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Silicon and tin(IV) phthalocyanines, which have been demonstrated as simple-to-synthesize materials for n-type organic thin-film transistors (OTFTs), have relatively shallow lowest unoccupied molec...

PURPOSE To fabricate a 1D stemless plastic scintillation detector (SPSD) array using organic photodiodes and to use the detector to measure small field profiles and output factors. METHODS An organic photodiode array was fabricated by spin coating a mixture of P3HT and PCBM organic semiconductors onto an ITO-coated glass substrate and depositing aluminum top contacts. Four bulk scintillators of various dimensions were placed on top of the photodiode array. A fifth scintillator was used that had been segmented by laser etching and the septa filled with black paint. Each detector array was first calibrated using a reference field of 95 cm SSD, 5 cm depth, and 10×10 cm2 field size for a 6 MV photon beam. After calibration, profiles were measured for three small field sizes: 0.5×0.5 cm2 , 1×1 cm2 , and 2×2 cm2 . Using the central pixel of the array, output factors were measured for field sizes of 0.5×0.5 cm2 to 25×25 cm2 . Small field profiles were compared to film measurements and output factors compared to ion chamber measurements. RESULTS The segmented scintillator measured profiles that were in good agreement with film for all three field sizes. Output factors agreed to within 1.2 % of ion chamber over the field size range of 1×1 cm2 to 25×25 cm2 . At 0.5×0.5 cm2 the segmented scintillator underestimated the output factor compared to film and a microDiamond detector. Bulk scintillators failed to produce good agreement with film for measured profiles and deviations from ion chamber for output factors were apparent at field sizes below 5×5 cm2 . In comparison to a bulk scintillator of dimensions 5×5×0.5 cm3 the etched scintillator saw a reduction of 5.1, 7.1, and 10.5 times the signal for field sizes of 0.5×0.5 cm2 , 1×1 cm2 , and 2×2 cm2 , respectively. The reduction of signal comes from reduced cross-talk which was present in all of the bulk scintillator geometries to various degrees. CONCLUSION A 1D SPSD array was demonstrated with various scintillator designs. The etched scintillator array demonstrated excellent small field profile measurements when compared to film and output factors (down to 1×1cm2 field size) when compared to micro ion chamber and diamond detector measurements. This article is protected by copyright. All rights reserved.

The size of crystal grains in lead halide perovskite thin films remains a vital design feature for durable optoelectronic devices. With larger crystals and reduced grain boundaries per surface area...

Cells with lithium-metal anodes are viewed as the most viable future technology, with higher energy density than existing lithium-ion batteries. Many researchers believe that for lithium-metal cells, the typical liquid electrolyte used in lithium-ion batteries must be replaced with a solid-state electrolyte to maintain the flat, dendrite-free lithium morphologies necessary for long-term stable cycling. Here, we show that anode-free lithium-metal pouch cells with a dual-salt LiDFOB/LiBF4 liquid electrolyte have 80% capacity remaining after 90 charge–discharge cycles, which is the longest life demonstrated to date for cells with zero excess lithium. The liquid electrolyte enables smooth dendrite-free lithium morphology comprised of densely packed columns even after 50 charge–discharge cycles. NMR measurements reveal that the electrolyte salts responsible for the excellent lithium morphology are slowly consumed during cycling. Extensive efforts have recently been geared towards developing all-solid-state batteries largely because of their potential to enable high-energy-density Li anodes. Here, the authors report a high-performance lithium pouch cell with no excess lithium, enabled by just a dual-salt liquid electrolyte.

