Published on Web 09/22/2009

Upconversion Luminescence of Monodisperse CaF2:Yb3+/Er3+ Nanocrystals

Fluorescent labeling materials have been attracting considerable nanocrystals were compared with those of NaYF4:Yb3+/Er3+
interest for their biological applications.1 However, conventional nanocrystals. The results indicate that CaF2 is a promising host
downconversion fluorescent materials, including organic dyes and material for producing desirable UC luminescence and has potential
semiconductor quantum dots, have their intrinsic limitations.1d,2 applications in fluorescent labels for biomolecules.
Furthermore, these downconversion fluorescent materials are excited
by ultraviolet (UV) or short wavelength visible (vis) radiation, which
have very limited penetration into tissues, strong autofluorescence,
and potential cytotoxic and carcinogenic effects.3 To solve these
problems above, the development of alternative biological lumi-
nescent labels through the use of up-converting rare-earth (RE)
nanophosphors has been carried out and sparked considerable
interest.4 It offers an attractive optical labeling technique in
biological studies without many of the constraints associated with
organic fluorophores and quantum dots. RE nanocrystals have sharp
absorption and emission lines, high quantum yields, long lifetimes,
and superior photostability.5 In particular, the upconversion (UC)
technique utilizes near-infrared excitation rather than UV excitation, Figure 1. (a) TEM image of CaF2:Yb3+/Er3+ nanocrystals, (b) magnified
thereby significantly minimizing background autofluorescence, image of CaF2:Yb3+/Er3+ nanocrystals, (c) HRTEM image of an individual
CaF2:Yb3+/Er3+ nanocrystal, and (d) XRD pattern of CaF2:Yb3+/Er3+
photobleaching, and photodamage to biological specimens. Up to nanocrystals.
now, many RE-doped nanomaterials have been prepared,6 and many
strategies have been developed for their application in diagnostic
and analytical pathology.7
Among various UC nanomaterials, fluorides are efficient hosts
for UC luminescence of RE ions due to their appropriate energy
phonons to produce strong UC fluorescence.8 Especially, NaYF4
is acknowledged as the most efficient UC host material at present.9
Previous investigations have shown that the UC luminescence in
RE doped NaYF4 strongly depends on the phase and particle
size.9,10 For example, the UC efficiency of green emission in
hexagonal NaYF4:Yb3+/Er3+ is ∼10 times stronger than that in cubic Figure 2. UC luminescence spectra of cubic CaF2:Yb3+(20%)/Er3+(2%)
NaYF4:Yb3+/Er3+, and again that of bulk cubic NaYF4:Yb3+/Er3+ and cubic NaYF4:Yb3+(20%)/Er3+(2%) nanocrystals dissolved in cyclo-
is ∼102-103 times stronger than that in nanosize cubic NaYF4.9 hexane excited with a 980 nm laser. Inset shows the luminescence
photograph of CaF2:Yb3+/Er3+ nanocrystals dissolved in cyclohexane under
However, compared with the cubic sample, hexagonal NaYF4 980 nm excitation.
nanocrystals usually have larger particle sizes. Therefore, it is of
vital importance to enhance the UC efficiency of the nanocrystals Figure 1a,b show the transmission electron microscopy (TEM)
with a smaller size. images of the as-synthesized CaF2:Yb3+/Er3+ nanocrystals. They
CaF2, a very important fluoride, has been used as an attractive are monodisperse, with a diameter of ∼7 nm. The high-resolution
host for phosphors with interesting up/down-conversion luminescent transmission electron microscopy (HRTEM) image of a single
properties.11 The edge of the fundamental absorption band in CaF2 nanoparticle is shown in Figure 1c. The measured lattice spacing
lies in the vacuum UV at ∼12 eV. CaF2 has a well-known fluorite is ∼0.27 nm, corresponding to the distance of the {200} planes of
structure, in which Ca2+ ions lie at the nodes in a face-centered the cubic CaF2. This image also reveals the single-crystal nature
lattice, while F- ones lie at the centers of the octants.12 In RE doped of the product. The corresponding XRD pattern is presented in
CaF2 nanocrystals, the substitution of a cation requires a negative Figure 1d, and the peaks matched very well with the standard cubic
