Study of Nd2+ absorption in x-irradiated CaF2, SrF2, BaF2 crystals

The absorption spectra of x-irradiated alkaline-earth fluoride (CaF₂, SrF₂, BaF₂) crystals doped with Nd³⁺ ions have been investigated. X-irradiation results in creating the absorption bands of inter-configuration 4fⁿ–4fⁿ⁻¹–5 d¹ transitions of Nd²⁺. The charge reduction of the neodymium by irradiation is not temperature-stable and the ions reoxidation (Nd²⁺ → Nd³⁺) occurs under heating to 570 K in CaF₂, 520 K in SrF₂ and 470 K in BaF₂.     

Behavior of the magnetic subsystems in Nd2BaNiO5

The temperature dependences of the heat capacity, the magnetic susceptibility, and the splitting of the ground Kramers doublet of the Nd³⁺ ion in the chain magnet Nd₂BaNiO₅ are studied. An antiferromagnetic phase transition manifests itself as anomalies in all these dependences. The parameters of the Nd-Ni and Nd-Nd interactions are estimated. The field dependence of the magnetization has two anomalies. A strong magnetic anisotropy prevents the magnetic moments of the Nd³⁺ ion from deviating from axis c in the crystal even in an external magnetic field. The processes of magnetization and the internal specific features of a chain of spins S = 1 are discussed.     

Spectroscopic study of neodymium-doped potassium-lead double chloride Nd3+:KPb2Cl5 crystals

Optical spectra, radiative and nonradiative transition intensities, and luminescence kinetics of neodymium-doped potassium-lead double chloride crystals Nd³⁺:KPb₂Cl₅, (Nd³⁺:KPC) are investigated. Crystals were grown by the Stockbarger-Bridgman technique. Experimental studies of absorption and luminescence spectra are performed, intensity parameters are obtained by the Judd-Ofelt method, radiative transition probabilities and branching ratios are calculated, and nonradiative transition probabilities are estimated. Luminescence kinetics of ² K _13/2, ² P _3/2, and ⁴ D _3/2 radiative levels of neodymium under selective excitation in the 355-nm region are studied.     

Upconverted 5d-4f luminescence from Er and Nd ions doped into fluoride hosts excited by ArF and KrF excimer lasers

We report on observation of upconverted VUV luminescence due to 5d-4f radiative transitions in Er³⁺ and Nd³⁺ ions doped into some fluoride crystals, under excitation by ArF and KrF excimer lasers, respectively. Only spin-forbidden 5d-4f luminescence of Er³⁺ (at 165 nm) was detected from the LiYF₄:Er³⁺ crystal whereas both spin-forbidden (at 169 nm) and spin-allowed (at 160.5 nm) components are observed from the BaY₂F₈:Er³⁺ crystal, the latter being much weaker than in the case of one-photon excitation. Nd³⁺ 5d-4f luminescence at 180 and 173 nm has been detected from the LiYF₄:Nd³⁺ and LaF₃:Nd³⁺ crystals, respectively. The shift of short-wavelength edge of 5d-4f emission spectra towards longer wavelengths is observed under temperature increase from 15 to 293 K. The observed effects in the spectra of Er³⁺ and Nd³⁺ doped crystals were interpreted as a result of reabsorption of 5d-4f luminescence escaping from the bulk of the crystals.     

Absorption of Dy3+ and Nd3+ ions in BaR 2F8 single crystals

The Dy³⁺ absorption and excitation spectra of BaY₂F₈ and BaYb₂F₈ single crystals are investigated in the ultraviolet, vacuum ultraviolet, and visible ranges at a temperature of 300 K. These crystals exhibit intense broad absorption bands due to the spin-allowed 4f-5d transitions in the range (56–78) × 10^?3 cm^?1 and less intense absorption bands that correspond to the spin-forbidden transitions in the range (50–56) × 10^?3 cm^?1. The Nd³⁺ absorption spectra of BaY₂F₈ single crystals are studied in the range (34–82) × 10^?3 cm^?1 at 300 K for different crystal orientations.     

