Large exchange-driven intrinsic circular dichroism of a chiral 2D hybrid perovskite.

In two-dimensional chiral metal-halide perovskites, chiral organic spacers endow structural and optical chirality to the metal-halide sublattice, enabling exquisite control of light, charge, and electron spin. The chiroptical properties of metal-halide perovskites have been measured by transmissive circular dichroism spectroscopy, which necessitates thin-film samples. Here, by developing a reflection-based approach, we characterize the intrinsic, circular polarization-dependent complex refractive index for a prototypical two-dimensional chiral lead-bromide perovskite and report large circular dichroism for single crystals. Comparison with ab initio theory reveals the large circular dichroism arises from the inorganic sublattice rather than the chiral ligand and is an excitonic phenomenon driven by electron-hole exchange interactions, which breaks the degeneracy of transitions between Rashba-Dresselhaus-split bands, resulting in a Cotton effect. Our study suggests that previous data for spin-coated films largely underestimate the optical chirality and provides quantitative insights into the intrinsic optical properties of chiral perovskites for chiroptical and spintronic applications.

Metformin alleviates lung ischemia-reperfusion injury in a rat lung transplantation model.

Background: Lung ischemia-reperfusion injury (LIRI) is among the complications observed after lung transplantation and is associated with morbidity and mortality. Preconditioning of the donor lung before organ retrieval may improve organ quality after transplantation. We investigated whether preconditioning with metformin (Met) ameliorates LIRI after lung transplantation. Methods: Twenty Lewis rats were randomly divided into the sham, LIRI, and Met groups. The rats in the LIRI and Met groups received saline and Met, respectively, via oral gavage. Subsequently, a donor lung was harvested and kept in cold storage for 8 h. The LIRI and Met groups then underwent left lung transplantation. After 2 h of reperfusion, serum and transplanted lung tissues were examined. Results: The partial pressure of oxygen (PaO2) was greater in the Met group than in the LIRI group. In the Met group, wet-to-dry (W/D) weight ratios, inflammatory factor levels, oxidative stress levels and apoptosis levels were notably decreased. Conclusions: Met protects against ischemia-reperfusion injury after lung transplantation in rats, and its therapeutic effect is associated with its anti-inflammatory, antioxidative, and antiapoptotic properties.

Ultrathin Magnesium-Based Coating as an Efficient Oxygen Barrier for Superconducting Circuit Materials.

Scaling up superconducting quantum circuits based on transmon qubits necessitates substantial enhancements in qubit coherence time. Over recent years, tantalum (Ta) has emerged as a promising candidate for transmon qubits, surpassing conventional counterparts in terms of coherence time. However, amorphous surface Ta oxide layer may introduce dielectric loss, ultimately placing a limit on the coherence time. In this study, a novel approach for suppressing the formation of tantalum oxide using an ultrathin magnesium (Mg) capping layer is presented. Synchrotron-based X-ray photoelectron spectroscopy studies demonstrate that oxide is confined to an extremely thin region directly beneath the Mg/Ta interface. Additionally, it is demonstrated that the superconducting properties of thin Ta films are improved following the Mg capping, exhibiting sharper and higher-temperature transitions to superconductive and magnetically ordered states. Moreover, an atomic-scale mechanistic understanding of the role of the capping layer in protecting Ta from oxidation is established based on computational modeling. This work provides valuable insights into the formation mechanism and functionality of surface tantalum oxide, as well as a new materials design principle with the potential to reduce dielectric loss in superconducting quantum materials. Ultimately, the findings pave the way for the realization of large-scale, high-performance quantum computing systems.

Probing Oxidation-Driven Amorphized Surfaces in a Ta(110) Film for Superconducting Qubit.

