LiMgPO4:Tb,B - A new sensitive OSL phosphor for dosimetry

Optically Stimulated Luminescence (OSL) technique has emerged as a serious competitor to Thermally Stimulated Luminescence (TSL) technique in various dosimetric applications, especially after the development of crystalline alumina (Al₂O₃:C) doped with carbon. Since then, several attempts are being made to develop other possible materials for OSL based dosimetric applications. Efforts conducted in our laboratory in this direction have led to the development of a new phosphor, Lithium Magnesium Phosphate doped with terbium and boron (LiMgPO₄:Tb,B). This phosphor is prepared by solid-state diffusion method involving conventional air furnaces with operating temperature 1000 °C and easily amenable to large scale production without compromising primary dosimetric advantages. In this work we present some of the dosimetric OSL characteristics of this phosphor. The phosphor exhibits a main TSL peak at 250 °C. The phosphor also emits OSL, when the irradiated phosphor is stimulated with 470 nm light with the OSL sensitivity 1.3 times that of commercially available Al₂O₃:C. Photoluminescence (PL) emission spectrum consists of sharp lines characteristics of Tb³⁺ emission. The OSL discs made out of this phosphor are reusable up to at least 50 cycles, the phosphor exhibits dose linearity up to 1 kGy. Minimum detectable dose is found to be 20 μGy and fading of the OSL signal is found to be about 16% in four days, after which the OSL signal stabilizes.     

Photoluminescence and XEL in Y2O3:Eu phosphor

Eu-activated Y₂O₃ phosphors were prepared by combustion synthesis and also by precipitation techniques. Photoluminescence and X-ray excited luminescence of prepared Y₂O₃:Eu phosphor, under two different techniques were compared and reported in this paper. Y₂O₃:Eu³⁺ phosphor were prepared by precipitation technique followed by annealing at 900 °C. It gives cubic nature of the particle that may be more favourable for high lumen output. X-ray excited luminescence of Y₂O₃:Eu³⁺ phosphors also reported in this paper.     

Photon emission mechanisms of different phosphors

A comparison is made between the different mechanisms involved in the electron and photon excitation processes of four different phosphors. The green luminescence peak of SrAl₂O₄:Eu²⁺, Dy³⁺ phosphor is normally asymmetrical and tails towards the longer wavelengths. The observed peak in the longer wavelength region is associated with preferential alignment of one of the Eu²⁺ d-orbitals. Four Gaussian peaks fitted to the cathodoluminescent (CL) and photoluminescent (PL) spectra of broad band emission spectra of X₁-Y₂SiO₅:Ce phosphor may be attributed to the two different sites (A1 and A2) of the Ce³⁺ ion in the host matrix and the difference in orientation of the neighbour ions in the complex crystal structure. Co-activation of Ce³⁺ with Eu³⁺ quenches the red emission from Eu³⁺ and considerably increases the blue emission from Ce³⁺ in a SiO₂ matrix. In nanoparticulate PbS the emission data show a blue shift from the normal emission at ∼3200 nm in PbS bulk to ∼560-700 nm. The blue shifting of the emission wavelengths from 3200 to ∼560-700 nm is attributed to quantum confinement of charge carriers in the restricted volume of nanoparticles.     

Study on TL and OSL characteristics of indigenously developed CaF2:Mn phosphor

CaF₂:Mn phosphor is known for its high thermoluminescent sensitivity and dose linearity up to few kGy. In the present study CaF₂ phosphor with different concentration of Mn dopant was prepared and was characterized through different techniques. The phosphor was prepared through chemical root using CaCO₃, HF acid and MnCl₂ as raw materials following co-precipitation method. TL sensitivity of the prepared phosphor was compared with other well established phosphors used for radiation dosimetry. It was found that the TL sensitivity is higher by a factor of 10 with respect to LiF:Mg, Ti, TLD-100 and half to that of CaSO₄:Dy (0.05 mol%) phosphor. X-ray diffraction, TL emission spectrum and ESR spectrum taken of the prepared phosphor confirms the crystal structure, Mn²⁺ emission and incorporation Mn in the crystal, respectively. No significant fading of the dosimetric peak was observed of the prepared phosphor for a storage period of 45 days. The dose linearity of the phosphor was found to be in the range of 50 Gy-3 kGy within an uncertainty of about 10%. An attempt was made to determine the kinetic parameters of TL glow curve and the parameters related to optically stimulated luminescence. In view of its long range of dose linearity, it can be used for the dosimetry of commercial irradiator generally used for the irradiation of food and grains in our country.     

