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Ceramics International 41 (2015) 7411–7420
www.elsevier.com/locate/ceramint

Controlled synthesis of β-NaYF4:Yb3 þ /Er3 þ microstructures

with morphology- and size-dependent upconversion luminescence
Mingye Dinga,b,n, Shilong Yinc, Yaru Nib, Chunhua Lub,nn, Daqin Chena, Jiasong Zhonga,
Zhenguo Jia, Zhongzi Xub
a
College of Materials & Environmental Engineering, Hangzhou Dianzi University, Hangzhou 310018, PR China
b
State Key Laboratory of Materials-Orient Chemical Engineering, College of Materials Science and Engineering, Nanjing Tech University, Nanjing 210009,
PR China
c
College of Chemistry & Materials Engineering, Changshu Institute of Technology, Changshu 215500, Jiangsu, PR China
Received 5 February 2015; accepted 9 February 2015
Available online 14 February 2015

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.

Keywords: β-NaYF4; Hydrothermal; Morphology-controlled synthesis; Upconversion

1. Introduction crystal structures and compositions. To achieve this goal, many

Currently, the synthesis of inorganic nano- or micromateri-
als with controllable shapes and sizes may have a great effect
on their physical, chemical, magnetic, and catalytic properties
[1–3]. Until now, a variety of inorganic materials, including
oxides, sulfides, oxyfluorides, fluorides, have been successfully
synthesized with multiple morphologies and sizes, such as rods,
tubes, boxes, cubes, plates, octahedrons, bipyramids [4–10].
However, controllable synthesis of micro- and nanocrystals has
been still a challenging issue, because of the complexity of their
n
Corresponding author at: College of Materials & Environmental Engineer-
ing, Hangzhou Dianzi University, Hangzhou 310018, PR China.
Tel./fax: þ86 0571 87713542.
nn
Corresponding author. Tel.: þ 86 25 83587252; fax: þ86 25 83587220.
E-mail addresses: dmy2014@hdu.edu.cn (M. Ding),
chhlu@126.com (C. Lu).
approaches have been adopted to synthesize inorganic func-
tional materials with well-defined morphologies, such as molten
salt, solvothermal, sol–gel, coprecipitation, and hydrothermal
methods [11–16]. Among them, the hydrothermal method has
proven to be an effective and convenient process for synthesiz-
ing various inorganic materials with diverse shapes and sizes.
Lanthanide-doped upconversion (UC) materials have arose
increasing research interest because of their potential applications
in the fields of compact solid-state lasers [17], optical telecom-
munications [18], three-dimensional displays [19,20], solar cells
[21,22], photocatalysis [23,24], and especially biological labeling,
imaging, and therapy [25–27]. Until now, a variety of host
materials including oxides [28,29], oxyfluorides [6,30], fluorides
[8,31], and chloride [32,33], have been reported to be host lattices
for performing multicolor UC emissions. Among them, hexago-
nal NaYF4 (β-NaYF4) is regarded as excellent host matrix for

