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Ceramics International 41 (2015) 7411–7420
www.elsevier.com/locate/ceramint
Abstract
Hexagonal NaYF4 microcrystals with controllable morphologies and tunable sizes have been successfully synthesized by a facile hydrothermal
method. The influences of the molar ratios of trisodium citrate (Cit3 ) to Y3 þ and pH values on the phase and morphology evolution were
investigated and discussed in detail. It is found that trisodium citrate and pH value as two significant external factors play key roles in the
formation of the anisotropic architectures of β-NaYF4 microcrystals. Taking hexagonal β-NaYF4 microprisms as a candidate, the possible
formation mechanism has been proposed on the basis of time-dependent experiments. In addition, the upconversion (UC) luminescence properties
of β-NaYF4:Yb3 þ /Er3 þ samples were systematically studied and discussed. The results reveal that the UC luminescence properties are strongly
dependent on their morphologies and sizes. This study not only provides important information for shape-controlled synthesis of other complex
rare earth fluoride compounds, but also gives a reference for exploration of morphology- and size-dependent UC luminescence properties.
& 2015 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
http://dx.doi.org/10.1016/j.ceramint.2015.02.054
0272-8842/& 2015 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
7412 M. Ding et al. / Ceramics International 41 (2015) 7411–7420
achieving highly efficient UC emission of lanthanide ions 8:1) of Cit3 :Y3 þ , pH values in the reaction solution (3, 5, 7
(Ln3 þ ), owing to its low photon energy, low nonradiative decay and 9), and hydrothermal times (3, 6 and 12 h) were selected to
rates, and high radiative emission rates [34]. To date, many investigate the effects of these factors on the morphologies and
efforts are devoted to synthesizing lanthanide-doped β-NaYF4 UC luminescence properties of the final products. The pH value
nano- and microcrystals with various morphologies, such as of the mixing solution was adjusted to a specific value by adding
nanowires, nanorods, nanotubes, microtubes, microrods, micro- NaOH solution (1 M) or HCl solution (1 M).
spheres, microdisks, and microplates [12,35–37]. However, little
has been done on the systematic investigation of the morphology- 2.3. Characterization
and size-dependent UC luminescence properties. Understanding
how the UC luminescence properties change with particle shape Powder X-ray diffraction (XRD) measurements were per-
and size is of important significance in the design of highly formed on a ARL X' TRA diffractometer at a scanning rate of
efficient UC materials. In addition, the mechanism underlying the 10 1/min in the 2θ range from 101 to 801 with Cu Kα radiation
phase and morphology evolution of NaYF4 crystals under the (λ=0.15406 nm). SEM micrographs were obtained using a
external conditions is still not very clear. Therefore, there is a field emission scanning electron transmission microscope (FE-
further need to understand the dynamic process governing nuc- SEM, SU8010, Hitachi). Transmission electron microscopy
leation and growth of the complex fluorides. (TEM) were recorded on JEM-200CX with a field emission
In this paper, uniform and well-defined β-NaYF4 microcrys- gun operating at 200 kV. Images were acquired digitally on a
tals with various morphologies, such as microtubes, microrods, Gatan multiple CCD camera. UC emission spectra were
microplates, microprisms, and submicrorods, have been success- recorded with a Jobin Yvon FL3-221 fluorescence spectro-
fully synthesized through a facile hydrothermal process. The photometer equipped with a 980 nm laser diode Module
effects of molar ratios of trisodium citrate (Na3Cit) to Y3 þ and (K98SA3M-54W, China) as the excitation source. All the
pH values in the initial solution on the final morphology and measurements were performed at room temperature.
