The adsorption of Sn(IV)TPyP (mesotetrapyridylporphyrin) in sodium hectorite was studied using ultraviolet-visible and luminescence spectroscopy. The adsorbed complex was found to demetallate forming the TPyP dication as the clay is dehydrated. This process was found to be reversible indicating that the Sn4+ ion remains in the vicinity of the porphyrin upon demetallation. The luminescence spectrum of the adsorbed complex was found to be a composite of the Sn(IV)TPyP and the dication spectra. The presence of a band at 750 nm in the luminescence spectrum of the adsorbed species suggested an enhanced interaction between the π-systems of the pyridyl substituents and the porphin nucleus. This is believed to result from a decrease in the dihedral angle between the nucleus and the substituents when they are squeezed between the clay sheets.

Dehydration-induced luminescence (DIL), the emission of light from a clay paste upon dehydration, was characterized experimentally for a colloidal kaolinite. The relationship between total photon count of the emitted light and film thickness is linear up to a thickness of 30 μm. The photon emission was obtained over a critical range of water contents (25-60%) of the oven-dry clay, and the kinetics of photon emission was presumed to be closely associated with the kinetics of film dehydration. Whether drying proceeded throughout the bulk or via a moving front was undetermined, but in either mode it was preceded by the formation of a thin dry film at the interface with the atmosphere. Grinding of the kaolinite for several minutes by mortar and pestle before paste preparation resulted in an overall increase of photon emission compared to unground kaolinite and in the formation of more than one emission peak, as well as a prolongation of the light emission. This effect on the kinetics of light emittance was observed for about two months after the application of the mechanical stress and suggests a means of detecting the mechanical stress history of a clay.

An estimate was made of the spectral characteristics of the emitted light using optical filters and by incorporating tryptophan and salicylic acid into the kaolinite paste where they acted as fluorescent probes. The latter technique shifted the frequency of the light emitted by the kaolinite from the ultraviolet to the visible range where it was less effectively reabsorbed. The first method showed that the wavelengths of 97% of the emitted light was <460 nm and that 75% of the light had wavelengths <410 nm. The second method showed that the total intensity of DIL increased in the presence of fluorescence molecules, suggesting that the emittance was in the ultraviolet range.

Several new, room-temperature luminescent phenomena, resulting from the interaction of kaolin and various amino compounds, have been observed. The emission of light from kaolin pastes (treated with quinoline, pyridine, hydrazine, monoethanolamine, n-butylamine, and piperidine) was shown to decay monotonically over a period of hours to days. More light was released by a given amino compound after it was dried and purified. Hydrazine, in addition to the monotonically decaying photon release, produces delayed pulses of light with peak emission wavelength of 365 nm which last between several hours and several days. These photon bursts are acutely sensitive to the initial dryness of the hydrazine, both in the number of bursts and the integrated photon output. The amount of light and the capacity of the kaolin to produce the delayed burst appeared to be strongly dependent on preliminary heating and on gamma-irradiation, analogous to the dehydration-induced light pulse previously reported from the Ames Research Center. A small, delayed burst of photons occurred when piperidine and n-butylamine were removed by evaporation into an H2SO4 reservoir.

The intercalation of europium ions (Eu3+) into the interlayer space of a layered silicate, magadiite, was conducted by ion-exchange reactions between magadiite and europium(III) chloride. X-ray diffraction and elemental analysis results indicated that Eu3+ cations were intercalated into the interlayer space of magadiite. The ion exchange between Eu3+ and Na+ occurred preferentially so that the adsorbed Eu3+ amounts were controlled quantitatively. Thermal transformation of the original layered structure was suppressed by the intercalation of Eu3+. The resulting intercalation compounds exhibited photoluminescence arising from the intercalated Eu3+. The luminescence intensity varied in accordance with the amount of Eu3+ absorbed, suggesting that the self-quenching occurred at higher loading levels. The luminescence intensity was also changed by the heat treatment, corresponding to the change in the surroundings of the Eu3+ adsorbed, induced by the removal of the adsorbed water molecules and the hydroxyl groups of the silicate.

Deep Springs Valley (DSV) is a hydrologically isolated valley between the White and Inyo mountains that is commonly excluded from regional paleohydrology and paleoclimatology. Previous studies showed that uplift of Deep Springs ridge (informal name) by the Deep Springs fault defeated streams crossing DSV and hydrologically isolated the valley sometime after eruption of the Pleistocene Bishop Tuff (0.772 Ma). Here, we present tephrochronology and clast counts that reaffirms interruption of the Pliocene–Pleistocene hydrology and formation of DSV during the Pleistocene. Paleontology and infrared stimulated luminescence (IRSL) dates indicate a freshwater lake inundated Deep Springs Valley from ca. 83–61 ka or during Late Pleistocene Marine Isotope Stages 5a (MIS 5a; ca. 82 ka peak) and 4 (MIS 4; ca. 71–57 ka). The age of pluvial Deep Springs Lake coincides with pluvial lakes in Owens Valley and Columbus Salt Marsh and documents greater effective precipitation in southwestern North America during MIS 5a and MIS 4. In addition, we hypothesize that Deep Springs Lake was a balanced-fill lake that overflowed into Eureka Valley via the Soldier Pass wind gap during MIS 5a and MIS 4. DSV hydrology has implications for dispersal and endemism of the Deep Springs black toad (Anaxyrus exsul).

