Journal of Luminescence 161 (2015) 389–394

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Journal of Luminescence
journal homepage: www.elsevier.com/locate/jlumin

Structure and photoluminescence characterization of Tb3 þ -doped

LaPO4 nanorods prepared via the microwave-assisted method
Duong Thi Lien, Duong Thi Mai Huong, Le Van Vu, Nguyen Ngoc Long n
Centre for Materials Science, Faculty of Physics, Hanoi University of Science, Vietnam National University, 334 Nguyen Trai, Thanh Xuan, Hanoi, Vietnam

art ic l e i nf o a b s t r a c t

Article history: LaPO4 nanopowders doped with 1, 2… 10, 11, 15 and 20 mol% Tb3 þ have been prepared by the microwave-
Received 29 August 2014 assisted method. Transmission electron microscope (TEM) images indicated that the nanopowders are comp-
Received in revised form osed of nanorods. X-ray diffraction (XRD) analysis showed that the prepared nanorods exhibit hexagonal
7 January 2015
crystal structure and the diffraction peaks were shifted towards the higher 2θ angle side with increasing Tb3 þ
Accepted 25 January 2015
Available online 3 February 2015
dopant concentration. Raman scattering measurement found out that some of scattering lines were shifted
and broadened to higher wavenumber side with increasing Tb3 þ concentration. It is discovered that the
Keywords: photoluminescence (PL) of Tb3 þ ions results from the radiative intra-configurational f–f transitions that occur
Lanthanum orthophosphate from the 5D4 exited state to the 7FJ (J¼0,1–6) ground states; the photoluminescence excitation (PLE) of Tb3 þ
Nanorods
ions takes place from the 7F6 ground state to the 5DJ (J¼0,1–4), 5L10, 5GJ (J¼2–4), 5HJ and 5IJ exited states. It was
Microwave-assisted method
observed that the photoluminescence intensity reached a maximum in the samples doped with 15 mol% Tb3 þ .
Raman scattering
Photoluminescence Double-exponential decay of the 5D4-7F5 emission was observed with lifetimes of  5 ns and 6.35 ms.
& 2015 Elsevier B.V. All rights reserved.

1. Introduction [12,17,24,25], thin films [18], nanoparticles [8–11,13,14,16,21,22]

Rare earth phosphates have become a topic of growing interest
during the past few years due to their potential applications in
optical materials, phosphors, lasers, light-emitting diodes (LED),
sensors, displays and luminescent lamps [1–3]. One of the present-
day actual tasks is the fabrication of relatively cheap rare earth
phosphate nanopowders because their luminescence efficiency is
expected to increase when the size of particles decreases to nano-
scale [4,5]. Recently, lanthanide orthophosphate (LaPO4) has been
reported to act as an excellent host for cerium, terbium, and euro-
pium ions, to synthesize phosphors emitting a variety of colors for
development of photoluminescent materials with applications in
optoelectronic devices, solid-state lasers, white LEDs, displays, and
phosphors [6–13]. Very recently, it has been found that rare-earth-
doped LaPO4 is one of the best candidates for biomedical applica-
tions such as fluorescence resonance energy transfer (FRET) assays,
biolabelling, optical imaging or phototherapy [14–16]. For synthesis
of the rare-earth-doped LaPO4 various methods including sol–gel
[16–18], hydrothermal synthesis [13,16,19,20], co-precipitation
[21–23], polyol-mediated synthesis [8] and microwave-assisted
technique [9–12] have been developed. The LaPO4 nanostructures
with various morphologies such as nanowires [19,23], nanorods
and microspheres [20] were obtained.
Microwave irradiation is used as a heating method, which is
generally quite fast, simple and efficient in energy. In the last two
decades microwave-assisted technique has been developed and is
widely used in various fields of chemistry [26]. The effect of heating
is created by the interaction of the dipole moment of the molecules
with the high frequency electromagnetic radiation (2.45 GHz). The
application of microwave irradiation to materials science has shown
very rapid growth due to its unique reaction effects such as rapid
volumetric heating and the consequent dramatic increase in reaction
rates, etc. By using the microwave-assisted technique, authors of the
earlier works [9–11] have synthesized LaPO4 nanoparticles with
monoclinic crystal structure. Only Ma et al. [12] reported on LaPO4:
Ce3 þ , Eu3 þ , Tb3 þ nanorods with hexagonal structure prepared by
the microwave method. Hence, we tried to use this method for
synthesis of LaPO4:Tb3 þ nanorods.
In this paper we report the preparation of LaPO4 nanorods doped
with terbium (Tb3 þ ) ions by microwave-assisted technique. Our
studies are focused on the Tb3 þ concentration effect on XRD, Raman
scattering spectra, PL properties of the LaPO4:Tb3 þ nanorods.
2. Experimental

