ARTICLE IN PRESS

Journal of Crystal Growth 311 (2009) 47534758

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Journal of Crystal Growth

journal homepage: www.elsevier.com/locate/jcrysgro

Selective synthesis of hexagonal and monoclinic LaPO4:Eu3 + nanorods by a

hydrothermal method
Mei Yang a,b, Hongpeng You a,b,, Guang Jia a,b, Yeju Huang a,b, Yanhua Song a,b, Yuhua Zheng a,b,
Kai Liu a,b, Lihui Zhang a,b
a
State Key Laboratory of Rare Earth Resource Utilization, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, PR China
b
Graduate University of the Chinese Academy of Sciences, Beijing 100049, PR China

a r t i c l e in fo abstract

Article history: The hexagonal and monoclinic LaPO4:Eu3 + nanorods can be selectively synthesized through a simple
Received 1 April 2009 hydrothermal method by only adjusting the reaction temperature. Hexagonal and monoclinic
Received in revised form LaPO4:Eu3 + nanorods can be prepared at 120 and 180 1C, respectively. The phase conversion of
31 August 2009
LaPO4:Eu3 + under different temperatures is investigated in detail. Moreover, the inuence of the
Accepted 19 September 2009
temperature on the intensity and the shift of the peaks of the excitation and emission spectra is
Communicated by H. Fujioka
Available online 26 September 2009 discussed, and the decay lifetime of the Eu3 + ions of the sample obtained at different temperature also
have been investigated in this paper.
Keywords: & 2009 Elsevier B.V. All rights reserved.
A1. Nanostructures
A2. Hydrothermal crystal growth
B1. Nanomaterials
B1. Phosphates

1. Introduction successful evolution of the crystal structure needs the changes

In the past decades, there have been an increase in interest and
research on one- dimensional nanosized lanthanide compounds
and lanthanide-ion-doped materials resulting from the special 4f
shell of their ions, which make them nd potential applications in
light phosphor powder, advanced at panel display, eld emission
display devices, biological and chemical labels and so on [19].
For instance, lanthanum orthophosphate (LaPO4) as an ideal host
in uorescent lamps, cathode ray tubes, and plasma display
panels has been intensively investigated, and they have formed a
class of chemically stable materials [1014]. As we know, LaPO4
has several polymorphic forms including hexagonal, tetragonal
and monoclinic modications. Generally, the phase evolution of
LaPO4 could be achieved by changing two or more reaction
factors. For instance, Fang and her co-partners once reported the
preparation of hexagonal LnPO4
1.5H2O (Ln=La-Tb) by hydro-
thermal method, which can be converted into monoclinic
monazite-structured product after being calcined at 900 1C in air
[15]. Fang et al. also issued another report on the selective
synthesis of hexagonal and tetragonal DyPO4 nanorods. The
 Corresponding author at: Chinese Academy of Sciences, Changchun Institute of
Applied Chemistry, State Key Laboratory of Rare Earth Resource Utilization,
Renmin Street 5625, Changchun 130022, PR China. Tel.: +8643185692798;
fax: + 8643185698041.
E-mail address: hpyou@ciac.jl.cn (H. You).
of both temperature and pH of the reaction system at the same
time [16].
In this paper, the conversion of the crystal structure of LaPO4
nanorods was obtained by only changing reaction temperature.
The pure hexagonal and monoclinic LaPO4 can be prepared at 120
and 180 1C with a simple hydrothermal method, respectively. Our
study may open a novel and facile route for the design and
synthesis of different phase structures of lanthanide phosphate
compounds.
2. Experimental procedures
Disodium Ethylenediamine Tetraacetate [EDTA-2Na or Na2H2L,
where L4 = (CH2COO)2N(CH2)2N(CH2COO)42 ], Cetaltrimethylam-
monium Bromide (CTAB), and Na3PO4
12H2O were purchased
from Beijing Chemical Corporation, all of them are analytical
grade and were used as received without further purication.
La0.95Eu0.05Cl3
6H2O was obtained by dissolving La2O3 (99.99%)
and Eu2O3 (99.99%) (Wuxi Yiteng Rare Earth Limited Corporation,
China) in concentrated HCl solution under heating with agitation,
and subsequently evaporated until desired product is obtained.
In a typical synthesis, 0.78 g La0.95Eu 0.05Cl3
6H2O and 0.81 g
Na2H2L were dissolved in 20 ml distilled water to form a
transparent solution. 1.1 g CTAB and 1.1 g Na3PO4
12H2O dissolved
in 20 ml ethanolwater solution were added into the transparent

0022-0248/$ - see front matter & 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.jcrysgro.2009.09.027
 ARTICLE IN PRESS
4754 M. Yang et al. / Journal of Crystal Growth 311 (2009) 47534758

solution with a magnetic stirring. The pH value of the solution was

subsequently adjusted to 0.51 using concentrated HCl. The
resultant solution was transferred into a Teon-lined autoclave
(volume, 50 ml) and maintained at 90210 1C for 10 h. The
resulting precipitate was washed three times with distilled water
and ethanol, and dried at 60 1C for 12 h in air.