Stark structure and exchange splittings of Nd<Superscript>3+</Superscript> ion levels in chain nickelate Nd<Subscript>2</Subscript>BaNiO<Subscript>5</Subscript>

Diffuse transmittance spectra of polycrystalline samples of chain nickelate Nd₂BaNiO₅ were measured with high resolution (0.1 cm^-1) over wide ranges of wavenumbers (1500–20000 cm^-1) and temperatures (4.2–300 K). The energies of 54 Stark sublevels of the Nd³⁺ ion and exchange splittings of some of them were determined in the magnetically ordered state of Nd₂BaNiO₅ (T _N = 47.5 ± 1 K). It was shown that the low-temperature magnetic properties of Nd₂BaNiO₅ are determined by exchange splitting (32 cm^-1) of the ground state.     

Crystal structure,thermal expansion and magnetic properties of Nd2Cu0.8Ge3 compound

A new ternary intermetallic compound, Nd₂Cu_0.8Ge₃, was synthesized and its crystal structure was determined by Rietveld refinement of X-ray powder diffraction data. The Nd₂Cu_0.8Ge₃ compound crystallizes in space group I4₁/amd (No. 141), with a tetragonal a-ThSi₂ structure type, and a=0.41783(2) nm, c=1.43689(9) nm, Z=2 and D_calc=7.466 g/cm³. Using the high temperature powder X-ray diffraction (HTXRD) technique, the lattice thermal expansion behavior of the compound was investigated in the temperature range of 298–648 K, and the result shows that its unit-cell parameters increased anisotropically when temperature increased. The magnetic susceptibility measured in the temperature range of 5–300 K indicated antiferromagnetic order of Nd₂Cu_0.8Ge₃ at low temperatures, and the magnetic susceptibility can be well described over the range of 50–300 K using Curie–Weiss law. The calculated effective magnetic moment (μ_eff) is 3.53 μ_B and dominated by the contribution of the Nd³⁺ ions.     

High-temperature VUV spectroscopy of KYF4 crystals doped with Nd3+, Er3+ and Tm3+ ions

Thermal quenching of 5d-4f luminescence from Nd³⁺, Er³⁺ and Tm³⁺ ions doped into KYF₄ crystals has been investigated in the temperature range up to ∼750 K where this luminescence is completely quenched. The obtained temperatures of thermal quenching (T_q) are ∼270, 495, 450 K for Nd³⁺, Er³⁺, Tm³⁺, respectively. At high temperatures, thermal quenching of 5d-4f luminescence from Nd³⁺ and Er³⁺ is accompanied by the appearance of 4f-4f luminescence from the lower-energy 4f levels. It has been shown that the dominating mechanism of thermal quenching for Nd³⁺ and Er³⁺ ions is thermally stimulated non-radiative transitions (intersystem crossing) from the 5d states to lower-energy 4f levels, namely ²G(2)_9/2 and ²F(2)_7/2, respectively, whereas for the Tm³⁺ ion, thermally stimulated ionization of 5d electrons to the conduction band states is responsible for thermal quenching of 5d-4f luminescence. The energy gap between the lowest Tm³⁺ 5d level and the bottom of the KYF₄ conduction band has been estimated to be 0.66 eV.     

Synthesis and near-infrared luminescence properties of LaOCl:Nd3+/Yb3+

Near-infrared emitting phosphors LaOCl:Nd³⁺/Yb³⁺ were prepared by the solid-state method, and their structures and luminescent properties were investigated by using X-ray diffraction and photoluminescence analysis, respectively. The studies shows that tetragonal LaOCl:Nd³⁺/Yb³⁺ can be synthesized by the solid-state reaction at 600 °C for 3 h. Upon 353 nm UV excitation, LaOCl:Nd³⁺/Yb³⁺ sample shows strong near-infrared emission lines in the region of 1060–1150 nm (corresponding to ⁴F_3/2 → ⁴I_J′ transition of Nd³⁺, J′ = 9/2, 11/2, 13/2, 15/2) and 980–1050 nm (corresponding to ²F_5/2 → ²F_7/2 transition of Yb³⁺). The decreasing emission intensity of Nd³⁺ with increasing doping concentration of Yb³⁺ proved the energy transfer in LaOCl:Nd³⁺/Yb³⁺. The possible near-infrared emission and energy transfer mechanism between Nd³⁺ and Yb³⁺, as well as the energy transfer efficiency of LaOCl:Nd³⁺/Yb³⁺ were discussed.     