n
Corresponding author. La1  xTbxPO4 nanopowders with x¼ 0, 0.01… 0.11, 0.15 and 0.20
E-mail addresses: longnn@vnu.edu.vn, ngocnglong@gmail.com (N. Ngoc Long). have been prepared from the chemicals such as La2O3 powders,

http://dx.doi.org/10.1016/j.jlumin.2015.01.050
0022-2313/& 2015 Elsevier B.V. All rights reserved.
390 D. Thi Lien et al. / Journal of Luminescence 161 (2015) 389–394

bulk Tb, HNO3 acid, and NH4H2PO4 by using microwave irradiation.

In a typical synthesis, a stoichiometric amount of La2O3 was
dissolved in diluted HNO3 acid (30%) under vigorous magnetic
stirring for 15 min to form La(NO3)3 transparent solution. A stoi-
chiometric amount of Tb was dissolved in diluted HNO3 acid (30%)
under vigorous stirring for 15 min to produce Tb(NO3)3 aqueous
solution. An appropriate amount of NH4H2PO4 was dissolved in
double distilled water under constant stirring for 15 min to prepare
NH4H2PO4 solution. Stoichiometric amounts of La(NO3)3 and
Tb(NO3)3 aqueous solutions were mixed, and then appropriate
amounts of NH4H2PO4 solution were added into the mixed nitrate
solution under stirring for 30 min, obtaining an opalescent solution.
The resulting solution was then transferred into a 100 ml flask. The
flask containing the above solution was put in a microwave oven
(SANYO, EM-D9553) with irradiation powers of 300, 450 and 750 W
for 20, 30 and 40 min. The obtained precipitate was centrifuged,
washed with distilled water and absolute alcohol to remove chemi-
cals possibly remaining in the final products, and was dried at 75 1C
for 12 h in air.
Crystal structure of the powders was analyzed by X-ray diffrac-
tion (XRD) using an X-ray diffractometer SIEMENS D5005, Bruker,
Germany with Cu-Kα1 (λ ¼1.54056 Å) irradiation. The surface
morphology of the samples was observed by using a JEOL JEM
1010 transmission electron microscope (TEM). The composition of
the samples was determined by an energy-dispersive X-ray spectro-
meter (EDS) OXFORD ISIS 300 attached to the JSM 5410 LV, JEOL,
Japan scanning electron microscope (SEM). Raman measurements
were carried out by using LabRam HR800, Horiba spectrometer
with 632.8 nm excitation. The PL and the PLE spectra measured
at room temperature were carried out on a spectrofluorometer
Fluorolog FL 3-22 Jobin-Yvon-Spex, USA with a 450 W xenon lamp
as an excitation source.

3. Results and discussion Fig. 1. (a) XRD patterns of LaPO4 powders doped with different Tb concentrations
prepared with a microwave irradiation power of 450 W for 30 min, and (b) the shift
of diffraction peaks to the higher 2θ angle side with increasing Tb3 þ concentration.
Typical XRD patterns of LaPO4 nanopowders doped with 0, 7, 15
and 20 mol% Tb3 þ concentrations prepared with an irradiation
power of 450 W for 30 min are shown in Fig. 1a. All the peaks in the
XRD patterns clearly indicate that the LaPO4 undoped and doped
with Tb3 þ samples possess hexagonal crystal structure. No other
diffraction peaks are detected except for the LaPO4 related peaks.
The lattice constants determined from the XRD patterns are
a¼b¼ 7.088 Å, c¼ 6.489 Å and c/a¼0.9155 which are in agreement
with the standard values a¼ b¼ 7.042 Å, c¼6.445 Å and c/a¼0.9158
(JCPDS card no. 04-0635). The average sizes of the crystallites were
estimated by Debye–Scherrer's formula [27]:

