Optical Materials 27 (2005) 12351239 www.elsevier.

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Thermoluminescence properties of new ZnO nanophosphors exposed to beta irradiation

zquez a,*, R. Bernal b, S.E. Burruel-Ibarra a, C. Cruz-Va H. Grijalva-Monteverde a, M. Barboza-Flores b
a

n en Pol meros y Materiales de la Universidad de Sonora, Apartado Postal 130, Hermosillo, Sonora 83000, Mexico Departamento de Investigacio b n en F sica de la Universidad de Sonora, Apartado Postal 5-088, Hermosillo, Sonora 83190, Mexico Centro de Investigacio Received 18 October 2004; accepted 10 November 2004

Abstract Novel ZnO nanophosphors were synthesized by thermal annealing of ZnS powders obtained by precipitation in a chemical bath deposition reaction. Pellet-shape samples were exposed to beta radiation in order to investigate their dosimetric capabilities under ionizing radiation. The dependence of thermoluminescence response in the 0.1510.5 kGy dose range increased as the radiation dose increased. The composition and structure of the ZnO samples are dependent on the annealing time and temperature. Energy-dispersive X-ray spectrometry analyses and X-ray diraction patterns, conrmed the change from amorphous ZnS to nanocrystalline ZnO (zincite) structure. The samples were beta irradiated and their thermoluminescence response as a function of dose exhibited good linear ranges, which make them very promising detectors and dosimeters suitable for ionizing radiation. 2004 Elsevier B.V. All rights reserved.
Keywords: Dosimetry; Thermoluminescence; Radiation detectors; Zinc oxide; Nanophosphors

1. Introduction Zinc oxide (ZnO) is a direct band gap semiconductor with many attractive features. Its 3.4 eV band gap energy at room temperature may be modied introducing impurities; for instance, diminishes by Cd doping and increases when doped with Mg. The most common crystalline structure in ZnO is hexagonal (zincite) [1]. Among other defects existing in ZnO are the interstitial Zn ions, oxygen vacancies and hydrogen [1]. ZnO exhibits striking features useful for the development of components for optoelectronic applications. Thus, the physical properties of ZnO have been intensively investigated focused mainly in the characterization of its optical and electrical properties, for which it

Corresponding author. zquez). E-mail address: cathy@correom.uson.mx (C. Cruz-Va

has rapidly emerged as a promising optoelectronic material suitable to be used in numerous potential technological applications. Examples of applications include thin lm gas sensors, varistors, ultraviolet and visible lasers and solar cells components [14]. The thermally stimulated luminescence technique, commonly termed as thermoluminescence (TL), is widely accepted as a useful and reliable technique to study defects in insulators and semiconductors materials, but the more widely spread and successful application of the TL is in the eld of radiation dosimetry [5]. Many phosphor materials, synthetic as well as natural, have been characterized to evaluate its feasibility as thermoluminescence dosimeters (TLD), applicable in several low dose dosimetry areas, such as environmental dosimetry, clinical dosimetry, among others. High doses applications, involving doses greater than 102 Gy, may be found inside nuclear reactors or during food sterilization and materials testing [5,6].

0925-3467/$ - see front matter 2004 Elsevier B.V. All rights reserved. doi:10.1016/j.optmat.2004.11.016

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A particular material may or not be useful for radiation dosimetry depending on the kind of radiation to be used and on the dose range values to be measured. If the goal is to measure very low doses, a high sensitivity dosimetric material is required. In high dose dosimetry, it is an important feature that the TL response as a function of dose does not exhibit a superlinear or sublinear behavior, because it is possible to have an underestimation or overestimation of the actual absorbed dose. Many materials, in particular the conventional thermoluminescence dosimeters, suer from severe superlinearity at high dose levels, and therefore the number of materials available for these applications is limited [5,6]. ZnO exhibits TL under irradiation with dierent sources and striking radiation hardness [710]. Moreover, ZnO is inert to environmental conditions, non-toxic and insoluble in water. In spite of these characteristics, there is not much information related to the potential applicability of ZnO in TL dosimetry. The lack of interest to use ZnO as dosimetric material is due perhaps to the great amount of other important applications, for instance in optoelectronics, and also to the low eciency of the TL emission reported for the samples previously studied [79]. The physical properties of a material depend upon the procedure followed to make it. To growth ZnO thin lms on distinct substrates is a major goal in materials chemistry. Among the methods to synthesize ZnO and other compounds thin lms, the chemical bath deposition (CBD) method is well recognized because it is versatile and non-expensive. During the deposit of thin lms through the CBD technique, a quantity of material precipitates in the bottom of the solution and can be collected as powder. In this work, we report the synthesis and thermoluminescence properties of new pellet- shape ZnO nanophosphors, obtained by thermal annealing of ZnS powder precipitated during de deposition of ZnS thin lms, employing a CBD method recently reported [11]. The employed method is easy and non-expensive. The samples were exposed to beta radiation to study their TL and dosimetric characterization and the results obtained show that these phosphors are very suitable as detectors and TL dosimeters.

