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.     

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     

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-     

Size-dependent photoluminescence properties under vacuum ultraviolet excitation of Zn2SiO4:Mn nanophosphors

The Zn₂SiO₄:Mn²⁺ nanophosphors with different particle sizes were synthesized via the hydrothermal method by adjusting the concentrations of surfactant and the hydrothermal temperature. The behavior of the photoluminescence as a function of phosphor particle sizes under vacuum ultraviolet excitation was investigated. Higher critical quenching concentration with decreasing particle size of the Zn₂SiO₄:Mn²⁺ nanophosphors was observed. This is ascribed to the hindrance of energy transfer between luminescence centers under vacuum ultraviolet excitation. The prolonged decay time in smaller samples provides further evidence that the energy transfer confinement has an effect on the photoluminescence properties.     

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.     

VUV spectroscopy of Ce<Superscript>3+</Superscript>-doped Na<Subscript>0.4</Subscript>Lu<Subscript>0.6</Subscript>F<Subscript>2.2</Subscript> single crystals

The short-wave transmission spectrum of Na_0.4Lu_0.6F_2.2 with the visible/ultraviolet transmission edge of 8 eV was studied. Absorption spectra of the 4f—5d transitions of the Ce³⁺ ion in the region of 4–8 eV were studied in Ce³⁺-doped Na_0.4Lu_0.6F_2.2 single crystals. Luminescence spectra in the ultraviolet and visible spectral regions, luminescence decay kinetics and reflection and luminescence excitation spectra in the visible/ultraviolet and ultraviolet regions (4–20 eV) were investigated at helium and room temperatures.     

Time-Resolved Vacuum Ultraviolet Spectroscopy of Er<Superscript>3+</Superscript> Ions in the SrF<Subscript>2</Subscript> Crystal

The photoluminescence and photoexcitation spectra as well as the luminescence decay kinetics of Er³⁺ ions in the visible ultraviolet and vacuum ultraviolet (VUV) regions have been studied by the method of low-temperature, time-resolved VUV-spectroscopy on excitation by synchrotron radiation. In the VUV spectral region of the luminescence of SrF₂:1% Er³⁺, the 146.5-nm band with a time of decay of less than 0.6 nsec was revealed together with the well-known emission band at 164.3 nm (decay constant in the microsecond range). Its possible nature is discussed. The specific features of the formation of photoexcitation spectra of the f-f and f-d transitions in the Er³⁺ ion are considered. Competition between the processes of excitation of f-f and d-f luminescence has been revealed. It manifests itself in the inverse relationship of their photoexcitation spectra in a range of energies of incident photons that are close to the position of the 4fⁿ⁻¹5d configuration levels. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 72, No. 4, pp. 519–523, July–August, 2005.     

Mechanism of photoluminescence excitation of Mn<Superscript>2+</Superscript> ions in ZnS crystals

The mechanisms of photoluminescence excitation of Mn²⁺ ions in ZnS crystals have been investigated on the basis of complex analysis of the temperature dependences of the photoluminescence and photoluminescence-excitation spectra of ZnS:Mn crystals. The activation energy of a manganese luminescence center was estimated at E_a = 0.17 ± 0.05 eV. It is shown that E_a represents an energy band with a width ΔE_a = 0.1 eV, within which a manganese luminescence center can experience radiationless recombination. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 72, No. 6, pp. 788–793, November–December, 2005.     

On the Luminescence of Ce<Superscript>3+</Superscript>, Eu<Superscript>3+</Superscript>, and Tb<Superscript>3+</Superscript> in Novel Borate LiSr<Subscript>4</Subscript>(BO<Subscript>3</Subscript>)<Subscript>3</Subscript>

This paper reports on the photoluminescence (PL) and time-resolved properties of Ce³⁺, Eu³⁺, and Tb³⁺ in novel LiSr₄(BO₃)₃ powder phosphors. Ce³⁺ shows an emission band peaking at 420 nm under 350-nm UV excitation. Energy transfer from Ce³⁺ to Mn²⁺ takes place in the co-doped samples. Eu³⁺ shows red emission under near UV excitation. LiSr₄(BO₃)₃:Eu³⁺ phosphor could be a suitable candidate for phosphor-converted solid state lighting. The luminescence lifetime is 2.13 ms for Eu³⁺ in LiSr₄(BO₃)₃:0.001Eu³⁺. As Eu³⁺ concentration increasing, the decay curves deviate from exponential behavior. Tb³⁺ shows the strongest ⁵D₄→⁷ F₅ emission line at 540 nm. Decay curves of ⁵D₄→⁷ F₅ and ⁵D₃→⁷ F₅ emission with different Tb³⁺ concentrations were also measured. Cross-relaxation process is discussed based on the decay curves.     

