Appl Phys B (2011) 102: 641–649

DOI 10.1007/s00340-010-4233-1

Solvent and surfactant effect on the self-assembly and

luminescence properties of ZrO2 :Eu3+ nanoparticles
T. López-Luke · E. De la Rosa · V.H. Romero ·
C. Ángles-Chávez · P. Salas

Received: 21 April 2010 / Revised version: 7 August 2010 / Published online: 17 September 2010
© Springer-Verlag 2010

Abstract ZrO2 :Eu3+ nanocrystals ranging from 17 to 1 Introduction

43 nm were prepared by the facile precipitation method with
a hydrothermal process. The crystallite size was strongly in- Europium is the most used lanthanide to produce red light
fluenced by the solvent composition and enhanced with the emission for applications such as fluorescent tubes for light-
presence of surfactant. The use of ethanol combined with ing applications, color television, x-ray photography and
surfactant stabilizes 50 wt% of the monoclinic phase, while detection systems [1–5]. Special attention has received
the use of water only results in 100 wt% tetragonal phase. the synthesis and characterization of lanthanides doped
80% of nanobelts were obtained preparing the sample with nanomaterials due to their behavior and subsequent de-
ethanol and surfactant as a results of the self-assembly of sirable properties, which mainly come from the high sur-
nanoparticles. The photoluminescence emission peak cen- face/volume ratio resulting from the particle nanosize
tered at 606 nm dominates the emission band for nanobelts, [6–8]. Some interesting phenomena have been observed
while for nanoparticles it is dominated by a peak centered as the particle size decreases, and they have arisen from
at 612 nm. Such differences were explained in terms of transformation of the local symmetry, which can be de-
the site symmetry occupying Eu3+ in the host that in turn duced from variations of the spectra [9]. Quantum con-
depends on the crystalline phase. Changes in the intensity finement effect is not expected due to the localization of
ratio I (612 nm)/I (606 nm) is proposed as a tool to ana- electrons in atomic orbital of active ions; however, the
lyzing changes in the monoclinic/tetragonal phase compo- excitation dynamic is influenced by the nanoscopic inter-
sition. The calculated asymmetry ratio R = 7F2 /7 F1 ∼ 1.2 action that can induce and enhancement in the fluores-
suggest a high degree of crystallinity of the prepared sam- cence emission. Thus, the nanophosphors promise high
ples. performance materials for photonic applications. Differ-
ent crystalline structures have been used to support Eu-
ropium such as YAG, GGG, Y2 SiO5 , BaTiO3 and the two
most studied Y2 O3 :Eu3+ and YVO4 :Eu3+ [10–15]. How-
ever, the development of new phosphors with better perfor-
mance for applications in solid-state lighting deserves spe-
T. López-Luke · E. De la Rosa () · V.H. Romero
Centro de Investigaciones en Óptica, A.P. 1-948, León Gto 37160, cial attention. Recently, it has been reported that lanthanide
Mexico doped ZrO2 nanocrystals are excellent candidates for vis-
e-mail: elder@cio.mx ible light emission either by pumping with an ultra violet
(UV) source [16–18] or by a near infrared (NIR) sources
C. Ángles-Chávez
Instituto Mexicano del Petróleo, Programa de Ingeniería [19–21]. Their optical properties such as a high refractive
Molecular, A.P.11-848, Mexico, DF 07730, Mexico index and their better chemical and photochemical stabil-
ity than other oxide hosts make these nanophosphors suit-
P. Salas able for photonic applications. Moreover, these nanocrystals
Centro de Física Aplicada y Tecnología Avanzada, Universidad
Nacional Autónoma de México, A.P. 1-1010, Querétaro, Qro have a very low phonon energy (470 cm−1 ) that increases
76000, Mexico the number and the probability of radiative transitions in
642 T. López-Luke et al.

