Applied Surface Science 258 (2012) 68146818

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Applied Surface Science

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Rapid combustion method for surface modication of strontium aluminate phosphors with high water resistance
Qu Yang a , Yingliang Liu a, , Caixia Yu a , Guoxian Zhu a,b , Lei Sha a , Yunhua Yang a , Mingtao Zheng c , Bingfu Lei a
a b c

Department of Chemistry, Jinan University, Guangzhou 510632, Peoples Republic of China School of Chemistry Science and Technology, Zhanjiang Normal University, Zhanjiang 524048, Peoples Republic of China College of Science, South China Agricultural University, Guangzhou 510642, Peoples Republic of China

a r t i c l e

i n f o

a b s t r a c t
A rapid combustion method was introduced into surface modication of strontium aluminate phosphors, which improved the water resistance of phosphors. X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), transmission electron microscopy (TEM), highresolution transmission electron microscopy (HRTEM), pH measurements and photoluminescence (PL) spectrophotometry were used to characterize the phosphors before and after modication respectively. Experimental results showed that compact layer of SrAl2 B2 O7 substance was formed on the surface of strontium aluminate phosphors by direct chemical reaction between strontium aluminate and boracic acid. SrAl2 B2 O7 substance is chemically stable in water and could improve water resistance of strontium aluminate phosphors effectively. 2012 Elsevier B.V. All rights reserved.

Article history: Received 9 October 2011 Received in revised form 21 February 2012 Accepted 19 March 2012 Available online 29 March 2012 Keywords: Strontium aluminate phosphors Rapid combustion method Surface modication

1. Introduction Rare earth ions co-doped strontium aluminate (such as SrAl2 O4 :Eu2+ , Dy3+ ) phosphors are one of the most efcient long afterglow materials with excellent persistent luminescene at green region [1]. As their high initial luminescent intensity and long afterglow time, strontium aluminate phosphors were widely used in many elds such as luminescent paint, luminescent plastic, luminescent ceramic and so on [24]. However, weak water resistance is still a mortal drawback for this class of phosphors, limiting their application in water-based paints or other moist elds [5,6]. Monoclinic SrAl2 O4 phase possesses the structure of three dimensional network of corner-sharing AlO4 tetrahedron, which form connected open channels where water molecules could enter into and break bonds of O Sr O easily [7,8]. The hydrolysis process occurred as following equation [9]: SrAl2 O4 + 4H2 O Sr2+ + 2OH + 2Al(OH)3 (1)

chemical method [11]. Furthermore, researchers encapsulated strontium aluminate phosphors with inorganic materials such as silica [9] and alumina [12] by chemical precipitation process, and modied phosphors with uoride [13], phosphate [14,15], ligands [16,17] and polymer [18,19] by direct reactions between phosphors and surface treatment reactant. But all of these treated methods required elaborate equipments, complex processes or lengthy treatment time. It was signicant to develop a simple method which could improve water resistance of strontium aluminate phosphors effectively. In the present work, a rapid combustion method was applied for surface modication of strontium aluminate phosphors. And detail studies on the crystal structures, luminescence property and water resistance of phosphors both treated and untreated have been carried out. 2. Experimental 2.1. Experimental procedure SrAl2 O4 :Eu2+ , Dy3+ phosphors were prepared by typical hightemperature solid-state reaction. -Al2 O3 (99.999%), SrCO3 (AR), Eu2 O3 (99.999%), and Dy2 O3 (99.999%) powders were mixed at mole ratio of 1:1:0.005:0.01 and then sintered at 1350 C for 4 h in weak reduction atmosphere (N2 + 5% H2 ). Then the phosphors obtained were grinded to powders. In a typical modication process, SrAl2 O4 :Eu2+ , Dy3+ phosphors pre-manufactured were mixed with carbamide (AR) and boracic acid (AR) at weight ratio of

Therefore, improving the water resistance of strontium aluminate phosphors by different methods of surface treatment has been a key issue in their applications. Su and co-workers had coated red emitting phosphors of alkaline earth sulde with SiO2 or TiO2 using the solgel process [10] and with ZnO or Al2 O3 using wet

Corresponding author. Tel.: +86 2085221813; fax: +86 2085221813. E-mail address: tliuyl@jnu.edu.cn (Y. Liu). 0169-4332/$ see front matter 2012 Elsevier B.V. All rights reserved. doi:10.1016/j.apsusc.2012.03.105

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1:1.5:1. After that, the mixtures were burnt at 600 C, 700 C, 800 C and 900 C in air for 5 min respectively. The modied phosphors were obtained after resultant mixtures were washed with distilled water for three times and then dried at 60 C for 24 h.