The minerals of carletonite group, fluorcarletonite, KNa4Ca4[Si8O18](CO3)4(F,OH)·H2O and carletonite, Na4Ca4[Si8O18](CO3)4(OH,F)·H2O, were investigated using a multi-method approach. A detailed comparative chemical study of the minerals was carried out using electron probe microanalysis and Fourier transform infrared spectroscopy. Using X-ray techniques and the results obtained, geometrical and distortion characteristics of the mineral structures are calculated and the successful crystal-structure refinement of these two natural compounds are given. Using spectroscopic and luminescence methods and ab initio calculations, it is shown that hole defects (CO3)•– are responsible for the colouration of the samples studied. Luminescence due to 5d–4f transition in Ce3+ ions is observed in both investigated compounds. Moreover, luminescence attributed to intrinsic luminescence, corresponding to the decay of electronic excitations of (CO3)2– complexes in the carletonite sample, is registered for the first time in phyllosilicates. An analysis of the optical absorption spectra and g-tensor values suggests that (CO3)•– defects in the crystal structure are localised in the C1 positions. Identification of these specific properties for these sheet silicates, with a two-dimensional infinite tetrahedral polymerisation, indicates that carletonites could be prospective materials for novel phosphors and luminophores.

Hydrothermal carbon microsphere (HTC) is a carbon-based fluorescent material, which can be synthesized by hydrothermal carbonization of glucose. In this article, a series of 4ZnO·B2O3·H2O:Ln3+/HTC (where Ln = Eu or Tb) composites were prepared under hydrothermal conditions. The effects of the glucose concentration on the morphology, photoluminescence (PL) intensity and emission color of Zn3.64:Eu0.24[B2O7]·H2O/HTCx and Zn3.55:Tb0.3[B2O7]·H2O/HTCy were investigated. The relationship between morphology and PL intensity of composites was discussed. The results revealed that the presence of HTC did not change the original emission color of 4ZnO·B2O3·H2O:Ln3+ (where Ln = Eu or Tb) materials, but greatly increased their PL intensity, the sphere-like morphology composites have the strongest PL intensity. The Zn3.64:Eu0.24[B2O7]·H2O/HTCx and Zn3.55:Tb0.3[B2O7]·H2O/HTCy emit bright red light and green light, respectively, under respective excitation wavelengths. The present research suggests that the 4ZnO·B2O3·H2O:Ln3+/HTC (where Ln = Eu or Tb) composites may be candidates of red and green phosphors for display and lighting applications.

Cerium-doped lanthanum magnesium bulk aluminate (La1–xCexMgAl11O19, x = 0.03–0.50; abbreviated as LMA) was prepared via the Pechini sol–gel method after heating at 1200 °C for 2 h. The resulting single-phase ceramics was studied in terms of its structure using X-ray diffraction and optical properties using photoluminescence, its decay time, and radioluminescence spectroscopy. The diffraction and electron microscopy demonstrated LMA's plate-shaped nanocrystals with structure anisotropy and relatively broad particle size distribution. The optical measurements fully manifested the complexity of the LMA crystal structure. The radioluminescence study of cerium-doped LMA is here presented for the first time and, thus, contributes to the basic knowledge of Ce-doped materials. Additionally, the magnetic susceptibility exhibiting paramagnetic behavior of Ce3+ ions is presented. The magnetic data were interpreted in terms of local atomic Hamiltonian involving the crystal field and the Zeeman effect applied on the ground state J = 5/2 multiplet.

Diatoms are unicellular photosynthetic algae that autonomously fabricate a porous organized biosilica shell refined in billion years of evolution. They represent an inexhaustible source of low cost, biocompatible mesoporous silica. Despite the major advances in the genomic field, studies on diatom cell biology are still hampered by a lack of cellular tools. In particular, cell staining assays of diatoms viability are still limited or not well performant. Here we provide a phosphorescent organometallic iridium complex (Ir-Fcx) suitable to act as staining agent to detect diatoms viability.