Recent advances in superconducting qubit technology have led to significant progress in quantum computing, but the challenge of achieving a long coherence time remains. Despite the excellent lifetime performance that tantalum (Ta) based qubits have demonstrated to date, the majority of superconducting qubit systems, including Ta-based qubits, are generally believed to have uncontrolled surface oxidation as the primary source of the two-level system loss in two-dimensional transmon qubits. Therefore, atomic-scale insight into the surface oxidation process is needed to make progress toward a practical quantum processor. In this study, the surface oxidation mechanism of native Ta films and its potential impact on the lifetime of superconducting qubits were investigated using advanced scanning transmission electron microscopy (STEM) techniques combined with density functional theory calculations. The results suggest an atomistic model of the oxidized Ta(110) surface, showing that oxygen atoms tend to penetrate the Ta surface and accumulate between the two outermost Ta atomic planes; oxygen accumulation at the level exceeding a 1:1 O/Ta ratio drives disordering and, eventually, the formation of an amorphous Ta2O5 phase. In addition, we discuss how the formation of a noninsulating ordered TaO1-δ (δ < 0.1) suboxide layer could further contribute to the losses of superconducting qubits. Subsurface oxidation leads to charge redistribution and electric polarization, potentially causing quasiparticle loss and decreased current-carrying capacity, thus affecting superconducting qubit coherence. The findings enhance the comprehension of the realistic factors that might influence the performance of superconducting qubits, thus providing valuable guidance for the development of future quantum computing hardware.

Impact of Varying the Photoanode/Catalyst Interfacial Composition on Solar Water Oxidation: The Case of BiVO4(010)/FeOOH Photoanodes.

Photoanodes used in a water-splitting photoelectrochemical cell are almost always paired with an oxygen evolution catalyst (OEC) to efficiently utilize photon-generated holes for water oxidation because the surfaces of photoanodes are typically not catalytic for the water oxidation reaction. Suppressing electron-hole recombination at the photoanode/OEC interface is critical for the OEC to maximally utilize the holes reaching the interface for water oxidation. In order to explicitly demonstrate and investigate how the detailed features of the photoanode/OEC interface affect interfacial charge transfer and photocurrent generation for water oxidation, we prepared two BiVO4(010)/FeOOH photoanodes with different Bi:V ratios at the outermost layer of the BiVO4 interface (close to stoichiometric vs Bi-rich) while keeping all other factors in the bulk BiVO4 and FeOOH layers identical. The resulting two photoanodes show striking differences in the photocurrent onset potential and photocurrent density for water oxidation. The ambient pressure X-ray photoelectron spectroscopy results show that these two BiVO4(010)/FeOOH photoanodes show drastically different Fe2+:Fe3+ ratios in FeOOH both in the dark and under illumination with water, demonstrating the immense impact of the interfacial composition and structure on interfacial charge transfer. Using computational studies, we reveal the effect of the surface Bi:V ratio on the hydration of the BiVO4 surface and bonding with the FeOOH layer, which in turn affect the band alignments between BiVO4 and FeOOH. These results explain the atomic origin of the experimentally observed differences in electron and hole transfer and solar water oxidation performance of the two photoanodes having different interfacial compositions.

Cobalt Oxide-Coated Single Crystalline Bismuth Vanadate Photoanodes for Efficient Photoelectrochemical Chlorine Generation.

Bismuth vanadate (BiVO4) is an outstanding photoanode material for photoelectrochemical water splitting. In this work, a series of single crystalline BiVO4 photoanodes are synthesized by pulsed laser deposition (PLD). Once coated with a thin layer of cobalt oxide (CoOx) cocatalyst, also by PLD, the photoanodes support efficient photoelectrochemical generation of chlorine (Cl2) from brine under simulated solar light. The activity of the chlorine generation reaction (ClER) is optimized when the thickness of CoOx is about 3 nm, with the faradic efficiency of ClER exceeding 60%. Detailed studies show that the CoOx cocatalyst layer is amorphous, uniform in thickness, and chemically robust. As such, the cocatalyst also effectively protects the underlying BiVO4 photoanodes against chlorine corrosion. This work provides insights into using artificial photosynthesis for byproducts that carry significant economic value while avoiding the energetically expensive oxygen evolution reactions.

