Effect Of EDTA On Luminescence Property Of Eu+3 Doped YPO4 Nanoparticles

A. K. Parchur,1 G. S. Okram,2 R. A. Singh,3 R. Tewari,4 Lina Pradhan,5 R. K. Vatsa5,* and R. S. Ningthoujam5,a)

2

Department of Physics, Banaras Hindu University, Varanasi- 221005, India UGCDAE Consortium for Scientific Research University Campus, Khandwa Road, Indore-452001, India 3 Department of Physics and Electronics, Dr. Hari Singh Gour University, Sagar- 470003, India 4 Material Science Division, Bhabha Atomic Research Centre, Mumbai-400085, India 5 Chemistry Division, Bhabha Atomic Research Centre, Mumbai-400085, India *E-mail: rkvatsa@yahoo.com

Abstract. Nanoparticles of Eu3+ doped YPO4 have been prepared using ethylene glycol (EG). Ethylene diamine tetra acetic acid (EDTA) is used as a complexing agent. X-ray diffraction results show that the nanoparticles are crystalline in tetragonal structure. Based on William-Hall relation, the effective crystallite size and strain developed in lattice are found to be 28 nm and 0.002, respectively. With the addition of EDTA, there is a slight shift towards the lower wavelength in emission peaks. Asymmetric ratio of electric to magnetic dipole transition intensities are found to decrease with addition of EDTA. Emission intensity decreases with EDTA because of decrease of particle size as well as decrease of number of Eu3+ activators per unit volume. These materials are dispersible in water, which may have potential biological applications. Keywords: EDTA complex, Luminescence, nanoparticles PACS: 78.55.Fv, 78.55.Qr, 79.60.Jv

INTRODUCTION
Lanthanide ion doped luminescence materials are the subject of intensive study, in part because of their multidimensional potential applications. These are used in field emission displays (FED), cathode ray tubes (CRT) and plasma display panels.1-4 YPO4 doped with lanthanide ions are promising scintillation materials due to their high energy band gap (~9.23 eV) and refractive index of ~1.72. Based on the space group, I41/amd, YPO4 has four chemical units per unit cell (z = 4).2 There are several reports on the synthesis routes of YPO4 crystals doped with Eu3+ ions such as hydrothermal, sol-gel, co-precipitation and solid state reaction methods. In recent years, ethylene glycol (EG) and ethylenediamine tetraacetic acid (EDTA) are used as solvent and capping agents respectively for the preparation of nanoparticles. As the size of metal ions increases, H2O molecules can bind to metal ions in addition to six co-ordinations from EDTA. Thus, coordination numbers for rare-earth ion/lanthanide ions with EDTA in water medium can be as high as 8 or 9.

In the present study, the effect of EDTA on luminescence property of YPO4:Eu is discussed.

EXPERIMENTAL
2 at.% Eu+3- doped YPO4 nanoparticles via EDTA (EDTA mol% = 0, 20 and 50 with respect to YPO4) complexion were prepared using ethylene glycol (EG) as medium at 180 C for 3 h. 0.5 g of Y2O3 and 0.032 mg of Eu2O3 were dissolved together in concentrated nitric acid (HNO3) in 250 ml two necks round bottom flask and excess of acid was removed by evaporation at 80 C. To this reaction medium, di-sodium EDTA (0, 20, 50 mol% with respect to Y3+) dissolved in 50 ml of distilled water was added and stirred for 1 h so that complexion between metal ions and EDTA take place. 100 ml of EG and 1.615 gm of ammonium dihydrogen phosphate was added to this and heated at 180 C for 3 h. The white precipitate was appeared and was collected using centrifuge. X-ray diffraction (XRD) data of prepared nanoparticles were recorded using PW 1071 Philips xray diffractometer with Cu k radiation (1.5405 ) having Ni filter. Strain developed in nanoparticles is

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CP1313, International Conference on Physics of Emerging Functional Materials (PEFM-2010) edited by D. K. Aswal and A. K. Debnath 2010 American Institute of Physics 978-0-7354-0868-5/10/$30.00

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calculated using WilliamsHall equation.5 Transmission electron microscopic (TEM) images of samples were recorded using a JEOL microscope. Infrared (IR) spectrum was measured with a FT-IR spectrometer (Bomem MB 102). Photoluminescence (PL) spectra and luminescence decay were recorded with EDINBURGH instrument (model F920) equipped with 450 W xenon lamp as the excitation source and s Flash lamp.

RESULTS AND DISCUSSION

The XRD patterns of as-prepared samples of Eu+3doped YPO4 nanoparticles capped with EDTA (EDTA mol% = 0, 20 and 50 with respect to YPO4) are shown in Fig. 1(A). Without EDTA, the peaks are distinct, but with the addition of EDTA, the peaks could not be observed distinctly. The peaks correspond to tetragonal phase with space group (I41/amd). The lattice parameters are a = b = 6.915, c = 6.011 , and unit cell volume V = 287.41 3. Since the peaks are broad, the effective crystallite size (Deff) is calculated using William-Hall relation. The Deff and strain developed in lattice are calculated to be 28 nm and 0.002, respectively.

