Despite the exciting progress on power conversion efficiencies, the commercialization of the emerging lead (Pb) halide perovskite solar cell technology still faces significant challenges, one of which is the inclusion of toxic Pb. Searching for Pb-free perovskite solar cell absorbers is currently an attractive research direction. The approaches used for and the consequences of Pb replacement are reviewed herein. Reviews on the theoretical understanding of the electronic, optical, and defect properties of Pb and Pb-free halide perovskites and perovskite derivatives are provided, as well as the experimental results available in the literature. The theoretical understanding explains well why Pb halide perovskites exhibit superior photovoltaic properties, but Pb-free perovskites and perovskite derivatives do not.

From Lead Halide Perovskites to Lead-Free Metal Halide Perovskites and Perovskite Derivatives

Tin-based perovskites with excellent optoelectronic properties and suitable band gaps are promising candidates for the preparation of efficient lead-free perovskite solar cells (PSCs). However, it is challenging to prepare highly stable and efficient tin-based PSCs because Sn2+ in perovskites can be easily oxidized to Sn4+ upon air exposure. Here we report the fabrication of air-stable FASnI3 solar cells by introducing hydroxybenzene sulfonic acid or its salt as an antioxidant additive into the perovskite precursor solution along with excess SnCl2 . The interaction between the sulfonate group and the Sn2+ ion enables the in situ encapsulation of the perovskite grains with a SnCl2 -additive complex layer, which results in greatly enhanced oxidation stability of the perovskite film. The corresponding PSCs are able to maintain 80 % of the efficiency over 500 h upon air exposure without encapsulation, which is over ten times longer than the best result reported previously. Our results suggest a possible strategy for the future design of efficient and stable tin-based PSCs.

Antioxidant Grain Passivation for Air-Stable Tin-Based Perovskite Solar Cells

The tremendous interest focused on organic-inorganic halide perovskites since 2012 derives from their unique optical and electrical properties, which make them excellent photovoltaic materials. Pb-based halide perovskite solar cells, in particular, currently stand at a record efficiency of ≈23%, fulfilling their potential toward commercialization. However, because of the toxicity concerns of Pb-based perovskite solar cells, their market prospects are hindered. In principle, Pb can be replaced with other less-toxic, environmentally benign metals. Sn-based perovskites are thus the far most promising alternative due to their very similar and perhaps even superior semiconductor characteristics. After years of effort invested in Sn-based halide perovskites, sufficient breakthroughs have finally been achieved that make them the next runners up to the Pb halide perovskites. To help the reader better understand the nature of Sn-based halide perovskites, their optical and electrical properties are systematically discussed. Recent progress in Sn-based perovskite solar cells, focusing mainly on film fabrication methods and different device architectures, and highlighting roadblocks to progress and opportunities for future work are reviewed. Finally, a brief overview of mixed Sn/Pb-based systems with their anomalous yet beneficial optical trends are discussed. The current challenges and a future outlook for Sn-based perovskites are discussed.

“Unleaded” Perovskites: Status Quo and Future Prospects of Tin-Based Perovskite Solar Cells

Tin-based perovskites with narrow bandgaps and high charge-carrier mobilities are promising candidates for the preparation of efficient lead-free perovskite solar cells (PSCs). However, the crystalline rate of tin-based perovskites is much faster, leading to abundant trap states and much lower open-circuit voltage (Voc ). Here, hydrogen bonding is introduced to retard the crystalline rate of the FASnI3 perovskite. By adding poly(vinyl alcohol) (PVA), the OH…I- hydrogen bonding interactions between PVA and FASnI3 have the effects of introducing nucleation sites, slowing down the crystal growth, directing the crystal orientation, reducing the trap states, and suppressing the migration of the iodide ions. In the presence of the PVA additive, the FASnI3 -PVA PSCs attain higher power conversion efficiency of 8.9% under a reverse scan with significantly improved Voc from 0.55 to 0.63 V, which is one of the highest Voc values for FASnI3 -based PSCs. More importantly, the FASnI3 -PVA PSCs exhibit striking long-term stability, with no decay in efficiency after 400 h of operation at the maximum power point. This approach, which makes use of the OH…I- hydrogen bonding interactions between PVA and FASnI3 , is generally applicable for improving the efficiency and stability of the FASnI3 -based PSCs.

