Investigation of red-emitting CaMoO4: Eu3+ phosphor by partitioning of substitutional PO4 3- ions via solid-state reaction method.

To investigate the impact of PO4 3- anionic groups, the trivalent europium ion-doped calcium molybdate (CaMoO3-PO4:xEu3+, where x = 0.5, 1.0, 1.5, 2.0, and 2.5 mol%) phosphors were synthesized using the solid-state reaction method. The detailed study of the phosphor materials was carried out by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), Fourier transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS), optical diffuse reflectance spectroscopy (DRS), and photoluminescence (PL) spectroscopy. The XRD results indicate that the substitution of PO4 3- anion and Eu3+ dopant ion did not affect the crystal structures of the CaMoO4 phosphors. Ultraviolet-visible (UV-vis) absorption analysis revealed the change of absorption edge of both un-doped and Eu3+-doped CaMoO4-PO4 phosphors. Under the 394 nm UV-excitation, the recorded PL spectra showed an intense peak at 615 nm corresponding to the Eu3+: 5D0 → 7F2 transition. The results of the Commission Internationale de l'Eclairage (CIE) diagram reported that the color of the emissions lies in the red color zone and there is no change in the CIE coordinates of the overall emission for Eu3+-doped CaMoO4-PO4 as Eu concentration changes. Thus, these observations led to finding the best red components for white light-emitting diode applications.

Phase Separation of Br-Doped CsPbI3: A Combined Cluster Expansion, Monte Carlo, and DFT Study.

Cluster expansion, which is a method that describes the concentration-dependent thermodynamic properties of materials while maintaining density functional theory accuracy, was used to predict new (CsPbIxBr1-x) structures. The cluster-expansion method generated 42 new stable (CsPb)xIyBrz (where x = 1 to 3 and y and z = 1 to 8) structures and these were ranked as meta-stable structures based on their enthalpies of formation. Monte Carlo calculations showed that CsPbI0.5Br0.5 composition separates into different phases at 300 K, but changes to a homogeneous phase at 700 K, suggesting that a different phase of CsPbI3 may exist at higher temperatures. Among the 42 predicted structures, randomly selected structures around iodide-rich, 50:50, and bromine-rich sites were studied further by determining their electronic, optical, mechanical, and thermodynamic properties using first-principle density functional theory. The materials possess similar properties as cubic Br-doped CsPbI3 perovskites. The mechanical properties of these compounds revealed that they are ductile in nature and mechanically stable. This work suggests that the introduction of impurities into CsPbI3 perovskite materials, as well as compositional engineering, can alter the electronic and optical properties, making them potential candidates for solar cell applications.

Unexpected Roles of Interstitially Doped Lithium in Blue and Green Light Emitting Y2O3:Bi3+: A Combined Experimental and Computational Study.

To enhance the photoluminescence of lanthanide oxide, a clear understanding of its defect chemistry is necessary. In particular, when yttrium oxide, a widely used phosphor, undergoes doping, several of its atomic structures may be coupled with point defects that are difficult to understand through experimental results alone. Here, we report the strong enhancement of the photoluminescence (PL) of Y2O3:Bi3+ via codoping with Li+ ions and suggest a plausible mechanism for that enhancement using both experimental and computational studies. The codoping of Li+ ions into the Y2O3:Bi3+ phosphor was found to cause significant changes in its structural and optical properties. Interestingly, unlike previous reports on Li+ codoping with several other phosphors, we found that Li+ ions preferentially occupy interstitial sites of the Y2O3:Bi3+ phosphor. Computational insights based on density functional theory calculations also indicate that Li+ is energetically more stable in the interstitial sites than in the substitutional sites. In addition, interstitially doped Li+ was found to favor the vicinity of Bi3+ by an energy difference of 0.40 eV in comparison to isolated sites. The calculated DOS showed the formation of a shallow level directly above the unoccupied 6p orbital of Bi3+ as the result of interstitial Li+ doping, which may be responsible for the enhanced PL. Although the crystallinity of the host materials increased with the addition of Li salts, the degree of increase was minimal when the Li+ content was low (<1 mol %) where major PL enhancement was observed. Therefore, we reason that the enhanced PL mainly results from the shallow levels created by the interstitial Li+.

Tunable emission from LiBaBO3 :Eu3+ ;Bi3+ phosphor for solid-state lighting.

Europium (Eu3+ ) and bismuth (Bi3+ ) co-activated LiBaBO3 powder phosphors were synthesized by a solid-state reaction and the structure, particle morphology, optical and photoluminescent properties were investigated. X-Ray diffraction patterns of the LiBaBO3 phosphors crystallized in a pure monoclinic phase, i.e. there were no secondary phases due to either incidental impurities or undecomposed starting materials. Scanning electron microscopy images showed that the powders were made up of fluffy needle-like particles that were randomly aligned. The band-gap of the LiBaBO3 host was estimated to be 3.33 eV from the UV/vis absorption data. Blue emission was observed from the LiBaBO3 host, which is ascribed to self-activation of the host matrix. In addition, greenish-blue (493 nm) and red (613 nm) emissions were observed from europium-doped samples and were attributed to the emissions of Eu2+ and Eu3+ , respectively. Furthermore, after codoping with Bi3+ , the emission intensity of Eu3+ located at 613 nm was significantly enhanced. From the Commission Internationale de I'Eclairage (CIE) color coordinates, white emission was observed from LiBa1-x BO3 :xEu3+ (x = 0.020 and 0.025) phosphor powders with color coordinates of x = 0.368, y = 0.378 and x = 0.376, y = 0.366, respectively.

Structural, optical and photoluminescence properties of Eu3+ doped ZnO nanoparticles.

