10522 Inorg. Chem.

2010, 49, 10522–10535

DOI: 10.1021/ic101541q

Eu3þ/Tb3þ-Doped La2O2CO3/La2O3 Nano/Microcrystals with Multiform

Morphologies: Facile Synthesis, Growth Mechanism, and Luminescence
Properties
Guogang Li, Chong Peng, Cuimiao Zhang, Zhenhe Xu, Mengmeng Shang, Dongmei Yang, Xiaojiao Kang,
Wenxin Wang, Chunxia Li, Ziyong Cheng, and Jun Lin*

State Key Laboratory of Rare Earth Resources Utilization, Changchun Institute of Applied Chemistry,
Chinese Academy of Sciences, Changchun 130022, People’s Republic of China, and
Graduate University of the Chinese Academy of Sciences, Beijing 100049, People’s Republic of China
Received July 31, 2010

LaCO3OH nano/microcrystals with a variety of morphologies/sizes including nanoflakes, microflowers, nano/microrhombuses,

two-double microhexagrams sandwichlike microspindles, and peach-nucleus-shaped microcrystals have been synthesized
via a facile homogeneous precipitation route under mild conditions. A series of controlled experiments indicate that the pH
values in the initial reaction systems, carbon sources, and simple ions (NH4þ and Naþ) were responsible for the shape
determination of the LaCO3OH products. A possible formation mechanism for these products with diverse architectures has
been presented. After annealing at suitable temperatures, LaCO3OH was easily converted to La2O2CO3 and La2O3 with the
initial morphologies. A systematic study on the photoluminescence and cathodoluminescence properties of Eu3þ- or Tb3þ-
doped La2O2CO3/La2O3 samples has been performed in detail. The excitation and site-selective emission spectra were
recorded to investigate the microstructure, site symmetry, and difference in the 5D0 f 7F2 transition of Eu3þ ions in La2O2CO3
and La2O3 host lattices. In addition, the dependence of the luminescent intensity on the morphology for the as-prepared
La2O2CO3/La2O3:Ln3þ (Ln = Eu, Tb) samples has been investigated. The ability of generating diverse morphologies and
multiemitting colors for different rare-earth activator ion (Ln = Eu, Tb) doped La2O2CO3/La2O3 nano/microstructures provides
a great opportunity for the systematic evaluation of morphology-dependent luminescence properties, as well as the full
exploration of their application in many types of color display fields.

1. Introduction and optoelectronic devices, etc.5 To date, many efforts have

Recently, the synthesis of inorganic nano/microstructures been made to explore excellent approaches to the fabrication
with novel and controllable morphologies has stimulated of shape-controllable inorganic crystals to enhance their per-
considerable attention in the whole chemical and material formance in currently existing applications. Among them, the
science world, because it is well-known that the chemical and wet chemical route has been proved to be one of the most
physical properties of the materials closely interrelate with effective and convenient approaches in preparing various
geometrical factors such as morphology, size, dimensionality inorganic materials with diversely controllable morphologies
as well as composition, crystal type, and phase. Accordingly, and architectures in terms of cost and potential for large-scale
rational control over these factors allows us not only to production.6 Generally, it can be classified as two kinds: the
observe unique properties of the materials but also to tune first one is the template method, which employs either hard
their chemical and physical properties as desired, which has templates such as polymeric core supports and sacrificial
potential application in many fields, including catalysis,1 metal substrates or soft templates such as micelles in emul-
optics,2 biological labeling,3 magnetism,4 nanoelectronics sions or ionic liquids.7 The other one is the template-free

*To whom correspondence should be addressed. E-mail: [email protected]. (5) (a) Im, S. H.; Lee, Y. T.; Wiely, B.; Xia, Y. N. Angew. Chem., Int. Ed.
(1) Sun, C. W.; Sun, J.; Xiao, G. L.; Zhang, H. R.; Qiu, X. P.; Li, H.; 2005, 44, 2154. (b) Cheng, F. C.; Zhao, J. Z.; Li, C. S.; Ma, H.; Chen, J.; Shen,
Chen, L. Q. J. Phys. Chem. B 2006, 110, 13445. P. W. Inorg. Chem. 2006, 45, 2038.
(2) (a) Mai, H. X.; Zhang, Y. W.; Si, R.; Yan, Z. G.; Sun, L. D.; You, (6) Lin, J.; Yu, M.; Lin, C. K.; Liu, X. M. J. Phys. Chem. C 2007, 111,
L. P.; Yan, C. H. J. Am. Chem. Soc. 2006, 128, 6426. (b) Wang, X.; Zhuang, J.; 5835.
Peng, Q.; Li, Y. D. Inorg. Chem. 2006, 45, 6661. (7) (a) Han, W.; Fan, S.; Li, Q.; Hu, Y. Science 1997, 277, 1287. (b) Yada,
(3) Yi, G. S.; Lu, H. C.; Zhao, S. Y.; Ge, Y.; Yang, W. J.; Chen, D. P.; M.; Mihara, M.; Mouri, S.; Kuroki, M.; Kijima, T. Adv. Mater. 2002, 14, 309. (c)
Guo, L. H. Nano Lett. 2002, 2, 733. Sun, X. M.; Li, Y. D. Angew. Chem., Int. Ed. 2004, 43, 3827. (d) Jacob, D. S.;
(4) Lu, H. C.; Yi, G. S.; Zhao, S. Y.; Chen, D. P.; Guo, L. H.; Cheng, J. Bitton, L.; Grinblat, J.; Felner, I.; Koltypin, Y.; Gedanken, A. Chem. Mater. 2006,
J. Mater. Chem. 2004, 14, 1336. 18, 3162.