Highly Stable and Efficient FASnI 3 ‐Based Perovskite Solar Cells by Introducing Hydrogen Bonding

Despite the notable progress in perovskite solar cells, maintaining long-term operational stability and minimizing potentially leaked lead (Pb2+) ions are two challenges that are yet to be resolved. Here we address these issues using a thiol-functionalized 2D conjugated metal–organic framework as an electron-extraction layer at the perovskite/cathode interface. The resultant devices exhibit high power conversion efficiency (22.02%) along with a substantially improved long-term operational stability. The perovskite solar cell modified with a metal–organic framework could retain more than 90% of its initial efficiency under accelerated testing conditions, that is continuous light irradiation at maximum power point tracking for 1,000 h at 85 °C. More importantly, the functionalized metal–organic framework could capture most of the Pb2+ leaked from the degraded perovskite solar cells by forming water-insoluble solids. Therefore, this method that simultaneously tackles the operational stability and lead contamination issues in perovskite solar cells could greatly improve the feasibility of large-scale deployment of perovskite photovoltaic technology. Two-dimensional conjugated metal–organic frameworks used as an electron-extraction layer enable the realization of highly stable perovskite solar cells with minimized lead ion leakage.

2D metal-organic framework for stable perovskite solar cells with minimized lead leakage

Recently, the evolved intermediate phase based on iodoplumbate anions that mediates perovskite crystallization has been embodied as the Lewis acid-base adduct formed by metal halides (serve as Lewis acid) and polar aprotic solvents (serve as Lewis base). Based on this principle, it is proposed to constitute efficient Lewis acid-base adduct in the SnI2 deposition step to modulate its volume expansion and fast reaction with methylammonium iodide (MAI)/formamidinium iodide (FAI) (FAI is studied hereafter). Herein, trimethylamine (TMA) is employed as the additional Lewis base in the tin halide solution to form SnY2 -TMA complexes (Y = I- , F- ) in the first-step deposition, followed by intercalating with FAI to convert into FASnI. It is shown that TMA can facilitate homogeneous film formation of a SnI2 (+SnF2 ) layer by effectively forming intermediate SnY2 -TMA complexes. Meanwhile, its relatively larger size and weaker affinity with SnI2 than FA+ ions will facilitate the intramolecular exchange with FA+ ions, thereby enabling the formation of dense and compact FASnI3 film with large crystalline domain (>1 µm). As a result, high power conversion efficiencies of 4.34% and 7.09% with decent stability are successfully accomplished in both conventional and inverted perovskite solar cells, respectively.

Realizing Efficient Lead-Free Formamidinium Tin Triiodide Perovskite Solar Cells via a Sequential Deposition Route

Infection remains a major cause of morbidity and mortality in hospital. As uncontrolled early infection may develop into systemic infection and eventually progress to sepsis, it is important to address infection at an early stage. Furthermore, early detection and prompt diagnosis of infection are the basis of clinical intervention. However, as a result of the interference of complex aetiologies, including fever and trauma, problems regarding the sensitivity and specificity of current diagnostic indices remain, such as for C-reactive protein (CRP), procalcitonin (PCT), white blood cells (WBC), neutrophil ratio (NEU%), interleukin-6 (IL-6) and D-dimer. As a result, there is an urgent need to develop new biomarkers to diagnose infection.From January to October 2021, consecutive patients in the emergency department (ED) were recruited to investigate the feasibility of fibulin-2 as a diagnostic indicator of early infection. Fibulin-2 concentrations in plasma were determined with enzyme-linked immunosorbent assay (ELISA). The performance of fibulin-2 for predicting infection was analysed by receiver operating characteristic (ROC) curves.We found that the plasma fibulin-2 level was elevated in patients with infection compared with those without infection. ROC curve analysis showed that the area under the curve (AUC) for fibulin-2 was 0.712. For all patients included, the diagnostic ability of fibulin-2 (AUC 0.712) performed as well as CRP (AUC 0.667) and PCT (AUC 0.632), and better than WBC (AUC 0.620), NEU% (AUC 0.619), IL-6 (AUC 0.561) and D-dimer (AUC 0.630). In patients with fever, fibulin-2 performed as well as PCT and better than the other biomarkers in infection diagnosis. In particular, fibulin-2 performed better than all these biomarkers in patients with trauma.Fibulin-2 is a novel promising diagnostic biomarker for predicting infection. 

