Mn(II)-Activated Zero-Dimensional Zinc(II)-Based Metal Halide Hybrids with Near-Unity Photoluminescence Quantum Yield.

As derivatives of metal halide perovskite materials, low-dimensional metal halide materials have become important materials that have attracted much attention in recent years. As one branch, zinc-based metal halides have the potential for practical applications due to their lead-free, low-toxicity and high-stability characteristics. However, pure zinc-based metal halide materials are still limited by their poor optical properties and cannot achieve large-scale practical applications. Therefore, in this work, we report an organic-inorganic hybrid zero-dimensional zinc bromide, (TDMP)ZnBr4, using transition metal Mn2+ ions as dopants and incorporating them into the (TDMP)ZnBr4 lattice. The original non-emissive (TDMP)ZnBr4 exhibits bright green emission under the excitation of external UV light after the introduction of Mn2+ ions with a PL peak position located at 538 nm and a PLQY of up to 91.2%. Through the characterization of relevant photophysical properties and the results of theoretical calculations, we confirm that this green emission in Mn2+:(TDMP)ZnBr4 originates from the 4T1 → 6A1 optical transition process of Mn2+ ions in the lattice structure, and the near-unity PLQY benefits from highly localized electrons generated by the unique zero-dimensional structure of the host material (TDMP)ZnBr4. This work provides theoretical guidance and reference for expanding the family of zinc-based metal halide materials and improving and controlling their optical properties through ion doping.

Boosting Blue Self-Trapped Exciton Emission in All-Inorganic Zero-Dimensional Metal Halide Cs2ZnCl4 via Zirconium (IV) Doping.

Low-dimensional metal halides with efficient luminescence properties have received widespread attention recently. However, nontoxic and stable low-dimensional metal halides with efficient blue emission are rarely reported. We used a solvothermal synthesis method to synthesize tetravalent zirconium ion-doped all-inorganic zero-dimensional Cs2ZnCl4 for the first time. Bright blue emission in the range of 370 nm-700 nm with a emission maximum at 456 nm was observed in Zr4+:Cs2ZnCl4 accompanied by a large Stokes shift, which was due to self-trapped excitons (STEs) caused by the lattice vibrations of the twisted structure. Simultaneously, the PLQY of Zr4+:Cs2ZnCl4 achieve an impressive 89.67%, positioning it as a compelling contender for future applications in blue-light technology.

Unravelling the doping effect of potassium ions on structural modulation and photocatalytic activity of graphitic carbon nitride.

Graphitic carbon nitride (GCN), as a promising photocatalyst, has been intensely investigated in the photocatalytic fields, but its performance is still unsatisfactory. To date, metal ion doping has been proven to be an effective modification method to improve the photocatalytic activity of GCN. More importantly, comprehensive understanding of the doping mechanism will be of benefit to synthesize efficient GCN based photocatalysts. In this work, K+-doped GCN samples were prepared via heating the mixture of the preheated melamine and a certain amount of KCl at different synthetic temperatures. XRD and Raman characterization studies indicated that the introduction of K+ could improve its crystallinity at higher temperature but reduce its crystallinity at lower temperature. Moreover, FTIR and SEM-EDS measurements implied that K+ are found dominantly in the surface of the ion-doped sample prepared at lower temperature, while they are found both in the surface and bulk of the ion-doped sample prepared at higher temperature. These observations revealed that K+ distributed in the surface of the ion-doped GCN could inhibit its crystal growth, while K+ distributed inside of the ion-doped GCN could promote its crystallinity. Owing to the greater inducing effect of the bulk K+ than the disturbing effect of the surface K+, the improvement of the crystallinity for K+-doped GCN was achieved. As a result, the K+-doped GCN with higher crystallinity yielded an obviously higher H2 evolution rate than that with lower crystallinity under visible light irradiation (>420 nm). Besides, it was observed that the K+-doped GCN prepared at higher temperature exhibits significantly greater adsorption capacity for methylene blue than the K+-doped GCN prepared at lower temperature. This work would provide an insight into optimizing metal ion doped GCN with high photocatalytic activity.

S,N-rich luminous covalent organic frameworks for Hg2+ detection and removal.

