Luminescence spectroscopy of Ln-doped Bi-containing phosphates and molybdates

The photoluminescence (PL) emission and excitation spectra of undoped and doped with rare-earth (RE = Eu, Tb) ions K₃Bi₅(PO₄)₆ and K₂Bi(PO₄)(MoO₄) crystals are studied in 3.7–14 eV region of the excitation photon energies at T = 8 and 300 K. The mechanisms of the host-related and RE-related luminescence in 3.7–7 eV region of the excitation photon energies are revealed in comparative analysis of the PL spectra of studied compounds. It is assumed that the excitation mechanisms of host luminescence of K₃Bi₅(PO₄)₆ and K₂Bi(PO₄) (MoO₄) crystals below 4.8 eV are related to Bi³⁺ ions in oxygen surrounding. An efficient energy transfer from the Bi³⁺-related luminescence centers to the emitting RE centers exists in crystals with low concentration of the RE dopants (1%). The PL excitation spectra of K₃Bi₅(PO₄)₆ crystals with high concentration of Eu dopants are formed by O – Eu CT transitions.     

Luminescence of some zirconium-containing compounds under vacuum ultraviolet excitation

Photoluminescence of compounds that contain stoichiometric zirconium has been studied under vacuum ultraviolet excitation. The compounds show emission peaking at 280-320 nm while the excitation spectra show some bands in 130-190 nm region. The ultraviolet emission is explained as Zr to O charge transfer transition. The luminescence result and structural information classify the studied compounds into two groups. The former group involves ZrP₂O₇, CaZr(PO₄)₂, NaZr₂(PO₄)₃, Ca₂ZrSi₄O₁₂, Ca₃ZrSi₂O₉ and SrZrSi₂O₇, which show rather intense luminescence and do not have any infinite Zr-O-Zr-O-3D chain or link in their structure. The latter group is CaZrO₃ and ZrSiO₄, which do contain infinite Zr-O-Zr-O-3D chain and show quite weak luminescence. Luminescence of Ca_1−xMn_xZr(PO₄)₂ has also been studied. By replacing a part of Ca with Mn, ultraviolet emission of the host weakens and visible emission peaking at 540 nm appears. It is claimed that transfer of absorbed energy from Zr to Mn occurs.     

Violet-blue-shift of emission and enhanced luminescent properties of Ca3(PO4)2:Ce3+ phosphor induced by substitution of Gd3+ ions

Ca₃(PO₄)₂:1mol%Ce³⁺/xGd³⁺ (where x = 0.5, 1.0, 3.0 and 5.0 mol%) phosphors were synthesized by the conventional combustion synthesis method. The X-ray diffraction patterns showed their rhombohedral structure with space group of R3c. The optical properties including reflectance, excitation and emission were investigated. The band gaps of the phosphors were calculated from diffuse reflectance spectra data using the Kubelka–Munk function. The photoluminescence (PL) excitation spectra exhibited the broadband 4f–5d transition of Ce³⁺ ions centered at ~265 nm. The PL emission properties of the Ca₃(PO₄)₂:Ce³⁺/Gd³⁺ phosphors were studied as a function of the Gd³⁺ ion concentration. The Ca₃(PO₄)₂:Ce³⁺/Gd³⁺ phosphor had a wide emission band ranging from 320 to 400 nm, and peaking at 365 nm. This emission is ascribed to the transition from the higher 5d band to ²F_7/2, ²F_5/2 states of the Ce³⁺ ion. The 365 nm peak shifted to longer wavelengths with increasing concentration of the Gd³⁺ ion. The CIE chromaticity diagram of Ca₃(PO₄)₂:Ce³⁺/Gd³⁺ phosphor showed tunable emission colour from violet to violet-blue, suggesting that this phosphor can act as a source of violet-blue colour for application in information displays, phototherapy and photoluminescent liquid crystal displays.     

