Single Crystal Research Articles

Insights into luminescence and energy transfer processes in Ce3+- and Tb3+ co-doped (Gd, Y)3Al2Ga3O12 garnet single crystals

Driven by the pursuit of optimizing the luminescent properties of garnet-based single crystals for X-ray imaging applications, this work reports on the successful synthesis and in-depth characterization of GYAGG crystals doped with Ce³⁺ or Tb³⁺ ions, and doubly-doped with both of them. Micro-pulling down synthesis yielded crystals with a single cubic phase confirmed by X-ray diffraction. Photoluminescence (PL) and radioluminescence (RL) measurements on Ce³⁺,Tb³⁺ co-doped GYAGG revealed bidirectional energy transfer processes. Characteristic broadband 5d1→4f emission of Ce³⁺ centres peaking at 530 nm and narrow 4f→4f emission lines of Tb³⁺ ions starting from 5D4 level within 480-630nm were observed. At higher doping levels, cross-relaxation in Tb³⁺ pairs resulted depleted 5D3 state and only the emission from 5D4 one was observed in the spectra. Analysis of PL decay characteristics corroborated the spectral observations, confirming progressively decreasing Ce³⁺ decay time (down to 40 ns at 15% Tb3+) due to enhanced Ce³⁺→Tb³⁺ energy transfer. Similarly, the Tb³⁺ decay time accelerated by more than 60% after the Ce³⁺ co-doping. Notably, co-doping with 0.5% Ce³⁺ and 10-15% Tb³⁺ doubled the luminescence intensity of RL spectra compared to 0.5% Ce³⁺-doping alone, attributed to the increased density of emitting centres.

Synthesis and fluorescence properties of a two-dimensional Cd-complex for the ratiometric fluorescence detection of Zn2+ ions

The two-dimensional complex [Cd3(L)(2,2′-bpy)2]n (1) was synthesized solvothermally from 4,5-di(3,5-dicarboxylphenoxy)phthalic acid (H6L) and 2,2′-bipyridine (2,2′-bpy) and fully characterized by elemental analysis, infrared spectroscopy, single crystal and powder X-ray diffraction. Complex 1 displays high stability in water and resistance towards acidic and basic media. Fluorescence studies revealed that it may be acted as a ratiometric fluorescence probe to detect Zn2+ ions in water with a superior detection limit of 3.48 nM. The fluorescence recognition mechanism stems from weak interactions between Zn2+ ions and complex 1. Its pronounced stability and recyclability suggest that the new material may be used for high-precision detection of Zn2+ ions in real-life aqueous samples, even under acidic and basic conditions.

Enhanced ferroelectric and piezoelectric properties of SrBi2Ta2O9 thin films through crystalline orientation

This study investigates the fabrication of SrBi2Ta2O9 (SBT) thin films on single crystal (100) Nb:STO substrates using pulsed laser deposition. We systematically varied substrate temperatures and deposition rates to examine their impact on the crystallinity and consequently, on the ferroelectric and piezoelectric properties of the SBT thin films. The SBT thin film developed at 850 °C with a deposition rate of 0.34 nm/pulse showed lower remanent polarization and piezoelectric coefficients, a result of its c-oriented crystallinity. In contrast, SBT thin films produced at 750 °C with deposition rates of 0.37 nm/pulse demonstrated enhanced ferroelectric and piezoelectric responses due to mixed a-oriented crystallinity. In particular, the SBT thin film, fabricated at 750 °C with a lower deposition rate of 0.04 nm/pulse, demonstrated the most enhanced ferroelectric and piezoelectric properties due to its highly refined a-oriented crystallinity. Our findings illuminate the relationship between the characteristics of the crystals and functional properties in SBT thin films, highlighting the integration of a-domains within c-domains as a key strategy for optimizing SBT film performance and opening avenues for designing specialized Bi-layered perovskite thin films.

