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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
0022-0248/$ - see front matter & 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.jcrysgro.2009.09.027
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4754 M. Yang et al. / Journal of Crystal Growth 311 (2009) 47534758
2.1. Characterization
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.
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M. Yang et al. / Journal of Crystal Growth 311 (2009) 47534758 4755
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 In the emission spectra, the 5D07FJ (J: 1, 2, 3, 4) transitions can
the band number in the FT-IR spectra of monoclinic LaPO4. be observed, the corresponding peaks are located at 585, 591
Fig. 6 displays the excitation and emission spectra of the (5D07F1), 612, 619 (5D07F2), 650 (5D07F3), and 683, 694 nm
products obtained at 120 and 180 1C. In the excitation spectra, the (5D07F4). Among the emission lines of the Eu3 + ions, the
broad bands ranging from 200 to 300 nm with a maximum at magnetic-dipole transition 5D07F1 (591 nm) is the most promi-
260 nm are associated with the charge transfer (CT) transition nent group, which is characterized by orange-red emission.
from the 2p orbital of the O2 ions to the 4f orbital of the Eu3 + Emission from the higher energy levels (5D1, 5D2) of the Eu3 +
ions, while the other peaks in the longer wavelength region ions is not detected due to multiphoton relaxation based on the
located at 322, 363, 385, 396, and 468 nm are assigned to the vibration of phosphate groups (ca. 1067 cm 1), which can bridge
direct excitation of the ff shell transitions of the Eu3 + ions. the gaps between the higher energy levels (5D1, 5D2) and the
Comparing the two excitation spectra, it can be found that the lowest 5D0 level of the Eu3 + ions effectively. The intensity of the
location of the CT in the excitation spectra shows a red shift about transitions between different J-number levels depends on
4 nm with the enhancement of temperature. As reported by the symmetry of the local environment of the Eu3 + ions and can
previous studies [2022], the peak position of the CT band in be described in terms of the JuddOfelt theory [2325].
different host lattices is related to both the length of EuO bond Comparing the two emission spectra, it can be found that the
and the coordination environment about the Eu3 + ions. It is xed intensity of the strongest peak belonging to the 5D07F1 is
in a particular crystal eld, but it varies as a function of the host different in the two cases, the strongest peak locates at 589 nm
lattice. The variation is proportional to the EuO bond distance: in the emission spectrum obtained at 120 1C, but it changes to
the longer the EuO bond is, the longer the wavelength of the CT 593 nm when the temperature is enhanced to 180 1C. A similar
band position will be. In the hexagonal LaPO4:Eu3 + , the Ln3 + is difference can be observed for the components of 5D07F2
eight-coordination, and the average EuO bond distance is transition, the location of the strongest peaks changes from 610
0.2497 nm, while in the monoclinic LaPO4:Eu3 + , the Ln3 + to 619 nm as the temperature changes from 120 to 180 1C. These
is nine-coordination and the average LaO bond distance is results should be due to the different lattice structures of the two
0.2611 nm, according to the calculation of the phase structure of phases of LaPO4:Eu3 + nanorods, which depends on the orientation
the two phase of LaPO4. This indicates that the average EuO bond of the unique crystal axis relative to the polarization vector of the
distance is longer in monoclinic LaPO4:Eu3 + than that in incident light [26].
hexagonal LaPO4:Eu3 + , and as a consequence, a small red shift Fig. 7 shows the decay curves of the Eu3 + ions in LaPO4:Eu3 +
of the CT band could be observed. nanorods obtained at different reaction conditions. The decay
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M. Yang et al. / Journal of Crystal Growth 311 (2009) 47534758 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
Fig. 5. Excitation (a) and emission (b) spectra of the products obtained at 120 and
180 1C.
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
Acknowledgments [14] L. Li, W.G. Jiang, H.H. Pan, X.R. Xu, Y.X. Tang, J.Z. Ming, Z.D. Xu, R.K. Tang, J.
Phys. Chem. C 111 (2007) 4111.
[15] Y.P. Fang, A.W. Xu, A.M. Qin, Cryst. Growth Des. 5 (2005) 1221.
This project is nancially supported by the National Basic Research [16] Y.P. Fang, A.W. Xu, R.Q. Song, J. Am. Chem. Soc. 125 (2003) 16025.
Program of China (973 Program, Grant no. 2007CB935502) and the [17] L. Li, Wenge Jiang, H.H. Pan, X.R. Xu, Y.X. Tang, J.Z. Ming, Z.D. Xu, R.K. Tang,
National Natural Science Foundation of China (Grant no. 20771098). Phys. Chem. C 111 (2007) 4111.
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London, 1974.
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