Morphology-dependent luminescence behavior of Y<Subscript>2-x</Subscript>Gd<Subscript>x</Subscript>O<Subscript>3</Subscript>:Eu<Superscript>3+</Superscript> thin-film phosphors grown by a laser ablation

Y_2-xGd_xO₃:Eu³⁺ luminescent thin films have been grown on Al₂O₃(0001) substrates using pulsed laser deposition. Films grown under different deposition conditions have been characterized using microstructural and luminescence measurements. The crystallinity, surface morphology and photoluminescence (PL) of the films are highly dependent on the amount of Gd present. The photoluminescence (PL) brightness data obtained from Y_2-xGd_xO₃:Eu³⁺ films grown under optimized conditions have indicated that Al₂O₃(0001) is one of the most promising substrates for the growth of high-quality Y_2-xGd_xO₃:Eu³⁺ thin-film red phosphors. In particular, the incorporation of Gd into the Y₂O₃ lattice could induce a remarkable increase of PL. The highest emission intensity was observed with Y_1.35Gd_0.60Eu_0.05O₃, whose brightness was increased by a factor of 3.1 in comparison with that of Y₂O₃:Eu³⁺ films. This phosphor may be promising for application in flat-panel displays. PACS 78.20.-e; 78.55.-m; 78.66.-w     

Photoluminescence behavior of pulsed laser deposited ZnGa<Subscript>2</Subscript>O<Subscript>4</Subscript> thin-film phosphors grown on various substrates

ZnGa₂O₄ thin-film phosphors have been grown on Si(100), Al₂O₃(0001) and MgO(100) substrates using pulsed laser deposition. The structural characterization was carried out on a series of ZnGa₂O₄ films grown on various substrates under various substrate temperatures and oxygen pressures. The films grown on these substrates not only have different crystallinity and surface morphology, but also different Zn/Ga composition ratio. The crystallinity and photoluminescence (PL) of the ZnGa₂O₄ films are highly dependent on the deposition conditions, in particular the stoichiometry ratio of Zn/Ga and the kind of substrate. The variation of Zn/Ga in the films also depends on not only the oxygen pressure but also the substrate temperature during deposition. The PL properties of pulsed laser deposited ZnGa₂O₄ thin films have indicated that Al₂O₃(0001) and MgO(100) are promising substrates for the growth of high-quality ZnGa₂O₄ thin films and that the luminescence brightness depends on the substrate. The luminescence spectra show a broad band extending from 350 to 600 nm and peaking at 460 nm. Received: 11 July 2002 / Accepted: 31 July 2002 / Published online: 28 October 2002 RID="*" ID="*"Corresponding author. Fax: +82-51-6206356, E-mail: jhjeong@pknu.ac.kr     

Enhanced Up-Conversion Emission in Al<Superscript>3+</Superscript> Co-Doped ZnGa<Subscript>2</Subscript>O<Subscript>4</Subscript>:Yb<Superscript>3+</Superscript>,Tm<Superscript>3+</Superscript> Powder Phosphors

Yb³⁺-Tm³⁺ co-doped up-conversion powder phosphors using Zn(Al_xGa_1-x)₂O₄ (ZAGO) as the host materials were synthesized via solid-state reaction successfully. In addition, the morphology, structural characterization and up-conversion luminescent properties were all investigated by scanning electron microscope (SEM), x-ray diffraction (XRD) and fluorescence spectrophotometer (F-7000), respectively. Under the excitation of a 980 nm laser, all as-prepared powders can carry out blue emission at about 477 nm (corresponding to ¹G₄ → ³H₆ transition of Tm³⁺ ions), and red emission at about 691 nm (attributed to ³F₃ → ³H₆ transition of Tm³⁺ ions). Also, the influence of doping Al³⁺ ions were investigated. In brief, the doping of Al³⁺ ions has no effect on the position of emission peak. Howbeit the up-conversion efficiency and intensity of ZAGO:Yb,Tm phosphors are stronger than ZGO:Yb,Tm and ZAO:Yb,Tm phosphors, while the crystallinity is the opposite. More particularly, all as-prepared powder phosphors emit strong luminescence, which is observable by the naked eye, demonstrating the potential applications in luminous paint, luminescent dye, etc.     

