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Optical Materials
journal homepage: www.elsevier.com/locate/optmat
Ruhr-Universitt Bochum, Anorganische Chemie I Festkrperchemie und Materialien, D-44780 Bochum, Germany
University of Wrocaw, Faculty of Chemistry, F. Joliot-Curie 14, PL-50383 Wrocaw, Poland
a r t i c l e
i n f o
Article history:
Received 17 February 2011
Accepted 11 April 2011
Available online 20 May 2011
Keywords:
Alkaline earth uorides
Quantum cutting
Ionic liquids
Morphology
Nanoparticles
a b s t r a c t
Bulk alkaline earth uorides co-doped with optically active ions are prominent materials for luminescent
applications. However, for phosphor materials the changeover to the nanoscale is a tightrope walk
between achieving desirable features of small particles such as reduced light scattering and unwanted
drawbacks such as a high surface defect concentration which is likely to result in quenching of luminescence. A new preparation route via ionic liquids allows obtaining pure and oxygen-free alkaline earth uorides co-doped with Eu3+ and Gd3+ on the nanoscale with excellent quantum cutting abilities.
2011 Elsevier B.V. All rights reserved.
1. Introduction
Nanotechnology is currently one of the most popular research
topics because of device miniaturization and the search for new
materials with exceptional properties and property combinations.
Many chemical and physico-chemical properties of a material
change from the bulk to the nanosize regime. This applies also to
optical properties and nanotechnology has also become important
in the eld of phosphor chemistry [1]. Although nanoparticles are
dened as having a size below 100 nm, really amazing properties
occur at particle sizes below 10 nm because the fraction of surface
atoms is signicant. The different behavior of surface atoms is
caused by the reduced number of neighbor atoms compared to
the saturated coordination environment of a volume atom. Furthermore, stabilities of polymorphs depend on the particle size and may
be different from the bulk [2]. Particle size may also affect physicooptical properties such as emission lifetime, quantum efciency and
concentration quenching [3]. In addition, the symmetry and crystal
eld as well as the refractive index can deviate from the bulk.
Taking a phosphor material to the nanoscale is a borderline
walk between achieving desirable features such as reduced light
scattering and unwanted troubles arising from the large surface
area. Although uoride materials are extremely interesting for
luminescent applications because of their high chemical stability,
their wide band gap, the possible high dopant ion level, the good
mechanical properties and comparatively high moisture resistance,
Corresponding author.
E-mail address: anja.mudring@rub.de (A.-V. Mudring).
0925-3467/$ - see front matter 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.optmat.2011.04.019
nanocrystalline uoride materials are commonly not used and often not explored because their favorable properties are considerably reduced by surface species such as OH or NH or oxide
contaminations introduced during the synthesis. These make efcient multiphonon relaxation possible and one of the major advantages of uoride materials, the low phonon energies, is lost. Indeed,
the synthesis of pure, quenching species-free nanouorides is
rather difcult. Recently, we developed a microwave synthesis of
nanocrystalline lanthanide uorides using ionic liquids as the solvent, reactant and in situ stabilizer, all in one [4,5]. The obtained
nanomaterials with a particle size below 10 nm had excellent
photo-physical properties and no surface quenching species could
be detected. However, lanthanide uorides are problematic with
respect to their pyro-hydrolytic and hydrolytic stability [6]. To
simultaneously improve the stability beyond lanthanide uorides
and to check generalization of our synthesis protocol, different
host materials have been considered. Alkaline earth uorides prot
from a substantially higher pyro-hydrolytic and hydrolytic stability. Besides, concentration quenching of optically active lanthanide
ions usually occurs at higher concentrations in smaller particles
and in alkaline earth uorides co-doped with rare earth ions, solid
solutions can be produced over a wide range of concentrations
[1,7,8]. Despite this, only few reports on nanocrystalline alkaline
earth uoride particles have appeared until now [912].
Alkaline earth uorides MF2 (M = Ba, Sr, Ca), crystallizing in the
cubic CaF2 type of structure [13], can be doped to a high degree
with trivalent lanthanide uorides. The lanthanide ions occupy
the M2+ sites of the host material. The substitution of a divalent
metal cation by a trivalent ion requires charge compensation
which is achieved by the introduction of additional uoride anions
337
2. Experimental
Synthesis and sample handling were carried out using standard
Schlenk and Argon-glove box techniques. The starting chemicals,
1-methylimidazole (99%, Sigma Aldrich), chlorobutane (99%, Acros), acetonitrile (99.5%, J.T. Baker), sodium tetrauoroborate
(98%, Aldrich), dichloromethane (99.9%, Fisher Scientic), barium
acetate (99%, ABCR), strontium acetate (99%, ABCR), calcium acetate hydrate (99%, ABCR), europium (III) acetate hydrate (99.9%,
ABCR), gadolinium (III) acetate tetrahydrate (99.9%, ABCR), ethylene glycol (99%, J.T. Baker) and ethanol (p.a., Riedel de Hen) were
used as received. The ionic liquid 1-butyl-3-methylimidazolium
tetrauoroborate, [C4mim][BF4], was synthesized according to a
common literature procedure [19].
2.1. Nanoparticle synthesis
In a typical reaction an appropriate amount of the alkaline earth
acetates, gadolinium acetate tetrahydrate and europium acetate
338
Fig. 1. Powder diffraction patterns of BaF2 co-doped with Eu3+ and different amounts of Gd3+ (left) and corresponding electron diffraction images (right).
Table 1
Lattice constants and molar volume for BaF2 co-doped with Eu 1% and Gd 525% as
obtained from Rietveld renements.