2.2. Characterizations of phosphors The crystal structures of phosphors were analyzed by powder X-ray diffraction (XRD, Bruker D8) using Cu K ( = 0.15405 nm) radiation. Surface element of phosphors was measured by X-ray photoelectron spectroscopy (XPS, Kratos AIXS Ultra DLD). The morphological and sophisticated micrographs of phosphors were measured by scanning electron microscopy (SEM, Philips XL-30), transmission electron microscopy (TEM, Philips TECNAI 10) and high-resolution transmission electron microscopy (HRTEM, FEI Tecnai G2 F20). Water resistance of phosphors was measured by recording pH value changes of their water suspensions (containing 0.5 g phosphors and 20 ml distilled water). The luminescence spectra and afterglow decay curves were measured using a Hitachi F-4500 uorescence spectrometer equipped with 150 W Xe lamp as the excitation source. All measurements were carried out at room temperature.

Fig. 2. XPS survey scan spectra of samples: (a) untreated, (b) treated at 600 C, (c) treated at 800 C.

aluminate and boracic acid in the process of combustion as following equation: 2H3 BO3 B2 O3 + 3H2 O (2) (3)

3. Results and discussion 3.1. Structural analysis of phosphors The XRD proles of phosphors untreated and treated at temperatures of 600 C, 700 C, 800 C and 900 C were showed in Fig. 1. Compared with XRD patterns of SrAl2 O4 :Eu2+ , Dy3+ (JCPDS No. 34-0379), there was no peak of impurity in XRD patterns of phosphors untreated (Fig. 1(a)), treated at 600 C (Fig. 1(b)) and 700 C (Fig. 1(c)). However, three new peaks at 11.05 , 25.68 and 33.57 appeared when treated at 800 C (Fig. 1(d)). According to JCPDS cards (JCPDS No. 47-0182), these three peaks were indexed to (1 1 1), (4 0 0) and (3 3 3) crystal planes of cubic SrAl2 B2 O7 . It supposed that SrAl2 B2 O7 was formed after modication. What is more, XRD patterns of samples treated at 900 C (Fig. 1(e)) showed integrated XRD prole of SrAl2 B2 O7 (JCPDS No. 47-0182). This means that direct chemical reaction had happened between strontium

SrAl2 O4 + B2 O3 SrAl2 B2 O7

As seen from the equation, the boracic acid would lose all its water and transform to boron oxide at temperatures above 150 C, then boron oxide started to soften at 325 C and became uid at 500 C [20]. A typical SrAl2 B2 O7 synthesization process was pretreated at 550 C in air and then heated at 950 C [21,22], and carbamide often played the role of fuel in combustion method [2326]. What is more, researchers reported that SrAl2 O4 could be converted to SrAl2 B2 O7 at high B2 O3 contents in the synthesization process of strontium aluminate [27,28]. It is supposed that the surface chemical reaction also happened at 600 C and 700 C but the layer formed on the surface of phosphors was amorphous. On the other hand, the consistency of XRD proles between phosphors treated and untreated suggested that the bulk structure of SrAl2 O4 :Eu2+ , Dy3+ was not destroyed during the combustion process and the chemical reactions just occurred on the surface of phosphors when combustion temperature was 600 C, 700 C or 800 C. 3.2. XPS analysis of phosphors According to XPS survey scan spectra (Fig. 2), it could be found photoelectron peaks of O 1s, Sr 3s, Sr 3p, Sr 3d, Al 2s and Al 2p on XPS spectra of both treated and untreated SrAl2 O4 :Eu2+ , Dy3+ phosphors. But there were no photoelectron peaks of Eu and Dy due to their very small doped amounts. XPS survey scan spectra of samples treated at 600 C (Fig. 2(b)) and 800 C (Fig. 2(c)) showed obvious photoelectron peak of B 1s, which conrmed the existence of boracic element on the surface of treated phosphors. And the photoelectron peak of B 1s at 191.6 eV further revealed that the state of boracic element was accorded with SrAl2 B2 O7 compound. What
Table 1 Surface element composition of both treated and untreated phosphors. Element O Sr Al B Untreated (at.%) 68.84 6.86 24.30 0 Treated at 600 C (at.%) 64.23 2.53 15.52 17.72 Treated at 800 C (at.%) 59.65 1.65 20.75 17.95

Fig. 1. XRD proles of samples: (a) untreated, (b) treated at 600 C, (c) treated at 700 C, (d) treated at 800 C, (e) treated at 900 C.

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Fig. 3. SEM images of samples: (a) and (b) untreated, (c) and (d) treated at 600 C.

Fig. 4. TEM and HRTEM images of samples: (a) and (b) untreated, (c) and (d) treated at 600 C.

