Photoluminescence Spectroscopy Research Articles

Reversible Interconversion between Ag2 and Ag6 Clusters and Their Responsive Optical Properties.

The exploration of structural interconversion in clusters triggered by external stimuli has attracted significant interest due to its potential to elucidate structure-property relationships of metal clusters. In this study, two types of silver clusters, Ag2 and Ag6, are synthesized. Interestingly, the clusters exhibit reversible transformations in response to changes in the solvent conditions. The structures and optical properties of these clusters are thoroughly characterized using techniques such as mass spectrometry, single-crystal X-ray diffraction, photoluminescence, and radioluminescence spectroscopy. While both Ag2 and Ag6 display excellent photoluminescence properties, Ag2 demonstrates superior performance in X-ray radioluminescence compared to Ag6. Flexible scintillator films fabricated from Ag2 clusters exhibit outstanding X-ray imaging capabilities, achieving a spatial resolution of 15.0 lp/mm and an impressive detection limit for an X-ray dose of 0.58 μGy s-1. This detection limit is nearly 10 times lower than the typical dose rate used in X-ray diagnostics (5.5 μGy s-1). This work introduces a novel approach for designing thiol-free silver clusters capable of solvent-dependent reversible interconversion, offering new insights into the development of silver clusters for advanced X-ray imaging applications.

Unusually high oxidation states of manganese in high optical basicity silicate glasses

Unusually high oxidation states of manganese were stabilized within a cesium-barium silicate (CBS) glass system of extremely high optical basicity. The highest basicity was obtained for the metasilicate glass 40Cs2O–10BaO–50SiO2 (mol%) with an optical basicity of Λ = 0.81. The presence of Mn5+ (d2) as well as Mn6+ (d1) is confirmed by UV–Vis, photoluminescence, and Raman spectroscopy. The UV–Vis spectrum is dominated by the Mn3+ (d4) absorption at 526 nm for low-basicity glasses, which is replaced by a peak at 679 nm (Mn5+) and, finally, a band at 603 nm (Mn6+) in the glass with the highest basicity (Λ = 0.81). In this glass, the Mn5+/Mn6+ ratio varies with the melting conditions. Photoluminescence (PL) spectroscopy under 633 nm excitation confirms the presence of Mn5+, showing the narrow, forbidden 1E →3A2 transition located at 1191 nm with vibrational sidebands at 1245 nm and 1290 nm. The measured static fluorescence intensity due to Mn5+ grows exponentially with increasing optical basicity. The near infrared fluorescence decay was bi-exponential, with time constants of 14 and 51 μs. The absence of Mn4+ in CBS glasses was confirmed by PL and electron paramagnetic resonance (EPR) spectroscopy. Despite initial doping as MnO2, metastable Mn4+ disproportionates into lower and higher valent manganese species, followed by reduction or oxidation of manganese to a stable species as ruled by the basicity of the glass and oxygen availability during melting. A structural study of the glasses by Raman spectroscopy revealed a resonance enhancement effect for the symmetric stretching mode of MnO4-tetrahedra at ∼800 cm−1 with overtones observed at higher frequencies.

Dielectric behavior and defects of nitrogen-containing single crystal diamond films

Single crystal diamond (SCD) film, as a new substrate material, has attracted growing attention because of its low dielectric loss. The nitrogen was usually introduced into microwave plasma chemical vapor deposition (MPCVD) process in order to enhance the growth rate of SCD films. So SCD films with nitrogen were prepared by MPCVD compared with the undoped film. The impurities and defects of diamond films were characterized by Raman spectroscopy, Fourier transform infrared spectroscopy (FTIR) and photoluminescence spectroscopy (PL). The dielectric behavior of SCD films was measured using the LCR measurement in the frequency range of 1 kHz to 110 MHz. The results indicate that the primary dielectric loss in SCD films is conductivity loss and space charge polarization below 1 MHz, while the main dielectric loss is dipole orientation polarization and electronic relaxation polarization in the frequency range of 1 MHz to 110 MHz. Point defects like substitutional N+, NV− and SiV− exert a significant influence on polarization loss. This is essential to improve the growth of SCD with excellent dielectric properties.

