Near-infrared photoluminescence and thermally stimulated current in Cu3Ga5Se9 layered crystals: A comparative study

Near-infrared photoluminescence (PL) and thermally stimulated current (TSC) spectra of Cu₃Ga₅Se₉ layered crystals grown by Bridgman method have been studied in the photon energy region of 1.35–1.46 eV and the temperature range of 15–115 K (PL) and 10–170 K (TSC). An infrared PL band centered at 1.42 eV was revealed at T = 15 K. Radiative transitions from shallow donor level placed at 20 meV to moderately deep acceptor level at 310 meV were suggested to be the reason of the observed PL band. TSC curve of Cu₃Ga₅Se₉ crystal exhibited one broad peak at nearly 88 K. The thermal activation energy of traps was found to be 22 meV. An energy level diagram demonstrating the transitions in the crystal band gap was plotted taking account of results of PL and TSC experiments conducted below room temperature.     

Optical and luminescence properties of Dy3+ ions in phosphate based glasses

Phosphate glasses with compositions of 44P₂O₅ + 17K₂O + 9Al₂O₃ + (30 − x)CaF₂ + xDy₂O₃ (x = 0.05, 0.1, 0.5, 1.0, 2.0, 3.0 and 4.0 mol %) were prepared and characterized by X-ray diffraction (XRD), differential thermal analysis (DTA), Fourier transform infrared (FTIR), optical absorption, emission and decay measurements. The observed absorption bands were analyzed by using the free-ion Hamiltonian (H_FI) model. The Judd–Ofelt (JO) analysis has been performed and the intensity parameters (Ω_λ, λ = 2, 4, 6) were evaluated in order to predict the radiative properties of the excited states. From the emission spectra, the effective band widths (Δλ_eff), stimulated emission cross-sections (σ(λ_p)), yellow to blue (Y/B) intensity ratios and chromaticity color coordinates (x, y) have been determined. The fluorescence decays from the ⁴F_9/2 level of Dy³⁺ ions were measured by monitoring the intense ⁴F_9/2 → ⁶H_15/2 transition (486 nm). The experimental lifetimes (τ_exp) are found to decrease with the increase of Dy³⁺ ions concentration due to the quenching process. The decay curves are perfectly single exponential at lower concentrations and gradually changes to non-exponential for higher concentrations. The non-exponential decay curves are well fitted to the Inokuti–Hirayama (IH) model for S = 6, which indicates that the energy transfer between the donor and acceptor is of dipole–dipole type. The systematic analysis of revealed that the energy transfer mechanism strongly depends on Dy³⁺ ions concentration and the host glass composition.     

Signatures for Coexistence of Monoclinic and Hexagonal Phases in GaTe Nanoflakes

The burgeoning two-dimensional (2D) layered materials provide a powerful strategy to realize efficient light-emitting devices. Among them, gallium telluride (GaTe) nanoflakes, showing strong photoluminescence (PL) emission from multilayer to bulk crystal, relax the stringent fabrication requirements of nanodevices. However, detailed knowledge on the optical properties of GaTe varies as layer thickness is still missing. Here we perform thickness-dependent PL and Raman spectra, as well as temperature-dependent PL spectra of GaTe nanoflakes. Spectral analysis reveals a spectroscopic signature for the coexistence of both the monoclinic and hexagonal phases in GaTe nanoflakes. To understand the experimental results, we propose a crystal structure where the hexagonal phase is on the top and bottom of nanoflakes while the monoclinic phase is in the middle of the nanoflakes. On the basis of temperature-dependent PL spectra, the optical gap of the hexagonal phase is determined to be 1.849 eV, which can only survive under temperature higher than 200 K with the increasing phonon population. Furthermore, the strength of exciton-phonon interaction of the hexagonal phase is estimated to be 1.24 meV/K. Our results prove the coexistence of dual crystalline phases in multilayer GaTe nanoflakes, which may provoke further exploration of phase transformation in GaTe materials, as well as new applications in 2D light-emitting diodes and heterostructure-based optoelectronics.     