ion for compensation, and therefore, some interesting luminescence CaF2:Yb3+(20%) crystal structure data (01-087-0976 in the JCPDS
properties can be expected. database). In addition, excessive NaF was also found in the XRD
Herein, we successfully prepared sub-10 nm monodispersed pattern.
CaF2:Yb3+/Er3+ nanocrystals according to our reported liquid-solid- Figure 2 shows the UC luminescence spectrum of the as-prepared
solution (LSS) strategy (Supporting Information).6e These as- CaF2:Yb3+/Er3+ nanocrystals in cyclohexane under 980 nm excita-
prepared nanocrystals not only can be transparently dispersed in tion. The spectral peaks correspond to the following transitions:
2
cyclohexane but also present bright UC luminescence under 980 H9/2 f 4I15/2 (∼410 nm), 2H11/2 f 4I15/2 (∼524 nm), 4S3/2 f 4I15/2
nm excitation. The UC luminescence properties of CaF2:Yb3+/Er3+ (∼541 nm), and 4F9/2 f 4I15/2 (∼654 nm). It is obvious that the
14200 9 J. AM. CHEM. SOC. 2009, 131, 14200–14201 10.1021/ja906732y CCC: $40.75  2009 American Chemical Society
 COMMUNICATIONS
4 4
dominant emission is located in the green luminescence range. The S3/2 f I15/2 gradually increased with increasing excitation power,
eye-visible green UC fluorescence photo of the transparent colloid which was discussed in the Supporting Information.16
solution of the CaF2:Yb3+/Er3+ nanocrystals in cyclohexane is In conclusion, monodispersed CaF2:Yb3+/Er3+ nanocrystals have
shown in the inset of Figure 2. been prepared via a facile wet chemical technology. These
To evaluate if CaF2 is an efficient UC host material, the UC as-prepared nanocrystals not only can be transparently dispersed
luminescence properties of CaF2:Yb3+/Er3+ nanocrystals were in cyclohexane but also can be converted into water-soluble by
compared with those of NaYF4:Yb3+/Er3+ nanocrystals. The TEM oxidizing oleic acid ligands with the Lemieux-von Rudloff reagent.
images and XRD patterns of NaYF4:Yb3+/Er3+ nanocrystals with Under 980 nm excitation, the colliodal solutions of the as-prepared
different morphologies, sizes, and phases are shown in Figures S1 sample in cyclohexane and the oxidized sample in water both
and S2 in the Supporting Information. Obviously, the mean sizes present bright green UC luminescence. The UC luminescence
of hexagonal nanocrystals are much larger than that of the cubic properties of CaF2:Yb3+/Er3+ nanocrystals were compared with
sample. Under 980-nm excitation, the hexagonal NaYF4:Yb3+/Er3+ those of NaYF4:Yb3+/Er3+ nanocrystals with different phases and
nanocrystals as well as cubic NaYF4:Yb3+/Er3+ nanocrystals with particle sizes. The results indicated that CaF2 is a promising host
more than 10 nm in size can exhibit much stronger UC lumines- material for producing desirable UC luminescence. In addition, these
cence than the CaF2:Yb3+/Er3+ nanocrystals. However, in com- luminescent properties show that these water-soluble CaF2:Yb3+/
parison with the sub-10 nm NaYF4:Yb3+/Er3 nanocrystals, the Er3+ nanocrystals have potential applications in biological labeling
emission intensities of CaF2:Yb3+/Er3+ nanocrystals are slightly and imaging.
stronger (Figure 2), indicating that CaF2 is a promising host material
Acknowledgment. This work was supported by NSFC (90606006
for producing desirable UC luminescence. Of course, many factors
and 10979032), the State Key Project of Fundamental Research
might be responsible for the UC luminescence properties of RE-
for Nanoscience and Nanotechnology (2006CB932300).
doped nanocrystals, such as crystal structure, size, shape, and the
number of ions surrounding RE ions, on which no final conclusion Supporting Information Available: Experiment procedures, Popu-
has yet been reached. lation and photoluminescence processes, and Figure S1-S5. This
material is available free of charge via the Internet at http://pubs.acs.org.

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of 2H11/2/4S3/2 f 4I15/2 to 4F9/2 f 4I15/2 as well as 2H11/2 f 4I15/2 to JA906732Y

J. AM. CHEM. SOC. 9 VOL. 131, NO. 40, 2009 14201