PURPOSE To fabricate a stemless plastic scintillation detector (SPSD) and characterize its linearity and reproducibility, and its dependence on energy and dose per pulse; and to apply it to clinical PDD and output factor measurements. METHODS An organic bulk heterojunction photodiode was fabricated by spin coating a blend of P3HT and PCBM onto an ITO-coated glass substrate and depositing aluminum top contacts. Eljen scintillators (~5 × 5 × 5 mm3 ; EJ-204, EJ-208, and EJ-260) or Saint-Gobain scintillators (~3 × 3 × 2 mm3 ; BC-400 and BC-412) were placed on the opposite side of the glass using a silicone grease (optical coupling agent) creating the SPSD. Energy dependence was measured by using 100, 180, and 300 kVp photon beams from an orthovoltage treatment unit (Xstrahl 300) and 6 and 10 MV photons from a Varian TrueBeam linear accelerator. Linearity, dose per pulse dependence, output factors, and PDDs were measured using a 6 MV photon beam. PDDs and output factors were compared to ion chamber measurements. A control device was fabricated by substituting polystyrene (PS) for the P3HT/PCBM layer. No photocurrent should be generated in the control device and so any current measured is due to Compton current in the electrodes, wires, and surroundings from the irradiation. Output factors were corrected by subtracting the signal measured using the control device from the photodiode measured signal to yield the photocurrent. RESULTS Each SPSD had excellent linearity with dose having an r2 of 1 and sensitivities of 1.07 nC/cGy, 1.04 nC/cGy, 1.00 nC/cGy and 0.10 nC/cGy, and 0.10 nC/cGy for EJ-204, EJ-208, EJ-260 (5 × 5 × 5 mm3 volumes), BC-400, and BC-412 (3 × 3 × 2 mm3 volumes), respectively. No significant dose per pulse dependence was measured. Output factors matched within 1% for the large scintillators for field sizes of 5 × 5 cm2 to 25 × 25 cm2 , but there was a large under-response at field sizes below 3 × 3 cm2 . After correcting the signal of the small scintillators by subtracting the current measured using the PS control, the output factors agreed with the ion chamber measurements within 1% from field sizes 1 × 1 cm2 to 20 × 20 cm2 . The impact of Cerenkov emissions in the scintillator was effectively corrected with a simple reflective coating on the scintillator. In comparison to a 6 MV photon beam, the large scintillator SPSDs exhibited 37%, 52%, and 73% of the response at energies 100 kVp, 180 kVp and 300 kVp, respectively. CONCLUSION The principle of the SPSD was demonstrated. Devices had excellent linearity, reproducibility, and no significant dose per pulse dependence, and a simple reflective coating was sufficient to correct for Cerenkov emissions from within the scintillator. The devices demonstrated similar energy dependence to other scintillator detectors used in a radiotherapy setting.

Non-toxic and air-stable silver bismuth iodide semiconductors are promising light absorber candidates for photovoltaic applications owing to a suitable band gap for multi- or single-junction solar cells. Recently, solution-based film fabrication approaches for several silver bismuth iodide stoichiometries have been investigated. The current work reports on a facile and reproducible two-step coevaporation/annealing approach to deposit compact and pinhole-free films of AgBi2I7, AgBiI4 and Ag2BiI5. X-ray diffraction (XRD) in combination with scanning electron microscopy (SEM)/energy-dispersive X-ray spectroscopy (EDX) analysis reveals formation of pure cubic (Fdm) phase AgBi2I7, cubic (Fdm) or rhombohedra (Rm) phase AgBiI4, each with >3 μm average grain size, or the rhombohedral phase (Rm) Ag2BiI5 with >200 nm average grain size. A phase transition from rhombohedral to cubic structure is investigated via temperature-dependent X-ray diffraction (TD-XRD). Planar-junction photovoltaic (PV) devices are prepared based on the coevaporated rhombohedral AgBiI4 films, with titanium dioxide (TiO2) and poly(3-hexylthiophene) (P3HT) as electron- and hole-transport layers, respectively. The best-performing device exhibited a power conversion efficiency (PCE) of as high as 0.9% with open-circuit voltage (VOC) > 0.8 V in the reverse scan direction (with significant hysteresis).

Halide semiconductors are undergoing a period of intense interest, buoyed by the outstanding optoelectronic properties of hybrid perovskites. It is worthwhile to consider whether related materials sharing unique aspects of the perovskite chemistry, such as the incorporation of metals that provide lone pair s electrons when integrated within the halide lattice, might yield semiconductors with comparable properties. One such metal that has not been widely studied in the context of photovoltaics is monovalent indium. In this work, we investigate a method of depositing films of indium(I) iodide, coupled with optoelectronic characterization and incorporation of these films into thin-film solar cells. We find that, although indium(I) iodide exhibits a photovoltaic effect, it is likely to be compromised by difficult-to-remove defects, e.g., iodine vacancies, which are expected to introduce recombination centers deep within the band gap.

Organic thin film transistors (OTFT) were investigated as a novel radiation detector. The OTFTs were fabricated on a flexible PET substrate with a PMMA dielectric layer and a pentacene semiconductor. OTFTs were irradiated up to 400 Gy using kilovoltage (100 and 180 kVp) and megavoltage (6 and 18 MV) photon beams. One OTFT was irradiated to 1000 Gy using 6 MV to observe the longevity of the device. Irradiating the devices caused a positive threshold voltage shift in each device. The magnitude of the threshold voltage shift per unit dose decreased with accumulated dose until it stabilized after approximately 200 Gy. The sensitivity ranged from 2 to 10 mV/Gy at low accumulated dose and decreased to 0.5–1.5 mV/Gy after 200 Gy of accumulated dose across the various OTFTs. After 400 Gy all of the devices were still functional with a loss in mobility of about 15, 14, 12 and 9% for beam qualities of 100 kV, 180 kV, 6 MV, and 18 MV, respectively. After 1000 Gy using 6 MV the OTFT was still functional with a sensitivity of 0.8 ± 0.1 mV/Gy after 300 Gy. This study showed that an OTFT on a flexible substrate shows a measureable response to photon irradiation of various qualities.