rare earth doped samples. Recently, it has been demon- Cl3 Eu·6H2 O at 2 mol% of Eu2 O3 and dissolved in three
strated that the crystalline phase (monoclinic, tetragonal and different H2 O/EtOH ratios: (a) 100% H2 O (50 ml of dis-
cubic) of lanthanide doped ZrO2 nanocrystals depends on tilled water), (b) 100% EtOH (50 ml ethanol) and (c) 50%
the lanthanide concentration and the annealing temperature H2 O/50% EtOH (25 ml of H2 O and 25 ml of EtOH). The
[20, 22]. Because the crystalline phase determines the crys- non-ionic surfactant Pluronic F-127 was added to samples
talline field surrounding the active ion, it is expected that the prepared in H2 O with different molar ratios of Pluronic
structure of the emitted signal could be affected. Thus, it is Mrp = F-127/ZrO2 = 0, 0.0041, 0.0082, 0.01, 0.02 and
important to understand how the active ion is inserted in the 0.03. Precipitation was obtained by adding 60 ml of am-
crystalline structure and how this affects the luminescence monium hydroxide, adjusting the pH = 10. The resulting
properties. It is well known that one of the Eu3+ electronic suspension was transferred into a sealed autoclave and hy-
4f → 4f orbital transitions and the transition from the 2p drothermal treatment was carried out at 80, 140 and 200◦ C
O2− orbital to the 4f Eu3+ orbital, producing the excited for 24 h. After that, the autoclave was allowed to cool nat-
charge transfer band (CTB), are strongly dependent on the urally and the solution was washed twice with absolute
environment crystalline field [23]. Eu3+ is very sensitive to ethanol and water in a centrifuge to 3000 rpm during 10 min.
the surrounding field and has been used to study the effect of All samples were annealed at 1000◦ C during 5 h and re-
crystallite size, crystalline structure, and in general, how the moved from the furnace as soon as the time was completed;
synthesis process influences the luminescence properties of the sample prepared with 50/50% (EtOH/H2 O) was also an-
nanophosphors, in particular ZrO2 nanophosphors [16, 18, nealed at 800◦ C. In all cases, the heating rate was 5◦ C/min
24, 25]. and stayed at 300 and 500◦ C for 2 h.
Different methods have been reported for the preparation
of europium doped ZrO2 nanocrystals, the most used are the 2.2 Structural characterization
microemulsion method [26], precipitation [27], combustion
[28], sol–gel [29] and spray pyrolysis [30, 31]. The particle X-ray diffraction (XRD) patterns were obtained using a
size, crystalline structure and morphology of nanoparticles SIEMENS D-5005 equipment using a Cu tube with Kα ra-
are strongly influenced by the synthesis conditions. Dissolv- diation at 1.5405 Å, scanning in the 20–80◦ 2θ range with
ing and mixing the raw materials of metal (M) and europium increments of 0.02◦ and a sweep time of 2 s. Scanning
in an organic compound affect the distribution of ions in the transmission electron microscopy (STEM) analysis was per-
liquid-state solvent, and determine the synthesized particle formed in a JEM-2200FS microscope with an accelerating
size. Dispersing agents also affect the nanoparticle disper- voltage of 200 kV. Images were acquired by a high-angle
sion and therefore the nanoparticle size and surface defects
annular dark field (HAADF) detector. The samples were
[20, 32]. Thus, a systematic characterization of the com-
ground, suspended in isopropanol at room temperature and
bined effect of solvent and surfactant on the morphology
dispersed with ultrasonic agitation; a drop of the solution
and luminescence properties is necessary. In this paper, the
was placed on a 3 mm diameter carbon film supported on a
luminescence characterization of Eu3+ emission is reported
holey copper grid.
as a function of solvent (H2 O/EtOH) and surfactant F-127
The Fourier transform infrared (FTIR) spectra were ob-
concentration. ZrO2 :Eu3+ nanocrystals were fabricated by
tained using a Spectrophotometer Bruker Vector 33. Mea-
a precipitation method with a hydrothermal process and we
surements were performed by transmittance technique, with
determined the optimal condition to enhance the emitted
samples prepared with KBr (1:2 weight ratio). The spectrum
signal. Changes in the Rf 2 = I (612 nm)/I (606 nm) ratio
was obtained in the medium-infrared region from 1000 to
were proposed to be used as an indicator of the symmetry of
4000 cm−1 with 20 scans per spectrum. Before measure-
the coordination polyhedron of Eu3+ ion, and therefore the
ments, the equipment was calibrated with polystyrene refer-
tetragonal/monoclinic structural composition.
ence.