基于混酸回流制备碳点的中和过程

Carbon dots (C dots) are relatively novel carbon nanomaterials that have attracted significant interest due to their unique photoluminescence, good biocompatibility, and stability. The preparation methods of C dots was usually summarized into "top-down" and "bottom-up", and mixed acid reflux is a top-down strategy that can be used to synthesize C dots, during which neutralization is a necessary step that can significantly influence the properties and potential applications of the final product. Previously, this research area mainly focused on tuning the properties of C dots by changing the starting materials and/or varying the reaction conditions; the influence of the reagents used during neutralization has been largely ignored. As the previously reported C dots prepared by mixed acid reflux were obtained from different starting materials under varied conditions, a meaningful comparison is difficult. Herein, yellow-emitting C dots were prepared by mixed acid-refluxing a carbon-rich material derived from fullerene carbon soot. For the same batch of as-prepared C dots, the influences of four reagents, i.e., NaOH, Na₂CO₃, K₂CO₃, and NH₃·H₂O, during neutralization on the structures and photoluminescence of the resulting C dots were investigated in detail. The results of thermogravimetric analysis, Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy clearly showed that the reagent used during neutralization can affect the degree of dissociation of the acidic functional groups on the C dots. This is further supported by examination of the C dot/surfactant mixtures where subtle changes in the phase behavior were observed. Structural changes of the C dots cause variations in their surface states, ultimately altering the optical characteristics, including UV-vis absorption and fluorescence. Among the treated C dots, the sample prepared with Na₂CO₃ showed the strongest emission under the same excitation wavelength, while that prepared with NH₃·H₂O exhibited a distinct red shift (~8 nm) in the emission curve. The results presented herein provide clear evidence that neutralization reagent selection is important for optimizing the properties of the resulting C dots obtained by mixed acid reflux. In addition, the photoluminescence of the C dots can be influenced by their counterions, providing a novel method for tuning the properties of C dots while explaining their behavior in saline solutions. In short, the basicity of the neutralizing reagent and the type of counterions affect the structure of the C dots surface, which brings different performances. This work reminds researchers that it is necessary to use the type of neutralizing reagent as an experimental condition when preparing C dots in the future.     

喹喔啉酮类JNK3抗肿瘤抑制剂的绿色合成——推荐一个综合化学实验

介绍了一个荧光光谱方面新的实验项目:以苝和六苯基噻咯作为发光物质的特征分子,通过测定其不同聚集状态下的荧光光谱,观察聚集荧光淬灭ACQ(aggregation-causedquenching)和聚集诱导发光AIE(aggregationinduced emission)两种不同的发光现象;利用晶体学数据库CCDC (Cambridge Crystallographic Data Centre)检索特征分子的晶体结构,从分子晶体结构层面分析AIE和ACQ发光现象产生的原因,在此基础上探讨不同发光机制和分子状态的关系。论文详细描述了实验的设计思想、实验内容和实验结论,并结合教学过程,分析了该实验在开阔学生视野、提高认知水平及培养科研素养等方面所取得的教学效果。     

Cucurbit[8]uril-induced diarylethene thermally activated delay fluorescence supramolecular switch for sequential energy transfer

Constructing molecular switches based on supramolecular assembly strategy is a research hotspot. In this work, we constructed an all visible-light-regulated supramolecular photo-switch based on pyridinium-modified diarylethene derivative (DTE-Me) and cucurbit[8]uril (CB[8]). CB[8] not only accelerated the photochromic process under 365 nm ultraviolet light but also shifted the absorption of open formed DTE-Me to the visible region, which led to efficient photocyclization under 450 nm visible light irradiation, while DTE-Me and DTE-Me/CB[7] remained unchanged under the same irradiating condition. Moreover, the complexation with CB[8] could induce the strong thermally activated delayed fluorescence (TADF) of guest molecular at 550 nm, which further shifted to 670 nm through two-step sequential energy transfer with sulforhodamine B (SRB) and Cy5. This energy transfer process could also be regulated with visible light, and the application for information encryption was also demonstrated. This assembly provides a convenient approach to construct all visible light-regulated TADF photo-switch.     