First-principles calculations can accelerate the search for novel high-performance thermoelectric materials. However, the prediction of the thermoelectric properties is strongly dependent on the approximations used for the calculations. Here, thermoelectric properties were calculated with different computational approximations (i.e., PBE-GGA, HSE06, spin–orbit coupling and DFT-D3) for three layered XYZ2 compounds (TmAgTe2, YAgTe2, and YCuTe2). In addition to the computations, the structural, electrical and thermal properties of these compounds were measured experimentally and compared to the computations. An enhanced prediction of the crystal structure and heat capacity was achieved with the inclusion of van der Waals interactions due to more accurate modeling of the interatomic forces. In particular, a large shift of the acoustic phonons and low-frequency optical phonons to lower frequencies was observed from the dispersion-optimized structure. From the phonon dispersion curves of these compounds, the ultralow thermal conductivity in the investigated XYZ2 compounds could be described by a recent developed minimum thermal conductivity model. For the prediction of the electrical conductivity, a temperature-dependent relaxation time was used, and it was limited by acoustic phonons. While HSE06 has only a small influence on the electrical properties due to a computed band gap energy of >0.25 eV, the inclusion of both van der Waals interactions and spin–orbit coupling leads to a more accurate band structure, resulting in better prediction of electrical properties. Furthermore, the experimental thermoelectric properties of YAgTe2, TmAg0.95Zn0.05Te2 and TmAg0.95Mg0.05Te2 were measured, showing an increase in zT of TmAg0.95Zn0.05Te2 by more than 35% (zT = 0.47 ± 0.12) compared to TmAgTe2.

Highly regioregular poly(3-hexylthiophene) derivatives with varying degrees of fluorine substitution on the thiophene moieties have been demonstrated in photovoltaic devices and characterized using ultraviolet and inverse photoelectron spectroscopy. As fluorine content is increased, an increase in ionization energy of 0.3 eV is observed for 50% fluorination compared to non-fluorinated poly(3-hexylthiophene). The electron affinity is observed to increase to a lesser extent with increased fluorination, consistent with a systematic increase in the optical bandgaps of up to 0.12 eV. Bulk heterojunction photovoltaic devices made from polymer:PC 61 BM blends achieve power conversion efficiencies of 3%, however film morphologies measured using atomic force microscopy indicate that strong phase separation with increasing fluorination limits device performance. UV–vis spectra of thin films of the fluorinated materials exhibit a long tail in the red, extending to longer wavelengths than non-fluorinated poly(3-hexylthiophene). Photovoltaic devices similarly exhibit non-zero quantum efficiency in this region. This behavior has been attributed to a low energy, interchain charge transfer state.

The incorporation of fluorine atoms along the conjugated polymer backbone is an effective strategy to tune the electro-optical properties of donor–acceptor based copolymers. We report here an efficient way to synthesize and purify new mono-fluorinated thiophene derivatives for the synthesis of fluorinated dithienobenzothiadiazole (DTBT) comonomers. It was observed that the reactivity and regioselectivity of the direct (hetero)arylation polymerization (DHAP) were modified upon the amount and the positioning of the fluorine atoms on the DTBT moiety. Indeed, the polymerization time went from 66 h (for non-fluorinated DTBT, M1) to only 11 min (for tetra-fluorinated DTBT, M2). In addition to enhanced reactivity, the degree of fluorination of the flanking thiophene of the DTBT moiety also modulates the electro-optical properties, lowering both the bandgap and stabilizing the ionization energy level. Indeed, P1 (with non-fluorinated flanking thiophene) has a bandgap of 1.73 eV and an ionization energy (IE) of 4....