Mechanism of exosomes from adipose-derived mesenchymal stem cells on sepsis-induced acute lung injury by promoting TGF-ß secretion in macrophages.

OBJECTIVE: Acute lung injury (ALI) caused by sepsis is a life-threatening condition characterized by uncontrollable lung inflammation. The current study sought to investigate the mechanism of adipose-derived mesenchymal stem cell-derived exosomes (ADMSC-Exos) in attenuating sepsis-induced ALI through TGF-ß secretion in macrophages. METHODS: Adipose-derived mesenchymal stem cell-derived exosomes (ADMSC-Exos) were extracted from ADMSCs and identified. Septic ALI mouse models were established via cecal ligation and puncture (CLP), followed by administration of ADMSC-Exos or sh-TGF-ß lentiviral vector. Mouse macrophages (cell line RAW 264.7) were treated with lipopolysaccharide (LPS), co-cultured with Exos and splenic T cells, and transfected with TGF-ß siRNA. The lung injury of CLP mice was evaluated, and levels of inflammatory indicators and macrophage markers were measured. The localization of macrophage markers and TGF-ß was determined, and the level of TGF-ß in lung tissues was measured. The effect of TGF-ß knockdown on sepsis-induced ALI in CLP mice was evaluated, and the percentages of CD4+CD25+Foxp3+ Tregs in mononuclear cells/macrophages and Foxp3 levels in lung tissues/co-cultured splenic T cells were examined. RESULTS: ADMSC-Exos were found to alleviate sepsis-induced ALI, inhibit inflammatory responses, and induce macrophages to secrete TGF-ß in CLP mice. TGF-ß silencing reversed the alleviating effect of ADMSC-Exos on sepsis-induced ALI. ADMSC-Exos also increased the number of Tregs in the spleen of CLP mice and promoted M2 polarization and TGF-ß secretion in LPS-induced macrophages. After knockdown of TGF-ß in macrophages in the co-culture system, the number of Tregs decreased, suggesting that ADMSC-Exos increased the Treg number by promoting macrophages to secrete TGF-ß. CONCLUSION: Our findings suggest ADMSC-Exos can effectively alleviate sepsis-induced ALI in CLP mice by promoting TGF-ß secretion in macrophages.

Chemical Profiles of the Oxides on Tantalum in State of the Art Superconducting Circuits.

Over the past decades, superconducting qubits have emerged as one of the leading hardware platforms for realizing a quantum processor. Consequently, researchers have made significant effort to understand the loss channels that limit the coherence times of superconducting qubits. A major source of loss has been attributed to two level systems that are present at the material interfaces. It is recently shown that replacing the metal in the capacitor of a transmon with tantalum yields record relaxation and coherence times for superconducting qubits, motivating a detailed study of the tantalum surface. In this work, the chemical profile of the surface of tantalum films grown on c-plane sapphire using variable energy X-ray photoelectron spectroscopy (VEXPS) is studied. The different oxidation states of tantalum that are present in the native oxide resulting from exposure to air are identified, and their distribution through the depth of the film is measured. Furthermore, it is shown how the volume and depth distribution of these tantalum oxidation states can be altered by various chemical treatments. Correlating these measurements with detailed measurements of quantum devices may elucidate the underlying microscopic sources of loss.

Machine Learning-Based Prognostic Model for Patients After Lung Transplantation.