The challenge for simultaneous detection and removal of Hg2+ is the design of bifunctional materials bearing abundant accessible chelating sites with high affinity. Covalent-organic frameworks (COFs) are attracting more and more attention as potential bifunctional materials for Hg2+ detection due to their large specific surface area, ordered pores, and abundant chelating sites. Here, a new luminous S,N-rich COFBTT-AMPD based on hydrophilic block unit of 2,2'-azobis(2-methylpropionamidine) dihydrochloride (AMPD) was constructed, which improved the solubility and affinity for Hg2+ greatly. Another S-rich fused-ring unit of benzotrithiophene tricarbalaldehyde (BTT) enhanced the conjugation of COFBTT-AMPD, and the methyl-rich chains block unit of AMPD effectively suppressed the aggregation-caused quenching. Thus, the COFBTT-AMPD emitted strong fluorescence at 546 nm in liquid and solid as well as different solvent with a wide pH range, which was used for the visual detection and removal of Hg2+ (detection limit: 2.6 nM, linear range: 8.6 × 10-3-20 µM, monolayer adsorption capacity: 476.19 mg g-1) successfully. COFBTT-AMPD-based fabric and light-emitting diode coatings were further constructed to realize the visual detection of Hg2+ vapor. The results reveal the potential of S,N-rich luminous COFBTT-AMPD for Hg2+ detection and remediation in the environment.

H2O-NH4+-Induced Emission Modulation in Sb3+-Doped (NH4)2InCl5·H2O.

Lead-based metal halide perovskites have received widespread attention for their promising application prospects in the field of lighting and display due to their excellent optical properties. However, the toxicity of lead may hinder their further commercial application. Herein, a zero-dimensional (0D) metal halide (NH4)2InCl5·H2O with an orthorhombic structure and the Pnma space group was produced. With doping with Sb3+, these products exhibit one highly efficient and wide yellow emission band (∼450-850 nm) in their photoluminescence (PL) spectra, which covers almost the entire visible spectral range at room temperature; however, they give two emission bands with long decay lifetimes (microseconds) at low temperature. Temperature-dependent steady-state PL, transient PL spectroscopy, temperature-dependent Raman spectra characterization, and theoretical band structure calculations confirm that the dual-band emission at low temperature originates from the dual vibronic levels of the self-trapped exciton (STE) in the hole-vibration state, whose vibration energy is related to the H2O-NH4+ connection in the valence band. This result proves that the vibronic state in STE formation involves both electrons and holes in the excited states, the opposite of this happens in the electron-vibration band in most perovskite halides. These results provide new insight into the luminescent mechanism of Sb3+ in halide perovskites, especially used for emission color modulation by the temperature-dependent electron- or hole-vibration processes.

Light Emission Enhancement of (C3H10N)4Pb1-xMnxBr6 Metal-Halide Powders by the Dielectric Confinement Effect of a Nanosized Water Layer.

Organic-inorganic hybrid metal halides have been widely studied as a kind of phosphor materials for high-performance white light-emitting diodes. In this paper, a series of organic-inorganic metal-halide (C3H10N)4Pb1-xMnxBr6 powders with different Mn2+ ion doping concentrations were synthesized by mechanochemical methods, giving broadband white light emission with a photoluminescence quantum yield of 36.1% at room temperature, which turn green with a much larger intensity at 80 K. Interestingly, its emission converted from white to red after 100 °C treatments and turned back to white again when exposed to moist air for a while. This emission variation was caused by the adsorbed water layer on the surface of product powders via the dielectric confinement. The red emission from no water powders is identified to occur from the Mn ferromagnetic pair in point-shared octahedral sites, while the broadband white emission originated from the surface water-assisted dielectric confinement and surface polarization which combine the self-trapped excitons and d-d transitions of Mn ions and Mn pairs in the product. Moreover, this white emission can transform into green color at 80 K with a much stronger intensity, caused by the even efficient surface dielectric confinement by the adsorbed frozen water layer. This special compound has the advantages of simple preparation, low cost, and good stability and even contains water molecule in the air, giving a near-perfect white emission, with CIE of (0.33, 0.35) and correlated color temperatures at around 5733 K, which may be used for different applications such as sensing, solid-state lighting, and display.

Sound Detection Monitoring Tool in CNC Milling Sounds by K-Means Clustering Algorithm.

Computer numerical control (CNC) is a machine used in the manufacturing industry to produce components quickly for the engineering field or the desired shape. In the milling process carried out by CNC machines, sometimes vibrations occur that cause unwanted cracks or damage, which if left unchecked, will cause more severe damage. For this reason, this study describes how to monitor and analyze the sound produced by CNC during the milling process. This study uses six sound sample videos from YouTube, and there are two modes: (1) the operating mode is three different shapes with XY, XZ, and XYZ axes, and the second (2) is based on material differences. Namely, wood, Styrofoam, and plastic. The sound generated from all samples of the CNC milling processes will be detected using a sound detection program that has been designed in the LabVIEW using a simple microphone. The resulting sound frequency will be analyzed using the fast Fourier transform (FFT) process in spectral measurements, which will produce the amplitude and frequency of the detected sound in real time in the form of a graph. All frequency results that have been obtained from the sound detection monitoring tool in the CNC milling machine will be imported into the K-means clustering algorithm where the different frequencies between the resonant frequency and noise will be classified. Based on the experiments conducted, the sound detection program can detect sounds with a significant level of sensitivity.