0:9λ
D¼
β cos θ
where β is the full width at half maximum (FWHM) in radians of
the diffraction peaks, θ is Bragg's diffraction angle and
λ ¼1.54056 Å. The average sizes of the LaPO4 nanocrystallites were
estimated to be 10 nm.
It is noted from Fig. 1a that with increasing Tb3 þ concentration in
the XRD patterns was as well observed an amorphous phase. The
XRD analysis results for the samples prepared with different micro-
wave irradiation powers showed that XRD patterns of the samples Fig. 2. EDS spectra of LaPO4 nanopowders doped with 9 mol% and 20 mol% Tb3 þ
synthesized with a low (300 W) irradiation power exhibited a little concentrations.
amorphous phase; the samples synthesized with a higher (450 and
750 W) irradiation power possessed better crystallinity. Learning with coordination number of 9 (1.095 Å) is smaller than that of La3 þ
XRD patterns in more detail, we revealed that the diffraction peaks ion (1.216 Å) [28].
were shifted towards the higher 2θ angle side with increasing Tb3 þ Typical EDS spectra of the LaPO4 nanopowders doped with 9 and
concentration (see Fig. 1b), which exhibited a shrink of host lattice. 20 mol% Tb3 þ are shown in Fig. 2. The amount of Tb obtained by EDS
The reason for this shrink is because the radius of Tb3 þ dopant ion analysis in 9 and 20 mol% doped LaPO4 samples was 1.43 and 3.26 at%,
 D. Thi Lien et al. / Journal of Luminescence 161 (2015) 389–394
respectively. It can be seen that the amounts of Tb obtained by EDS
analysis is much less than those added during synthesis. The carbon
(C) and aluminium (Al) weak peaks observed in the EDS spectra
originated from the carbon tape used to glue the powders in the EDS
measurement.
The TEM images of LaPO4 nanopowders depicted in Fig. 3
indicate that the powders are composed of the nanorods which
are around 10–15 nm in diameter and the length ranging from
300 to 800 nm. Most of earlier works [9–11] indicated that the
products obtained by the microwave-assisted method were LaPO4
nanoparticles with monoclinic crystal structure. The only work of
Lin Ma et al. [12] informed that by using the microwave method
they received LaPO4 nanorods with hexagonal structure.
It is well known that Raman scattering spectroscopy is becoming a
powerful technique for the characterization of materials. For example,
Raman spectroscopy has been applied to LaPO4 [29,30] and TbPO4
[31] phosphors for studying pressure effect on their structure stability.
Our Raman measurements were performed at room temperature
in the wavenumber range from 100 to 1200 cm  1. Fig. 4 depicts
room-temperature Raman spectra of Tb3 þ -doped LaPO4 nanopow-
ders with hexagonal crystal structure, which are in good agreement
with the results reported recently by Ref. [32] for Tb3 þ -doped LaPO4
nanowires prepared by hydrothermal technique at low temperature.
Fig. 3. (a) Low magnified and (b) high magnified TEM images of LaPO4 nanopow-
ders prepared by the microwave-assisted method.
391
Fig. 4. Room-temperature Raman scattering spectra of Tb doped LaPO4 nanopow-
ders prepared by the microwave-assisted method. Various Tb3 þ concentrations are
shown in the figure.
As can be seen from the figure, the Raman spectrum of hexagonal
LaPO4 nanopowders exhibits five scattering line groups. First
group consists of 226 cm  1 line in the range of 100–300 cm  1;
second group: 377, 413 and 466 cm  1 lines in the range of
375–500 cm  1; third group: 544, 573 and 624 cm  1 lines in the
range of 525–625 cm  1; fourth group: 974 cm  1 line in the range
of 950–980 cm  1; and fifth group: 1029, 1049 and 1084 cm  1
lines in the range of 990–1100 cm  1.
The observed Raman bands were assigned to the lattice vibrations
and typical vibrational bands of the (PO4)3 tetrahedron [33–35].
Indeed, a free (PO4)3 ion has the four normal vibrational modes:
O–P–O E-bending ν2(E), O–P–O F2-bending ν4(F2), P–O symmetric
stretching ν1(A1) and P–O asymmetric stretching ν3(F2). The Raman
scattering lines of hexagonal LaPO4 nanorods and their assignment
are listed in Table 1 compared with infrared (IR) absorption lines.
From Table 1 it is found that the ν2(E) mode appears only in Raman
spectra, meanwhile the lattice vibrational, ν4(F2), ν1(A1) and ν3(F2)
modes appear both in Raman and in IR spectra.
To investigate influence of Tb3 þ dopant, the Raman spectra of
the LaPO4 nanorods undoped and Tb3 þ -doped with different
concentrations were measured. The results are presented in two
regions: from 100 cm  1 to 700 cm  1 (Fig. 5a) and from 925 cm  1
to 1100 cm  1 (Fig. 5b).
It can be found that some scattering lines (226, 573, 624, 974 and
1084 cm  1) are clearly shifted and broadened to higher wavenumber
side. Of which a considerable change is observed for the 974 cm  1
line. Table 2 lists the position and FWHM of the 974 cm  1 line
assigned to the P–O symmetric stretching modes ν1(A1). As can be
seen from Table 2, for the undoped LaPO4 samples the Raman peak of
ν1(A1) modes is at 974.6 cm  1 with FWHM of 5.5 cm  1 and when
increasing Tb3 þ dopant concentration up to 20 mol%, the corre-
sponding Raman peak of ν1(A1) modes is at 979.1 cm  1 with FWHM
of 12.9 cm  1, i.e. is shifted by 5.5 cm  1 and broadened by 7.4 cm  1
towards the higher frequency.
Phenomenon that the Raman scattering lines are shifted and
broadened to higher wavenumber when doping 6 H-SiC crystal
with N-, Al-, B-, V-impurities was investigated in detail by Refs.
[42,43] and was attributed to the coupling interaction between
phonons and carrier plasmon. Studying pressure effect on struc-
ture stability of LaPO4 [29,30] and TbPO4 [31] by Raman spectro-
scopy, the authors of Refs. [29,31] had revealed that all Raman
modes were shifted and broadened to higher wavenumber with
increasing pressure. According to Lacomba-Perales et al. [30], the
pressure induced a decrease in lattice parameter and bond length,
resulting in the shift and broadening of Raman modes. In our case
of Tb3 þ -doped LaPO4 nanorods, the radius of Tb3 þ ion is smaller
392 D. Thi Lien et al. / Journal of Luminescence 161 (2015) 389–394

