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IOP PUBLISHING NANOTECHNOLOGY
Nanotechnology 19 (2008) 345606 (5pp) doi:10.1088/0957-4484/19/34/345606

An efficient and user-friendly method for

the synthesis of hexagonal-phase
NaYF4:Yb, Er/Tm nanocrystals with
controllable shape and upconversion
fluorescence
Zhengquan Li1 and Yong Zhang2,3,4
1
Singapore-MIT Alliance, National University of Singapore, 117576, Singapore
2
Division of Bioengineering, Faculty of Engineering, National University of Singapore,
7 Engineering Drive 1, 117574, Singapore
3
Initiative of Nanoscience and Nanotechnology, National University of Singapore,
9 Engineering Drive 1, 117576, Singapore

E-mail: biezy@nus.edu.sg

Received 4 March 2008, in final form 10 June 2008

Published 16 July 2008
Online at stacks.iop.org/Nano/19/345606

Abstract
Hexagonal-phase NaYF4 :Yb, Er/Tm nanocrystals are the best IR-to-visible upconverting
materials to date, but user-friendly methods for making pure hexagonal-phase NaYF4 :Yb,
Er/Tm nanocrystals with upconversion fluorescence are still lacking. Most of the methods
reported so far require excess fluoride reactants in a high-temperature reaction which are very
unfriendly to users and raise safety concerns. In this work, an efficient and user-friendly method
was developed for the synthesis of uniform hexagonal-phase NaYF4 :Yb, Er/Tm nanocrystals
with upconversion fluorescence, by forming small solid-state crystal nuclei and further growth
and ripening of the nuclei. NaYF4 :Yb, Er/Tm nanoplates, nanospheres and nanoellipses were
also selectively produced by varying the concentration of the surfactant. All the nanocrystals
showed strong upconversion fluorescence, and fluorescence from the nanoplates was observed
even when the laser power density was reduced to about 50 mW cm−2 . These nanocrystals have
great potential for use in biology and medicine as fluorescent labels or imaging probes.
S Supplementary data are available from stacks.iop.org/Nano/19/345606

1. Introduction under short wavelength radiation, which decreases the

Conventional down-conversion fluorescent labelling materials
such as organic dyes and semiconductor nanocrystals show
visible fluorescence under excitation of UV or blue light.
These single-photon fluorescent materials emit lower-energy
photons after absorbing higher-energy UV or visible photons.
Their disadvantages include low light penetration depth
and possible severe photo-damage to living organisms.
Furthermore, many biological samples show auto fluorescence
4 Address for correspondence: Division of Bioengineering, Faculty of
Engineering, Blk, E3A-04-15, National University of Singapore,
7 Engineering Drive 1, 117574, Singapore.
sensitivity of detection [1, 2]. Upconversion fluorescent
nanoparticles convert near-infrared (NIR) light to visible light
by emitting higher-energy photons after absorbing lower-
energy photons [3, 4]. Compared to down-conversion
fluorescent materials, upconversion nanoparticles have the
following advantages: high light penetration depth in tissues,
no photo-damage to living organisms, weak autofluorescence
from cells or tissues, low background light and high sensitivity
for detection [3, 4]. To date, hexagonal-phase NaYF4 :Yb,
Er/Tm crystals have been demonstrated to be the best NIR-to-
visible upconverting materials [5]. It is important to develop
efficient and convenient methods for synthesizing high quality

