UVC dosimetry properties of Mn and Ce doped KCl thermoluminescent phosphor produced by co-precipitation method

doi:10.1016/j.nimb.2019.08.008

Nuclear Instruments and Methods in Physics Research Section B: Beam Interactions with Materials and Atoms

Volume 458, 1 November 2019, Pages 97-104

https://doi.org/10.1016/j.nimb.2019.08.008 Get rights and content

Highlights

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KCl:Mn and KCl:Ce TL phosphors were synthesized by co-precipitation method for the first time.
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UVC dosimetry properties of the produced microcrystalline were studied.
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It showed that the above TL phosphors can be used for UVC dosimetry.
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Different TL structure under gamma irradiation makes it possible to identify UVC component in mixed radiation field.

Abstract

Potassium chloride microcrystalline doped with Mn and Ce was successfully synthesized for the first time by the co-precipitation method and its thermoluminescence (TL) UVC dosimetry properties were investigated. The highest TL sensitivity was achieved at 0.3 and 0.5 mol% of Mn and Ce impurities respectively. The optimum annealing regime was found at 673 K for 15 min. The TL response is linear for illumination with UVC lamp up to 500 s. The optical band gap of 4.16 and 4.34 eV was obtained accordingly for the synthesized Mn and Ce doped KCl phosphor using the absorption spectrum. T_m-T_stop and computerized glow curve deconvolution procedures were used to identify the component TL glow peaks and kinetic parameters of the produced phosphor. Desired dosimetric features, besides the simple glow curve structure and separated glow peaks of the synthesized phosphors, presents them as good candidates for UVC dosimetry.

Introduction

Thermoluminescence (TL) is the emission of ultraviolet or visible light from an insulator or semiconductor following warming the sample. Heating is the secondary stimulation process to release the charge carriers (previously produced by irradiation and transferred to trapping centers) from trapping states and lastly recombine with the opposite charges in recombination centers. The TL phenomenon is observed in regular crystals contaminated with impurities and imperfections in the lattice. Alkali halide crystals doped with different metallic impurities have been found to act as high sensitive TL phosphors [1]. Among alkali halides, TL of KCl has been reported in last decades [2], [3], [4]. TL is not accompanied by thermally stimulated conductivity in KCl, confirming that localized transitions are responsible for TL in this material [1]. In other words, by warming the sample, electrons previously trapped due to irradiation, undergo direct transition from trapping centers to recombination centers [5], [6]. It has been proposed that various TL glow peaks in this phosphor are the result of releasing electrons from different types of F centers at different temperature intervals [7].

Depending on the biological effects of radiation, three regions can be identified in UV spectrum; UV-A (315–400 nm), UV-B (280–315 nm) and UV-C (200–280 nm) [8]. In UV dosimetry, the TL signal can be produced directly by UV illumination or by phototransferred thermoluminescence (PTTL) in which the sample is firstly irradiated with gamma rays prior to UV illuminations [9]. In PTTL phenomenon charges are transferred from the deep traps to shallow traps when the phosphor is exposed to ultraviolet light [10]. The intrinsic sensitivity of the conventional TL dosimeters to UV radiation is usually small; however some of them show a PTTL behavior that permits to re-assessment of very low absorbed doses [11].

The depletion of ozone layer in the last decades has increased the flux of UV radiation on the earth surface and amongst different types of UV radiation; the UVC amplification factor has been higher. Considering damaging effect of UVC radiation on persons and environment, it is important to monitor the UVC dose rate on the earth.

Optically stimulated luminescence and thermoluminescence properties of KCl:Eu⁺² under UV-C irradiation has been studied. The UVC damage mechanism has been explained by the existence of Eu⁺³ in damaged crystals [12], [13]. TL properties of KCl:Eu⁺² under beta and UV radiation have demonstrated good linearity for both types of radiations. It has been reported that the reusability still exists after three cycles for UV irradiation and the TL glow curve has not the same structure on UV and beta irradiation [14]. TL glow curve of KCl:Eu²⁺ under X-ray irradiation was investigated and three component glow peaks at 370, 390 and 470 K were identified. Also examining PTTL in this phosphor showed that the dosimetric glow peak at 470 K is intensely associated to the F and F_z centers and the TL response under UV illumination is linear with the irradiation time over four orders of magnitude [15], [16].