X-ray absorption spectroscopy and X-ray photoelectron spectroscopy studies of CaSO4:Dy thermoluminescent phosphors

Extended X-ray absorption fine structure (EXAFS) measurements have been carried out on CaSO₄:Dy phosphor samples at the Dy L₃ edge with synchrotron radiation. Measurements were carried out on a set of samples which were subjected to post-preparation annealing at different temperatures and for different cycles. The EXAFS data have been analysed to find the Dy-S and Dy-O bond lengths in the neighbourhood of the Dy atoms in a CaSO₄ matrix. The observations from EXAFS measurements were verified with XANES and XPS techniques. On the basis of these measurements, efforts were made to explain the loss of thermoluminescence sensitivity of CaSO₄:Dy phosphors after repeated cycles of annealing at 400 °C in air for 1 h.     

Study of the luminescent properties of KMgF3:Sm

The photoluminescence (PL), radioluminescence (RL) and thermoluminescence (TL) of KMgF₃ doped at several Sm concentrations have been investigated. The maximum TL and RL yield under beta irradiation has been observed in KMgF₃:Sm 0.02 mol%. The glow curve of this doped perovskite is made up of at least five peaks located at 95, 120, 160, 270, and 330 °C. The third peak appears to be the most convenient for personal or environmental dosimetry, since it shows no fading and good linearity within the investigated dose range (0.020-200 Gy). From the RL and PL spectra it has been found that most of KMgF₃:Sm emission is located at wavelengths higher than 650 nm. This emission, which is characteristic of Sm²⁺, makes this doped compound attractive for fiber-optic dosimetry.     

Thermoluminescence of terbium-doped double fluorides

This paper presents the thermoluminescence (TL) characteristics of the double fluorides: K₂YF₅, K₂GdF₅ and K₂LuF₅ doped with Tb³⁺, which were studied in the temperature range from 30 to 400 °C. Materials which presented better response to the irradiation with beta particles and with ultraviolet radiation were: K₂YF₅:Tb (1 at.% Tb³⁺) and K₂LuF₅:Tb (1 at.% Tb³⁺); meanwhile, K₂YF₅:Tb at high concentrations (10 and 20 at.% Tb³⁺) as well as K₂LuF₅:Tb (1 at.% Tb³⁺) and K₂LuF₅:Tb (1 at.% Tb³⁺) presented good response to gamma radiation. The intensity of the thermoluminescent response induced in these materials by ionizing radiation has determined that their dosimetric characteristics should be studied further as this may allow the development of potentially useful TL materials for radiation dosimetry.     

Reactivity of hydrogen peroxide towards Fe3O4, Fe2CoO4 and Fe2NiO4

The kinetics of CRUD oxidation by H₂O₂ has been studied using aqueous suspensions of metal oxide powder. Fe₃O₄, Fe₂CoO₄ and Fe₂NiO₄ were used as model compounds for CRUD. In addition, the activation energies for the reaction between H₂O₂ and the three CRUD models were determined. The rate constants at room temperature were determined to 6.6 (±0.4) × 10⁻⁹, 3.4 (±0.4) × 10⁻⁸ and 1.6 × 10⁻¹⁰ m min⁻¹ for Fe₃O₄, Fe₂CoO₄ and Fe₂NiO₄, respectively. The corresponding activation energies are 52 ± 4, 44 ± 5 and 57 ± 7 kJ mol⁻¹, respectively. The mechanism of the reaction is briefly discussed indicating that the final solid product in all three cases is Fe₂O₃. In addition to the experimental studies, the theoretical grounds for kinetics of reactions in particle suspensions are discussed. The theoretical discussion is also used to explain the somewhat unexpected trends in reactivity observed experimentally.     