pubs.acs.org/IC Published on Web 10/20/2010 r 2010 American Chemical Society

Article Inorganic Chemistry, Vol. 49, No. 22, 2010 10523
method, which is facile and efficient compared with the because RE doping levels can be controlled over a wide range
template method.8 The addition of a template to the reaction without changing host crystal structures. RE ions can be
system involves a complicated process and may brighten in homogeneously substituted for La3þ ions, which results in
impurities because of the incomplete removal of the template. good luminescent properties. As such, La2O3:Eu3þ have been
Therefore, the latter method seems to be more attractive and investigated as red phosphors.15 Besides lanthanum oxides,
promising because of its higher yield and simplicity. lanthanum oxycarbonates with hexagonal type II structure
Field-emission displays (FEDs) are considered to be the are also suitable for the host materials of phosphors16,17
most promising next-generation flat-panel display technique because they have a high chemical stability against both water
because of their potential to provide display with a thin panel, and carbon dioxide, and the structure of type II oxycarbo-
self-emission, wide viewing, quick response time, high bright- nates is similar to conventional A-type lanthanum sesquiox-
ness, high contrast ratio, light weight, and low-power con- ides. However, it is difficult to obtain type II oxycarbonates in
sumption.9 In order to realize the full-color FEDs, one of the a single phase using conventional methods because tetragonal
most important factors is to develop highly efficient trichro- type I or monoclinic type Ia oxycarbonates are formed via the
matic low-voltage phosphors. Rare-earth (RE) ion-doped thermal decomposition of acetates, carbonates, and oxalates,
luminescent materials display interesting optical character- or it is necessary to heat the oxide at 773 K at least for 1 week
istics and abundant emission colors, which are poised to under a humid CO2 atmosphere to obtain type II oxycarbo-
be exploited in the development of displays and phosphor nates.17 Therefore, exploring facile and efficient methods to
applications. This is largely because of their unique intra prepare RE ion-doped lanthanum oxides and oxycarbonates
4f transitions, which are less influenced by the ligand field is helpful for their applications in displays and phosphors.
(because of shielding of the 4f orbitals by the outer 5s and 5p On the other hand, among compounds of the RE family,
orbitals), leading to sharp emissions.10 For example, the lanthanum compounds with various morphologies have been
trivalent europium (Eu3þ) ion is well-known as a red-emitting synthesized, such as nanorods, macropores, nanowires, and
activator because of its 5D0 f 7FJ (J = 0, 1, 2, 3, 4) transitions nanoplates of La2O3,18 nanospheres, nanowires, and nano-
and the trivalent terbium (Tb3þ) ion is commonly employed rods of La(OH)3,18a,19 needlelike and spherical La2(CO3)3,20
as a green activator because of the efficient emission originat- nanowires of LaPO4,21 triangular nanoplates and flakes of
ing from the 5D4 f 7FJ (J = 6, 5, 4, 3) transitions.11 Except LaF3,22 etc., but rare-earth hydroxycarbonates with novel
for activators, suitable host materials for RE ion doping are morphologies have rarely been investigated especially for
also important for the preparation of highly efficient phos- lanthanum hydroxycarbonates.23
phors. Among various RE3þ-activated luminescent materi- Herein, we employed a facile and efficient homogeneous
als, yttrium-based lattices, such as Y2O3,12 YBO3,13 YVO4,14 precipitation method to successfully prepare lanthanum
among others, are usually used as hosts because of their suit- hydroxycarbonates (LaCO3OH) at mild conditions. More-
able crystal structure and high chemical stability. In com- over, by simple changes of the carbon sources [CO(NH2)2,
parison with Y, La is more abundant in RE mineral resources Na2CO3, NaHCO3, (NH4)2CO3, and NH4HCO3] and pH
and La2O3 is much cheaper than Y2O3. However, the devel- values of the initial solution, multiform LaCO3OH products
opment of La-based materials is still inadequate, and La2O3 such as flakes, flowers, rhombuses, two-double hexagrams,
is overstocked in the RE industry. It is valuable to funda- sandwichlike spindles, peach-nucleus-shaped crystals, and
mentally and practically study the La-based materials for the so on were obtained. The effects of the solution pH and car-
balanced utilization of the RE natural resources. Further- bon sources on the crystal phase, size, and morphology of the
more, inorganic compounds containing lanthanum are LaCO3OH products were studied in detail, and a formation
recognized as excellent host materials for RE activators
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10524 Inorganic Chemistry, Vol. 49, No. 22, 2010 Li et al.
mechanism was proposed. After annealing of the as-prepared
LaCO3OH products at different temperatures (600 and
800 °C, respectively) for only several hours, the La2O2CO3
and La2O3 products were obtained with maintained morpho-
logies. More importantly, we concentrated on the photolu-
minescence (PL) and cathodoluminescence (CL) properties
of La2O2CO3/La2O3:Eu3þ or Tb3þ phosphors in an effort to
adjust the emission colors of the final products. The excitation
and site-selective emission spectroscopy were applied to
investigate the microstructure, site symmetry, and difference
in the 5D0 f 7F2 transition of Eu3þ ions in La2O2CO3 and
La2O3 host lattices. In addition, we also investigated the effect
of the morphologies of La2O2CO3/La2O3:Eu3þ or Tb3þ
phosphors on their luminescence properties.
Figure 1. XRD patterns of the as-prepared LaCO3OH products using
2. Experimental Section CO(NH3)2 as the carbon source at different pH values of (a) 2, (b) 7, and
(c) 10 at 90 °C for 2 h. The standard data of orthorhombic LaCO3OH
Chemicals and Materials. The initial rare-earth oxides, (JCPDS no. 49-0981) were used as references.
including La2O3 (99.999%), Eu 2O3 (99.999%), and Tb4O7
(99.999%), were purchased from Science and Technology Par- transform infrared spectroscopy (FT-IR) spectra were performed
ent Company of Changchun Institute of Applied Chemistry, on a Perkin-Elmer 580B IR spectrophotometer using the KBr
and other chemicals including HNO3 (65-68 wt %), NH3 3 H2O pellet technique. Thermogravimetric and differential thermal
(25 wt %), CO(NH2)2, Na2CO3, NaHCO3, (NH4)2CO3, and analysis (TG-DTA) data were recorded with a thermal analysis
NH4HCO3 (analytical grade) were purchased from Beijing instrument (SDT 2960, TA Instruments, New Castle, DE) with a
Chemical Company. All chemicals were of analytical-grade heating rate of 10 °C min-1 in an air flow of 100 mL min-1. The
reagents and were used directly without further purification. morphology and composition of the samples were inspected using
Preparation of LaCO3OH. A lanthanum nitrate stock solu- a field-emission scanning electron microscope (S-4800, Hitachi)
tion of 0.5 M was prepared by dissolving the corresponding equipped with an energy-dispersive X-ray (EDX) spectrometer.
metal oxide in nitric acid at elevated temperature. In a typical Low- to high-resolution transmission electron microscopy (TEM)
procedure, 15 mL of La(NO3)3 (0.5 M) was added into a 300 mL and selected area electron diffraction (SAED) patterns were
of aqueous solution. After vigorous stirring for 10 min, 0.25 mol recorded using a FEI Tecnai G2 S-Twin with a field-emission gun
of CO(NH3)2 was added into the above solution and then operating at 200 kV. Images were acquired digitally on a Gatan
distilled water was added to make a total volume of 500 mL. multipole CCD camera. PL excitation and emission spectra were
The pH of the mixture was subsequently adjusted to 2 by adding recorded with a Hitachi F-4500 spectrophotometer equipped with
HNO3 (1 M), and the beaker was wrapped with a polyethylene a 150 W xenon lamp as the excitation source. For the excitation
film. After additional agitation for 30 min, the mixed solution and site-selective emission measurements, the excitation source
was heated on a hot plate with strong stirring to 90 °C within was a dye laser (Spectron Laser Systems SL4000) pumped by the
60 min and then maintained at 90 °C for 2 h. The suspension was second harmonic (532 nm) of a pulsed Nd:yttrium aluminum
naturally cooled to room temperature, and the resulting pre- garnet laser (Spectron Laser Systems SL802G). The laser beam
cipitates were separated by centrifugation, respectively washed was focused on the sample with a cross-sectional area of about
with deionized water and anhydrous ethanol in sequence four 3 mm2. The pulse energy was about 5 mJ with a 10 Hz repetition
times, and then dried at 80 °C in air for 12 h. The as-prepared rate and a 5 ns duration. The sample was placed in a helium-
product was denoted as P1. Other samples (P2-P15) were gas-flow cryostat for measurements in the variable-temperature
prepared by a similar procedure except for different carbon region (10-305 K). The luminescence was dispersed by a 75 cm
sources and pH conditions. The pH of the mixture was adjusted monochromator (Acton Research Corp. Pro-750) and observed
to a specific value by adding NH3 3 H2O (25 wt %) or a HNO3 with a photomultiplier tube (Hamamatsu R928). Suitable filters were
(1 M) solution. The detailed experimental parameters are sum- used to eliminate the intense laser scattering. The excitation spec-
marized in Table 1 in the Supporting Information. It should be tra of the 7F0 f 5D0 transition were obtained by monitoring the
stated that all samples reacted through a homogeneous precipi- total luminescence by setting the monochromator in zero order of
tation process at 90 °C for 2 h. diffraction to pass all of the 5D0 f 7FJ (J = 1, 2, ..., 6) emission in
Preparation of LaCO3OH:Ln3þ and La2O2CO3/La2O3:Ln3þ which a 580 nm cutoff filter was used. Time-integrated signals
(Ln = Eu, Tb). First, La2O3, Eu2O3, and Tb4O7 were dissolved from a digital storage oscilloscope (LeCroy 9310A) were recorded
in dilute HNO3, respectively, resulting in the formation of a for the emission and excitation spectra under pulsed laser excita-
colorless stock solution of La(NO3)3 (0.5 M) and Ln(NO3)3 tion. CL measurements were carried out in an ultrahigh-vacuum
(Ln = Eu, Tb; 0.2 M). In a typical synthesis, stoichiometric chamber (<10-8 Torr), where the phosphors were excited by an
La(NO3)3 and Ln(NO3)3 (solution) were dissolved in deionized electron beam in the voltage range of 0.5-5.0 kV and different
water, resulting in the formation of a colorless solution of filament currents, and the emission spectra were recorded using
La(NO3)3 and Ln(NO3)3 (Ln = Eu, Tb); Ln3þ/(La3þ þ Ln3þ) = an F-4500 spectrophotometer. The PL quantum yield (QY) was
0.1-10 mol %. Then LaCO3OH:Ln3þ products can be obtained measured by an absolute PL QY measurement system C9920-02.
through the same preparation process of the LaCO3OH pro- All of the measurements were performed at room temperature.
ducts as stated above. The final La2O2CO3:Ln3þ and La2O3:
Ln3þ (Ln = Eu, Tb) products were retrieved through a heat 3. Results and Discussion
treatment of the LaCO3OH:Ln3þ products at 600 and 800 °C in
air for 4 h, respectively. 3.1. Structure, Morphology, and Growth Mechanism
Characterization. Power X-ray diffraction (XRD) measure- of LaCO3OH. Structure. The composition and phase purity
ments were performed on a D8 Focus diffractometer at a scanning of the products were first examined by XRD. Figure 1
rate of 10° min-1 in the 2θ range from 10° to 80°, with graphite- shows the XRD patterns of the La2CO3OH products
monochromatized Cu KR radiation (λ = 0.154 05 nm). Fourier prepared by using CO(NH3)2 as the carbon source with a
Article Inorganic Chemistry, Vol. 49, No. 22, 2010 10525