BaF2, Eu 1%, Gd (%)
a, c ()
Vm/106 (3)
5
10
15
20
6.1598(4)
6.1488(3)
6.1472(5)
4.3054(3)
6.2188(7)
4.2462(3)
6.1900(6)
58.43
58.11
58.07
57.64
25
55.81
339
Fig. 2. Representative TEM micrographs of Eu3+ and Gd3+ co-doped alkaline earth uorides.
BaF2:Eu 1 %, Gd 5 %
Intensity / a.u.
Intensity / a.u.
BaF2:Eu 1 %, Gd 5 %
BaF2:Eu 1 %, Gd 10 %
BaF2:Eu 1 %, Gd 15 %
BaF2:Eu 1 %, Gd 10 %
BaF2:Eu 1 %, Gd 15 %
BaF2:Eu 1 %, Gd 20 %
BaF2:Eu 1 %, Gd 20 %
BaF2:Eu 1 %, Gd 25 %
500
BaF2:Eu 1 %, Gd 25 %
550
600
650
700
300
Wavelength / nm
Intensity / a.u.
SrF2: Eu 1 %, Gd 15 %
CaF2: Eu 1 %, Gd 15 %
400
500
400
450
500
550
Wavelength / nm
Fig. 3. Room temperature emission spectra of Eu3+ and Gd3+ co-doped BaF2
7
nanoparticles excited at kex = 393 nm (5L6
F0,1).
300
350
600
700
Wavelength / nm
Fig. 4. Room temperature excitation spectra (left) monitored at kem = 592 nm
7
(5D0 ? 7F1) and emission spectra (right) excited at kex = 393 nm (5L6
F0,1) of SrF2
and CaF2 co-doped with 1% Eu3+ and 15% Gd3+.
Fig. 5. Room temperature excitation spectra Eu3+ and Gd3+ co-doped BaF2
nanoparticles monitored at kem = 592 nm (5D0 ? 7F1).
1,5
BaF2:Gd, Eu
QY=172 %
6
ex. 202 nm ( G J)
6
ex. 305 nm ( PJ )
1,0
0,5
0,0
500
550
600
650
Wavelength / nm
700
2,0
SrF2:Gd, Eu
QY=191 %
1,5
1,0
0,5
0,0
500
550
600
650
Normalized intensity
2,0
Normalized intensity
Normalized intensity
340
2,0
CaF 2:Gd, Eu
1,5
1,0
0,5
0,0
700
500
Wavelength / nm
Fig. 6. Emission spectra of 1% Eu3+ and 15% Gd3+ co-doped alkaline earth uorides excited via 6GJ
cutting abilities.
close to 200% [28]. For BaF2:Gd 1%, Eu 1% bulk materials, downconversion with a quantum yield of 194% was reported [29]. In
case of our nanomaterials we do not observe any energy transfer
from Gd3+ to Eu3+ under VUV excitation for the same low concentration of active centers, suggesting a different rare earth ion distribution in the nanoscale material. (For the bulk, the lanthanide ion
clustering tendency was already observed with 1% co-doping [29].)
Our study implies that the distribution of Ln3+ ions at low dopant
concentration (up to 5%, dominating europium transitions in excitation) could be more random in nanomaterials, thus hampering
Ln3+Ln3+ interactions. Nevertheless, for particles with active ion
concentrations starting from 10%, we observed efcient GdEu energy transfer. The efciency of the quantum cutting process was
estimated from the different intensity ratios of 5D1,2 and 5D0 emis8
sion under excitation at 202 nm (6GJ
S transition) and 305 nm
8
(6PJ
S transition) of gadolinium according to the procedure described by Wegh et al. [30]. As the excitation spectra of europium
and gadolinium co-doped BaF2 suggested that the most efcient
EuGd energy transfer occurs for a Gd3+ concentration of 15%
(and 1% Eu3+) we have determined the quantum cutting efciency
for all co-doped samples in the alkaline earth uoride series at that
concentration (Fig. 6, every spectrum is normalized on the emission from the 5D1 level). Indeed, down-conversion is very effective
and the efciencies were calculated to 170% for BaF2, 190% for SrF2
and 150% for CaF2 doped with 1% Eu3+ and 15% Gd3+.
4. Conclusion
Microwave assisted synthesis employing the ionic liquid
[C4mim][BF4] as the reaction medium and reaction partner is a
new and easy synthetic route to pure, oxygen-free Eu3+ and Gd3+
co-doped alkaline earth uorides. Particle sizes below 10 nm for
the co-doped BaF2 and below 20 nm for CaF2 and SrF2 could be
achieved. It was shown for BaF2, that these small nanoparticles
aggregate with increasing lanthanide dopant concentration from
plates to spheres. Variation of the Gd3+ dopant concentration also
has a strong inuence on the optical properties and the Eu3+
Gd3+ energy transfer. A doping degree of 15% Gd3+ yielded the best
results and we were able to obtain highly efcient quantum cutters
with 190% efciency for strontium uoride, 170% for barium uoride and 150% for calcium uoride, respectively.
Acknowledgments
AVM would like to acknowledge support from the European
Research Council through an ERC Starting Grant (EMIL, Contract
QY=153 %
550
600
650
700
Wavelength / nm
8
no. 200475), the Fonds der Chemischen Industrie through a Dozentenstipendium for A.-V.M. as well as a Doktorandenstipendium for
C.L. and DESY (proposal no. II-20090181). E.Z. and J.C. would like to
thank for support from grant POIG.01.01.02-02-006/09 of the Minister of Science and Higher Education (Poland).
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