size have been investigated in detail. Tanking β-NaYF4 micro-
prisms as a typical example, the possible formation mechanism 3. Results and discussion
for the phase and morphology evolution process of β-NaYF4 has
been proposed. Finally, the upconversion luminescence proper- It is generally accepted that not only the intrinsic structure but
ties of the as-obtained β-NaYF4:Yb3 þ /Er3 þ microcrystals with also a series of external factors, including reaction temperature,
different shapes are investigated to discuss the relationship bet- time, pH value, and organic additives, have dramatic influence on
ween luminescence intensities and particle morphologies. the crystallization process and shape evolution of the final crystals
in a solution-based system [38,39]. In our previous study, it is
2. Experimental section found that the molar ratios of NaF–Y3 þ can strongly control the
phase and morphology of the as-synthesized β-NaYF4 products
2.1. Materials [37]. As a continuation and extension of this work, we mainly
focus on the effects of molar ratios of Cit3 –Y3 þ and pH values
All chemicals are of analytical grade and were used without in the initial solution on the phases and morphologies of the final
further purification. YCl3 6H2O (99.99%), YbCl3.6H2O (99.99%), products.
ErCl3 6H2O (99.9%) were purchased from Beijing Founde Star
Science & Technology Co., Ltd. (China). NaF (98%), C6H5 3.1. Effect of sodium citrate content
Na3O7.2H2O (99%) were provided by Sinopharm Chemical Rea-
gent Co., Ltd. (China). As we all known, organic additives play significant roles in
various solution-phase synthetic processes by controlling nuclea-
2.2. Synthesis tion, crystallization, and growth of crystalline materials [40].
Here, we focus our attention on the important influence of the
In a typical procedure for the synthesis of β-NaYF4, 2 mmol Cit3 /Y3 þ molar ratios on the phase and morphology of the final
YCl3 6H2O were firstly dissolved in 10 mL H2O with magnetic products. Fig. 1 shows the corresponding XRD patterns of the
stirring to form rare earth chloride solution. Then this solution samples synthesized at 220 1C for 24 h with different molar ratios
was added into 20 mL aqueous solution containing 2 mmol tri- of Cit3 –Y3 þ . As shown, the diffraction peaks of all the
sodium citrate (Na3Cit) to form the metal–citrate complex. After products can be well indexed to a hexagonal phase of NaYF4
vigorous stirring for 30 min, 30 mL aqueous solution containing with lattice constants a¼ 0.596 nm and c¼ 0.353 nm, according
12 mmol of NaF was introduced into the above solution. After to JCPDS card no. 28-1192 [41]. The results reveal that pure β-
additional agitation for 15 min, the as-obtained mixing solution NaYF4 samples can be successfully synthesized with different
was transferred into a Teflon bottle held in a stainless steel molar ratios of Cit3 :Y3 þ . Notably, the relative intensity of
autoclave, sealed, and maintained at 220 1C for 24 h. As the diffraction peak changes with different Cit3 /Y3 þ molar ratios,
autoclave was cooled to room temperature naturally, the pre- revealing the shape evolution of the as-synthesized β-NaYF4
cipitates were separated by centrifugation, washed with deionized crystals.
water and ethanol in sequence, and then dired in air at 80 1C for The representative FE-SEM images of β-NaYF4 samples
12 h. In addition, different molar ratios (0, 2:1, 1:1, 2:1, 4:1 and synthesized with different molar ratios of Cit3 –Y3 þ are shown
M. Ding et al. / Ceramics International 41 (2015) 7411–7420 7413
in Fig. 2. Without sodium citrate (Na3Cit), the as-obtained β- usually used as “shape modifier” to control the growth rate of
NaYF4 are prone to growing into irregular structures with an different crystal faces through modifying crystal growth dyna-
average length of 13.49 μm, as presented in Fig. 2a. The coarse mically. As a surfactant molecule, citrate anions can selectively
surface of these microparticles can be clearly seen from the adsorb on some crystal faces and decrease their growth rate,
high-magnification image (inset in Fig. 2a). Once Na3Cit is resulting in a highly anisotropic growth. This phenomenon has
introduced into the reaction system, significant change happens also been reported in the formation of ZnO nanoplates [36,42].