Figure 2. Influence of the pH values on the shapes of the nano/microcrystals with CO(NH3)2 as the carbon source: (A and B) elliptical nanoflakes and
microflowers obtained at pH = 2; (C and D) rhombic microplates obtained at pH = 7; (E and F) sandwichlike microspindles obtained at pH = 10.

homogeneous precipitation process at 90 °C for 2 h under To further validate the formation of LaCO3OH products,
various pH conditions of (a) pH=2, (b) pH=7, and (c) we measured the FT-IR of the as-prepared products by
pH = 10. On the basis of the Joint Committee on Power using the P2 sample as a representative example, as shown
Diffraction Standard (JCPDS) reference database, the in Figure S2 (Supporting Information). The absorptions
diffraction peaks of the three samples can be assigned to between 3300 and 3700 cm-1 with peaks at 3540 and 3433
a pure orthorhombic LaCO3OH phase, which coincides well cm-1 are due to the stretching mode of OH, νOH, which are
with the literature values (JCPDS no.49-0981). No peak shifts assigned to structural OH and adsorbed H2O in the pro-
and other impurity phases appear in this figure, indicating the ducts, respectively.23b The strong peaks at 1418-1484 cm-1
high purity and crystallinity of the products. It is worth are attributed to the ν3 mode of carbonate CO32- species,
pointing out that the XRD patterns of the three samples also while the band at 1518 cm-1 might result from carboxylate
show that there are large differences in the relative intensities groups. The minute bands appearing at 1070-863, 812, and
based on (110), (021), (012), and (121) peaks compared 722-690 cm-1 are assigned to the ν1, ν2, and ν4 modes of
with the standard data, indicating the possibility of different CO32-, respectively. These observed very strong features in
preferential orientation growth under different pH values. the spectrum of the P2 sample substantiate the claim that
Except for the use of CO(NH3)2 as the carbon source, we also the products are composed of La(CO3)OH.23c
investigate the effects of NaHCO3, NH4HCO3, Na2CO3, and Morphology. The morphologies and dimensions of the
(NH4)2CO3 used as carbon sources on the crystal struc- products are summarized in Table 1 (Supporting Infor-
tures and morphologies of the products. The cases of using mation). From Table 1 in the Supporting Information, it
NaHCO3, NH4HCO3, Na2CO3, and (NH4)2CO3 as car- is found that the carbon sources and pH values of
bon sources are similar to that of using CO(NH3)2 as the the initial reaction system are two categories of predomi-
carbon source. The XRD peaks of P4-P11 samples all can nantly influencing factors in the determination of the
be indexed as a pure orthorhombic LaCO3OH phase, shapes and sizes of the as-formed products, which will
indicating that the different carbon sources do not change be discussed in the following paragraphs.
the crystal phases of the products. However, when P4 is A. CO(NH2)2 as the Carbon Source. The scanning
compared with P6, P8, and P10 samples, the differences in electron microscopy (SEM) images provide direct informa-
the relative intensities based on (011), (110), (020), (111), tion about the sizes and typical shapes of the as-synthesized
(021), (012), and (121) peaks indicate different preferential LaCO3OH products grown under different experimental
orientation growth under the different carbon sources, as conditions. Figure 2 shows the representative SEM images
shown in Figure S1 (Supporting Information). In general, of the LaCO3OH products prepared using CO(NH2)2 as
the above results suggest that different products have the carbon source at different pH values. The sample (P1)
different growth habits under diverse reaction conditions. obtained at pH = 2 is composed of a great deal of elliptical
10526 Inorganic Chemistry, Vol. 49, No. 22, 2010 Li et al.

Figure 3. SEM images of LaCO3OH microcrystals obtained under different carbon sources and pH values: (A) NaHCO3, pH = 7; (B) NH4HCO3, pH = 7;
(C) NaHCO3, pH = 10; (D) NH4HCO3, pH = 10. The insets are corresponding magnified micrographs.

nanoflakes and microflowers that consist of conjunctions of the obtained LaCO3OH products have dramatic differ-
of nanoflakes in terms of both edge-to-edge and edge-to- ences relative to the products obtained by using CO(NH2)2.
surface (Figure 2A,B). The lengths and thicknesses of these Figure 3 depicts typical SEM images of the corresponding
ellipselike nanoflakes are 3.5-5.0 μm and 10-30 nm, re- products (P4-P7) using NaHCO3 and NH4HCO3 as the
spectively, and the diameter of the microflowers is about carbon sources and under different pH values. It can be seen
5.0 μm. When the pH value of the initial solution is not clearly that when using NaHCO3 as the carbon source and at
adjusted (pH = 7; P2), the morphology of the product pH=7, double-deck-like microhexagrams with 4.0-5.5 μm
varies greatly. It can be seen clearly from Figure 2C that diameter (the distance between two opposite vertexes) and
there are a large number of perfect rhombic microplates 1.5-2.5 μm thickness are observed. The magnified SEM
with a size of 1.5-2.5 μm in side length and 100-200 nm in images of one isolated hexagram demonstrate the presence
thickness. Interestingly, the top/bottom surfaces exhibit of six scrappy angles and rugate endothecium, as shown
concave centers (Figure 2C, inset). The magnified SEM in the insets of Figure 3A. With an increase of the pH to 10,
image (Figure 2D) clearly shows that the individual rhom- the morphology of LaCO3OH microcrystals is still a two-
bic microplate has a highly smooth surface, equal side double hexagram. However, the higher resolution SEM
lengths, and uniform thickness. In addition, the EDX spec- image of individual hexagrams (Figure 3C, inset) shows
trum of P2 reveals the presence of La, O, and C (H cannot that it is different from that obtained at pH = 7, of which
be detected by this method), which is consistent with the the diameter and thickness shrink to 4.0-5.0 and 1.0-
results of XRD and FT-IR. When the pH value is in- 1.5 μm, respectively. If CO(NH2)2 is replaced by NH4HCO3
creased to 10 with NH3 3 H2O (25 wt %), the morphology and with the pH value of the initial solution at 7, the
of the product (P3) is converted to sandwichlike micro- obtained products present a flowerlike morphology with
spindles with 300-700 nm thickness and 2.0-3.0 μm an approximate diameter of 4.0-7.0 μm. More careful
length, as shown in Figure 2E. From its magnified SEM examination of the magnified SEM image (Figure 3B,
image (Figure 2F), it is found that a single spindle con- inset) shows clearly that these microflowers are composed
sists of two layers and the center thickness of the spindle of a lot of spinous protuberances. Moreover, when the
is greater than the edge thickness, which results in the for- experiment is performed at pH = 10, irregular microhex-
mation of a deeper concave than that of the P2 sample. agrams and microflowers simultaneously are observed,
At the same time, a protuberant part appears in the short- indicating the higher pH values are disadvantageous to
axis direction of these microspindles. In summary, the forming uniform and regular microcrystals when using
morphologies undergo variations from elliptical nanoflakes NH4HCO3 as the carbon source.
to rhombic microplates and then to sandwichlike micro- C. Na2CO3 and (NH4)2CO3 as the Carbon Sources.
spindles with increases of the pH values from 2 to 10 when When Na2CO3 and (NH4)2CO3 are used as the carbon
using CO(NH3)2 as the carbon source. All of the experi- sources and the other experimental conditions remain
mental parameters except for the pH values of the initial unchanged, the morphologies of the as-formed products
solution are identical from the P1 to P3 samples, indicating are also different from those observed products using
that the difference of morphologies of the LaCO3OH CO(NH2)2 as the carbon source, as shown in Figure 4. At
products is caused by variation of the pH values. pH = 7, irregular two-double microrhombic LaCO3OH
B. NaHCO3 and NH4HCO3 as the Carbon Sources. products with an average size of 1.5 μm length and
Upon substitution of CO(NH2)2 for NaHCO3 and 0.75 μm thickness are observed by using Na2CO3 as the
NH4HCO3 as the carbon source while keeping the other carbon source (Figure 4A). If the carbon source is
experimental parameters unchanged, the morphologies (NH4)2CO3 and the pH = 7, the obtained products are
Article Inorganic Chemistry, Vol. 49, No. 22, 2010 10527

Figure 4. SEM images of LaCO3OH microcrystals at pH = 7 with different carbon sources: (A) Na2CO3; (B) (NH4)2CO3.