Luminescence performance of KCl:Ce³⁺ crystals was studied by Bangaru et al. and it deduced that TL efficiency reduces with low concentration of Ce³⁺ ions in comparison with pure KCl [17]. Also, investigating the TL characteristics of KCl:Tb³⁺ revealed that the glow curve includes two component peaks at 423, 513 K and Tb³⁺ impurity is responsible for TL emission in this phosphor [18]. Spectroscopic properties of electric colored KCl:Tl and KCl:Tl + Ca grown by Czochralski method has been considered in order to identify the defects made during electron injection. It was found that the new formed defects show intense photoluminescence in the near infrared region [19]. TL structure of gamma irradiated KCl:Dy prepared by wet chemical method has also been reported. TL dose response in this phosphor is linear for absorbed doses between 0.08 and 0.75 kGy for the optimized Dy concentration of 0.1 mol%. This phosphor has been recommended for dosimetry in this range of gamma dose [2]. In an experiment on luminescence features of KCl co-doped with Eu²⁺ and Eu³⁺, it was concluded that the product material in the solid state may be suitable for fabricating optical devices for industrial applications [20]. Kumari and Chandramani by producing mixed crystals of KCl-KBr doped with gold, showed that luminescence efficiency and optical absorption depend on the gold impurity concentration [21]. By studying thermally stimulated exo-electron emission and TL of KCl:Ag single crystal, it proposed that the 275 nm emission band of TL at 400 K may be due to competing radiative decays of the excited Ag⁺ centers [22].

In this work KCl:Mn and KCl:Ce phosphors were produced by co-precipitation route as a low-cost and facile synthesis method and their optical properties and UVC dosimetry features were obtained for the first time.

Section snippets

Experimental procedure

Manganese (cerium) doped KCl microcrystalline powder was prepared by co-precipitation method. The raw materials were pure potassium, ethanol, diethyl malonate, toluene, acetyl chloride, manganese chloride (MnCl₂, 99.99%) and cerium nitrate (Ce(No₃)₂, 99.99%) all purchased from Merck chemicals. Initially, 0.3 g of pure potassium was added to 10 ml of ethanol on a stirrer and left to be mixed by a magnetic-blender for 3 h. Next, 2 ml diethyl malonate, 10 ml toluene and 2.6 ml acetyl chloride were

XRD, SEM and EDS pattern:

The XRD pattern of the provided material exhibits a cubic structure and is matched with the standard data of KCl from ICSD collection (code no. 04-0587). In Fig. 1 the average crystallite size of 320 nm was obtained from the more intense diffraction from (2 0 0) plane using Debye-Scherrer formula. The cubic shape and homogeneity of the synthesized particles is observed in Fig. 2. Energy dispersive X-ray analysis (EDX) is an X-ray technique for identifying the elemental composition of materials.

Conclusion

The produced KCl phosphor with optimized Mn and Ce dopants of 0.3 and 0.5 mol% were synthesized through co-precipitation method as an inexpensive and simple route of production. Absorption spectrum, the optical band gap and TL dosimetry characteristics such as annealing regime, reusability and dose response under UVC illumination were examined and the number of glow peak components and kinetic parameters were determined. It was found that the TL response is linear at a wide range of the

Declaration of Competing Interest

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

Acknowledgement

The authors are grateful to research council of the University of Kashan for providing financial support to undertake this work (Grant number 785216).

References (33)

S.V. Moharil et al.
Mechanism of thermoluminescence in alkali halides
J. Lumin.
(1992)
B.L. Diffey
Sources and measurement of ultraviolet radiation
Methods
(2002)
I. Aguirre de carcer et al.
Preliminary results on the identification of ultraviolet and beta radiation exposure in KCl:Eu²⁺ single crystals by thermoluminescence
Nucl. Instr. Meth. Phys. Res. B
(2009)
I. Aguirre de carcer et al.
Thermoluminescence of KCl:Eu⁺² under ultraviolet irradiation at different temperatures
Radiat. Meas.
(1998)
S. Bangaru et al.
Luminescence studies on gamma irradiated KCl:Ce³⁺ crystals
Physica B
(2012)
H.G. Balian et al.
Figure-of-merit (FOM), an improved criterion over the normalized chi-squared test for assessing goodness-of-fit of gamma-ray spectral peaks
Nucl. Instr. Meth. Phys. Res. B
(1977)
A.C. Coleman et al.
On the validity and accuracy of the initial rise method investigated using realistically simulated thermoluminescence curves
Radiat. Meas.
(2018)
S.W.S. McKeever
Thermoluminescence of Solids
(1985)
P.M. Bhujbal et al.
KCl:Dy phosphor for thermoluminescence dosimetry of ionizing radiation
Luminescence
(2013)
R. Rodriguez-Mijangos et al.
Thermoluminiscence response of an alloy quaternary ionic crystal exposed to high energy radiation
J. Energy Power Eng.
(2016)

S. Bangaru et al.

Thermoluminescence and photoluminescence studies on γ-ray-irradiated Ce3+, Tb3+-doped potassium chloride single crystals

Luminescence

(2016)

A.J.J. Bos

Thermoluminescence as a Research Tool to Investigate Luminescence Mechanisms. Luminescence Materials, Faculty of Applied Sciences

(2017)

M. Jain et al.

Stimulated luminescence emission from localized recombination in randomly distributed defects

J. Phys: Condens. Matter.

(2012)

J.S. Nagpal

Ultraviolet Dosimetry Using Thermoluminescent Phosphors

(1998)

H. Duran-Munoz et al.

Study on the photo-transfer thermoluminescence in Eu doped potassium chloride

Mater. Res. Soc. Symp. Proc.