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
(Ln3 þ ), owing to its low photon energy, low nonradiative decay
rates, and high radiative emission rates [34]. To date, many
efforts are devoted to synthesizing lanthanide-doped β-NaYF4
nano- and microcrystals with various morphologies, such as
nanowires, nanorods, nanotubes, microtubes, microrods, micro-
spheres, microdisks, and microplates [12,35–37]. However, little
has been done on the systematic investigation of the morphology-
and size-dependent UC luminescence properties. Understanding
how the UC luminescence properties change with particle shape
and size is of important significance in the design of highly
efficient UC materials. In addition, the mechanism underlying the
phase and morphology evolution of NaYF4 crystals under the
external conditions is still not very clear. Therefore, there is a
further need to understand the dynamic process governing nuc-
leation and growth of the complex fluorides.
In this paper, uniform and well-defined β-NaYF4 microcrys-
tals with various morphologies, such as microtubes, microrods,
microplates, microprisms, and submicrorods, have been success-
fully synthesized through a facile hydrothermal process. The
effects of molar ratios of trisodium citrate (Na3Cit) to Y3 þ and
pH values in the initial solution on the final morphology and
size have been investigated in detail. Tanking β-NaYF4 micro-
prisms as a typical example, the possible formation mechanism
for the phase and morphology evolution process of β-NaYF4 has
been proposed. Finally, the upconversion luminescence proper-
ties of the as-obtained β-NaYF4:Yb3 þ /Er3 þ microcrystals with
different shapes are investigated to discuss the relationship bet-
ween luminescence intensities and particle morphologies.
2. Experimental section
2.1. Materials
All chemicals are of analytical grade and were used without
further purification. YCl3  6H2O (99.99%), YbCl3.6H2O (99.99%),
ErCl3  6H2O (99.9%) were purchased from Beijing Founde Star
Science & Technology Co., Ltd. (China). NaF (98%), C6H5
Na3O7.2H2O (99%) were provided by Sinopharm Chemical Rea-
gent Co., Ltd. (China).
2.2. Synthesis
In a typical procedure for the synthesis of β-NaYF4, 2 mmol
YCl3  6H2O were firstly dissolved in 10 mL H2O with magnetic
stirring to form rare earth chloride solution. Then this solution
was added into 20 mL aqueous solution containing 2 mmol tri-
sodium citrate (Na3Cit) to form the metal–citrate complex. After
vigorous stirring for 30 min, 30 mL aqueous solution containing
12 mmol of NaF was introduced into the above solution. After
additional agitation for 15 min, the as-obtained mixing solution
was transferred into a Teflon bottle held in a stainless steel
autoclave, sealed, and maintained at 220 1C for 24 h. As the
autoclave was cooled to room temperature naturally, the pre-
cipitates were separated by centrifugation, washed with deionized
water and ethanol in sequence, and then dired in air at 80 1C for
12 h. In addition, different molar ratios (0, 2:1, 1:1, 2:1, 4:1 and
8:1) of Cit3 :Y3 þ , pH values in the reaction solution (3, 5, 7
and 9), and hydrothermal times (3, 6 and 12 h) were selected to
investigate the effects of these factors on the morphologies and
UC luminescence properties of the final products. The pH value
of the mixing solution was adjusted to a specific value by adding
NaOH solution (1 M) or HCl solution (1 M).
2.3. Characterization
Powder X-ray diffraction (XRD) measurements were per-
formed on a ARL X' TRA diffractometer at a scanning rate of
10 1/min in the 2θ range from 101 to 801 with Cu Kα radiation
(λ=0.15406 nm). SEM micrographs were obtained using a
field emission scanning electron transmission microscope (FE-
SEM, SU8010, Hitachi). Transmission electron microscopy
(TEM) were recorded on JEM-200CX with a field emission
gun operating at 200 kV. Images were acquired digitally on a
Gatan multiple CCD camera. UC emission spectra were
recorded with a Jobin Yvon FL3-221 fluorescence spectro-
photometer equipped with a 980 nm laser diode Module
(K98SA3M-54W, China) as the excitation source. All the
measurements were performed at room temperature.
3. Results and discussion
It is generally accepted that not only the intrinsic structure but
also a series of external factors, including reaction temperature,
time, pH value, and organic additives, have dramatic influence on
the crystallization process and shape evolution of the final crystals
in a solution-based system [38,39]. In our previous study, it is
found that the molar ratios of NaF–Y3 þ can strongly control the
phase and morphology of the as-synthesized β-NaYF4 products
[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
in the initial solution on the phases and morphologies of the final
products.
3.1. Effect of sodium citrate content
As we all known, organic additives play significant roles in
various solution-phase synthetic processes by controlling nuclea-
tion, crystallization, and growth of crystalline materials [40].
Here, we focus our attention on the important influence of the
Cit3 /Y3 þ molar ratios on the phase and morphology of the final
products. Fig. 1 shows the corresponding XRD patterns of the
samples synthesized at 220 1C for 24 h with different molar ratios
of Cit3 –Y3 þ . As shown, the diffraction peaks of all the
products can be well indexed to a hexagonal phase of NaYF4
with lattice constants a¼ 0.596 nm and c¼ 0.353 nm, according
to JCPDS card no. 28-1192 [41]. The results reveal that pure β-
NaYF4 samples can be successfully synthesized with different
molar ratios of Cit3 :Y3 þ . Notably, the relative intensity of
diffraction peak changes with different Cit3 /Y3 þ molar ratios,
revealing the shape evolution of the as-synthesized β-NaYF4
crystals.
The representative FE-SEM images of β-NaYF4 samples
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-
NaYF4 are prone to growing into irregular structures with an
average length of 13.49 μm, as presented in Fig. 2a. The coarse
surface of these microparticles can be clearly seen from the
high-magnification image (inset in Fig. 2a). Once Na3Cit is
introduced into the reaction system, significant change happens
in the shape and size of the final products. When the molar ratio
of Cit3 :Y3 þ is 1:2, the morphology of the as-obtained sample
is the hexagonal microplates with concave centers, indicating
that the citrate ions are responsible for the obvious shape
transition. As shown in Fig. 2b, the mean size is calculated to be
about 0.81 μm in thickness and 2.23 μm in diameter. Although
the exact reason for this change is not very clear, the explanation
can be provided as follows. As we know, organic additives is
usually used as “shape modifier” to control the growth rate of
different crystal faces through modifying crystal growth dyna-
mically. As a surfactant molecule, citrate anions can selectively
adsorb on some crystal faces and decrease their growth rate,
resulting in a highly anisotropic growth. This phenomenon has
also been reported in the formation of ZnO nanoplates [36,42].
With the increase of Cit3 /Y3 þ molar ratio up to 1:1, the as-
obtained sample consists of hexagonal microrods with protrud-
ing centers, of which the average length is about 5.36 μm and
diameter is about 3.32 μm (Fig. 2c). The magnified SEM image
(Inset in Fig. 2c) shows a close-up review of one isolated
microrod, which clearly displays the crow-like top end of
hexagonal microrods. At higher molar ratio of 2:1, the as-
synthesized product presents hexagonal prism morphology with

