Efficient and stable air-processed ternary organic solar cells incorporating gallium-porphyrin as electron cascade material

Two gallium porphyrins, a tetraphenyl GaCl porphyrin, termed as (TPP)GaCl, and an octaethylporphyrin GaCl porphyrin, termed as (OEP)GaCl, were synthesized to use as an electron cascade in ternary organic bulk heterojunction films. A perfect matching of both gallium porphyrins’ energy levels with that of poly(3-hexylthiophene-2,5-diyl) (P3HT) or poly[N-9′-heptadecanyl-2,7-carbazole-alt-5,5-(4′,7′-di-2-thienyl-2′,1′,3′-benzothiadiazole)] (PCDTBT) polymer donor and the 6,6-phenyl C71 butyric acid methyl ester (PCBM) fullerene acceptor, forming an efficient cascade system that could facilitate electron transfer between donor and acceptor, was demonstrated. Therefore, ternary organic solar cells (OSCs) using the two porphyrins in various concentrations were fabricated where a performance enhancement was obtained. In particular, (TPP)GaCl-based ternary OSCs of low concentration (1:0.05 vv%) exhibited a ~17% increase in the power conversion efficiency (PCE) compared with the binary device due to improved exciton dissociation, electron transport and reduced recombination. On the other hand, ternary OSCs with a high concentration of (TPP)GaCl (1:0.1 vv%) and (OEP)GaCl (1:0.05 and 1:0.1 vv%) showed the poorest efficiencies due to very rough nanomorphology and suppressed crystallinity of ternary films when the GaCl porphyrin was introduced to the blend, as revealed from X-ray diffraction (XRD) and atomic force microscopy (AFM). The best performing devices also exhibited improved photostability when exposed to sunlight illumination for a period of 8 h than the binary OSCs, attributed to the suppressed photodegradation of the ternary (TPP)GaCl 1:0.05-based photoactive film

Optimization of the hydrogen response characteristics of halogen-doped SnO2

The increasing demand for efficient sensing devices with facile low-cost fabrication has attracted a lot of scientific research effort in the recent years. In particular, the scientific community aims to develop new candidate materials suitable for energy-related devices, such as sensors and photovoltaics or clean energy applications such as hydrogen production. One of the most prominent methods to improve materials functionality and performance is doping key device component(s). This paper aims to examine in detail, both from a theoretical and an experimental point of view, the effect of halogen doping on the properties of tin dioxide (SnO2) and provide a deeper understanding on the atomic scale mechanisms with respect to their potential applications in sensors. Density Functional Theory (DFT) calculations are used to examine the defect processes, the electronic structure and the thermodynamical properties of halogen-doped SnO2. Calculations show that halogen doping reduces the oxide bandgap by creating gap states which agree well with our experimental data. The crystallinity and morphology of the samples is also altered. The synergy of these effects results in a significant improvement of the gas-sensing response. This work demonstrates for the first time a complete theoretical and experimental characterization of halogen-doped SnO2 and investigates the possible responsible mechanisms. Our results illustrate that halogen doping is a low-cost method that significantly enhances the room temperature response of SnO2

Core-shell carbon-polymer quantum dot passivation for near infrared perovskite light emitting diodes

High-performance perovskite light-emitting diodes (PeLEDs) require a high quality perovskite emitter and appropriate charge transport layers to facilitate charge injection and transport within the device. Solution-processed n-type metal oxides represent a judicious choice for the electron transport layer (ETL); however, they don't always present suitable surface properties and energetics in order to be compatible with the perovskite emitter. Moreover, the emitter itself exhibits poor nanomorphology and defect traps that compromise the device performance. Here we modulate the surface properties and interface energetics of the tin oxide (SnO2) ETL with the perovskite emitter by using an amino functionalized difluoro{2-[1-(3,5-dimethyl-2H-pyrrol-2-ylidene-N)ethyl]-3,5-dimethyl-1H-pyrrolato-N}boron (BDP) compound and passivate the defects present in the perovskite with carbon-polymer core-shell quantum dots (PCDs) inserted into the perovskite precursor. Both these approaches synergistically improve the perovskite layer nanomorphology and enhance the radiative recombination. These properties resulted in the fabrication of near infrared (NIR) PeLEDs based on formamidinium lead iodide (FAPbI3) with a high radiance of 92 W sr-1 m-2, an external quantum efficiency (EQE) of 14% and reduced efficiency roll-off

High efficiency blue organic light-emitting diodes with below-bandgap electroluminescence