(2013)

A. Delgado et al.

A simple UV irradiator for low dose reassessment with LiF TLD-100

Radiat. Prot. Dosim.

(1996)

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Dosimetry properties of Mn and Ce doped KCl phosphor in UVC irradiation have been studied and four peaks at 381, 400, 468, and 494 K for KCl:Mn and three peaks at 398, 454, and 522 K temperatures in their TL glow curves have been reported [19]. Study of optical absorption and TL in X-irradiation of KCl:Sr has shown that the TL process is due to the recombination of interstitial halogen atoms with vacancy centers [20]. Also a cathodoluminescence study of metal-hydroxyl materials has been done by Garcia et al. [21].
Manganese and cerium doped potassium chloride (KCl:Mn and KCl:Ce) were produced by the co-precipitation method with ultrasonic waves. Characterization of the samples material was carried out using X-ray diffraction (XRD), scanning electron microscope (SEM), and energy dispersive spectrometer (EDS) patterns. The optimum amount of manganese and cerium concentration with the most thermoluminescence (TL) sensitivity was obtained at 0.3 mol% in KCl:Mn and 0.5 mol% in KCl:Ce samples. To evaluate the number of component glow peaks and the kinetic parameters of the TL glow curve of synthesized materials, computerized glow curve deconvolution (CGCD) and Tm-Tstop methods were used. The thermoluminescence properties of phosphors were studied at different doses. The TL response was linear in the range of 10–1000 Gy. Other TL features of the prepared material are also discussed.
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However, under the external thermal disturbance, these trapped electrons would obtain higher energy to escape traps, returning to the excited state and producing thermoluminescence (Qi et al., 2018; Singh et al., 2021). Nanomaterials because of their exceptional TL properties compared with their bulk counterparts have attracted much attention (Salah, 2011; Talebi et al. 2019; Kashefi Biroon et al., 2019; Zahedifar et al., 2017). Studies on different luminescent nanomaterials have illustrated their excellent properties such as simple TL glow curve structure and linear TL dose response over a wider range of absorbed dose in comparison with those of corresponding microcrystalline samples (Zahedifar et al., 2016).
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Both dimer and monomer luminescence centers were also reported for In+ and Ag− ions dopants [17,18]. Various transition metals were also examined in alkali halide single crystal host [19–23]. Different emission lines are observed both in pure sample (self-luminescence of intrinsic centers) and doped sample (localized exciton on impurity center).
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Polymer film blend of polyvinyl alcohol, trichloroethylene and cresol red for gamma radiation dosimetry
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View full text

UVC dosimetry properties of Mn and Ce doped KCl thermoluminescent phosphor produced by co-precipitation method

Highlights

Abstract

Introduction

Section snippets

Experimental procedure

XRD, SEM and EDS pattern:

Conclusion

Declaration of Competing Interest

Acknowledgement

J. Lumin.

Methods

Nucl. Instr. Meth. Phys. Res. B

Radiat. Meas.

Physica B

Nucl. Instr. Meth. Phys. Res. B

Radiat. Meas.

Thermoluminescence of Solids

KCl:Dy phosphor for thermoluminescence dosimetry of ionizing radiation

Luminescence

Thermoluminiscence response of an alloy quaternary ionic crystal exposed to high energy radiation

J. Energy Power Eng.

Thermoluminescence and photoluminescence studies on γ-ray-irradiated Ce3+, Tb3+-doped potassium chloride single crystals

Luminescence

Thermoluminescence as a Research Tool to Investigate Luminescence Mechanisms. Luminescence Materials, Faculty of Applied Sciences

Stimulated luminescence emission from localized recombination in randomly distributed defects

J. Phys: Condens. Matter.

Ultraviolet Dosimetry Using Thermoluminescent Phosphors

Study on the photo-transfer thermoluminescence in Eu doped potassium chloride

Mater. Res. Soc. Symp. Proc.

A simple UV irradiator for low dose reassessment with LiF TLD-100

Radiat. Prot. Dosim.