Thin film radiation-detecting diodes fabricated in the laboratory, such as an organic bulk heterojunction, often contain conductive leads, indium tin oxide traces and metallic interconnects which are exposed to the high-energy photon beam during operation. These components generate extraneous radiation-induced currents, that, if not accounted for, will erroneously be attributed to the detector. In commercial devices, these contributions are mitigated by minimizing the size of these components, an approach that is often not feasible in a research lab. Here we demonstrate a method to measure these extraneous signals, and by subtraction, correct the gross signal to accurately reflect the signal generated in the active volume of the diode itself. The method can effectively correct the extraneous signal. The method showed promise over a range of photon beam energies, dose rates, and field sizes., Graphical abstract Image, graphical abstract

Carrier scattering processes are studied in CH

The geometry of organic π-conjugated small molecules can impact the morphology of blended-thin films and subsequent performance in opto-electronic devices. In this report, we investigate the role of molecular conformation of perylene diimide (PDI) dimers designed to act as non-fullerene acceptors in organic solar cells. A series of three PDI dimers is presented in which the PDI chromophores are directly linked via the bay position (PDI2, 3) or separated by one (PDI2Ac, 4) or two (PDI2Ac2, 5) acetylene spacers. In all cases, the exo-position of the PDI dimers is N-annulated. New compounds 4 and 5 were synthesized via an optimized and facile synthetic pathway. Directly linked PDI dimers adopted a highly twisted conformation whereas adding two acetylene spacers rendered the PDI chromophores coplanar. 1H NMR spectroscopic analysis of each dimer revealed a highly sensitive electronic structure that is strongly influenced by the acetylene spacers. It was found that compounds 4 and 5 with less twisted structures exhibited similar electron affinities but lower ionization potentials, lower organic solvent solubility, and red-shifted optical absorption spectra when compared to the highly twisted dimer 3. In addition, 4 and 5 showed a stronger tendency to aggregate in both solution and the solid state. This had a large impact on the performance of organic solar cells using these materials as electron acceptors. Bulk-heterojunction solar cells based upon a PTB7-Th:3 active layer could reach high power conversion efficiencies of 5.23%. In contrast, PTB7-Th:4 and PTB7-Th:5 based devices had ∼5 times lower performance owing to the formation of unfavourable active layer morphologies.

Recent work shows promise for LiBF4 as an electrolyte salt for high voltage lithium-ion batteries. LiBF4 is more hydrolytically stable than LiPF6, and in some cases has proved to be more stable at high voltage. This work shows that 1.0 M electrolytes consisting of equal parts LiBF4 and LiPF6 have better performance in certain high voltage (4.35 V) lithium-ion cells than electrolytes with LiPF6 or LiBF4 alone. This is shown using long-term cycling and ultra-high precision coulometry on lithium-ion cells, with and without electrolyte additives. Ultra-high precision coulometry showed that electrolyte with 1:1 LiPF6:LiBF4 and no other additives performed as well as electrolyte with LiPF6 and state-of-the-art additive blends in these cells. The synergism between LiPF6 and LiBF4 was explored using XPS, symmetric cells and EIS analysis. These show that LiBF4 reduces impedance growth at the positive electrode, while LiPF6 improves passivation at the negative electrode.

The synthesis, characterization, and photovoltaic performance of a series of N-annulated PDI materials is presented. Four novel N-annulated PDI compounds are reported, each of which can be synthesized in gram scale without the need for purification using column chromatography. N-Annulation of the PDI chromophore results in a decrease in electron affinity and lowering of the ionization potential, and renders the chromophore insoluble in organic solvents. Installation of an alkyl group improves the solubility. Single crystal X-ray analysis reveals a bowing of the aromatic backbone and compression of phenyl rings adjacent to the N atom. A brominated N-annulated PDI derivate represents a valuable synthon for creating novel multi-PDI chromophore materials. To demonstrate the utility of the new synthon for making electron transporting materials, a dimerization strategy was employed to create a dimeric PDI material. The PDI dimer has excellent solubility and film forming ability along with energetically deep HOM...

Perylene diimide derivatives have been under intense investigation to replace fullerenes as the electron accepting component in organic photovoltaics, with molecular complexity continuing to grow. Simple alkyl-substituted perylene diimide monomers at the imide nitrogen position, however, have not been extensively investigated. Herein we demonstrate that subtle alkyl-substitutions at the imide-nitrogen position lead to significant changes in solubility, thin-film self-assembly and optical properties. When blended with a small-molecule donor to form all small-molecule, fullerene-free, solution processed organic solar cells, we show that the photovoltaic device performance and consistency can be tuned via alkyl-chain modifications. In addition we have simplified the device fabrication process by utilizing a silver cathode coupled with a small-molecule-ionic interlayer and achieved comparable performance to devices fabricated with a traditional Ca/Al cathode.