Figure 5. Typical SEM images of the P2 product obtained at early stages. The corresponding reaction durations were (a) 10, (b) 30, (c) 60, (d) 120 min at 90 °C.

peach-nucleus-shaped microcrystals with 2.5-3.5 μm length ism of the LaCO3OH products with multiform morphol-
and 1.0-1.5 μm center thickness. The magnified SEM image ogies, the representative P2 sample formed at early stages
indicates that the single peach-nucleus-shaped microcrys- was collected for SEM analysis. It was found that, after
tal is composed of a great deal of smaller nanoparticles reaction of the La(NO3)3 and CO(NH2)2 solution at 90 °C
(Figure 4B1), which indicates that these microcrystals may for 10 min, a white precipitate was formed. As seen from
originate from the self-assembly of these nanoparticles. the SEM image shown in Figure 5a, the white precipitate
Moreover, its center thickness is greater than the edge is comprised of amorphous spherical nanoparticles.
thickness (Figure 4B2). However, when using Na2CO3 and Moreover, the EDX spectrum indicates the presence of
(NH4)2CO3 as the carbon sources and the pH is adjusted to La, O, and C elements in the white precipitate. Therefore,
10, the obtained products are all irregular microcrystals, as it is believed that the perfect microrhombuses originated
shown in Figure S3 (Supporting Information). This result from these amorphous nanoparticles, which formed dur-
indicates that the higher pH is also disadvantageous to ing the early growth stage. Interestingly, some hexagonal
forming well-defined microcrystals when using Na2CO3 prisms with an average size of 1.5 μm length and 1.0 μm
and (NH4)2CO3 as the carbon sources. thickness were observed after an aging time of 30 min
Growth Mechanism. In general, the growth of crystals at 90 °C (Figure 5b), which possibly results from the
and the formation of various morphologies are complex inherent crystal structure of orthorhombic LaCO3OH.
processes that are the cooperative result of inherent With the reaction time prolonged to 60 min, the crystal
structures and external experimental conditions such as continued to grow and formed some irregular rhombuses,
pH values in the initial solution, carbon sources, and so as shown in Figure 5c. Finally, the morphology comple-
on. To gain a better understanding of the growth mechan- tely evolved to perfect microrhombuses (Figure 5d) after
10528 Inorganic Chemistry, Vol. 49, No. 22, 2010 Li et al.
determined that the preferential growth orientation of the
rhombic microplates is along [101]. Furthermore, the pre-
ferential growth direction of the LaCO3OH crystal varies
with a change of the external experimental conditions,
which results in the formation of multiform LaCO3OH
products.
In conclusion, the above results indicate that the car-
bon sources and pH values are critical factors responsible
for the final morphologies of the as-prepared LaCO3OH
products; namely, different carbon sources and pH values
induce the crystals to grow along different directions and
form multiform LaCO3OH products. In addition, simple
ions such as NH4þ and Naþ have also different effects on
the morphologies. When P4 was compared with P6, P5
with P7, or P8 with P10, with the exception of the use of
different carbon sources of NaHCO3, NH4HCO3, Na2CO3,
and (NH4)2CO3, these LaCO3OH products with different
morphologies were synthesized under identical reaction
conditions of [La3þ] = 0.5 M and the same pH value,
reaction temperature, and time (90 °C, 2 h), indicating
that the nature of the simple ions (NH4þ and Naþ) also
contributes to the formation of various architectures.
The cations NH4þ and Naþ in the reaction system have a
guiding effect on the changes in the microstructures of the
as-prepared LaCO3OH crystals. Wang and co-workers
had suggested that the cations coming from the different
fluoride sources XF (X = Kþ, Hþ, NH4þ, Naþ, Rbþ, and
Csþ) selectively adsorbed on the different crystal facets of
EuF3 nanoparticles, resulting in the formation of various
shapes.24 Other workers have found that the simple ions
direct the growth of nanoparticles into different shapes,
highlighting the importance of these species.25 It is there-
Figure 6. (a) TEM image of LaCO3OH rhombic microplates with fore reasonable to assume a similar situation for the effects
CO(NH2)2 as the carbon source at pH = 7 and (b) the corresponding of Naþ andNH4þ on the morphologies. At the early stages
HRTEM image and SAED pattern obtained from a head region con-
tained in the whole rectangle. of the reactions, because of strong interactions between
Naþ and NH4þ cations and CO32- or HCO32- anions, these
a reaction time of over 2 h. The whole process may be two cations can be selectively adsorbed on specific facets
simply described by the following reactions: of the initial LaCO3OH crystals and change their surface
energy. However, because of the different ion radii of Naþ
COðNH2 Þ2 þ 2H2 O f CO3 2 - þ 2NH4 þ and NH4þ, the relative growth rates of various crystal
facets are different, leading to the formation of a variety
NH3 3 H2 O f NH4 þ þ OH - of morphologies. Scheme 1 shows the possible formation
mechanism for LaCO3OH nano/microcrystals with dif-
La3þ þ CO3 2 - þ OH - f LaCO3 OH ferent morphologies under different carbon sources and
pH values.
To further study the fine structure and examine the typical 3.2. Phase Identification and Morphology of La2O2-
growth direction of the perfect LaCO3OH microrhombuses, CO3 and La2O3. Thermal decomposition of the homoge-
TEM was performed. Figure 6A is a representative TEM neously precipitated/hydrothermal precursor is a simple
image of an individual rhombic microplate parallel to route toward tailored rare-earth and metal oxides.26,27
the substrate. The very regular cross section can be clearly
observed, indicating that the morphology of the as-prepared (24) (a) Wang, M.; Huang, Q. L.; Hong, J. M.; Chen, X. T.; Xue, Z. L.
products presents a perfect rhombus. As disclosed by the Cryst. Growth Des. 2006, 6, 1972. (b) Wang, M.; Huang, Q. L.; Hong, J. M.;
corresponding high-resolution TEM (HRTEM) image Chen, X. T.; Xue, Z. L. Cryst. Growth Des. 2006, 6, 2169.
(25) (a) Xia, T.; Li, Q.; Liu, X. D.; Meng, J.; Cao, X. Q. J. Phys. Chem. B
(Figure 6B), which was taken with the electron beam per- 2006, 110, 2006. (b) Li, C. X.; Quan, Z. W.; Yang, P. P.; Yang, J.; Lian, H. Z.; Lin,
pendicular to the edge of the microplate, the sample is struc- J. J. Mater. Chem. 2008, 18, 1353.
turally uniform with interplanar distances of about 0.30 nm, (26) (a) Yang, J.; Li, C. X.; Quan, Z. W.; Zhang, C. M.; Yang, P. P.; Li,
Y. Y.; Yu, C. C.; Lin, J. J. Phys. Chem. C 2008, 112, 12777. (b) Xu, A. W.;
which corresponds to the d-spacing value of the (121) Fang, Y. P.; You, L. P.; Liu, H. Q. J. Am. Chem. Soc. 2003, 125, 1494. (c) Wang,
planes. The SAED pattern of the P2 sample (Figure 6d, J. C.; Liu, Q.; Liu, Q. F. J. Mater. Chem. 2005, 15, 4141. (d) Bai, X.; Song, H. W.;
inset) taken from the head region of a single rhombic micro- Yu, L. X.; Yang, L. M.; Liu, Z. X.; Pan, G. H.; Lu, S. Z.; Ren, X. G.; Lei, Y. Q.;
plate reveals its single-crystal structure, and the diffraction Fan, L. B. J. Phys. Chem. B 2005, 109, 15236.
(27) (a) Zhang, J.; Liu, Z. G.; Lin, J.; Fang, J. Cryst. Growth Des. 2005, 5,
spots can be indexed as the (121) and (111) reflections of 1527. (b) Li, G. G.; Peng, C.; Li, C. X.; Yang, P. P.; Hou, Z. Z.; Fan, Y.; Cheng,
the orthorhombic LaCO3OH phase, in accordance with the Z. Y.; Lin, J. Inorg. Chem. 2010, 49, 1449. (c) Wang, X.; Li, Y. D. Chem.;Eur.
XRD result. On the basis of the above results, it can be J. 2003, 9, 5627. (d) Qiu, X. Q.; Li, G. S.; Li, L. P. J. Mater. Res. 2007, 22, 908.
Article Inorganic Chemistry, Vol. 49, No. 22, 2010 10529
Scheme 1. Schematic Illustration for the Possible Formation Process of LaCO3OH Microcrystals with Various Morphologies Using Different Carbon
Sources of (a) CO(NH2)2, (b) NaHCO3, (c) NH4HCO3, (d) Na2CO3, and (e) (NH4)2CO3 and at Different pH Values (2, 7, and 10)