Table 1
Summary of experimental parameters and corresponding morphologies and
dimensions of the productsa.

Sample Molar ratio Phase Morphology Length Diameter

Cit3  :Y3 þ (μm) (μm)

CY-1 0:1 β-NaYF4 Irregular particles 13.49 1.80

CY-2 0.5:1 β-NaYF4 Microplates with 0.81 2.23
concave centers
CY-3 1:1 β-NaYF4 Microrods with 5.36 3.32
crown-like ends
CY-4 2:1 β-NaYF4 Microprisms with 1.55 3.96
protruding centers
CY-5 4:1 β-NaYF4 Microprisms with 2.07 4.47
protruding centers
CY-6 8:1 β-NaYF4 Hexagonal 5.20 3.42
Fig. 1. XRD patterns for β-NaYF4 samples prepared with different molar microrods
ratios of Cit3  –Y3 þ : (a) 0 (without Cit3  ), (b) 0.5, (c) 1, (d) 2, (e) 4, and (f) 8.
The standard data of hexagonal NaYF4 (JCPDS no. 28-1192) is shown as a
a
All samples were hydrothermally treated at 220 1C for 24 h, NaF:
3þ
reference. Y ¼ 6:1, pH¼ 7.

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
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
corresponding sample has no obvious morphological change
except for the increase of the sizes to 2.07 μm in length and
4.47 μm in diameter. At the 8:1 M ratio of Cit3 :Y3 þ , the as-
obtained product is composed of uniform hexagonal microrods
with 3.42 μm in diameter and 5.40 μm in length. Based on the
above investigation, it can be concluded that the final shape of
the as-prepared products can be precisely tuned by changing the
molar ratio of Cit3 –Y3 þ . The corresponding morphologies
and dimensions of the final samples synthesized with different
Cit3  /Y3 þ molar ratios are summarized in Table 1.
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
(JCPDS no. 74-0911) and β-NaYF4 (JCPDS no. 28-1192) is given as a
reference.
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.
3.2. Effect of pH values.
It is well known that pH values have dramatic effect on the
crystal phase, morphology and size of the final products. Here,
we focus our attention on the effect of pH values in our
reaction system. Fig. 3 demonstrates the corresponding XRD
patterns of the samples synthesized at 220 1C for 24 h with
different pH values. At pH ¼ 3, the product consists of
preponderantly YF3 along with minor β-NaYF4, as displayed
in the XRD pattern (Fig. 3a). With the increase of pH value
from 5 to 9, all the peaks of three samples are characteristic of
a pure β-phase of NaYF4. Careful observation reveals that the
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
microplates is a little more protruding than that of the edge
parts. Upon a further increase of pH value to 9, the sample is
of a great deal of submicrorods with hexagonal prismatic
 M. Ding et al. / Ceramics International 41 (2015) 7411–7420 7415