The influence of precursor solutions containing an amount of silver bismuth sulfide nanoparticles (AgBiS2 NPs) on the characteristics of CH3NH3PbI3 perovskites solar cells

The utilization of organo-metal halide perovskites as absorbers in thin-film solar cells has garnered considerable interest from the scientific community in recent times. In this study, we present the introduction of silver bismuth sulfide nanoparticles (AgBiS2 NPs) doped into perovskite thin films composed of CH3NH3PbI3 thin film. Our results demonstrate that the perovskites' morphology and structure were significantly improved. The effects of AgBiS2 NPs concentration on the optical, mechanical, and crystallographic properties of CH3NH3PbI3 perovskite thin films were investigated. The findings from the structure investigations revealed that an increase in the concentration of AgBiS2 NPs resulted in a transition from a low-crystalline to a polycrystalline structure of the perovskite thin films. An elevation in the concentration of AgBiS2 NPs from 2 to 8 mg/mL led to the development of perovskite films of superior quality, consisting entirely of PbI3 and CH3NH3. These films exhibited almost impeccable deposition, compactness, and uniformity, and their particle size reached an approximate value of 1.3 μm. Furthermore, an increase in the optical absorption coefficient (∼105 cm−1) in the visible spectrum and subsequent enhancements in photoluminescence (PL) and ultraviolet–visible (UV–Vis) absorption spectroscopy serve as further evidence of the film's enhanced quality. When AgBiS2 NPs are doped into perovskites, the films' quality is significantly improved; they acquire a uniform surface morphology, an exceptional crystal structure, and enhanced light absorption, all of which contribute to accelerated PL quenching and charge transfer. Power conversion efficiency (PCE) was enhanced across all photovoltaic parameters through the use of larger granules in bulk-heterojunction solar cells, as opposed to undoped heterojunction solar cells. The PCE of the perovskite device with CH3NH3PbI3 base is 17.04 % at the optimal concentration of 6 mg/mL AgBiS2 NPs. These findings indicate that the doping of CH3NH3PbI3 perovskite thin films with AgBiS2 NPs is essential for the achievement of high crystallinity, a large particle size, and a high absorption coefficient. These properties are advantageous for the high-power conversion efficiency of solar cell applications.

Arsenic-doped HgCdTe: FTIR photoluminescence and photoreflectance spectroscopy study

Photoluminescence (PL) and photoreflectance (PR) spectroscopy were used for the optical study of arsenic doping of HgCdTe grown by molecular beam epitaxy (MBE). Un-doped and arsenic-doped material with cadmium telluride molar fraction x = 0.29 grown under similar conditions and subjected to similar types of annealing was studied. The PL spectra of the un-doped material featured signatures of intrinsic defects associated with mercury vacancy, excessive tellurium, and related complexes. In the arsenic-doped material, optical signatures of these defects appeared to be suppressed. After arsenic activation, shallow (7–8 meV) acceptor levels were found in the material. These were attributed to the dopant activation, which was confirmed with electrical studies showing p-type conductivity with hole concentration ∼1016 cm−3. The studies showed that the actual pattern of arsenic doping in HgCdTe can be indeed screened by intrinsic defects, which are inherent to MBE-grown HgCdTe and tend to interact with the dopant.

Synthesis, characterization, and in-vitro bioimaging applications of green emissive AgInS2-based core multi and alloyed shell (AgInS2/CdS/ZnS and AgInS2/ZnS/CdS) nanocrystals

This study explores the synthesis, characterization, and preliminary bioimaging applications of green-emissive AgInS2-based nanocrystals (NCs) featuring core-multi and alloyed shell structures, specifically AgInS2/CdS/ZnS and AgInS2/ZnS/CdS. The nanocrystals were synthesized using a controlled hot-injection method, which ensured the formation of uniform core–shell structures. Detailed characterization through X-ray diffraction (XRD), transmission electron microscopy (TEM), and photoluminescence spectroscopy confirmed the successful development of these core-multi and alloyed shell architectures. The photoluminescence quantum yields (QY) were determined to be approximately 25 % for AgInS2/CdS/ZnS and 30 % for AgInS2/ZnS/CdS, highlighting their efficient luminescent properties. In preliminary bioimaging studies, these nanocrystals exhibited effective cellular imaging capabilities. They showed pronounced fluorescence with minimal background interference in A549 and U87MG cells, suggesting their potential for precise and targeted imaging applications. Despite these promising results, further investigation is needed to fully understand the specificity of these nanocrystals and their interaction mechanisms with various cell types. The observed quantum yields and targeted imaging capabilities indicate that AgInS2-based nanocrystals are promising candidates for advanced bioimaging technologies.