After the synthesis of the lanthanum carbonate hydroxide as shown in Figure S6 in the Supporting Information. No
precursors, we employ P1-P3 samples as examples to second phase appears, indicating that LaCO3OH was com-
investigate the effect of calcination on the crystallization pletely converted to La2O3 at 800 °C for 4 h. In summary,
and morphology of the as-prepared products. Figure S4 the phase transformation processes can be simply depicted
(Supporting Information) shows TG-DTA curves of the as follows:
representative P2 sample. The results for the P1 and P3 873 K
samples are similar to those for the P2 sample and will not 2LaCO3 OH sf La2 O2 CO3 þ CO2 þ H2 O
be shown here. On the basis of TG-DTA data, it can be
seen clearly that thermal decomposition of the LaCO3OH 1073 K
precursors undergoes two phase transformation processes La2 O2 CO3 sf La2 O3 þ CO2
when the temperature is elevated from room temperature to
Figure 7 shows typical SEM, TEM, and HRTEM
800 °C. The first one is the transformation from LaCO3OH
images of La2O2CO3 (M2) and La2O3 (N2) samples. From
to La2O2CO3 with the turning point at 480 °C, and the
Figure 7a-d, it can be seen that the La2O2CO3 and La2O3
second one is the transformation from La2O2CO3 to La2O3
samples inherited their parents’ morphologies, but their
with the turning point at 724 °C. Therefore, in order to
size was slightly shrunk in comparison with the LaCO3OH
obtain the corresponding La2O2CO3 and La2O3 products,
products in that the density of the former is higher than that
we calcined the P1-P3 samples at 600 and 800 °C for 4 h,
of the latter. LaCO3OH was converted to La2O2CO3 and
and the obtained products are denoted as M1-M3 and
La2O3, and their surfaces became rough during subsequent
N1-N3, respectively. Figure S5 in the Supporting Informa-
calcination processes at different temperatures with the
tion shows the XRD patterns of the M1-M3 samples. The
gradual elimination of H2O and CO2. Nevertheless, con-
diffraction peaks of M2 and M3 can be readily indexed to a
version did not lead to changes in the morphologies. Such a
pure hexagonal La2O2CO3 phase [space group P63/mmc
transformation was common for rare-earth hydroxide and
(No. 194)] according to JCPDS no. 37-0804, while that
other metal compound decomposition.26b,d,27a,27b The
of M1 is assigned to a pure monoclinic La2O2CO3 phase
morphologies were maintained perhaps because of the
(JCPDS no. 48-1113). No additional peaks of other phases
higher activation energies needed for the collapse of these
have been found, indicating that the LaCO3OH precursors
structures.28 The same situation holds for other La2O2CO3
were completely converted to La2O2CO3 at 600 °C for 4 h.
and La2O3 samples such as M1, M3, N1, and N3 samples,
When the P1-P3 samples were calcined at 800 °C for 4 h,
the XRD patterns of N1-N3 samples are all indexed to a (28) (a) Yang, J.; Quan, Z. W.; Kong, D. Y.; Liu, X. M.; Lin, J. Cryst.
pure hexagonal La2O3 phase [space group P3m1 (No. Growth Des. 2007, 7, 730. (b) Yang, J.; Lin, C. K.; Wang, Z. L.; Lin, J. Inorg.
164)], which coincides very well with JCPDS no. 05-0602, Chem. 2006, 45, 8973.
10530 Inorganic Chemistry, Vol. 49, No. 22, 2010 Li et al.