Research of the Spin-Hamiltonian Parameters and Defect Structure for the Trigonal Mn<Superscript>4+</Superscript> Centers in Y<Subscript>2</Subscript>Ti<Subscript>2</Subscript>O<Subscript>7</Subscript>:Mn<Superscript>4+</Superscript> Crystal

The high-order perturbation formulas founded on the two-mechanism model are applied in this paper to compute the spin-Hamiltonian parameters (g factors g _//, g _⊥ and zero-field splitting D) of the trigonal Mn⁴⁺ centers in Y₂Ti₂O₇:Mn⁴⁺ crystal. In this model, besides the contributions from the traditional crystal-field (CF) mechanism (in the CF theory) related to CF excited states, those from the charge-transfer (CT) mechanism connected with CT excited states are contained. The calculated results are reasonably coincident with the observed values. The calculations show that the contributions of CT mechanism to spin-Hamiltonian parameters (in particular, the g factors) for (MnO₆)^8? clusters are large and cannot be neglected. The defect structure of trigonal (MnO₆)^8? clusters in Y₂Ti₂O₇:Mn⁴⁺ crystals is also evaluated. The results are discussed.     

Improved photoluminescence of pulsed-laser-ablated Y<Subscript>1-x</Subscript>Gd<Subscript>x</Subscript>VO<Subscript>4</Subscript>:Eu<Superscript>3+</Superscript> thin film phosphors by Gd substitution

Gd-substituted Y_1-xGd_xVO₄:Eu³⁺ luminescent thin films have been grown on Al₂O₃(0001) substrates using pulsed-laser deposition. The films grown under different deposition conditions have been characterized using microstructural and luminescent measurements. The crystallinity, surface morphology, and photoluminescence (PL) of the films are highly dependent on the amount of Gd. The photoluminescence (PL) brightness data obtained from Y_1-xGd_xVO₄:Eu³⁺ films grown under optimized conditions have indicated that the PL brightness is more dependent on the surface roughness than the crystallinity of the films. In particular, the incorporation of Gd into the YVO₄ lattice could induce a remarkable increase of PL. The highest emission intensity was observed with Y_0.57Gd_0.40Eu_0.03VO₄ thin film whose brightness was increased by a factor of 2.5 and 1.9 in comparison with that of YVO₄:Eu³⁺ and GdVO₄:Eu³⁺ films, respectively. This phosphor have application to flat panel displays. PACS 78.20.-e; 78.55.-m; 78.66.-w     

Tunable emission and efficient energy-transfer properties of Ce<Superscript>3+</Superscript> and Mn<Superscript>2+</Superscript> co-doped Ba<Subscript>3</Subscript>Gd(PO<Subscript>4</Subscript>)<Subscript>3</Subscript> phosphors

MgO powders subjected to Q-switched laser pulses in water were characterized by X-ray/electron diffraction and optical spectroscopy to have a significant optical property change with accompanied transformation into the phase assemblages of periclase, brucite and liquid-crystalline lamella. The periclase nanoparticles tended to have {111} habit planes parallel to the basal layers of lamella and brucite flakes more or less rolled as fibers, ribbons or tubes. A significant internal compressive stress was built up for periclase and brucite but not the more flexible lamellar phase. The colloidal suspension containing the densified periclase nanoparticles within the rolled brucite/lamellae flakes showed UV–visible absorption corresponding to a minimum band gap of ca. 5 eV.     

High-frequency EPR of Cr<Superscript>2+</Superscript> ions in CdGa<Subscript>2</Subscript>S<Subscript>4</Subscript>

High-frequency broad-band (65–240 GHz) EPR is used to study impurity centers of bivalent chromium in a CdGa₂S₄ crystal. It is found that the EPR spectra correspond to tetragonal symmetry. The spin Hamiltonian H = βB · g · S + B ₂ ⁰ O ₂ ⁰ + B ₄ ⁰ O ₄ ⁰ + B ₄ ⁴ O ₄ ⁴ with the parameters B ₂ ⁰ =23659±2 MHz, B ₄ ⁰ =1.9±1 MHz, |B ₄ ⁴ |=54.2±2 MHz, g_‖=1.93±0.02, and g_⊥=1.99±0.02 is used to describe the observed spectra. It is concluded that chromium ions occupy one of the tetrahedrally coordinated cation positions.     