in the shape and size of the final products. When the molar ratio With the increase of Cit3 /Y3 þ molar ratio up to 1:1, the as-
of Cit3 :Y3 þ is 1:2, the morphology of the as-obtained sample obtained sample consists of hexagonal microrods with protrud-
is the hexagonal microplates with concave centers, indicating ing centers, of which the average length is about 5.36 μm and
that the citrate ions are responsible for the obvious shape diameter is about 3.32 μm (Fig. 2c). The magnified SEM image
transition. As shown in Fig. 2b, the mean size is calculated to be (Inset in Fig. 2c) shows a close-up review of one isolated
about 0.81 μm in thickness and 2.23 μm in diameter. Although microrod, which clearly displays the crow-like top end of
the exact reason for this change is not very clear, the explanation hexagonal microrods. At higher molar ratio of 2:1, the as-
can be provided as follows. As we know, organic additives is synthesized product presents hexagonal prism morphology with
Table 1
Summary of experimental parameters and corresponding morphologies and
dimensions of the productsa.
Fig. 2. SEM images for β-NaYF4 samples synthesized with different molar ratios of Cit3 –Y3 þ : (a) 0 (without Cit3 ), (b) 0.5, (c) 1, (d) 2, (e) 4, and (f) 8. Insets
are higher-magnification images for the corresponding samples.
7414 M. Ding et al. / Ceramics International 41 (2015) 7411–7420
protruding centers, as shown in Fig. 2d. It can be calculated that 3.2. Effect of pH values.
the average thickness is about 1.55 μm the diameter is about
3.96 μm. When the molar ratio of Cit3 /Y3 þ reaches 4:1, the It is well known that pH values have dramatic effect on the
corresponding sample has no obvious morphological change crystal phase, morphology and size of the final products. Here,
except for the increase of the sizes to 2.07 μm in length and we focus our attention on the effect of pH values in our
4.47 μm in diameter. At the 8:1 M ratio of Cit3 :Y3 þ , the as- reaction system. Fig. 3 demonstrates the corresponding XRD
obtained product is composed of uniform hexagonal microrods patterns of the samples synthesized at 220 1C for 24 h with
with 3.42 μm in diameter and 5.40 μm in length. Based on the different pH values. At pH ¼ 3, the product consists of
above investigation, it can be concluded that the final shape of preponderantly YF3 along with minor β-NaYF4, as displayed
the as-prepared products can be precisely tuned by changing the in the XRD pattern (Fig. 3a). With the increase of pH value
molar ratio of Cit3 –Y3 þ . The corresponding morphologies from 5 to 9, all the peaks of three samples are characteristic of
and dimensions of the final samples synthesized with different a pure β-phase of NaYF4. Careful observation reveals that the
Cit3 /Y3 þ molar ratios are summarized in Table 1. relative peak intensities are different from each other, which
can be ascribed to different preferential orientation growth of
the as-synthesized crystals.
At different pH values, the as-obtained products exhibit
different morphologies and sizes, as shown in Fig. 4. In the
case of pH ¼ 3, the product consists of spherical-like nanopar-
ticles with an average diameter of 50 nm (Fig. 4a). With the
rise of pH value to 5, regular hexagonal microrods with
average size of 1.73 μm in diameter and 2.91 μm in length can
be successfully synthesized and observed in Fig. 4b. Interest-
ingly, the presence of concave centers can be clearly seen on
the top/bottom surfaces, which displays in the magnified FE-
SEM image (Inset in Fig. 4b). At pH ¼ 7, the product is
composed of relatively uniform microplates, of which the
thickness is about 1.31 μm and the diameter is about 3.68 μm
(Fig. 4c). More careful examination of the higher magnifica-
tion FE-SEM image presents clearly that the center part of
Fig. 3. XRD patterns for the as-prepared products at different pH values: (a)
pH¼3, (b) pH¼ 5, (c) pH¼ 7, and (d) pH¼ 9. The standard data of YF3
microplates is a little more protruding than that of the edge
(JCPDS no. 74-0911) and β-NaYF4 (JCPDS no. 28-1192) is given as a parts. Upon a further increase of pH value to 9, the sample is
reference. of a great deal of submicrorods with hexagonal prismatic
Fig. 4. SEM images of the as-prepared samples at different pH values: (a) pH¼ 3, (b) pH¼ 5, (c) pH¼ 7, and (d) pH¼9. Insets are higher-magnification images for
the corresponding products.
