Eliminating the Burn-in Loss of Efficiency in Organic Solar Cells by Applying Dimer Acceptors as Supramolecular Stabilizers.

The meta-stable active layer morphology of organic solar cells (OSCs) is identified as the main cause of the rapid burn-in loss of power conversion efficiency (PCE) during long-term device operation. However, effective strategies to eliminate the associated loss mechanisms from the initial stage of device operation are still lacking, especially for high-efficiency material systems. Herein, the introduction of molecularly engineered dimer acceptors with adjustable thermal transition properties into the active layer of OSCs to serve as supramolecular stabilizers for regulating the thermal transitions and optimizing the crystallization of the absorber composites is reported. By establishing intimate π-π interactions with small-molecule acceptors, these stabilizers can effectively reduce the trap-state density (Nt) in the devices to achieve excellent PCEs over 19%. More importantly, the low Nt associated with an initially optimized morphology can be maintained under external stresses to significantly reduce the PCE burn-in loss in devices. This research reveals a judicious approach to improving OPV stability by establishing a comprehensive correlation between material properties, active-layer morphology, and device performance, for developing burn-in-free OSCs.

Assessing intra- and inter-molecular charge transfer excitations in non-fullerene acceptors using electroabsorption spectroscopy.

Organic photovoltaic cells using Y6 non-fullerene acceptors have recently achieved high efficiency, and it was suggested to be attributed to the charge-transfer (CT) nature of the excitations in Y6 aggregates. Here, by combining electroabsorption spectroscopy measurements and electronic-structure calculations, we find that the charge-transfer character already exists in isolated Y6 molecules but is strongly increased when there is molecular aggregation. Surprisingly, it is found that the large enhanced charge transfer in clustered Y6 molecules is not due to an increase in excited-state dipole moment, Δµ, as observed in other organic systems, but due to a reduced polarizability change, Δp. It is proposed that such a strong charge-transfer character is promoted by the stabilization of the charge-transfer energy upon aggregation, as deduced from density functional theory and four-state model calculations. This work provides insight into the correlation between molecular electronic properties and charge-transfer characteristics in organic electronic materials.

Development of favipiravir dry powders for intranasal delivery: An integrated cocrystal and particle engineering approach via spray freeze drying.

The therapeutic potential of pharmaceutical cocrystals in intranasal applications remains largely unexplored despite progressive advancements in cocrystal research. We present the application of spray freeze drying (SFD) in successful fabrication of a favipiravir-pyridinecarboxamide cocrystal nasal powder formulation for potential treatment of broad-spectrum antiviral infections. Preliminary screening via mechanochemistry revealed that favipiravir (FAV) can cocrystallize with isonicotinamide (INA), but not nicotinamide (NCT) and picolinamide (PIC) notwithstanding their structural similarity. The cocrystal formation was characterized by differential scanning calorimetry, Fourier-transform infrared spectroscopy, and unit cell determination through Rietveld refinement of powder X-ray analysis. FAV-INA crystalized in a monoclinic space group P21/c with a unit cell volume of 1223.54(3) Å3, accommodating one FAV molecule and one INA molecule in the asymmetric unit. The cocrystal was further reproduced as intranasal dry powders by SFD, of which the morphology, particle size, in vitro drug release, and nasal deposition were assessed. The non-porous flake shaped FAV-INA powders exhibited a mean particle size of 19.79 ± 2.61 µm, rendering its suitability for intranasal delivery. Compared with raw FAV, FAV-INA displayed a 3-fold higher cumulative fraction of drug permeated in Franz diffusion cells at 45 min (p = 0.001). Dose fraction of FAV-INA deposited in the nasal fraction of a customized 3D-printed nasal cast reached over 80 %, whereas the fine particle fraction remained below 6 % at a flow rate of 15 L/min, suggesting high nasal deposition whilst minimal lung deposition. FAV-INA was safe in RPMI 2650 nasal and SH-SY5Y neuroblastoma cells without any in vitro cytotoxicity observed. This study demonstrated that combining the merits of cocrystallization and particle engineering via SFD can propel the development of advanced dry powder formulations for intranasal drug delivery.

