Luminescent materials with dolomite structure

doi:10.1016/0254-0584(86)90039-8

Materials Chemistry and Physics

Volume 14, Issue 3, March 1986, Pages 253-258

https://doi.org/10.1016/0254-0584(86)90039-8 Get rights and content

Abstract

Dolomites of the type MZr(BO₃)₂ (M = Ca, Sr, Ba) are reported. The Pb²⁺ ion is an efficient luminescent activator in these compounds. The Stokes shift is large. The Tb³⁺ ion is sensitized by Pb²⁺ (R_c ~ 9 Å). The Ti⁴⁺ ion shows at 300 K medium efficiency due to thermal quenching.

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The vacuum referred electron binding energies in the S01 and P13 states of Pb2+ and Tl+ in inorganic compounds
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An overview of the spectroscopic data on ${Tl}^{+}$ and ${Pb}^{2 +}$ in 37 and 126 different inorganic compounds, respectively, is presented. Using the metal-to-metal charge transfer and A-band transition energies, the electron binding energies in the ${}^{1}S_{0}$ ground state and ${}^{3}P_{1}$ excited state of ${Tl}^{+}$ and ${Pb}^{2 +}$ were determined relative to the vacuum level. By constructing vacuum referred binding energy (VRBE) diagrams that display the energy levels of the ${Tl}^{+}$ and ${Pb}^{2 +}$ activator ion together with that of the host compound, insight in the luminescent properties of these activated compounds are gained. The obtained VRBEs of the electron in the ${}^{1}S_{0}$ and ${}^{3}P_{1}$ states of ${Tl}^{+}$ and ${Pb}^{2 +}$ are compared to those of ${Bi}^{3 +}$ .
Photoluminescence study of a novel UV emitting phosphor Sr<inf>2</inf>Mg(BO<inf>3</inf>)<inf>2</inf>:Pb2+,Gd3+
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The emission of Pb2+ can, for example, vary from ultraviolet to red [25]. This not only makes the Pb2+ ion used in black-lamp phosphor (e.g. BaSi2O5:Pb2+) [26], but also used as a sensitizer for the luminescence of some rare earth ions [27,28]. In the electronic transitions of Pb2+, non-shielded s and p orbitals are involved.
Photoluminescence properties of a novel UV emitting phosphor Sr₂Mg(BO₃)₂:Pb²⁺,Gd³⁺ with varying concentration of Pb²⁺ and Gd³⁺ were studied. Crystal structure and co-ordination of prepared phosphor was confirmed using powder X-ray diffraction and FT-IR. SEM images of prepared powder samples show the irregular grains with agglomeration phenomena. Under the excitation of Hg line of 254 nm phosphor materials show two emissions at 313 nm and 330 nm, which could be applicable in phototherapy for combination therapy of narrowband UVB plus PUVA.
On the role of the network modifier PbO in Sm3+-doped borate glasses
2014, Journal of Luminescence
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This band, however, does not appear in glasses where the PbO concentration exceeds 60 mol%. It originates from luminescence of Pb2+ ions which are not chemically bound in the borate glass network [4]. For a lead concentration of 20–40% the Pb2+ emission overlaps strongly with the Sm3+ absorption bands, i.e. the lead-related emission excites the Sm3+ ions.
A series of Sm³⁺-doped lead borate glasses with a lead oxide (PbO) content varying from 20 mol% to 80 mol% and a samarium oxide (Sm₂O₃) content of 1 mol% is investigated. In addition to the network changes in the glass structure, the lead doping has a significant influence on the fluorescence properties of Sm³⁺ and on the tuneable intrinsic fluorescence of Pb²⁺ itself. The Pb²⁺ excitation band shifts monotonously to lower energies; its intensity is significantly reduced for a PbO content of 50 mol% and more. For a concentration of 30 mol%, the Pb²⁺ emission overlaps with the intense ⁶H_5/2 to ⁶P_5/2 Sm³⁺ excitation band enabling for radiative and non-radiative energy transfers. Lifetime measurements of excited Sm³⁺ show in all cases non-single exponential decay and were fitted by the Inokuti–Hirayama model indicating non-radiative dipole–dipole interaction between neighbouring Sm³⁺ ions.
Synthesis and PL study of UV emitting phosphor KCa<inf>4</inf>(BO <inf>3</inf>)<inf>3</inf>:Pb2+
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This diversity is depending strongly on the site occupied by Pb2+ ions, electronegativity of the ligand, crystal structure of the host lattice and temperature [15,16]. Some scientists have studied the photoluminescence properties of Pb2+ in various inorganic borates with different structure, such as LiCaBO3 [17], Li6CaB3O8.5 [18], Sr2Mg(BO3)2, Ba2Mg(BO3)2 [19] SrLaBO4 & CaLaBO4 [20], BaAl2B2O7 [21], SrAl2B2O7 [22], SrB2O4 [23], Sr6YAl(BO3)6 & Sr5La2Mg(BO3)6 [24], CaZr(BO3)2 [25], Ca2La2BO6.5, Ca2B5O9Cl & CaB2O4 [26], the spectroscopic data is given in Table 2. The luminescence intensities of Pb2+ doped phosphors always depend on the doped Pb2+ ions concentration [27–29].
Pb²⁺ doped KCa₄(BO₃)₃ materials were prepared by a novel solution combustion synthesis technique which is slight variation of combustion synthesis method. The synthesized materials were characterized by powder XRD and FT-IR. Scanning Electron Microscopy (SEM) observation indicated that the microstructure of the phosphor consisted of irregular grains which get finer and shaped in doped sample as compared to pure. The photoluminescence properties of synthesized materials were investigated using Spectrofluorometer at room temperature. The emission and excitation bands of the synthesized phosphors were observed at 335 nm and 260 nm respectively. The concentration of Pb²⁺ for which optimum emission is obtained was found to be 0.005 mol. The critical transfer distance (R₀) for optimum concentration was determined to be 16.88 Å. The Stokes shift of KCa₄(BO₃)₃:Pb²⁺ was measured to be 8756 cm⁻¹. The phosphor could find application in medical and lamp industry.
Samarium fluorescence efficiency in high mass density borate glasses
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Citation Excerpt :
The 280 nm excitation band is caused by an interaction between Pb2+ and Sm3+: Photon energies of approx. 4 eV excite the Pb2+ ions in the glass from the electronic ground state 1S0 to the upper states 3P0,1,2 (triplet) and 1P1 (singlet). After excitation the Pb2+ ion relaxes radiatively from the 3P0 excited state to the 1S0 ground state (Blasse et al., 1986). The emission band is more than 1 eV red-shifted with respect to the absorption band.
A series of Sm³⁺-doped lead borate glasses with a lead oxide content varying from 20 mol% to 80 mol% is investigated. Raman spectroscopy was used to investigate the influence of the network modifier content on the glass structure, in particular, on the phonon spectrum of the different lead borate glasses. In addition to the significant changes in the glass structure, the lead doping also has a significant influence on the fluorescence properties of Sm³⁺ co-doped glasses.
Synthesis and photoluminescence of LiCaBO <inf>3</inf>: M (M: Pb 2+ and Bi 3+) phosphor
2012, Journal of Luminescence
Citation Excerpt :
For example, the stokes shifts of CaO: Bi+3 (CN: 4), LiCaBO3: Bi+3 (CN: 7) and CaZrO3: Bi+3(CN: 8), which are 1822, 6440 and 6476 cm−1, respectively [22,29,30,31]. Additionally, it is known that the magnitude of the Stokes shift is correlated to the environments of cation site in host lattice [15]. For example, in CaHfO3 [22], CaZrO3 [22,30], CaO [29,30,31], CaSO4 [32], the Stokes shifts for Bi3+ is approximately 6289, 6476, 1822 and 1793 cm−1, respectively.
Pure, Pb²⁺ and Bi³⁺ doped LiCaBO₃ materials were prepared by a solution combustion synthesis method. The phase of LiCaBO₃ were determined using the powder XRD and FTIR. The photoluminescent properties of Pb²⁺ and Bi³⁺ doped LiCaBO₃ materials were investigated using spectrofluorometer at room temperature. The emission bands of LiCaBO₃: Pb²⁺ and LiCaBO₃: Bi³⁺ were observed at 296 and 378 nm, respectively. LiCaBO₃ with different Pb²⁺ and Bi³⁺ doping concentrations were analyzed at room temperature. The Stokes shifts of LiCaBO₃: Pb²⁺ and LiCaBO₃: Bi³⁺ were calculated to be 3952 and 6440 cm⁻¹, respectively.