LiMgPO4:Tb,B OSL phosphor - CW and LM OSL studies

In the adjoining paper, the authors have proposed LiMgPO₄:Tb,B (LMP) OSL phosphor as a potential alternative to α-Al₂O₃:C for dosimetry applications. This calls for developing an understanding on TL and OSL aspects of this highly sensitive LMP phosphor. CW and LM OSL processes were therefore studied experimentally and kinetic analysis was carried out using theoretical models. Continuous wave (CW) OSL curve for LMP phosphor was found not to follow single decaying exponential implying that the CWOSL curve does not follow first order kinetics. Under pre-readout annealing at 125, 200 and 300 °C for 10 s, the nature of decay profile was unaffected and same holds true for optically bleached CWOSL curves. From linearly modulated (LM) OSL studies, it was found that the shape/geometrical factor μ_g was ∼0.72 ± 0.03 for wide range of doses (up to 12 Gy studied) and peak position “t_m” was also independent of dose. The μ_g was found to be unaffected with pre-readout annealing at 125, 200 and 300 °C for 10 s and optical bleaching, however it was found that peak position “t_m” shifted towards higher side in time with increase of optical bleaching. Dose dependence tests were also carried out for LMOSL curves and it was found that peak position “t_m” was independent of dose, which is typical characteristic of curves following first order kinetics. Hence LM-OSL curve might be mixture of more than one component.Further from CW and LM OSL studies, it was also found that the individual contribution from first, second and third TL peak toward OSL is ∼33%, ∼45% and ∼22%, respectively. Traps beyond 350 °C were found not to contribute towards OSL when stimulated using blue LEDs. In the present paper, the CW and LM OSL processes for LMP phosphor were studied experimentally and their kinetic analysis was carried out.     

Luminescence studies on gamma irradiated RbCl:Sm and RbBr:Smcrystals

This paper presents and discusses the results obtained on the thermoluminescence (TL) and other optical studies of gamma irradiated RbCl:Sm³⁺ and RbBr:Sm³⁺ crystals. Samarium when doped into the RbCl and RbBr is found to enter the host lattice in its trivalent state and act as electron trap during gamma irradiation, there by partially converting itself to Sm²⁺. The photoluminescence (PL) spectra of both RbCl and RbBr crystals doped with Sm exhibit the strong red/orange emissions of Sm corresponding to ⁴G_5/2 → ⁶H_9/2 (red) and ⁴G_5/2 → ⁶H_7/2 (orange) transitions. Z₃ centers are observed in RbBr on F bleaching subsequent to gamma irradiation and a TL glow peak attributable to the same has been identified. The thermoluminescence (TL) glow curve explains the defect annihilation process to be due to the mobilization of two different kinds of traps created as a result of exposure to high energy irradiation in both the cases. Spectral distribution under the thermoluminescence emission (TLE) and optically stimulated emission(OSL), support the idea that defect annihilation process to be due to thermal release of F electron in RbCl:Sm³⁺ and in RbBr:Sm³⁺ crystals. Both Sm³⁺ and Sm²⁺ emissions were observed in the thermoluminescence emission of the crystals.     

Swelling and optical properties of Si3N4 films irradiated in the electronic regime

Silicon nitride layers of 140 nm thickness were deposited on silicon wafers by low pressure chemical vapour deposition (LPCVD) and irradiated at GANIL with Pb ions of 110 MeV up to a maximum fluence of 4 × 10¹³ cm⁻². As shown in a previous work these irradiation conditions, characterized by a predominant electronic slowing-down (S_e = 19.3 keV nm⁻¹), lead to damage creation and formation of etchable tracks in Si₃N₄. In the present study we investigated other radiation-induced effects like out of plane swelling and refractive index decrease. From profilometry, step heights as large as 50 nm were measured for samples irradiated at the highest fluences (>10¹³ cm⁻²). From optical spectroscopy, the minimum reflectivity of the target is shifted towards the high wavelengths at increasing fluences. These results evidence a concomitant decrease of density and refractive index in irradiated Si₃N₄. Additional measurements, performed by ellipsometry, are in full agreement with this interpretation.     