2 Experimental section 2.3 Photoluminescence characterization

2.1 Sample preparation Photoluminescence (PL) characterization was performed

with a 75 W white light source (Xenon Lamp). Excitation
ZrO2 :Eu3+ nanocrystals were prepared by a precipitation was performed at 256 nm and the fluorescence emission
method. ZrOCl2 ·8H2 O and Cl3 Eu·6H2 O were supplied by was analyzed with an Acton Research modular 2300 spec-
Aldrich, Inc. An ammonium hydroxide solution at 30% in trofluorometer and a R955 Hamamatsu photomultiplier tube
volume was used as precipitant and was supplied by Karal for visible emission. The system was PC controlled with
(3010). In a typical sample, Eu3+ doped ZrO2 was ob- the Spectra-Sense software. All measurements were done at
tained with 2.73 g of ZrOCl2 ·8H2 O mixed with 0.23 g of room temperature. Nanopowder was compacted on pellets
Solvent and surfactant effect on the self-assembly and luminescence properties of ZrO2 :Eu3+ nanoparticles 643

with 25 mg and 5 mm in diameter. Special care was taken

to keep the alignment of the setup in order to compare the
intensities between different characterized samples.

3 Results and discussions

3.1 Structural characterization

Representative XRD patterns for different samples are

shown in Fig. 1. The phase composition for all prepared
samples is listed in Table 1 and was estimated by using the
expression

Im (−1, 1, 1) + Im (1, 1, 1)
Cm = and
Im (−1, 1, 1) − Im (1, 1, 1) + Im (1, 0, 1)
Ct = 1 − Cm