vacuum [11]. Then, 0.06 g of the synthesized ZnS powder were weighted to make each pellet-shaped sample, and next placed into a 7 mm diameter cylindrical mold. Finally, the sample was comprised at 0.5 ton during 3 min using an hydraulic press. With this procedure, 0.8 mm thickness pellets were obtained. Afterwards, the pellets just obtained were subjected to a sintering process at temperatures of 500 or 700 C during 10 or 24 h under air atmosphere using a Thermolyne 4000 furnace. The zinc (II) complex used, Zn(en)3SO4, was synthesized by adding an aqueous ethylenediamine solution to an aqueous ZnSO4 7H2O solution in a mole ratio of 3:1. The colorless zinc (II) complex obtained was re-crystallized from water. ZnS JMC Puratronic, 99.99%, was sintered and its TL measured to be used for comparison with the synthesized ZnS samples. A Ris TL/OSL model TL/OSL-DA-15 unit equipped with a 90Sr beta source was used to perform beta irradiations and the TL measurements. All irradiations were accomplished using a 5 Gy/min dose rate at room temperature (22 C). The TL measurements were carried out under N2 atmosphere using a heating rate of 5 C/s. The X-ray diraction (XRD) patterns were collected with a Rigaku Geigerex diractometer equipped with a graphite monochromator by using ). Scanning electron microCuKa radiation (k = 1.542 A scope (SEM) images and the samples composition were obtained using a JEOL JSM-5410LV scanning electron microscope equipped with an Oxford EDS analyzer operating at 15 keV.

3. Results and discussion Energy-dispersive X-ray spectrometry (EDS) analyses carried out on the non-sintered pellets reveled a proportion of 69:31 weight percent for Zn:S, too close to that of the ZnS (67.1:32.9). Non-sintered ZnS pellets were beta irradiated up to 100 Gy dose with no detection of TL emission. When ZnS pellets were sintered for 10 h at 500 C, clearly dened TL glow curves were obtained after exposure to similar irradiation doses. The TL eciency did not signicantly increased when the 24 h thermal treatments were performed at the same temperature. The shape of TL curves revealed that it is composed of several overlapped TL peaks. There is a noticeable enhancement of the TL eciency when the annealing temperature is increased from 500 C up to 700 C. Together with the enhancement of the TL eciency, a change in the relative intensities of the peaks appears. Samples sintered at 700 C during 10 and 24 h exhibit no meaningful dierences in the TL intensity glow peaks. Thus, the TL eciency is more dependent on the annealing temperature rather than on the sintering time.

2. Experimental A controlled chemical bath deposition reaction was carried out to synthesize ZnS powder as follow: 80 ml of a 0.1 M CS(NH2)2 (thiourea) solution was added to 250 ml of an 8 mM Zn(en)3SO4 solution with stirring. Then, 50 ml of a 4 M NaOH solution was added. The reaction was allowed to proceed at 60 C by stirring for 10 h. White-grayish ZnS powder was collected by ltration. It was washed with deionized water and dried in