M. Ding et al. / Ceramics International 41 (2015) 7411–7420 7415
Fig. 6. SEM images for NaYF4 samples (NaF/Y3 þ ¼ 6, Cit3 /Y3 þ ¼ 4) under similar conditions for preparing CY-5 as a function of reaction time: (a, b) 3 h,
(c, d) 12 h, (e, f) 24 h and (g) schematic illustration for the possible formation process of β-NaYF4 microprisms.
the morphology of sample changes from hexagonal microprisms crystal facets increases significantly with the increment of pH
to hexagonal microrods. values, resulting in the decrease of crystal growth rate in all the
directions. So, the diameter and length of particles decrease
3.4.2. Effect of pH value in initial solution systematically and β-NaYF4 submicrorods can be obtained.
As one of external factors, pH value in initial solution plays a
significant role in the crystal growth of β-NaYF4 crystals. It is 3.5. UC luminescence properties
generally accepted that the differences of pH values can induce
directly to the different adsorption ability of Cit3 anions on the Up till now, hexagonal NaYF4 (β-NaYF4) has been regarded
different crystal facets, consequently resulting in various mor- as efficient host lattice for multicolor UC process because of its
phologies of β-NaYF4 microcrystals. At low pH value (pHo7), lower photon energy. However, the relative luminescent inten-
Cit3 ions could partly combine with H þ ions in the acid sities of lanthanide-doped β-NaYF4 products with various
environment, leading to the decrease of the complexing ability of morphologies are different from each other. The exact reason
Cit3 –Y3 þ to some degree. As a result, the decrease in the for the difference is still not very clear. Herein, we select Yb3 þ /
capping ability of Cit3 on {0001} planes results in faster growth Er3 þ as co-doped ions pairs to investigate the UC luminescence
rate along [0001] direction than that along other directions. properties of β-NaYF4 samples with different morphologies.
Subsequently, β-NaYF4 microrods can be obtained. However, as Remarkably, the crystal structure and morphology of the final
the pH value increases gradually, the capping effect of Cit3 on product could not be changed by the doping with small amount
{0001} facets is enhanced. Consequently, the slower growth rate of lanthanide ions. Yb3 þ /Er3 þ co-doped β-NaYF4 crystals with
along [0001] direction leads to the formation of microprisms. four shapes, including submicrorods (H-4), microplates (CY-2),
Interestingly, the capping ability of sodium citrate on all the microprisms (CY-5), and microrods (CY-6), are selected to
Fig. 7. (a) Room-temperature UC emission spectra, (b) the peak area of green and red emissions, (c) luminescent photographs and corresponding CIE chromaticity
diagram of the as-synthesized β-NaYF4:20%Yb3 þ , 2%Er3 þ crystals with different morphologies, and (d) decay profiles of the 4F9/2 (Er3 þ )-4I15/2 (Er3 þ )
transition (652 nm) in the as-prepared samples. (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this
article.)
7418 M. Ding et al. / Ceramics International 41 (2015) 7411–7420
investigate the effect of morphology on the UC luminescence be attributed to their different specific surface areas. The
properties (For clarity, these four samples are denoted as sample specific surface areas of S1, S2, S3, and S4 are calculated
S1, S2, S3, and S4, respectively). Fig. 7 shows the UC emission and shown in Table S1 (Supporting information). Compared to
spectra of β-NaYF4: 20%Yb3 þ , 2%Er3 þ samples (S1, S2, S3, submicrorods (S1), microplates (S2), microprisms (S3), β-
and S4) under 980 nm laser excitation. As presented in Fig. 7a, NaYF4: Yb3 þ /Er3 þ microrods (S4) have smallest surface area,
the green emission at 520 nm and 539 nm can be assigned to the which may lead to the strongest luminescence intensity.