Importance: Although numerous prognostic factors have been found for patients after lung transplantation (LTx) over the years, an accurate prognostic tool for LTx recipients remains unavailable. Objective: To develop and validate a prognostic model for predicting overall survival in patients after LTx using random survival forests (RSF), a machine learning algorithm. Design, Setting, and Participants: This retrospective prognostic study included patients who underwent LTx between January 2017 and December 2020. The LTx recipients were randomly assigned to training and test sets in accordance with a ratio of 7:3. Feature selection was performed using variable importance with bootstrapping resampling. The prognostic model was fitted using the RSF algorithm, and a Cox regression model was set as a benchmark. The integrated area under the curve (iAUC) and integrated Brier score (iBS) were applied to assess model performance in the test set. Data were analyzed from January 2017 to December 2019. Main Outcomes And Measures: Overall survival in patients after LTx. Results: A total of 504 patients were eligible for this study, consisting of 353 patients in the training set (mean [SD] age, 55.03 [12.78] years; 235 [66.6%] male patients) and 151 patients in the test set (mean [SD] age, 56.79 [10.95] years; 99 [65.6%] male patients). According to the variable importance of each factor, 16 were selected for the final RSF model, and postoperative extracorporeal membrane oxygenation time was identified as the most valuable factor. The RSF model had excellent performance with an iAUC of 0.879 (95% CI, 0.832-0.921) and an iBS of 0.130 (95% CI, 0.106-0.154). The Cox regression model fitted by the same modeling factors to the RSF model was significantly inferior to the RSF model with an iAUC of 0.658 (95% CI, 0.572-0.747; P < .001) and an iBS of 0.205 (95% CI, 0.176-0.233; P < .001). According to the RSF model predictions, the patients after LTx were stratified into 2 prognostic groups displaying significant difference, with mean overall survival of 52.91 months (95% CI, 48.51-57.32) and 14.83 months (95% CI, 9.44-20.22; log-rank P < .001), respectively. Conclusions and relevance: In this prognostic study, the findings first demonstrated that RSF could provide more accurate overall survival prediction and remarkable prognostic stratification than the Cox regression model for patients after LTx.

Liproxstatin-1 Alleviates Lung Transplantation-induced Cold Ischemia-Reperfusion Injury by Inhibiting Ferroptosis.

BACKGROUND: Primary graft dysfunction, which is directly related to cold ischemia-reperfusion (CI/R) injury, is a major obstacle in lung transplantation (LTx). Ferroptosis, a novel mode of cell death elicited by iron-dependent lipid peroxidation, has been implicated in ischemic events. This study aimed to investigate the role of ferroptosis in LTx-CI/R injury and the effectiveness of liproxstatin-1 (Lip-1), a ferroptosis inhibitor, in alleviating LTx-CI/R injury. METHODS: LTx-CI/R-induced signal pathway alterations, tissue injury, cell death, inflammatory responses, and ferroptotic features were examined in human lung biopsies, the human bronchial epithelial (BEAS-2B) cells, and the mouse LTx-CI/R model (24-h CI/4-h R). The therapeutic efficacy of Lip-1 was explored and validated both in vitro and in vivo. RESULTS: In human lung tissues, LTx-CI/R activated ferroptosis-related signaling pathway, increased the tissue iron content and lipid peroxidation accumulation, and altered key protein (GPX4, COX2, Nrf2, and SLC7A11) expression and mitochondrial morphology. In BEAS-2B cells, the hallmarks of ferroptosis were significantly evidenced at the setting of both CI and CI/R compared with the control, and the effect of adding Lip-1 only during CI was much better than that of only during reperfusion by Cell Counting Kit-8. Furthermore, Lip-1 administration during CI markedly relieved LTx-CI/R injury in mice, as indicated by significant improvement in lung pathological changes, pulmonary function, inflammation, and ferroptosis. CONCLUSIONS: This study revealed the existence of ferroptosis in the pathophysiology of LTx-CI/R injury. Using Lip-1 to inhibit ferroptosis during CI could ameliorate LTx-CI/R injury, suggesting that Lip-1 administration might be proposed as a new strategy for organ preservation.

Aggregation-Induced emission photosensitizer with lysosomal response for photodynamic therapy against cancer.

