ARTICLE IN PRESS

Journal of Luminescence 129 (2009) 449–455

Contents lists available at ScienceDirect

Journal of Luminescence
journal homepage: www.elsevier.com/locate/jlumin

Surfactant effect on the upconversion emission and decay time

of ZrO2:Yb-Er nanocrystals
D. Solı́s a, T. López-Luke a,b, E. De la Rosa a,, P. Salas c, C. Angeles-Chavez d
a
Centro de Investigaciones en Óptica, A.P. 1-948, León, Gto. 37160, México
b
IIM, UMSNH, C.U., Morelia, Mich. 58060, México
c
Centro de Fı́sica Aplicada y Tecnologı́a Avanzada, Universidad Nacional Autónoma de México, A.P. 1-1010, Querétaro, Qro. 76000, México
d
Instituto Mexicano del Petróleo, Cd. México, D.F. 07730, México

a r t i c l e in fo abstract

Article history: Luminescent properties of doped ZrO2:Er3+ and codoped ZrO2:Yb3+–Er3+ nanocrystals with average size
Received 31 July 2008 54 nm were analyzed as a function of non-ionic surfactant (Pluronic F-127) concentration. Surfactant
Received in revised form and non-surfactant samples were prepared by the sol–gel micelle process with hydrothermal aging and
7 November 2008
annealed at 1000 1C for 5 h. The introduction of the surfactant reduces the presence of impurities such
Accepted 18 November 2008
Available online 3 December 2008
as OH and CO2 on both samples, and increments the tetragonal phase for codoped nanocrystals. It
induces an increment larger than 90% and 70% for doped and codoped, respectively, for an optimum
PACS: molar ratio of 0.0082. The observed enlargement of fluorescence decay time is partly the result of the
73.22.f nanosize effect but is dominated by the reduction of impurities attached on the nanocrystalline surface.
73.63.Bd
& 2008 Elsevier B.V. All rights reserved.
78.47.p
78.47.Cd
78.55.m
78.67.Bf

Keywords:
Decay time
Up-conversion
Nanocrystals
Surfactant
Pluronic-127
ZrO2
Yb
Er
Luminescence

1. Introduction increase the efficiency of the UPC process and in some cases can
induce upconversion whereas it is not possible in the single ion. In
Recently, interest has been increased in the application of this case, the emission is the result of energy transfer from donors
nanoparticles in the design of photonic systems because of their to acceptors [4] such as Tm, Ho and Er [5,6]. Perhaps the most
luminescent properties and crystallite size [1,2]. Special attention studied system is Yb–Er. Upconversion of Er3+ doped and
has been given to rare-earth-doped nanophosphors emitting in sensitized with Yb3+ has been widely studied in matrices such
the visible range by the upconversion process. Upconversion as GGG [7], NaLiF [8], ZrO2 [9], LaF3 [10,11], Y2O3 [12] and YAG
(UPC) is the generation of visible or UV light by excitation with [13]. The excited state of the Yb3+ ion (10,000 cm1) has a broad
larger wavelengths, usually NIR, of trivalent rare-earth ions absorption band between 800 and 1100 nm and a much higher
supported into a solid-state host. Several studies on the Er3+ ion absorption cross-section than the 4I11/2 excited state of Er3+. The
reveal high-efficiency emission around 550 and 650 nm under 780 large spectral overlap between Yb3+ emission (2F5/2-2F7/2) and
and 980 nm excitations [3]. Co-doping rare-earth ions with Yb Er3+ absorption (4I15/2-4I11/2) results in an efficient resonant
energy transfer (ET) from Yb3+ to Er3+ in Yb3+–Er3+-codoped
systems. It is well-known that in the upconversion emission of
 Corresponding author. Tel.: +524774414200. rare-earth ions, the highest phonon frequencies of the host lattice
E-mail addresses: [email protected], [email protected] (E. De la Rosa). are responsible for non-radiative relaxation, resulting in a

