Luminescence properties of highly Cr co-doped Nd:YAG powder produced by sol-gel method

We examined luminescence properties of highly chromium co-doped Nd:YAG powders fabricated by the sol-gel method. Though the maximum luminescence intensity of Cr:YAG was at 3.0 mol% of Cr³⁺ concentration, we found that the enhancement effect on Nd:YAG by co-doping Cr³⁺ was continued until 6.0 mol% of Cr³⁺ concentration. This phenomenon is well-explained by a simple energy transfer model derived from the rate equations between Cr³⁺ and Nd³⁺. The enhancement of sensitization for Nd³⁺ activator by high co-doped Cr³⁺ is very effective for making a miniaturized or thin film-type solar laser.     

Luminescence properties of Cr:ZnSe: Comparison between a single crystal and a film deposited by RF magnetron co-sputtering

We investigated the optical properties of a Cr²⁺:ZnSe film deposited by radiofrequency magnetron co-sputtering and compared them with those of a single crystal. The mid-infrared room temperature photoluminescence spectra under direct (1850 nm) and indirect (458 nm) excitation revealed that chromium has been incorporated in the Cr²⁺ active state. The difference of Cr²⁺ fluorescence lifetime values (measured between 10 and 400 K) between both samples was attributed to the presence in the film of firstly a large amount of chromium in a valence state different from the Cr²⁺ active state and secondly structural defects in the ZnSe host matrix. Visible photoluminescence measurements were carried out in order to identify these structural defects.     

Structural and luminescence characterization of synthetic Cr-doped Ni3(PO4)2

Ni_3–xCr_2x/3(PO₄)₂ (x=0 and 0.02) microcrystalline powders were obtained as single phases via a modified sol–gel Pechini-type in situ polymerizable complex method. The samples were characterized using scanning electron microscopy, X-ray diffraction, cathodoluminescence (CL), and thermoluminescence (TL) techniques. We found that Cr³⁺ doping modified the average particle and distribution. The mean particle size was 0.441 μm for Ni₃(PO₄)₂ and 0.267 μm for Ni_2.98Cr_0.013(PO₄)₂. The results also reveal that Cr³⁺ doping notably enhanced the CL and TL UV-blue emission.     

Paraquat release control using intercalated montmorillonite compounds

A representative herbicide, paraquat (PQ; 1,1′-dimethyl-(4,4′-bipyridium) dichloride) was intercalated into montmorillonite by solution and solid state reaction methods. In a typical solution process paraquat aqueous solution was mixed with montmorillonite (Kunipia-F) aqueous suspension, which resulted in a paraquat-montmorillonite layer complex with a basal spacing of 1.3 nm. A paraquat-montmorillonite complex was also easily prepared by solid state reaction method. The mixture of paraquat and Na-montmorillonite was ground under ambient temperature. The basal spacing of the mixture increased to 1.3 nm after grinding for 30 min. In order to achieve the pH dependent releasing of intercalated PQ molecules, the PQ-montmorillonite complex was coated with cellulose acetate phthalate. The polymer modified PQ-montmorillonite complex exhibited a strongly suppressed PQ releasing in the acidic pH domain, while an enhanced PQ releasing at the neutral pH range, respectively.     

X-ray diffraction studies of intercalation compounds prepared from aniline salts and montmorillonite by a mechanochemical processing

Inorganic-organic intercalation compounds comprised of montmorillonite (MMT) and aniline salts with different counter anions were prepared by a mechanochemical processing. The intercalation process and the formed structure of intercalation compounds were investigated via X-ray diffraction analysis. The amounts of intercalated species were very likely dependent on the types of counter anions and increased with decreasing the size of counter anions during the mechanochemical processing. Very interestingly, much larger interlayer expansions of 1.51 nm was observed for aniline hydrofluoride AnF- and aniline hydrochloride AnCl-MMT systems in higher intercalates loading levels, suggesting that neutral guest molecules also introduce within the interlayer regions together with anilinium cations by van der Waals interactions. Judging from the larger interlayer expansions and the size of guest molecules, intercalated species are expected to prefer a tri-molecular layer arrangement with their aromatic rings perpendicular to the silicate sheets. In contrast, for aniline hydrobromide AnBr-MMT, the interlayer expansion was ca. 0.52 nm, which reveals that only anilinium cations are introduced by ion exchange and they probably adopt a vertical orientation in the interlayers. It is inferred that aniline hydroiodide AnI-MMT compounds have a heterogeneous structure containing both anilinium and sodium cations in the interlayers. Different intercalation behaviors during the mechanochemical processing strongly suggest the smaller the size of counter anions, the more guest molecules can be intercalated into the confined clay interlayers in highly ordered arrangements.     