Table 2 as presented in Fig. 5b. At a reaction time of 12 h, α-NaYF4

Summary of experimental parameters and corresponding morphologies and disappears thoroughly and pure β-NaYF4 can be successfully
dimensions of the productsa.
synthesized (Fig. 5c). The above results reveal that the phase
Sample pH Phase Morphology Length Diameter transition (α-β ) takes place along with the reaction time.
values (μm) (μm) At the meantime, the morphology evolution of NaYF4
crystals is carefully investigated by quenching the reaction at
H-1 3 YF3 þβ-NaYF4 Nanoparticles – –
different time intervals. Fig. 6 shows the FE-SEM and TEM
H-2 5 β-NaYF4 Microrods with 2.91 1.73
concave centers images of the different intermediate products obtained at diff-
H-3 7 β-NaYF4 Microplates with 1.31 3.68 erent reaction stage. Notably, the three samples exhibit obser-
protruding centers vably different morphologies during the crystal growth. At a
H-4 9 β-NaYF4 Submicrorods with 0.92 0.71 short reaction time of 3 h, the sample consists of spherical
protruding centers
particles with a mean diameter of 38 nm (Fig. 6a and b). With
All samples were hydrothermally treated at 220 1C for 24 h, NaF:Y3 þ ¼6:1,
a the further reaction, from 3 h to 6 h, the product is the mixture
Cit3  :Y3 þ ¼ 1:1. of mostly α-NaYF4 and minor β-NaYF4, which is composed of
hexagonal microprisms of 2.8 μm in diameter and 1.2 μm in
thickness as well as a small amount of α-NaYF4 nanoparticles
(Fig. 6c). Careful observation reveals that a small amount of
nanoparticles are attached on the surface of microprisms
(Fig. 6d). On aging for a longer period up to 12 h, α-NaYF4
nanoparticles disappear completely and only β-NaYF4 micro-
prisms can be observed clearly (Fig. 6e and f). Based on the
time-dependent results, a possible phase and shape evolution
mechanism is shown in Fig. 6g and depicted as follows. At the
beginning, the Cit3 anions and Y3 þ cations are mixed with the
desired amount, resulting in the formation of the Y3 þ –Cit3 
complexes via strong coordination interaction. Under the con-
ditions of high temperature and high pressure, the chelating
ability of the complexes could be weakened and the Y3 þ ions
can be released into the reaction system gradually. During this
progress, the Na þ , Y3 þ , and F  ions can diffuse rapidly
throughout the reaction solution to generate small nuclei. At a
Fig. 5. XRD patterns for NaYF4 samples (NaF/Y3 þ ¼ 6, Cit3  /Y3 þ ¼4) as a short reaction time, these nuclei can only grow into irregular α-
function of reaction time. (a) 3 h, (b) 6 h and (c) 12 h. The standard data of NaYF4 nanoparticles. But in the present environment, these α-
cubic NaYF4 (JCPDS no. 77-2042) and hexagonal NaYF4 (JCPDS no. NaYF4 nanoparticles are unstable and may be susceptible to
28-1192) is given as a reference. slow phase transformation (α-β). A dissolution–renucleation
process takes place and more stable β-NaYF4 microprisms are
structure, whose mean length and diameter are 0.92 μm and formed. Obviously, the phase transformation directly leads to
0.71 μm, respectively. The changes in morphology and dimen- the dramatic change in the morphology of the samples, which
sion of the products prepared at different pH values are listed can be ascribed to different characteristic unit cell structures of
in Table 2. these seeds [38]. The cubic α-NaYF4 seeds have isotropic
unit cell structure, leading to an isotropic growth of particles.
Thus spherical-like nanoparticles are observed in order to
3.3. Effect of reaction time minimize the surface energy of crystallographic planes. Differ-
ent cubic phase, hexagonal β-NaYF4 seeds have anisotropic unit
To shed light on the phase and shape evolution of hexagonal cell structure, which can induce to anisotropic growth along
NaYF4 crystals, taking β-NaYF4 microprisms (CY-5) as an crystallographic reactive directions to form hexagonal-shaped
example, detailed time-dependent experiments were carefully structures.
investigated under similar reaction conditions. Fig. 5 shows the
XRD patterns of the intermediates synthesized at different 3.4. Growth mechanism of β-NaYF4 microcrystals
reaction intervals as well as standard data of cubic NaYF4 (α-
NaYF4) and hexagonal NaYF4 (β-NaYF4) phases for compar- It is well known that the crystal growth and shape evolution
ison. As shown, the products display distinctively different process could be significantly influenced by external experimental
XRD patterns at different reaction times. At a short reaction conditions and inherent structures. In our experiments, the mor-
time of 3 h, the as-obtained sample exhibits diffraction patterns phologies and dimensions of the as-synthesized samples can be
corresponding to cubic-system NaYF4 (JCPDS no. 77-2042) controlled through tuning sodium citrate dosage and pH value in
(Fig. 5a). With the reaction proceeding for 6 h, a new hexagonal the initial solution. Based on a series of experimental results, the
(β) NaYF4 phase emerges in addition to the cubic NaYF4 phase, possible formation mechanism of β-NaYF4 microcrystals with
7416 M. Ding et al. / Ceramics International 41 (2015) 7411–7420

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.

various morphologies and sizes is shown in Scheme 1 and

described as follows.