0957-4484/08/345606+05$30.00 1 © 2008 IOP Publishing Ltd Printed in the UK

Nanotechnology 19 (2008) 345606
and monodispersed NaYF4 :Yb, Er/Tm nanocrystals for various
biomedical applications.
Some efforts have been made in the synthesis of
hexagonal-phase NaYF4 nanocrystals in recent years.
However, annealing cubic-phase nanocrystals or long-time hy-
drothermal treatment may produce hexagonal-phase crystals,
but mixed crystal phases with large size and non-uniformity
are often produced [6, 7]. A liquid–solid reaction in or-
ganic solvent has been used to obtain oil-dispersed hexagonal-
phase NaYF4 nanocrystals, but it is difficult to remove exces-
sive NaF reactants. Very recently, thermal decomposition of
mixed trifluoroacetates has been used to produce high qual-
ity α - and β -phase NaYF4 nanocrystals [8–10]. However, py-
rolysis of trifluoroacetates produces very toxic fluorinated and
oxyfluorinated carbon species, and as such all the experiments
must be carefully carried out in extremely ventilated chem-
ical hoods [9]. Although hexagonal-phase NaYF4 crystals
are more thermodynamically stable than cubic-phase crystals,
cubic-phase crystals are more easily produced in the solution.
The methods developed so far for obtaining pure hexagonal-
phase NaYF4 nanocrystals all require excessive amounts of
fluoride reagents to react at high temperatures (160–330 ◦ C),
while cubic-phase impurities are usually produced with stoi-
chiometric amounts of fluoride reactants in the same condi-
tions. Use of excessive fluoride reactants (HF, NH4 F, NH4 HF2 ,
NaF, CF3 COOH, etc) at high temperatures may raise some
safety concerns, because fluoride reactants have a low decom-
position temperature and are readily hydrolysed to produce HF
gas or fluorinated species.
It would be a good idea to convert all the reactive fluoride
reactants to solid-state products (small crystal nuclei) before
the subsequent crystal growth/ripening. Our strategy is to
consume a stoichiometric amount of fluoride reagents entirely
at room temperature to form small solid NaYF4 crystal nuclei,
and then increase the temperature to improve the quality and
uniformity of the nanocrystals (at this time there are no fluoride
reagents in the solution). In this work, an efficient and user-
friendly method was developed to obtain pure hexagonal-
phase NaYF4 :Yb, Er/Tm nanocrystals. Plate-like, sphere-
like and ellipse-like nanocrystals were selectively synthesized
by varying the surfactant concentration. The as-prepared
nanocrystals showed strong upconversion fluorescence, and
the fluorescence from the plate-like nanocrystals could be
observed even when the laser power density was reduced to
about 50 mW cm−2 .
2. Experimental section
2.1. Synthesis of NaYF4 :Yb, Er/Tm nanocrystals
All the chemicals were purchased from Sigma-Aldrich and
used without further purification. NaYF4 :18%Yb, 2%Er plate-
like nanocrystals were synthesized following this protocol:
YCl3 (0.1562 g), YbCl3 (0.0503 g) and ErCl3 (0.0055 g)
were mixed with 3 ml oleic acid (OA) and 17 ml octadecene
(ODE) in a 50 ml flask and heated to 160 ◦ C to form
a homogeneous solution, and then cooled down to room
temperature. 10 ml methanol solution containing NaOH
2
Z Li and Y Zhang
(0.01 g) and NH4 F (0.148 g) were slowly added into the flask
and quickly formed solid-state precipitates in the solution. The
mixed solution was stirred for 30 min, and ensured that all
fluoride has consumed completely. Subsequently, the solution
was slowly heated to evaporate methanol, degassed at 100 ◦ C
for 10 min, and then heated to 300 ◦ C and maintained for 1 h
under argon atmosphere. After the solution was cooled down
naturally, nanocrystals were precipitated from the solution with
ethanol and washed with ethanol/water (1:1 v/v) for three
times. Synthesis of NaYF4 :18%Yb, 2%Er sphere-like and
ellipse-like nanocrystals were performed following a similar
protocol with the amount of oleic acid changed to 6 ml and
10 ml, respectively. Different shaped NaYF4 :25%Yb, 0.3%Tm
nanocrystals were also synthesized by changing the molar ratio
of the reagents (YCl3 :YbCl3 :TmCl3 ) to 74.7:25:0.3. Some
other ligands/solvents could also be used to replace OA and
ODE in the above process. For example, trioctylphosphine
oxide (TOPO) and stearic acid could be used as the ligands to
replace OA, and eicosene and trioctylamine could be used as
high-boiling solvents to replace ODE, respectively. OA/ODE
were chosen due to their cost effectiveness, biocompatibility
and efficiency, which have been used in the synthesis of
quantum dots [11].
2.2. Characterization
Transmission electron microscopy (TEM) images were
recorded on a JEOL 2010F transmission electron microscope.
High-resolution TEM (HRTEM) and energy-dispersive x-ray
analysis (EDXA) were carried out using a JEOL 3010F TEM.
X-ray powder diffraction (XRD) was performed on a Siemens
D5005 x-ray powder diffractometer equipped with Co Kα
radiation (λ = 1.788 97 Å). Fluorescence spectra were
recorded on a Hitachi F-500 fluorescence spectrophotometer
equipped with a near-infrared (NIR) laser with emission at
980 nm.
3. Results and discussion
The shapes of the NaYF4 :Yb, Er/Tm nanocrystals prepared by
different amounts of OA was demonstrated in figure 1. TEM
images of the nanocrystals in figures 1(A) and (B) showed
that, when 6 ml OA was added to the precursor solution, the
nanocrystals were polyhedral in shape with a uniform size of
21 nm in diameter and could be self-assembled on the grid
surface with a long range order. The crystal lattice of the
(100) plane was shown in the high-resolution TEM image in
figure 1(C). Elliptical nanocrystals with a width of 17 nm
and a length of 22 nm were obtained by further increasing
the amount of OA to 10 ml in the experiment, as shown in
figure 1(D). When the amount of OA used was decreased to
3 ml, the TEM images in figures 1(E) and (F) showed that the
NaYF4 :Yb, Er/Tm nanocrystals were uniform in size with a
hexagonal plate-like shape. The nanoplate consisted of a flat
hexagonal top surface with an edge length of ∼30 nm and six
rectangular side surfaces with an area of ∼30 nm × 45 nm.
A two-dimensional crystal lattice of the nanoplate was shown
in the high-resolution TEM image in figure 1(G), indicating
Nanotechnology 19 (2008) 345606 Z Li and Y Zhang