Migration of Mn<Superscript>2+</Superscript> excitations in Cd<Subscript>0.5</Subscript>Mn<Subscript>0.5</Subscript>Te crystal

The experimentally obtained intensity decay curves for the 2-eV intracenter luminescence band of Mn²⁺ ions in Cd_0.5Mn_0.5Te semiconductor solid solution at a temperature of 77 K have been simulated by the Monte Carlo method. The calculations show that the initial nonexponential behavior of the intensity decay curves at the band wings, as well as the time dependence of the band peak energy, are determined by the fast migration of excitations through the Mn²⁺ ion subsystem. There are more than 200 jumps per each emitted photon, and the migration rate increases by almost two orders of magnitude in comparison with the rate at 4 K. The analysis of the simulation results and the calculation based on the experimental data show the interaction between ions to be resonant. The estimate derived from the Anderson criterion suggests that the excited state is not delocalized. An increase in the migration rate with an increase in temperature significantly reduces the inhomogeneous broadening dispersion.     

luminescence of BaGa<Subscript>2</Subscript>Se<Subscript>4</Subscript> crystals activated by Eu<Superscript>2+</Superscript> and Ce<Superscript>3+</Superscript> ions

We have studied the effect of doping with Eu²⁺ and Ce³⁺ ions on the photoluminescence (PL) of BaGa₂Se₄ crystals in the temperature range 77–300 K. We have established that the broad bands with maxima at wavelengths 456 nm and 506 nm observed in the photoluminescence spectra of BaGa₂Se₄:Ce³⁺ crystals are due to intracenter transitions 5d → ²F_7/2 and 5d →²F_5/2 of the Ce³⁺ ions, while the broad photoluminescence band with maximum at 521 nm in the spectrum of BaGa₂Se₄:Eu²⁺ is associated with 4f⁶ 5d → 4f⁷ (⁸S_7/2) transitions of the Eu²⁺ ion. We show that in BaGa₂Se₄:Eu²⁺,Ce³⁺ crystals, excitation energy is transferred from the Ce³⁺ ions to the Eu²⁺ ions.     

Spontaneous luminescence of Eu<Superscript>3+</Superscript> ions in porous Y<Subscript>2</Subscript>O<Subscript>3</Subscript> nanospheres

A study of the luminescence of Eu³⁺ ions in Y₂O₃ nanospheres indicates a significant influence of the porous structure of nanoparticles on the luminescence of dopant ions. It is shown that filling the nanopores of initially porous Y₂O₃ nanospheres shortens the decay time of the spontaneous luminescence of doping europium ions. The change in the decay time is associated with the change in the effective refractive index of the porous nanospheres.     

Anisotropy of nonlinear absorption in Co<Superscript>2+</Superscript>:MgAl<Subscript>2</Subscript>O<Subscript>4</Subscript> crystal

Anisotropy of the nonlinear absorption of Co²⁺ ions in MgAl₂O₄ single crystal at the wavelengths of 1.35 and 1.54 μm has been experimentally demonstrated. The experimental data are analyzed in the framework of a phenomenological model when the Co²⁺ ions are described as three sets of linear dipoles oriented along the crystallographic axes. Ground-state and excited state absorption cross-sections at 1.35 and 1.54 μm are evaluated to be σ_gsa=(4.0±0.3)×10^-19, σ_esa=(3.6±0.4)×10^-20 cm² and σ_gsa=(5.1±0.3)×10^-19, σ_esa=(4.6±0.4)×10^-20 cm², respectively. PACS 42.55.Rz; 71.20.Be     

Tunable bluish green to yellowish green Ca<Subscript>2(1-x)</Subscript>Sr<Subscript>2x</Subscript>Al<Subscript>2</Subscript>SiO<Subscript>7</Subscript>:Eu<Superscript>2+</Superscript> phosphors for potential LED application