Concentration quenching and migration of excitations in a bulk Cd<Subscript>0.5</Subscript>Mn<Subscript>0.5</Subscript>Te crystal

The curves of intracenter luminescence decay for Mn²⁺ ions in the Cd_0.5Mn_0.5Te semiconductor solid solution, obtained in a low-temperature experiment, have been simulated by the Monte Carlo method. The features of the kinetics of the 2-eV band in the time interval where significant nonexponentiality of relaxation at different points of the emission band profile manifests itself, as well the integral kinetics and energy relaxation, have been considered. Migration of ion excitations and concentration quenching (which was previously disregarded) are considered to be the main mechanisms determining the kinetic curve formation. It was established that excitation by 2.34-eV photons leads to both selective (intracenter) and band excitation of Mn²⁺ ions. Comparison of the results of numerical simulation and experiment showed that the characteristic values of the migration and quenching rates (W _m and W _q , respectively) are close in magnitude and W _{q, m} ≈ 0.1/τ, where τ is the lifetime at the long-wavelength band wing with the exponential kinetics. The estimated quantum yield (0.56) indicates significant influence of the concentration quenching on the 2-eV luminescence quantum yield in Cd_{1 ? x} Mn _x Te and Zn_{1 ? x} Mn _x S crystals with a high concentration of Mn²⁺ ions.     

Luminescence and electronic excitations in Li<Subscript>6</Subscript>Gd(BO<Subscript>3</Subscript>)<Subscript>3</Subscript>: Ce<Superscript>3+</Superscript> crystals

This paper reports on a study of the luminescence emitted by Li₆Gd(BO₃)₃: Ce³⁺ crystals under selective photoexcitation to lower excited states of the host ion Gd³⁺ and impurity ion Ce³⁺ within the 100–500-K temperature interval, where the mechanisms of migration and relaxation of electronic excitation energy have been shown to undergo noticeable changes. The monotonic 10–15-fold increase in intensity of the luminescence band at 3.97 eV has been explained within a model describing two competing processes, namely, migration of electronic excitation energy over chains of Gd³⁺ ions and vibrational energy relaxation between the ⁶ I _j and ⁶ P _j levels. It has been shown that radiative transitions in Ce³⁺ ions from the lower excited state 5d ¹ to ² F _5/2 and ² F _7/2 levels of the ground state produce two photoluminescence bands, at 2.08 and 2.38 eV (Ce1 center) and 2.88 and 3.13 eV (Ce2 center). Possible models of the Ce1 and Ce2 luminescence centers have been discussed.     

High-energy frenkel cation exciton and specific features of its self-trapping in the CdI<Subscript>2</Subscript>-PbI<Subscript>2</Subscript> crystal system

It has been shown using atomic-force microscopy that the PbI₂ impurity is embedded in the CdI₂ crystal lattice in the form of nanocrystalline inclusions. The model of a high-energy cation exciton related to the ³ P ₂ state of a free Pb²⁺ ion has been considered for the impurity absorption (excitation) band at 3.23 eV. The resonance narrow photoluminescence bands with the split absorption band at 3.12 and 3.20 eV have been compared with the emission of a free Frenkel exciton. It has been demonstrated that, in the temperature range 25–45 K, there arises a self-trapped exciton state, and the main role in its formation is played by the bending vibrations of the CdI₂ crystal lattice. The potential barrier separating the self-trapped state from the free exciton is 23 meV. The photoluminescence band at 2.4 eV is assigned to the emission of the self-trapped high-energy cation exciton of PbI₂ in the CdI₂ crystal lattice.     

