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RARE METALS

Vol. 30, No. 6, Dec 2011, p. 572


DOI: 10.1007/s12598-011-0431-1

Microwave-assisted synthesis of CePO4 nanorod phosphor with violet emission

Nuengruethai Ekthammathata, Titipun Thongtema,d, Anukorn Phuruangratb, and Somchai Thongtemc,d


a
Department of Chemistry, Faculty of Science, Chiang Mai University, Chiang Mai 50200, Thailand
b
Department of Materials Science and Technology, Faculty of Science, Prince of Songkla University, Hat Yai, Songkhla 90112, Thailand
c
Department of Physics and Materials Science, Faculty of Science, Chiang Mai University, Chiang Mai 50200, Thailand
d
Materials Science Research Center, Faculty of Science, Chiang Mai University, Chiang Mai 50200, Thailand
Received 10 November 2010; received in revised form 30 June 2011; accepted 11 July 2011
© The Nonferrous Metals Society of China and Springer-Verlag Berlin Heidelberg 2011

Abstract

Monoclinic and hexagonal CePO4 nanoparticles and nanorods were successfully synthesized from Ce(NO3)3·6H2O and Na3PO4·12H2O solu-
tions at pH 1-5 by a 180 W microwave radiation for 60 min. The products were characterized by X-ray diffraction (XRD), Fourier transform
infrared (FTIR) spectroscopy, and scanning electron microscopy (SEM). XRD patterns revealed that the products are hexagonal CePO4
structures at pH 2-5, and monoclinic CePO4 structures at pH 1. SEM characterization shows that these products were nanoparticles, short
nanorods, and long nanorods, controlled by the pH of the precursor solutions. Optical properties of the nanorods were also investigated by
ultraviolet-visible (UV-vis) and photoluminescence (PL) spectroscopy.

Keywords: microwave radiation, monoclinic CePO4, hexagonal CePO4, direct energy gap

efficient emitters of green light [12], optoelectronic devices


1. Introduction
[13], and ceramic applications [14]. CePO4 has two crystal
Since the discovery of carbon nanotubes by Iijima in structures: hexagonal and monoclinic, which is controlled
1990, one-dimensional (1D) nanomaterials including nano- by the temperatures and synthesis methods. Hexagonal
rods, nanotubes, nanowires, and nanofibers have been inten- CePO4 could be synthesized at low temperature [12-13]. The
sively studied. These 1D materials have unique chemical structural characteristics, such as size, morphology, crystal
and physical properties, owing to the effects of quan- structure, and composition of the complex, have the influ-
tum-size and different morphologies [1-2]. In comparison ence on the physicochemical property. Thus, materials sci-
with zero-dimensional (0D) structure, the anisotropic shape entists have developed the process used to synthesize and
of the 1D structure provided a better model in the electronic control the size and morphology of the complexes to be 1D
transport, optical and mechanical properties on size con- structure [12-13, 15].
finement, and dimensionality [1, 3]. Their luminescent In this research, a simple microwave method was devel-
properties are different from those of the bulks, such as ag- oped to synthesize 1D CePO4 nanostructures. The effects of
gregation-enhanced emission, fluorescence narrowing, mul- the pH precursors on phase, size, and morphology of the
ticolor emission, and tunable and switchable emission from products were studied by X-ray diffraction (XRD), Fourier
doped nanostructures. The 1D nanostructure is more appro- transform infrared (FTIR) spectroscopy, scanning electron
priate for active nanodevices and interconnections [1, 4]. microscopy (SEM), and ultraviolet-visible (UV-vis) and
Thus, in the past two decades, 1D nanostructured materials photoluminescence (PL) spectroscopy.
have extremely attracted their research interest [1, 4-6].
Lanthanide orthophosphate LnPO4 (Ln = La, Ce, Pr, Nd,
2. Experimental
Sm, Eu, Gd, Tb, Dy, Ho) has a number of characteristic
properties in which researchers are interested [7-10]. Cerium To synthesize 1D CePO4 nanostructures, all chemical re-
phosphate (CePO4) nanomaterial has received interest since agents were of analytical grade and were used without fur-
the end of the 1960s [11]. It has luminescence property, ther purification. Each of 0.003 mol of Ce(NO3)3·6H2O and
therefore, it can be applied for luminescent lamp as highly Na3PO4·12H2O was dissolved in 80 mL deionized water and