Influence of pH on Growth, Structural, Thermal, Linear and Nonlinear Optical Properties of L-Asparagine Monohydrate Single Crystal

This report present investigation on influence of pH on growth, structural, thermal, linear and nonlinear optical properties of L-asparagine monohydrate (LAM) single crystal for first time. Single crystals of LAM were grown at different pH by solution growth method by allowing slow evaporation of solvent. Crystal grown at pH 6.4 grows slowly as compare to other crystals grown at other pH values. The slight variation in lattice parameters of grown crystals has been confirmed by powder X-ray diffraction study. FT-IR study confirms the presence of functional groups of LAM in all grown crystals. Influence of pH on optical quality of crystals has been discussed. The crystal grown at pH 5.4 has maximum optical transparency and shows 2 and 20 % more transmission than crystals grown at pH 4.4 and 6.4, respectively. Other optical parameters like cutoff wavelength (λmax), band gap (Eg), linear refractive index (n), reflectance, extinction coefficient (k), electrical susceptibility (χ), optical conductivity(σop), electrical conductivity (σel) and Urbach energy (Eu) of all crystals have been evaluated from transmission data. The LAM crystal grown at pH 6.4 show high values of third order nonlinear optical parameters,as compare to other grown crystals, that attest its suitability for applications like higher harmonic generation, optical switching, optical limiting and other photonic applications over other grown crystals. Thermal stability of the grown crystals has been attested by TG-DTA study.

Optical studies of fluorescein dye doped sulphamic acid single crystal

Fluorsceine, a dye used in lasers and non-linear optics have been studied for its interaction with crystal matrix (Sulphamic acid). Present study reveals the effect of fluorescein dye on sulphamic acid single crystals that are grown by slow evaporation solution technique at room temperature. Cell Parameters and crystal structure of pure sulphamic and 0.1 mol % fluorescein dye doped crystals is confirmed by Single Crystal XRD. The crystal structure is found to be orthorhombic and space group Pbca. Slight increase is noticed in cell parameters. Vibrational bands are assigned by FTIR and Raman spectroscopy. UV–Vis spectroscopy is also studied to find out band gap energy which is found to increase from 5.13 eV to 5.2 eV due to dye doping in crystal. Decrease in cutoff wavelength confirms that the synthesized crystals are permissible material for electro-optic application.

Rigid symmetric Rhodamine fluorescent dyes as fast selective detection of aluminum and iron ions applied to cell imaging

Fluorescent probe molecules have the advantages of good selectivity, high sensitivity, and easy operation, which have attracted much attention. In this paper, a novel symmetric rhodamine fluorescent probe with structural rigidity was synthesized by a simple reaction using rhodamine 6G as raw material. And it was characterized by NMR and electrospray spray mass spectrometry. Single crystal was prepared by solvent evaporation method, which was the first single crystal of the compound reported domestically and internationally. Special spiral ring structures were observed inside the crystal. Among different competing cations, the probe exhibited high selectivity and good sensitivity towards Al3+ and Fe3+ metal ions. The limits of detection were 0.76 nM and 0.49 nM, respectively. In the presence of Al3+ and Fe3+, the solution changed from colorless to pink. At the same time, there was a significant shift in the UV-vis spectrum and fluorescence emission spectrum. The UV-vis absorption peak appeared at 530 nm, while the emission at 556 nm was turned on. In addition, biological experiments have shown that the RP probe has good membrane permeability and has the potential to detect Al3+ and Fe3+ in Hela cells.

Temperature behavior of Ce3+ emission in (Lu,Y)2SiO5 single crystals excited by vacuum ultraviolet synchrotron light

Cerium doped (Lu,Y)2SiO5 (or LYSO) single crystals have been studied by means of luminescence excitation spectroscopy in the temperature range from 7 up to 300 K. Vacuum ultraviolet excitations in 4.5–8 eV energy range from synchrotron radiation of 1.5 GeV storage ring of MAX IV synchrotron facility. It is shown that both type of Ce3+ emission centers (seven and six coordinated centers) are excited under any excitation energy used. It was concluded that the same energy transfer processes from host lattice to impurity ions are involved independently on coordination of Ce3+. It is also demonstrated that excitonic mechanism of energy transfer is dominant under chosen excitation and intrinsic and bound excitons are included in excitation of Ce3+ luminescence in LYSO.

Furan-based AIE supramolecular self-assembly system for fluorescence detection of Ag+

A novel furan-based Aggregation-Induced Emission (AIE) supramolecular self-assembling gelator (BM) was designed and synthesized, which could self-assemble into a stable supramolecular gel (OBM) in the 1,2-propanediol. OBM demonstrates “turn-off” fluorescence detection of Ag+, with excellent selectivity and a low limit of detection (LOD) of 1.168×10−8 M. The self-assembly process and ion recognition sensing mechanism of OBM were comprehensively investigated by Fourier-transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), X-ray diffraction (XRD), X-ray Photoelectron Spectroscopy (XPS), and rheological measurements. More importantly, single crystal were successfully obtained to validate the self-assembly process. This study provides a novel approach to constructing a multifunctional AIE self-assembly system.