CuIn (Se,Te)2 Absorbers With Bandgaps <1 eV for Bottom Cells in Tandem Applications

ABSTRACTThin‐film solar cells reach high efficiencies and have a low carbon footprint in production. Tandem solar cells have the potential to significantly increase the efficiency of this technology, where the bottom‐cell is generally composed of a Cu(In,Ga)Se2 absorber layer with bandgaps around 1 eV or higher. Here, we investigate CuIn(Se1 − xTex)2 absorber layers and solar cells with bandgaps below 1 eV, which will bring the benefit of an additional degree of freedom for designing current‐matched two‐terminal tandem devices. We report that CuIn(Se1 − xTex)2 thin films can be grown single phase by co‐evaporation and that the bandgap can be reduced to the optimum range (0.92–0.95 eV) for a bottom cell. From photoluminescence spectroscopy, it is found that no additional non‐radiative losses are introduced to the absorber when adding Te. However, losses occur in the final solar cell due to non‐optimized interfaces. Nevertheless, a device with 9% power conversion efficiency is demonstrated with a bandgap of 0.97 eV and , the highest efficiency so far for chalcopyrites with band gap <1 eV. Interface recombination is identified as a major recombination channel for larger Te contents. Thus, further efficiency improvements can be expected with improved absorber/buffer interfaces.

Ternary ZnS/ZnO/Graphitic Carbon Nitride Heterojunction for Photocatalytic Hydrogen Production.

Ternary ZnS/ZnO/graphitic carbon nitride (gCN) photocatalysts were prepared by coupling gCN sheets with ZnO nanorods under solvothermal conditions followed by sulfurization using Na2S. SEM and TEM analyses show that small-sized ZnS particles (ca. 7.2 nm) deposit homogeneously on the surface of ZnO/gCN nanohybrids. Photoluminescence and electrochemical impedance spectroscopy show that ZnS allows for an enhanced charge separation efficiency as well as prolonged lifetime of photogenerated charge carriers, leading to improved hydrogen photoproduction under UV light irradiation compared to ZnO/gCN. Moreover, the deposition of ZnS nanoparticles improves the photostability of the ZnS/ZnO/gCN catalyst for hydrogen production. A double Z-scheme mechanism is proposed for hydrogen photoproduction using the ZnS/ZnO/gCN heterojunction.

Fabrication of silicon carbide color center nanoparticles by femtosecond laser ablation in liquid

Combined with the fabrication of low-dimensional materials, certain silicon carbide color centers can become excellent platforms for nano-optics, and be applied to quantum and biomedical fields. In this work, color center nanoparticles were prepared based on high purity semi-insulating silicon carbide substrate using liquid-assisted femtosecond laser machining. Effects of multi-pulse array ablation and line scanning fabrication were investigated, and parameters such as repetition frequency and pulse number were also optimized. We employed photoluminescence spectroscopy, field emission scanning electron microscopy and transient fluorescence spectroscopy to characterize optical properties and micromorphology of nanoparticles. The broadband photoluminescence within the range of 850–950 nm should be attributed to silicon vacancy color centers, and V1/V1’ zero-phonon lines were confirmed at low temperature. It is noted that the femtosecond laser annealing is critical for the luminescence enhancement of color center nanoparticles. The evolution of particles and cavitation bubbles during processing was elucidated. After optimization, silicon vacancy color center nanoparticles were prepared by multi-pulse (107) array ablation and 200 kHz pulse repetition frequency, with an average diameter of approximately 15 nm and an average density reaching 273.94 counts/μm2. The sample can be preserved stably in the form of nanoparticle solutions. Processing methods and corresponding conclusions of this study would be applicable to the femtosecond laser fabrication and micromorphology control of color center nanoparticles of various hard-brittle semiconductors.