Three low-cost propeller-shaped small molecules based on a triphenylamine core and the high-performance donor molecule 7,7′-[4,4-bis(2-ethylhexyl)-4H-silolo[3,2-b:4,5-b′]dithiophene-2,6-diyl]bis[6-fluoro-4-(5′-hexyl-[2,2′-bithiophen]-5-yl)benzo[c][1,2,5]thiadiazole] (DTS(FBTTh2)2) were investigated as hole-transporting materials in perovskite solar cells. Each hole-transporting material was designed with highly modular side arms, allowing for different bandgaps and thin-film properties while maintaining a consistent binding energy of the highest occupied molecular orbitals to facilitate hole extraction from the perovskite active layer. Perovskite solar cell devices were fabricated with each of the three triphenylamine-based hole-transporting materials and DTS(FBTTh2)2 and were compared to devices with 2,2′,7,7′-tetrakis(N,N-di-p-methoxyphenylamine)-9,9′-spirobifluorene (spiro-OMeTAD) hole-transporting layers. Each of our triphenylamine hole-transporting materials and DTS(FBTTh2)2 displayed surface morphologies that were considerably rougher than that of spiro-OMeTAD; a factor that may contribute to lower device performance. It was found that using inert, insulating polymers as additives with DTS(FBTTh2)2 reduced the surface roughness, resulting in devices with higher photocurrents.

In this work, we describe details of a two-step deposition approach that enables the preparation of continuous and well-structured thin films of Cs2SnI6, which is a one-half Sn-deficient 0-D perovskite derivative (i.e., the compound can also be written as CsSn0.5I3, with a structure consisting of isolated SnI64– octahedra). The films were characterized using powder X-ray diffraction (PXRD), scanning electron microscopy (SEM), thermogravimetric analysis (TGA), UV–vis spectroscopy, photoluminescence (PL), photoelectron spectroscopy (UPS, IPES, XPS), and Hall effect measurements. UV–vis and PL measurements indicate that the obtained Cs2SnI6 film is a semiconductor with a band gap of 1.6 eV. This band gap was further confirmed by the UPS and IPES spectra, which were well reproduced by the calculated density of states with the HSE hybrid functional. The Cs2SnI6 films exhibited n-type conduction with a carrier density of 6(1) × 1016 cm–3 and mobility of 2.9(3) cm2/V·s. While the computationally derived band str...

Copper barium thioselenostannate, Cu2BaSnS4−xSex (CBTSSe), absorbers employ low-toxicity and abundant metals while offering low-cost manufacturing options, controllable stoichiometry and band gap tunability (from 2 eV at x = 0 to 1.55 eV at x = 3). CBTSSe can therefore be considered a prospective candidate for maintaining or improving upon the advantages of already commercialized Cu(In,Ga)(S,Se)2 (CIGSSe) and CdTe absorbers. In this study, we focus on solution-deposited stoichiometric CBTSSe films with band gap of 1.59 eV (x ≈ 3) and explore the fundamental film properties. Temperature- and excitation-dependent photoluminescence studies reveal a dominant defect emission at ~1.5 eV and a second deep defect feature at 1.15 eV. From time-resolved terahertz measurements, we find a charge carrier (electron and hole sum) mobility of ~140 cm2/Vs—i.e., comparable to values in CIGSSe or Cu2ZnSnS4−xSex (CZTSSe)—as well as a two-component minority carrier lifetime. A longer-lived lifetime component (~2 ns) arises from bulk recombination. However, strong recombination at the (bare) surface leads to a ~50 ps lifetime, inferior to state-of-the-art CIGSSe or CZTSSe absorbers. This recombination issue may worsen for CBTSSe/CdS interfaces, due to a cliff-like band alignment with 0.6 eV band offset, as revealed by ultraviolet photoemission spectroscopy. A low number of charge carriers within the absorber further contributes to a high series resistance. Employing these films, we also report the highest performance achieved from solution-processed trigonal CBTSSe thin-film photovoltaic devices, with open circuit voltage, short-circuit current density, fill factor and efficiency of 470 mV, 14.3 mA/cm2, 43.6% and 2.9%, respectively. The physical measurements provided on the solution-processed CBTSSe absorber further point to critical areas for future improvement of CBTSSe and related photovoltaic cells in the quest for higher efficiency devices based on earth abundant metals.

