Optical Materials 47 (2015) 95–98

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Optical Materials
journal homepage: www.elsevier.com/locate/optmat

Luminescence properties of Eu3+-doped SiO2–LiYF4 glass–ceramic

microrods
C.E. Secu ⇑, M. Secu
Optical Processes in Nanostructured Materials Department, National Institute of Materials Physics, P.O. Box MG-7, Bucharest-Magurele 077125, Romania

a r t i c l e i n f o a b s t r a c t

Article history: Photoluminescence properties of the glass–ceramics microrods containing Eu3+-doped LiYF4 nanocrystals
Received 16 April 2015 have been studied and characterized. Judd–Ofelt parameters and quantum efficiency has been computed
Received in revised form 6 June 2015 from luminescence spectra and discussed by comparison to the glass ceramic bulk and pellet. The radia-
Accepted 6 July 2015
tive decay rate Arad is higher in the glass ceramic rods (221 s1) than in the glass ceramic bulk (130 s1)
Available online 9 July 2015
but the quantum efficiency computed is very low (21%) compared to the glass–ceramic bulk (97%). There
are effective non-radiative decay channels that might be related to an influence of the dimensional con-
Keywords:
straints imposed by the membrane pores during xerogel formation and subsequent glass ceramization.
Glass ceramics
Nanocrystals
Ó 2015 Elsevier B.V. All rights reserved.
Photoluminescence

1. Introduction conducting sol–gel synthesis within the pores of various micro-

One-dimensional nanostructures such as nanorods, nanowires,
and nanotubes, have attracted extensive attention as a result of
their novel size-dependent properties [1]. They can be used for
the efficient transport of electrons and optical excitations and sus-
tain the next generation of optoelectronic nanodevices. Due to
their diameters below the wavelength of light and the high aspect
ratio, nanowires can act as efficient light waveguides linking indi-
vidual components to form complex networks [2,3], optoelectronic
nanodevices [4] and nanowire lasers [5,6]. Therefore in the last
years there has been an increased interest toward synthesis of such
materials having luminescence properties: alkaline-earth fluoride
nanowires [7], rare earth doped fluoride nanorods [8], Eu-doped
LaPO4 nanostructures [9], ZnO nanorods [10] or Eosin-Y doped sil-
ica nano and micro-rods [11].
In order to exploit for the applications their nanoscale optical
and electronic properties it is necessary to obtain such nanostruc-
tures with a predictable morphology, crystallinity, monodisperse
and stable. Among various synthesis methods that have been used
sol–gel method represents an useful and convenient method
because of its advantages: lower processing temperature, the abil-
ity to control the purity and homogeneity of the final materials on
a molecular level and the large compositional flexibility. By combi-
nation with a template membrane it provides a new general route
for preparing one-dimensional nanostructures (nanowires) [12] by
⇑ Corresponding author at: National Institute of Materials Physics, P.O. Box MG-7,
077125 Bucharest-Magurele, Romania.
E-mail address: cesecu@infim.ro (C.E. Secu).
and nanoporous template membrane ([13] and references therein).
The template technique consists in filling the pores of a membrane
(anodic alumina or etched ion track membranes) with a certain
material, which adopts the exact shape of the hosting pore ([13]
and references therein). The capillary force drives the sol into the
pores if the sol has good wettability for the template. After
the pores were filled with sol, the template is withdrawn from
the sol and dried. Then the sample is fired at elevated temperatures
to remove template and to densify the xerogel nanorods. Glass
ceramic silica rods in which Eu-doped BaF2 nanocrystals are
embedded have been prepared by using this method [14].
Through a controlled nucleation and crystallization processes the
initial xerogel rods are thermally converted into glass ceramic rods
composed by low phonon energy nano-crystalline fluoride phase
dispersed within the glass matrix.
The aim of the paper is to study and to characterize the lumi-
nescence properties of the glass–ceramics microrods containing
Eu3+-doped LiYF4 nanocrystals by comparison to the corresponding
bulk and a silicate glass by using Judd–Ofelt formalism.
2. Experimental
For the preparation of the Eu3+-doped (1%) (95SiO2–5LiYF4)
(mol%) xerogels and glass–ceramic rods we used synthesis from
liquid solution of organometallic tetraethylorthosilicate (TEOS)
precursor corresponding to a chemical reaction implying metal
alkoxides and water in an alcoholic solvent [15,16]. In the first step
tetraethoxysilane (TEOS) was hydrolyzed under constant stirring