The role of interfacial donor-acceptor percolation in efficient and stable all-polymer solar cells.

Polymerization of Y6-type acceptor molecules leads to bulk-heterojunction organic solar cells with both high power-conversion efficiency and device stability, but the underlying mechanism remains unclear. Here we show that the exciton recombination dynamics of polymerized Y6-type acceptors (Y6-PAs) strongly depends on the degree of aggregation. While the fast exciton recombination rate in aggregated Y6-PA competes with electron-hole separation at the donor-acceptor (D-A) interface, the much-suppressed exciton recombination rate in dispersed Y6-PA is sufficient to allow efficient free charge generation. Indeed, our experimental results and theoretical simulations reveal that Y6-PAs have larger miscibility with the donor polymer than Y6-type small molecular acceptors, leading to D-A percolation that effectively prevents the formation of Y6-PA aggregates at the interface. Besides enabling high charge generation efficiency, the interfacial D-A percolation also improves the thermodynamic stability of the blend morphology, as evident by the reduced device "burn-in" loss upon solar illumination.

Improved Structural Order and Exciton Delocalization in High-Member Quasi-Two-Dimensional Tin Halide Perovskite Revealed by Electroabsorption Spectroscopy.

Engineering of quasi-two-dimensional (quasi-2D) tin halide perovskite structures is a promising pathway to achieve high-performance lead-free perovskite solar cells, with recently developed devices demonstrating over 14% efficiency. Despite the significant efficiency improvement over the bulk three-dimensional (3D) tin perovskite solar cells, the precise relationship between structural engineering and electron-hole (exciton) properties is not fully understood. Here, we study exciton properties in high-member quasi-2D tin perovskite (which is dominated by large n phases) and bulk 3D tin perovskite using electroabsorption (EA) spectroscopy. By numerically extracting the changes in polarizability and dipole moment between the excited and ground states, we show that more ordered and delocalized excitons are formed in the high-member quasi-2D film. This result indicates that the high-member quasi-2D tin perovskite film consists of more ordered crystal orientations and reduced defect density, which is in agreement with the over 5-fold increase in exciton lifetime and much improved solar cell efficiency in devices. Our results provide insights on the structure-property relationship of high-performance quasi-2D tin perovskite optoelectronic devices.

Renewed Prospects for Organic Photovoltaics.

Organic photovoltaics (OPVs) have progressed steadily through three stages of photoactive materials development: (i) use of poly(3-hexylthiophene) and fullerene-based acceptors (FAs) for optimizing bulk heterojunctions; (ii) development of new donors to better match with FAs; (iii) development of non-fullerene acceptors (NFAs). The development and application of NFAs with an A-D-A configuration (where A = acceptor and D = donor) has enabled devices to have efficient charge generation and small energy losses (Eloss < 0.6 eV), resulting in substantially higher power conversion efficiencies (PCEs) than FA-based devices. The discovery of Y6-type acceptors (Y6 = 2,2'-((2Z,2'Z)-((12,13-bis(2-ethylhexyl)-3,9-diundecyl-12,13-dihydro-[1,2,5]-thiadiazolo[3,4-e]-thieno[2″,3″:4',5']thieno-[2',3':4,5]pyrrolo-[3,2-g]thieno-[2',3':4,5]thieno-[3,2-b]indole-2,10-diyl)bis(methanylylidene))bis(5,6-difluoro-3-oxo-2,3-dihydro-1H-indene-2,1-diylidene))dimalononitrile) with an A-DA' D-A configuration has further propelled the PCEs to go beyond 15% due to smaller Eloss values (∼0.5 eV) and higher external quantum efficiencies. Subsequently, the PCEs of Y6-series single-junction devices have increased to >19% and may soon approach 20%. This review provides an update of recent progress of OPV in the following aspects: developments of novel NFAs and donors, understanding of the structure-property relationships and underlying mechanisms of state-of-the-art OPVs, and tasks underpinning the commercialization of OPVs, such as device stability, module development, potential applications, and high-throughput manufacturing. Finally, an outlook and prospects section summarizes the remaining challenges for the further development of OPV technology.

Quasi-2D Bilayer Surface Passivation for High Efficiency Narrow Bandgap Perovskite Solar Cells.

