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Synthesis of Hexagonal Yb3R,Er3R-Doped NaYF4

Nanocrystals at Low Temperature
By Helmut Schafer,* Pavel Ptacek, Henning Eickmeier, and Markus Haase

The highest upconversion efficiencies

known today are observed for Yb3Er3
ion couples embedded in macrocrystalline
hexagonal-phase(b-phase)NaYF4 matrices.[2426]
Based on that, synthesis procedures for
lanthanide-doped b-phase NaYF4 nanomaterials have been developed.[19,2632] However, the synthesis of hexagonal-phase
nanoscale Yb3,Er3-doped NaYF4 material with a particle size below 15 nm, which
is suitable as possible bio-probes for
imaging, is difficult.
Chow et al. synthesized hexagonal
particles with a diameter of about 10 nm
and a very narrow size distribution by
decomposing multiprecursors such as
CF3COONa, (CF3COO)3Y, (CF3COO)3Yb,
and (CF3COO)3Er/(CF3COO)3Tm in oleylamine at a temperature above 300 8C.[31] However the particle
size distribution in solution extracted from dynamic light
scattering (DLS) measurements, as well as the yield of the
synthesis, were not shown.
In fact, most of the described synthesis procedures for the
preparation of rare-earth-doped nanosized NaYF4 in its hexagonal
state are based on the co-thermolysis of rare earth trifluoroacetates
and sodium trifluoroacetate in high boiling solvents, such as oleic
acid, oleylamine, 1-octadecene, or solvent mixtures of these
compounds.[31,33,34] Generally the procedures, known from the
literature, which lead to b-phase NaYF4 require a quite high
reaction temperature. In addition, we found in some cases the yield
to be rather low. As a result, we decided to look for alternative routes
which would allow the generation of small (b-phase) NaYF4
particles at lower temperature in high yield.
Herein, we describe a novel method to synthesize nanoscale
Yb3,Er3-doped hexagonal NaYF4:Yb,Er. These nanocrystals with
a diameter of 430 nm are synthesized in oleylamine or in a
mixture of oleylamine and oleic acid at temperatures in the range of
20280 8C. To the best of our knowledge, a synthesis procedure
which allows the production of nanoscale hexagonal NaYF4 at
ambient temperature has not been reported up to now. The
synthesis is based on the reaction of the metal carbonates
Y2(CO3)3, Yb2(CO3)3, Er2(CO3)3, and Na2CO3 with ammonium
fluoride. The precursors decompose and form pure nanosized
Yb3,Er3-doped b-NaYF4 in high yield. The transmission
electron microscopy (TEM) images reveal that the particles are
well separated, but have a relatively broad size distribution.
Transparent solutions containing 1 wt% of the post-treated
particles in 2-propanol display visible upconversion emission
upon continuous wave (CW) excitation at 978 nm. In addition to

Nanocrystals of NaYF4 doped with Yb3R and Er3R are synthesized in

oleylamine using Y2(CO3)3, Yb2(CO3)3, Er2(CO3)3, Na2CO3, and NH4F as
precursors. In contrast to other starting materials normally used for such
syntheses, these precursors react even at room temperature to form
hexagonal-phase (b-phase) NaYF4:Er,Yb nanoparticles. Cubic-phase
(a-phase) NaYF4:Yb,Er particles are formed only at elevated temperatures
(>250 -C). The formation of the cubic phase at high temperatures can be
suppressed by replacing pure oleylamine with oleic acid/oleylamine mixtures.
Under optimized reaction conditions, particles with an average particle size of
about 7 nm are generated in 84% yield. Heat treatment (30 min, 280 -C) of the
particles significantly increases the luminescence efficiency. A transparent
solution of the heat-treated, nanometer-sized phosphor in toluene shows
intense visible light emission upon excitation in the near infrared.