Accurate measurements of radiation dose are essential prerequisites for the safe and effective use of ionizing radiation in diagnostic and therapeutic medical applications. Recently, dosimeters based on organic polymers have been developed for this purpose. In this work, Poly(3-hexylthiophene-2,5-diyl) (P3HT) based organic diodes were evaluated as potential radiation dosimeters by quantifying the radiation-induced photocurrent under various measurement conditions. Control devices were fabricated in which the P3HT was replaced by polystyrene (PS) for the purpose of quantifying the non-photocurrent contribution to the measured signal. Net photocurrent was determined by subtracting the signal from the PS devices from the signal in the P3HT devices under identical measurement conditions. The responses of these devices were tested in various beam qualities: 100 kVp, 180 kVp, 300 kVp and 6 MV, 18 MV photons. The influences of electric field, film thickness and dose rate on dosimeter sensitivity were investigated. The diodes produced a linear increase in current with increasing dose rate. They demonstrated an increase in sensitivity with increased instantaneous dose rate and an increase in sensitivity at the lowest average dose rates studied here. The sensitivities for different energies were 22.9 nC/Gy, 21.8 nC/Gy and 21.4 nC/Gy for 100 kVp, 180 kVp and 300 kVp, respectively; and 14.5 nC/Gy, 14.7 nC/Gy for 6 MV and 18 MV, respectively for device with P3HT thickness 29 μm.

The purpose of this work is to fabricate and characterize the response of a P3HT/PCBM bulk heterojunction organic photodiode to photon beams with respect to dose rate, total dose, and energy. A bulk heterojunction (BHJ) organic photodiode was fabricated by spin coating a blend of P3HT and PCBM onto an ITO-coated glass substrate and then depositing aluminum top contacts. Control devices were made by spin coating polystyrene instead of the P3HT/PCBM layer. The devices were irradiated with a 6 MV photon beam with dose rates of 100–600 cGy/min. Energy dependence was measured for energies of 100, 180, and 300 kVp and 6 and 10 MV. Photocurrent in the BHJ was calculated by subtracting the average current measured using the four PS devices from that measured with each of the four BHJ diodes to correct for current collected by the electrodes and the wires/connectors. The sensitivities of the four BHJ devices were within the range of 3.7–4.3 pC/cGy. The range of values is mostly due to inter-device variation and not due to variation between readings on the ITO and Al electrodes of a single device. The diodes exhibit an energy dependence with more than 4 times the response at 100 kVp than at 6 MV. The direction and magnitudes of the measured currents after correction for the electrode/lead currents were consistent with photocurrent. The photocurrents increased linearly with dose rate indicating they could be suitable in radiation sensing applications.

The lead halide hybrid perovskites have gained considerable attention in recent years due to their stellar performance as absorber layers in solution-processed solar cells, with efficiencies recently reaching over 22 percent [1]. Owing to their large spin-orbit coupling, these materials are also of interest for spintronic applications, in which the presence of lead may be less of an impediment to their adoption [2]. Measurements of spin dynamics in bulk CH3NH3PbI3-xClx have been reported in recent years [3,4,5], the spin-dependent optical Stark effect was demonstrated in 4F-PEPI [6], and a large Rashba effect has been predicted in both bulk and 2D perovskites [2], highlighting the need for further studies of the spin-related properties of these materials. Here we report spin-dependent measurements of carrier kinetics in butylammonium methylammonium lead iodide 2D perovskite and measurements of the coherent carrier response in 3D CH3NH3PbI3. Both experiments provide direct evidence of the impact of Rashba on the carrier kinetics in these systems, further supporting the potential for developing spin-optoelectronic devices using these materials. [1] https://www.nrel.gov/pv/assets/images/efficiency_chart.jpg. [2] M. Kepenekian and J. Even, J. Phys. Chem. Lett. 8, 3362 (2017). [3] D. Giovanni et al. Nano Lett. 15, 1553 (2015). [4] C. Zhang et al. Nat. Phys. 11, 427 (2015). [5] P. Odenthal et al. Nat. Phys. 13, 894 (2017). [6] D. Giovanni et al. Science Advances 2, e1600477 (2016).

Bulk-heterojunction (BHJ) molecular blends prepared from small molecules based on diketopyrrolopyrrole (DPP) and perylene-diimide (PDI) chromophores have been studied using optical absorption, cyclic voltammetry, photoluminescence quenching, X-ray diffraction, atomic force microscopy, and current-voltage measurements. The results provided useful insights into the use of DPP and PDI based molecules as donor-acceptor composites for organic photovoltaic (OPV) applications. Beside optoelectronic compatibility, the choice of active layer processing conditions is of key importance to improve the performance of BHJ solar cells. In this context, post-production treatments, viz. thermal and solvent vapour annealing, and the use of 1,8-diiodooctane as a solvent additive were employed to optimize the morphology of blend films. X-ray diffraction and atomic force microscopy indicated that the aforementioned processing strategies led to non-optimal composite morphologies with significantly large crystallites in comparison to exciton diffusion lengths. Although the open circuit voltage of the OPV devices was satisfactory (0.78 V), it was anticipated that the bulky domains hamper charge dissociation and transport, which resulted in low photovoltaic performance.