3.4.1. Effect of sodium citrate amount

In our study, it can be reasonably inferred that Na3Cit has two
major effects on adjusting the final morphologies of β-NaYF4
microcrystals. First, it is used as well-known chelating agent to
slow down the nucleation and subsequent growth of hexagonal
NaYF4 crystals, which has already been well demonstrated.
Second, as a capping agent, sodium citrate has dramatic effects
on the anisotropic growth of β-NaYF4 crystals by selectively
absorbing on the different crystal facets, leading to a diverse
outlook of hexagonal NaYF4 microcrystals. Taking a fundamen-
tal understanding about the general principle of crystal growth is
very helpful for us to explain the morphology change of β-NaYF4
products synthesized with different Cit3 /Y3 þ molar ratios. As Scheme 1. Schematic illustration for the possible formation and subsequent
shape evolution of β-NaYF4 microcrystals with various morphologies under
we known, the β-NaYF4 crystals with hexagonal prism shape has
different experimental conditions.
four crystal axes (assistant axes and principle axis) and eight
crystal facets (top/bottom planes and side planes), as shown in
inset of Scheme 1 [43]. When sodium citrate is introduced into (1100)), which induces to a relative enhancement of the growth
the reaction system, the Cit3– anions preferentially absorb on the rate in the [0001] direction, leading to thicker hexagonal β-NaYF4
top/bottom planes ({0001}), which can lower the surface energy, prisms. With the further increase of sodium citrate dosage, the
resulting in the slower growth rate along [0001] direction and growth rate in the [0001] direction is a little faster than that in the
subsequent the formation of hexagonal microprisms. With the [1100], [0110], and [1010] directions because of larger scale of
increase of sodium citrate amount, some Cit3 anions cap on the sodium citrate capped on the six side planes. As a result, the
six side planes ((1010), (1010), (0110), (0110), (1100), and length of the as-synthesized microparticles increases, as well as
 M. Ding et al. / Ceramics International 41 (2015) 7411–7420 7417