Novel Eu3+-Doped Glasses in the MoO3-WO3-La2O3-B2O3 System: Preparation, Structure and Photoluminescent Properties.

Novel multicomponent glasses with nominal compositions of (50-x)MoO3:xWO3:25La2O3:25B2O3, x = 0, 10, 20, 30, 40, 50 mol% doped with 3 mol % Eu2O3 were prepared using a conventional melt-quenching method. Their structure, thermal behavior and luminescent properties were investigated by Raman spectroscopy, differential thermal analysis and photoluminescence spectroscopy. The optical properties of the glasses were investigated by UV-vis absorption spectroscopy and a determination of the refractive index. Physical parameters such as density, molar volume, oxygen molar volume and oxygen packing density were determined. The glasses are characterized by a high glass transition temperature. Raman analysis revealed that the glass structure is built up mainly from tetrahedral (MoO4)2- and (WO4)2- units providing Raman bands of around 317 cm-1, 341-352 cm-1, 832-820 cm-1 and 928-935 cm-1. At the same time, with the replacement of MoO3 with WO3 some fraction of WO6 octahedra are produced, the number of which increases with the increasing WO3 content. A strong red emission from the 5D0 level of Eu3+ ions was registered under near-UV (397 nm) excitation using the 7F0 → 5L6 transition of Eu3+. Photoluminescence (PL) emission gradually increases with increasing WO3 content, evidencing that WO3 is a more appropriate component than MoO3. The integrated fluorescence intensity ratio R (5D0 → 7F2/5D0 → 7F1) was calculated to estimate the degree of asymmetry around the active ion, suggesting a location of Eu3+ in non-centrosymmetric sites. All findings suggest that the investigated glasses are potential candidates for red light-emitting phosphors.

Effects of acoustic shock waves on the structural and optical properties of cadmium borate

Cadmium borate (CdB₂O₄), an inorganic compound combining transition metals and non-metals, has a broad range of optical applications. In this study, CdB₂O₄ was subjected to acoustic transient pressure using a semi-automatic Reddy tube, with shock pulses applied at counts of 100, 200, 300, and 400 at a Mach number of 1.5, corresponding to a transient pressure of 0.59 MPa and a temperature of 520 K. Control and shock-treated samples were analyzed using XRD, Raman, FTIR, SEM, UV-DRS, and photoluminescence spectroscopy to investigate shock wave effects. The XRD analysis revealed peak disappearance, the formation of new peaks, increased crystallinity, and instability in crystallite size. Raman spectroscopy showed peak disappearance, shifts, and broadening of lattice modes. SEM indicated increased particle size and agglomeration under shock conditions, consistent with changes in crystallinity. UV-DRS analysis shows a slight change in their band gap. Photoluminescence exhibited fluctuating trends in luminescent properties after the shock treatment. The findings reveal that CdB₂O₄'s structural and optical properties are sensitive to acoustic pressure, suggesting its potential for tailored optical behavior in specific applications. These results enhance our understanding of how acoustic pressure affects CdB₂O₄ and open new possibilities for optimizing its use in high-pressure applications.

Synergy of the heterojunction and defects engineering in Zr-doped TbFeO3@g-C3N4 photo-nanocatalyst towards enhanced visible-light-driven antibiotics degradation and H2 production

Environmental remediation and energy production are major concerns of the globe for sustainable development. Solar-driven photo nanocatalysts have shown great potential to be a suitable contender to solve these issues, however, their catalytic efficiency is the major concern which depends on the e−/h+ pair separation. The present study developed TbFe0.95Zr0.05O3/g-C3N4 heterostructure employing facile hydrothermal methods to promote e−/h+ pair separation. Though, TbFe0.95Zr0.05O3/g-C3N4 achieved the highest photo-degradation of 95.96 % for Norfloxacin (NOR) in 90 min, and 4864 μmol h−1g−1 of H2 evolution in 4 h under simulated visible-light, with 3.3, 2.8 and 2.1 times higher efficiency than pristine and doped catalysts (TbFeO3, g-C3N4 and TbFe0.95Zr0.05O3). The creation of oxygen vacancies (OVs) by Zr4+ doping at Fe3+ sites through charge compensation may increase catalytic efficiency, confirmed through X-ray photoelectron spectroscopy (XPS), and optical properties through Raman, and photoluminescence spectroscopy (PL). The catalyst works well throughout four cycles (85.19 % for NOR in the 4th cycle), demonstrating its chemical stability and cyclic potential. Thus, heterojunction and OVs synergistically enhance catalytic efficiency with higher activation in the visible solar spectrum and long e−/h+ charge separation lifetime.