A series of solid solutions with a general formula of Ca_2(1-x)Sr_2xAl₂SiO₇:Eu²⁺ were synthesized by a high temperature solid state reaction. The structure, diffuse reflection spectra, photoluminescence spectra, color-coordinate parameters and lifetimes of phosphors were investigated. XRD results show that Ca₂Al₂SiO₇ is totally miscible with Sr₂Al₂SiO₇. These solid solution phosphors show a broad excitation band of 350–450 nm that matches well with the output lights of near-UV LEDs and tunable emission from bluish green to yellowish green. These optical properties originate from the 4f⁷–4f⁶5d transition of Eu²⁺ ions. The crystal field strength was considered to be tailed by controlling the host composition, which leads to the shift of absorption band and emission band, and the varying of color coordinates. PACS  78.55.-m; 42.70.-a; 61.05.C-     

Luminescent properties of SrMg<Subscript>2</Subscript>(PO<Subscript>4</Subscript>)<Subscript>2</Subscript>:Eu<Superscript>2+</Superscript>, and Mn<Superscript>2+</Superscript> as a potential phosphor for ultraviolet light-emitting diodes

Eu²⁺ and Mn²⁺ co-doped SrMg₂(PO₄)₂ phosphors with blue and red two emission bands were prepared by the high temperature solid state method and their luminescent properties have been investigated as a function of activator and co-activator concentrations. Resonance-type energy transfers from Eu²⁺ to Mn²⁺ were discovered by directly overlapping the Eu²⁺ emission spectrum and the excitation spectrum of Mn²⁺. Efficiencies of energy transfer were also calculated according to the changes of relative intensities of Eu²⁺ and Mn²⁺ emission. According to the principle of energy transfer, we demonstrated that the phosphor SrMg₂(PO₄)₂:Eu²⁺,Mn²⁺ with double emission bands exhibited a great potential as a phosphor for ultraviolet light-emitting diodes and the relative intensities of blue and red emission could be tuned by adjusting the contents of Eu²⁺ and Mn²⁺. PACS 78.55.-m     

Electro-optic properties of epitaxial Sr<Subscript>0.6</Subscript>Ba<Subscript>0.4</Subscript>Nb<Subscript>2</Subscript>O<Subscript>6</Subscript> films grown on MgO substrates using Li<Subscript>x</Subscript>Ni<Subscript>2-x</Subscript>O buffer layer

Textured Li_xNi_2-xO (LNO) thin films have been fabricated on (001)MgO substrates by pulsed laser deposition technique. The as-deposited LNO films shows a conductivity of 2.5×10^-3 Ω m and possess a transmittance of about 35% in the visible region. Subsequent deposition of Sr_0.6Ba_0.4Nb₂O₆ (SBN60) thin film on these LNO-coated MgO substrates resulted in a textured SBN layer with a 〈001〉 orientation perpendicular to the substrate plane. Phi scans on the (221) plane of the SBN layer indicated that the films have two in-plane orientations with respect to the substrate. The SBN unit cells were rotated in the plane of the film by ± 8.2° as well as ± 45° with respect to the LNO/MgO substrate. Besides the highly (00l)-orientation, the SBN films also exhibited a dense microstructure as shown by scanning electron microscopy. The electro-optic coefficient (r₃₃) of the SBN film was measured to be 186 pm/V. On the basis of our results, we have demonstrated that the LNO film can be used as a buffer layer as well as a transparent bottom electrode for waveguide applications. The SBN/LNO heterostructure is also a suitable candidate for integrated electro-optics devices. PACS  42.79.Gn; 42.82.Et; 78.20.Ci     

Photoluminescence of nanostructured Zn<Subscript>2</Subscript>SiO<Subscript>4</Subscript>:Mn<Superscript>2+</Superscript> ceramics under UV and VUV excitation

The photoluminescence of Zn₂SiO₄:Mn²⁺ ceramics with a particle size of 120 ± 10 nm, which is excited in the range of 3.5–5.8 eV and subjected to synchrotron radiation with photon energies of up to 20 eV, is investigated. Nanoscale Zn₂SiO₄:Mn²⁺ ceramics possesses intense luminescence with a maximum of 2.34 eV, the position and half-width of the band are independent of the excitation energy. It is found that the photoluminescence at 2.34 eV decays nonexponentially upon ultraviolet excitation. In the case of nanoscale ceramics is irradiated by vacuum ultraviolet, an additional photoluminescence-excitation channel is likely to occur due to interaction of band states and intrinsic vacancy-like defects of the Zn₂SiO₄ matrix.     