Photosensitizers play a key role in bioimaging and photodynamic therapy (PDT) of cancer. However, conventional photosensitizers usually do not achieve the desired efficacy in PDT due to their poor photostability, targeting ability, and responsiveness. Herein, we designed a series of photosensitizers with aggregation-induced emission (AIE) effect using benzothiazole- triphenylamine (BZT-triphenylamine) as the parent nucleus. The synthesized compound SIN ((E)-2-(4-(diphenylamino)styryl)-3-(4-iodobutyl)benzo[d]thiazol-3-ium) exhibits good biocompatibility, photostability, and bright emission in the near-infrared range (600-800 nm). The fluorescence emission intensity is responsive to viscosity, with significant fluorescence enhancement (48 times) and high fluorescence quantum yield (4.45 %) at high viscosity. Moreover, SIN has particular lysosome targeting properties with a Pearson correlation coefficient (PCC) of 0.97 and has good 1O2 generation ability under white light irradiation, especially in a weak acidic environment. Thus, SIN can realize good bioimaging ability and photodynamic therapeutic efficacy under the highly viscous and weakly acidic environment of lysosomes in the tumor cells. This study indicates that SIN has potential as a multifunctional organic photosensitizer for bioimaging and PDT of tumor.

Deciphering phase evolution in complex metal oxide thin films via high-throughput materials synthesis and characterization.

Discovery of structure-property relationships in thin film alloys of complex metal oxides enabled by high-throughput materials synthesis and characterization facilities is demonstrated here with a case-study. Thin films of binary transition metal oxides (Ti-Zn) are prepared by pulsed laser deposition with continuously varying Ti:Zn ratio, creating combinatorial samples for exploration of the properties of this material family. The atomic structure and electronic properties are probed by spatially resolved techniques including x-ray absorption near edge structures (XANES) and x-ray fluorescence (XRF) at the Ti and Zn K-edge, x-ray diffraction, and spectroscopic ellipsometry. The observed properties as a function of Ti:Zn ratio are resolved into mixtures of five distinguishable phases by deploying multivariate curve resolution analysis on the XANES spectral series, under constraints set by results from the other characterization techniques. First-principles computations based on density function theory connect the observed properties of each distinct phase with structural and spectral characteristics of crystalline polymorphs of Ti-Zn oxide. Continuous tuning of the optical absorption edge as a function of Ti:Zn ratio, including the unusual observation of negative optical bowing, exemplifies a functional property of the film correlated to the phase evolution.

Anterior hilum anastomosis versus posterior hilum anastomosis in a mouse lung transplantation model.

Objectives: The mouse orthotopic lung transplantation (LTx) model is of enormous research value in lung transplantation. This study compares 2 anastomotic methods (anterior and posterior hilum anastomosis) of mouse LTx in term of difficulty, operation time, and postoperative effects. Methods: Twenty mice received LTx with slipknots for anterior hilum anastomosis (AH group), and 28 received LTx with a microvessel clip for posterior hilum anastomosis (PH group), all by a single surgeon. The operation time was recorded and the grafts were evaluated 24 hours after surgery. Results: The success rates in the recipient animals were 85% (17/20) in AH group and 89% (25/28) in PH group (P > .05). The recipient operation time and back table time in AH group were longer than those in PH group (52.8 ± 5.0 vs 47.3 ± 5.7 minutes, 27.8 ± 3.9 vs 25.3 ± 2.8 minutes, P < .05), but the warm ischemia time did not differ significantly (13.1 ± 2.1 vs 12.2 ± 2.6 minutes, P = .258), meaning that the time discrepancies predominantly originated from the hilum treatment. In AH group, 2 cases failed due to pulmonary venous thrombosis and atelectasis respectively at 24 hours after LTx, but none failed in PH group. No significant difference was observed in the postoperative performance of the successful recipients (thoracic radiographs, macroscopic appearance, oxygenation index, pulmonary compliance, pathologic changes) between the 2 groups. Conclusions: Compared with anterior hilar anastomosis, posterior hilum anastomosis with a microvessel clip is less complicated and less time-consuming in the management of hilar structures and causes fewer postoperative complications.