High power diode-pumped passively Q-switched and mode-locking Nd:GdVO4 laser at 912 nm

A high power diode-end-pumped passively Q-switched and mode-locking (QML) Nd:GdVO₄ laser at 912 nm was demonstrated for the first time, to the best of our knowledge. A Z-type laser cavity with Cr⁴⁺:YAG crystals as the intracavity saturable absorber were employed in the experiments. Influence of the initial transmission (T_U) of the saturable absorber on the QML laser performance was investigated. Using the T_U = 95% Cr⁴⁺:YAG, as much as an average output power of 2.0 W pulsed 912 nm laser was produced at an absorbed pump power of 25.0 W, then the repetition rates of the Q-switched envelope and the mode-locking pulse were ~ 224 kHz and ~ 160 MHz, respectively. Whereas the maximum output power was reduced to 1.3 W using the T_U = 90% Cr⁴⁺:YAG, we obtained a 100% modulation depth for the mode-locking pulses inside the Q-switched envelope.     

Characterization and ethylene adsorption of natural and modified clinoptilolites

The ethylene adsorption of Turkey clinoptilolite-rich tuff from Gordes and Bigadic region of western of Anatolia and their exchanged forms (K⁺, Na⁺ and Ca²⁺) were investigated. The clinoptilolite samples were characterized using XRD, TG-DTA and nitrogen adsorption methods. Adsorption isotherms for ethylene on natural and modified forms of both adsorbents at 277 K and 293 K were obtained at pressures up to 38 kPa. Uptake of ethylene increased as Na-CLN < Ca-CLN < K-CLN < Natural CLN for Gordes zeolite at 277 K, 293 K and for Bigadic zeolite at 277 K. For Bigadic zeolites at 293 K, uptake of ethylene increased in the order Ca-CLN < Na-CLN < K-CLN < Natural CLN. It was found that ethylene adsorption capacity of Bigadic clinoptilolite samples was much greater than Gordes clinoptilolite samples except K⁺ modified forms at both temperatures. These results show that both natural clinoptilolites have a considerable potential for the removal of ethylene.     

Diode-pumped passively Q-switched 912 nm Nd:GdVO4 laser and pulsed deep-blue laser by intracavity frequency-doubling

A diode-end-pumped passively Q-switched 912 nm Nd:GdVO₄/Cr⁴⁺:YAG laser and its efficient intracavity frequency-doubling to 456 nm deep-blue laser were demonstrated in this paper. Using a simple V-type laser cavity, pulsed 912 nm laser characteristics were investigated with two kinds of Cr⁴⁺:YAG crystal as the saturable absorbers, which have the different initial transmissivity (T_U) of 95% and 90% at 912 nm. When the T_U = 95% Cr⁴⁺:YAG was used, as much as an average output power of 2.8 W 912 nm laser was achieved at an absorbed pump power of 34.0 W, and the pulse width and the repetition rate were ∼ 40.5 ns and ∼ 76.6 kHz, respectively. To the best of our knowledge, this is the highest average output power of diode-pumped passively Q-switched Nd³⁺-doped quasi-three-level laser. Employing a BiBO as the frequency-doubling crystal, 456 nm pulsed deep-blue laser was obtained with a maximum average output power of 1.2 W at a repetition rate ∼ 42.7 kHz.     