The structure, particle morphology and luminescent properties of europium (Eu3+) doped ZnO nanoparticles (NPs) prepared by co-precipitation method are discussed. When excited using a 325nm He-Cd laser, undoped ZnO NPs exhibited weakly the well-known ultraviolet excitonic recombination emission (at ~384nm) and strongly broad band visible emissions associated with defects (at ~600nm). In addition, the ZnO NPs exhibited green emission at ~600nm associated with defects when excited using a monochromatized xenon lamp. Upon Eu3+ doping line emissions attributed to 5D0→7F1,2,3,4 transitions of Eu3+ ions were observed when the materials were excited using a monochromatized xenon lamp. The exchange interaction mechanism is identified as the cause for concentration quenching of the luminescence of Eu3+ doped ZnO NPs in this study.

Up-conversion luminescence in Yb(3+)-Er(3+)Tm(3+) co-doped Al(2)O(3)-TiO(2) nano-composites.

The sol gel method was used to prepare rare-earths (Yb3+-Er3+ and Yb3+-Tm3+) co-doped Al2O3-TiO2 nano-composite powder phosphors and their up-conversion luminescence properties were investigated. Mixed oxides of titania (TiO2) rutile phase and an early stage crystallization of alumina (Al2O3) phase were confirmed from the X-ray diffraction data with the average crystallite size of ∼36nm. The rutile phase TiO2 was further confirmed by selected area diffraction analysis of the composites. Microscopy analysis showed interesting rod-like morphologies with rough surfaces indicating that a spherulitic growth process took place during the crystal growth. Photoluminescence characterization of the phosphors was carried out under near infra-red excitation at 980nm and the prominent emission bands were observed in the visible region at 523, 548 and 658nm for the Yb3+-Er3+ co-doped systems. Emission in bands extending from the visible to near infra-red regions were observed at 480, 650, 693 and 800nm for the Yb3+-Tm3+ co-doped systems. These upconverted emissions and energy transfer mechanisms taking place are discussed in detail.

Ultra-sensitive and selective NH3 room temperature gas sensing induced by manganese-doped titanium dioxide nanoparticles.

The study of the fabrication of ultra-high sensitive and selective room temperature ammonia (NH3) and nitrogen dioxide (NO2) gas sensors remains an important scientific challenge in the gas sensing field. This is motivated by their harmful impact on the human health and environment. Therefore, herein, we report for the first time on the gas sensing properties of TiO2 nanoparticles doped with various concentrations of manganese (Mn) (1.0, 1.5, 2.0, 2.5 and 3.0mol.% presented as S1, S2, S3, S4 and S5, respectively), synthesized using hydrothermal method. Structural analyses showed that both undoped and Mn-doped TiO2 crystallized in tetragonal phases. Optical studies revealed that the Mn doped TiO2 nanoparticles have enhanced UV→Vis emission with a broad shoulder at 540nm, signifying induced defects by substituting Ti4+ ions with Mn2+. The X-ray photoelectron spectroscopy and the electron paramagnetic resonance studies revealed the presence of Ti3+ and singly ionized oxygen vacancies in both pure and Mn doped TiO2 nanoparticles. Additionally, a hyperfine split due to Mn2+ ferromagnetic ordering was observed, confirming incorporation of Mn ions into the lattice sites. The sensitivity, selectivity, operating temperature, and response-recovery times were thoroughly evaluated according to the alteration in the materials electrical resistance in the presence of the target gases. Gas sensing studies showed that Mn2+ doped on the TiO2 surface improved the NH3 sensing performance in terms of response, sensitivity and selectivity. The S1 sensing material revealed higher sensitivity of 127.39 at 20 ppm NH3 gas. The sensing mechanism towards NH3 gas is also proposed.

Deep level defect correlated emission and Si diffusion in ZnO:Tb(3+) thin films prepared by pulsed laser deposition.

Terbium (Tb(3+)) doped zinc oxide (ZnO) or (ZnO:Tb(3+)) thin films were grown on silicon substrates by the pulsed laser deposition technique at different growth temperatures that were varied from room temperature (RT) to 400°C. The effects of substrate temperature on the structural and optical properties of the ZnO:Tb(3+) films were investigated by X-ray diffraction, scanning electron microscopy, X-ray photoelectron spectroscopy and RT photoluminescence spectroscopy. The band to band and deep level defect emissions were observed for all substrate temperatures. The silicon that has diffused from the substrate has occupied the position of the Zn vacancies in the ZnO:Tb(3+) thin films at the higher substrate temperatures (400°C). A blue emission was observed for all the ZnO:Tb(3+) thin films deposited at the different substrate temperatures.

Effects of thermal treatment and depth profiling analysis of solution processed bulk-heterojunction organic photovoltaic cells.

We report the use of solution processed zinc oxide (ZnO) nanoparticles as a buffer layer inserted between the top metal electrode and the photo-active layer in bulk-heterojunction (BHJ) organic solar cell (OSC) devices. The photovoltaic properties were compared for devices annealed before (Device A) or after (Device B) the deposition of the Al top electrode. The post-annealing treatment was shown to improve the power conversion efficiency up to 2.93% and the fill factor (FF) up to 63% under AM1.5 (100mW/cm(2)) illumination. We performed the depth profile/interface analysis and elemental mapping using the time-of-flight secondary ion mass spectrometry (TOF-SIMS). Signals arising from (27)Al, (16)O, (12)C, (32)S, (64)Zn, (28)Si, (120)Sn and (115)In give an indication of successive deposition of Al, ZnO, P3HT:PCBM and PEDOT:PSS layers on ITO coated glass substrates. Furthermore, we discuss the surface imaging and visualize the chemical information on the surface of the devices.