Table 1
Experimental Raman scattering and infrared (IR) absorption frequencies (cm  1) at room temperature of the hexagonal LaPO4 and assignment.

Groups, assignment [33–35] Raman (this work) Raman [32] IR [35] IR [36] IR [37] IR [38] IR [39] IR [40] IR [41]

Lattice vibrations 178 Not seen Not seen Not seen Not seen Not seen
202
100–300 226 228 228 215
253
ν2(E) 377 376 Not seen Not seen Not seen Not seen Not seen Not seen Not seen
375–500 413 414
466 466
ν4(F2) 544 545 540 542 542 541 542 542 538
525–625 573 575 570 570 569 570 566 567
593
624 625 615 615 617 613 619 615 615
ν1(A1) 974 977 949 971 966 956 Not seen Not seen 961
950–980 (Raman) (Shoulder)
ν3(F2) 991 Not fully resolved Not fully resolved Not fully resolved
990–1100 1029 1020 1052 1050 1012
1049 1039 1043 1044
1085 1070
1084 1090

Table 2
The P–O symmetric stretching modes ν1(A1) in Raman spectra of the LaPO4
nanorods doped with different Tb3 þ concentrations.

LaPO4 Undoped 5 mol% 11 mol 15 mol% 20 mol%

Tb3 þ % Tb3 þ Tb3 þ Tb3 þ

Position (cm  1) 974.6 975.6 976.7 977.7 979.1

FWHM (cm  1) 5.5 8.0 10.7 11.7 12.9

Fig. 6. PLE and PL spectra measured at room temperature of LaPO4 nanopowders

doped with 15 mol% Tb3 þ .