The study of green laser performances by using composite crystals of different initial transmissions

This paper reported a passively Q-switched green laser of LD pumped linear cavity structure by using Nd:YAG/Cr⁴⁺:YAG composite crystal and the type II phase matching KTP crystal. The dependence of average output power, pulse width and pulse repetition rate on pump power at different initial transmissions of Cr⁴⁺:YAG were measured and analyzed. With Cr⁴⁺:YAG of 80% initial transmission, under pump power of 13.97 W, the output average power is up to 681 mW, with pulse width of 200 ns and pulse repetition rate of 9.1 kHz. The laser operates in a fundamental mode.     

Photoemission study of the modification of the electronic structure of transition-metal overlayers on TiO2 surfaces II. Cr on TiO2(0 0 1)

The electronic states of the Cr overlayers on TiO₂(0 0 1) surfaces have been investigated using angle-resolved and resonant photoemission spectroscopy with synchrotron radiation. At lower coverages, Cr deposition on TiO₂(0 0 1) creates two well separated in-gap emissions due to the formation of surface Ti³⁺ (3d¹) ions and Cr³⁺ (3d³) ions. At higher coverages, the in-gap emission is developed into the 2-peak-structure emission of Cr 3d character. The corresponding state is considered to be of metallic nature from the viewpoint of the high ability of oxygen adsorption, but has no Fermi edge, indicating a possibility of forming small Cr clusters on TiO₂(0 0 1) at this stage.     

Y3Al5O12 ceramic absorbers for the suppression of parasitic oscillation in high-power Nd:YAG lasers

The objective of this study was to identify a material suitable to absorb radiation at the wavelength of neodymium-doped Yttrium Aluminum Garnet (Y₃Al₅O₁₂:YAG), 1064 nm. M-(M= Sm³⁺, Co²⁺, Co³⁺, Cr³⁺, and Cr⁴⁺) doped highly transparent YAG ceramics were fabricated, and their absorption spectra were measured. Unlike Co²⁺ and Cr³⁺-doped ceramic samples, Co³⁺ and Cr⁴⁺ and Sm³⁺-doped:YAG ceramics were found to have significant absorption at 1064 nm. However, the Sm³⁺-doped YAG clearly emerged as the best candidate because it is also transparent at 808 nm, the pumping wavelength laser diode (LD), and also at most absorption bands used for flash-lamp pumping.     

Ultrafast laser pulses generated from the chromium-doped cunyite laser

Femtosecond pulses were generated from a Cr⁴⁺: Cunyite laser using a combination of a broadband semiconductor saturable absorber mirror (SESAM), chirped mirrors, and passive mode locking. The astigmatically compensated asymmetric X-cavity with a 4.5-mm-long Cr⁴⁺:Ca₂GeO₄ sample was operated with a 2.5% output coupler. Dispersion compensation was achieved using chirped mirrors. During self-starting mode-locked operation, pulses as short as 365 fs were generated at a pulse repetition rate of 100 MHz with output power of 70 mW and a spectral bandwidth of 5.2 nm at the center wavelength of 1432 nm.     

Hydrogen adsorption on rhodium: Hydride formed on the surface of thin rhodium films

H₂ interaction with thin Rh films deposited on Pyrex glass under UHV conditions has been studied by simultaneous measurement of work function changes ΔΦ and hydrogen pressure P, at selected constant temperatures: 78 and 298 K. Prior to the adsorption experiments the thin film topography was illustrated using the AFM and STM methods. The influence of hydrogen adsorption on the resistance of thin Rh film was examined in the course of an independent experiment. The number of sites accessible for adsorption on the thin Rh film surface was found determining population of oxygen adatoms within the monolayer at 78 K, when incorporation of these adspecies below the surface is negligible. It was established that at all examined temperatures hydrogen adsorption led to coverage Θ approaching 1 under equilibrium pressure below 10⁻³ Pa, increasing the work function. Under higher H₂ pressure an additional uptake of hydrogen leading to Θ ∼ 1.68 at 298 K, and to Θ ∼ 2 at 78 K is reached. On this surface at low temperatures there exist weakly bound, reversibly adsorbed, positively charged adspecies characteristic for hydrogen adsorption on transition metal hydrides. The change of thin Rh film resistance caused by hydrogen adsorption was not measurable.     