where m and t stand for the monoclinic and tetragonal phase

of the host and I stands for the intensity of each diffrac-
tion peak. According to these patterns, the sample prepared Fig. 1 X-ray diffraction patterns of ZrO2 :Eu3+ nanoparticles doped
in water without surfactant presents 100% tetragonal phase, at 2 mol% prepared with different H2 O/EtOH ratio, with and with-
see Fig. 1a. However, the addition of surfactant promotes out surfactant, with a hydrothermal temperature of 80◦ C and annealed
at 1000◦ C. (a) Mrp = 0 and H2 O; (b) Mrp = 0 and EtOH; (c) Mrp
the formation of monoclinic phase. For Mrp = 0.0082 and = 0.0082 and EtOH; (d) Mrp = 0.0082 and 50/50 vol%; (e) Mrp =
Mrp = 0.03 the monoclinic phase was 5 and 10 wt%, re- 0.0082 and 50/50 vol% but T = 800◦ C
spectively. Samples prepared in EtOH without surfactant
present a crystalline phase composition of 70 wt% of tetrag- in the synthesis have in the crystalline phase composition;
onal and 30 wt% of monoclinic phases, see Fig. 1b. In this both EtOH and surfactant contribute to stabilize the mono-
case, the addition of Mrp = 0.0082 promotes an increment clinic phase.
on the monoclinic phase to 50 wt%, see Fig. 1c. Neverthe- The average crystallite size was calculated by the well-
less, EtOH exhibits a stronger capacity than surfactant as far known Scherrer’s equation D = (0.9λ)/(β cos θ ), where
as the stabilization of monoclinic phase is concerned. Inter- λ = 1.5406 Å is the X-ray wavelength, θ is the diffrac-
estingly, the combined effect is stronger than what was ob- tion angle and β is the corrected half-width of the strongest
served individually. This combination effect opens the pos- diffraction peak. The calculated average crystallite size de-
sibility to explore different combinations of surfactant and pends on the solvent, surfactant, hydrothermal and anneal-
solvent in order to control the crystalline phase composition. ing temperature. All calculated values are listed in Table 1.
In spite of this, the use of surfactant in a combination of both The crystallite size of the sample prepared in water with-
solvents (water/ethanol) reduces the monoclinic phase for- out surfactant was 17 ± 1 nm, and an increment of 41% on
mation, see Fig. 1d. In this case, the monoclinic phase for- the crystallite size was observed with the presence of sur-
mation was completely avoided by reducing the annealing factant. However, the crystallite size does not change by in-
temperature to 800◦ C, see Fig. 1e. This is in correspondence creasing the surfactant concentration. The crystallite size for
with previous results where it was shown that the lower the samples prepared in EtOH was 27 ± 1 nm, and increases
annealing temperature the larger the tetragonal phase con- 22% with the introduction of surfactant. Interestingly, the
tent. Notice that the tetragonal crystalline phase is also sta- effect of surfactant in the growing of nanocrystals is twice
bilized by the content of Eu3+ , as has been reported previ- as much for samples prepared in water than for samples pre-
ously [18, 29, 33]. It was also observed that temperature of pared in ethanol only. Nevertheless, the crystallite size for
hydrothermal process stabilize the tetragonal phase. An in- samples prepared in ethanol is 60% larger than for samples
crement of 80% of tetragonal phase was observed for sam- prepared in water. No effect was observed on crystallite size
ples prepared in EtOH and 140◦ C of hydrothermal process by the combination of H2 O/EtOH/surfactant and the crystal-
compared with the sample prepared at 80◦ C. However, for lite size was similar than that obtained for EtOH/surfactant.
samples prepared in EtOH at 200◦ C the tetragonal phase di- An increment of 20% and 25% on the crystallite size was
minishes to 52%. These results confirm the important role observed by the increment of the hydrothermal temperature
that solvent, surfactant and the hydrothermal process used to 140◦ C and 200◦ C, respectively. As was expected, the
644 T. López-Luke et al.

Table 1 Phase composition and

crystallite size of ZrO2 :Eu3+ Solvent Molar ratio Phase composition Crystallite size
prepared with different solvent, Pluronic/ZrO2 (wt%) (±1 nm)
annealing and hydrothermal
temperature. All the samples H2 O 0 t = 100 17 nm
prepared are annealed at
m=0
1000◦ C and a hydrothermal
temperature of 80◦ C H2 O 0.0082 t = 100 24 nm
m=0
EtOH 0 t = 70 27 nm
m = 30
EtOH 0.0082 t = 50 33 nm
m = 50
H2 O–EtOH 0.0082 t = 100 34 nm
m=0
H2 O–EtOHa 0.0082 t = 100 17 nm
m=0
a Samples were annealed at EtOHb 0.0082 t = 80 41 nm
800◦ C m = 20
b Samples were treated at 140◦ C EtOHc 0.0082 t = 60 43 nm
c Samples were treated at 200◦ C m = 40
during the hydrothermal process

