Angewandte
Communications
Nanocrystals
NaYF4 :Yb,Er/NaYF4 Core/Shell Nanocrystals with High Upconversion
Luminescence Quantum Yield
Christian Homann, Lisa Krukewitt, Florian Frenzel, Bettina Grauel, Christian Wgrth,
Ute Resch-Genger,* and Markus Haase*
Abstract: Upconversion core/shell nanocrystals with different
mean sizes ranging from 15 to 45 nm were prepared via
a modified synthesis procedure based on anhydrous rare-earth
acetates. All particles consist of a core of NaYF4 :Yb,Er, doped
with 18 % Yb3+ and 2 % Er3+, and an inert shell of NaYF4, with
the shell thickness being equal to the radius of the core particle.
Absolute measurements of the photoluminescence quantum
yield at a series of different excitation power densities show that
the quantum yield of 45 nm core/shell particles is already very
close to the quantum yield of microcrystalline upconversion
phosphor powder. Smaller core/shell particles prepared by the
same method show only a moderate decrease in quantum yield.
The quantum yield of 15 nm core/shell particles, for instance, is
reduced by a factor of three compared to the bulk upconver-
sion phosphor at high power densities (100 W cm@2) and by
approximately a factor of 10 at low power densities (1 W cm@2).
Core/shell structures are widely used to improve the photo-
luminescence quantum yield of luminescent nanocrystals.[1]
Since radiationless deactivation at the particle surface is
usually the main energy-loss mechanism in small particles,
a shell of a suitable material enhances the luminescence of
semiconductor quantum dots as well as of lanthanide-doped
nanophosphors.[1b] For example, by improving the synthesis
methods for core/shell particles, the quantum yield of the
band gap emission of cadmium chalcogenide nanocrystals has
been increased from rather low values 30 years ago to more
than 99 % today.[2] In the case of quantum dots the shell
consists of a wide band gap semiconductor with suitable
position of the valence and conduction band energy to confine
the charge carriers in the core.[3] In nanophosphors, where
energy migration to the surface takes place via adjacent
dopant ions, the undoped host material is an obvious choice
for the shell material. This approach also minimizes the lattice
mismatch between the core and the shell.[1a,d, 4] One example is
[*] C. Homann, Prof. Dr. M. Haase
Institut ffr Chemie Neuer Materialien
Fachbereich Biologie/Chemie
Universit-t Osnabrfck
Barbarastrasse 7, 49076 Osnabrfck (Germany)
E-mail: markus.haase@uni-osnabrueck.de
L. Krukewitt, F. Frenzel, B. Grauel, Dr. C. Wfrth, Dr. U. Resch-Genger
Federal Institute for Materials Research and Testing (BAM)
Division Biophotonics
Richard-Willstaetter-Strasse 11, 12489 Berlin (Germany)
E-mail: ute.resch@bam.de
Supporting information and the ORCID identification number(s) for
the author(s) of this article can be found under:
https://doi.org/10.1002/anie.201803083.
Angew. Chem. Int. Ed. 2018, 57, 8765 –8769 T 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chemie
International Edition: DOI: 10.1002/anie.201803083
German Edition: DOI: 10.1002/ange.201803083
5 nm LaPO4 :Ce,Tb nanocrystals, the nanocrystalline ana-
logue of the standard lamp phosphor.[5] The high concen-
tration of Ce3+ dopant ions in the crystal lattice sensitizes the
material to UV radiation, but also results in fast energy
migration to the particle surface.[6] The nanocrystalline
material therefore greatly benefits from a shell of undoped
LaPO4 which increases the quantum yield of its Tb3+ emission
to 70 %.[7] Site-selective Eu3+ spectroscopy showed that the
Eu3+ surface sites of LaPO4 :Eu particles are converted into
Eu3+ bulk sites when a shell of LaPO4 is formed on the
LaPO4 :Eu particles. The resulting LaPO4 :Eu/LaPO4 core/
shell particles therefore exhibit only three different Eu3+ sites
corresponding to the three lattice sites known from bulk
LaPO4 :Eu.[8] The particles grow via a sol-gel-sol transition, as
shown by studying the crystal-field splitting of the Nd3+ ions
during the formation of LaPO4 :Nd particles.[9] Thus, the
molecular precursors react even at low temperatures and
form very small LaPO4 :Nd particles at early stages of the
synthesis.[9] These small particles form a gel during heat-up,
which later converts into a colloid of larger particles. Since the
lattice energy of monazite-type LaPO4 is very high, the
nanocrystals display negligible solubility in the diphenylether
solvent used for their synthesis. This is in contrast to NaREF4
(RE = rare earth) particles which grow via Ostwald-ripening
in an oleic acid/octadecene solvent mixture and must there-
fore be weakly soluble in this solvent system at elevated
temperature.[10] The solubility of the NaREF4 materials
complicates the formation of core/shell structures which are
widely used to improve the optical properties of NaYF4
upconversion nanocrystals and other NaREF4 particles.[11]
Owing to their solubility, the core particles can release ions
into the solution during heat-up and these ions can be
incorporated into the shell, if shell growth starts at high
temperature. It could be shown by Eu3+ spectroscopy that
intermixing of core and shell material takes place during the
formation of a NaGdF4 shell on small NaEuF4 core particles.[4]
Recently, this intermixing of core and shell has been
confirmed also for NaYF4 upconversion nanocrystals.[12]
Graded shells have also been discussed for quantum dots
with core/shell structures.[13]
One reason for the use of NaYF4 as the host material for
IR emissive lanthanide dopants is the low phonon frequencies
of the NaYF4 lattice.[14] To take full advantage of this property,
however, impurities with high-frequency vibrations, such as
OH@ groups, must not be incorporated into the crystal lattice.