The effects of water on the photovoltaic performance of methylammonium lead iodide perovskite devices has recently become a topic of interest within the perovskite community. However, existing studies report contrasting and sometimes contradictory observations. In this work, small concentrations of water, consistent with those present in air-exposed DMF, were systematically incorporated directly into the PbI2 precursor solution in order to investigate its effect on the performance of sequentially spin-coated, inverted perovskite solar cells. Increasing concentrations of water in the PbI2 solution were found to have a negative impact on photovoltaic performance. The addition of water was observed to exaggerate the scan-rate and directional-dependent hysteresis and introduce new transient behaviours in comparison to the “dry” devices. Interestingly, the addition of water was also found to improve the long-term device stability in comparison with devices fabricated from “dry” precursors.

The importance of device structure and active-layer processing when screening non-fullerene acceptors was demonstrated through the organic solar cell device performance optimization of a solution processable non-fullerene, all small-molecule bulk heterojunction (BHJ) blend. Key tuning parameters were identified; notably, the largest improvement in performance was achieved by switching from the conventional device architecture (ITO/PEDOT:PSS/D-A BHJ/Ca/Al) to an inverted structure (ITO/ZnO/D-A BHJ/MoOx/Ag), approximately doubling the power conversion efficiency from best cells of 0.5%–1.0%, demonstrating the importance of investigating more than a single architecture when screening novel non-fullerene acceptors.

The synthesis of π-conjugated organic small molecules with n-octyl substituted thiophene phthalimide end-capping units have been reported. A combination of absorption and emission spectroscopy, cyclic voltammetry, ultraviolet photoelectron spectroscopy, density functional theory calculations and atomic force spectroscopy were used to elucidate the impact of molecular dimensionality on photophysical properties and self-assembly.

Computational, thin-film deposition, and characterization approaches have been used to examine the ternary halide semiconductor Cs3Sb2I9. Cs3Sb2I9 has two known structural modifications, the 0-D dimer form (space group P63/mmc, no. 194) and the 2-D layered form (P3m1, no. 164), which can be prepared via solution and solid-state or gas-phase reactions, respectively. Our computational investigations suggest that the layered form, which is a one-third Sb-deficient derivative of the ubiquitous perovskite structure, is a potential candidate for high-band gap photovoltaic (PV) applications. In this work, we describe details of a two-step deposition approach that enables the preparation of large grain (>1 μm) and continuous thin films of the lead-free layered perovskite derivative Cs3Sb2I9. Depending on the deposition conditions, films that are c-axis oriented or randomly oriented can be obtained. The fabricated thin films show enhanced stability under ambient air, compared to methylammonium lead(II) iodide per...

Furan has often been considered as a more sustainable alternative to thiophene in organic electronics. Herein we demonstrate that replacing thiophene with furan in a phthalimide based molecular semiconductor results in a complete loss of electron mobility when evaluated using organic thin film transistors (OTFTs). Although optical, electronic, thermal, and structural characterization show subtle effects substituting furan for thiophene, theoretical dimer modeling employing the respective single crystal structures of the two molecules reveals a loss of degeneracy between the lowest unoccupied molecular orbital (LUMO) and LUMO+1 molecular orbitals in the bifuran-containing molecule. These results demonstrate that minor changes to molecular structure can result in large differences in device performance.

Despite the significant progress in fabricating hybrid organic-inorganic lead halide perovskite solar cells, their toxicity and low stability remain as major drawbacks, thereby hindering large-scale commercialization. Given the isoelectronic nature of lead(II) and bismuth(III) ions, potentially stable and nontoxic alternatives for efficient light absorption in thin-film photovoltaic (PV) devices may be found among bismuth-based halide semiconductors. However, high-quality polycrystalline films of many of these systems have not been demonstrated. Here we present a versatile and facile two-step coevaporation approach to fabricate A₃Bi₂I₉ (A = Cs, Rb) and AgBi₂I₇ polycrystalline films with smooth, pinhole-free morphology and average grain size of >200 nm. The process involves an initial two-source evaporation step (involving CsI, RbI or AgI, and BiI₃ sources), followed by an annealing step under BiI₃ vapor. The structural, optical, and electrical characteristics of the resulting thin films are studied by X-ray diffraction, optical spectroscopy, X-ray/UV photoelectron spectroscopy, and scanning electron microscopy.