Enthalpy measurements of La2Te3O9 and La2Te4O11

Enthalpy increment measurements on La₂Te₃O₉(s) and La₂Te₄O₁₁(s) were carried out using a Calvet micro-calorimeter. The enthalpy values were analyzed using the non-linear curve fitting method. The dependence of enthalpy increments with temperature was given as: H°(T) − H°(298.15 K) (J mol⁻¹) = 360.70T + 0.00409T² + 133.568 × 10⁵/T − 149 923 (373 ? T (K) ? 936) for La₂Te₃O₉ and H°(T) − H°(298.15 K) (J mol⁻¹) = 331.927T + 0.0549T² + 29.3623 × 10⁵/T − 114 587 (373 ? T (K) ? 936) for La₂Te₄O₁₁.     

A cubic-to-monoclinic structural transformation in the sesquioxide Dy2O3 induced by ion irradiation

Polycrystalline pellets of the sesquioxide Dy₂O₃ were irradiated at cryogenic temperature with Kr⁺⁺ ions to a fluence of 1 × 10²⁰ Kr/m². The crystal structure of the irradiated Dy₂O₃ was observed to change from a cubic, so-called C-type rare-earth sesquioxide structure to a monoclinic, B-type rare-earth sesquioxide structure upon ion irradiation. This transformation is accompanied by a decrease in molecular volume (or density increase) of approximately 9%.     

The high-temperature behaviour of PuPO4 monazite and some other related compounds

Thermal behaviour and lattice parameters of monazites MPO₄ (M³⁺ = Ce³⁺, Nd³⁺ and Pu³⁺) and cheralite CaTh(PO₄)₂ were studied using high-temperature X-ray diffraction. Heat treatment under inert atmosphere caused the decomposition of PuPO₄ and CaTh(PO₄)₂ into the corresponding oxides above 1473 K. The influence of the cation type within the crystallographic structure on the thermal expansion coefficient and the possible cation substitutions are discussed in the frame of nuclear waste management.     

Swift heavy ion induced structural modifications in zircon and scheelite phases of ThGeO4

Structural modifications in the zircon and scheelite phases of ThGeO₄ induced by swift heavy ions (93 MeV Ni⁷⁺) at different fluences as well as pressure quenching effects are reported. X-ray diffraction and Raman measurements at room temperature on the irradiated zircon phase of ThGeO₄ indicate the occurrence of stresses that lead to a reduction of the cell volume up to 2% followed by its transformation to a mixture of nano-crystalline and amorphous scheelite phases. Irradiation of the zircon phase at liquid nitrogen temperature induces amorphization at a lower fluence (7.5 × 10¹⁶ ions/m²), as compared to that at room temperature (6 × 10¹⁷ ions/m²). Scheelite type ThGeO₄ irradiated at room temperature undergoes complete amorphization at a lower fluence of 7.5 × 10¹⁶ ions/m² without any volume reduction. The track radii deduced from X-ray diffraction measurements on room temperature irradiated zircon, scheelite and low temperature irradiated zircon phases of ThGeO₄ are, 3.9, 3.5 and 4.5 nm, respectively. X-ray structural investigations on the zircon phase of ThGeO₄ recovered after pressurization to about 3.5 and 9 GPa at ambient temperature show the coexistence of zircon and disordered scheelite phases with a larger fraction of scheelite phase occurring at 9 GPa. On the other hand, the scheelite phase quenched from 9 GPa shows crystalline scheelite phase pattern.     

Amorphisation of ZnAl2O4 spinel under heavy ion irradiation

ZnAl₂O₄ spinels have been irradiated with several ions (Ne, S, Kr and Xe) at the IRRSUD beamline of the GANIL facility, in order to determine irradiation conditions (stopping power, fluence) for amorphisation. We observed by transmission electron microscopy (TEM) that with Xe ions at 92 MeV, individual ion tracks are still crystalline, whereas an amorphisation starts below a fluence of 5 × 10¹² cm⁻² up to a total amorphisation between 1 × 10¹³ and 1 × 10¹⁴ cm⁻². The coexistence of amorphous and crystalline domains in the same pristine grain is clearly visible in the TEM images. All the crystalline domains remain close to the same orientation as the original grain. According to TEM and X-ray Diffraction (XRD) results, the stopping power threshold for amorphisation is between 9 and 12 keV nm⁻¹.     