In the solid-state synthesis of fluoride-based phosphor
materials, absolute exclusion of moisture and other sources
of OH@ is thus mandatory. Similarly, the high-frequency
vibrations of surface ligands and solvent molecules partially
8765
 Angewandte
Communications Chemie

quench the upconversion luminescence of NaYF4 nanocrys- core particles. If x is close to one, on the other hand, the
tals. Quenching is very pronounced in aqueous colloidal composition of the a-NaxYF3+x precursor particles matches
solutions, as shown by spectroscopic studies.[15] Even for more closely the composition of the b-NaYF4 phase. This
NaYF4 :Yb,Er/NaYF4 core/shell nanocrystal powders, the leads to the nucleation of a large number of b-NaYF4 seeds
upconversion emission is found to be weaker than the and a small final particle size. All core particles were doped
emission of microcrystalline upconversion phosphors, and with 18 % Yb3+ and 2 % Er3+, that is, in the concentration
the observed diminution in upconversion luminescence range known to yield the highest quantum yield for the bulk
depends on the surface-to-bulk ratio of the particles.[16] material.[24]
Quantitative studies, however, are rare, especially of powders, The inert b-NaYF4 shell was prepared in a similar way by
as the characterization of the luminescence properties of heating b-NaYF4 :Yb,Er core particles in the presence of
scattering solids is much more challenging compared to a large number of a-NaxYF3+x particles. The undesired
transparent solutions.[17] Absolute measurements of the nucleation of b-NaYF4 particles of pure shell material was
quantum yield of upconversion materials are particularly minimized by using a-NaxYF3+x particles with very low x as
difficult, as this quantity strongly depends on the excitation the shell precursor (x < 1).[21] Figure 1 demonstrates that this
power density (P) a result of the nonlinear nature of the method, previously developed to prepare sub 10 nm core/
upconversion process. Therefore, after the first publication of shell particles with a core size of only 5 nm, can also be used
such measurements on upconversion nanocrystals by van for the synthesis of core/shell particles with larger cores. The
Veggel et al.,[18] only a very small number of publications has TEM images also show that larger particles tend to be more
appeared on absolute measurements of the quantum yield of facetted than smaller ones and that the larger particles are
dispersed and solid upconversion materials.[11b, 15b, 16a, 19]
Herein, we present the results of absolute measurements of
the quantum yield of upconversion core/shell particles with
different sizes, capped with oleic acid. Upconversion nano-
crystals with improved quantum yield should be beneficial for
a variety of applications. Possible applications as well as the
synthesis and optical properties of these nanomaterials have
already been summarized in a large number of Review
articles.[1a, 16a, 20]
The b-NaYF4 core particles as well as the b-NaYF4 shell
were prepared in an oleic acid/octadecene solvent mixture
using small (3–5 nm) a-NaxYF3+x particles as precursor (x ,
1). The synthesis procedure is based on an earlier method for
very small NaYF4 :Yb,Er/NaYF4 core/shell particles which
was improved by two modifications:[21] First, the RE oleates
were replaced by RE acetates, as already reported by
others.[22] In contrast to the synthesis of RE oleates, no
sodium compounds are used in the synthesis of rare-earth
acetates. Therefore, the ratio of sodium to rare earth, known
to determine the final particle size, cannot be affected by
impurities contained in the rare-earth compounds. Second, we
treated the RE acetates with acetic anhydride after their
synthesis to reduce the amount of water introduced into the
reaction. Elemental analysis in fact indicates that the acetates
are anhydrous (see Supporting Information). For the same
reason, the oleic acid/octadecene solvent was dried at 100 8C
under vacuum before the acetates were dissolved under the
same conditions. The resulting clear solution of RE oleates in
oleic acid/octadecene was then used to prepare a-NaxYF3+x
precursor particles at 200 8C, using sodium oleate and
ammonium fluoride as sodium and fluoride sources, respec-
tively (see Supporting Information for details). By redispers-
ing the purified precursor particles in fresh solvent and
heating the resulting solution at 300 8C, monodisperse b-
NaYF4 :Yb,Er core particles were obtained. The size of the Figure 1. TEM images of b-NaYF4 :Yb,Er particles of different size
core particles was varied by using different ratios of sodium to before (left column) and after the formation of a shell of b-NaYF4 (right
column). In all cases, core particles and shell precursor were com-
rare earth in the synthesis of the precursor particles leading to
bined in a molar ratio of 1 to 7. All core particles were doped with
different values of x for the a-phase.[23] As discussed 18 mol % Yb3+ and 2 mol % Er3+. The TEM images were also used to
previously, nucleation of b-NaYF4 seeds is low, if x is small, derive size histograms of the samples (see text and Supporting
leading to the formation of a small number of large b-NaYF4 Information for detail).