Luminescence of LiTb(PO3)4:Sm3+ and energy transfer from Tb3+ to Sm3+ under vacuum ultraviolet–ultraviolet excitation

The photoluminescence (PL) of LiTb(PO₃)₄, LiGd_0.97Sm_0.03(PO₃)₄, and LiTb_0.97Sm_0.03(PO₃)₄ under vacuum ultraviolet (VUV)/ultraviolet (UV) excitation were studied. We observed the VUV–UV sensitization of Sm³⁺ emission (561 nm, 601 nm, 649 nm, and 710 nm) by Tb³⁺ in LiTb(PO₃)₄:Sm³⁺, which leads to the yellow light emission (486 nm, 546 nm, 561 nm, 587 nm, 601 nm, 621 nm, 649 nm, and 710 nm) of LiTb(PO₃)₄:Sm³⁺ phosphor under UV and VUV excitation. The emission is a result of partial energy transfer from Tb³⁺ to Sm³⁺, which is discussed in detail in terms of the excitation and emission spectra and decay curves.     

Line emission of SrBe2Si2O7:Eu2+ and BaBe2Si2O7:Eu2+

The compounds SrBe₂Si₂O₇ and BaBe₂Si₂O₇ both have the barylite structure. With 254 nm excitation, the Eu²⁺-activated compounds give UV emission peaking at 360 nm (Sr) and at 375 nm (Ba). Maximum quantum efficiencies of 40% (Sr) and 65% (Ba) were measured. The emission consists of a 5d-4f band emission as well as 4f-4f line emission, in contrast to many other Eu²⁺-activated oxides which generally show only 5d-4f band emission. At 77°K, both compounds show only the 4f-4f line emission peaking at 360 nm. At higher temperatures, 5d-4f band emission shows up at the cost of the line emission. A thermal equilibrium is assumed between the lowest excited 5d and 4f levels. The energy difference between these levels, calculated from the variation in the line-band intensity ratio with temperature, was computed to be 0.15 eV (Sr) and 0.09 eV (Ba). The occurrence of the line emission in the barylites is correlated with the weakness of the crystal field at the Eu²⁺ ions and with the high quenching temperature of the 5d-4f band emission.     

Structure twinning,electronic and photoluminescence properties of yavapaiite-type orthophosphate BaTi(PO4)2

A ternary orthophosphate BaTi(PO₄)₂ has been prepared using a high temperature molten salt method and structurally determined by single crystal X-Ray diffraction analysis. It crystallizes in yavapaiite-type structure with monoclinic space group C2/m. The structure was refined by a non-merohedral twinning model with the twin law (−0.435 1.4350 −0.564 −0.435 0 0.097 −0.099 1). Band structure calculation using the density functional theory (DFT) method indicates that BaTi(PO₄)₂ has a direct bond gap of about 3.00 eV, which is well fitted with the experimental value of 2.95 eV. The photoluminescence excitation and emission spectra, decay curve, and the color coordinates for BaTi(PO₄)₂ were investigated. It can be efficiently excited by UV light (270 nm) and presents blue–green emission (centered at 506 nm), which may be attributed to the lattice defect emission.     

A time-resolved luminescence spectroscopy study of non-linear optical crystals K2Al2B2O7

We report the results of complex study of luminescence and dynamics of electronic excitations in K₂Al₂B₂O₇ (KABO) crystals obtained using low-temperature luminescence-optical vacuum ultraviolet spectroscopy with sub-nanosecond time resolution under selective photoexcitation with synchrotron radiation. The paper discusses the decay kinetics of photoluminescence (PL), the time-resolved PL emission spectra (1.2–6.2 eV), the time-resolved PL excitation spectra and the reflection spectra (3.7–21 eV) measured at 7 K. On the basis of the obtained results three absorption peaks at 4.7, 5.8 and 6.5 eV were detected and assigned to charge-transfer absorption from O^2? to Fe³⁺ ions; the intrinsic PL band at 3.28 eV was revealed and attributed to radiative annihilation of self-trapped excitons, the defect luminescence bands at 2.68 and 3.54 eV were separated; the strong PL band at 1.72 eV was revealed and attributed to a radiative transition in Fe³⁺ ion.     

Near infrared and charge transfer luminescence of trivalent ytterbium in KLa(PO3)4 powders

The polycrystalline powders of condensed polyphosphates KLa_(1 ? x)Yb_x(PO₃)₄ (x = 5, 10, 15, 20%) with linear chain were prepared by solid-state reaction. These samples were characterized by X-ray diffraction, FTIR and Raman scattering spectroscopies. The obtained powders are formed by single monoclinic phase of type III of condensed polyphosphate KLa(PO₃)₄ (KLP) crystallized with P2₁ space group. Lattice parameters varied as a function of the ytterbium concentration. As the Yb³⁺ concentration increased, the crystal lattice parameters were decreased. For the first time, near infrared (NIR) and UV–Visible spectroscopy of Yb³⁺ in KLa(PO₃)₄ powders, at room temperature, are carried out. In the IR range, a broad band relative to the fundamental ²F_5/2 → ²F_7/2 emission was registered. In the UV–Visible spectra, two bands typical of the Yb³⁺ charge transfer band (CTB) luminescence are observed. The registered decay times of these two emission types showed low sensibility to the Yb³⁺ concentration in KLa(PO₃)₄.     