Figure 8. PL excitation and emission spectra of (a) La2O2CO3:Eu3þ

(5 mol %; solid line) and La2O3:Eu3þ (5 mol %; dashed line) and
(b) La2O2CO3:Tb3þ (1 mol %; solid line) and La2O3:Tb3þ (1 mol %; dashed
line) with rhombic shape. The insets are their corresponding lumines-
Figure 7. (a) SEM, (c) TEM, and (e) HRTEM images for the La2O2CO3 cence photographs under 254 nm UV light excitation.
sample (M2). (b) SEM, (d) TEM, and (f ) HRTEM images for the La2O3
sample (N2). The insets show their corresponding FT-IR images from
HRTEM images. of various optically activated lanthanide ions.15,16 In
addition, it should be mentioned that the existence of
of which the corresponding SEM images are shown in other lanthanide ions in La2O2CO3 and La2O3 did not
Figure S7 (Supporting Information). In addition, the SEM change the phase, crystallization, and morphology of the
and TEM images of the M2 and N2 samples also indicate products in our present work. Accordingly, we mainly
that these microrhombuses were further composed of fine focused on the luminescence properties of Eu3þ- and
and closely linked nanoparticles with a size range from Tb3þ-doped La2O2CO3 and La2O3 nano/microstruc-
several tens to hundreds of nanometers, which is consistent tures, in an effort to reveal that our current homogeneous
with the above growth mechanism of lanthanum carbo- precipitation method following a heat treatment process
nate hydroxides. The fine structures of the M2 and N2 is a facile and efficient process for the preparation of
samples were studied by the HRTEM technique. Figure 7e carbonate oxide and oxide phosphors with multinovel
is the corresponding HRTEM image for the M2 sample, in morphologies. Herein the La2O2CO3/La2O3: Eu3þ or
which the lattice fringes show the imaging characteristics of Tb3þ samples with rhombic microplate shapes were used
the La2O2CO3 crystal where d spacings of 0.352 and 0.322 as representative examples to investigate their PL and CL
nm correspond to the distances of the (100) and (102) properties. The doping concentrations of Eu3þ and Tb3þ
planes, respectively. The HRTEM images (Figure 7f ) of in La2O2CO3 and La2O3 hosts have been optimized in our
the N2 sample clearly show lattice fringes with interplanar experiments and were 5, 5, 1, and 1 mol % of La3þ, res-
spacings of 0.310 and 0.308 nm, which all correspond to the pectively. Upon 254 nm UV light radiation, these phos-
(002) plane of La2O3. The FT-IR images for the M2 and N2 phors show bright red, red, green, and green luminescence
samples indicate that they are hexagonal La2O2CO3 and to the naked eye, respectively, and the corresponding
La2O3 structures, respectively. These results further con- luminescence digital photographs are shown as the insets.
firm the presence of highly crystalline La2O2CO3 and Figure 8 shows the PL excitation and emission spectra
La2O3 phases after annealing of LaCO3OH at a suitable of La2O2CO3:Eu3þ (5 mol %), La2O3:Eu3þ (5 mol %),
heat treatment, agreeing well with the XRD results. La2O2CO3:Tb3þ (1 mol %), and La2O3:Tb3þ (1 mol %)
3.3. Luminescence Properties. PL Properties of La2- samples. Detailed assignments for the excitation and emis-
O3CO3/La2O3:Eu3þ or Tb3þ. Our experimental results sion peaks and luminescent properties, for example, CIE
and previous reports have shown that La2O2CO3 and chromaticity coordinates, lifetimes, QY, emission colors,
La2O3 are good host materials for the luminescence and so on, are listed in Table 2 (Supporting Information).
Article Inorganic Chemistry, Vol. 49, No. 22, 2010 10531
The excitation spectrum of La2O2CO3:Eu3þ (5 mol %; the emission and excitation lines between the 5D0 and
7
Figure 8a, solid line) monitored with 610 nm shows two F0 levels are nondegenerate. This reveals the presence
broad excitation bands (the weak one with a range from of crystallographic nonequivalent sites in a given host
200 to 234 nm centered at 226 nm and the strong one with matrix.32 The site-selective excitation spectroscopic tech-
a range from 234 to 350 nm centered at 280 nm) and a nique (dye laser with a continuous wavelength in the
number of line excitation peaks (the strongest one is region of 7F0 f 5D0 of Eu3þ) is a good method to
located at 468 nm for the 7F0 f 5D2 transition) of Eu3þ. investigate the distribution of metal cations at different
The strong band centered at 280 nm is due to the charge- atomic sites in a microstructure, which plays a significant
transfer transition between O2- and Eu3þ,29 and the weak role in tailoring the physical properties of the material for
broad band peaking at 226 nm should be ascribed to the device applications. In this work, the different Eu3þ sites
host absorption.30 Upon excitation with 280 nm UV, the in the La2O2CO3 and La2O3 host lattices were selectively
La2O2CO3:Eu3þ (5 mol %) sample shows a strong red excited with a tunable dye laser and the luminescence
luminescence, and the corresponding emission spectrum spectra of each site were recorded separately. Parts a and
consists of the characteristic transitions of Eu3þ within b of Figure 9 show the excitation spectra corresponding
its 4f6 configuration, i.e., 5D1 f 7F1 (535 nm), 5D0 f 7F0 to the 7F0 f 5D0 transition in La2O2CO3 and La2O3
(580 nm), 5D0 f 7F1 (590 nm), 5D0 f 7F2 (610, 625 nm), matrices, respectively, obtained by monitoring the 5D0 f
and 5D0 f 7F3 (653 nm). The strongest one is located 7
F2 transition at 20 and 300 K. The excitation spectrum of
at 610 nm. For the La2O3:Eu3þ (5 mol %) sample, the La2O2CO3:Eu3þ (5 mol %) microrhombus sample con-
excitation spectrum (monitored by Eu3þ5D0 f 7F2 at sists of two strong peaks at 579.0 and 580.3 nm as well as a
625 nm; Figure 8a, left dashed line) consists of a intense weak peak at 580.8 nm, which are denoted as Eu3þ (M1),
broad band from 250 to 330 nm with the maximum at Eu3þ (M2), and Eu3þ (M3), respectively. No other line
291 nm, a weak broad band from 200 to 250 nm with the corresponding to the 7F0 f 5D0 transition was detected at
peak around 230 nm, and some Eu3þ excitation peaks. The temperatures of 20 and 300 K. The occupation probabil-
broad band around 291 nm is also attributed to the charge- ity of the major sites Eu3þ (M1) and Eu3þ (M2) is
transfer band (CTB) of Eu3þ-O2-,29 and the band peak- dominant. The minor site Eu3þ (M3) is weakly occupied
ing around 230 nm is related to the host excitation, i.e., because of its weak excitation intensity. The results in
electronic transitions from the O 2p valence band to the La Figure 9a clearly indicate that the Eu3þ ions occupy three
5d6s conduction band.30 The emission spectrum of La2O3: different intrinsic crystallographic sites in the La2O2CO3
Eu3þ (5 mol %; Figure 10a, right dashed line) obtained by matrix, which is consistent with the previous report.33 For
excitation into 291 nm contains exclusively the character- the La2O3:Eu3þ (5 mol %) microrhombus sample, its
istic emission of Eu3þ, as shown in Table 2 in the Support- excitation spectrum monitored at 20 K consists of the
ing Information. On the basis of the above analyses, it can strongest line at 580.9 nm and two weak peaks at 579.2
be clearly seen that there are two great differences in the PL and 581.3 nm, which are labeled as Eu3þ (N2), Eu3þ (N1),
spectra of the La2O2CO3:Eu3þ (5 mol %) and La2O3:Eu3þ and Eu3þ (N3), respectively. The occupation probability
(5 mol %) samples, as follows: First, the excitation peak of the major site Eu3þ (N2) is dominant, and the minor
of La2O3:Eu3þ (5 mol %) moved 11 nm to a shorter- sites Eu3þ (N1) and Eu3þ (N3) are weakly occupied
wavelength direction than that of La2O2CO3:Eu3þ (5 mol %). because of its weak excitation intensity. The results in
Second, the 5D0 f 7F2 transition intensity ratio of 625 to Figure 9b clearly show that there is only one intrinsic
610 nm is greatly enhanced in La2O3:Eu3þ (5 mol %) in crystallographic site of La3þ for the Eu3þ ions in the
comparison with that in La2O2CO3:Eu3þ (5 mol %). La2O3 matrix, which is also consistent with the previous
For RE-doped luminescence materials, the local envi- report.34 The other Eu3þ ions may exist in the term of the
ronment of the activator ions is believed to have a crucial cluster of Eu3þ ions.35 However, the weak excitation
impact on the luminescence behavior, and it is important peaks of La2O3:Eu3þ (5 mol %; 579.2 and 581.3 nm)
to explain the differences in the spectra of different disappear when the monitoring temperature is elevated to
microstructures. There are many reports on studies of the 300 K, and there is only a strong line at 580.5 nm. The
site symmetry of activators of the RE-doped lumines- possible reason is that the heat movement swells between
cence materials,31 while the corresponding systematic the adjacent ions and temperature quenching occurs with
research on Eu-doped La2O2CO3 and La2O3 phosphors an increase of the monitoring temperature.
has not been achieved. Eu3þ (4f6 configuration) is widely In addition, the site-selective emission spectra under
used as a probe of the surrounding symmetry because the M1, M2, and M3 line excitations for La2O2CO3:Eu3þ
(5 mol %) and N1, N2, and N3 line excitations for La2O3:
(29) (a) Park, J. K.; Park, S. M.; et al. J. Mater. Sci. Lett. 2001, 20, 2231. Eu3þ (5 mol %) at 20 and 300 K are also shown in parts c
(b) Lin, C. C.; Liu, R. S.; Tang, Y. S.; Hu, S. F. J. Electrochem. Soc. 2008, 155, and d of Figure 9, respectively. The different emission
J248. (c) Ghys, J. D.; Mauricot, R.; Caillier, B.; Guillot, P.; Beaudette, T.; Jia,
G. H.; Tanner, P. A.; Cheng, B. M. J. Phys. Chem. C 2010, 114, 6681.
(d) Fernandes, J. A.; Ferreira, R. A. S.; Pillinger, M.; Carlos, L. D.; Gonc-alves, (32) (a) Gorller-Walrand, C.; Binnemans, K. In Handbook on the Physics
I. S.; Ribeiro-Claro, P. J. A. Eur. J. Inorg. Chem. 2004, 19, 3913. and Chemistry of Rare Earths; Gschneidner, K. A., Jr., Eyring, L., Eds.; North-
(30) Prokofiev, A. V.; Shelykh, A. I.; Melekh, B. T. J. Alloys Compd. 1996, Holland: Amsterdam, The Netherlands, 1996; Vol. 23. (b) Liu, Y. S.; Luo, W. Q.;
242, 41. Li, R. F.; Chen, X. Y. Opt. Lett. 2007, 32, 566. (c) Luo, W. Q.; Li, R. F.; Liu, G. K.;
(31) (a) Jia, C. J.; Sun, L. D.; Yan, Z. G.; Pang, Y. C.; L. S. Z.; Yan, C. H. Antonio, M. R.; Chen, X. Y. J. Phys. Chem. C 2008, 112, 10370.
Eur. J. Inorg. Chem. DOI: 10.1002/ejic.201000038. (b) Lehmann, O.; K€ompe, (33) Paul Attfield, J.; Ferey, G. J. Solid State Chem. 1989, 82, 132.
K.; Haase, M. J. Am. Chem. Soc. 2004, 126, 14935. (c) Song, H. W.; Yu, L. X.; (34) Hoefdraad, H. E. Chem. Phys. Lett. 1975, 32, 216.
L€u, S. Z.; Wang, T.; Liu, Z. X.; Yang, L. M. Appl. Phys. Lett. 2004, 85, 470. (35) (a) Zhang, S. Y.; Huang, Y. L.; Jin Seo, H. J. Electrochem. Soc. 2010,
(d) Sudarsan, V.; van Veggel, F. C. J. M.; Herring, R. A.; Raudsepp, M. J. Mater. 157, J186. (b) Jin Seo, H.; Tsuboi, T.; Jang, K. W. Phys. Rev. B 2004, 70, 205113.
Chem. 2005, 15, 1332. (e) Jia, G. H.; Tanner, P. A.; Duan, C. K.; Dexpert-Ghys, J. (c) Huang, Y. L.; Cao, Y. Q.; Jiang, C. F.; Shi, L.; Tao, Y.; Jin Seo, H. Jpn. J. Appl.
J. Phys. Chem. C 2010, 114, 2769. Phys. 2008, 47, 6364.
10532 Inorganic Chemistry, Vol. 49, No. 22, 2010 Li et al.

Figure 9. Excitation spectra in the region of the 7F0 f 5D0 transition in (a) La2O2CO3:Eu3þ (5 mol %) and (b) La2O3:Eu3þ (5 mol %) microrhombus
samples at 20 and 300 K. Site-selective emission spectra of 5D0 f 7F2 under different site-selective excitations into Eu3þ in (c) La2O2CO3:Eu3þ (5 mol %) and
(d) La2O3:Eu3þ (5 mol %) microrhombus samples at 20 and 300 K.