low annealing temperature (800◦ C) reduces the crystallite pared with EtOH have more possibilities to agglomerate
size to 17 nm ±1 nm corresponding to a 50% reduction. and grow than primary particles prepared with water that
Combining the crystallite phase and crystallite size results have a higher dielectric constant, ε = 78.5. The fact that
discussed above is reasonable to conclude that both, EtOH surfactant affects crystallite size is probably a result of the
and surfactant, stimulate the tetragonal crystallite grow in particular surfactant used in this experiment. The surfac-
such a way that turn on monoclinic phase. The combina- tant is soluble in H2 O, however for higher concentration
tion of both, EtOH and surfactant, promotes a stronger ef- the micelles aggregate creating several nanocrystal nuclei
fect arrested with the presence of water and in turn avoid- that coalesce forming bigger crystallites. It was also ob-
ing the formation of monoclinic phase. The hydrothermal served that for samples prepared with surfactant in EtOH the
temperature promotes a controlled grow of tetragonal crys- nanocrystals are bigger than nanocrystals prepared in wa-
tallites, however not sufficiently to change to monoclinic ter. This is explained by the poor solubility of surfactant in
phase. EtOH that forms larger micelle aggregates resulting in big-
It is well known that the energy barrier Vb between ger nanocrystals.
two nanoparticles, which prevents aggregations, depends The morphology of nanoparticles obtained for different
strongly on the dielectric constant of the solvent. It is cal- preparation conditions are observed in the HAADF images
culated by the expression Vb = −Akα/12 + 2πεαψ, where shown in Fig. 2. Samples prepared in water without surfac-
A is the effective Humaker constant, k the Debye–Huckel tant produce agglomerated spherical nanocrystals as is ob-
parameter, α the particle diameter, ε the dielectric constant served in Fig. 2a. However, the addition of surfactant from
of the solution and ψ the surface potential [34]. The Hu- Mrp = 0.0042 to 0.03 produces spherical particles with an
maker constant and Debye–Huckel parameter remain con- average crystallite size of 20 nm, see Fig. 2b. In this case, no
stant in selected experimental conditions. The surface po- significant changes were observed in the crystallite size for
tential is the same for all prepared samples, Vb being only different surfactant concentration. The use of EtOH with-
dependent on ε. Therefore, the increment of nanoparticle out surfactant results in a bigger particle size with different
size for samples prepared with EtOH or EtOH/H2 O solu- morphology, mixed with some belt-like formations as is ob-
tion is probably due to the electrostatic attraction between served in Fig. 2c. With the introduction of surfactant (Mrp =
initially precipitated primary particles. The increment is rel- 0.0082), the formation of belts was promoted obtaining a
atively small compared to the primary particles prepared yield up to 80% and only 20% of spherical particles. The
with water, this is probably due to the low dielectric con- average size of nanobelts is ∼900 nm ± 10 nm large and
stant of the EtOH/H2 O and EtOH solution, ε = 23.5 and ∼200 nm ± 10 nm width, see Fig. 2d. Notice the combined
22.41, respectively [34]. This condition is also true for so- effect of surfactant and EtOH in the belt formation. Micelle
lution at boiling point. Therefore, primary particles pre- shape (e.g. spheres, rod, lamellar, etc.) depends on the con-
Solvent and surfactant effect on the self-assembly and luminescence properties of ZrO2 :Eu3+ nanoparticles 645

Fig. 2 HAADF images of

ZrO2 :Eu3+ nanoparticles
prepared with H2 O or EtOH,
with and without surfactant,
with a hydrothermal
temperature of 80◦ C and
annealed at 1000◦ C.
(a) Mrp = 0 and H2 O;
(b) Mrp = 0.0082 and H2 O;
(c) Mrp = 0 and EtOH;
(d) Mrp = 0.0082 and EtOH