Photoluminescence and thermoluminescence characterization of Eu- and Dy -activated Ca3(PO4)2 phosphor

Rare-earth-doped polycrystalline Ca₃(PO₄)₂:Eu, Ca₃(PO₄)₂:Dy and Ca₃(PO₄)₂:Eu,Dy phosphors prepared by a modified solid-state synthesis has been studied for its X-ray diffraction, thermoluminescence (TL) and photoluminescence (PL) characteristics. The PL emission spectra of the phosphor suggest the presence of Eu³⁺ ion in Ca₃(PO₄)₂:Eu and Dy³⁺ ion in Ca₃(PO₄)₂:Dy lattice sites. The TL glow curve of the Ca₃(PO₄)₂:Eu compounds has a simple structure with a prominent peak at 228 °C, while Ca₃(PO₄)₂:Dy peaking at 146 and 230 °C. TL sensitivity of phosphors are compared with CaSO₄: Dy and found 1.52 and 1.20 times less in Ca₃(PO₄)₂:Eu and Ca₃(PO₄)₂:Dy phosphors, respectively. The Ca₃(PO₄)₂:Eu,Dy phosphors shows switching behavior under two different excitation wavelengths and enhancement in PL intensity of Dy³⁺ ions were reported. The paper discusses the photoluminescence and thermoluminescence behavior of Eu³⁺ and Dy³⁺ ion in Ca₃(PO₄)₂ hosts, it may be applicable to solid-state lighting as well as thermoluminescence dosimetry applications.     

Luminescent properties of Mg3Ca3(PO4)4: Eu2+ blue-emitting phosphor for white light emitting diodes

A blue-emitting phosphor, Eu²⁺-activated Mg₃Ca₃(PO₄)₄ phosphor was synthesized by conventional solid-state reaction. X-ray powder diffraction (XRD) analysis confirmed the phase formation. Photoluminescence (PL) results showed that Mg₃Ca₃(PO₄)₄: Eu²⁺ could be efficiently excited by UV–visible light from 250 to 430 nm, which matched well with the emission wavelengths of near-UV and UV LED chips. The effects of the doped-Eu²⁺ concentration in Mg₃Ca₃(PO₄)₄: Eu²⁺ on the PL were also investigated. The result reveals that Mg₃Ca₃(PO₄)₄: Eu²⁺ is a potential blue-emitting phosphor for white LEDs.     

A potential red emitting K4Ca(PO4)2: Eu3+ phosphor for white light emitting diodes

Europium (III) ions doped red phosphors K₄Ca(PO₄)₂ were prepared first time by high temperature solid state reaction method. The prepared phosphors structure was examined by X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, scanning electron microscopy (SEM), and energy dispersive spectroscopy (EDS) analyses. The thermal properties of the synthesized phosphor were investigated by differential scanning calorimetry (DSC) analysis. Photoluminescence (PL) spectra of K₄Ca(PO₄)₂:Eu³⁺ phosphors have shown strong red emission at 618 nm (⁵D₀→⁷F₂) with near UV an excitation wavelength of λ_exc=394 nm (⁷F₀→⁵L₆). In addition, the decay curves and CIE color coordinate measurements are also carried out. Hence, emission and excitation characterization of synthesized phosphors shows that the phosphors may be a promising red component for the application in the white light emitting diodes (WLEDs).     

Luminescence properties of novel NaBa4(BO3)3:Ce, Eu phosphors

Novel Eu³⁺, Ce³⁺ activated NaBa₄(BO₃)₃ phosphors were synthesized by solid-state reactions. The excitation spectrum of NaBa₄(BO₃)₃:Ce³⁺ consists of an intense band peaking at 350 nm and a weak band in the higher energy side, and the emission spectrum exhibits a blue band with a maximum at about 420 nm. The Eu³⁺ emission in NaBa₄(BO₃)₃ consists of the transitions from ⁵D₀ to ⁷F_J, and the excitation spectrum consists of broad excitation band peaking at 270 nm and some intense narrow lines. The optimum doped concentration, the critical distance of the concentration quenching, and the fluorescence lifetime have also been investigated.     