spectra in La2O2CO3 and La2O3 host lattices for the 2D (La2O22þ)n layers connected with O2- ions. Because
5
D0 f 7F2 transition are observed. For La2O2CO3:Eu3þ the size of CO32- is bigger than that of O2-, the average
(5 mol %), the emission spectra obtained at 300 K are Eu-O distance in La2O2CO3 is larger than that in La2O3,
similar to those at 20 K, which all show a higher 5D0 f 7F2 which results in CTB of Eu3þ in the former moving
emission intensity around 625 nm than around 610 nm. In to high energy. This is the reason that the excitation peak
contrast, the 5D0 f 7F2 emission intensity around 625 nm of La2O2CO3:Eu3þ (5 mol %) locates at 280 nm, which
is much lower than that around 610 nm for La2O3:Eu3þ moves 11 nm to a shorter-wavelength direction relative to
(5 mol %) at 20 and 300 K except for the site-selective that of La2O3:Eu3þ (5 mol %). Furthermore, it can be
excitation in Eu3þ (N1) having an equivalent value (R = seen clearly from Figure S8c in the Supporting Informa-
1.01) that may be due to the different Eu3þ ion clusters tion that there are seven oxygen atoms coordinated with
from the Eu3þ (N3) site. Because of the morphology, La3þ ions in La2O3. Strong 5D0 f 7F2 emissions appear at
the size and Eu3þ-doped concentration are basically iden- approximately 625 nm because of Eu3þ present in the
tical for the La2O2CO3:Eu3þ (5 mol %) and La2O3:Eu3þ hexagonal La2O3 lattice with C3v symmetry. When O2-
(5 mol %) microrhombus samples, so these discrepancies ions are replaced with CO32- groups, the coordinated
should be attributed to their different microstructures, O2- ions with La3þ ions increase to 10 in the La2O2CO3
which results in Eu3þ ions locating in different crystal host, which make the Eu3þ ions have a lower symmetry in
symmetries and coordination environments in the La2O2- La2O3 compared with those in La2O2CO3. Because of the
CO3 and La2O3 hosts. Figure S8 in the Supporting Infor- hypersensitivity of the 5D0 f 7F2 transition of Eu3þ, the
mation shows 3D model structures and coordination environment has a crucial effect on the relative intensity
environments with oxygen atoms of La2O2CO3 and La2O3. of different 5D0 f 7F2 emission peaks. Si et al.36 reported
La2O2CO3 is believed to have layerlike structures, con-
taining 2D (La2O22þ)n layers held together by CO32- (36) (a) Si, R.; Zhang, Y. W.; You, L. P.; Yan, C. H. Angew. Chem., Int.
groups, as shown in Figure S8a in the Supporting Ed. 2005, 44, 3256. (b) Si, R.; Zhang, Y. W.; Zhou, H. P.; Sun, L. D.; Yan, C. H.
Information. Similarly, La2O3 can also be considered as Chem. Mater. 2007, 19, 18.
Article Inorganic Chemistry, Vol. 49, No. 22, 2010 10533

Figure 10. Typical CL spectra of (a) La2O2CO3:Eu3þ (5 mol %), (b) La2O2CO3:Tb3þ (1 mol %), (c) La2O3:Eu3þ (5 mol %), and (d) La2O3:Tb3þ (1 mol %)
samples with rhombic microplate shapes. The insets are their corresponding luminescence photographs under 3.0 kV voltage electron-beam excitation.

that enhancement of the intensity ratio of the peak at spectral profiles, which are all attributed to 5D4 f 7FJ
625 nm to the peak at 610 nm in Eu2O3 nanodisks in (J = 6, 5, 4, 3) transitions of Tb3þ corresponding to
comparison with that of the Eu2O3 bulk materials is due 5
D4 f 7F6 (488 nm), 5D4 f 7F5 (542 and 548/549 nm),
to the lower symmetry of Eu3þ in the former, which is 5
D4 f 7F4 (588 nm), and 5D4 f 7F3 (620 nm), respec-
consistent with our observation. Because Eu3þ ions sub- tively, as shown in Figure 8b.37 The strongest emissions
stitute for La3þ in La2O2CO3 and La2O3, they have a all locate at 542 nm and are indexed to the 5D4 f 7F5
lower symmetry in La2O3 than in La2O2CO3, which transition of Tb3þ. Upon monitoring with the 542 nm
results in a great enhancement of the intensity ratio of emission, the excitation spectra of La2O2CO3:Tb3þ
the peak at 625 nm to the peak at 610 nm of the 5D0 f 7F2 (1 mol %) and La2O3:Tb3þ (1 mol %) all consist of two
transition of Eu3þ. broad bands. The former broad band is attributed to the
The luminescence decay curves of the 5D0 f 7F2 emis- host absorption, and the latter broad band is due to the
sion after the M1-M3 and N1-N3 line excitations at diff- 4f8-4f75d1 transition of Tb3þ. However, there are some
erent temperatures (20, 100, 200, and 300 K) were mea- differences in the range and maximum of the two excita-
sured. All of the exponential decay curves can be fitted tion bands in the La2O2CO3 and La2O3 hosts. The exci-
into a single-exponential function as I = I0 exp(-t/τ), tation spectrum of the La2O2CO3:Tb3þ (1 mol %) ranges
where I0 is the initial emission intensity for t = 0 and τ is from 200 to 300 nm with a maximum at 257 nm, while that
the lifetime. The detailed luminescence lifetimes of Eu3þ of La2O3:Tb3þ (1 mol %) ranges from 200 to 320 nm with
ions are listed in Table 3 (Supporting Information). For a maximum at 236 nm. All of these differences can be
La2O2CO3:Eu3þ (5 mol %), the 5D0 decay times in the M1 attributed to the different coordination environments and
and M3 sites decrease with an increase of the temperature, symmetries around the Tb3þ ions in the La2O2CO3 and
presenting a typical temperature-quenching behavior, while La2O3 hosts.
the 5D0 decay time in the M2 site is close to a constant In summary, the microstructures (coordination environ-
0.87 ms from 20 to 300 K, indicating a relatively steady ment and symmetry) of La2O2CO3 and La2O3 have a
luminescence site. Similarly, for La2O3:Eu3þ (5 mol %), the crucial effect on Eu3þ or Tb3þ luminescence properties.
N2 site is a relatively steady luminescence center. Because The above investigations not only provide important
the 5D0 decay time in the N2 site basically maintains a experimental evidence for RE luminescence studies but also
constant 0.72 ms, while those of in the N1 and N3 sites con- disclose the correlation between the microstructure and
tinuously decrease with an increase in the temperature from luminescence behavior, which could be used as a guide to
20 to 300 K. The temperature-quenching behavior of the the design and synthesis of novel luminescence materials.
5
D0 decay time in the N1 and N3 sites are obvious, as shown CL Properties of La2O3CO3/La2O3:Eu3þ or Tb3þ. In
in Table 3 in the Supporting Information. The results are order to explore the potential of the as-synthesized
consistent with those of the excitation and site-selective
emission spectra. (37) Granadeiro, C. M.; Ferreira, R. A. S.; Soares-Santos, P. C. R.;
On the other hand, the La2O2CO3:Tb3þ (1 mol %) and Carlos, L. D.; Trindade, T.; Nogueira, H. I. S. J. Mater. Chem. 2010, 20,
La2O3:Tb3þ (1 mol %) phosphors show similar emission 3313.
10534 Inorganic Chemistry, Vol. 49, No. 22, 2010 Li et al.
La2O2CO3/La2O3:Eu3þ or Tb3þ samples to be used as CL
materials, their CL properties have been investigated in detail.
The La2O2CO3/La2O3:Eu3þ or Tb3þ products are stable
under electron-beam excitation. Parts a-d of Figure 10 show
typical CL spectra of the representative La2O2CO3:Eu3þ (5
mol %), La2O2CO3:Tb3þ (1 mol %), La2O3:Eu3þ (5 mol %),
and La2O3:Tb3þ (1 mol %) samples with rhombic microplate
shape, respectively, the profiles of which are similar to those
of their PL spectra. Under low-voltage electron-beam excita-
tion, La2O2CO3:Eu3þ (5 mol %) and La2O3:Eu3þ (5 mol %)
show the characteristic emission of Eu3þ (5DJ f 7FJ0 , where
J = 0, 1, 2 and J0 =1-5), and La2O2CO3:Tb3þ (1 mol %)
and La2O3:Tb3þ (1 mol %) exhibit the 5D4 f 7FJ (J = 3, 4,
5, 6) characteristic transitions within the Tb3þ 4f 8 electron
configuration, as shown in Figure 10a-d. During excitation
with 3.0 kV voltage, the above La2O2CO3:Eu3þ (5 mol %),
La2O2CO3:Tb3þ (1 mol %), La2O3:Eu3þ (5 mol %), and
La2O3:Tb3þ (1 mol %) samples respectively show bright red,
red, green, and green luminescence to the naked eye, as
depicted in the luminescent photographs from the insets in
Figure 10a-d, and their corresponding CIE chromaticity
coordinates are determined to be (x = 0.6260, y = 0.3503),
(x = 0.2521, y = 0.6052), (x = 0.5463, y = 0.3947), and
(x=0.2682, y=0.6366), respectively.
The CL emission intensities of the La2O2CO3:Eu3þ
(5 mol %), La2O2CO3:Tb3þ (1 mol %), La2O3:Eu3þ
(5 mol %), and La2O3:Tb3þ (1 mol %) samples with
rhombic shape also have been investigated as a function
of the accelerating voltage and the filament current, as
shown in Figure 11. When the filament current is fixed
at 90 mA, the CL intensity increases with an increase in
the accelerating voltage from 1.5 to 3.5 kV (Figure 11a). Figure 11. CL intensities of the La2O2CO3:Eu3þ (5 mol %), La2O2CO3:
Tb3þ (1 mol %), La2O3:Eu3þ (5 mol %), and La2O3:Tb3þ (1 mol %)
Similarly, under a 3.0 kV voltage electron-beam excita- samples with rhombic shape as a function of (a) accelerating voltage and
tion, the CL intensity also increases with an increase in (b) filament current.
the filament current from 85 to 97 mA (Figure 11b). The
increase in the CL brightness with an increase in the ele- Finally, using the La2O2CO3:Eu3þ (5 mol %) sample
ctron energy and filament current is attributed to the prepared by CO(NH2)2 as the carbon source at different
deeper penetration of the electrons into the phosphor pH values for representative examples, we also investi-
body and the larger electron-beam current density. The gated the effect of morphologies/sizes on their PL and CL
electron penetration depth can be estimated using the intensities. Parts a and b of Figure 12 show a comparison of
empirical formula L [Å] = 250(A/F)(E/Z1/2)n, where n = the luminescent intensities of La2O2CO3:Eu3þ (5 mol %)
1.2/(1-0.29 log Z), A is the atomic or molecular weight samples with three different morphologies/sizes under
of the material, F is the bulk density, Z is the atomic 291 nm UV light and low-voltage electron-beam excita-
number or the number of electrons per molecule in the case tion, respectively (here it should be mentioned that all of
of compounds, and E is the accelerating voltage (kV).38 the experimental conditions were kept identical in order
For La2O2CO3:Eu3þ (5 mol %), La2O2CO3:Tb3þ to avoid the experimental errors). It can be seen that
(1 mol %), La2O3:Eu3þ (5 mol %), and La2O3:Tb3þ rhombic phosphors have a higher PL/CL intensity than
(1 mol %) samples, the estimated electron penetration that of flake/flowerlike and sandwichlike spindle phos-
depth at 3.0 kV is about 5.8, 6.6, 5.9, and 6.7 nm, phors. It is well-known that the surface area of the mate-
respectively. For CL, the Eu3þ and Tb3þ ions are excited rials increases with a decrease in the size. The large surface
by the plasma produced by the incident electrons. The area results in a large number of defects into the phosphor
deeper the electron penetration depth, the more plasma crystal, which have serious impairment in the PL/CL
will be produced, which results in more Eu3þ and Tb3þ intensity for phosphors because they provide nonradia-
ions being excited and, thus, an increase in the CL tive recombination routes for electrons and holes. In
intensity. From Figure 11, it can be seen that the La2O2- order to be as efficient as possible for the phosphors, the
CO3:Eu3þ (5 mol %) sample always has a higher CL number of electron/hole recombinations via optically
intensity than the La2O3:5 mol % Eu3þ sample under the active centers must be maximized. If the surface area is
same excitation conditions, indicating that La2O2CO3 is a greatly reduced by increasing crystallite size, the phos-
better host than La2O3 for the Eu3þ ion doping. The same phor with fewer defects would show great improvement
situation is available to the La2O2CO3:Tb3þ (1 mol %) in the PL/CL intensity.39 On the other hand, smooth and
and La2O3:Tb3þ (1 mol %) samples. fewer exposed surfaces are also favorable to decreasing
the surface area and surface defects. Although the flake/
(38) Feldman, C. Phys. Rev. 1960, 117, 455. flowerlike and sandwichlike spindle samples have larger
Article Inorganic Chemistry, Vol. 49, No. 22, 2010 10535
of the carbon sources and pH values on the shapes of
LaCO3OH and LaCO3OH:Ln3þ (Ln = Eu, Tb) nano/micro-
structures have been investigated in detail. The intrinsic
crystal structure of LaCO3OH and a variety of external
factors account for the ultimate shape evolutions of the
products. It is meaningful to investigate the morphological
growth process of LaCO3OH and LaCO3OH:Ln3þ (Ln = Eu,
Tb) nano/microcrystals, which can provide important infor-
mation to the fields of crystal growth and design and may be
extended to the morphology-controlled creation of other rare-
earth carbonate systems with complex forms. During calcina-
tion of the LaCO3OH:Ln3þ (Ln = Eu, Tb) nano/microstruc-
tures at suitable temperatures (600 and 800 °C), we obtained
the morphology-maintained La2O2CO3/La2O3:Ln3þ (Ln =
Eu, Tb). More importantly, a systematic study on the PL and
CL properties of La2O2CO3/La2O3:Ln3þ (Ln =Eu, Tb) has
been explored in order to obtain multicolor-emitting phos-
phors. The microstructures of La2O2CO3 and La2O3 and the
occupations of the Eu3þ ions have been investigated by the
excitation and site-selective emission spectra of Eu3þ in the
two hosts. Eu3þ ions occupy three different sites in La2O2CO3
by the replacement of La3þ, while they mainly occupy a site
in the La2O3 matrix. In addition, there exist some clusters of
Eu3þ ions in La2O3. The difference in excitation and emission
spectra of Eu3þ- or Tb3þ-doped La2O2CO3 and La2O3 should
be attributed to the different coordination environments and
symmetries of Eu3þ ions in La2O2CO3 and La2O3 matrices.
The experimental results also indicate that the optical proper-
ties of the La2O2CO3/La2O3:Ln3þ (Ln = Eu, Tb) phosphors
Figure 12. (a) PL and (b) CL emission spectra of the La2O2CO3:Eu3þ with different microarchitectures are strongly dependent on
(5 mol %) samples with three different morphologies (flake/flowerlike,
rhombic, and sandwichlike spindle).
their morphologies and sizes.