Temperature Effect on Photoelectrochemical Water Splitting: A Model Study Based on BiVO4 Photoanodes.

Photoelectrochemical (PEC) water splitting is typically studied at room temperature. In this work, the temperature effect on PEC water splitting is studied using crystalline BiVO4 thin film photoanode as a model system. Systematic temperature-dependent electrochemical study demonstrates that the PEC activity is boosted at elevated electrolyte temperatures and indicates that thermal energy plays a main role in improving charge carrier transport in the bulk of BiVO4. Irreversible surface reconstruction is observed after PEC reactions at elevated temperature in the presence of hole scavengers, with regularly spaced stripes emerging on BiVO4 grains. The surface-reconstructed photoanode exhibits up to 40% improvement in photocurrent densities and ∼ 0.25 V shift of photocurrent onset to favorable direction. Detailed investigation shows the formation of an amorphous layer without stoichiometric change at the reconstructed surface. This work provides insights of the temperature effect on the photoelectrode in solar water splitting and reveals the non-negligible effect of hole scavengers in photoelectrochemical measurement.

Design nanoporous metal thin films via solid state interfacial dealloying.

Thin-film solid-state interfacial dealloying (thin-film SSID) is an emerging technique to design nanoarchitecture thin films. The resulting controllable 3D bicontinuous nanostructure is promising for a range of applications including catalysis, sensing, and energy storage. Using a multiscale microscopy approach, we combine X-ray and electron nano-tomography to demonstrate that besides dense bicontinuous nanocomposites, thin-film SSID can create a very fine (5-15 nm) nanoporous structure. Not only is such a fine feature among one of the finest fabrications by metal-agent dealloying, but a multilayer thin-film design enables creating nanoporous films on a wider range of substrates for functional applications. Through multimodal synchrotron diffraction and spectroscopy analysis with which the materials' chemical and structural evolution in this novel approach is characterized in details, we further deduce that the contribution of change in entropy should be considered to explain the phase evolution in metal-agent dealloying, in addition to the commonly used enthalpy term in prior studies. The discussion is an important step leading towards better explaining the underlying design principles for controllable 3D nanoarchitecture, as well as exploring a wider range of elemental and substrate selections for new applications.

Survival and outcomes after lung transplantation for connective tissue disease-associated interstitial lung diseases.

BACKGROUND: Lung transplantation (LTx) is the most important treatment for end-stage lung diseases. However, the treatment of connective tissue disease-associated interstitial lung diseases (CTD-ILD) using LTx is still controversial especially for polymyositis/dermatomyositis-associated interstitial lung disease (PM/DM-ILD). METHODS: Patients diagnosed with idiopathic pulmonary fibrosis (IPF) (n=180) and CTD-ILD (n= 36) from 1st January 2015 to 31st December 2019 were recruited into the study. We set polymyositis/dermatomyositis (PM/DM) as a single subgroup, and all the patients underwent LTx at the Wuxi People's Hospital. RESULTS: We found that patients with non-myositis connective tissue-related ILD (NM-CTLD) were younger (p=0.007) and had a higher percentage of females (p=0.000) than patients with IPF. PM/DM-ILD was associated with a higher incidence of primary graft dysfunction (PGD) (p=0.006) and a longer time in the intensive care unit (ICU) (p=0.000). The cumulative survival rates of patients with PM/DM-ILD were significantly lower than those with IPF (log rank, p=0.003). However, there were no significant differences when compared with the cumulative survival rates of patients with NM-CTLD and IPF (log rank, p=0.528). Age- and gender-adjusted Cox proportional hazard analyses indicated that post-LTx PGD (HR 1.498, 95% CI 1.227-1.828, p=0.000) and duration of ICU (HR 1.027, 95% CI 1.007-1.047, p=0.000) were the independent contributors of disease status to survival. Lung infection was the leading cause of post-LTx death in the groups, where the incidence was 65.3% (47/72) in IPF, 66.7% (8/12) in NM-CTLD, and 66.7% (4/6) in PM/DM-ILD. CONCLUSIONS: This study found that patients with NM-CTLD had a similar survival outcome with IPF. However, patients with PM/DM-ILD-performed LTx had a lower survival rate than those with IPF. Key Points • Previous studies have shown that the myopathies associated ILD patients had similar post-LTx outcomes with IPF patients. However, our retrospective analysis indicated that patients with PM/DM-ILD-performed LTx had a lower survival rate than those with IPF. • Patients with NM-CTLD had a similar survival outcome with IPF. • We also found that PM/DM-ILD was associated with a higher incidence of PGD and a longer time in the ICU.