Corresponding author: Titipun Thongtem, E-mail: ttpthongtem@yahoo.com; Anukorn Phuruangrat, E-mail: phuruangrat@hotmail.com
Ekthammathat N. et al., Microwave-assisted synthesis of CePO4 nanorod phosphor with violet emission 573

followed by 15 min vigorous stirring. The pH of the precur- 0.64344 nm for the monoclinic structure, and a = b =
sor solutions was adjusted to be 1-5 by 37% HNO3. Each of 0.69604 nm and c = 0.64511 nm for the hexagonal struc-
the solutions with different pH values was put in a micro- ture. These were in good accordance with those of the
wave oven (Electrolux, EMS 2820, 2.45 GHz), heated by a standard values. Unit cell volumes (V) were respectively
180 W power for 60 min, and naturally cooled to room calculated from equations (3) and (4) for monoclinic and
temperature. Finally, white precipitates were synthesized, hexagonal structures [17] below.
filtered, washed by deionized water and 95% ethanol several V = abc sin β (3)
times, dried at 80°C for 12 h, and collected for further char-
acterization. V = a 2 c sin 60 (4)
Phase, morphologies, and optical properties of the prod- They were 0.29548 nm3 for monoclinic and 0.27067 nm3
ucts were characterized by X-ray diffraction (XRD, Philips for hexagonal structures. It should be noted that the decrease
X’Pert MPD) using Cu Kα line and scanned at 2θ angle, in the cell volume of both structures indicated that these lat-
ranging from 10° to 60° with a scanning rate of 0.04° per tices were more distorted, as compared to the corresponding
step. The XRD data were analyzed by X'Pert HighScore bulks.
Plus program in combination with The Joint Committee on
Powder Diffraction Standards (JCPDS). Field emission
scanning electron microscopy (FE-SEM, JEOL JSM-6335F)
was operated at 15.0 kV with LaB6 electron gun. Fourier
transform infrared spectroscopy (FTIR, Perkin Elmer RX
spectrophotometer) was analyzed at a greater than 400-4000
cm−1 range with 4 cm−1 resolution, with the diluted samples
by KBr for 40 times. Photoluminescence (PL, Perkin Elmer
LS50B Fluorescence spectrometer) and UV-visible (Perkin
Elmer Lambda 25 UV-vis spectrometer) spectra were also
analyzed at room temperature.