Bulk-compositional changes of Ni2Al3 and NiAl3 during ion etching

Bulk-compositional changes of Ni₂Al₃ and NiAl₃ in a Ni-50 wt% Al alloy during ion etching have been investigated by transmission electron microscopy and energy dispersive X-ray spectroscopic analyses. After etching with 7, 5 and 3 keV Ar⁺ ions for 15, 24 and 100 h nickel contents in both Ni₂Al₃ and NiAl₃ exceeded greatly those in the initial compounds and increased with the decrement of the sputtering energy. After 100 h etching with 3 keV Ar⁺ ions the compositions of these two compounds reached a similar value, about Ni_80-83Al_12-15Fe_3-4Cr_1-2 (at%). A synergistic action of preferential sputtering, radiation-induced segregation and radiation-enhanced diffusion enables the altered-layers at the top and bottom of the film extend through the whole film. The bulk-compositional changes are proposed to occur in the unsteady-state sputtering regime of ion etching and caused by an insufficient supply of matter in a thin film.     

Effect of swift heavy ion irradiation on nanocrystalline CaS:Bi phosphors: Structural, optical and luminescence studies

Luminescence studies of CaS:Bi nanocrystalline phosphors synthesized by wet chemical co-precipitation method and irradiated with swift heavy ions (i.e. O⁷⁺-ion with 100 MeV and Ag¹⁵⁺-ion with 200 MeV) have been carried out. The samples have been irradiated at different ion fluences in the range 1 × 10¹²-1 × 10¹³ ions/cm². The average grain size of the samples before irradiation was estimated as 35 nm using line broadening of XRD (X-ray diffraction) peaks and TEM (transmission electron microscope) studies. Our results suggest a good structural stability of CaS:Bi against swift heavy ion irradiation. The blue emission band of CaS:Bi³⁺ nanophosphor at 401 nm is from the transition ³P₁ → ¹S₀ of the Bi³⁺. We have observed a decrease in lattice constant (a) and increase of optical energy band gap after ion irradiation. We presume this change due to grain fragmentation by dense electronic excitation induced by swift heavy ion. We have studied the optical and luminescent behavior of the samples by changing the ion energy and also by changing dopant concentration from 0.01 mol% to 0.10 mol%. It has been examined that ion irradiation enhanced the luminescence of the samples.     

Thermoluminescence properties of isostructural K2YF5 and K2GdF5 crystals doped with Tb in response to α, β and X-ray irradiation

The thermoluminescence (TL) properties of isostructural fluoride K₂YF₅ and K₂GdF₅ crystals doped with Tb³⁺ of different concentrations have been studied in the temperature range from 30 to 500 °C after α, β and X-ray irradiation. Strongly different structures of TL glow curves following α or β irradiation have been found for Tb³⁺ doped K₂YF₅ for all studied concentrations of Tb³⁺ whereas for K₂GdF₅ crystals the different TL curves after α or β irradiation are detected only for heavily doped samples. On the other hand, all the studied materials show similar TL glow curves after β or X-ray irradiation. It has been discovered that K₂YF₅ doped with 1 at.% Tb³⁺ has TL radiation sensitivity to β irradiation of the same order as that of the well known TLD-100 (LiF:Mg,Ti) phosphor and much higher sensitivity to α irradiation. The TL mechanism in K₂YF₅ and K₂GdF₅ doped with Tb³⁺ is discussed by taking into account the TL emission spectra from irradiated samples, which are identical to the emission spectra of the Tb³⁺ ions in these hosts under photo-excitation, and the kinetics parameters obtained with the method of various heating rates.     

Interferences in electron emission from O2 by 30 MeV O impact

Interference structures in the ejected electron spectra for 30 MeV O^5,8+ + O₂ are investigated. The measured electron yields were studied for electron energies from 5 to 400 eV and observation angles of 30°, 60°, 90°, 120° and 150° with respect to the incident beam direction. Experimental molecular cross-sections were normalized to theoretical molecular one-center cross-sections revealing oscillatory structures suggestive of secondary interferences as evidenced by the independence on the observation angle. An oscillation interval for 30 MeV O^5,8+ + O₂ of Δk ∼ 4 a.u. is found, a value two times larger than that previously observed for 3 MeV H⁺ + N₂. No obvious evidence for primary Young-type interferences was seen.