sizes than the rhombic sample, the latter has a higher Acknowledgment. This project is financially supported
luminescent intensity than the former because of the by the National Basic Research Program of China (Grants
smooth and fewer exposed surfaces. Therefore, the emis- 2007CB935502 and 2010CB327704) and the National
sion intensity difference in the PL and CL results of the Natural Science Foundation of China (NSFC Grants
La2O2CO3/La2O3:Ln3þ (Ln = Eu, Tb) products should 50702057, 50872131, and 20921002). The authors also
be attributed the cooperative results of the particle size thank Prof. Hyo Jin Seo and Dr. Liang Shi from Pukyong
and shape, which are related to surface areas and defects. National University for their kind help in the measure-
The specific surface area determined by the Brunauer- ment of the excitation and site-selective emission spectra
Emmett-Teller method on the flake/flowerlike, rhombic, of Eu3þ ions in the La2O2CO3/La2O3:Eu3þ samples.
and sandwichlike spindle La2O2CO3:Eu3þ (5 mol %)
samples were 7.8362, 0.0081, and 0.9918 m2 g-1, respec- Supporting Information Available: XRD patterns of the
tively, which is consistent with the above conclusion. as-prepared LaCO3OH products at pH = 7 using other carbon
sources (Figure S1), FT-IR spectra of the as-synthesized La-
Accordingly, a large number of electrons and holes in the
CO3OH product (P2; Figure S2), parameters of the representative
excited state will return to the ground state via optically experiments and the morphologies and sizes of the corresponding
radiative recombination routes for the rhombic sample. products (Table 1), SEM images of LaCO3OH microcrystals at
This is the reason that the PL/CL intensity of the rhombus pH = 10 with different carbon sources: Na2CO3 and (NH4)2CO3
is higher than that of flake/flowerlike and sandwichlike (Figure S3), TG-DTA curves of LaCO3OH precursors (P2)
spindle samples. (Figure S4), XRD patterns of La2O2CO3 products (M1-M3)
obtained by calcining LaCO3OH (P1-P3) at 600 °C for 4 h
4. Conclusion (Figure S5), XRD patterns of La2O3 products (N1-N3) obtained
by calcining LaCO3OH (P1-P3) at 800 °C for 4 h (Figure S6),
In summary, systematic manipulation of the morphologies SEM images of La2O2CO3 and La2O3 (M1, M3, N1, and N3)
and architectures of LaCO3OH and LaCO3OH:Ln3þ (Ln = products (Figure S7), summary of the PL properties of La2O2CO3/
Eu, Tb) nano/microcrystals on a large scale has been success- La2O3:Eu3þ and Tb3þ samples (Table 2), schematic drawing of the
fully achieved using a simple and mild solution-growth crystal and 3D model structures and coordination environment
method free of any templates and catalysts. The influences with O2- of La2O2CO3 and La2O3 (Figure S8), and 5D0 f 7F2
emission decay times of Eu3þ ions at different crystal sites and
(39) (a) Yang, J.; Liu, X. M.; Li, C. X.; Quan, Z. W.; Kong, D. Y.; Lin, J. temperatures (20-300 K) in the La2O2CO3 and La2O3 hosts
J. Cryst. Growth 2007, 303, 480. (b) Yang, J.; Li, C. X.; Cheng, Z. Y.; Zhang, (Table 3). This material is available free of charge via the Internet
X. M.; Quan, Z. W.; Zhang, C. M.; Lin, J. J. Phys. Chem. C 2007, 111, 18148. at http://pubs.acs.org.