1. Introduction
Luminescent nanocrystals have attracted a great deal of attention
for their potentially wide range of applications, including display
devices,[1] lasers,[2] and biological imaging agents.[39] Recently a
new subgroup of these materials has been developed, which is
capable of converting long wavelength radiation into shorter
wavelengths by the so-called photon upconversion, and which
therefore offers new opportunities for biological tagging applications.[1014] The energy of two IR photons is transferred to one
lanthanide dopant ion, resulting in excitation of this ion into a 4f
state at high energy. Visible light is emitted when the ion
subsequently relaxes to the ground state. Excitation in the near
infrared (NIR) has some advantages; it induces only a weak
autofluorescence background, avoids photodegradation in biotagging applications, and hence increases the sensitivity of the
method. It is well known that generally small particle sizes, defect
surface states as well as coordinating solvent molecules hamper
optical efficiency.[15,16] Quenching of the fluorescence could be
reduced by growing a passivating shell around the particles, which
separates the light-emitting ions from solvent molecules and
ligands. This core/shell concept was also investigated in the case of
fluoride nanoparticles.[1723]
fer, P. Ptacek, H. Eickmeier, Prof. M. Haase
[*] Dr. H. Scha
University of Osnabrueck
Institute of Chemistry
ck (Germany)
Barbarastr.7, 49069 Osnabru
E-mail: Helmut.Schaefer@uni-osnabrueck.de

DOI: 10.1002/adfm.200900642

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Figure 1. a) Powder XRD pattern of b-NaYF4: 78% Y, 20% Yb, 2.0% Er

naocrystals obtained from the synthesis carried out at room temperature in
oleylamine. b) Powder XRD pattern of the sample obtained from the solidstate reaction carried out at room temperature.

the optical properties, the structure of the product, the influence of

the reaction temperature and of oleic acid on the particle size and
crystal phase are discussed.

2. Results and Discussion

Figure 1a displays the X-ray diffraction (XRD) data of the product
obtained by stirring the rare-earth carbonates, Na2CO3, and NH4F
in oleylamine for 48 h at room temperature. All diffraction peaks in
Figure 1a can be easily indexed to the hexagonal phase of
NaYF4:Yb,Er (powder diffraction file (PDF) 281192). There are no
signals which can be assigned to the cubic phase of NaYF4. In fact,
even grinding the dry powders (i.e., Na2CO3, NH4F, and the rareearth carbonates) in a mortar at room temperature immediately
leads via solid-state reaction to the release of ammonia and finally
to the formation of nanoscale hexagonal NaYF4. Figure 1b shows
the powder pattern of the solid mixture after standing at room
temperature for 168 h. Again, the main diffraction peaks can be
assigned to the b-phase of NaYF4:Yb,Er, although some impurities,
such as NaF (peaks at 2u 398 or 56.38) and cubic-phase NaYF4
(peaks at 2u 28.28 or 32.78) are also present in the sample.
In the case of a solid-state reaction, the diffusion is very often the
rate-limiting step. Because of quite long corresponding free paths,
high reaction temperatures are necessary. Our synthesis procedures work even at room temperature. We trace this specific
behavior mainly to the formation of ammonia gas. Obviously,
because of the high mobility of ammonia gas, diffusion
processes become unnecessary, and this leads to a much faster
reaction compared to other solid-state reactions. We tried to
generate NaYF4 alternatively via the solid-state reaction of NaF and
the rare-earth carbonates. Even after 200 h, no reaction takes place
at low temperature, indicating that the formation of ammonia is
crucial for this solid-state reaction to work at low temperatures.

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In order to accelerate the reaction in oleylamine, we slightly

increased the reaction temperature to 55 8C. In this case, the
reaction was already completed after 120 min. This temperature is
much lower than the temperatures usually employed for reactions
in the oleylamine/oleic acid/octadecene solvent system. The
synthesis procedure with this setting is presented in the
experimental section and provided the best results of this study.
The corresponding powder pattern of this sample can be taken
from Figure 2. A further increment of the reaction temperature up
to 280 8C has two effects: 1) constantly during the reaction (2 h), we
obtained an increment of the average particle size. 2) The growth of
the particle size runs parallel to the increase of the molar ratio of
cubic to hexagonal phase. Figure 3a shows the corresponding
powder pattern of the sample obtained from a synthesis carried out
at 280 8C. The line broadening of the signals is much weaker in
comparison with that of the signals in Figure 1 due to the fact that
larger particles were obtained in the synthesis at 280 8C than in the
reaction at lower temperatures. The sample already contains a high
percentage of cubic-phase NaYF4 as well as NaF. The signals
marked with symbols belong to cubic NaYF4 (2u 28.15 and
32.718) or NaF (2u 38.88 and 56.38). The optical properties of this
sample were not satisfactory. We traced the relatively low
upconversion efficiency of this sample mainly to the lower
upconversion efficiency of cubic-phase Yb,Er-doped NaYF4. At
290 8C, the percentage of cubic NaYF4 was even higher. According
to the phase diagram published by Thoma et al., the hexagonal bphase is the thermodynamically most stable phase at low
temperatures whereas the cubic a-phase represents the high
temperature modification which is only metastable at room
temperature.[35] At low reaction temperatures, the predominant
formation of the hexagonal b-phase is therefore expected from
thermodynamics. However, most synthesis procedures published
so far seem to be based on kinetically controlled reactions: even at a
temperature of 200 8C the cubic is usually obtained, and it is known
that high temperatures promote the generation of the b-phase
(hexagonal) NaYF4. Mai et al.[27] systematically investigated the