0022-2313/$ - see front matter & 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.jlumin.2008.11.015
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450 D. Solı́s et al. / Journal of Luminescence 129 (2009) 449–455

reduction of quantum efficiency. Then, matrices with low to-point resolution, 0.20 nm). The Fourier transform infrared
phonon energy are much more favorable in promoting the (FTIR) spectra were obtained using a Spectrophotometer Spec-
upconversion process. trum BX, FTIR system from Perkin-Elmer with a DTGS detector at
Zirconium dioxide (ZrO2) is chemically and thermally stable 4 cm1 spectral resolution and Beer-Norton anodization. Measure-
[14–16] and has a low phonon energy of about 470 cm1, which is ments were performed in the attenuated total reflectance (ATR)
very small compared to that of other hosts such as YAG mode using 100 mg of nanophosphor covering the whole active
(850 cm1)[17] or Y2O3 (597 cm1) [18]. This low phonon energy area of the ATR device. The spectrum was obtained in the
opens up the possibility of higher efficient luminescence of active medium-infrared region from 1000 to 4000 cm1 with 20 scans
ions incorporated into the host [19]. Thus, combining the proper- per spectra. Before measurements, the equipment was calibrated
ties of rare-earth ions, nanosize effect, and good qualities of ZrO2, by verifying that the power energy was 80% and the spectral
the study of luminescence properties in zirconium oxide nano- response was calibrated with a polystyrene film as a reference.
crystals is worthy of attention. ZrO2 has been studied with
different rare-earth ions, such as Yb–Tm [20], Yb–Ho [21], Er3+
2.3. Photoluminescence characterization
and Yb3+–Er3+ [3]. There, it has been shown that visible emission
depends on the concentration of both ions. Furthermore, depen-
For ZrO2:Er3+ and ZrO2:Yb3+–Er3+ samples, photoluminescence
dence of the luminescence efficiency on particle size, reduction of
(PL) characterization was performed using a CW semiconductor
the organic remnants and the phonon energy of the host has been
laser diode with a 350 mW pumping source centered at 970 nm.
reported [22–24]. However, to our knowledge no detailed analysis
The fluorescence emission was analyzed with a Spectrograph
of decay time dependence has been reported. Electron confine-
SpectraPro 2300i. The system was PC controlled with Spectra-
ment effect is not expected due to the localization of electrons in
Sense software. The fluorescence lifetimes for ZrO2:Er3+ samples
the atomic orbitals of active ions. However, excitation dynamics
were measured using a 10-ns pulsed tunable Optical Parametric
could be influenced by the nanoscopic interaction that can induce
Oscillator (OPO from Spectra Physics) centered at 970 nm, along
an enhancement of fluorescence emission.
with the monochromator, a R955 Hamamatsu photomultiplier
In this work, ZrO2:Er3+ and ZrO2:Yb3+–Er3+ samples were
and a Le Croy Digital Oscilloscope. Fluorescence lifetimes for
synthesized by a sol–gel micelle method. Both 0.2 mol% Er3+-
ZrO2:Yb3+–Er3+ samples were performed using the laser diode, an
doped and 2–1 mol% Yb3+–Er3+-codoped ZrO2 were studied in
SR540 chopper (Stanford) and a Tektronix TDS 3052B oscilloscope.
order to determine a correlation between particle size, annealing
All measurements were done at room temperature. Samples were
time and surfactant concentration on the emission intensity and
supported in 1 mm capillary tubes in order to guarantee the same
decay time of 562, 654, 1036 and 1526 nm emissions. The effect of
quantity of excited material. Special care was taken to maintain
sensitizer, both structural and luminescence, was evaluated.
the alignment of the set-up in order to compare the intensity of
the upconverted signal between different characterized samples.

2. Experimental section
3. Results and discussion
2.1. Sample Preparation
3.1. Structural characterization
The synthesis of ZrO2 nanophosphors doped at 0.2 mol% Er3+
and 2–1 mol% Yb3+–Er3+ was carried out by the sol–gel micelle The XRD patterns of ZrO2:Yb3+–Er3+ and ZrO2:Er3+ nanocrystals
method. All chemicals used were reactive grades and supplied annealed at 1000 1C are shown in Fig. 1. The phase composition
by Aldrich Inc. The samples were obtained using zirconium
n-propoxide (ZP), erbium nitrate (Er(NO3)3  5H2O) and ytterbium
chloride (YbCl3  6H2O) as precursors. All components were mixed
in a solution of ethanol (40 mol), hydrochloric acid (0.3 mol) and
nitric acid (0.9 mol), added at room temperature applying
vigorous stirring. In the micelle method, surfactant was added
at a molar ratio (Pluronic/ZrO2) of 0.0082, though 0.01 was also
used for Er-doped samples (Mrp ¼ 0.0082, 0.01). After that,
samples were stirred for 1 h and hydrothermally treated at 80 1C
for 24 h. The autoclave allowed a natural cooling and the gel was
washed twice with absolute ethanol. All samples were annealed at
1000 1C, some samples were removed from the furnace as soon as
the final temperature was reached (annealed 0 min (00 )) and some
samples were kept there for 5 h. In all cases, the heating rate was
5 1C/min and stayed at 300 and 500 1C for 2 h.