Highly Efficient Cool-White Photoluminescence of (Gua)3Cu2I5 Single Crystals: Formation and Optical Properties.

Zero-dimensional lead-free organic-inorganic hybrid metal halides have drawn attention as a result of their local metal ion confinement structure and photoelectric properties. Herein, a lead-free compound of (Gua)3Cu2I5 (Gua = guanidine) with a different metal ion confinement has been discovered, which possesses a unique [Cu2I5]3- face-sharing tetrahedral dimer structure. First-principles calculation demonstrates the inherent nature of a direct band gap for (Gua)3Cu2I5, and its band gap of ∼2.98 eV was determined by experiments. Worthy of note is that (Gua)3Cu2I5 exhibits a highly efficient cool-white emission peaking at 481 nm, a full-width at half-maximum of 125 nm, a large Stokes shift, and a photoluminescence quantum efficiency of 96%, originating from self-trapped exciton emission. More importantly, (Gua)3Cu2I5 single crystals have a reversible thermoinduced luminescence characteristic due to a structural transition scaled by the electron-phonon coupling coefficients, which can be converted back and forth between cool-white and yellow color emission by heating or cooling treatment within a short time. In brief, as-synthesized (Gua)3Cu2I5 shows great potential for application both in single-component white solid-state lighting and sensitive temperature scaling.

Distinct green electroluminescence from lead-free CsCuBr2 halide micro-crosses.

Low-dimensional, lead-free, and cuprous-based halide compounds of Cs3Cu2Br5 micro-rods and CsCuBr2 micro-crosses (MCs) were synthesized via a simple solution method. The CsCuBr2 MCs were quite stable in air. Distinct green electroluminescence at 527 nm originating from CsCuBr2 MCs was observed at a low driving voltage of less than 3 V.

Development and validation of a penumbra-based predictive model for thrombolysis outcome in acute ischemic stroke patients.

The use of thrombolysis in acute ischemic stroke is restricted to a small proportion of patients because of the rigid 4·5-h window. With advanced imaging-based patient selection strategy, rescuing penumbra is critical to improving clinical outcomes. In this study, we included 155 acute ischemic stroke patients (84 patients in training dataset, age from 43 to 80, 59 males; 71 patients in validation dataset, age from 36 to 80, 45 males) who underwent MR scan within the first 9-h after onset, from 7 independent centers. Based on the mismatch concept, penumbra and core area were identified and quantitatively analyzed. Moreover, predictive models were developed and validated to provide an approach for identifying patients who may benefit from thrombolytic therapy. Predictive models were constructed, and corresponding areas under the curve (AUC) were calculated to explore their performances in predicting clinical outcomes. Additionally, the models were validated using an independent dataset both on Day-7 and Day-90. Significant correlations were detected between the mismatch ratio and clinical assessments in both the training and validation datasets. Treatment option, baseline systolic blood pressure, National Institutes of Health Stroke Scale score, mismatch ratio, and three regional radiological parameters were selected as biomarkers in the combined model to predict clinical outcomes of acute ischemic stroke patients. With the external validation, this predictive model reached AUCs of 0·863 as short-term validation and 0·778 as long-term validation. This model has the potential to provide quantitative biomarkers that aid patient selection for thrombolysis either within or beyond the current time window.

Regional Coherence Alterations Revealed by Resting-State fMRI in Post-Stroke Patients with Cognitive Dysfunction.