Study of VUV emission and γ-ray responses of Nd:BaF2 scintillaotor

Nd³⁺ 1%, 5% and 10% doped BaF₂ single crystals were grown by the micro-pulling down method. Photoluminescence properties, including excitation and emission spectra and luminescence decay were measured under synchrotron radiation excitation at the Superlumi station in HASYLAB at DESY (Hamburg, Germany). The Nd³⁺ related 5d-4f emission lines peaking around 180 nm, 230 nm, and 260 nm, identified as the 5d–⁴I_j, 5d–⁴F_j, and 5d–²G_j transitions, were observed under 140–168 nm excitation. In photoluminescence decay under the 160 nm excitation, the dominant component decay time is about 12, 2.5 and 1.2 ns for Nd³⁺ 1%, 5% and 10% concentration, respectively. The decay time shortening is explained by the concentration quenching effect. Transmittance of Nd1% sample is about 80% for wavelengths above 185 nm. Finally, gamma-ray responses, non-proportionality and energy resolution of Nd1% sample were compared with the undoped BaF₂ scintillator. The light yield of the Nd1%:BaF₂ is about 93% of that of undoped BaF₂. ^©2009 Elsevier Ltd. All rights reserved.     

Energy levels fitting and crystal-field calculations of Nd3+ doped in GYSGG crystal

The single crystal Nd³⁺-doped in GdY₂Sc₂Ga₃O₁₂ (Nd³⁺:GYSGG) was grown by Czochralski method successfully, and its absorption spectra was analyzed in a wider spectral wavelength range at 7.6 K and 300 K, respectively. The free-ions and crystal-field parameters were fitted to the experimental energy levels at 7.6 K and 300 K with the root mean square deviation of 11.25 and 12.48 cm^?1, respectively. According to the crystal-field calculations, 116 levels of Nd³⁺ at 7.6 K and 114 levels of Nd³⁺ at 300 K were assigned. The fitting results of free-ions and crystal-field parameters were compared with those already reported of Nd³⁺:GSGG and Nd³⁺:YSAG. The results indicated that the free-ions parameters are similar to those of the Nd³⁺ in GYSGG, GSGG and YSAG crystals, and the crystal-field interaction of GSGG and YSAG is stronger than that of GYSGG, which results in the dual-wavelength properties of Nd³⁺:GYSGG crystal.     

Nd3+ near UV and visible fluorescence in YAP:Nd

The present paper summarizes detailed investigations of Nd³⁺ fluorescence spectra in YAP:Nd laser crystal in the broad spectral range of 370–1100 nm at liquid nitrogen temperature. Especially, Nd³⁺ near UV and visible fluorescence spectra were studied for the first time in this crystal. The Nd³⁺ near UV and visible fluorescence spectra of this crystal consist of many narrow lines (up to 50). The Nd³⁺ near UV and visible fluorescence lines arise mainly from⁴D_3/2 and²P_3/2 Nd³⁺ terms (transitions from⁴D_3/2,²P_3/2 to lower lying Nd³⁺ levels are responsible for their appearance). At room temperature the fluorescence spectra consist of broad bands with narrow lines (mainly⁴D_3/2⁴F_3/2,⁴F_5/2 and²H_9/2 transitions).     

Nd photoluminescence study of Nd-doped Si-rich silica films obtained by reactive magnetron sputtering

Nd³⁺-doped silicon-rich silicon oxide (SRSO) thin films have been fabricated by reactive magnetron sputtering of a pure silica target topped with Nd₂O₃ chips. The concentration of Nd ions in the deposited layers is controlled by the number of Nd₂O₃ chips, whereas the incorporation of silicon excess is monitored by the hydrogen partial pressure, P_H2, introduced in the Ar plasma, owing to the ability of hydrogen to reduce the oxygen released by the sputtering of the silica target. Photoluminescence (PL) experiments were made at room temperature using a nonresonant excitation line from an Ar laser. The influences of Nd³⁺ content and P_H2 have been studied to optimize the Nd³⁺ emission. PL spectra reveal a two order of magnitude enhancement of the Nd³⁺ emission around both 0.9 and 1.1 μm, when Si nanoclusters (Si-nc) are formed in the same Nd³⁺-doped matrix. The dependence of the Nd³⁺ PL with P_H2 and Nd concentration is indicative of the occurrence of an efficient energy transfer from the Si-nc to the rare earth ions. The radiative lifetime is also deduced and commented in the light of Nd³⁺-Si-nc coupling.     

