efficiency loss is investigated. It is found that a significant energetic barrier (≈250 meV) exists at the perovskite/organic BHJ interface. This interfacial barrier prevents efficient transport of photogenerated charge carriers (holes) from the BHJ layer to the perovskite layer, leading to charge accumulation at the perovskite/BHJ interface. Such accumulation is found to cause undesirable recombination of charge carriers, lowering surface photovoltage of the photoactive layers and device efficiency via fill factor loss. The results highlight a critical role of the interfacial energetics in such integrated cells and provide useful guidelines for photoactive materials (both perovskite and organic semiconductors) required for high‐performance devices.     

Design and Characterisation of Titanium Nitride Subarrays of Kinetic Inductance Detectors for Passive Terahertz Imaging

We report on the investigation of titanium nitride (TiN) thin films deposited via atomic layer deposition (ALD) for microwave kinetic inductance detectors (MKID). Using our in-house ALD process, we have grown a sequence of TiN thin films (thickness 15, 30, 60 nm). The films have been characterised in terms of superconducting transition temperature \(T_\mathrm{c}\), sheet resistance \(R_\mathrm{s}\) and microstructure. We have fabricated test resonator structures and characterised them at a temperature of 300 mK. At 350 GHz, we report an optical noise equivalent power \(\hbox {NEP}_\mathrm{opt} \approx 2.3\times 10^{-15}~\hbox {W}/\sqrt{\hbox {Hz}}\), which is promising for passive terahertz imaging applications.     

Energetic Control of Redox-Active Polymers toward Safe Organic Bioelectronic Materials

Avoiding faradaic side reactions during the operation of electrochemical devices is important to enhance the device stability, to achieve low power consumption, and to prevent the formation of reactive side-products. This is particularly important for bioelectronic devices, which are designed to operate in biological systems. While redox-active materials based on conducting and semiconducting polymers represent an exciting class of materials for bioelectronic devices, they are susceptible to electrochemical side-reactions with molecular oxygen during device operation. Here, electrochemical side reactions with molecular oxygen are shown to occur during organic electrochemical transistor (OECT) operation using high-performance, state-of-the-art OECT materials. Depending on the choice of the active material, such reactions yield hydrogen peroxide (H₂O₂), a reactive side-product, which may be harmful to the local biological environment and may also accelerate device degradation. A design strategy is reported for the development of redox-active organic semiconductors based on donor–acceptor copolymers that prevents the formation of H₂O₂ during device operation. This study elucidates the previously overlooked side-reactions between redox-active conjugated polymers and molecular oxygen in electrochemical devices for bioelectronics, which is critical for the operation of electrolyte-gated devices in application-relevant environments.