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A Clinical Diagnostic Study: Fibulin-2 is a Novel Promising Biomarker for Predicting Infection

Cough is a common complication after pulmonary resection. However, the factors associated with cough that develop after pulmonary resection are still controversial. In this study, we used the Simplified Cough Score (SCS) and the Leicester Cough Questionnaire (LCQ) score to investigate potential risk factors for postoperative cough. Between January 2017 and June 2021, we collected the clinical data of 517 patients, the SCS at three days after surgery and the LCQ at two weeks and six weeks after surgery. Then, univariate and multivariate analyses were used to identify the independent risk factors for postoperative cough. The clinical baseline data of the cough group and the non-cough group were similar. However, the cough group had longer operation time and more blood loss. The patients who underwent lobectomy were more likely to develop postoperative cough than the patients who underwent segmentectomy and wedge resection, while the patients who underwent systematic lymph node dissection were more likely to develop postoperative cough than the patients who underwent lymph node sampling and those who did not undergo lymph node resection. When the same lymph node management method was applied, there was no difference in the LCQ scores between the patients who underwent wedge resection, lobectomy and segmentectomy. The lymph node resection method was an independent risk factor for postoperative cough (p < 0.001). Conclusions: Lymph node resection is an independent risk factor for short-term cough after pulmonary resection with video-assisted thoracoscopic surgery, and damage to the vagus nerve and its branches (particularly the pulmonary branches) is a possible cause of short-term cough. The mechanism of postoperative cough remains to be further studied.

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Lymph Node Dissection Is a Risk Factor for Short-Term Cough after Pulmonary Resection

Introduction: Skeletal muscle impact injury occurs frequently during sports, falls, and road traffic accidents. From the reported studies on skeletal muscle injury, it is difficult to determine the injury parameters. Therefore, we developed a new model of gastrocnemius impact injury in rats with a bioimpact machine, with which the experimental operation could be conducted in feasibility from the recorded parameters. Through this novel model, we study the skeletal muscle impact injury mechanisms by combining temporal and spatial variation. Methods: The gastrocnemius of anesthetized rats was injured by a small pneumatic-driven bioimpact machine; the moving speed and impact force were determined, and the whole impact process was captured by a high-speed camera. We observed the general condition of rats and measured the changes in injured calf circumference, evaluating calf injuries using MRI, gait analysis system, and pathology at different times after the injury. Results: The gastrocnemius was injured at an impact speed of 6.63 m/s ± 0.25 m/s and a peak force of 1,556.80 N ± 110.79 N. The gait analysis system showed that the footprint area of the RH limb decreased significantly on the first day and then increased. The calf circumference of the injured limb increased rapidly on the first day post-injury and then decreased in the next few days. MRI showed edema of subcutaneous and gastrocnemius on the first day, and the area of edema decreased over the following days. HE staining showed edema of cells, extensive hyperemia of blood vessels, and infiltration of inflammatory cells on the first day. Cell edema was alleviated day by day, but inflammatory cell infiltration was the most on the third day. TEM showed that the sarcoplasmic reticulum was dilated on the first day, the mitochondrial vacuolation was obvious on the second day, and the glycogen deposition was prominent on the fifth day. Conclusion: In our experiment, we developed a new and effective experimental animal model that was feasible to operate; the injured area of the gastrocnemius began to show “map-like” changes in the light microscope on the third day. Meanwhile, the gastrocnemius showed a trend of “edema-mitochondrial vacuolation-inflammatory cell aggregation” after impact injury.

Chengyi Mao

Papers

Realizing Efficient Lead-Free Formamidinium Tin Triiodide Perovskite Solar Cells via a Sequential Deposition Route

A Clinical Diagnostic Study: Fibulin-2 is a Novel Promising Biomarker for Predicting Infection

Lymph Node Dissection Is a Risk Factor for Short-Term Cough after Pulmonary Resection

Research on skeletal muscle impact injury using a new rat model from a bioimpact machine