OBJECTIVES: Post-stroke cognitive dysfunction greatly influences patients' quality of life after stroke. However, its neurophysiological basis remains unknown. This study utilized resting-state functional magnetic resonance imaging (fMRI) to investigate the alterations in regional coherence in patients after subcortical stroke. METHODS: Resting-state fMRI measurements were acquired from 16 post-stroke patients with poor cognitive function (PSPC), 16 post-stroke patients with good cognitive function (PSGC) and 30 well-matched healthy controls (HC). Regional homogeneity (ReHo) was used to detect alterations in regional coherence. Abnormalities in regional coherence correlated with scores on neuropsychological scales. RESULTS: Compared to the HC and the PSGC, the PSPC showed remarkably decreased ReHo in the bilateral anterior cingulate cortex and the left posterior cingulate cortex/precuneus. ReHo in the bilateral anterior cingulate cortex positively correlated with the scores on the Symbol Digit Modalities Test (r = 0.399, P = 0.036) and the Complex Figure Test-delayed recall subtest (r = 0.397, P = 0.036) in all post-stroke patients. Moreover, ReHo in the left posterior cingulate cortex/precuneus positively correlated with the scores on the Forward Digit Span Test (r = 0.485, P = 0.009) in all post-stroke patients. CONCLUSIONS: Aberrant regional coherence was observed in the anterior and posterior cingulate cortices in post-stroke patients with cognitive dysfunction. ReHo could represent a promising indicator of neurobiological deficiencies in post-stroke patients.

Wall characteristics and mechanisms of ischaemic stroke in patients with atherosclerotic middle cerebral artery stenosis: a high-resolution MRI study.

OBJECTIVE: To evaluate the characteristics of atherosclerotic middle cerebral artery (MCA) stenosis by high-resolution magnetic resonance imaging (HR-MRI) and determine the relationship between wall characteristics and infarction patterns. METHODS: Thirty-six patients with acute ischaemic stroke due to MCA stenosis underwent diffusion-weighted magnetic resonance imaging (DWI) and HR MRI. Wall characteristics of MCA, including irregular surface, superior location, T2-hyperintense of plaques and positive remodelling (PR), were analysed. Characteristics of acute infarct on DWI were categorised according to the number (single or multiple infarcts) and the pattern of cerebral infarcts (cortical, border zone or perforating artery territory infarcts). The relationship between wall characteristics and infarction patterns was evaluated. RESULTS: PR was observed in 20 patients, irregular surface plaque in 18 patients, superior location of plaques in 14 patients and T2-hyperintense foci in 13 patients. Seventeen patients had multiple acute cerebral infarcts and 13 showed single acute cerebral infarcts. Border zone infarcts were the most common (76.5%) among multiple acute infarcts. Penetrating artery infarcts (PAI) accounted for 76.9% of all single infarcts. Multiple infarcts were more frequently observed in patients with PR (P = 0.007) or plaque surface irregularity (P = 0.035). Single infarcts, especially PAI, were more prevalent in patients with superior plaque (P = 0.030). No statistically significant differences were observed between multiple and single infarcts in patients with T2-hyperintense lesions (P = 0.638). CONCLUSIONS: PR or irregular surface plaques were associated with artery-to-artery embolism. Superior location of plaques was associated with PAI. HR-MRI provides insights into intracranial atherosclerosis in vivo, predictive of infarction patterns.

Aberrant functional connectivity of default-mode network in type 2 diabetes patients.

OBJECTIVES: Type 2 diabetes mellitus is associated with increased risk for dementia. Patients with impaired cognition often show default-mode network disruption. We aimed to investigate the integrity of a default-mode network in diabetic patients by using independent component analysis, and to explore the relationship between network abnormalities, neurocognitive performance and diabetic variables. METHODS: Forty-two patients with type 2 diabetes and 42 well-matched healthy controls were included and underwent resting-state functional MRI in a 3 Tesla unit. Independent component analysis was adopted to extract the default-mode network, including its anterior and posterior components. Z-maps of both sub-networks were compared between the two groups and correlated with each clinical variable. RESULTS: Patients showed increased connectivity around the medial prefrontal cortex in the anterior sub-network, but decreased connectivity around the posterior cingulate cortex in the posterior sub-network. The decreased connectivity in the posterior part was significantly correlated with the score on Complex Figure Test-delay recall test (r = 0.359, p = 0.020), the time spent on Trail-Making Test-part B (r = -0.346, p = 0.025) and the insulin resistance level (r = -0.404, p = 0.024). CONCLUSION: Dissociation pattern in the default-mode network was found in diabetic patients, which might provide powerful new insights into the neural mechanisms that underlie the diabetes-related cognitive decline. KEY POINTS: • Type 2 diabetes mellitus is associated with impaired cognition • Default- mode network plays a central role in maintaining normal cognition • Network connectivity within the default mode was disrupted in type 2 diabetes patients • Decreased network connectivity was correlated with cognitive performance and insulin resistance level • Disrupted default-mode network might explain the impaired cognition in diabetic population.

[Diagnostic efficiency of decline rate of signal intensity and apparent diffusion coefficient with different b values for differentiating benign and malignant breast lesions on diffusion-weighted 3.0T magnetic resonance imaging].