2.1. Characterization

XRD patterns were measured by a Rigaku-D X-ray powder

diffractometer with Cu Ka radiation (l =1.5418 A). The morphol-
ogy of the samples was inspected using a eld emission scanning
electron microscope (FESEM) (HITACHI S-4800). Transmission
electron microscope (TEM) images and electron diffraction
patterns were taken using a JEOL JEM 2010 at an accelerating
voltage of 200 kV. Fourier transform infrared spectroscopy (FT-IR)
Fig. 1. XRD patterns of the products maintained at 90210 1C for 10 h.
spectra were obtained with a PerkinElmer Spectrum One FT-IR

Fig. 2. TEM images and SAED patterns of the products obtained at different temperature for 10 h: (a) 90 (b) 120, (c) 150, (d) 180, and (e) 210 1C.
 ARTICLE IN PRESS
M. Yang et al. / Journal of Crystal Growth 311 (2009) 47534758 4755

Spectrometer by the KBr pellet technique. The excitation and

emission spectra were recorded on a HITACHI F-4500 uorescence
spectrophotometer equipped with a 150 W xenon lamp as the
excitation source. The luminescence decay curves were carried
out with a Lecroy Wave Runner 6100 digital oscilloscope (1 GHz)
using a tunable laser (pulse width = 4 ns, gate= 50 ns) as the
excitation source (Continuum Sunlite OPO). All the measurements
were performed at room temperature.