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Fig. 1 shows the X-ray diraction (XRD) pattern of a pellet sintered at 700 C during 24 h together with the reference lines of zincite (JCPDS #36-1451). The pellet pattern coincides with that of the mentioned reference, except for the weaker peaks at angles lower than 30, which can be associated with impurities in the material. These small signals could be associated to the thermal decomposition of a small part of the material when the samples are annealed, induced by the evaporation of thiourea and the Zn(en)3SO4 complex, which precipitate together with the ZnS powder during the reaction [12]. ZnO occurs naturally as the mineral zincite [1]. The XRD pattern of a sample annealed 24 h at 500 C also coincides with zincite. Fig. 1 exhibits no peaks associated to the presence of crystalline ZnS, neither are observed in XRD patterns from samples annealed at 500 C. This in spite that EDS analyses of samples revealed mixtures of a molar ratio ZnS:ZnO of 0.46:0.54, after annealing at 500 C for 24 h, and ZnS:ZnO of 0.1:0.9 if annealed at 700 C during 24 h. There is no crystallization of ZnS with the performed thermal annealing and, thus it is not observed in the XRD patterns. By increasing the amount of crystalline ZnO an improvement of the TL eciency was observed. Thermal annealing induces the ZnS to ZnO transformation and crystallization afterwards. Fig. 2 shows the scanning electron microscopy (SEM) image of a pellet before being sintered (a) and after sintered at 700 C during 24 h (b). Fig. 2(b) allows us to discover the presence of nanosized 50500 nm ZnO grains. The improved TL eciency under thermal annealing is due to crystallization of nanometric ZnO particles clearly observed in Fig. 2(b) compared to the ZnS amorphous structure seen in Fig. 2(a).

Fig. 2. Scanning electron microscopy (SEM) image of a pellet before being sintered (a), and after sintered at 700 C during 24 h (b).

Fig. 3 shows the TL glow curves of pellets sintered during 24 h at 700 C after exposed to beta radiation in the dose range from 0.15 to 10.5 kGy. A maximum

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Fig. 1. X-ray diraction pattern of pellets subjected to thermal annealing at 700 C during 24 h. The vertical lines correspond to zincite, JCPDS #36-1451.

Fig. 3. TL glow curves of pellets sintered during 24 h at 700 C after exposure to beta radiation in the dose range 0.1510.5 kGy.

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of the TL glow emission is located at around 220 C. Up to the maxima dose investigated no saturation was observed in the behavior of the TL curves but their intensities increased with larger doses as displayed in Fig. 3. The whole thermogram exhibits a complex structure in the form of a broad curve indicating the overlap of several TL glow peaks. Many materials suer from severe superlinearity at high dose levels. The ZnO nanophosphors here reported exhibited a superlinear dependence of the total TL (integrated TL) as a function of irradiation dose. This inconvenience was xed by applying a two steps thermal annealing previous to irradiation: at 300 C for 30 min followed for a second annealing at 200 C during 30 min. It was veried that this procedure guarantee a good TL reproducibility. The TL glow curves shown in Fig. 3 were obtained following this pre-irradiation protocol. Fig. 4 shows the integrated TL as a function of dose, up to 10.5 kGy, of a pellet sintered 24 h at 700 C. It exhibits a remarkable good dosimetric response in which there are no indications of response saturation. It should be noticed that the dosimetric behavior is linear for doses of the order of 102 Gy. The integrated TL fades down to 55% of its value just after irradiation in a 2 h period after which tends to remain with a constant value. For comparison, ZnS powder commercially available was subjected to similar thermal treatments as the synthesized one, obtaining extremely low TL response. It was not possible to fabricate compressed pellets from the commercial ZnS under the same conditions used in the sintering process, obtaining a very poor TL emission compared with that of our ZnO sintered samples. Fig. 5 shows the TL glow curves of one synthesized ZnS pellet sintered 24 h at 700 C after 600 Gy of beta exposure (curve (a)), and that obtained from commercially avail8

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Fig. 5. TL glow curves of one synthesized ZnS pellet sintered 24 h at 700 C after 600 Gy of beta exposure (curve (a)), and that obtained from commercially available ZnS powder subjected to the same thermal treatment (curve (b)) and exposed to 800 Gy of the same radiation.

able ZnS powder subjected to the same thermal treatment (curve (b)) and exposed to 800 Gy of the same radiation. 4. Conclusions We have presented experimental evidence about a novel ZnO nanophosphor obtained by thermal annealing of ZnS powder synthesized by a CBD method. It exhibited good thermoluminescence properties and may be considered as a promising material to be used in thermoluminescence dosimetry. The synthesis of ZnO nanophosphors enhanced the TL eciency as compared to that of ZnO obtained from commercially available ZnS. Acknowledgments The authors gratefully acknowledge the nancial sup xico), under port for this work from CONACyT (Me xico) Grant Grant J35222-E, from SESIC-SEP (Me PROMEP-UNISON-PTC-01-01, and from Universidad de Sonora.

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References
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Fig. 4. Integrated TL as a function of dose, of pellets sintered 24 h at 700 C, for doses up to 10.5 kGy of beta radiation.

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