The combination of comprehensive surface passivation and effective interface carriers transfer plays a critical role in high-performance perovskite solar cells. A 2D structure is an important approach for surface passivation of perovskite film, however, its large band gap could compromise carrier transfer. Herein, we synthesize a new molecule 2-thiopheneethylamine thiocyanate (TEASCN) for the construction of bilayer quasi-2D structure precisely on a tin-lead mixed perovskite surface. This bilayer structure can passivate the perovskite surface and ensure effective carriers transfer simultaneously. As a result, the open-circuit voltage (Voc ) of the device is increased without sacrificing short-circuit current density (Jsc ), giving rise to a high certified efficiency from a credible third-party certification of narrow band gap perovskite solar cells. Furthermore, theoretical simulation indicates that the inclusion of TEASCN makes the bilayer structure thermodynamically more stable, which provides a strategy to tailor the number of layers of quasi-2D perovskite structures.

Factors That Prevent Spin-Triplet Recombination in Non-fullerene Organic Photovoltaics.

Managing the dynamics of spin-triplet electronic states is crucial for achieving high-performance organic photovoltaics. Here we show that the replacement of fullerene with non-fullerene acceptor (NFA) molecules leads to suppression of triplet recombination and thus more efficient charge generation. This indicates that the relaxation of charges to the local triplet exciton state, although energetically allowed, is outcompeted by the thermally activated separation of interfacial charge-transfer excitons (CTEs) in the NFA-based system. By rationalizing our results with Marcus theory, we propose that triplet recombination in the fullerene system is driven by the small energy difference and strong electronic couplings between the CTE state and the lowest-lying triplet exciton state (T1) of fullerene acceptor molecules. In contrast, the large energy difference and small electronic couplings between these states in the NFA-based blends lead to sufficiently slow triplet relaxation rate compared to the charge separation rate (≪1010 s-1), thus preventing triplet recombination.

Long-lived and disorder-free charge transfer states enable endothermic charge separation in efficient non-fullerene organic solar cells.

Organic solar cells based on non-fullerene acceptors can show high charge generation yields despite near-zero donor-acceptor energy offsets to drive charge separation and overcome the mutual Coulomb attraction between electron and hole. Here, we use time-resolved optical spectroscopy to show that free charges in these systems are generated by thermally activated dissociation of interfacial charge-transfer states that occurs over hundreds of picoseconds at room temperature, three orders of magnitude slower than comparable fullerene-based systems. Upon free electron-hole encounters at later times, both charge-transfer states and emissive excitons are regenerated, thus setting up an equilibrium between excitons, charge-transfer states and free charges. Our results suggest that the formation of long-lived and disorder-free charge-transfer states in these systems enables them to operate closely to quasi-thermodynamic conditions with no requirement for energy offsets to drive interfacial charge separation and achieve suppressed non-radiative recombination.

Delocalization of exciton and electron wavefunction in non-fullerene acceptor molecules enables efficient organic solar cells.

A major challenge for organic solar cell (OSC) research is how to minimize the tradeoff between voltage loss and charge generation. In early 2019, we reported a non-fullerene acceptor (named Y6) that can simultaneously achieve high external quantum efficiency and low voltage loss for OSC. Here, we use a combination of experimental and theoretical modeling to reveal the structure-property-performance relationships of this state-of-the-art OSC system. We find that the distinctive π-π molecular packing of Y6 not only exists in molecular single crystals but also in thin films. Importantly, such molecular packing leads to (i) the formation of delocalized and emissive excitons that enable small non-radiative voltage loss, and (ii) delocalization of electron wavefunctions at donor/acceptor interfaces that significantly reduces the Coulomb attraction between interfacial electron-hole pairs. These properties are critical in enabling highly efficient charge generation in OSC systems with negligible donor-acceptor energy offset.

Organic Photodetectors for Next-Generation Wearable Electronics.