Tailoring sub-5 nm Fe-doped CeO2 nanocrystals within confined spaces to boost photocatalytic hydrogen evolution under visible light

This work aimed to study the efficiency of the reverse micelle (RM) preparation route in the syntheses of sub-5 nm Fe-doped CeO2 nanocrystals for boosting the visible-light-driven photocatalytic hydrogen production from methanol aqueous solutions. The effectiveness of confining precipitation reactions within micellar cages was evaluated through extensive physicochemical characterization. In particular, the nominal composition (0–5 mol% Fe) was preserved as ascertained by ICP-MS analysis, and the absence of separate iron-containing crystalline phases was supported by X-ray diffraction. The effective aliovalent doping and modulation of the optical properties were investigated using UV-Vis, Raman, and photoluminescence spectroscopies. 2.5 mol% iron was found to be an optimal content to achieve a significant decrease in the band gap, enhance the concentration of oxygen vacancy defects, and increase the charge carrier lifetime. The photocatalytic activity of Fe-doped CeO2 prepared at different Fe contents with RM preparation was studied and compared with undoped CeO2. The optimal iron load was identified to be 2.5 mol%, achieving the highest hydrogen production (7566 μmol L−1 after 240 min under visible light). Moreover, for comparison, the conventional precipitation (P) method was adopted to prepare iron containing CeO2 at the optimal content (2.5 mol% Fe). The Fe-doped CeO2 catalyst prepared by RM showed a significantly higher hydrogen production than that obtained with the sample prepared by the P method. The optimal Fe-doped CeO2, prepared by the RM method, was stable for six reuse cycles. Moreover, the role of water in the mechanism of photocatalytic hydrogen evolution under visible light was studied through the test in the presence of D2O. The obtained results evidenced that hydrogen was produced from the reduction of H+ by the electrons promoted in the conduction band, while methanol was preferentially oxidized by the photogenerated positive holes.

A novel barium zirconate titanate/Fe-MOF nanocomposite: Synthesis, characterization, and photocatalytic mechanism

The synthesis of a metal-organic framework (MOF) matrix of MIL-100 (Fe) loaded with BaTi0.85Zr0.15O3 (BTZ) nanoparticles (NPs) was achieved by an easy one-pot solvothermal procedure and encasing of BTZ NPs. X-ray diffraction (XRD), photoluminescence spectroscopy (PL), UV-Vis reflectance spectroscopy (DRS), Transmission electron microscopy (TEM), scanning electron microscopy (SEM), and N2 adsorption-desorption were deployed for the characterization of the synthesized samples. The degradation efficiency for tetracycline (TC), among the photocatalytic BTZ/MIL-100(Fe) nanocomposites with varied BTZ percentages (10, 20, 30, and 40 wt% BTZ), revealed that (30 wt%), offered the best outcome. At 0.8 g L-1 of the catalyst, pH 9, 30 ppm TC solution, and 180 min irradiation time, as the optimal conditions, the degradation efficiency of TC molecules reached >90. Based on the study of some scavenging agents, the importance of the reactive species in TC photodegradation followed the trend of photogenerated e-, hydroxyl radicals, superoxide radicals, and photogenerated h+. TC degradation occurred through reduction and oxidation pathways via a direct Z-scheme mechanism. This work aims to describe the use of MOF-based materials as a visible-light-driven photocatalyst towards TC.