3. Results and discussion


Fig. 1 shows XRD patterns of CePO4 synthesized in solu-
tions with the pH of 1, 2, 3, 4, and 5 by a 180 W microwave Fig. 1. XRD patterns of CePO4 synthesized in the solutions
radiation for 60 min. These patterns were identified to cor- with different pH values by microwave radiation at 180 W for
respond with the pure monoclinic CePO4 phase with JCPDS 60 min.
database No. 77-0429 [16] (a = 0.67700 nm, b = 0.69900
FTIR spectra (Fig. 2) show the vibrations of PO 34− tet-
nm, and c = 0.64500 nm, V = 0.29667 nm3) for the product
rahedrons of CePO4 materials at pH 1, 3, and 5. By using
synthesized in the solution with pH 1 and hexagonal CePO4
group theory calculation, PO 34− tetrahedrons have four vi-
phase of the JCPDS database No. 75-1880 [16] (a = b =
brational modes: A1 + E + 2F2. A1 and E were Raman (R)
0.70550 nm, and c = 0.64390 nm, V = 0.27755 nm3) for the
active, and 2F2 were R and IR doubly active. The ν1(A1),
product synthesized in the solutions with pH 2, 3, 4, and 5.
ν2(E), ν3(F2), and ν4(F2) were symmetric stretching, symmet-
Their lattice parameters were respectively calculated from
ric bending, asymmetric stretching, and asymmetric bending
plane spacing equations (1) and (2) for monoclinic and hex-
modes. The symmetry of PO 34− tetrahedrons in the CePO4
agonal structures [17] below.
crystals decreases from Td to C1, thus the non-IR mode be-
1 1 ⎡⎢ h 2 k 2 sin 2 β l 2 2hl cos β ⎤⎥ comes IR active [18]. The vibrations of phosphate ( PO 34− )
= + + 2− (1)
d 2 sin 2 β ⎢⎣⎢ a 2 b2 c ac ⎥⎦⎥ tetrahedrons in CePO4 crystals were detected over the
400-1400 cm−1 range and appeared as three bands at 1057,
1 4
d 2
=
2
(h2 + hk + k 2 ) + c12 l 2 (2) 617, and 533 cm−1. The 1057 cm−1 mode was assigned as the
3a asymmetric stretching vibration of PO 34− groups. Other
where a, b, and c are the lattice parameters; h, k, and l two bands were attributed to the O−P−O asymmetric bend-
are the Miller indices; d is the plane spacing, and β is the ing vibrations [6, 19]. No vibration of NO 3− anions from
angle between the a and c axes (103.6°). Their lattice pa- the residual Ce(NO3)3·6H2O was detected in these spectra,
rameters were a = 0.67470 nm, b = 0.70026 nm, and c = proving that the as-synthesized CePO4 nanostructure has
574 RARE METALS, Vol. 30, No. 6, Dec 2011

very high purity. Moreover, two broad bands at 3440 and mation mechanism of 1D CePO4 phosphor nanomaterials
1644 cm−1 are assigned as the O−H stretching and bending was explained as equations (5) and (6) below.
vibrations of H2O adsorbed on the surface of CePO4. PO 34− + nH + → H n PO (3 −n)−
(5)
4
−n)−
Ce 3+ + H n PO (3
4 → CePO 4 + nH + (6)
Generally, shape of the products is controlled by the pa-
rameters relating to kinetics and thermodynamics. In this
case, the formation of CePO4 nanorods was explained in
term of the thermodynamics, relating to the surface energy
and chemical potential [20]. During the reaction, H+ ions
−n)−
first reacted with PO 34− ions to form H n PO (3 4 ions.
3+ (3− n ) −
Due to the addition of Ce ions, H n PO 4 ions slowly
released PO 34− ions to form CePO4. It was likely that Ce3+
ions were adsorbed onto the surface of the initially formed
tiny hexagonal CePO4 nanorods, due to the strong
interaction between Ce3+ and PO 34− ions on the particle
surfaces. High chemical potential favored the growth of 1D
nanomaterials. High mobility of ions promoted the
Fig. 2. FTIR spectra of CePO4 synthesized in the solutions
reversible paths between solutions and precipitates. Thus,
with pH 1, 3, and 5 by microwave radiation at 180 W for 60
these ions will have more chance to reside in their perfect
min.
lattice [12]. Generally, LnPO4 (Ln = La-Dy) tended to grow
The influence of pH on the formation of CePO4 was as 1D nanorods/nanowires, possibly due to the 1D
characterized by SEM. The morphologies of the characteristics of the infinite linear chains of their hexagonal
as-synthesized CePO4 images (Fig. 3) can be classified into structures. By adjusting the pH of the precursors to be 1, the
two groups, the CePO4 nanoparticles and nanorods in the pH concentration of H+ ions in the reaction system was
ranges of 1-5. The products were composed of agglomerated increased. The chemical potential was increased as well. The
nanoparticles with pH 3-5. They became short nanorods at preferential adsorption of H+ onto certain crystal facets
pH 1.5-2. A number of nanorods with 2-3 µm in length and seemed to raise the electrostatic potential on the crystal
50 nm in diameter (aspect ratio of 40-60) were synthesized surfaces of prior hexagonal CePO4 nanorods. In order to
in the pH 1. The morphology evolution of CePO4 is shown reduce the surface energy, the atoms of the crystal surfaces
by a schematic diagram in Fig. 4. were rearranged [6, 13]. Thus, the 1D CePO4 nanorods were
On the basis of the experimental results, a possible for- finally synthesized under the microwave radiation.