Next-generation wearable electronics will need to be mechanically flexible and stretchable such that they can be conformally attached onto the human body. Photodetectors that are available in today's market are based on rigid inorganic crystalline materials and they have limited mechanical flexibility. In contrast, photodetectors based on organic polymers and molecules have emerged as promising alternatives due to their inherent mechanical softness, ease of processing, tunable optoelectronic properties, good light sensing performance, and biocompatibility. Here, the recent advances of organic photodetectors in terms of both optoelectronic and mechanical properties are outlined and discussed, and their application in wearable electronics including health monitoring sensors, artificial vision, and self-powering integrated devices are highlighted.

Donor Polymer Can Assist Electron Transport in Bulk Heterojunction Blends with Small Energetic Offsets.

Conventional organic solar cell (OSC) systems have significant energy offsets between the donor and acceptor both at the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energy levels. Because of this, in a bulk heterojunction (BHJ) system, electrons typically transport in acceptors, whereas holes typically transport in donors. It is not favorable for electrons to hop back and forth between the donor and acceptor because the hopping is energetically disfavored. In such conventional OSC systems, the addition of donor polymer to acceptor films should typically reduce the electron mobility. In this study, a surprisingly large increase (up to 30×) in electron mobility is observed in an OSC blend when introducing a polymer donor into small molecular acceptor. By ruling out morphology reasons, it is shown that the donor polymer can assist the electron transport by providing "bridges" or a "shortcut" for electron transport across the domains of small molecular acceptors. This can happen because, for these systems, the LUMO offset is small. The study shows the benefits of donor-assisted electron transport in BHJ systems with small energetic offsets. This finding could be also applied to other fields to tune the optimized charge transport property of organic materials or slush blends.

Credibility Judgment Predictors for Child Sexual Abuse Reports in Forensic Psychiatric Evaluations.

OBJECTIVE: We intended to analyze the credibility judgment in written forensic psychiatric reports of child sexual abuse registered in Southern Taiwan. METHODS: Ninety-six cases of child sexual abuse between August 2010 and October 2017 encountered in two hospitals were analyzed. The. RESULTS: in these reports were categorized into credible and non-credible. We identified the factors that distinguished between the two groups in bivariate analyses using chi-square test. A binary logistic regression analysis was performed to determine whether the factors that significantly correlated in the bivariate analyses were independent predictors of credible judgments. RESULTS: Among 96 cases, 70 (73%) were judged as credible. Consistent testimonies of children (odds ratio=40.82) and multiple abuse events (odds ratio=6.05) were positive variables independently related to the sexual abuse allegations judged as credible. CONCLUSION: The number of allegations judged as credible in this study was slightly higher than that reported in other studies. Our findings about predictors for credible cases are not in line with those reported previously. Due to the differences in resources of the cases and backgrounds of the evaluators among multiple studies, direct comparisons with previous studies must be treated with caution.

Dual-gate organic phototransistor with high-gain and linear photoresponse.

The conversion of light into electrical signal in a photodetector is a crucial process for a wide range of technological applications. Here we report a new device concept of dual-gate phototransistor that combines the operation of photodiodes and phototransistors to simultaneously enable high-gain and linear photoresponse without requiring external circuitry. In an oppositely biased, dual-gate transistor based on a solution-processed organic heterojunction layer, we find that the presence of both n- and p-type channels enables both photogenerated electrons and holes to efficiently separate and transport in the same semiconducting layer. This operation enables effective control of trap carrier density that leads to linear photoresponse with high photoconductive gain and a significant reduction of electrical noise. As we demonstrate using a large-area, 8 × 8 imaging array of dual-gate phototransistors, this device concept is promising for high-performance and scalable photodetectors with tunable dynamic range.

Efficient Nonfullerene Organic Solar Cells with Small Driving Forces for Both Hole and Electron Transfer.