Figure 2. Observed X-ray powder diffraction profile of the b-NaYF4: 78% Y,

20% Yb, 2.0% Er (Sample 1) from the synthesis carried out at 55 8C after
heat treatment (grey line), Rietveld fit (black line), and residuum. Line
pattern of a) b-NaYF4: 57% Y, 39% Yb, 4.0% Er (PDF 28-1192); b) cubic
NaYF4 (ICSD 60257), c) NaF (PDF 01-073-1922).

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Figure 3. a) Powder XRD pattern of the sample obtained from the synthesis carried out at 280 8C without the additional oleic acid. b) Line pattern
of b-NaYF4: 57% Y, 39% Yb, 4,0% Er (PDF 28-1192).

Figure 4. a) Powder XRD pattern of the sample obtained from the synthesis carried out at 280 8C with the additional oleic acid. b) Line pattern of
b-NaYF4: 57% Y, 39% Yb, 4.0% Er (PDF 28-1192).

thermal decomposition of the trifluoroacetates Na(CF3COO) and

(RE)(CF3COO)3 where RE Pr, Nd, Y, and the elements
between Sm and Lu in the periodic tablein oleylamine and 1octadecene. On the basis of its a ! b phase transition behavior,
Na(RE)F4 along the rare-earth series was divided into three groups.
(I: Pr and Nd; II: Sm to Tb; III: Dy to Lu, Y). For the oleylamine
(OA)/octadecene (ODE) reaction system, b-Na(RE)F4 in groups I
and III was formed only under drastic conditions (high Na/RE,
330 8C, and long reaction time). Meanwhile, those in group II
could be formed even under mild conditions.[27] They traced this
different behavior to the different ionic radii of the RE3 ions
relative to the ionic radius of Na. Our samples with the
composition NaYF4:Yb,Er would belong to group III and therefore
should only be generated at high temperatures. But on the contrary,
we obtained the hexagonal (b) phase of our material in case of low
temperatures and the cubic phase at temperatures at 280 8C or
above 280 8C. The different behavior of these different synthesis
procedures might have been caused by a different reaction
mechanism or growth mechanism.
In the final experiment, we tried to suppress the undesired
formation of cubic-phase NaYF4 with the help of additional
components. The reaction temperature (280 8C) and reaction time
(2 h) were left unchanged. We modified the procedure by adding
oleic acid to the reaction mixture. We used a solvent mixture
consisting of 5 mL oleic acid and 22 mL oleylamine. As can
be taken from Figure 4, oleic acid successfully prevents
the formation of cubic-phase NaYF4. In fact, in the trifluoroacetates synthesis of NaYF4 the content of oleic acid in the reaction
mixture is often increased to promote the formation of the
hexagonal phase.[27] We assume that, after adding oleic acid, an
increase of a dissolutionrecrystallization transformation process
occurs. Generally dissolutionrecrystallization transformation
processes are supposed to be responsible for the influence on
the intrinsic crystalline phase (cubic and/or hexagonal phase) as
well as on the growth regime (thermodynamic versus kinetic).[36]
This leads us to the conclusion that in different solvent mixtures,
different dissolutionrecrystallization behavior induces different

crystalline phases. Figure 5 shows the TEM image of the sample.