Fig. 3. SEM images of CePO4 synthesized in the solutions with pH 1 (a), 1.5 (b), 2 (c), 3 (d), 4 (e), and 5 (f) by microwave radiation
at 180 W for 60 min, respectively.
Ekthammathat N. et al., Microwave-assisted synthesis of CePO4 nanorod phosphor with violet emission 575

with two small shoulder peaks at 238 and 260 nm in ultra-


violet region of the as-synthesized CePO4 nanorods were
detected, due to the 4f-5d electron transitions of Ce3+ in the
CePO4 phase [22]. The energy level for Ce3+ ions (inset of
Fig. 5(a)) shows three electron transitions as 2F5/2 → 2F7/2,
2
F5/2 → 2D3/2, and 2F5/2 → 2D5/2. The lowest energy transition
(2F5/2 → 2F7/2) was a Laporte forbidden µ to µ transition
corresponding to the fn to fn transition. Other two electron
transitions, 2F5/2 → 2D3/2 and 2F5/2 → 2D5/2, were Laporte al-
lowed transitions [21]. Two major absorption peaks of
Fig. 4. Schematic diagram for the formation of CePO4 nano- CePO4 nanorods at 277 and 216 nm were assigned as 2F5/2
rods. → 2D3/2 and 2F5/2 → 2D5/2. The shoulders at 238 and 260 nm
were spit by the crystal field effect, and the electronic transi-
Fig. 5(a) shows UV-visible spectrum of the monoclinic tion of 2F5/2 → 2F7/2 was no longer detected. The direct band
CePO4 nanorods for the solution pH of 1 in the range of gap of CePO4 nanorods (Fig. 5(b)) was determined from the
200-650 nm wavelength. In general, the optical absorption plot of (αhv)2 versus hv, where α is the absorbance, h is the
of CePO4 material has two electron transition modes in the Planck constant, and v is the frequency [23]. The direct band
f-f orbital appearing in the IR region (λmax~440 nm) and the gap (Eg) of CePO4 nanorods was 4.1 eV.
f-d transition in the ultraviolet region (λ~190-300 nm) [21]. The room temperature photoluminescence of CePO4
Two strong absorption peaks at 216 and 277 nm coupled nanorods was investigated using an excitation wavelength of
250 nm, as shown in Fig. 6. The PL curve exhibits a broad
luminescent band in the major blue, minor violet, and green
wavelength range. Similar results were detected in the col-
lective emission spectra of rare earth phosphates. By using
Gaussian analysis, the board emission band in 300-650 nm
was separated into five components at 372, 419, 466, 488,
and 509 nm. Each represents the different type of electronic
transitions, linked with the structural arrangement or surface
defects.

Fig. 6. PL spectrum of CePO4 nanorods synthesized in the


solution with pH 1, using microwave radiation at 180 W for 60
min.

Fig. 5. (a) UV-vis absorption and (b) (αhv)2 versus hv curve of


4. Conclusions
CePO4 nanorods synthesized in the solution with pH 1, using
microwave radiation at 180 W for 60 min. Monoclinic CePO4 nanorods with 2-3 µm in length and
576 RARE METALS, Vol. 30, No. 6, Dec 2011

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