2.2. Structural characterization

The X-ray diffraction (XRD) patterns were obtained using a

SIEMENS D-5005 equipment provided with a Cu tube with Ka
radiation at 1.5405 Å, scanning in the 20–701 2y range with
increments of 0.021 and a sweep time of 2 s. Transmission electron
microscopy (TEM) was performed in a Tecnai G2 F30 S-Twin
transmission electron microscope operating at 300 kV. The Fig. 1. X-ray diffractions patterns as a function of surfactant concentration for
microscope is equipped with a Schottky-type field emission gun samples (a) ZrO2:Yb–Er, Mrp ¼ 0.0082—5 h, (b) ZrO2:Yb–Er, Mrp ¼ 0—5 h (c)
and an S-Twin objective lens (Cs ¼ 1.2 mm; Cc ¼ 1.4 mm; point- ZrO2:Er, Mrp ¼ 0.0082—5 h and (d) ZrO2:Er Mrp ¼ 0.0082—0 min.
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D. Solı́s et al. / Journal of Luminescence 129 (2009) 449–455 451

was estimated using the expression [25]: to monoclinic. For low concentrations of dopant, the tetragonal
crystalline structure is dominated by annealing time since the
Im ð1; 1; 1Þ þ Im ð1; 1; 1Þ content of this phase increases from 4.9% to 21.2% when the time
Cm ¼
Im ð1; 1; 1Þ þ Im ð1; 1; 1Þ þ It ð1; 0; 1Þ is reduced from 5 h to 0 min, as is shown on the XRD pattern of
Ct ¼ 1  Cm (1) Fig. 1c and d.
The crystallite size was calculated by the Sherrer equation as
where m and t stand for the monoclinic and tetragonal phase of
follows [27]:
the host and I stands for the integrated intensity of each peak. The
phase composition of both samples annealed for 5 h without 0:9l
the surfactant is dominated by the tetragonal (60 wt%) and the D¼ (2)
b cos y
monoclinic (96 wt%) crystalline phase, respectively. This confirms
the influence of ion concentration on the stabilization of the where l stands for the X-ray wavelength, b for the corrected half-
tetragonal phase, as was reported previously [26]. Interestingly, width of the strongest diffraction peak and y denotes the
the tetragonal phase was increased to 85 wt% after the addition of diffraction angle. The crystallite size for samples prepared with
Pluronic F-127 on codoped samples, see Fig. 1a and b. However, in the surfactant, Mrp ¼ 0.0082, was 54 nm and 37 nm for samples
ZrO2:Er3+ the surfactant concentration does not induce any annealed 5 h and 0 min, respectively. The introduction of Pluronic
appreciable change on the phase composition. This difference keeps nanocrystals well dispersed even for a long annealing time
suggests an increment on particles dispersion arresting growing as is shown in Fig. 2. The average particle size of ZrO2:Yb3+–Er3+
crystallite size and then avoiding the conversion from tetragonal and ZrO2:Er3+ nanophosphors synthesized with surfactant

Fig. 2. TEM micrographs of nanoparticles. (a) ZrO2:Yb–Er, Mrp ¼ 0.0082—5 h and (b) its particle size distribution. ZrO2:Er, Mrp ¼ 0.0082 annealed during (c) 5 h and (d)
0 min.

Table 1
Particle size and fluorescence decay time as function of Pluronic F-127 concentration and annealing time.

Sample Annealing time Particle size (nm) Fast decay time (ms) Slow decay time (ms) Effective decay time (ms)

Without surfactant 5h 90 26 – 26
Mrp ¼ 0.0082 5h 81 85 115 84
Mrp ¼ 0.0082 0 min 54 38 48 39
Mrp ¼ 0.01 5h 62 81 107 85
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452 D. Solı́s et al. / Journal of Luminescence 129 (2009) 449–455