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 Angewandte
Communications Chemie

elongated along the crystallographic c-axis. The elongation is

in accord with the anisotropic broadening of the XRD peaks
which has been included in the Rietveld analysis of the XRD
data. The XRD data, as well as size histograms of the samples
shown in Figure 1 are provided in the Supporting Informa-
tion. In order to simplify the size histograms and to allow
a better comparison of samples with different particle
morphology, the size of the nanocrystals with cylindrical or
hexagonal prismatic shape is given in the following as the
diameter of a sphere with identical volume. Thus, the
calculated mean sizes of the core particles shown in the first
row of Figure 1 are 6, 11, and 23 nm, respectively. Similarly,
the mean sizes of the corresponding core/shell particles are
given as 15, 22, and 45 nm throughout this work. The shell
increases the size of the core particle by roughly a factor of
two in all cases, since core and shell materials were always
combined in a molar ratio of 1 to 7. The particle volume is
therefore expected to increase by a factor of 8 and the mean
particle diameter by a factor of two. A detailed description of
how the shell growth increases the particles size along and
perpendicular to the c-axis is given in Figure S4 (Supporting
Information).
The quantum yield of the upconversion emission of the
core and core/shell particles under NIR-excitation was
determined absolutely with a previously described integrating
sphere set-up[17] at different excitation power densities P (see
Supporting Information). Solely nanoparticle powders were
used for comparability to measurements with a commercial
micrometer-sized b-NaYF4 :Yb,Er upconversion phosphor
previously reported.[17] The results of the quantum yield
measurements are summarized in Figure 2 a). The use of Figure 2. a) Upconversion quantum yield of core and core/shell par-
powder samples (see Figure 2 a)) limits the highest P to the ticles as function of excitation power density. The quantum yield of the
point where decomposition of the oleic acid ligands results in core/shell particles with a size of 45 nm is already very similar to the
sample darkening. For dispersed particles, where the heat quantum yield of a commercial microcrystalline upconversion phos-
generated by excitation can be more easily dissipated, much phor powder (black). All data were derived by absolute measurements
higher P can be used. As expected, the inert shell of b-NaYF4 with an integrating sphere set-up. Sizes: 15 nm (green), 22 nm (blue),
and 45 nm (red), open symbols stand for core particles, full symbols
strongly reduces the energy transfer to the particle surface,
for core–shell particles. b) Luminescence decay of the Yb3+ emission
resulting in a much higher quantum yield of the core/shell of b-NaYF4 :Yb,Er/NaYF4 core/shell particles with a size of
particles. Moreover, the micrometer-sized upconversion 15 nm (green), 22 nm (blue), and 45 nm (red). With increasing parti-
phosphor and all core/shell samples display a similar P cles size, the luminescence lifetime approaches the value of the bulk
dependence of the quantum yield. This result agrees well with upconversion phosphor (black). Open symbols stand for core particles,
the upconversion luminescence characteristics previously full symbols for core–shell particles.
observed for 25 nm-sized core only b-NaY-
F4 :17 %Yb3+,3 %Er3+ upconversion nanocrystals measured
in dispersion and as powder.[17] At low P, the quantum yield of crystal lattice of our nanocrystals. Such centers are known to
all samples increases with increasing P until it reaches quench the luminescence of Yb3+, Er3+, Eu3+, and other RE
saturation for P of 20 W cm@2 to 40 W cm@2. The maximum ions.