http://dx.doi.org/10.1016/j.optmat.2015.07.009
0925-3467/Ó 2015 Elsevier B.V. All rights reserved.
96 C.E. Secu, M. Secu / Optical Materials 47 (2015) 95–98

with a mixed solution of ethanol and water and using glacial acetic
acid as catalyst; molar ratio was 1:4:10:0.5. Then another solution
of Eu(CH3COO)3, Y(CH3COO)3, Li(CH3COO) and CF3COOH with the
molar ratio for Eu:Y:Li:F of 1:5:20:255 was prepared by and added
to the first solution, followed by stirring for 1 h at room tempera-
ture. The liquid sol was allowed to fill the pores of a track etched
polycarbonate membrane (30 lm thickness, 1 lm pore diameter
and 108 cm2 pore density) [15] used as template and then kept
at room temperature for aging and strengthening. Then the mem-
brane was dissolved in dichloromethane and the solution depos-
ited on quartz slides (for optical measurements) or platinum foils
(for electron microscopy measurements). In order the obtain glass
ceramic microrods we annealed the slides or the platinum foil at
530 °C in air as resulted from thermal analysis measurements [15].
Scanning Electron Microscopy (SEM) images of xerogel nano
and micro-rods were recorded using a TESCAN LYRA 3 XMU
SEM–FIB scanning electron microscope.
Photoluminescence (PL) and lifetimes measurements have been
performed at room temperature by using a commercial Jobin Yvon
spectrophotometer Fluoromax 4-P; the spectra were corrected
with the spectral sensitivity.
3. Theoretical background
the Arad rate was obtained by summing over the radiative rates
A0–J for each 5D0 ? 7FJ transition contributing to the emission spec-
trum (see Table 1). The emission quantum efficiency of the emitting
level is given by: g = Arad/Atot where Atot = 1/s = Arad + Anrad (and s is
the observed lifetime).
4. Results
4.1. Scanning electron microscopy
In Fig. 1 are depicted the SEM images of the glass ceramic
microrods recorded at two different magnifications. We have
observed microrods of about 0.5 lm diameter and tens of lm
length showing nanostructures of about 70 nm inside them.
4.2. Photoluminescence measurements
In Fig. 2 are depicted the PL spectra recorded in the Eu3+-doped
glass ceramic bulk and microrods; typical 5D0 ? 7FJ transitions
(J = 1–4) of the Eu3+-ion can be recognized. We noticed that the
spectral position of the bands and their splitting in the glass–
ceramic and pellet are almost identical; in the silica glass the
luminescence bands are broad.