Fig. 5. Green emission intensity of ZrO2:Er samples as a function of surfactant

concentration and annealing time.
Fig. 3. FT-IR spectra for surfactant and non-surfactant samples of ZrO2:Yb-Er
(2–1 mol%). Attenuation of OH groups could be observed.
characteristic of the nanopowder. The OH was produced during
the hydrolysis and condensation process and cannot be removed
completely through a long-time heat treatment. The presence of
this component is inherent in the sol–gel process and is one of the
main problems of the method. The other components are the
result of different organic compounds used in the synthesis
process. These include the organic part of zirconium n-propoxide,
the high quantity of alcohol and surfactant. The introduction of
surfactant reduces the residual OH component, as can be
observed in the FTIR spectrum displayed in Fig. 3 and was
reported recently [28–30]. The surfactant works as a dispersing
agent and its function is to weaken the organic bond. Then it
reduces organic impurities, enhances the crystallization and,
under optimum concentration, maintains the particle size [28].

3.2. Luminescence properties

3.2.1. Fluorescence emission

The fluorescence obtained after excitation at 970 nm shows
two visible emission bands, green and red, as the result of the
Fig. 4. Up-conversion emission spectra of ZrO2:Yb-Er and ZrO2:Er. The inset shows
upconversion process, see Fig. 4. Such bands are assigned to
the blue emission spectra and a picture of the green emission of the codoped 2
sample. ZrO2:Er luminescence is amplified by 3  .
H11/2+4S3/2-4I15/2 and 4F9/2-4I15/2 transitions of the Er ion,
respectively and are the result of the absorption of two photons
either from the pumping or from the energy transfer between
(Mrp ¼ 0.0082) and annealed at 1000 1C during 5 h is 75 and neighboring ions [30]. Upconverted emission depends on the ion
82 nm, respectively. With a short annealing time (0 min at concentration, for Er-doped nanocrystals is strongly dominated by
1000 1C) the average particle size of ZrO2:Er3+ nanocrystals the green band, the red band being only 5% of the total signal
decreased from 82 to 54 nm, suggesting a clear dependence on emitted. Experimental results show that fluorescence emission is
the annealing time. Considering that the average of crystallites per strongly dependent on the annealing time and on the surfactant
particle is 1.4, we can conclude that samples prepared with concentration (Pluronic F-127), as is shown in Fig. 5 for ZrO2:Er
Pluronic present high crystallite dispersion. The particle size for nanocrystals. The figure describes the behavior of the integrated
different annealing times and surfactant concentrations is shown green signal for different combinations of annealing time and
in Table 1. surfactant content. The upconverted signal was increased with the
The presence of organic residuals was analyzed by performing content of Pluronic and diminished for concentrations higher than
FTIR spectroscopy. Fig. 3 shows the FTIR spectra for codoped Mrp ¼ 0.0082. With that concentration, the integrated signal
samples prepared with and without a surfactant annealed at obtained by annealing for 5 h at 1000 1C is notably higher (97%)
1000 1C 5 h. The spectra present several resonant stretching bands than the signal obtained without the surfactant for samples
associated with different residual components such as OH annealed for 5 h and 70% for samples annealed for 0 min. Such a
(3200–3800 and 1200–1400 cm1), CH2 (3000 cm1), CH–CH2/ strong increment in the emitted signal is related with the
CH2 (1500–1750 cm1), CHQCH (1050 cm1) and H–CQO reduction of organic impurities as a result of the annealing time
(800 cm1). The band centered at 2350 cm1 is associated increment (0 min to 5 h) and the use of Pluronic F-127 during the
with CO2 adsorbed to the surface, partly during the synthesis synthesis process [30]. The former controls the crystallite size and
process and partly during measurements due to the granular the surfactant disperses nanocrystals, reducing the agglomeration
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Thus, the red enhancement depends on the concentration of both

ions, Er due to the cross-relaxation process and Yb due to ET
[3,31]. The overall signal intensity in the visible range increases
65% with the optimum concentration of surfactant. Such en-
hancement is the result of the reduction of impurities as was
discussed before. Interestingly, the enhancement is different for
each emission band. The intensity increased 75% and 60% for
green and red bands, respectively. However, a slight increment of
6% was observed for the blue emission. It has been reported that
OH ions on the surface would result in an enhancement of the
red band and a reduction of the green emission by phonon
coupling of 4F7/2-4F9/2 and 4I11/2-4I13/2 transitions [18]. Thus,
the larger enhancement of the green band suggests a reduction of
OH groups as was confirmed from FTIR spectra. However, an
excess of OH groups produce high-energy vibrational modes
(3200–3800 cm1), which could strongly quench the excited 4I13/2
state of the Er3+ ion by multiphonon relaxation. This intermediate
level is responsible for the green and red emissions, respectively.
Then, such excess can produce a deleterious effect on the overall