Blue organic light-emitting diodes require high triplet interlayer materials, which induce large energetic barriers at the interfaces resulting in high device voltages and reduced efficiencies. Here, we alleviate this issue by designing a low triplet energy hole transporting interlayer with high mobility, combined with an interface exciplex that confines excitons at the emissive layer/electron transporting material interface. As a result, blue thermally activated delay fluorescent organic light emitting diodes with a below-bandgap turn-on voltage of 2.5 V and an external quantum efficiency of 41.2% were successfully fabricated. These devices also showed suppressed efficiency roll-off maintaining an EQE of 34.8% at 1000 cd m-2. Our approach paves the way for further progress through exploring alternative device engineering approaches instead of only focusing on the demanding synthesis of organic compounds with complex structures

Strain relaxation and multidentate anchoring in n-type perovskite transistors and logic circuits

This is the author accepted manuscriptData availability: Source data are provided with this paper. Additional data related to this work are available from the corresponding authors upon request.Code availability statement: All codes (software) used in the calculation and visualization are publicly available and the condition of their usage in the publication is an appropriate citation.The engineering of tin halide perovskites has led to the development of p-type transistors with field-effect mobilities of over 70 cm2 V-1 s-1 . However, due to their background hole doping, these perovskites are not suitable for n-type transistors. Ambipolar lead halide perovskites are potential candidates, but their defective nature limits electron mobilities to around 3-4 cm2 V-1 s-1, which makes the development all-perovskite logical circuits challenging. Here, we report formamidinium lead iodide perovskite n-type transistors with field-effect mobilities of up to 33 cm2 V-1s-1 measured in continuous bias mode. This is achieved through strain relaxation of the perovskite lattice using a methyl ammonium chloride additive, followed by suppression of undercoordinated lead through tetramethyl ammonium fluoride multidentate anchoring. Our approach stabilizes the alpha phase, balances strain, and improves surface morphology, crystallinity, and orientation. It also enables low-defect perovskite–dielectric interfaces. We use 46 the transistors to fabricate unipolar inverters and eleven-stage ring oscillator

A Silanol-Functionalized Polyoxometalate with Excellent Electron Transfer Mediating Behavior to ZnO and TiO 2 Cathode Interlayers for Highly Efficient and Extremely Stable Polymer Solar Cells

Combining high efficiency and long lifetime under ambient conditions still poses a major challenge towards commercialization of polymer solar cells. Here we report a facile strategy that can simultaneously enhance the efficiency and temporal stability of inverted photovoltaic architectures. Inclusion of a silanol-functionalized organic–inorganic hybrid polyoxometalate derived from a PW9O34 lacunary phosphotungstate anion, namely (nBu4N)3[PW9O34(tBuSiOH)3], significantly increases the effectiveness of the electron collecting interface, which consists of a metal oxide such as titanium dioxide or zinc oxide, and leads to a high efficiency of 6.51% for single-junction structures based on poly(3-hexylthiophene):indene-C60 bisadduct (P3HT:IC60BA) blends. The above favourable outcome stems from a large decrease in the work function, an effective surface passivation and a decrease in the surface energy of metal oxides which synergistically result in the outstanding electron transfer mediating capability of the functionalized polyoxometalate. In addition, the insertion of a silanol-functionalized polyoxometalate layer significantly enhances the ambient stability of unencapsulated devices which retain nearly 90% of their original efficiencies (T90) after 1000 hours

Outcome in patients perceived as receiving excessive care across different ethical climates: a prospective study in 68 intensive care units in Europe and the USA

Purpose: Whether the quality of the ethical climate in the intensive care unit (ICU) improves the identification of patients receiving excessive care and affects patient outcomes is unknown. Methods: In this prospective observational study, perceptions of excessive care (PECs) by clinicians working in 68 ICUs in Europe and the USA were collected daily during a 28-day period. The quality of the ethical climate in the ICUs was assessed via a validated questionnaire. We compared the combined endpoint (death, not at home or poor quality of life at 1 year) of patients with PECs and the time from PECs until written treatment-limitation decisions (TLDs) and death across the four climates defined via cluster analysis. Results: Of the 4747 eligible clinicians, 2992 (63%) evaluated the ethical climate in their ICU. Of the 321 and 623 patients not admitted for monitoring only in ICUs with a good (n = 12, 18%) and poor (n = 24, 35%) climate, 36 (11%) and 74 (12%), respectively were identified with PECs by at least two clinicians. Of the 35 and 71 identified patients with an available combined endpoint, 100% (95% CI 90.0–1.00) and 85.9% (75.4–92.0) (P = 0.02) attained that endpoint. The risk of death (HR 1.88, 95% CI 1.20–2.92) or receiving a written TLD (HR 2.32, CI 1.11–4.85) in patients with PECs by at least two clinicians was higher in ICUs with a good climate than in those with a poor one. The differences between ICUs with an average climate, with (n = 12, 18%) or without (n = 20, 29%) nursing involvement at the end of life, and ICUs with a poor climate were less obvious but still in favour of the former. Conclusion: Enhancing the quality of the ethical climate in the ICU may improve both the identification of patients receiving excessive care and the decision-making process at the end of life