The particle size distribution is quite broad with sizes ranging
from 20 to 55 nm. However, the sample gained from the synthesis
carried out at 55 8C consists of essentially smaller particles, and we
favored the particles gained from this procedure. Table 1 gives an
overview of the different settings and the achieved results. Figure 2
shows the measured powder XRD patterns of the sample achieved
at 55 8C together with the Rietveld refinement and diffraction lines
of b-NaYF4: 57% Y, 39% Yb, 4,0% Er (PDF 28-1192), a-NaYF4 (PDF
01-077-2042), and NaF (PDF 01-073-1922). Using three phases
consisting of b-NaYF4: 57% Y, 39% Yb, 4.0% Er (PDF 28-1192),
cubic NaYF4 (space group Fm3m, Inorganic Crystal Structure
Database (ICSD) 60257), and NaF (cubic, PDF 01-073-1922) as the
structural model for the sample, led to minimal differences
between observed and calculated X-ray powder diffraction profiles.
The main diffraction peaks can be easily indexed to pure

Adv. Funct. Mater. 2009, 19, 30913097

Figure 5. TEM image of b-NaYF4: 78% Y, 20% Yb, 2.0% Er nanocrystals

obtained from the synthesis carried out at 280 8C with additional amount of
oleic acid.

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Table 1. Overview of the various settings.

Medium

Temp.

Time

Heat-treatment

Phase

Reference

Solid state
reaction
OAM [a]
OAM [a]

RT [b]

168 h

b NaF

1b

RT [b]
55 8C

48 h
2h


30 min/280 8C

b
b

OAM [a]
OAM/OA [a]

280 8C
280 8C

2h
2h




a/b NaF
b NaF

1a
Fig. 511
(Sample 1)
Fig. 2
Fig. 34

[a] OAM Oleylamine; OA Oleic acid. [b] RT room temperature.

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hexagonal-phase NaYF4:Yb,Er (PDF 28-1192) (b). There are only

small extra peaks, which belong to cubic-phase NaYF4 (2u 28.18)
or NaF (2u 38.88 and 56.38) However, the purity of the sample,
derived from quantitative phase analyses performed with the help
of the Fullprof refinement, was calculated to be more than 97%. In
the case of the hexagonal phase, the best agreement between
observed and calculated profiles was obtained by predefinition of
spherical particles. The diffractogram is well fitted by the Rietveld
method yielding a value of a 5.99 A, b 5.99 A, and c 3.52 A for
the hexagonal unit cell and a mean crystallite size of 7 nm. This
result is in accord with the size deduced from TEM images (Fig. 6).
A histogram of the particle size distribution, derived from the TEM
diameter of
200 nanocrystals (from several overview TEM
images), can be taken from Figure 7. It shows a relatively broad
distribution of the size ranging from 410 nm.
Dark field imaging showed that the predominant species are
single crystals, so we trace the broad size distribution derived from
TEM images mainly to the broad size distribution of the single
crystallites. Of course, a broad size distribution also means a
distribution of surface properties, and this is not ideal for biotagging experiments. On the other hand, bio-tagging experiments
will always be performed in solution. This is why we always show
DLS measurements which give information about the size

distribution obtained in solution. Our nanoparticles form

transparent colloidal solutions in unpolar or more or less polar
organic solvents, such as toluene or butanol. In these solutions, the
nanocrystals are reasonably well dispersed, as shown by DLS
measurements, indicating an average hydrodynamic diameter of
approximately 21 nm (Fig. 8). About 90% of the particles are in the
size range of 1832 nm diameter.
Unfortunately the as-prepared nanocrystals gained from these
low temperature syntheses (RT, 55 8C) showed a weak upconversion efficiency. In order to improve the optical properties of the
phosphor, we decided to perform a post-treatment of the crystals
gained from the synthesis carried out at 55 8C. Heat treatment
(280 8C, 30 min, N2 gas) of the purified powder improved the
optical properties and did not influence the particle size (as
indicated by the XRD powder data, TEM images, or DLS

Figure 6. a) TEM image of b-NaYF4: 78% Y, 20% Yb, 2.0% Er nanocrystals

(sample 1) after heat treatment (30 min, 280 8C).

Figure 8. Characterization by DLS: Particle size and size distribution of bNaYF4: 78% Y, 20% Yb, 2.0% Er nanocrystals (sample 1) after heat
treatment (30 min, 280 8C).

Figure 7. Histogram of the particle size distribution, derived from the TEM
diameter of
200 nanocrystals (from several overview TEM images).