Synthesis and photoluminescence properties of MZr2(PO4)3:Eu3+; Bi3+ (M=Na; K) phosphors

A series of new red phosphors, MZr₂(PO₄)₃:Eu³⁺; Bi³⁺ (M=Na; K), were synthesized using the solidstate reaction method, and their photoluminescence spectra were measured. The MZr₂(PO₄)₃:Eu³⁺; Bi³⁺ (M=Na; K) phosphors were efficiently excited by an ultraviolet (UV; 395 nm) source, and showed intense orange-red emission at 595 nm. Further investigation of the concentration-dependent emission spectra indicated that the MZr₂(PO₄)₃:Eu³⁺; Bi³⁺ (M=Na; K) phosphors exhibit the strongest luminescence intensity when y = 0.01 in NaZr_2(0:95−y)(PO₄)₃:Eu_0.10³⁺, Bi_2y ³⁺ and y = 0.09 in NaZr_2(0.95−y)(PO₄)₃:Eu_0.10³⁺, Bi_2y ³⁺, whereas the relative PL intensity decreases with increasing Bi³⁺ concentration due to concentration quenching. The addition of Bi³⁺ widens the excitation band of NaZr_2(0.95−y)(PO₄)₃:Eu_0.10³⁺, Bi_2y ³⁺ around 320 nm, which provides the useful idea of broadening the excitation band around 300–350 nm to fit the ultraviolet chip.     

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.     

Spectral structure of barium–phosphate–silicate phosphor Ba10(PO4)4(SiO4)2:EuM+

The new apatite–silicate phosphor doped with Eu ions in Ba₁₀(PO₄)₄(SiO₄)₂ matrix was synthesized through solid-state reaction. It was found that the as-synthesized phosphor displayed apparent mixture of band and line emission peaks giving rise to pseudo white light. The narrow emission bands peaking at 410 nm can be assigned to the 4f⁶5d→4f⁷(⁸S_7/2) transition of Eu²⁺ ions, and the other band at 507 nm is ascribed to anomalous fluorescent emission. One group of line emission peaking at 595 nm and 613 m were due to the ⁵D₀→⁷F₁ and ⁵D₀→⁷F₂ transition of Eu³⁺ ions. The occurrence of photostimulated luminescence and discrete emission lines in violet (410 nm), green (507 nm) and red (595 nm and 613 nm) colors indicate that this material has potential application in fields of white-light-emitting.     

Optical and theoretical investigations of V ions in CdZnTe crystal

High-resistivity CdZnTe:V crystals are investigated by photoluminescence (PL) and by time-resolved PL in the infrared spectral range. A double peaked emission band is detected around 0.8 eV and it is related to vanadium doping. No-phonon lines of the internal transitions were detected. This emission is interpreted as a balance between the ⁴T₁(⁴P)→⁴T₁(⁴F) internal transition and an electronic transition from the conduction band to the ⁴T₁(⁴F) ground state of V²⁺. The corresponding decay time after laser excitation gives evidence to the contribution of two different recombination processes. These two emission bands are separated by time-resolved luminescence. Crystal-field calculations of the detected transition energies based on Tanabe-Sugano scheme are presented and the Racah parameter B and crystal-field intensity D_q were determined.In addition, a model is developed in terms of one-electron orbital, to explain the characteristics of the PL excitation processes of V²⁺. Excitations with above and below band edge energy confirm the proposed schemes.     