Dynamics of charged and neutral silicon-vacancy color centers in electron-irradiated 28Si-doped single crystal chemical vapor deposition diamond upon annealing: Optical spectroscopy study

Diamond synthesis with silicon-vacancy (SiV) color centers is of high interest to nanophotonics and optical quantum technologies. The methods to control and/or maximize concentration of Si atoms incorporated in diamond lattice, and coupled to vacancies, together with improving crystallinity of diamond structure, are in demand. Here, we studied the effect of heat treatment of electron-irradiated single crystal CVD diamond doped with 28S isotope, on evolution of the neutral SiV0 and negatively charged SiV− centers. The crystal subjected to stepwise annealing at temperatures Tann from 200 °C to 1640 °C has been analyzed with photoluminescence (PL) and optical absorption spectroscopies at room and low-temperature (T = 5 K). We found a complex non-monotonous behavior of SiV0 and SiV− intensity both in absorption and PL, with sharp rise at Tann > 600 °C, reaching a maximum concentration peak, decline at 850 °C, and a repeated elevation to higher Tann, reflecting creation and annihilation processes of these defects. Moreover, we detected a group of seven lines of a Si-related defect in the range 828–871 nm, which strongly correlate with annealing dynamics of the SiV− and, especially, of SiV0 centers, and estimated the isotope spectral shift. In parallel, dynamics of other optical centers such as NV, R11 and GR1, in course of the annealing is traced. The controlled annealing opens the way to preparation of the SiV color centers with optimized optical properties, promising for quantum technologies.

Photoluminescent carbon colloids prepared by laser fragmentation of carbon from waste coffee grounds

Colloidal suspensions of carbon nanostructures (CNSs) were prepared by laser fragmentation in various liquid media using heat-treated coffee grounds as carbon precursor. A study by calorimetry was done in powder of waste coffee grounds to determine the temperature of obtaining carbon. The experiments were carried out in two stages, the first one consisted in obtaining the carbon source, for which powder of waste coffee grounds was thermally treated in air. The as-obtained carbon was characterized by scanning electron microscopy, energy dispersive X-ray spectroscopy, Raman spectroscopy and infrared spectroscopy. In the second step the as-obtained carbon was separately dispersed in four liquid media (acetone, toluene, methanol and isopropyl alcohol) to be fragmented by using a ns-pulsed Nd:YAG laser at its 1064 nm fundamental emission. The morphological features of the carbon nanostructures were obtained by transmission electron microscopy, while the optical properties of the colloidal suspensions were characterized by UV-Vis and photoluminescence spectroscopies. Results indicate that carbon nanostructures are successfully obtained in the four liquid media after the fragmentation process. The four colloidal suspensions show photoluminescent properties, which are seen to depend on the liquid medium nature. We found that the liquid medium also influences the efficiency of the laser fragmentation.

Mongrel synthesis of tin (IV) based 3-aminopyridine with hydrogen halides: Structural, optical, thermal analysis, DFT, Hirshfeld surface analysis and antibacterial investigations

The novel organic-inorganic hybrid materials (C5H7N4)2 [SnCl6] 2- (1) and (C5H7N4)2 [SnBr6]2-(2) have been synthesized and characterized by single-crystal X-ray diffraction at room temperature. Both compounds demonstrate the crystal system was triclinic with Pī space group. Hirshfeld surface analysis investigate the intermolecular interactions and crystal packing derived by single-crystal XRD data reveals the closer contacts associated with strong interactions. Infrared spectrum of both compounds shows the NH stretching band at 3396 cm−1 which indicates a protonated amine group. The product crystals optical characteristics were inspected using UV–visible and photoluminescence spectroscopy. The thermal characteristics were evaluated simultaneously using thermogravimetric (TG) and differential thermal analysis. Tin formal oxidation state was determined as +4 through bond valence sum calculations and CSM shows the ideal octahedral geometry of the anions. DFT calculations utilizing the B3LYP method with the LanL2DZ basis set provide optimized geometries and molecular electrostatic potential maps. We explored the energy difference between (HOMO) and (LUMO) orbitals to understand molecular electrical transport capabilities. The biological activity of the investigated compounds are examined against pathogens which indicates efficacy against bacterial strains.