OBJECTIVE: To investigate the diagnostic efficiency of decline rate of signal intensity and apparent diffusion coefficient with different b values for differentiating benign and malignant breast lesions on diffusion-weighted 3.0 T magnetic resonance imaging. METHODS: A total of 152 patients with 162 confirmed histopathologically breast lesions (85 malignant and 77 benign) underwent 3.0 T diffusion-weighted magnetic resonance imaging. Four b values (0, 400, 800 and 1 000 s/mm²) were used. The signal intensity and ADC values of breast lesions were measured respectively. The signal intensity decline rate (SIDR) and apparent diffusion coefficient decline rate (ADCDR) were calculated respectively. SIDR = (signal intensity of lesions with low b value-signal intensity of lesions with high b value)/signal intensity of lesions with low b value, ADCDR = (ADC value of lesions with low b value-ADC value of lesions with high b value) /ADC value of lesions with low b value. The independent sample t-test was employed for statistical analyses and the receiver operating characteristic (ROC) curve for evaluating the diagnosis efficiency of SIDR and ADCDR values. RESULTS: Significant differences were observed in SIDR between benign and malignant breast lesions with b values of 0-400, 400-800 and 800-1 000 s/mm². The sensitivities of SIDR for differentiating benign and malignant breast lesions were 61.2%, 68.2% and 67.1%, the specificities 74.0%, 85.7% and 67.5%, the diagnosis accordance rates 67.3%, 76.5% and 67.3%, the positive predictive values 72.2%, 84.1% and 69.5% and the negative predictive values 63.3%, 71.0% and 65.0% respectively. Significant differences were observed in ADCDR between benign and malignant breast lesions with b values of 400-800 s/mm² and 800-1 000 s/mm². The sensitivities of SDR for differentiating benign and malignant breast lesions were 80.0% and 65.9%, the specificities 72.7% and 65.0%, the diagnostic accordance rates 76.5% and 65.4%, the positive predictive values 76.4% and 67.5% and the negative predictive values 76.7% and 63.3% respectively. CONCLUSION: The decline rate of signal intensity and apparent diffusion coefficient with different b values may be used for differentiating benign and malignant breast lesions. And the diagnostic efficiency with b values of 400-800 s/mm² is optimal.

Improvement of silicon solar cell efficiency by ion beam sputtered deposition of AlOxNy thin films.

Negative charge material, AlOxNy, has been fabricated to passivate the surface of p-type silicon. The fabrication of AlOxNy was possible by using ion beam sputtering deposition to deposit AlN thin film on the surface of a p-type silicon wafer and following annealing in oxygen ambient. Capacitance-voltage analysis shows the fixed charge density has increased from 10(11) cm(-2) to 2.26×10(12) cm(-2) after annealing. The solar cell efficiency increased from 15.9% to 17.3%, which is also equivalent to the reduction of surface recombination velocity from 1×10(5) to 32 cm/s.

Modulation of the polarization state of light using a weak anisotropic thin film.

The polarization state of light is modulated by an anisotropic thin film. An anisotropic MgF(2) film is deposited onto a plate that is put in contact with a BK7 prism to form a BK7 prism/film/air configuration. It is shown that the polarization state of reflected light can be easily modulated from a linear state to a circular state by rotating the thin-film plate.

Improved broadband and quasi-omnidirectional anti-reflection properties with biomimetic silicon nanostructures.

Nature routinely produces nanostructured surfaces with useful properties, such as the self-cleaning lotus leaf, the colour of the butterfly wing, the photoreceptor in brittlestar and the anti-reflection observed in the moth eye. Scientists and engineers have been able to mimic some of these natural structures in the laboratory and in real-world applications. Here, we report a simple aperiodic array of silicon nanotips on a 6-inch wafer with a sub-wavelength structure that can suppress the reflection of light at a range of wavelengths from the ultraviolet, through the visible part of the spectrum, to the terahertz region. Reflection is suppressed for a wide range of angles of incidence and for both s- and p-polarized light. The antireflection properties of the silicon result from changes in the refractive index caused by variations in the height of the silicon nanotips, and can be simulated with models that have been used to explain the low reflection from moth eyes. The improved anti-reflection properties of the surfaces could have applications in renewable energy and electro-optical devices for the military.

Optical constant determination of an anisotropic thin film via polarization conversion.

This study presents a simple method for determining the optical constants of an anisotropic thin film. The sensitivity of enhanced polarization conversion reflectance to optical constants is also calculated and analyzed. Based on the sensitivity calculation, the principal indices and columnar tilt angle can be derived from the polarization conversion reflectance angular spectrum.