Fig. 6. Energy-level diagram for the upconversion processes of ZrO2:Yb-Er

nanocrystals under 970 nm excitation.

and absorption of impurities on the crystallite surface. Enhance-

ment of visible emission has been reported; however, samples
prepared with Pluronic F-127 produce the highest signal emitted.
A strong enhancement of the green and red band emitted by
Yb3+–Er3+-codoped nanophosphor and a new band centered at
410 nm (4G11/2-4I15/2), see Fig. 4, has been observed with the
introduction of a sensitizer (Yb3+). This is the result of the larger
absorption cross-section of the sensitizer. The little difference in
the spectral profile structure for doped and codoped samples is
produced by the different phonon energy and crystalline field
surrounding the Er ion, as a result of different crystalline phases.
The mechanism of the upconverted emission of Er3+ has been well
established in the literature. A typical energy-level diagram for
the upconverted emission from a sample codoped with Yb3+ and Fig. 7. NIR emission spectra of ZrO2:Yb-Er-codoped samples. Eye-safe emission
Er3+ ions under infrared excitation is shown in Fig. 6. The Er3+ ion centered at 1550 nm of Er ion and the inset shows the characteristic emission of Yb
(acceptor) is excited by the energy transfer (ET) from the Yb3+ centered at 1036 nm.
(donor), which is excited directly (2F5/2-2F7/2) by the pumping
signal. Direct excitation of Er is also possible; however, energy
transfer is most probably due to the larger absorption cross-
section of Yb and the resonance between 2F5/2-2F7/2 and
4
I15/2-4I11/2 transitions of Yb and Er, respectively, as is shown in
the energy diagram in Fig. 6. Part of the 4I11/2 excited ions relaxes
non-radiatively to the 4I13/2 level and from there relaxes to the
ground state, producing the 1.532 mm emission band (4I13/2-4I15/2).
And part of it was promoted to 4F7/2 by ET from the relaxation
of another excited Yb or Er (4I11/2-4I15/2) ion. The 4F7/2 level
decays non-radiatively to 2H11/2+4S3/2 due to phonon energy. From
here, the population decays to the ground state, producing bright
green emissions centered at 520 and 550 nm, respectively. Part of
it decays non-radiatively to 4F9/2 to finally decay to the ground
state, (4F9/2-4I15/2) producing the red emission centered at
670 nm. And part of it is promoted to 4G7/2 by ET from another
excited Yb or Er ion, relaxing non-radiatively to 4G11/2 from where
it decays radiatively to the ground state, producing the blue
emission centered at 410 nm. The introduction of sensitizer
changes the ratio of green/red emission bands from 20 for
Er-doped samples to 1.3 for Yb–Er-codoped samples. The strong
enhancement of the red band is explained in terms of the cross- Fig. 8. Fluorescence decay times at 550 nm for ZrO2:Er samples: (a) Mrp ¼ 0 at
relaxation process (4S3/2+4I15/2)-(4I9/2+4I13/2) and the ET from an 1000 1C—5 h, (b) Mrp ¼ 0.0082 at 1000 1C—0 min and (c) Mrp ¼ 0.0082 at
Yb3+ ion to promote the population from 4I13/2-4F9/2 (see Fig. 6). 1000 1C—5 h.
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454 D. Solı́s et al. / Journal of Luminescence 129 (2009) 449–455