Fluorescence and Judd-Ofelt analysis of Nd ions in oxyfluoride glass ceramics containing CaF2 nanocrystals

Judd-Ofelt analyses of Nd³⁺ ions in the oxyfluoride glasses and glass ceramics containing CaF₂ nanocrystals are performed to evaluate the intensity parameters Ω_2,4,6, spontaneous emission probability, radiative lifetime, quantum efficiency, as well as stimulated emission cross-section. The influences of Nd³⁺-doping level and heating temperature on these parameters for the ⁴F_3/2→⁴I_J (J=9/2, 11/2, and 13/2) transitions are systematically discussed. The decrease of intensity parameter Ω₂ evidences the incorporation of Nd³⁺ ions into CaF₂ nanocrystals after crystallization. With increasing of Nd³⁺-doping level, the measured lifetime and quantum efficiency gradually decrease, while the stimulated emission cross-section keeps almost unchanged. For 1.0 mol% Nd³⁺-doped sample, both the emission intensity and the measured lifetime enhance with increasing of heating temperature up to 650 °C. The results indicate that the investigated glass ceramics are potentially applicable as the 1.06 um laser host.     

Thermoelectric power and ac conductivity of A-type Nd2O3

Measurement of thermoelectric power Θ of pressed pellets of A-type Nd₂O₃ from 550 to 1180K and electrical conductivity (σ) at dc, 50 Hz, 1.542 kHz and 3 kHz at different temperatures is reported. It is concluded that electrical conduction at high temperature (T>600K) in this solid is due to positive large polarons in O²⁻ : 2p (valence) band and negative intermediate polarons in Nd³⁺ : 5d (conduction band). The energy band gap of the solid has been found to be 2.44 eV. At low temperatures, conduction by hopping of charge carriers from one impurity centre to another has been predicted.     

Defect model and spin-Hamiltonian parameters for the tetragonal Nd center in the tetragonal phase of SrTiO3 crystal

The spin-Hamiltonian parameters (g factors g_∥, g_⊥ and hyperfine structure constants ¹⁴³A_∥, ¹⁴³A_⊥, ¹⁴⁵A_∥ and ¹⁴⁵A_⊥) of the tetragonal Nd³⁺ center in the low-temperature (T≈4.2 K) tetragonal phase of SrTiO₃ are calculated from a diagonalization (of energy matrix) method. In the method, the Zeeman and hyperfine interaction terms are attached to the conventional Hamiltonian and a 52×52 energy matrix concerning the ground term ⁴H_J (J=9/2, 11/2, 13/2, 15/2) is constructed. The Nd³⁺ center is attributed to Nd³⁺ occupying the 12-fold coordinated Sr²⁺ site in SrTiO₃. Differing from the defect model assumed in the previous paper that the tetragonal distortion of this Nd³⁺ center is due to the association of one interstitial oxygen ion at a nearest neighborhood of Nd³⁺ and the Nd³⁺ displacement Δz along C₄ axis, we suggest that it is due to the distortion of SrTiO₃ lattice in the tetragonal phase. The calculated g factors g_∥ and g_⊥ show good agreement with the experimental values, suggesting that our defect model of Nd³⁺ center in SrTiO₃ is reasonable. The experimental hyperfine structure constants were not reported and so our calculated results remain to be checked by EPR experiment.     