values of the upconversion quantum yield vary systematically Since the molar ratio of core and shell material is 1 to 7 for
with particle size and increase from 3.4 % for the 15 nm core/ all samples, the thickness of the shell depends on particle size
shell particles to approximately 9 % for the 45 nm core/shell and decreases from approximately 11 nm for the largest
particles. Within a factor of three, the same maximum (45 nm) particles to approximately 4 nm for the smallest
quantum yield is observed for all three particle sizes and the (15 nm) particles. The particle cores of the smallest particles
value of about 9 % found for the 45 nm core/shell particles is are therefore protected by the thinnest shells. Moreover, the
already very close to the quantum yield of the micrometer- smallest particles are expected to show the strongest inter-
sized upconversion phosphor powder of 10.3 at P = W cm@2.[17] mixing of core and shell during shell growth, as the solubility
This is the main outcome of this work, together with the of particles increases with decreasing particle size according
improved synthesis method for the core/shell particles. to the Gibbs–Thompson effect. In fact, the smallest core/shell
Presumably, the decreased water content in our synthesis particles not only show the smallest maximal value of the
resulted in a considerably lower number of OH-centers in the quantum yield but also the strongest decrease of the quantum

Angew. Chem. Int. Ed. 2018, 57, 8765 –8769 T 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim www.angewandte.org 8767

Communications
yield at low P. This is in accord with our earlier result for
10 nm core/shell particles. The improved synthesis procedure,
however, yields not only 45 nm core/shell particles with high
quantum yield but also reduces the difference in quantum
yield between the bulk upconversion phosphor and the
smallest core/shell particles.
The increase in quantum yield from 3.4 % for the 15 nm
particles to 10 % for the micrometer-sized UC phosphor is
also reflected in the luminescence decay curves. As shown in
Figure 2 b) the decay time of the Yb3+ emission increases
systematically with particle size. Since the concentration of
the Yb3+ sensitizer ions is much higher than the concentration
of the Er3+ emitters, energy migration is expected to occur
mainly via adjacent Yb3+ ions. The fact that the Yb3+ decay
times of the 45 nm core/shell particles and the upconversion
phosphor powder are already very similar indicates that the
11 nm thick shell effectively blocks luminescence quenching
on the particle surface.
A systematic variation with the particles size is not only
observed for the quantum yield and the luminescence life-
times but also for the red-to-green ratio in the emission
spectrum. It is well established that the red-to-green ratio
strongly increases with increasing P and this dependence is
observed for all our samples (Figure 3).[15b] Figure 3 shows
that the cross-over point where the red and the green
emission band have the same intensity, shifts systematically
to lower P with increasing particle size and, hence, increasing
quantum yield. Moreover, the cross-over points of the 45 nm
core/shell particles and the bulk phosphor are located at
similar P, in accord with their rather similar quantum yields.
This reflects once more the bulk-like behavior of the 45 nm
core/shell particles.
Figure 3. Red-to-green ratio of the upconversion emission of core/shell
particles as function of P. a) 15 nm, b) 22 nm, c) 45 nm and d) Bulk
material. The red-to-green ratio increases with increasing excitation
power density for all materials including the bulk phosphor powder.
The crossing points of the relative contributions of both colors, that is,
the P values where the red and the green emission match in intensity,
shift systematically to lower P values with increasing upconversion
quantum yield.
8768 www.angewandte.org T 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angewandte
Chemie
In conclusion, we have shown that NaYF4 :Yb,Er upcon-
version nanocrystals with an inert shell of NaYF4 can be
prepared in such a way that their maximum quantum yield
approaches the value of the bulk material. In future work, the
rate constants of the energy transfer processes will be
determined for particles of different size to develop a model
of the P-dependence of the red-to-green ratio, the quantum
yield and the luminescence lifetimes. Moreover, we will
expand this study to upconversion nanocrystals dispersed in
different solvents to determine the optimal shell thickness for
a given particle size and a given environment.
Acknowledgements
We thank the German Science Foundation DFG (grants RE
1203/18-1 and HA 1649/7-1) and the EU (COST 1403) for
financial support.
Conflict of interest
The authors declare no conflict of interest.
Keywords: luminescence · nanocrystals · NaYF4 ·
quantum yield · upconversion
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Manuscript received: March 13, 2018
Revised manuscript received: April 15, 2018
Accepted manuscript online: May 6, 2018
Version of record online: June 14, 2018
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