Judd–Ofelt theory is widely used to compute the JO intensity

4.3. Photoluminescence decay
parameters X2,4,6 and the coefficient of spontaneous emission
(radiative) A of the J–J0 transition; it assumes RE ions in
Time decay profile of the red PL band 5D0 ? 7F2 at 617 nm have
well-defined sites where energy transfer between ions in different
sites does not occur [17,18]. The JO intensity parameters give an been recorded under 394 nm excitation for glass ceramic micro-
rods and bulk samples (Fig. 3).
insight into the local structure and bonding in the vicinity of the
rare earth ions [18]: X2 parameter is environment sensitive (large PL decay curve recorded on the glass ceramic bulk sample
shows a single decay with the (7.33 ± 0.02 ms) characteristic life-
values were found for chemical bind with covalent character) and
X4, X6 are related to the viscosity of the material (for doped time [15]. In the glass ceramic rods sample the decay curve is
glasses). Then it can predicted important radiative properties of not exponential and we computed the effective decay time
R
Ln3+ ions in host matrix as the relative contribution to the emission 0.96 ± 0.002 ms; the effective decay time is given by I(t) dt/It=0.
spectrum (the branching ratio b) for any of the rare-earth transi-
tions as well as the radiative lifetime (sR). 5. Discussion
In the particular case of Eu3+ ions JO intensity parameters can be
computed from luminescence spectra [19–21]. The 5D0 ? 7F1 tran- The crystallization process of the xerogel is the results of the
sition is the only MD transition being practically independent of thermal decomposition of Li and Y-trifluoroacetate at about
the ion surrounding, the other ones 5D0 ? 7F2,4,6 having a purely 360 °C (with the formation of LiF and YF3) followed by the precip-
induced ED character [22]. By neglecting the matrix element U(6) itation of the LiYF4 nanocrystals in the glass–ceramic bulk [15] and
for the 5D0 ? 7F6 transitions the Einstein coefficient A0–k for spon- in the glass–ceramic microrods (Fig. 1). Photoluminescence spectra
taneous emission can be expressed as [19]: have shown a Stark splitting which is due to the degeneracy level
X D E2 removal by the crystal field indicating that a number of Eu3+-ions
3
A0—k ¼ ð64p4 e2 t3 e2 =3hc Þ  ð1=4pe0 Þ  v  Xk 5
D0 kU ðkÞ k7 F J are taken inside the LiYF4 nanocrystals [15]. By comparison, in
2;4
the silica glass Eu3+ ions experience a random and asymmetric
ð1Þ coordination and the PL bands are broad. As the spectral position
of the bands and their splitting in the glass–ceramic bulk and
where v is the Lorentz local field correction and the square
microrods are almost identical, this indicates a similar crystal field
reduced matrix elements h5D0||U(k)||7F2i2 = 0.0032 and
surrounding the Eu3+ ions, i.e. they are embedded dominantly
h5D0||U(k)||7F4i2 = 0.0023 [23].
inside the LiYF4 nanocrystals. Photoluminescence spectra analysis
In order to determine the spontaneous emission (radiative) Arad
and X2,4 experimental intensity parameters we have considered
the spectral data (luminescence spectra) at room temperature by Table 1
using the 5D0 ? 7F2,4 transitions and by taking the 5D0 ? 7F1 tran- Decay rates of radiative (Arad) and total (Atot) processes of 5D0 ? 7FJ transitions,
sition as the ‘‘reference’’ and an average index of 1.5 [19–21]. The luminescence lifetimes (s), intensity parameters (X2, X4) and quantum efficiencies
(g) computed from photoluminescence spectra.
spontaneous emission coefficients A0–2 and A0–4 are obtained by
using the relations [19]: Sample Arad Atot s X2 X4 g
(s1) (s1) (ms) (1020 cm2) (1020 cm2) (%)
A0—2 ¼ A0—1  ðS0—2 =S0—1 Þ  ðr2 =r1 Þ and
Eu3+-doped glass 221 1042 0.96 3.8 3.5 21
A0—4 ¼ A0—1  ðS0—4 =S0—1 Þ  ðr4 =r1 Þ ð2Þ ceramic
(microrods)
where S0–2 and S0–4 are the surfaces under the luminescence curves Eu3+-doped glass 130 139 7.33 1.7 1.5 97
related to the 5D0 ? 7F2 and 5D0 ? 7F4 transitions and r1, r2 and r4 ceramic (bulk)
are the energies of the 5D0 ? 7F1,2,4 transitions. For the 5D0 ? 7F1 Eu3+-LiYF4 (pellet) 120 122 8.16 1.4 2.4 100