Combustion synthesized MgAl2O4:Cr phosphors—An EPR and optical study

Magnesium aluminate (MgAl₂O₄) doped with trivalent chromium (Cr³⁺) was synthesized by the combustion method. The prepared sample was characterized by X-ray powder diffraction, Brunauer-Emmet-Teller (BET) adsorption isotherms and diffuse-reflectance UV-vis spectroscopy techniques. Electron paramagnetic resonance (EPR) and photoluminescence (PL) studies have been performed at room temperature and at 110 K. The EPR spectrum exhibit resonance signals at g=5.37, 4.53, 3.82, 2.26 and 1.96 characteristic of Cr³⁺ ions. The luminescence of Cr³⁺-activated MgAl₂O₄ exhibits a red emission peak around 686 nm from the synthesized phosphor particles upon 551 nm excitation. The luminescence is assigned to a transition from the upper ²E_g→⁴A_2g ground state of Cr³⁺ ions. By correlating EPR and optical data the crystal field splitting parameter (D_q), Racah inter-electronic repulsion parameter (B) and the bonding parameters have been evaluated and discussed. The bonding parameters suggests that the ionic nature of Cr³⁺ ions with the ligands and the Cr³⁺ ions are in distorted octrahedral environment.     

Mn, Cr-co-doped MgAl2O4 phosphors for white LEDs

The Mn-, Cr-doped and Mn, Cr-co-doped MgAl₂O₄ powders have been synthesized via a gel-solid reaction method. Energy transfer from Mn²⁺ to Cr³⁺ has been observed for the first time in the co-doped MgAl₂O₄ phosphors. When excited with blue light with a wavelength of 450 nm at room temperature, both green emission from Mn²⁺ around 520 nm and red emission from Cr³⁺ around 675and 693 nm were generated. Moreover, the color of the emission can be modified by controlling the doping concentrations of Mn²⁺ and Cr³⁺. Therefore, MgAl₂O₄: Mn²⁺, Cr³⁺ could be used as a single-phased phosphor for white LED with a blue LED chip. The energy transfer in terms of Mn²⁺ to Cr³⁺ is determined by means of radiation and reabsorption.     

Electron spin resonance of chromia-yttria solid solutions

Electron spin resonance spectra of chromia-yttria solid solutions have been studied at room temperature for Cr concentrations between 0.20 and 2.00 mol%. Isolated Cr³⁺ ions in sites with two different symmetries were observed, as well as well as Cr³⁺ ions coupled by the exchange interaction. The relative concentration of isolated to coupled Cr³⁺ ions decreases with increasing chromium concentration. The results are consistent with the assumption that the chromium ions occupy preferentially the C₂ symmetry sites. A theoretical calculation based on this model yields an effective range of the exchange interaction between Cr³⁺ ions of 0.64 nm, of the same order as that of Cr³⁺ ions in MgO.     

Preparation and hydrogen storage of activated rayon-based carbon fibers with high specific surface area

Activated carbon fibers were prepared from rayon-based carbon fibers by two step activations with steam and KOH treatments. Hydrogen storage properties of the activated rayon-based carbon fibers with high specific surface area and micropore volume have been investigated. SEM, XRD and Brunauer-Emmett-Teller (BET) were used to characterize the samples. The adsorption performance and porous structure were investigated by nitrogen adsorption isotherm at 77 K on the base of BET and density functional theory (DFT). The BET specific surface area and micropore volume of the activated rayon-based carbon fibers were 3144 m²/g and 0.744 m³/g, respectively. Hydrogen storage properties of the samples were measured at 77 and 298 K with pressure-composition isotherm (PCT) measuring system based on the volumetric method. The capacities of hydrogen storage of the activated rayon-based carbon fibers were 7.01 and 1.46 wt% at 77 and 298 K at 4 MPa, respectively. Possible mechanisms for hydrogen storage in the activated rayon-based carbon fibers are discussed.     