Elevated electrochemical property of LiMn<Subscript>2</Subscript>O<Subscript>4</Subscript> originated from nano-sized Mn<Subscript>3</Subscript>O<Subscript>4</Subscript>

By employment of nano-sized pre-prepared Mn₃O₄ as precursor, LiMn₂O₄ particles have been successfully prepared by facile solid state method and sol-gel route, respectively. And the reaction mechanism of the used precursors of Mn₃O₄ is studied. The structure, morphology, and element distribution of the as-synthesized LiMn₂O₄ samples are characterized by X-ray diffraction (XRD) and scanning electron microscope (SEM). Compared with LiMn₂O₄ synthesized by facile solid state method (SS-LMO), LiMn₂O₄ synthesized by modified sol-gel route (SG-LMO) possesses higher crystallinity, smaller average particle size (~175 nm), higher lithium chemical diffusion coefficient (1.17 × 10^?11 cm² s^?1), as well as superior electrochemical performance. For example, the cell based on SG-LMO can deliver a capacity of 85.5 mAh g^?1 at a high rate of 5 °C, and manifests 88.3% capacity retention after 100 cycles at 0.5 °C when cycling at 45 °C. The good electrochemical performance of the cell based on SG-LMO is ascribed mainly to its small particle size, high degree of dispersion, and uniform element distribution in bulk material. In addition, the lower polarization potential accelerates Li⁺ ion migration, and the lower atom location confused degree maintains integrity of crystal structure, both of which can effectively improve the rate capability and cyclability of SG-LMO.     

Bi<Subscript>2</Subscript>O<Subscript>3</Subscript> nanosquaresheets grown on Si substrate

A novel morphology of Bi₂O₃ nanomaterial (nanosquaresheets) has been successfully synthesized in large area by thermal evaporation of commercial Bi₂O₃ powder at high temperatures. The Bi₂O₃ nanosquaresheets (NSSs) are perfect regular squares and have sharp, uniform edges. The typical length of the sides is in the range of 200–600 nm. The thickness varies from 30 to 100 nm. Electron microscopy observations show that the Bi₂O₃ NSSs are single crystalline. The growth of Bi₂O₃ NSSs is probably controlled by a vapor–solid mechanism. The dominate growth directions are [2̄10] and [1̄2̄2] within the (245) planes. PACS 81.05.Hd; 81.10.Bk; 81.16.Be     

Photoluminescence of the nanosized xerogel Zn<Subscript>2</Subscript>SiO<Subscript>4</Subscript>:Mn<Superscript>2+</Superscript> in pores of anodic alumina

The photoluminescence properties of a composite material prepared by the introduction of the nanosized phosphor Zn₂SiO₄:Mn²⁺ into porous anodic alumina have been investigated. Scanning electron microscopy studies have revealed that Zn₂SiO₄:Mn²⁺ particles are uniformly distributed in 70% of the volume of the pore channels. The samples exhibit an intense luminescence in the range of 2.3–3.0 eV, which corresponds to the emission of different types of F centers in alumina. After the formation of Zn₂SiO₄:Mn²⁺ nanoparticles in the pores, an intense photoluminescence band is observed at 2.4 eV due to the ⁴T₁–⁶A₁ electronic transition within the 3d shell of the Mn²⁺ activator ion. It has been found that the maximum of the photoluminescence of Zn₂SiO₄:Mn²⁺ xerogel nanoparticles located in the porous matrix is shifted to higher energies, and the luminescence decay time decreases significantly.     

MgO:LiNbO<Subscript>3</Subscript> planar waveguide formed by MeV O<Superscript>2+</Superscript> implantation and its annealing characteristics

A z-cut magnesium-doped LiNbO₃ is implanted by O²⁺ at 1.5–4.5 MeV and with doses of 4–12 × 10¹⁴ ions/cm² at room temperature. Planar optical waveguides were obtained and characterized by the prismcoupling technique at wavelength of 633 and 1539 nm. Implanted samples were annealed at different temperatures and time durations. After different annealing treatments, mode profiles and optical losses were measured and analyzed.