Optimizing excited state adsorption and carrier dynamics of metal doped zinc oxide by p-d orbital modulation for efficient reverse saturation absorption

Doping metals can regulate the excited state adsorption and carrier transport efficiency of ZnO through p-d orbital coupling thereby improving its nonlinear performance. Herein, the thin film coatings consisting of ZnO, and M-ZnO (M=Al, Sn, Mg) were synthesized using the magnetron sputtering technique. ZnO exhibited the granular/stick structure, while the metal dopant atoms (M) were incorporated into the ZnO lattice, resulting in a homogeneous distribution. Photoluminescence spectroscopy reveals the quenched defect emission intensity, indicating a decrease in the rate of photo-induced electron-hole pair complexation. Mg exhibits an optimized effect to promote the saturation absorption of ZnO, resulting in the enhancement of the nonlinear absorption (NLA) coefficients for M-ZnO films. Al-ZnO and Sn-ZnO films exhibit reverse saturation absorption. Theoretical simulation shows that the additions of transition metal atoms favor the electron transfer through p-d orbital modulation of ZnO. The p-d hybridization causes the metal-d orbitals to cross the Fermi level and form an electron transport channel, thereby enhancing the excited state absorption, and effectively controlling the NLA process and mechanism. The excited state absorption of the M-ZnO films significantly rises. This research demonstrates that the optimization of excited state absorption through p-d orbital modulation is a highly effective strategy for the development of efficient and superior nonlinear optical absorbers.

Probing the role of hydrogen bond donors on the speciation and electrochemical behavior of Eu(III) in choline chloride-based DESs

This study explores the electrochemical properties and speciation of Eu(III) ions in choline chloride (ChCl)-based deep eutectic solvents (DESs), focusing on how different hydrogen bond donors—urea (U), ethylene glycol (EG), and malonic acid (MA)—influence the stability of europium complexes. Employing electrochemical methods, spectroscopic analysis, and theoretical approaches, the research examines how changes in hydrogen bonding during complexation affect Eu(III) coordination. Cyclic voltammetry highlights the role of complex formation and DES viscosity in controlling mass transport and electron transfer rates. Theoretical and experimental data show that the ChCl:1MA DES forms the most stable europium complex, driven by strong hydrogen bonding and robust Eu-DES interactions, as supported by optimized geometries and favorable electrochemical stability. This stability is further confirmed by the high negative binding and formation free energies of Eu(NO3)3·5H2O in all three DES systems. Photoluminescence spectroscopy reveals fluorophore formation due to interactions between hydrogen bonds and functional groups such as –NH2, –COOH, and –OH, enhancing the understanding of Eu3+-DES complexes for potential applications in materials science. By clarifying how hydrogen bond donors affect Eu(III) speciation and reactivity, this research advances lanthanide chemistry in DESs and opens avenues for designing Eu(III)-based materials with specialized properties for various technological uses.

Luminescent color modulation of Zn/BaAl2O4:0.2%Eu phosphors for LED application

Spinel-type aluminate (ZnAl2O4) doped with europium (Eu) ions has garnered considerable attention in the field of luminescence. This study explores a series of Zn/BaAl2O4:0.2%Eu phosphors (x = 0∼0.25, x is for the mole fraction of BaAl2O4), fabricated through a high temperature solid-phase reaction method in air or reduction environment. In the case of phosphors synthesized in air, the photoluminescence emission (PL) spectra show a series of sharp emission peaks at 570 nm, 589 nm, 620 nm, 660 nm, and 710 nm, which are generated by the 5D0-7FJ (J = 0, 1, 2, 3, 4) level transitions in Eu3+. Time-resolved photoluminescence and X-ray photoelectron spectroscopy (XPS) characteristics also validate the presence of Eu3+ in samples synthesized in air. An intriguing observation is the abnormally strong emission peak at 570 nm under 346 nm excitation, originating from the Eu3+5D0-7F0 level transition. For x = 0.15, the corresponding CIE color coordinate is (0.3246, 0.3449), suggesting its potential application as a mono-doped and uni-matrix white phosphor. On the other hand, phosphors synthesized in reduction environment exhibit PL spectra with a wide emission band spanning from 400 nm to 550 nm, resulting from the electric-dipole-allowed transition of f-d state of Eu2+. The partial substitution of Zn2+ with Ba2+ significantly enhances the Eu2+ luminescence intensity. Moreover, an elevation of the mole fraction of Zn/BaAl2O4:0.2%Eu leads to a notable redshift (450 nm→500 nm) in the emission peaks of Eu2+ caused by lattice expansion, providing the adjustability of emitting color.