Crystal growth,spectral characterization and structural studies of a luminescent coordination polymer of calcium(II) complex of benzilic acid

Single crystals of a new calcium(II) complex of benzilic acid, [Ca(C₁₄H₁₁O₃)₂(C₁₄H₁₂O₃)₂] have been successfully grown by gel diffusion technique at room temperature. Single crystal X-ray diffraction study reveals that the compound belongs to orthorhombic system with space group Fddd. The adjacent CaO₈ units are linked via O–H–O interaction to form one dimensional polymeric chains. The extensive hydrogen bonding interactions lead to a supramolecular structure. The grown crystals were further characterized by elemental analysis, FT-IR, UV–Visible, thermogravimetric, powder X-ray diffraction and solid state photoluminescence studies.     

Tb3+掺杂锂铝硅酸盐玻璃的光致发光和辐照致发光

采用熔融-淬冷法制备了Tb3+掺杂锂铝硅酸盐闪烁玻璃,用紫外激发光谱、发射光谱及荧光寿命表征了光致发光性能,用X射线和阴极射线激发测试了辐射致发光性能。研究结果表明：低Tb3+掺杂浓度时,随着其浓度增大,Tb3+间的交叉弛豫增加导致了5D₃→7F_j跃迁的能量逐渐向5D₄→7F_j迁移转变,5D₃激发态的荧光寿命和发射强度均明显下降,5D₄-7F_j发射强度逐渐增大。较高Tb3+浓度时,其浓度继续增加会提升非辐射比例,是荧光寿命降低和荧光猝灭的最主要原因。比较光致发光和辐照致发光性能,发现随着激发源的能量上升,会增加激发态5D₃能级向5D₄能级的能量转移,同时,由于玻璃的密度低会导致辐照致发光效率随激发源的能量上升而下降。     

Effects of hydrogen annealing on the room temperature ferromagnetism and optical properties of Cr-doped ZnO nanoparticles

We explore the effects of hydrogen annealing on the room temperature ferromagnetism and optical properties of Cr-doped ZnO nanoparticles synthesized by the sol-gel method. X-ray diffraction and x-ray photoelectron spectroscopy data show evidence that Cr has been incorporated into the wurtzite ZnO lattice as Cr²⁺ ions substituting for Zn²⁺ ions without any detectable secondary phase in as-synthesized Zn_0.97Cr_0.03O nanopowders. The room temperature magnetization measurements reveal a large enhancement of saturation magnetization M_s as well as an increase of coercivity of H₂-annealed Zn_0.97Cr_0.03O:H samples. It is found that the field-cooled magnetization curves as a function of temperature from 40 to 400 K can be well fitted by a combination of a standard Bloch spin-wave model and Curie–Weiss law. The values of the fitted parameters of the ferromagnetic exchange interaction constant a and the Curie constant C of H₂-annealed Zn_0.97Cr_0.03O:H nanoparticles are almost doubled upon H₂-annealing. Photoluminescence measurements show evidence that the shallow donor defect or/and defect complexes such as hydrogen occupying an oxygen vacancy H_o may play an important role in the origin of H₂-annealing induced enhancement of ferromagnetism in Cr-H codoped ZnO nanoparticles.     

Oxygen photo-adsorption related quenching of photoluminescence in group-III nitride nanocolumns

GaN and InGaN nanocolumns of various compositions are studied by room-temperature photoluminescence (PL) under different ambient conditions. GaN nanocolumns exhibit a reversible quenching upon exposure to air under constant UV excitation, following a t^−1/2 time dependence and resulting in a total reduction of intensity by 85–90%, as compared to PL measured in vacuum, with no spectral change. This effect is not observed when exposing the samples to pure nitrogen. We attribute this effect to photoabsorption and photodesorption of oxygen that modifies the surface potential bending. InGaN nanocolumns, under the same experimental conditions do not show the same quenching features: The high-energy part of the broad PL line is not modified by exposure to air, whereas a lower-energy part, which does quench by 80–90%, can now be distinguished. We discuss the different behaviors in terms of carrier localization and possible composition or strain gradients in the InGaN nanocolumns.