Anisotropic quasi-static permittivity of rare-earth scandate single crystals measured by terahertz spectroscopy

We report the real-valued static and complex-valued quasi-static anisotropic permittivity parameters of rare-earth scandate orthorhombic single crystal GdScO3 (GSO), TbScO3 (TSO), and DyScO3 (DSO). Employing continuous-wave terahertz spectroscopy (0.2–1 THz), the complex permittivity was extracted using an anisotropic ambient-film-ambient model. Data obtained from multiple samples of the same oxides and different surface cuts were analyzed simultaneously. The zero-frequency limit of the modeled data indicates that at room temperature the real part of the dielectric tensor components for GSO are ɛa = 22.7, ɛb = 19.3, and ɛc = 28.1; for DSO, ɛa = 20.3, ɛb = 17.4, and ɛc = 31.1; and for TSO, ɛa = 21.6, ɛb = 18.1, and ɛc = 30.3, with a, b, and c crystallographic axes constituting the principal directions for the permittivity tensor. These results are in excellent agreement with expectations from theoretical computations and with scarcely available data from previous experimental studies. Furthermore, our results evidence a noticeable attenuation, which increases with frequency, and are very significant especially at the higher frequency end of the measurement and along the c-direction in all samples. We suggest the attenuation is most likely caused by the onset of absorption due to long-wavelength active optical phonon modes. These results are important for electronic and potential sub-terahertz applications (e.g., quarter-wave plate) benefiting from the large index contrast along different directions in these materials.

Error correction based artificial neural network in multi-modes CV-QKD with simultaneous type-I and type-II parametric-down conversion entangled photon source

We model simultaneous type-I and type-II phase matching in a single non-linear crystal (NLC), based on a double periodically poled lithium niobate crystal. We also discuss entanglement based continuous variable quantum key distribution (CV-QKD), and the security of such scheme is analyzed considering an eavesdropper being capable of individual attacks. We further demonstrate efficiency of the artificial neural network (ANN) algorithm during post-processing or errors correction in such CV-QKD protocols. Results show that employing simultaneous type-I and type-II SPDC process in single NLC is a potential source to generate high dimensional (or hyper-entangled) states, strongly required for quantum information processing tasks, an example of CV-QKD. Security analysis of such a CV-QKD protocol shows a strong advantage of employing the above entangled photon state source, given that it provides a higher secure key rate and thus a secure communication within a larger distance. In addition, the suggested error correction algorithm is less time consuming and highly efficient, since full synchronization is achieved just after a few number of updates of trusted parties’ tree-parity-machines. Our results sufficiently demonstrate that the suggested CV-QKD is able to distribute secure keys in nearby inter-city areas, and therefore allows lower-cost secure communication networks.

Square-planar nickel/copper(II) complexes of (E)-2-(((2-ethylphenyl)imino) (phenyl) methyl)phenol: Supramolecular analysis, keto-enol tautomerism, polymorphism and antibacterial activities

A new Schiff base proligand, (E)-2-(((2-ethylphenyl)imino)(phenyl)methyl)phenol (HL), was synthesized from 2-hydroxybenzophenone and 2-ethylaniline and its coordination chemistry with nickel(II) and copper(II) acetate explored. In solution, the proligand HL undergoes ketoimine -enolimine tautomerism which settles exclusively into an enolimine form in the solid-state. Interestingly, while a single crystalline habit was obtained for the nickel complex 1 (block-shaped single crystals), the copper species 2 was found to solidify in two detectable polymorphs: block-shaped crystals (2a, monoclinic space group P21/c) and rhombic crystals (2b, triclinic space group P-1). Single-crystal X-ray diffraction studies reveal that the N,O Schiff base ligand chelates the divalent metal ions with square-planar geometry in the isostructural 1 and 2a and in a distorted square-planar geometry with a dihedral chelate-plane angle of 27.9° in 2b. The copper complex 2 exhibits significant antibacterial activity against the E. coli and medium activity against S. aureus bacteria. The physical properties of the complexes were further probed using thermal techniques, while their electronic structure was investigated by electrochemistry and electronic absorption spectroscopy.