Synthesis and photoluminescence study of rare earth activated phosphor Na2La2B2O7

The photoluminescence properties in UV and N-UV excitable range for the phosphors of Na₂La₂B₂O₇: RE (RE=Eu, Tb, Ce, Sm, Gd) are investigated. The solution combustion synthesis technique was employed for the synthesis of the phosphors Na₂La₂B₂O₇: RE. The photoluminescence measurements of the phosphors were carried out on a HITACHI F7000 Fluorescence Spectrophotometer. The PL and PL excitation (PLE) spectra indicate that the main emission wavelength of Na₂La₂B₂O₇: Eu are 591 and 615 nm, Na₂La₂B₂O₇: Ce shows dominating emission peak at 387 nm and Na₂La₂B₂O₇: Tb displays green emission at 493, 544, 593 and 620 nm at 254 nm excitation, while Na₂La₂B₂O₇: Sm shows the main emission peak wavelengths 566 and 604 nm at 405 nm excitation and Na₂La₂B₂O₇: Gd shows dominating emission peak at 312 nm at 274 nm excitation. These phosphors may provide a new kind of luminescent materials under ultraviolet and near ultraviolet excitation for various applications.     

Blue emission in Eu2+ activated MgXAl10O17 (X = Sr,Ca) phosphors

Here we reported photoluminescence properties of Eu²⁺ activated in novel and existing MgXAl₁₀O₁₇ (X = Sr, Ca) phosphor which has been prepared by combustion synthesis at 550 °C under UV and near UV excitation wavelength. The PL emission properties of MgSrAl₁₀O₁₇:Eu²⁺ were monitored at 254 nm and 354 nm respectively keeping emission wavelength at 469 nm. Whereas novel MgCaAl₁₀O₁₇:Eu²⁺ exhibit emission band at 452 nm keeping excitation at 378 nm. These blue emission corresponds to 4f⁶5d¹ → 4f⁷ transition of Eu²⁺ ions. Further phosphor was analyzed by XRD for the confirmation of desired phase and purity.     

Optical characterization of fourfold (Td)- and sixfold (Oh)-transition-metal species in MgAl2O4:Co by time-resolved spectroscopy

This work investigates the origin of novel visible photoluminescence (PL) bands observed in the spinel MgAl₂O₄:Co²⁺. Besides the well-known fourfold-coordinated Co²⁺(T_d) PL at 670 nm [N.V. Kuleshov, V.P. Mikhailov, V.G. Scherbitsky, P.V. Prokoshin and K.V. Yumashev, J. Lumin. 55 (1993) 265.], a rich structured PL band at 686 nm was also observed that we associate with uncontrolled impurities of sixfold coordinated Cr³⁺(O_h) by time-resolved spectroscopy and lifetime measurements and their variation with temperature. We also show that the lifetime of the Co²⁺(T_d) emission at 670 nm varies from τ=6.7 μs to 780 ns on passing from T=10 to 290 K. This unexpected behaviour for T_d systems is related to the excited-state crossover (⁴T₁↔²E), making the emission band to transform from a narrow-like emission from ²E at low temperature to a broad structureless band from ⁴T₁ at room temperature.     

Thermally stimulated luminescence of Ca3(PO4)2 and Ca9Ln(PO4)7 (Ln = Pr,Eu, Tb,Dy, Ho,Er, Lu)

The series of whitlockite compounds Ca₃(PO₄)₂ and Ca₉Ln(PO₄)₇ (Ln = Pr, Eu, Tb, Dy, Ho, Er, Lu) was studied in radioluminescence (RL) and thermally stimulated luminescence (TSL) excited by X-rays. f-f emission lines of Ln³⁺ were observed in RL for Ca₉Ln(PO₄)₇ (Ln = Pr, Eu, Tb, Dy, Ho, Er) whereas d-d emission band of the impurity Mn²⁺ was observed in Mn:Ca₃(PO₄)₂ and Mn:Ca₉Lu(PO₄)₇ at 655 nm. In TSL, the Eu, Ho and Er compounds did not show any signal. As Eu³⁺, Ho³⁺ and Er³⁺ present the highest Ln³⁺/Ln⁴⁺ ionization potential (IP) of the series, this was interpreted as the inability of these lanthanides to trap a hole. On the contrary Pr³⁺ in Ca₉Pr(PO₄)₇, Tb³⁺ in Ca₉Tb(PO₄)₇, Dy³⁺ in Ca₉Dy(PO₄)₇, Mn²⁺ in Mn:Ca₃(PO₄)₂ and Mn:Ca₉Lu(PO₄)₇ were identified as hole traps and radiative recombination centers in the TSL mechanism. Ca₉Tb(PO₄)₇ was found to be a high intensity green persistent phosphor whereas Mn:Ca₉Lu(PO₄)₇ is a red persistent phosphor suitable for in vivo imaging application.