State-of-the-art organic solar cells (OSCs) typically suffer from large voltage loss (Vloss ) compared to their inorganic and perovskite counterparts. There are some successful attempts to reduce the Vloss by decreasing the energy offsets between the donor and acceptor materials, and the OSC community has demonstrated efficient systems with either small highest occupied molecular orbital (HOMO) offset or negligible lowest unoccupied molecular orbital (LUMO) offset between donors and acceptors. However, efficient OSCs based on a donor/acceptor system with both small HOMO and LUMO offsets have not been demonstrated simultaneously. In this work, an efficient nonfullerene OSC is reported based on a donor polymer named PffBT2T-TT and a small-molecular acceptor (O-IDTBR), which have identical bandgaps and close energy levels. The Fourier-transform photocurrent spectroscopy external quantum efficiency (FTPS-EQE) spectrum of the blend overlaps with those of neat PffBT2T-TT and O-IDTBR, indicating the small driving forces for both hole and electron transfer. Meanwhile, the OSCs exhibit a high electroluminescence quantum efficiency (EQEEL ) of ≈1 × 10-4 , which leads to a significantly minimized nonradiative Vloss of 0.24 V. Despite the small driving forces and a low Vloss , a maximum EQE of 67% and a high power conversion efficiency of 10.4% can still be achieved.

Outpatient rehabilitation resources and medical expenditure in children with attention-deficit hyperactivity disorder in Taiwan.

Attention-deficit hyperactivity disorder (ADHD) is a neurodevelopmental disorder in children. This study investigated the use of rehabilitation treatment in Taiwan. We selected children aged 3-12 years from the National Health Insurance Research Database from 2008 to 2012 and included them in the analysis. The children who received a diagnosis according to the International Classification of Diseases, Ninth Revision, Clinical Modification were divided into two groups: ADHD and non-ADHD. We used the chi-squared test, independent sample t test, and multiple regression analysis to conduct the analysis. The utilisation of rehabilitation resources was higher in the ADHD group than in the non-ADHD group. The number of school-aged children with ADHD was higher than the number of preschool-aged children (p < 0.001). The highest utilisation of rehabilitation resources was observed in clinics (p < 0.001). In terms of region, Taipei exhibited the highest utilisation of rehabilitation resources, and the East exhibited the lowest resource utilisation (p < 0.001). Prediction of the use of rehabilitation resources, average cost, average frequency of visits, and total annual cost was affected by factors such as the average frequency of rehabilitation use, demographic characteristics, and the hospital characteristics and location (p < 0.001). The number of children with ADHD and rehabilitation use are increasing yearly; however, limitations in payment restrict the growth of rehabilitation resource use in hospitals. Supplementation of rehabilitation resources at clinics accounts for more than 60%, however, the total annual cost is less than what is observed for hospitals (p < 0.001). Policies should be established to aid in the early detection and treatment of children with ADHD to improve treatment outcomes and reduce the family burden and treatment expenditure in the future.

Nonfullerene Acceptor Molecules for Bulk Heterojunction Organic Solar Cells.

The bulk-heterojunction blend of an electron donor and an electron acceptor material is the key component in a solution-processed organic photovoltaic device. In the past decades, a p-type conjugated polymer and an n-type fullerene derivative have been the most commonly used electron donor and electron acceptor, respectively. While most advances of the device performance come from the design of new polymer donors, fullerene derivatives have almost been exclusively used as electron acceptors in organic photovoltaics. Recently, nonfullerene acceptor materials, particularly small molecules and oligomers, have emerged as a promising alternative to replace fullerene derivatives. Compared to fullerenes, these new acceptors are generally synthesized from diversified, low-cost routes based on building block materials with extraordinary chemical, thermal, and photostability. The facile functionalization of these molecules affords excellent tunability to their optoelectronic and electrochemical properties. Within the past five years, there have been over 100 nonfullerene acceptor molecules synthesized, and the power conversion efficiency of nonfullerene organic solar cells has increased dramatically, from ∼2% in 2012 to >13% in 2017. This review summarizes this progress, aiming to describe the molecular design strategy, to provide insight into the structure-property relationship, and to highlight the challenges the field is facing, with emphasis placed on most recent nonfullerene acceptors that demonstrated top-of-the-line photovoltaic performances. We also provide perspectives from a device point of view, wherein topics including ternary blend device, multijunction device, device stability, active layer morphology, and device physics are discussed.

Ring-Fusion of Perylene Diimide Acceptor Enabling Efficient Nonfullerene Organic Solar Cells with a Small Voltage Loss.