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Materials Chemistry and Physics

Abstract

References (23)

J. Luminescence

C. R. Ac. Sci. Paris, Sér. C

J. Solid State Chem.

J. Solid State Chem.

J. Chem. Phys.

The major ternary structural families

J. Chem. Phys.

J. Chem. Phys.

J. Phys. Chem. Solids

Phys. Stat. Sol. (b)

Mat. Res. Bull.

J. Solid State Chem.

Cited by (22)

The vacuum referred electron binding energies in the S01 and P13 states of Pb<sup>2+</sup> and Tl<sup>+</sup> in inorganic compounds

Photoluminescence study of a novel UV emitting phosphor Sr<inf>2</inf>Mg(BO<inf>3</inf>)<inf>2</inf>:Pb<sup>2+</sup>,Gd<sup>3+</sup>

On the role of the network modifier PbO in Sm<sup>3+</sup>-doped borate glasses

Synthesis and PL study of UV emitting phosphor KCa<inf>4</inf>(BO <inf>3</inf>)<inf>3</inf>:Pb<sup>2+</sup>

Samarium fluorescence efficiency in high mass density borate glasses

Synthesis and photoluminescence of LiCaBO <inf>3</inf>: M (M: Pb <sup>2+</sup> and Bi <sup>3+</sup>) phosphor