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Figure 9. Photography of the upconversion luminescence in 1 wt% colloidal solutions of b-NaYF4: 78% Y, 20% Yb, 2.0% Er nanocrystals (sample
1) in toluene excited at 978 nm (invisible) with a laser power density of
about 10 W mm2. Overall laser power: 1.5 W.

measurements) nor the dispersibility in organic solvents. TEM

images from the as-prepared particles are shown in the Supporting
Information (Fig. S1 and S2). Probably the environment of the
light-emitting species Er3 in the as-synthesized material is not
optimal with respect to upconversion efficiency. After heat
treatment, the particles display a much higher upconversion
efficiency, most probably owing to the annealing of crystal defects
at higher temperatures. (See also the final section).
In the following sections, this sample is marked as sample 1. A
1 wt% solution of the heat-treated nanocrystals in 2-propanol show
intense light emission, detectable by the naked eye, upon excitation
in the NIR at 978 nm (Fig. 9). The laser power density was about
10 W mm2. Overall laser power: 1.5 W. The figure shows green
emission, as known from the emission of the bulk material.
Generally, rare-earth fluorides doped with the Yb3Er3 ion
couple show light emission mainly in the green (Er3: 2H11/2,
4
S3/2 ! 4I15/2) and red (Er3: 4F9/2 ! 4I15/2) spectral regions after
excitation in the NIR. The green to red ratio (GRR), defined as the
intensity ratio between the emission bands centered at about 550
and 670 nm, depends on the particle size, crystallographic phase,
and doping concentration. Figure 10 presents the fluorescence
spectra of a 1 wt% solution of the nanocrystals in 2-propanol.
Similar to cubic-phase NaYF4:Yb,Er prepared in our group using
the solvent N-(2-hydroxyethyl)ethylenediamine (HEEDA),[34] our
hexagonal sample showed a higher intensity in the red than in the
green spectral range (Fig. 10). For the GRR, we found a value of
about 0.6. Other groups found values depending on the host lattice
and the crystallite size, in the range of 1.9[37] to 30.[20]
In order to evaluate the upconversion quality of the particles, the
samples were compared with other well known upconversion
phosphors. We used hexagonal bulk NaYF4: 18% Yb3, 2% Er3
synthesized by K. Kramer (University of Bern) as a reference
substance. In addition, we compared our sample from the 55 8C
synthesis with cubic NaYF4: 20% Yb, 2% Er nanocrystals.
Figure 11 shows the emission spectra of the pure crystals of
cubic NaYF4 (a), sample 1 (b), and hexagonal bulk NaYF4 (c). The
average particle size of the compared samples differs and ranges
from 7 nm (sample 1) to more than 1 mm (hexagonal bulk NaYF4).
The average particle size of the cubic NaYF4 sample was 28 nm. In
addition, the doping concentration slightly differs. However, the

Adv. Funct. Mater. 2009, 19, 30913097

Figure 10. Emisson spectra of 1 wt% solutions of b-NaYF4: 78% Y, 20%

Yb, 2.0% Er nanocrystals (sample 1).

Figure 11. Emission spectra of pure crystals of a) cubic NaYF4: 78% Y, 20%
Yb, 2.0% Er nanocrystals generated in HEEDA; b) hexagonal (b) NaYF4:
78% Y, 20% Yb, 2.0% Er nanocrystals (sample 1); c) hexagonal bulk NaYF4:
18% Yb3, 2.0% Er.3

procedure is suitable in order to roughly compare the optical

properties of these materials.
Under the same excitation condition, the luminescence
intensity of sample 1 (Fig. 11b) is much more powerful than
the luminescence intensity of the cubic sample (Fig. 11a). The pure
crystals showed a GRR value of 0.6, the same value we found in
solution (see also Fig. 10). Figure 12, displaying double logarithmic
plots of the emitted light intensity versus the power density of the
exciting light, shows the upconversion efficiency of the synthesized probes in detail. The emission intensity of the bulk material
depends on the excitation power and is 23 orders of magnitude
higher than for the nanoscale sample 1. For example, at 1.78 W
laser power the efficiency ratio between the bulk sample (Fig. 11c)
and sample 1 was 120. At this value of laser power, the efficiency
ratio between sample 1 and the nanoscale cubic NaYF4:Yb,Er