A B C D

E F G H

Figure 1. TEM images of NaYF4 :Yb, Er nanospheres ((A)–(C), at different magnifications), nanoellipses (D), and nanoplates ((E)–(G), at
different magnifications) and Fourier transform of the TEM image in G (H).

A
(201)
(101)

(211)
(110)

(300) (002)
(100)

(111)
(200)

(210)

(102)

(112)
(220)

10 20 30 40 50 60 70 80
2θ (degree) Figure 3. Illustration of the formation of NaYF4 :Yb, Er/Tm
nanoplates, nanospheres and nanoellipses.
B

corresponding to cubic phases or other impurities were

Figure 2. XRD pattern (A) and EDXA spectrum (B) of NaYF4 :Yb,
Er nanoplates. (Note that Co Kα radiation was used for the XRD
measurement.)
its high crystallinity. The interplanar spacing of all the six
{100} planes was 5.2 Å, corresponding to the (100) plane of
NaYF4 crystals. The Fourier transform of the TEM image of a
single nanoplate in figure 1(H) further demonstrates a perfect
hexagonal crystal structure and uniformity of the nanoplates.
The x-ray diffraction (XRD) pattern and energy-dispersive
x-ray analysis (EDXA) result of the NaYF4 :Yb, Er nanoplates
is shown in figure 2. All the diffraction peaks could be
indexed to a pure phase-hexagonal NaYF4 crystal structure
(JCPDS standard card no. 28-1192). No diffraction peaks
observed, indicating the success in the synthesis of pure
hexagonal-phase NaYF4 nanocrystals via this convenient and
user-friendly approach. The EDXA result showed that all the
elements in the nanocrystals could be detected, including the
co-doped lanthanides Yb and Er. The amount of Y, Yb and
Er was quantified by using inductively coupled plasma-atomic
emission spectrometry (ICP-AES) and the Y/Yb/Er molar
ratio determined as 79.2/18.6/2.2, close to the stoichiometric
ratio for the chloride reactants used in the experiment.
The formation of the nanocrystals was studied by
monitoring the growth of the nanocrystals as illustrated in
figure 3. The reagents LnCl3 (Ln = Y, Yb, Er, Tm) were
dissolved in mixed OA/ODE at 160 ◦ C and a transparent
solution was formed. After the solution was cooled down
to room temperature, the NH4 F and NaOH immediately
reacted with LnCl3 and produced a yellow turbid solution with
amorphous NaYF4 crystal nuclei as shown in figure 3(A).
All the NH4 F was consumed completely. After methanol
was evaporated, the high-boiling ODE/OA mixture was heated
to 300 ◦ C and amorphous NaYF4 crystal nuclei started to
grow. Irregular NaYF4 nanocrystals were found after heating