3. Results and discussion

Fig. 1 shows the XRD patterns of the products obtained at

90210 1C for 10 h. It can be found that the temperature has an
important effect on the change of the crystalline structure. When
the reaction temperature is 90 1C, the main phase of the product is
hexagonal LaPO4
0.5H2O (JCPDS 46-1439), but there are other
peaks observed in the XRD pattern which may be due to the
impurity. Compared with the JCPDS standard card, they can be
speculated as the peaks of the NaLa(PO3)4. As the reaction
temperature increases to 120 1C, the peak positions agree well
with those in JCPDS 75-1881 and there are no additional peaks of
other phases have been found, these results indicate that the
product is pure hexagonal LaPO4. When the reaction temperature
is controlled at 150 1C, the intensity of the diffraction peaks of
hexagonal LaPO4 decreases and the peaks of the monoclinic LaPO4
appear. As the reaction temperature increases continually to
180 1C, all the diffraction peaks of the sample can be readily
indexed to that of JCPDS 32-0493, no any other peak can be
detected from the XRD pattern. This result testies the formation
of pure monoclinic phase of LaPO4. When reaction temperature is
enhanced to 210 1C, the intensity of the diffraction peaks of the
sample becomes stronger, and no any other peak appear, revealing
that the monoclinic LaPO4 phase remains unchanged. All these
results demonstrate that the phase of LaPO4 can be controlled
easily by changing the reaction temperature. The phase
conversion of LaPO4 can be interpreted in terms of the theory of
thermodynamics. The low-temperature hexagonal phase can
transform into stable monoclinic structure with enhancement of
Fig. 3. (a) FT-IR spectra of the products prepared at 120 and 180 1C for 10 h, (b) the
the reaction temperature because of the difference in free energy enlarged part of the FT-IR spectra of the products prepared at 180 1C with the range
and inter-energy between the hexagonal and monoclinic phases. from 400 to 1500 cm 1.
Fig. 2 shows typical TEM images of the products corresponding
to Fig. 1. It can be seen that the shape of the products is rod-like.
Both the lengths and the diameters of the rods change with the Figs. 3a gives the FT-IR spectra of hexagonal and monoclinic
enhancement of the temperatures. The rods are uniform in size LaPO4 obtained at 120 and 180 1C for 10 h, respectively. The bands
when the temperature is below 120 1C, and the diameter and the centered at 1630 and 3455 cm 1 can be due to the hydration
length increase with temperature ascends (Fig. 2a and b). When water (OH bond) of the hydrogen phase in the as-prepared
the temperature is enhanced to 150 1C, the length of the rods powders. The other bands present on the FT-IR spectra of the as-
become short and their sizes are not uniform (Fig. 2c). This change prepared powder are assigned to the phosphate groups. For the
may be attributed to the phase transition of the product. When product obtained at 120 1C, the band centered at 1052 cm 1 is a
the temperature is enhanced continually to 180 1C, the length of characteristic of the asymmetry stretch vibration of the PO34
the rods becomes long again, but their sizes are not uniform, groups, while the bands located at 616 and 542 cm 1 are
compared with the product obtained at 120 1C. As the temperature attributed to the bend vibration of OPO [17]. For the product
increases, the length and diameter of the rods also increase maintained at 180 1C (Fig. 3b), ve characteristic bands located at
(Fig. 2d and e). The selected area electronic diffraction (SAED) 1093, 1060, 1024, 993, and 954 cm 1 are due to the bend of the
patterns of the products obtained at 120, 150, and 180 1C are taken PO of PO34 + groups in the monoclinic LaPO4 (Fig. 4). The bands
from a single nanorod. It can be found that SAED patterns of the located at 541, 564, 579, and 617 cm 1 are attributed to the
products obtained at 120 and 180 1C consist of a set of diffraction asymmetry stretch vibration of the OPO of the PO34 + groups.
spots, which is consistent with the single-crystalline nature. These bands were characteristic of the vibrations of the phosphate
However, the SAED pattern of the product obtained at 150 1C groups in the monoclinic LaPO4 [18,19]. In the two FT-IR spectra, it
consists of two sets of diffraction spots. This result further can also be found that the number of the bands in the FT-IR
conrms that the product obtained at this temperature has two spectrum of monoclinic LaPO4 increases a lot, this should be due
phases. The indexes of the crystal faces are calculated and the to the change of the coordinate number of La from 8-fold
results shown in the images are consistent with the corresponding coordinated La atoms in hexagonal LaPO4 to 9-fold coordinated
XRD patterns given in Fig. 1. La atoms in monoclinic LaPO4 (Fig. 5). The distortion of the
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4756 M. Yang et al. / Journal of Crystal Growth 311 (2009) 47534758
Fig. 4. Simulated crystal structures of the two phases of LaPO4: (a, b) the structure of hexagonal LaPO4, and (c, d) the structure of monoclinic LaPO4.
tetrahedral phosphate groups further induces the increase in
the band number in the FT-IR spectra of monoclinic LaPO4.
Fig. 6 displays the excitation and emission spectra of the
products obtained at 120 and 180 1C. In the excitation spectra, the
broad bands ranging from 200 to 300 nm with a maximum at
260 nm are associated with the charge transfer (CT) transition
from the 2p orbital of the O2 ions to the 4f orbital of the Eu3 +
ions, while the other peaks in the longer wavelength region
located at 322, 363, 385, 396, and 468 nm are assigned to the
direct excitation of the ff shell transitions of the Eu3 + ions.
Comparing the two excitation spectra, it can be found that the
location of the CT in the excitation spectra shows a red shift about
4 nm with the enhancement of temperature. As reported by
previous studies [2022], the peak position of the CT band in
different host lattices is related to both the length of EuO bond
and the coordination environment about the Eu3 + ions. It is xed
in a particular crystal eld, but it varies as a function of the host
lattice. The variation is proportional to the EuO bond distance:
the longer the EuO bond is, the longer the wavelength of the CT
band position will be. In the hexagonal LaPO4:Eu3 + , the Ln3 + is
eight-coordination, and the average EuO bond distance is
0.2497 nm, while in the monoclinic LaPO4:Eu3 + , the Ln3 +
is nine-coordination and the average LaO bond distance is
0.2611 nm, according to the calculation of the phase structure of
the two phase of LaPO4. This indicates that the average EuO bond
distance is longer in monoclinic LaPO4:Eu3 + than that in