Controlled growth of 3R phase niobium diselenide and its properties

Inversion symmetry broken 3R phase transition metal dichalcogenides (TMDs) show fascinating prospects in spintronics, valleytronics, and nonlinear optics. However, the controlled synthesis of 3R phase TMDs is still a great challenge. In this work, two-dimensional 3R-NbSe2 single crystals up to 0.2 mm were synthesized for the first time through chemical vapor deposition method by designing a space-confined system. The crystal size and morphology can be controlled by the location of the stacked substrates and the amount of the Nb2O5 precursor. Scanning transmission electron microscopy and Raman measurements reveal the NbSe2 exhibits a pure 3R stacking mode with relatively weak interlayer van der Waals interactions. Importantly, 3R-NbSe2 shows obvious second harmonic generation signal which intensity intensified as thickness increases. Density functional theory calculations and optical absorption demonstrate the coexistence of metallic and semiconducting optical properties of 3R-NbSe2. We designed a NbSe2/WS2/NbSe2 photodetector utilizing the metallicity of 3R-NbSe2, which shows good performance especially an ultrafast response (6–7 μs, 0.5 ms–7.9 s for Au electrodes in literature). The proposed strategy and findings are of great significance for the growth of many other 3R-TMDs and applications of nonlinear optical and ultrafast devices.

Understanding dislocation plasticity of single crystalline Ta micropillars under dynamic loading

Recent experimental findings have shown that tantalum single crystals display strong anisotropy during Taylor impact testing in stark contrast to isotropic deformation in polycrystalline counterparts. In this study, a coupled dislocation dynamics and finite element model was developed to simulate the complex stress field under dynamic loading of a Taylor impact test and track the intricate evolution of the dislocation microstructure. Our model allowed us to investigate detailed motion of dislocations and their mutual interactions and the effect of varying simulation parameters, such as sample size, initial dislocation density, crystallographic orientation, and temperature. Simulation results show good agreement with experimental observations and shed light on the mechanical response at small-scale under extreme loading conditions. In addition, resolved shear stress analysis incorporating the effect of shear stress from impact was performed to quantitatively support and provide a means to understand the model predictions of the impact foot shape.

Enhancement of alpha/beta ratio in NaI:Tl,6Li neutron-gamma scintillators by rare earth co-doping

NaI:Tl,6Li bulk crystals are regarded as promising neutron-gamma (n-γ) scintillators because of low production cost and superior n-γ pulse shape discrimination (PSD) performance. In this work, some rare earth elements (Gd, Y, Lu and Sc) co-doped NaI:Tl,6Li single crystals were grown by the multi-ampoule Bridgman method. It was found that the rare earth co-doping significantly improves the pulse height discrimination (PHD) capability of NaI:Tl,6Li with high alpha/beta (α/β) ratio, approaching to 100%. The optimal α/β ratios achieved for Gd, Y, Lu and Sc co-doped NaI:Tl,6Li are 0.85, 0.93, 0.95, and 0.83, respectively. Electron equivalent energy per neutron interaction is above 3.96 MeV and can be as high as 4.54 MeV, close to the Q value of 4.78 MeV for 6Li(n, α)3H interaction. Moreover, the rare earth co-doped NaI:Tl,6Li crystals still maintain the superior PSD capability with figure of merit (FoM) in the range of 2.1-3.3. These results highlight the great potential of rare-earth co-doped NaI:Tl,6Li crystals serving as high-performance n-γ scintillators.

Optofluidic crystallithography for directed growth of single-crystalline halide perovskites

Crystallization is a fundamental phenomenon which describes how the atomic building blocks such as atoms and molecules are arranged into ordered or quasi-ordered structure and form solid-state materials. While numerous studies have focused on the nucleation behavior, the precise and spatiotemporal control of growth kinetics, which dictates the defect density, the micromorphology, as well as the properties of the grown materials, remains elusive so far. Herein, we propose an optical strategy, termed optofluidic crystallithography (OCL), to solve this fundamental problem. Taking halide perovskites as an example, we use a laser beam to manipulate the molecular motion in the native precursor environment and create inhomogeneous spatial distribution of the molecular species. Harnessing the coordinated effect of laser-controlled local supersaturation and interfacial energy, we precisely steer the ionic reaction at the growth interface and directly print arbitrary single crystals of halide perovskites of high surface quality, crystallinity, and uniformity at a high printing speed of 102 μm s−1. The OCL technique can be potentially extended to the fabrication of single-crystal structures beyond halide perovskites, once crystallization can be triggered under the laser-directed local supersaturation.