Energy transfer from the host to Er<Superscript>3+</Superscript> dopants in semiconductor SnO<Subscript>2</Subscript> nanocrystals segregated in sol–gel silica glasses

Undoped and Er³⁺-doped glass–ceramics of composition (100−x)SiO₂–xSnO₂, with x = 5 or 10 and with 0.4 or 0.8 mol% of Er³⁺ ions, were synthesised by thermal treatment of precursor sol–gel glasses. Structural studies were developed by X-Ray Diffraction. Wide band gap SnO₂ semiconductor quantum-dots embedded in the insulator SiO₂ glass are obtained. The mean radius of the SnO₂ nanocrystals, ranging from 2 to 3.2 nm, is comparable to the exciton Bohr radius. The luminescence properties have been analysed as a function of sample composition and thermal treatment. The results show that Er³⁺ ions are partially partitioned into the nanocrystalline phase. An efficient UV excitation of the Er³⁺ ions by energy transfer from the SnO₂ nanocrystal host is observed. The Er³⁺ ions located in the SnO₂ nanocrystals are selectively excited by this energy transfer mechanism. On the other hand, emission from the Er³⁺ ions remaining in the silica glassy phase is obtained by direct excitation of these ions.     

Luminescence and electronic excitations in KBe<Subscript>2</Subscript>BO<Subscript>3</Subscript>F<Subscript>2</Subscript> crystals

This paper reports on a study of the dynamics of electronic excitations in KBe₂BO₃F₂ (KBBF) crystals by low-temperature luminescent vacuum ultraviolet spectroscopy with nanosecond time resolution under photoexcitation by synchrotron radiation. The first data have been obtained on the kinetics of photoluminescence (PL) decay, time-resolved PL spectra, time-resolved PL excitation spectra, and reflection spectra at 7 K; the estimation has been performed for the band gap E _g = 10.6−11.0 eV; the predominantly excitonic mechanism for PL excitation at 3.88 eV has been identified; and defect luminescence bands at 3.03 and 4.30 eV have been revealed. The channels of generation and decay of electronic excitations in KBBF crystals have been discussed.     

Luminescence and electronic excitations in crystals K<Subscript>2</Subscript>Al<Subscript>2</Subscript>B<Subscript>2</Subscript>O<Subscript>7</Subscript> with defects

This paper reports on the results of the comprehensive study of the dynamics of electronic excitations in K₂Al₂B₂O₇ (KABO) crystals, obtained by low-temperature luminescence vacuum ultraviolet spectroscopy with nanosecond time resolution upon photoexcitation by synchrotron radiation. For the first time, the data have been obtained on the photoluminescence (PL) decay kinetics, PL spectra with time resolution, PL excitation spectra with time resolution, and reflection spectra at 7 K; the intrinsic nature of PL at 3.28 eV has been established; luminescence bands of defects have been separated in the visible and ultraviolet spectral regions; an intense long-wavelength PL band has been detected at 1.72 eV; channels of the formation and decay of electronic excitations in K₂Al₂B₂O₇ crystals have been discussed.     

Electronic excitations and defects in nanostructural Al<Subscript>2</Subscript>O<Subscript>3</Subscript>

A time-resolved cathodo-and photoluminescence study of nanostructural modifications of Al₂O₃ (powders and ceramics) excited by heavy-current electron beams, as well as by pulsed synchrotron radiation, is reported. It was found that Al₂O₃ nanopowders probed before and after Fe⁺ ion irradiation have the same phase composition (the γ-phase/δ-phase ratio is equal to 1), an average grain size equal to ～17 nm, and practically the same set of broad cathodoluminescence (CL) bands peaking at 2.4, 3.2, and 3.8 eV. It was established that Al₂O₃ nanopowders exhibit fast photoluminescence (PL) (a band at 3.2 eV), whose decay kinetics is described by two exponential stages (τ₁ = 0.5 ns, τ₂ = 5.5 ns). Three bands, at 5.24, 6.13, and 7.44 eV, were isolated in the excitation spectrum of the fast PL. Two alternate models of PL centers were considered, according to which the 3.2-eV luminescence either originates from radiative relaxation of the P^? centers (anion-cation vacancy pairs) or is due to the formation of surface analogs of the F⁺ center (F _S ⁺ -type centers). In addition to the fast luminescence, nano-Al₂O₃ was found to produce slow luminescence in the form of a broad band peaking at 3.5 eV. The excitation spectrum of the 3.5-eV luminescence obtained at T = 13 K exhibits two doublet bands with maxima at 7.8 and 8.3 eV. An analysis of the luminescent properties of nanostructural and single-crystal Al₂O₃ suggests that the slow luminescence of nanopowders at 3.5 eV is due to radiative annihilation of excitons localized near structural defects.     