Anisotropy of the magnetic properties of the cuprates Dy2BaCuO5 and Ho2BaCuO5: Magnetic and spectroscopic investigations

The magnetization of single crystals of the cuprates Dy₂BaCuO₅ and Ho₂BaCuO₅ along different crystallographic directions is measured using a SQUID magnetometer in fields up to 54 kOe. Spectroscopic investigations of the exchange splitting of the levels of Er³⁺ probe ions in these cuprates are also performed. It is shown that the cuprates investigated are highly anisotropic antiferromagnets, which display quasi-Ising behavior in a magnetic field. The nature of the two spontaneous magnetic phase transitions detected in Dy₂BaCuO₅ and Ho₂BaCuO₅ is analyzed. It is shown that the low-temperature transition is due to an increase in rare-earth-copper exchange. Zh. éksp. Teor. Fiz. 111, 318–331 (January 1997)     

Growth,spectral and laser properties of Nd3+:Na2La4(WO4)7 crystal

A Nd³⁺:Na₂La₄(WO₄)₇ crystal with dimensions of ? 17 × 30 mm³ was grown by the Czochralski method. The thermal expansion coefficients of Nd³⁺:Na₂La₄(WO₄)₇ crystal are 1.32 × 10^?5 K^?1 along c-axis and 1.23 × 10^?5 K^?1 along a-axis, respectively. The spectroscopic characteristics of Nd³⁺:Na₂La₄(WO₄)₇ crystal were investigated. The Judd–Ofelt theory was applied to calculate the spectral parameters. The absorption cross sections at 805 nm are 2.17 × 10^?20 cm² with a full width at half maximum (FWHM) of 15 nm for π-polarization, and 2.29 × 10^?20 cm² with a FWHM of 14 nm for σ-polarization. The emission cross sections are 3.19 × 10^?20 cm² for σ-polarization and 2.67 × 10^?20 cm² for π-polarization at 1,064 nm. The fluorescence quantum efficiency is 67 %. The quasi-cw laser of Nd³⁺:Na₂La₄(WO₄)₇ crystal was performed. The maximum output power is 80 mW. The slope efficiency is 7.12 %. The results suggest Nd³⁺:Na₂La₄(WO₄)₇ crystal as a promising laser crystal fit for laser diode pumping.     

Near infrared fluorescence and energy transfer in Ce/Nd Co-doped CaxSr1−xS

Novel near infrared (NIR) phosphors Ca_xSr_1−xS:Ce³⁺,Nd³⁺ were synthesized by a solid state reaction. The NIR emission was realized through an efficient absorption by the allowed 4f-5d transition of Ce³⁺ and efficient energy transfer to Nd³⁺ via well-matched energy levels. Ce³⁺ and Nd³⁺ content in CaS/SrS was optimized. It was found that CaS:Ce³⁺,Nd³⁺ gave much stronger NIR emission than that of SrS:Ce³⁺,Nd³⁺. Further studies on Ca_xSr_1−xS:Ce³⁺,Nd³⁺ indicated that both visible emission of Ce³⁺ and NIR emission of Nd³⁺ were observably affected by Ca/Sr ratio. The energy transfer efficiency, which can be estimated from fluorescence lifetime of Ce³⁺, increased from 52% to 74% for the Ca_xSr_1−xS:Ce³⁺,Nd³⁺ (x=0 to 1) series, accompanied with a shift of maximal emission wavelength of Ce³⁺ from 482 to 505 nm. The results showed that overlap between emission spectrum of Ce³⁺ and excitation spectrum of Nd³⁺ plays an important role in the energy transfer efficiency, and Ce³⁺ emitting in green or blue-greenish region sensitized the Nd³⁺ NIR fluorescence emission more efficiently than that in blue region.     

Doubly doped BaY2F8:Er,Nd VUV scintillator

Doubly doped BaY₂F₈:Er,Nd scintillation crystals were grown by modified micro-pulling-down method. The Er co-doping was chosen to enhance the energy transfer from the host lattice to the Nd³⁺ luminescence center via the 5d-levels of Er³⁺, which can be enabled by the overlap of Er³⁺ 5d-4f emission spectrum with the Nd³⁺ 4f-5d absorption. The energy transfer was clearly evidenced in the BaY₂F₈:Er,Nd. The processes are complicated by energy migration to killer centres and/or cross-relaxation processes. The luminescence and energy transfer mechanism are discussed.