Dual purpose of divalent metal ions (Cu2+, Zn2+, and Mg2+) doped 4-nitrophenyl hydrazone single crystals: a second order and third order NLO applications

Dual purpose of divalent metal ions (Cu2+, Zn2+, and Mg2+) doped 4-nitrophenyl hydrazone single crystals: a second order and third order NLO applications

Spectroscopic studies of Eu doped CaF2 single crystal

The Eu-doped CaF2 crystal is investigated for potential use in visible-region solid-state lasers. The single-crystal Eu: CaF2 has an FCC crystal structure and belongs to the space group Fm-3 m, as confirmed by single-crystal X-ray diffraction. A Raman shift of 324 cm−1 has been observed in a single crystal of Eu: CaF2. The vibrational mode at low frequency is suitable for minimizing non-radiative emissions and increasing radiative emissions. Eu: CaF2 crystal has two absorption bands, at 399 nm and 415 nm, corresponding to the 7F0→5L6 and 7F0→5D3 transitions, respectively. The strongest absorption peak (399 nm) is associated with the 7F0→5L6 electronic transition. The orange-red emission was observed at 588 nm (5D0→7F1), 612 nm (5D0→7F2), 648 (5D0→7F3), and 685(5D0→7F4) when excited at 399 nm. Measurements of the luminescence intensity ratio (R) between the 5D0→7F2 (electric dipole) transition and the 5D0→7F1 (magnetic dipole) transition predict that Eu3+ ions are situated at the symmetric sites in CaF2. The radiative parameters for the Eu: CaF2 crystal are calculated using the JOES code using the Judd-Ofelt theory. The calculated total radiative transition probability (AR) is 64.54 s−1, and the radiative lifetime (τR) is 15.57 ms. Radiative transition probabilities are 43.41,7.02 and 14.10, and branching ratios are 67.26 %,10.88 % and 21.85 % for 5D0→7F1, 5D0→7F25D0→7F4 transitions respectively.

Preparation, crystal structure and physicochemical characterization of a semi-organic l-glutamic acid lithium chloride single crystal for nonlinear optical applications

Preparation, crystal structure and physicochemical characterization of a semi-organic l-glutamic acid lithium chloride single crystal for nonlinear optical applications

Rapid microcantilever preparation for conditional fracture toughness evaluation

The Ga+ focused Ion Beam (FIB) or Xe+ Plasma FIB (PFIB) procedure has enabled the ability to make specimens where mechanical tests in the microscale regime can be achieved with high precision. Nevertheless, milling times can be long, and shape optimization can be arduous, limiting the ability to readily make a sufficient number of test samples. In this work, we present a sample preparation technique for microscale cantilever fabrication which streamlines the milling procedures by using combined electropolishing and FIB milling. Specifically, the procedure mitigates extensive undercutting requirements which reduces the fabrication time for the microcantilever to more than half that time as compared to direct milling methods from making similar geometries directly from the bulk material. This process is discussed along with specific aspects related to the sample alignment of the cantilever to specific fracture planes for single crystals. Furthermore, we comment on the applicability of this method to polycrystalline samples.

Vacancy modulation dramatically enhance thermoelectric performance of InTe single crystal

InTe single crystals have demonstrated great promise in the field of thermoelectric materials, particularly when oriented along the [110] direction. This specific crystal orientation exhibits higher electronic conductivity and lower thermal conductivity compared to other orientations of InTe. Through first-principles calculations, we identified the anisotropic valence band and phonon dispersion as the underlying factors. Moreover, reducing the density of In+ vacancies in InTe was found to lower the band effective mass and modulate carrier scattering, enhancing the material quality factor (B). To explore these findings, we systematically grew InTe single crystals, achieving exceptional thermoelectric performance. A record-breaking power factor of 12.0 μW·cm–1·K–2 and a dimensionless figure of merit (zT) of 0.5 at room temperature were obtained. Notably, InTe crystals oriented along [110] with low In+ vacancy density exhibited the highest average zT of 0.63 among InTe-based thermoelectric materials within the 300–473K temperature range. Furthermore, we introduced an effective method of reducing In+ vacancies through Indium vapor annealing, resulting in the highest reported carrier mobility of 182 cm2·V–1·s–1 for InTe. Our study highlights the potential for improving InTe's thermoelectric performance near room temperature through vacancy modulation and crystal orientation.