Optical properties of Cd<Subscript>0.6</Subscript>Mn<Subscript>0.4</Subscript>Te/Cd<Subscript>0.5</Subscript>Mg<Subscript>0.5</Subscript>Te quantum-well structures

Emission spectra of three Cd_0.6Mn_0.4Te/Cd_0.5Mg_0.5Te superlattices with Cd_0.6Mn_0.4Te quantum-well (QW) widths of 7, 13, and 26 monolayers, respectively, and the same thickness (46 monolayers) of the Cd_0.5Mg_0.5Te barriers have been studied. The QW width affects the shape and spectral position of the Mn²⁺ intracenter luminescence (IL) band as a result of the crystal field being dependent on the position of the manganese ion with respect to the interface. Measured in identical experimental conditions, the exciton luminescence as compared to the IL is substantially higher in intensity in a QW than in a bulk CdMnTe crystal. Some samples of superlattices and bulk crystals exhibit, in addition to the conventional IL band near 2.0 eV, a weaker band at about 1.45 eV. This band apparently derives from intracenter transitions in the Mn²⁺ ions in the regions where the crystal lattice has the rock-salt rather than the conventional zinc blende structure.     

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.     

Synthesis and luminescent properties of Eu<Superscript>3+</Superscript>- and Eu<Superscript>2+</Superscript>-activated sodium pyrophosphate Na<Subscript>4</Subscript>P<Subscript>2</Subscript>O<Subscript>7</Subscript>

The luminescent properties of Eu³⁺ and Eu²⁺ ions in sodium pyrophosphate, Na₄P₂O₇, have been studied. The excitation spectrum of the Eu³⁺ emission in Na₄P₂O₇ consists of several sets of bands in the range 280–535 nm due to 4f–4f transitions of Eu³⁺ ions and a broad band with a maximum at about 240 nm interpreted to be due to a charge transfer (CT) transition from oxygen 2p states to empty states of the Eu³⁺ 4f⁶-configuration. Although the CT band energy is large enough, the quantum efficiency (η) of the Eu³⁺ emission in Na₄P₂O₇ under CT excitation was estimated to be very low (η ≤ 0.01). In terms of a configurational coordinate model, this fact is interpreted as a result of the high efficiency of a radiationless relaxation from the CT state to the ⁷F₀ ground state of Eu³⁺ ions occupying sodium sites in Na₄P₂O₇. A strong reducing agent is required in order to stabilize Eu²⁺ ions in Na₄P₂O₇ during the synthesis. Several nonequivalent Eu²⁺ luminescence centers in Na₄P₂O₇ were found.     

Enhanced luminescence in ZnGa<Subscript>2</Subscript>O<Subscript>4-x</Subscript>S<Subscript>x</Subscript>:Mn<Superscript>2+</Superscript> thin-film phosphors grown on MgO(100) substrate

Mn-doped ZnGa₂O_4-xS_x thin-film phosphors have been grown using a pulsed laser deposition technique at varying growth conditions. Structural characterization was carried out on a series of ZnGa₂O_4-xS_x:Mn²⁺ films grown on MgO(100) substrates using Zn-rich ceramic targets. Oxygen pressure was fixed at 100 mTorr and substrate temperatures were varied from 500 to 700 °C. The results of X-ray-diffraction patterns showed that the lattice constants of the ZnGa₂O_3.95S_0.05:Mn²⁺ thin films decrease with the substitution of sulfur for the oxygen in ZnGa₂O₄. Measurements of photoluminescence (PL) properties of ZnGa₂O_4-xS_x:Mn²⁺ thin films have indicated that MgO(100) is one of the most promising substrates for the growth of high-quality ZnGa₂O_4-xS_x:Mn²⁺ thin films. In particular, the incorporation of sulfur into the ZnGa₂O₄ lattice could induce a remarkable increase of PL. The highest green-emission intensity was observed with ZnGa₂O_3.95S_0.05:Mn²⁺ films, whose brightness was increased by a factor of 3.5 in comparison with that of ZnGa₂O₄:Mn²⁺ films. This phosphor may be promising for application to flat-panel displays. PACS 78.20.-e; 78.55.-m; 78.66.-w