SiO2–Eu3+ (glass) 232 1351 0.74 4.2 3.8 17
MD transition A0–1 was estimated to be around 50 s1 [24]. Then
 C.E. Secu, M. Secu / Optical Materials 47 (2015) 95–98
Fig. 1. SEM images of the glass–ceramic rods recorded at two different magnifi-
cations; the right figure shows nanostructures of about 70 nm inside glass–ceramic
microrods.
by using group-theory arguments have shown that in the glass
ceramic Eu3+ ions are embedded in the LiYF4 nanocrystals as
Eu–O center and/or dimer centers with low symmetry (C2v) [15].
Fig. 2. Normalised photoluminescence spectra recorded on Eu3+-doped glass ceramic bulk and microrods by comparison to the silicate glass using 394 nm excitation; energy
levels scheme of the Eu3+-ions and the 5D0 ? 7FJ transitions (J = 1–4) are indicated.
97
Fig. 3. Photoluminescence decays (solid curves) recorded at 617 nm on Eu3+-doped
SiO2–LiYF4 glass ceramic bulk and microrods.
In order to get a quantitative characterization of the lumines-
cence properties of the glass–ceramic microrods and bulk we used
the Judd–Ofelt theory and the recorded luminescence spectra. The
emission quantum efficiency (g) of the emitting level has been
calculated for the Eu3+-doped glass–ceramic bulk and rods by
comparison to a pellet and a silicate glass. In addition, the X2,4
parameters have been computed from the rel. (1) by using the
Einstein’s coefficient of spontaneous emission A0–k determined
directly from luminescence spectra (see Table 1).
It is known that the radiative decay rate is influenced by the
local crystal structure around the RE-dopant. We observed that is
much higher in the Eu3+-doped glass–ceramic rods (almost double)
compared to the glass–ceramic bulk or pellet (see Table 1).
However the quantum efficiency computed is very low, is value
being comparable to the silica glass. This is an indication of very
effective non-radiative decay channels that cause high total decay
rates Atot and a decrease of the observed luminescence lifetime s.
There are several non-radiative decay channels that might be
responsible and can be discussed. On the LiYF4 nanocrystals sur-
face, we expect a high concentration of surface atoms and defects
[25,26] acting as trapping centers and non-radiatively dissipating
energy; the presence of a small number of hydroxyl ions (OH1)
might be involved. However both of these channels are active also
in glass ceramic bulk, too. Moreover their influence is quite weak
as the quantum efficiency is high as in the pellet (see Table 1).
Therefore it is reasonable to suppose that in the glass ceramic rods
98 C.E. Secu, M. Secu / Optical Materials 47 (2015) 95–98
the luminescence quenching is related to the Eu3+-ions concentra-
tion. It is likely that the local Eu3+-ions concentration within the
nanocrystals is higher than in the glass ceramic bulk and the
non-radiative transitions between close pairs [27,28] become
important, that result for the luminescence quenching. Hence,
Judd–Ofelt parameters calculations (from the luminescence spec-
tra) is not useful in the particular case of the glass ceramic rods.
This can explain the disagreement between the high value of the
environment sensitive parameter X2 (close the silicate glass where
of covalent bonding it is expected) and the ionic bonding experi-
enced by the Eu3+ in the LiYF4 nanocrystals.
6. Conclusion
We described the luminescence properties of oxy-fluoride glass
ceramic rods in which Eu3+-doped LiYF4 nanocrystals are embed-
ded in terms of JO parameters and quantum efficiency by
comparison to the bulk. The radiative decay rate is almost double
in the glass ceramic rods compared to the glass–ceramic bulk or
pellet but the quantum efficiency computed is very low. We sup-
pose that a high local concentration of the Eu3+ ions within the
nanocrystals is responsible for a high rate of non-radiative transi-
tions between close ions that result for the luminescence
quenching.
Acknowledgement
We acknowledge the financial support of the Romanian
Education and Research Ministry (IDEI Project No.
290/05.11.2011).
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