TEM image of YPO4:Eu without EDTA is shown in Fig. 1(B). Selected area electron diffraction (SAED) pattern shows that YPO4 nanoparticles are crystalline. It was clearly observed that as-prepared YPO4:Eu3+ samples contain many nanorods which bind together. Figure 1(C) shows the FT-IR spectra of the YPO4: Eu3+ with and without EDTA capping. The peaks at 523 and 635 cm-1 belong to the bending vibrations of (PO4)3-, whereas, the peaks at 883, 956 and 1009 cm-1 are due to stretching vibrations of (PO4)3-. The peaks at 2880 and 2940 cm-1 are due to stretching vibrations of CH2 group of ethylene glycol molecule. The bands centred at 1637 and 3449 cm-1 have been assigned to bending and stretching vibrations for O-H group of ethylene glycol molecule, which is used as capping agent for nanoparticles. However, stretching frequency of free O-H is 3650 cm-1. In this study, the red shifted broad band at 3344 cm-1 is a sign of presence of hydrogen bond in ethylene glycol molecules. Because of presence of hydrogen bond, the small particles are able to disperse in polar compounds such as water and methanol. With EDTA capping, the extra peaks at 1400 and 1632 cm-1 could be observed in addition to above peaks of YPO4:Eu3 and correspond to COO-1 vibration modes of EDTA. These materials are dispersible in water because of presence of capping agent on the surface of particles. Figure 2(a) shows emission spectra of Eu3+ doped YPO4 capped with EDTA (0, 20, 50 mol%) at 394 nm excitation. The characteristics peaks corresponding to f-f emission of Eu3+ at 591 nm (5D07F1) and 615 nm (5D07F2) can be seen. The electric dipole allowed transition depends on surrounding environment, whereas the magnetic dipole transition is independent of the surrounding environment. The luminescence intensity was calculated from the area under the magnetic and electric dipole transitions by fitting the Gaussian distribution function in the range of 583-630 nm. The symmetry around the Eu3+ ion can be understood using asymmetric ratio (A21).

FIGURE 1. (A) XRD patterns of YVO4:Eu capped with EDTA. (B) TEM image of YVO4:Eu. (C) IR spectra of YVO4:Eu capped with EDTA.

FIGURE 2. (a) The emission spectra of YPO4:Eu3+ /EDTA at 394 nm excitation. (b) Decay curve at 260 nm excitation and data are fitted with bi-exponential equation.

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On addition of EDTA (0, 20, 50 mol%), slight variation in luminescence intensity was found. With the increase of EDTA concentration, the peak positions of the magnetic and electric dipole transitions are slightly shifted to the lower wavelength and the asymmetric ratio of luminescence (A21) decreases. Table 1 gives the peak maximum, FWHM and A21 corresponding to the electric and magnetic dipole transitions at different excitation wavelengths (260 and 395 nm). With change of excitation wavelength from 260 to 395 nm, A21 value decreases. Luminescence intensity decreases with increasing concentrations of EDTA for both these excitations. TABLE 1: Peak positions, FWHM (w1 and w2) and their A21 for YPO4:Eu3+/EDTA at 260 and 395 nm excitations. EDTA is expressed in mol%.
EDTA

Eu3+ ions in a particle. av values for 0, 20 and 50 mol% EDTA capped YPO4:Eu3+ are found to be in range 0.51 - 0.75 ms.

CONCLUSIONS
Eu3+ doped YPO4 nanoparticles with and without EDTA have been prepared. The effective crystallite size and strain developed in lattice of Eu3+ doped YPO4 nanoparticles are found to be 28 nm and 0.002, respectively. The emission peaks at 591 nm (5D07F1 magnetic dipole transition) and 615 nm (5D07F2 electric dipole transition).are observed With addition of EDTA, there are following changes: (1) a slight shift towards the lower wavelength for emission peaks, (2) decrease in asymmetric ratio of electric to magnetic dipole transition intensities and (3) decrease in emission intensity. However, such phosphor materials stabilized by EDTA will be useful in biological work because these are dispersible in water.

Excitation at 260 nm
5

395 nm
A21
5

D07F1 (nm) 591.2 591.1 590.8

D07F2 (nm) 615.2 614.9 614.8

D 07F (nm) 591.9 591.7 591.7

D 07F2 (nm) 616.2 615.0 615.4

A21 (nm) 1.28 1.23 1.20

ACKNOWLEDGMENTS
A. K. Parchur acknowledges the nancial support provided by University Grants Commission, Govt. Of India through the D. S. Kothari Post Doctoral Fellowship and Prof. Ajay Gupta, Centre-Director, UGC-DAE CSR, Indore, for his encouragement during this work. Authors thank Dr. T. Mukherjee, Chemistry Group and Dr. D. Das Chemistry Division, BARC for their support and encouragement during this work

0 20 50

1.77 1.67 1.44

It has been observed that the FWHM of XRD peaks, increases with the increasing EDTA in sample. Surface/core atomic density increases with decrease of particle size. This is responsible for non-radiative process and thereby a decrease in luminescence intensity with increase of EDTA or decrease of particle size. In 50 at.% EDTA, A21 value is almost unchanged irrespective of excitation wavelengths and also least among samples. It is suggested that smaller size particles are more dominated by nonradiative process and thereby environment of Eu3+ in bulk/core region is influenced by surface. This establishes that environment of ion in core region for smaller particles are influenced by surface. With further decrease of particle size, environment of ion in core region is almost the same as that in surface. Thus, a slight variation in peak positions of electric and magnetic dipole transitions of Eu3+ with increase of EDTA are due to decrease of particle size of host. Also, the number of Eu3+ activators per unit volume decreases with increase of EDTA content in sample. Figure 2(b) shows the decay curves for 5D0 level of Eu3+ (260 nm excitation) for Eu3+-doped YPO4 with different concentrations of EDTA. Intensity decreases with increase of EDTA content in YPO4:Eu3+ sample. Biexponential fitting is better indicating distribution of

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