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Figure 12. Double logarithmic plots of the emitted light intensity versus
the power density of the exciting light for pure crystals of a) cubic NaYF4:
78% Y, 20% Yb, 2.0% Er nanocrystals generated in HEEDA; b) hexagonal
(b) NaYF4: 78% Y, 20% Yb, 2.0% Er nanocrystals (sample 1); c) hexagonal
bulk NaYF4: 18% Yb3, 2% Er.3

sample was approximately 10. This was not surprising because

hexagonal NaYF4 doped with Yb and Er is considered to be much
more efficient than the corresponding cubic-phase phosphor.
Generally the upconversion efficiency of nanoparticles depends on
the surface properties and the matrix of which the particles consist.
On the other hand, the efficiency of the matrix depends on the
phase purity, doping ratio, Na:M ratio, and preparation temperature as shown by Gudel et al.[37] However it remains an open
question as towhy the upconverson efficiency of hexagonal
NaYF4:Yb,Er is superior to that of others. Gudel and co workers
concluded that in an optimal probe Er3 ions should be
surrounded by several Yb3 neighbors for excitation energy
transfer. In addition, there should be optically inactive Y3 to avoid
energy migration from the active ion to killer traps.[37]
In summary, IR-to-visible upconversion fluorescent nanocrystals of hexagonal-phase NaYF4: 20% Yb, 2% Er were obtained in a
very rapid and straightforward synthesis by the decomposition of
the cheap precursors, Y2(CO3)3, Yb2(CO3)3 Er2(CO3)3, ammonium
fluoride, and Na2CO3 in oleylamine at 55 8C. The average particle
size, obtained by TEM images, was about 7 nm, and the size
distribution was broad. Raising the reaction temperature to 280 8C
led to an increase in the particle size. The higher reaction
temperature supports the formation of cubic-phase NaYF4 which
can only be suppressed by the addition of oleic acid. The
hydrophobic nanocrystals are easily dispersed in organic solvents,
producing a transparent colloidal solution. Heat treatment (280 8C;
30 min; N2 gas) of the purified powder improved the optical
properties. Owing to the desirable hexagonal phase, the solutions
of the crystals show very intense green emission upon excitation in
the NIR. The nanoparticles, as well as their dispersions in various
solvents, are potentially useful in optical nanodevices and
bioprobes.

Steinheim, Germany; Y2(CO3)3 (99.9%) and Yb2(CO3)3 (99.9%) were

supplied by SigmaAldrich, Steinheim, Germany; Er2(CO3)3 (99.9%) was
supplied by ChemPur, Karlsruhe, Germany.
In a typical synthesis of b-NaYF4:78% Y, 20% Yb, 2.0% Er samples under
nitrogen, 0.195 g (1.84 mmol) Na2CO3 was combined with 0.34 g
(9.2 mmol) of NH4F, 0.32 g (0.9 mmol) of Y2(CO3)3, 0.12 g (0.23 mmol)
of Yb2(CO3)3, and 11.8 mg (0.023 mmol) of Er2(CO3)3 in 25 mL oleylamine.
Water was removed in vacuum and the reaction mixture was stirred at 55 8C
for 120 min. After cooling down, the nanocrystals could be centrifuged.
Drying in air at 80 8C for 3 h yielded 0.2 g (84%) of the product.
Heat Treatment of the Nanocrystals: The nanocrystals were
heated under dry nitrogen gas up to 280 8C for 30 min, producing sample 1.
Characterization: X-ray diffraction data were recorded at room
temperature on an XPert Pro Diffractometer (Panalytical) with Bragg.
Brentano geometry using Cu Ka1 radiation (40 kV, 40 mA) l 1.5406 A
The average apparent crystallite size and the lattice parameters are
evaluated by structure profile refinements of X-ray powder diffraction data
collected at constant steps in scattering angle 2u using Fullprof program
[38] (version Feb. 2007. LLB, Juan Rodriguez Carvajal, Saclay France) [38]. A
Y2O3 powder standard was used to determine the instrumental resolution
function of the diffractometer. Emission spectra of colloidal solutions of the
nanocrystals and of the powders were measured with a Fluorolog 3
spectrometer (Jobin Yvon) combined with a continuous wave 978 nm laser
diode (LYPE 30-SG-WL978-F400). Quartz cuvettes (Hellma, QX) containing solutions of the samples or tubes with powder samples were placed
inside the spectrometer and excited using 978 nm light via an optical fiber.
All spectra were corrected for the sensitivity of the monochromators and
the detection system. TEM images were taken with a 200 KV JEOL JEM2100 microscope equipped with a charged-coupled device (CCD)-camera
(Gatan).

Acknowledgements
Supporting Information is available online from Wiley InterScience or from
the author.
Received: April 14, 2009
Published online: August 31, 2009

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3. Experimental
Preparation: Ammonium fluoride (98%) was supplied by Fluka,
Steinheim, Germany; Na2CO3 (99.5%) was supplied by SigmaAldrich,

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