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is more, the surface atomic percentage of samples treated at 600 C and 800 C listed in Table 1 was almost coincident, which means that surface compounds formed at 600 C and 800 C were alike. However, the atomic percentage of surface compounds were not exactly accord with theory crystal of SrAl2 B2 O7 as the XPS analysis was only performed semi-quanticationally and there was physical absorption of oxygen atom. 3.3. SEM and TEM analysis of phosphors Figs. 3 and 4 showed SEM and TEM images of phosphors untreated and treated at 600 C. As is shown in Fig. 3(a) and (b) and Fig. 4(a) and (b), untreated phosphors exhibited very clean and smooth surfaces and showed clear crystal lattice stripe of SrAl2 O4 :Eu2+ , Dy3+ . However, the surface of treated phosphors (Fig. 3(c) and (d)) was covered with compact layer and became more granulated compared with untreated phosphors. And TEM images of phosphors treated at 600 C (Fig. 4(c) and (d)) showed uniform and amorphous layer which thickness was about 15 nm. These further illuminates that surface substance formed after combustion treatment might improve water resistance of SrAl2 O4 :Eu2+ , Dy3+ phosphors. 3.4. Water resistance analysis of treated and untreated phosphors The pH value changes of both untreated and treated phosphors were showed in Fig. 5. The pH value of suspension of untreated phosphors went up rapidly, by the reason that SrAl2 O4 :Eu2+ , Dy3+ phosphors would degraded rapidly after it exposure to water and the hydrolysis process generated large amount of hydroxide [6]. On the contrary, pH values of suspensions of phosphors treated at different temperatures from 600 C to 800 C were stable entirely, suggesting that treated phosphors exhibited good hydrolysis stabilization. The compound SrAl2 B2 O7 was obtained by the crystallization of aluminoborate glasses several years ago and its crystal structure was described with a noncentrosymmetric space group in the trigonal system [22]. What is more, pH values of suspensions of phosphors treated at 900 C (Fig. 5(e)), which have proved to be SrAl2 B2 O7 did not show great changes after it was dispersed into water for 100 h. It could be deduced that SrAl2 B2 O7 had water resistance ability and just the SrAl2 B2 O7 layer formed on the surface of SrAl2 O4 :Eu2+ , Dy3+ phosphors that prevented strontium aluminate phosphors from contacting with water to hydrolyze.

Fig. 6. Luminescence emission spectra of samples: (a) untreated, (b) treated at 600 C, (c) treated at 700 C (d) treated at 800 C, (e) treated at 900 C.

3.5. Photoluminescence and afterglow measurements To determine luminescent properties of phosphors before and after treatment, photoluminescence and afterglow decay measurement of both treated and untreated phosphors was carried out at room temperature. As is shown in Fig. 6, there were no obvious changes for the emission peak of phosphors treated at 600 C (Fig. 6(b)), 700 C (Fig. 6(c)) and 800 C (Fig. 6(d)) compared with untreated phosphors (Fig. 6(a)), excluding a small decrease of photoluminescence intensity. And it could be found from afterglow decay curves (Fig. 7) that these phosphors showed similar afterglow decay trend with untreated phosphors. These implied that the bulk structure of SrAl2 O4 :Eu2+ , Dy3+ did not change after combustion reaction. As researchers reported, Eu2+ was the luminescent center of SrAl2 O4 :Eu2+ , Dy3+ matrix and it was easily oxygenated into Eu3+ if exposed to the air at high temperature [12]. However, Eu2+ was not oxygenated into Eu3+ because of ammonia atmosphere formed in combustion process and short combustion time. And it was the decrease of light absorbability or increase of light reection caused by surface substance that induced the decrease of photoluminescence and afterglow intensity. Meanwhile, it was the reason that base phase changed to SrAl2 B2 O7 at 900 C caused the emission peak of samples shifted to 425 nm and its afterglow

Fig. 5. Changes of pH values of samples: (a) untreated, (b) treated at 600 C, (c) treated at 700 C, (d) treated at 800 C, (e) treated at 900 C.

Fig. 7. Afterglow decay curves of samples: (a) untreated, (b) treated at 600 C, (c) treated at 700 C, (b) treated at 800 C, (e) treated at 900 C.

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intensity decreased [22]. These results revealed that the luminescent properties of SrAl2 O4 :Eu2+ , Dy3+ phosphors could maintained effectively at proper combustion temperatures, and the rapid combustion method was an effective surface modication approach for strontium aluminate phosphors. 4. Conclusions In this paper, SrAl2 O4 :Eu2+ , Dy3+ was successfully modied via rapid combustion method. The analytical results revealed that SrAl2 B2 O7 layer was formed on the surface of strontium aluminate through reaction between strontium aluminate and boracic acid, water resistance of the phosphors was improved after surface modication with little inuence of luminescence property. This new surface modication method was performed easily and feasible, it could also be used to modify other aluminate phosphors such as CaAl2 O4 , and it was supposed to be a useful surface modication method to improve application property or add multifunction to inorganic materials. Acknowledgment This present work was nancially supported by the National Natural Science Foundations of China (no. 21071063, 50872045). References
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