We report a novel small molecule acceptor (SMA) named FTTB-PDI4 obtained via ring-fusion between the thiophene and perylene diimide (PDI) units of a PDI-tetramer with a tetrathienylbezene (TTB) core. A small voltage loss of 0.53 V and a high power conversion efficiency of 10.58% were achieved, which is the highest value reported for PDI-based devices to date. By comparing the fused and nonfused SMAs, we show that the ring-fusion introduces several beneficial effects on the properties and performances of the acceptor material, including more favorable energy levels, enhanced light absorption and stronger intermolecular packing. Interestingly, morphology data reveal that the fused molecule yields higher domain purity and thus can better maintain its molecular packing and electron mobility in the blend. Theoretical calculations also demonstrate that FTTB-PDI4 exhibits a "double-decker" geometry with two pairs of mostly parallel PDI units, which is distinctively different from reported PDI-tetramers with highly twisted geometries and can explain the better performance of the material. This work highlights the promising design of PDI-based acceptors by the ring-fusion strategy.

Design of Donor Polymers with Strong Temperature-Dependent Aggregation Property for Efficient Organic Photovoltaics.

Bulk heterojunction (BHJ) organic solar cells (OSCs) have attracted intensive research attention over the past two decades owing to their unique advantages including mechanical flexibility, light weight, large area, and low-cost fabrications. To date, OSC devices have achieved power conversion efficiencies (PCEs) exceeding 12%. Much of the progress was enabled by the development of high-performance donor polymers with favorable morphological, electronic, and optical properties. A key problem in morphology control of OSCs is the trade-off between achieving small domain size and high polymer crystallinity, which is especially important for the realization of efficient thick-film devices with high fill factors. For example, the thickness of OSC blends containing state-of-the-art PTB7 family donor polymers are restricted to ∼100 nm due to their relatively low hole mobility and impure polymer domains. To further improve the device performance and promote commercialization of OSCs, there is a strong demand for the design of new donor polymers that can achieve an optimal blend morphology containing highly crystalline yet reasonably small domains. In this Account, we highlight recent progress on a new family of conjugated polymers with strong temperature-dependent aggregation (TDA) property. These polymers are mostly disaggregated and can be easily dissolved in solution at high temperatures, yet they can strongly aggregate when the solution is cooled to room temperature. This unique aggregation property allows us to control the disorder-order transition of the polymer during solution processing. By preheating the solution to high temperature (∼100 °C), the polymer chains are mostly disaggregated before spin coating; as the temperature of the solution drops during the spin coating process, the polymer can strongly aggregate and form crystalline domains yet that are not excessivelylarge. The overall blend morphology can be optimized by various processing conditions (e.g., temperature, spin-rates, concentration, etc.). This well-controlled and near-optimal BHJ morphology produced over a dozen cases of efficient OSCs with an active layer nearly 300 nm thick that can still achieve high FFs (70-77%) and efficiencies (10-11.7%). By studying the structure-property relationships of the donor polymers, we show that the second position branched alkyl chains and the fluorination on the polymer backbone are two key structural features that enable the strong TDA property. Our comparative studies also show that the TDA polymer family can be used to match with non-fullerene acceptors yielding OSCs with low voltage losses. The key difference between the empirical matching rules for fullerene and non-fullerene OSCs is that TDA polymers with slightly reduced crystallinity appear to match better with small molecular acceptors and yield higher OSC performances.

A Wide-Bandgap Donor Polymer for Highly Efficient Non-fullerene Organic Solar Cells with a Small Voltage Loss.

To achieve efficient non-fullerene organic solar cells, it is important to reduce the voltage loss from the optical bandgap to the open-circuit voltage of the cell. Here we report a highly efficient non-fullerene organic solar cell with a high open-circuit voltage of 1.08 V and a small voltage loss of 0.55 V. The high performance was enabled by a novel wide-bandgap (2.05 eV) donor polymer paired with a narrow-bandgap (1.63 eV) small-molecular acceptor (SMA). Our morphology characterizations show that both the polymer and the SMA can maintain high crystallinity in the blend film, resulting in crystalline and small domains. As a result, our non-fullerene organic solar cells realize an efficiency of 11.6%, which is the best performance for a non-fullerene organic solar cell with such a small voltage loss.