2
H11/2-4I15/2, and 4S3/2-4I15/2 transitions of Er3 þ ions, while
the red emission centered at 652 nm could be ascribed to the 4F9/ 4. Conclusion
3þ
2- I15/2 transition of Er
4
ions [44]. The integral intensities of
green and red emissions for sample S1, S2, S3, and S4 are shown In summation, uniform β-NaYF4 microcrystals with various
in Fig. 7b. It is found that the relative intensities of S1, S2, S3, morphologies and sizes have been successfully synthesized by
and S4 differ from each other under the same measurement simply tuning the molar ratios of Cit3 –Y3 þ and pH values in
conditions. As shown in Fig. 7b, the ranking of the emission the initial solution. The phase, morphology evolution for the as-
intensities is listed as follows: S1oS2oS3oS4. Evidently, synthesized samples under different reaction conditions were syst-
β-NaYF4:20Yb3 þ , Er3 þ microrods (S4) present the strongest ematically investigated, and the mechanism of how the external
emission intensity, while β-NaYF4:20Yb3 þ , Er3 þ submicrorods factors influence the anisotropic growth of hexagonal NaYF4 cry-
(S1) have the lowest emission intensity. Thereinto, the relative stals has been proposed. Based on a series of time-dependent
intensity of the former is about 4 times higher than that of the experiments, a possible formation mechanism for β-NaYF4 sam-
latter. In order to visualize the difference in the UC luminescence ples with diverse architectures have been presented. More imp-
intensities of the four samples, the photographs of UC lumines- ortantly, the UC luminescence properties of β-NaYF4: 20%Yb3 þ ,
cence of S1, S2, S3, and S4 under 980 nm laser excitation are 2%Er3 þ products with different morphologies and sized were
provided in Fig. 7c. The yellow emission of the four samples with investigated in detail. The results reveal that the UC luminescence
different intensities can be clearly seen by naked eyes. Remark- properties of Yb3 þ /Er3 þ co-doped β-NaYF4 samples are sig-
ably, S4 exhibits the strongest luminescence intensity, agreeing nificantly related to its shapes and sizes.
with the results in Fig. 7a and b. Simultaneously, the emission
decay profiles of 4F9/2-4I15/2 transition (652 nm) for the four
Acknowledgment
samples were measured at the excitation wavelength of 980 nm,
as shown in Fig. 7d. All the decay curves can be well fitted into a
The project was financially supported by Zhejiang Province
single exponential function: I(t)¼ I0 þ A1 exp( t/τ), where I and
Science Foundation of China (LQ14E020006), the Scientific
I0 are the luminescence intensities at time t and 1, τ is the
Research Foundation of Hangzhou Dianzi University
lifetime and A1 is a constant [45]. The lifetimes of the 4F9/2 state
(KYS205614041), the National Natural Science Foundation
for S1, S2, S3, and S4 are determined to be 126.8, 203.2, 268.6,
of China (61372025 and 21271170), and a Project funded by
and 327.5 μs, respectively. Obviously, the variation tendency of
the Priority Academic Program Development of the Jiangsu
the lifetimes agrees well with the change of UC luminescence
Higher Education Institutions (PAPD).
intensity. Based on the above results, the UC luminescence
properties of β-NaYF4:20%Yb3 þ , 2%Er3 þ samples with various
morphologies are forcefully dependent on their shapes and sizes. Appendix A. Supporting information
Although the exact reason for the morphology-dependent
UC luminescence is not very clear so far, the explanation for Supplementary data associated with this article can be found
this difference can be provided as follows. It is well known in the online version at http://dx.doi.org/10.1016/j.ceramint.
that the experimental lifetime of an excited state (τm) is 2015.02.054.
determined by the radiative transition rate (1/τR) and non-
radiative relaxation rate (WNR), which can be expressed as
1/τm ¼ 1/τR þ WNR [46]. Owing to the similar local crystal field References
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