The structural evolution of a functional isoindigo-based non-fullerene acceptor led to the development of three new materials to address the deficiencies of the original framework. Owing to the versatility of the structure and the flexibility of the synthetic procedures, these three new materials were accessible from previously optimized reaction conditions and similar precursor materials. The influence of structural modification on the optical, electrochemical and thermal properties were assessed and correlated with DFT calculations to provide compelling evidence for the effect of each substitution and how they relate to each particular adaptation. The structure–property relationships were investigated for their photovoltaic performance in solution processable BHJ devices fabricated in inverted architectures. Evaluation of device performance demonstrated that a single modification did not improve on the efficiency of the original structure, but the combination of both induced non-planarity, and increased electron affinity of the fourth iteration showed the potential of our framework, with PCE reaching 1.9%.

The design, synthesis, and characterization of seven phthalimide-based organic π-conjugated small molecules are reported. The new materials are based on a phthalimide–thiophene–CORE–thiophene–phthalimide architecture. The CORE units utilized were phthalimide (M2), diketopyrrolopyrrole (M3), isoindigo (M4), naphthalene diimide (M5), perylene diimide (M6), and difluorobenzothiadiazole (M7); they were specifically selected to progressively increase the electron affinity of the resulting compound. A small molecule with no core (M1) was synthesized for comparison. Each material was synthesized through optimized direct heteroarylation cross-coupling procedures using bench top solvents in air. Combinations of UV-visible spectroscopy (UV-vis), cyclic voltammetry (CV), differential scanning calorimetry (DSC), ultraviolet photoelectron spectroscopy (UPS) and density functional theory (DFT) were used to characterize each material. The use of various core acceptor building blocks with differing electron affinities resulted in the series M1–M7 having a range of energetically deep LUMO levels and a range of HOMO–LUMO gap energies. Meanwhile, the melting and crystallization temperatures of the molecules M1–M7 were also found to vary according to the change in central acceptor unit. Compounds M1–M7 were employed as acceptors in combination with either the polymeric donor P3HT or small molecule donor DTS(FBTTh2)2 to understand how the LUMO levels of each acceptor influences the open circuit voltage (Voc). It was found that, in general, Voc was only weakly related to the offset between the HOMO energy level of the donor and LUMO level of the acceptor used, with a Voc of up to 1.2 V being achieved for M1.

In recent years, the intensive development of π-conjugated small molecule acceptors has yielded viable alternatives to fullerene acceptors in state-of-the-art organic photovoltaic devices. Small molecule acceptors are designed to replicate the favourable electronic properties of fullerenes and to overcome their inherent optical and stability deficiencies. Concurrently, advances in device engineering through rigorous optimization have seen the development of intricate device architectures and led to impressive performance increases. This review highlights a number of recent high performance non-fullerene acceptors, focusing on the design of π-conjugated structures, device optimization and the ensuing power conversion efficiencies.

Leucine modulates muscle protein synthesis (MPS), with potential to facilitate accrual/maintenance of muscle mass. Animal models suggest that leucine boluses shortly after meals may prolong MPS and delay onset of a “muscle-full” state. However, the effects of nutrient “top-ups” in humans, and particularly older adults where deficits exist, have not been explored. We determined the effects of a leucine top-up after essential amino acid (EAA) feeding on anabolic signaling, MPS, and muscle energy metabolism in older men. During 13C6-phenylalanine infusion, 16 men (∼70 years) consumed 15 g of EAA with (n=8, FED + LEU) or without (n=8, FED) 3 g of leucine top-up 90 min later. Repeated blood and muscle sampling permitted measurement of fasting and postprandial plasma EAA, insulin, anabolic signaling including mTOR complex 1 (mTORC1) substrates, cellular ATP and phosphorylocreatine, and MPS. Oral EAA achieved rapid insulinemia (12.5 iU·ml−1 25 min post-feed), essential aminoacidemia (3000 μM, 45–65 min post-feed), and activation of mTORC1 signaling. Leucine top-up prolonged plasma EAA (2800 μM, 135 min) and leucine availability (1050 μM, 135 min post-feed). Fasting FSRs of 0.046 and 0.056%·h-1 (FED and FED + LEU respectively) increased to 0.085 and 0.085%·h-1 90–180 min post-feed and returned to basal rates after 180 min in both groups. Phosphorylation of mTORC1 substrates returned to fasting levels 240 min post-feed in both groups. Feeding had limited effect on muscle high-energy phosphates, but did induce eukaryotic elongation factor 2 (eEF2) phosphorylation. We demonstrate the refractoriness of muscle to nutrient-led anabolic stimulation in the postprandial period; thus, leucine supplements should be taken outside of meals, or with meals containing suboptimal protein in terms of either amount or EAA composition.