3
Nanotechnology 19 (2008) 345606 Z Li and Y Zhang

at 300 ◦ C for 20 min, and uniform NaYF4 nanocrystals were

obtained after heating for 1 h. These small nanocrystals A
were eventually grown into uniform nanocrystals with regular
shapes, suggesting that the Ostwald ripening mechanism
was dominant in the growing process [12]. If 3 ml OA
was initially added to the solution, hexagonal nanoplates
were formed (figure 3(B)), while spherical nanocrystals were
B
formed if more than 5 ml OA was used (figure 3(C)). The
spherical nanocrystals were further evolved into nanospheres
or nanoellipses respectively if 6 ml or 10 ml OA were initially
added into the solution. Different from other methods for
synthesis of fluoride nanocrystals in which excess amount of
reactive fluoride is required, this method provides a more user-
350 400 450 500 550 600 650 700
friendly synthetic condition. Wavelength (nm)
The formation process also showed that the concentration
of the ligand OA affected the growth rates of hexagonal- C D E F
phase NaYF4 :Yb, Er/Tm nanocrystals in different directions.
With a low ligand concentration, the nanocrystals grew
faster in the [100] direction than the [001] direction and,
as such, nanoplates were produced. With the increase in
OA concentration, the growth rates in both directions were
comparable and polyhedral nanocrystals were produced. The
growth rate in the [001] direction could be faster than in the
[100] direction with an even higher ligand concentration, so Figure 4. Photoluminescence spectra of NaYF4 :25%Yb, 0.3%Tm
elliptical nanocrystals were formed. (A) and NaYF4 :18%Yb, 2%Er (B) nanoplates (black), nanospheres
(red) and nanoellipses (green), and photographs of the nanospheres
Fluorescence spectra of 1 wt% transparent solution of in hexane (1 wt%) under excitation of an NIR laser (980 nm): total
NaYF4 :Yb, Er/Tm nanocrystals in hexane were measured at upconversion fluorescence of NaYF4 :25%Yb, 0.3%Tm
room temperature and given in figure 4. The emission peaks of nanospheres (C), total upconversion fluorescence of NaYF4 :18%Yb,
the NaYF4 :Yb, Er nanocrystals at 407, 521, 539 and 651 nm 2%Er nanospheres (D) and fluorescence of NaYF4 :18%Yb, 2%Er
were due to the transitions between energy levels 4 H9/2 , 4 H11/2 , nanospheres passing through red (E) or green (F) filters.
4
S3/2 and 4 F9/2 to 4 I15/2 of Er3+ . Two emission peaks of the
NaYF4 :Yb, Tm nanocrystals at 450 and 479 nm were due
to 1 D2 → 3 F4 and 1 G4 → 3 H6 transitions of Tm3+ [4]. wt% concentration in solution) [13]. Photographs showing the
The nanoplates showed stronger upconversion fluorescence strong fluorescence from 1 wt% solutions of the NaYF4 :Yb, Er
emission compared to nanospheres and nanoellipses. The main and NaYF4 :Yb, Tm nanospheres were also given in figure 4.
possible reason could be that the nanoplates have a relatively
larger size and smaller surface and thus less surface defects
which are usually fluorescence quenchers. On the other hand,
the surface OA absorption could also affect the fluorescence of 4. Conclusion
the nanocrystals because organic ligands with high energy C–H
or C–C vibrations are also fluorescence quenchers for nearby In summary, an efficient and user-friendly method was
lanthanide ions. The nanospheres and nanoellipses have more developed to synthesize pure hexagonal-phase NaYF4 :Yb,
surface area than the nanoplates, thus have more potential to Er/Tm nanocrystals with controllable shape and strong
absorb OA on their surface. The fluorescence from all the upconversion fluorescence. Different from previous methods
above nanocrystals could be observed by eye when excited
which required excess amounts of fluoride reactants in high-
by a commercial CW IR laser with emission at 980 nm. It
temperature reaction, this new method is based on diffusion-
is worth noting that strong fluorescence from the nanoplates
limited growth of the nanocrystals. All the fluoride reagents
could still be observed even when the power density of the laser
was reduced to about 50 mW cm−2 . To our knowledge, this in the solution have turned to solid-state nuclei at room
is the best NaYF4 :Yb, Er/Tm nanocrystal with the strongest temperature before further evolution of the nanocrystals at
upconversion fluorescence emission so far. Previous reports higher temperatures, and as such it provides a more user-
revealed that hexagonal-phase NaYF4 :Yb, Er powders showed friendly synthetic condition. Furthermore, NaYF4 :Yb, Er/Tm
4.4 times stronger upconversion fluorescence than cubic-phase nanoplates, nanospheres and nanoellipses were produced
powders, and the difference is even bigger when the size of by simply changing the ligand concentration. All these
the powders is of nanoscale order. The fluorescence intensity nanocrystals showed strong upconversion fluorescence, and
of the hexagonal NaYF4 :Yb, Er nanoplates is more than fluorescence from the nanoplates could still be observed even
80 times higher than that of the cubic PVP/NaYF4 :Yb, Er when the power density of the laser was reduced to about
nanocrystals we have previously reported (both samples with 1 50 mW cm−2 .

4
Nanotechnology 19 (2008) 345606
Acknowledgments
The authors would like to acknowledge the funding support
from an AcRF Tier 1 grant (WBS R-397-000-040-112) from
the Ministry of Education (MOE) and National University
of Singapore and a post-doctoral fellowship for ZL from
Singapore–Massachusetts Institute of Technology Alliance
(SMA). The authors also thank Dr Enyi Ye from the Institute
of Materials Research and Engineering (IMRE) for help with
the XRD experiments.
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