The majority of highly efficient perovskite light-emitting diodes (PeLED) contain PEDOT:PSS (poly(3,4-ethylenedioxythiophene):polystyrenesulfonate) as hole transport layer (HTL). However, the hygroscopic and acidic nature of PEDOT:PSS may lead to deterioration of PeLED performance. Moreover, due to its inferior electron-blocking properties, an additional electron-blocking layer (EBL) is required to establish charge balance and consequently obtain superior emission characteristics in typically electron-rich PeLED structures. In this work, PTAA (poly(bis(4-phenyl)(2,4,6-trimethylphenyl)amine)) serving both as HTL and EBL is employed to substitute PEDOT:PSS in PeLED. The perovskite CsPbBr3 is chosen as emissive layer (EML) material due to its high color purity and photoluminescence (PL) quantum yield. Dense CsPbBr3 films are fabricated on PTAA-coated ITO substrates by employing a one-step spin-coating approach based on nonstoichiometric perovskite precursor solutions. To suppress non-radiative recombination, a small amount of methylammonium bromide (MABr) is incorporated in the CsPbBr3 lattice. The resulting films exhibit excellent coverage and PL intensity. PeLED containing pure CsPbBr3 films as EML show a green emission with a peak at 520 nm, maximum luminance of 11,000 cd/m2, an external quantum efficiency (EQE) of 3.3 % and a current efficiency (CE) of 10.3 cd/A. Further enhancement to 21,000 cd/m2, 7.5 % and 27.0 cd/A is demonstrated by PeLED with MABr-doped CsPbBr3 layers.

Zinc Oxide (ZnO) has been shown to exhibit semiconducting and piezoelectric dual properties. This has led to a large commercial demand on ZnO for optoelectronics that operate at the blue-ultraviolet regions. Consequently, varying techniques have been devised to create different nanostructures of ZnO. Here, the single step synthesis of ZnO nanostructures was performed on Si(100) substrates with a thin ZnO seed-layer. A modified chemical vapor deposition (CVD) method was developed to accomplish the structure formation. Sb doping of the structures in the gas phase was performed to study its effects on structure and optoelectronic properties. Different structures were realized including nanofilaments, nanoparticles, microflowers, nanorods, nanotubes, and nanocolumns. Only nanorods/columns, and nanotubes are shown in this work. Morphology was examined using scanning electron microscopy (SEM). Energy-dispersive X-ray spectroscopy (EDS) and X-ray powder diffraction (XRD) were used for structural studies. Optoelectronic properties were explored using room-temperature photoluminescence (PL) spectroscopy. PL data show the relative decrease in the number of defects and increase in crystal quality upon increasing reaction time. Significant structural effects were also observed upon doping. Some structural defects might be attributed to the diffusion of Sb ions into the lattices of ZnO, replacement of Zn by Sb, and ionic radii difference. These stacking faults are most likely the reason behind the dominance and broadening of DLE peak.

Deep UV photoluminescence (PL) spectroscopy was employed to study optical properties of a sapphire substrate sample. The sample was photo-excited by the third harmonic laser of a Ti:sapphire pulse laser at wavelength ~ 266 nm which is a below bandgap excitation. In the low temperature (12 K) PL measurement, we observed two sharp atomic-like emissions in the ultraviolet region with peaks at 3.361 eV and 3.315 eV with spectral line-width of 0.85 and 3.30 nm respectively, in the PL spectrum. We performed temperature and power-dependent PL measurements of the sample and observed that the emission peak positions did not change with changing excitation power and sample temperature. We also performed X-ray photoelectron spectroscopy for chemical composition analysis of the sample to explore the origin of the atomic-like emission that could be used for single photon sources for quantum information technology. We will discuss a possible electronic transition and its origin in sapphire.

Polyhedral YVO4: Ln3+ (Ln = Eu, Sm, Yb/Er, Yb/Tm) microcrystals were fabricated via a facile sol–gel auto-combustion method using NH4VO3 as vanadium source in the presence of glycine. The X-ray diffraction patterns were well matched with pure YVO4, and the doped lanthanide ions did not change the host structure. The YVO4 microcrystals annealed from 500 to 1000 °C for 3 h were polyhedral and ranged in particle size from 0.1 to 2 μm. The luminescence properties of YVO4: Ln3+ (Ln = Eu, Sm, Yb/Er, Yb/Tm) samples indicated that all of the YVO4: Ln3+ samples exhibited typical emission spectra of Ln3+ cations, suggesting that the Ln3+ cations were well doped in YVO4 and could be excited efficiently through matrix absorption. In addition, the corresponding mechanisms of emission and energy transfer in the YVO4: Ln3+ are proposed.

In this study, we investigate quartz-based luminescence optical dating of Iron Age deposits at the archaeological site of Tell Damiyah in the Jordan valley. Ten samples, taken from different occupation layers from two different excavation areas, proved to have good luminescence characteristics (fast-component dominated, dose recovery ratio 1.032 ± 0.010, n=24). The optical ages are completely consistent with both available 14C ages and ages based on stylistic elements; it appears that this material was fully reset at deposition, although it is recognised that the agreement with age control is somewhat dependent on the assumed field water content of the samples. Further comparison with different OSL signals from feldspar, or investigations based on dose distributions from individual grains would be desirable to independently confirm the resetting of this material. It is concluded that the sediments of Tell Damiyah are very suitable for luminescence dating. Despite the relatively large associated age uncertainties of between 5 and 10%, OSL at tell sites has the potential to provide ages for material very difficult to date by conventional methods, and to identify reworked mixtures of older artifacts in a younger depositional setting.