intensity of the signal emitted. No correlation was found between impurities such as OH and CO2. Furthermore, the lower crystallite
other organic compounds and the photoluminescence intensity. size increases the surface defects, which induce deleterious effect
Fig. 7 shows the eye-safe emission centered at 1.52 mm on optical properties. This suggests that the effect of impurities is
associated with the 4I13/2-4I15/2 transition of the Er3+ ion. The stronger than the nanosize effect. The reduction on crystallite size
inset corresponds to the characteristic emission of Yb3+ centered enlarges but impurities and surface defects shorten the decay
at 1036 nm (2F5/2-2F7/2). As is expected, both near-infrared time. Impurities’ effect is observed in the sample annealed for
emission bands present a strong enhancement with the presence 0 min, where decay time is notably reduced even though particle
of the surfactant being 79% for eye-safe emission band and 70% for size was reduced.
Yb characteristic emission. As was discussed before, the presence The introduction of Yb as the sensitizer enlarges fluorescence
of OH produces a deleterious effect on the luminescence decay time. Such enlargement, independent of surfactant, is the
properties, especially in the near-infrared range. Thus, the strong result of the energy transfer process from Yb to Er. In the ET process,
enhancement of both bands indicates the OH reduction as can be decay time depends on the intermediate state of decay, which for Yb
observed in Fig. 3 [28–30]. In turn, the OH reduction by the is much larger than 4I11/2 of Er [36]. In addition, it has been shown
surfactant propitiates more energy transfer from the Yb3+ to Er3+ that the presence of Yb avoids clustering of the Er ion, enhancing all
by the decrement of the non-radiative process. spectroscopic properties [37]. Yb-Er-codoped nanocrystals also
present an increment on the effective decay time with the use of
3.2.2. Fluorescence decay time surfactant. Fig. 9 shows the corresponding plot for 562 and 654 nm.
The fluorescence decay times of Er3+-doped and Yb–Er- The effective decay time was 320 ms for the green band on both non-
codoped ZrO2 nanocrystals were obtained as a function of surfactant and surfactant-prepared samples. However, the former
annealing time and surfactant concentration. Fig. 8 shows the
decay time of emission at 550 nm of ZrO2:Er for samples prepared
with and without surfactant and the calculated values are listed in
Table 1. Notice the fast decay time, t ¼ 26 ms, of the sample
prepared without the surfactant being fitted to the single
exponential function. Such fast decay is produced by the presence
of a high concentration of impurities such as OH and CO2, which
can be corroborated from FTIR, and probably surface defects
produced by the crystallite size. It is not connected with
fluorescence quenching due to clustering ions considering the
low concentration of Er. The introduction of surfactant enlarges
the decay time but two exponential functions are required to fit
the experimental data. In this case and taking into account the
appropriate value of Mrp ¼ 0.0082,R1 the effective decay time
R1
calculated by teff ¼ 0 tIðtÞ dt 0 IðtÞ dt is larger than 200%
(teff ¼ 84 ms) with a fast decay 3 times larger and 115 ms for
slow or natural decay time, which is in agreement with others’
results reported for different hosts [31,32]. The enlargement of
fast decay time suggests a reduction of OH as is indicated in Fig.
3. Interestingly, for a high surfactant concentration but the same
annealing process, the effective decay time is the same even
though particle size diminished 20 nm. For optimum composition Fig. 9. Fluorescence decay times of ZrO2:Yb-Er samples: at 654 nm for (a)
of surfactant but annealing for 0 min, the crystallite size is 54 nm Mrp ¼ 0.0082 and (b) Mrp ¼ 0; at 562 nm for (c) Mrp ¼ 0.0082 and (d) Mrp ¼ 0.

and effective decay time diminished, being 50% faster than the
sample annealed for 5 h. These results, and considering also the
particle size of the sample prepared without surfactant, suggest
that fluorescence decay time is dominated by surface impurities
and perhaps by defects produced by the large surface-to-volume
ratio [33]. Probably, the major contribution of fast decay time is
produced by ions close or on the surface of nanocrystals, as has
been suggested [33]. For a particle much smaller than the
wavelength of the signal emitted, the decay time of nanoparticles
(tnp) should be inversely proportional to the refractive index of
the surrounding medium (ns). The decay time of bulk and
nanocrystals are related by the expression [34]:
nbc
tnp ¼ tbc (3)
neff
where tbc and nbc stand for decay time and refractive indexes of
the bulk crystal, respectively. The effective refractive index is
calculated by neff ¼ ð1  xÞns þ xnbc [35]. Here, x is the ‘‘filling
factor’’, that is the space fraction occupied by the nanoparticles.
The smaller the nanoparticles, the larger the decay time. Such
enlargement of tnp was observed as is shown in Table 1. However,
for the sample with Mrp ¼ 0.01 no enlargement was observed
Fig. 10. Fluorescence decay times of ZrO2:Yb-Er samples in the 1036 nm emission
even though crystallite size was reduced. In this particular case, it band associated with the 4F5/2 energy level of Yb. The inset shows the decay times
has been observed that there are higher concentrations of of the 1526 nm emission band associated with the 4I11/2 energy level of Er.
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D. Solı́s et al. / Journal of Luminescence 129 (2009) 449–455 455

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