Structural studies of Cr-doped mullite derived from single-phase precursors

Cr-doped mullites were prepared from single-phase precursors containing up to 9.60 wt% Cr₂O₃ using a sol-gel technique followed by thermal treatment. Particle induced X-ray emission spectroscopy and X-ray powder diffraction were used to characterize the samples. Mullites were orthorhombic, space group Pbam. Cr doping caused the increase of unit-cell parameters. Strongest expansion was noticed along c-axis followed by a and b (Δc/c=0.089, Δa/a=0.061, Δb/b=0.045% per mole Cr₂O₃). A second phase, namely θ-(Al,Cr)₂O₃, was revealed by XRD in the sample containing 9.60 wt% Cr₂O₃. The structure of mullites was refined by the Rietveld method, location of Cr³⁺ was performed by the EPR spectroscopy. At low chromium doping level (Cr₂O₃ content less than ∼5 wt%) Cr³⁺ ions were substituted for Al³⁺ in the AlO₆ octahedra of the mullite structure (M1 site). For higher doping level, Cr³⁺ ions were additionally substituted for Al³⁺ in the AlO₆ octahedra of the second phase [θ-(Al,Cr)₂O₃ at 1400 °C, or α-(Al,Cr)₂O₃ at 1600 °C] which segregated in the system. Substitution of Cr³⁺ for Al³⁺ on M1 site in the mullite structure resulted in increase of average distances in (M1)O₆ octahedron and decrease of average distances in T*O₄ tetrahedron, while average distances in TO₄ tetrahedron stayed almost constant.     

Energy transfer among three luminescent centers in full-color emitting ZnGa2O4:Mn, Cr phosphors

The ZnGa₂O₄:Mn²⁺, Cr³⁺ phosphors show three colors; the blue band of 380 nm from the charge transfer between Ga-O, the green band of 505 nm from Mn²⁺ and the red band of 705 nm from Cr³⁺. As a variation of Mn²⁺ or Cr³⁺ concentrations in ZnGa₂O₄:Mn²⁺, Cr³⁺, the relative emission intensity can be tuned. This phenomenon is explained in terms of the energy transfer based on four factors: the spectral overlap between the energy donors (Ga-O) and the energy accepters of Mn²⁺ or Cr³⁺, the absorption cross section of the energy accepters, the distance between them, and the decay time of the energy donors. ZnGa₂O₄:0.0025Mn²⁺, 0.010Cr³⁺ shows the CIE coordinates of x=0.4014, y=0.3368, which is a pure white light. The single-phased full-color emitting ZnGa₂O₄:Mn²⁺, Cr³⁺ phosphors can be applied to illumination devices.     

Interaction of divalent copper with two diaminealkyl hexagonal mesoporous silicas evaluated by adsorption and thermochemical data

Hexagonal mesoporous silicas chemically modified with ethylenediamine moieties were synthesized through the co-condensation of tetraethylorthosilicate (TEOS) with two different silylating agents: (i) N-[3-(trimethoxysilyl)propyl]-ethylenediamine and (ii) the new agent prepared from the incorporation of the ethylenediamine molecule into the epoxide group of the precursor 3-glycidoxypropyltrimethoxysilane. From these silylating agents under neutral n-octylamine template methodology, the respective MNN and MGNN inorganic-organic hybrids were synthesized. Elemental analysis showed that the number of pendant groups in these hybrids were 1.69 and 1.62 mmol g⁻¹, with pore diameters and surface areas of 1.81 and 1.53 nm and 663 ± 14 and 614 ± 16 m² g⁻¹. Infrared spectroscopy, nuclear magnetic resonance for ¹³C and ²⁹Si nuclei and X-ray diffraction patterns are in agreement with the success of the proposed synthetic methods, as confirmed for the formation of the mesoporous hybrids. Both mesoporous materials have been used for divalent copper adsorption from aqueous solution at 298 ± 1 K. The series of adsorption isotherms were adjusted to a modified Langmuir equation. The maximum number of moles adsorbed gave 1.4 ± 0.1 and 1.4 ± 0.2 mmol g⁻¹ for MNN and MGNN, respectively. The same interactions were calorimetrically followed and gave exothermic enthalpy, negative Gibbs free energy and positive entropy values. These favorable thermodynamic data indicate cation/nitrogen basic center interactions on the new mesoporous materials at the liquid/solid interface for both systems.