hexagonal LaPO4:Eu3 + , and as a consequence, a small red shift
of the CT band could be observed.
In the emission spectra, the 5D07FJ (J: 1, 2, 3, 4) transitions can
be observed, the corresponding peaks are located at 585, 591
(5D07F1), 612, 619 (5D07F2), 650 (5D07F3), and 683, 694 nm
(5D07F4). Among the emission lines of the Eu3 + ions, the
magnetic-dipole transition 5D07F1 (591 nm) is the most promi-
nent group, which is characterized by orange-red emission.
Emission from the higher energy levels (5D1, 5D2) of the Eu3 +
ions is not detected due to multiphoton relaxation based on the
vibration of phosphate groups (ca. 1067 cm 1), which can bridge
the gaps between the higher energy levels (5D1, 5D2) and the
lowest 5D0 level of the Eu3 + ions effectively. The intensity of the
transitions between different J-number levels depends on
the symmetry of the local environment of the Eu3 + ions and can
be described in terms of the JuddOfelt theory [2325].
Comparing the two emission spectra, it can be found that the
intensity of the strongest peak belonging to the 5D07F1 is
different in the two cases, the strongest peak locates at 589 nm
in the emission spectrum obtained at 120 1C, but it changes to
593 nm when the temperature is enhanced to 180 1C. A similar
difference can be observed for the components of 5D07F2
transition, the location of the strongest peaks changes from 610
to 619 nm as the temperature changes from 120 to 180 1C. These
results should be due to the different lattice structures of the two
phases of LaPO4:Eu3 + nanorods, which depends on the orientation
of the unique crystal axis relative to the polarization vector of the
incident light [26].
Fig. 7 shows the decay curves of the Eu3 + ions in LaPO4:Eu3 +
nanorods obtained at different reaction conditions. The decay
 ARTICLE IN PRESS
M. Yang et al. / Journal of Crystal Growth 311 (2009) 47534758
Fig. 5. Excitation (a) and emission (b) spectra of the products obtained at 120 and
180 1C.
Fig. 6. Decay curves for the 5D07F1 (591 nm) emission of the Eu3 + ions in
LaPO4:Eu3 + nanorods obtained at different temperatures for 10 h (l = 591 nm
(5D07F1), round circles: experimental data, solid line: tting results by I(t) = A
exp t/t).
curves of the Eu3 + ions can be well tted into single-exponential
function as I =I0 exp ( t/t) (where t is the 1/e lifetime of the
Eu3 + ions). The lifetime of the Eu3 + ions is determined to be 2.002,
4757
4.603, and 5.613 ms for the product prepared at 120, 150, and
180 1C, respectively. The lifetime increases gradually with the
enhancement of the temperature, this tendency should be due to
the gradual changes of the phase structure of the products and the
perfection of the crystal structure.
On the basis of the above experiments and analysis, the
samples may grow according to a nucleation and growth theory of
nanocrystals. At the beginning of the reaction, LaPO4:Eu3 + nuclei
were produced in the solution, which grew into nanorods in the
subsequent growth progress under the coexistence of CTAB and
EDTA. The possible process of growth is shown in Fig. 7.
The formation of nanorods may be determined by the inner 1D
innite linear chains of hexagonal structure of LaPO4 and external
powers. Fig. 8 shows the packing structure of hexagonal LaPO4
viewing along the a-axis, it can be described as innite linear
chains, parallel to the c-axis. Meanwhile, the activation energy of
the growth at the c-axis direction is lower than that of the growth
at the perpendicular to the c-axis direction from a thermodynamic
perspective [27]. This implies a higher growth rate along the
c-axis and a lower one perpendicular to the c-axis. It is the
structural feature that plays an important role in the highly
preferential growth along c-axis to form one-dimensional
nanorods.
The behavior of CTAB was considered to correlate with the
charge and stereochemical properties. As is well known, CTAB is
an ionic compound, which ionizes completely in water. The
resulted cation is a tetrahedron structure with a long hydrophobic
tail, while PO34 also has a tetrahedron geometry. Therefore, ion-
pairs between CTA + and PO34 could form due to electrostatic
interaction, which endows CTAB with the capability to control the
crystallization process by the charge and stereochemical com-
plementarities, and a process called molecule recognition could
be realized at the inorganic/organic interface. The added CTAB
was supposed to bind to certain faces of the crystals. Therefore,
the ions in the solution could be incorporated into the existing
nuclei at a steady rate and the nal shape and size could be well
controlled [2830]. Further, the anisotropy of CTAB itself probably
induced the axis orientation growth.
In addition, the addition of Na2H2L in the solution also plays an
important role in the formation of the product, which can provide
chelating ability and selectively bind to specic crystallographic
facets. In the beginning of the reaction, L4 reacted with Ln3 + ions
to form (LnL) complexes and decreased the free Ln3 + ion
concentrations in the solution and resulted in the slow generation
of nuclei. Reaction velocity can be adjusted through slow release
of the complex, which can regulate the kinetics of nucleation and
growth of the nuclei and further inuence the morphology and
structure of the nal product. After the addition of the phosphorus
source, an ion-exchange reaction between PO34 and L4 took
place leading to the formation of LaPO4:Eu3 + nanorods under
hydrothermal condition.
4. Conclusion
In summary, two pure phases of LaPO4:Eu3 + nanorods are
successfully synthesized through a hydrothermal method by only
changing the reaction temperature. The results indicate that the
phase conversion of the products has a close relationship with the
reaction temperature. The changes of the peaks of the lumines-
cent spectra as well as the decay lifetime of the samples also can
be affected by the temperature. Besides, a possible growth process
of the samples was suggested following the experimental results
and analysis. This paper provides a new example for the
preparation of the different phase structures of lanthanide
orthophosphate compounds.
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4758 M. Yang et al. / Journal of Crystal Growth 311 (2009) 47534758
Hydrothermal
Treatment Metalstable
Transparent
Supersaturated
Solution
Solution
Fig. 7. The possible process of the growth of LaPO4:Eu3 + nanorods.
Fig. 8. Packing view of LaPO4 along the a-axis.
Acknowledgments
This project is nancially supported by the National Basic Research
Program of China (973 Program, Grant no. 2007CB935502) and the
National Natural Science Foundation of China (Grant no. 20771098).
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