Fig. 5. Room-temperature Raman spectra in the wavenumber region (a) from

100 cm  1 to 700 cm  1 and (b) from 925 cm  1 to 1100 cm  1 of the LaPO4
nanopowders undoped and doped with 5, 11, 15 and 20 mol% Tb3 þ .
than that of La3 þ ion. Hence replacement of the La3 þ ions with the
Tb3 þ ions causes a shrinking host lattice (as observed from XRD
measurements), i.e. causes a decreasing lattice parameter and
bond length; and as a result of this, the vibrational modes are
shifted and broadened to higher wavenumber with increasing
Tb3 þ -dopant concentration.
Fig. 6 represents the room-temperature PLE spectrum mon-
itored at 543 nm and the PL spectrum under excitation wavelength
of 368 nm of Tb3 þ -doped LaPO4 nanorods with 15 mol%. As seen
below, the lines in the two spectra are interpreted as the optical
intra-configurational f–f transitions in the Tb3 þ ions. The room-
temperature PL spectra under excitation wavelength of 368 nm of
LaPO4 nanorods doped with various concentrations of Tb3 þ are
illustrated in Fig. 7. It can be seen from the inset of Fig. 7 that the
PL intensity achieved its maximal value for the samples doped
with 15 mol% Tb3 þ , in good agreement with the reported value of
16 mol% Tb3 þ for Tb-doped LaPO4 films [18]. When increasing
Tb3 þ concentration higher than 15% the PL intensity decreased.
This is a conventional concentration quenching effect.
Room-temperature PL spectrum under 368 nm excitation wave-
length of LaPO4 nanorods doped with 15 mol% of Tb3 þ is illustrated
 D. Thi Lien et al. / Journal of Luminescence 161 (2015) 389–394 393

Fig. 7. Room-temperature PL spectra with 368 nm excitation wavelength of LaPO4 Fig. 9. Typical PLE spectrum monitored at 543 nm emission line of LaPO4 nanopowder
nanopowders doped with various concentrations of Tb3 þ . doped with 15 mol% of Tb3 þ .

Fig. 8. Room-temperature PL spectrum under 368 nm excitation wavelength of

LaPO4 nanopowders doped with 15 mol% of Tb3 þ .

in Fig. 8. The groups of emission lines located at 489, 543, 585 and
620 nm are assigned to the emission transitions from the 5D4
excited state to the 7F6, 7F5, 7F4 and 7F3 ground states, respectively.
Some groups of very weak emission lines at 645, 667 and
681 nm are assigned to 5D4-7F2, 7F1 and 7F0 transitions, respec-
tively (see the inset of Fig. 8). It is noted that in the case of our
LaPO4:Tb3 þ nanorods the PL lines of Tb3 þ ions are poorly
resolved, that is the same as the result of Pankratov et al. [44,45]
for LaPO4:Ce,Tb nanopowder. The reason of this was suggested to
be a strong perturbation of the crystal field due to the small
nanoparticles size [44,45].
Our experimental results (not shown here) indicated that all the
emission line groups have the same excitation spectra, which prove
that all these lines possess the same origin. Typical PLE spectrum
monitored at 543 nm emission line of LaPO4-15% Tb3 þ nanorods is
Fig. 10. Luminescence decay curves at 550 nm of Tb3 þ ions doped in LaPO4
depicted in Fig. 9. The groups of excitation lines located around nanorods under 337 nm laser excitation with (a) 1 MΩ load resistor and (b) 50 Ω
283, 303, 317, 340, 350, 368, 377 and 486 nm are attributed to the load resistor.
absorption transitions from the 7F6 ground state to the 5IJ, 5HJ, 5D0,1,
5
GJ, 5D2, 5L10, 5D3 and 5D4 excited states, respectively. It should be
noted that LaPO4 has bandgap energy of around 8 eV and we used Decay curves of emission at 550 nm (5D4-7F5) of Tb3 þ ion
xenon lamp as an excitation source, therefore, the Tb3 þ ions could were measured with 1 MΩ and 50 Ω load resistors under 337 nm
be directly excited only by f–f transitions in the range of 2.5–4.4 eV, laser excitation. Typical decay curves in semi-logarithmic scale are
as presented above. In the work [45] authors excited LaPO4:Ce,Tb depicted in Fig. 10.
nanopowder by synchrotron radiation with energy of 3.7–40 eV. One can note that the decay curve in Fig. 10a almost obeys a
They revealed that the PL of Tb3 þ ions in nanosized LaPO4:Ce,Tb mono-exponential law with a long lifetime of 6.35 ms. It is well-
can be excited by excitonic transitions (including self-trapped and/ known that Tb3 þ f–f transitions are spin and parity forbidden and
or bound excitons) in the range of 6.5–8.5 eV. therefore the observed Tb3 þ luminescence decay is very long (in the
394 D. Thi Lien et al. / Journal of Luminescence 161 (2015) 389–394

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