Thin-film synthesis of superconductor-on-insulator A15 vanadium silicide.

We present a new method for thin-film synthesis of the superconducting A15 phase of vanadium silicide with critical temperature higher than 13 K. Interdiffusion between a metallic vanadium film and the underlying silicon device layer in a silicon-on-insulator substrate, at temperatures between 650 and 750 °C, favors formation of the vanadium-rich A15 phase by limiting the supply of available silicon for the reaction. Energy dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy, and X-ray diffraction verify the stoichiometry and structure of the synthesized thin films. We measure superconducting critical currents of more than 106 amperes per square centimeter at low temperature in micron-scale bars fabricated from the material, and an upper critical magnetic field of 20 T, from which we deduce a superconducting coherence length of 4 nm, consistent with previously reported bulk values. The relatively high critical temperature of A15 vanadium silicide is an appealing property for use in silicon-compatible quantum devices and circuits.

Exciton diffusion in solid solutions of luminescent lanthanide ß-diketonates.

In this article, a series of luminescent lanthanide ß-diketonate solid solutions, with the formula of TBAEuxM1-x(TTA)4 (TBA = tetrabutylammonium; M = La or Gd; TTA = 2-thenoyltrifluoroacetonate), are synthesized by co-precipitation. In the solid solutions, the emission efficiency of Eu3+ is significantly increased with the presence of non-luminescent chelates TBALa(TTA)4 and TBAGd(TTA)4. Low temperature luminescence spectroscopy studies indicate that the TTA- ligands in these non-luminescent chelates do emit phosphorescence with long lifetime. However, the ligand phosphorescence is strongly quenched in solid solutions with the luminescent chelate TBAEu(TTA)4, providing strong evidence for intermolecular energy transfer through the triplet excited states of the ligands. A quantitative analysis of Eu3+ emission enhancement and TTA- phosphorescence quenching reveals that each Eu3+ center may receive excitation energy from about 30 TTA- ligands, suggesting that the excitation energy has become exciton-like in the solid solutions. Based on the crystallography analysis of TBALn(TTA)4, it is discovered that TTA- ligands in neighboring Ln(TTA)4- units may form π-π stacks with intermolecular distance ≤3.5 Å, thus enabling efficient triplet exciton diffusion via exchange interaction.

Mid-infrared frequency doubling using strip-loaded silicon nitride on epitaxial barium titanate thin film waveguides.

Broadband mid-infrared (mid-IR) frequency doubling was demonstrated using nonlinear barium titanate (BTO) thin films. The device has a strip-loaded waveguide structure consisting of top silicon nitride (SiN) strips and an underneath BTO guiding layer. The epitaxial BTO was deposited on a strontium titanate (STO) substrate by pulsed-laser deposition. Through a SiN grating coupler, the pumping mid-IR light at wavelength λ=3.30-3.45µm was coupled into the nonlinear BTO layer, where the spectrum of the near-infrared (NIR) second-harmonic generation was characterized. The developed BTO waveguides provide a platform for mid-IR nonlinear integrated photonics and on-chip quantum optics.