Is prolonged infusion of piperacillin/tazobactam and meropenem in critically ill patients associated with improved pharmacokinetic/pharmacodynamic and patient outcomes? An observation from the Defining Antibiotic Levels in Intensive care unit patients (DALI) cohort

Objectives:We utilized the database of the Defining Antibiotic Levels in Intensive care unit patients (DALI) study to statistically compare the pharmacokinetic/pharmacodynamic and clinical outcomes between prolonged-infusion and intermittent-bolus dosing of piperacillin/tazobactam and meropenem in critically ill patients using inclusion criteria similar to those used in previous prospective studies.Methods: This was a post hoc analysis of a prospective, multicentre pharmacokinetic point-prevalence study (DALI), which recruited a large cohort of critically ill patients from 68 ICUs across 10 countries.Results: Of the 211 patients receiving piperacillin/tazobactam and meropenem in the DALI study, 182 met inclusion criteria. Overall, 89.0% (162/182) of patients achieved the most conservative target of 50% fT(> MIC) (time over which unbound or free drug concentration remains above the MIC). Decreasing creatinine clearance and the use of prolonged infusion significantly increased the PTA for most pharmacokinetic/pharmacodynamic targets. In the subgroup of patients who had respiratory infection, patients receiving beta-lactams via prolonged infusion demonstrated significantly better 30 day survival when compared with intermittent-bolus patients [86.2% (25/29) versus 56.7% (17/30); P=0.012]. Additionally, in patients with a SOFA score of >= 9, administration by prolonged infusion compared with intermittent-bolus dosing demonstrated significantly better clinical cure [73.3% (11/15) versus 35.0% (7/20); P=0.035] and survival rates [73.3% (11/15) versus 25.0% (5/20); P=0.025].Conclusions: Analysis of this large dataset has provided additional data on the niche benefits of administration of piperacillin/tazobactam and meropenem by prolonged infusion in critically ill patients, particularly for patients with respiratory infections

Co-infection and ICU-acquired infection in COIVD-19 ICU patients: a secondary analysis of the UNITE-COVID data set

Background: The COVID-19 pandemic presented major challenges for critical care facilities worldwide. Infections which develop alongside or subsequent to viral pneumonitis are a challenge under sporadic and pandemic conditions; however, data have suggested that patterns of these differ between COVID-19 and other viral pneumonitides. This secondary analysis aimed to explore patterns of co-infection and intensive care unit-acquired infections (ICU-AI) and the relationship to use of corticosteroids in a large, international cohort of critically ill COVID-19 patients.Methods: This is a multicenter, international, observational study, including adult patients with PCR-confirmed COVID-19 diagnosis admitted to ICUs at the peak of wave one of COVID-19 (February 15th to May 15th, 2020). Data collected included investigator-assessed co-infection at ICU admission, infection acquired in ICU, infection with multi-drug resistant organisms (MDRO) and antibiotic use. Frequencies were compared by Pearson's Chi-squared and continuous variables by Mann-Whitney U test. Propensity score matching for variables associated with ICU-acquired infection was undertaken using R library MatchIT using the "full" matching method.Results: Data were available from 4994 patients. Bacterial co-infection at admission was detected in 716 patients (14%), whilst 85% of patients received antibiotics at that stage. ICU-AI developed in 2715 (54%). The most common ICU-AI was bacterial pneumonia (44% of infections), whilst 9% of patients developed fungal pneumonia; 25% of infections involved MDRO. Patients developing infections in ICU had greater antimicrobial exposure than those without such infections. Incident density (ICU-AI per 1000 ICU days) was in considerable excess of reports from pre-pandemic surveillance. Corticosteroid use was heterogenous between ICUs. In univariate analysis, 58% of patients receiving corticosteroids and 43% of those not receiving steroids developed ICU-AI. Adjusting for potential confounders in the propensity-matched cohort, 71% of patients receiving corticosteroids developed ICU-AI vs 52% of those not receiving corticosteroids. Duration of corticosteroid therapy was also associated with development of ICU-AI and infection with an MDRO.Conclusions: In patients with severe COVID-19 in the first wave, co-infection at admission to ICU was relatively rare but antibiotic use was in substantial excess to that indication. ICU-AI were common and were significantly associated with use of corticosteroids