the morphology of sample changes from hexagonal microprisms
to hexagonal microrods.
3.4.2. Effect of pH value in initial solution
As one of external factors, pH value in initial solution plays a
significant role in the crystal growth of β-NaYF4 crystals. It is
generally accepted that the differences of pH values can induce
directly to the different adsorption ability of Cit3 anions on the
different crystal facets, consequently resulting in various mor-
phologies of β-NaYF4 microcrystals. At low pH value (pHo7),
Cit3 ions could partly combine with H þ ions in the acid
environment, leading to the decrease of the complexing ability of
Cit3 –Y3 þ to some degree. As a result, the decrease in the
capping ability of Cit3 on {0001} planes results in faster growth
rate along [0001] direction than that along other directions.
Subsequently, β-NaYF4 microrods can be obtained. However, as
the pH value increases gradually, the capping effect of Cit3 on
{0001} facets is enhanced. Consequently, the slower growth rate
along [0001] direction leads to the formation of microprisms.
Interestingly, the capping ability of sodium citrate on all the
crystal facets increases significantly with the increment of pH
values, resulting in the decrease of crystal growth rate in all the
directions. So, the diameter and length of particles decrease
systematically and β-NaYF4 submicrorods can be obtained.
3.5. UC luminescence properties
Up till now, hexagonal NaYF4 (β-NaYF4) has been regarded
as efficient host lattice for multicolor UC process because of its
lower photon energy. However, the relative luminescent inten-
sities of lanthanide-doped β-NaYF4 products with various
morphologies are different from each other. The exact reason
for the difference is still not very clear. Herein, we select Yb3 þ /
Er3 þ as co-doped ions pairs to investigate the UC luminescence
properties of β-NaYF4 samples with different morphologies.
Remarkably, the crystal structure and morphology of the final
product could not be changed by the doping with small amount
of lanthanide ions. Yb3 þ /Er3 þ co-doped β-NaYF4 crystals with
four shapes, including submicrorods (H-4), microplates (CY-2),
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
properties (For clarity, these four samples are denoted as sample
S1, S2, S3, and S4, respectively). Fig. 7 shows the UC emission
spectra of β-NaYF4: 20%Yb3 þ , 2%Er3 þ samples (S1, S2, S3,
and S4) under 980 nm laser excitation. As presented in Fig. 7a,
the green emission at 520 nm and 539 nm can be assigned to the
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/
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 Fig. 7b. It is found that the relative intensities of S1, S2, S3,
and S4 differ from each other under the same measurement
conditions. As shown in Fig. 7b, the ranking of the emission
intensities is listed as follows: S1oS2oS3oS4. Evidently,
β-NaYF4:20Yb3 þ , Er3 þ microrods (S4) present the strongest
emission intensity, while β-NaYF4:20Yb3 þ , Er3 þ submicrorods
(S1) have the lowest emission intensity. Thereinto, the relative
intensity of the former is about 4 times higher than that of the
latter. In order to visualize the difference in the UC luminescence
intensities of the four samples, the photographs of UC lumines-
cence of S1, S2, S3, and S4 under 980 nm laser excitation are
provided in Fig. 7c. The yellow emission of the four samples with
different intensities can be clearly seen by naked eyes. Remark-
ably, S4 exhibits the strongest luminescence intensity, agreeing
with the results in Fig. 7a and b. Simultaneously, the emission
decay profiles of 4F9/2-4I15/2 transition (652 nm) for the four
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
single exponential function: I(t)¼ I0 þ A1 exp( t/τ), where I and
I0 are the luminescence intensities at time t and 1, τ is the
lifetime and A1 is a constant [45]. The lifetimes of the 4F9/2 state
for S1, S2, S3, and S4 are determined to be 126.8, 203.2, 268.6,
and 327.5 μs, respectively. Obviously, the variation tendency of
the lifetimes agrees well with the change of UC luminescence
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.
Although the exact reason for the morphology-dependent
UC luminescence is not very clear so far, the explanation for
this difference can be provided as follows. It is well known
that the experimental lifetime of an excited state (τm) is
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
around Er3 þ ions, it is reasonably assumed that the difference
in the morphologies of β-NaYF4: Yb3 þ /Er3 þ samples has
little effect on the radiative decay rate of the transition. So, the
change of measured lifetimes can be ascribed to the different
nonradiative rate. As we known, the nonradiative rate is relate
to the ratio of surface area to volume, namely specific surface
area. The large specific surface area usually introduces a large
amount of surfaces defects into β-NaYF4: Yb3 þ /Er3 þ micro-
crystals, which can induce to the increment of nonradiative
rate, resulting in the decrease of UC luminescence intensity.
Therefore, the difference in UC luminescence intensities of β-
NaYF4:Yb3 þ /Er3 þ particles with different morphologies can
be attributed to their different specific surface areas. The
specific surface areas of S1, S2, S3, and S4 are calculated
and shown in Table S1 (Supporting information). Compared to
submicrorods (S1), microplates (S2), microprisms (S3), β-
NaYF4: Yb3 þ /Er3 þ microrods (S4) have smallest surface area,
which may lead to the strongest luminescence intensity.
4. Conclusion
In summation, uniform β-NaYF4 microcrystals with various
morphologies and sizes have been successfully synthesized by
simply tuning the molar ratios of Cit3 –Y3 þ and pH values in
the initial solution. The phase, morphology evolution for the as-
synthesized samples under different reaction conditions were syst-
ematically investigated, and the mechanism of how the external
factors influence the anisotropic growth of hexagonal NaYF4 cry-
stals has been proposed. Based on a series of time-dependent
experiments, a possible formation mechanism for β-NaYF4 sam-
ples with diverse architectures have been presented. More imp-
ortantly, the UC luminescence properties of β-NaYF4: 20%Yb3 þ ,
2%Er3 þ products with different morphologies and sized were
investigated in detail. The results reveal that the UC luminescence
properties of Yb3 þ /Er3 þ co-doped β-NaYF4 samples are sig-
nificantly related to its shapes and sizes.
Acknowledgment
The project was financially supported by Zhejiang Province
Science Foundation of China (LQ14E020006), the Scientific
Research Foundation of Hangzhou Dianzi University
(KYS205614041), the National Natural Science Foundation
of China (61372025 and 21271170), and a Project funded by
the Priority Academic Program Development of the Jiangsu
Higher Education Institutions (PAPD).
Appendix A. Supporting information
Supplementary data associated with this article can be found
in the online version at http://dx.doi.org/10.1016/j.ceramint.
2015.02.054.
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