centration and the molecular characteristic of copolymer and shape. In spite of this, nanoparticles with average crystallite
the nature of solvent [35]. Therefore, the formed belts are size of 14 nm, obtained by the reduction of the annealing
probably due to the fact that surfactant is no longer soluble temperature, do not present the belt formation, see Fig. 3d.
and contributes to a number of micelles aggregations as has
been reported recently [36]. Nonetheless, the yield of the 3.2 FTIR characterization
belt formation was not changed with the increment of sur-
factant. It has been suggested that by varying the copolymer Figure 4 shows the FTIR spectra of four characteristic sam-
ethylene oxide (EO) and propylene oxide (PO) composition ples. Several resonant stretching bands associated with dif-
ratio, and in presence of a diol group, the nanobelt formation ferent residual components were observed. The dominant
can be increased [35, 36]. absorption band is centered at 3352 cm−1 and corresponds
The increment of the hydrothermal temperature avoid the to OH stretching vibrations. This impurity was produced
self-assembled of nanocrystals, and only few nanobelts with during the hydrolysis and condensation processes where
poor morphology were observed, see HAADF images of the OH bond was formed due to the saturation of ethanol
Figs. 3a–b. Considering that an increment of hydrothermal and water. The presence of this component is inherent
temperature promotes an increment of nanocrystal size, it in the precipitation process and is one of the main prob-
is reasonable to assume the important role of the crystal- lems of the synthesis method. The other peaks are associ-
lite size on the self-assembly of nanocrystals. In the case of ated to compounds formed from ammonia. Peaks centered
nanoparticles prepared with 50/50 vol% (H2 O/EtOH), the at 1637 cm−1 and 1564 cm−1 are associated to OH and
average particle size is 34 nm, as is observed in Fig. 3c, C=N stretching vibrations, respectively. Peaks centered at
and this is in agreement with the crystallite size calculated 1398 cm−1 and 1365 cm−1 are associated to –OCH, the
by XRD. Such a particle size probably explains the absence peak centered at 1047 cm−1 is associated to C–N and the
of belt formation. Furthermore, these nanoparticles present peaks centered at 975 cm−1 , 825 cm−1 , 757 cm−1 , 667 cm−1
a much better dispersion and have a noticeable spherical are associated to N– oxides C–H stretching vibrations. Thus,
646 T. López-Luke et al.

Fig. 3 HAADF images of

ZrO2 :Eu3+ nanoparticles
prepared with Mrp = 0.0082
and annealed at 1000◦ C, with
different H2 O/EtOH ratio and
hydrothermal temperature (Th ).
(a) EtOH and Th = 140◦ C;
(b) EtOH and Th = 200◦ C;
(c) 50/50 vol% and Th = 80◦ C;
(d) 50/50 vol% and Th = 80◦ C
but T = 800◦ C

FTIR indicate the presence of different organic compounds

used in the synthesis process. These results suggest that
samples prepared with 50/50 vol% (H2 O/EtOH) have the
lowest concentration of O–H impurities, ∼10% lower than
samples prepared with 100% H2 O or 100% EtOH. This
is probably a result of the solvent saturation. In addition,
a lower annealing temperature increases the OH concentra-
tion. An increment of 23% on the OH content was observed
for samples annealed at 800◦ C, see Fig. 4d.

3.3 Luminescence properties

The room-temperature excitation spectra of ZrO2 :Eu3+ are

shown in Fig. 5. The broad band centered at 246, 244 and
239 nm corresponds to Eu–O ligand-to-metal charge trans-
Fig. 4 FTIR spectra of ZrO2 :Eu3+ prepared with Mrp = 0, different
fer (CT) transition for samples prepared in H2 O, H2 O/EtOH solvent composition and annealed at 1000◦ C. (a) 50/50 vol%; (b) H2 O;
(50%/50%) and EtOH, respectively. This is the result of the (c) EtOH; (d) 50/50 vol% and Ta = 800◦ C
electronic transitions from 2p orbital of O2− to 4f orbital
of Eu3+ . The CT energy position depends on the field of
ions surrounding O2− , the strength of anion binding, the size change in the covalence between O2− and Eu3+ . It has been
of the cation site and the coordination number [37]. Then, reported that for an oxide host in which the coordination of
the shifting to a higher energy of the CT band suggests a Eu3+ is higher than six-fold, the position of the charge trans-
Solvent and surfactant effect on the self-assembly and luminescence properties of ZrO2 :Eu3+ nanoparticles 647

Fig. 5 Excitation spectra of ZrO2 :Eu3+ nanocrystals for λemi =

612 nm; vertical dashed lines are just to identify the peak position

fer band is correlated with the Eu–O mean distance, shift-

ing to a higher energy by decreasing the bond length [29].
Fig. 6 The emission spectra of ZrO2 :Eu3+ for samples prepared with
Thus, the 5-nm shift to a higher energy of the CT band indi- Mrp = 0.0082, Th = 80◦ C, annealed at 1000◦ C and different solvent
cates the decrement of the bond length for samples prepared composition. (a) H2 O; (b) EtOH; (c) Mrp = 0 and EtOH; (d) EtOH
with EtOH, where the belts were obtained. The bond length and Th = 200◦ C; (e) 50/50 vol%; (f) 50/50 vol, Ta = 800◦ C
decrement of Eu–O could be associated with the decrease in
symmetry induced by the change from tetragonal to mono-
that have a dominant tetragonal phase with very low con-
cline crystalline structure. This was corroborated by measur-
tent of monoclinic phase, to 1.5 for samples prepared with
ing the excitation spectra for samples prepared in H2 O that
surfactant and EtOH that have the larger content of mon-
were little shifted to lower energy, almost similar as the one
oclinic phase (50 wt%), as was described above. However,
obtained for the mixture H2 O/EtOH and this is in agreement
samples prepared without surfactant, that result in a tetrag-
with the increment on tetragonal crystalline phase. These re-
onal phase (with very low content of monoclinic phase) has
sults also confirm that coordination of Eu3+ is higher than
a smaller value of R = 1.2. These results indicate that the
six-fold.
The photoluminescence shows a strong emission after samples prepared with surfactant, and therefore possessing
excitation at room temperature with a signal centered at more monoclinic phase, have higher asymmetry of the poly-
256 nm, see Fig. 6. The fluorescence obtained from 2 mol% hedron in the Eu3+ ion. This is in correspondence with the
doped ZrO2 :Eu3+ nanocrystals shows two strong emission symmetry/asymmetry introduced by the crystalline phase.
bands centered at 592 and 606 nm ascribed to 5 D0 →7 F1 The largest value of R was obtained for the sample with
and 5 D0 →7 F2 transitions, and two weak bands centered the higher content of monoclinic phase, that is, the struc-
at 579 and 650 nm ascribed to 5 D0 →7 F0 and 5 D0 →7 F3 , ture with more asymmetry. The calculated values reported
respectively. The 5 D0 →7 F1 is a magnetic dipole transi- in this paper are lower than those reported from powders ob-
tion (magnetically allowed) and is independent of the crys- tained by co-precipitation (R ∼ 2.6) [38], thin films (R ∼ 6)
talline local environment surrounding the active ion. The [39], powder (R ∼ 2.3–3.5) obtained by sol–gel [24, 29]
5 D →7 F is an electric dipole transition allowed only at
0 2
and powder obtained using a solvothermal method (R ∼ 9
low symmetries with no inversion center. It is a hypersen- for monoclinic phase) for ZrO2 :Eu3+ doped at 1 mol%,
sitive transition, very sensitive to the environment. Thus, as was reported recently [18]. Furthermore, calculated val-
the integrated intensity ratio R = 7F2 /7 F1 , also known as ues are much lower than those reported for bulk (R ∼ 5.3)
asymmetry ratio, indicates the asymmetry of the coordina- and nanocrystalline (R ∼ 6.5) powder of cubic Y2 O3 :Eu3+
tion polyhedron of the Eu3+ ion. The lower the R-value, [40]. The R ∼ 1.4 reported here is one of the lowest value
the higher the site symmetry of the Eu3+ ion. The asym- reported in the literature and suggests that coordination of
metry ratio was calculated considering the integrated inten- Eu3+ in the nanocrystals reported here presents a very low
sity of each emission band and very little changes were ob- distortion, indicating the high crystalline degree of the pre-
served for samples prepared at different experimental con- pared samples and the relevance of the synthesis process.
ditions. Calculated values range from 1.4 for samples pre- The structure and peak position of the emission spectra
pared with surfactant in water and the mixture H2 O/EtOH are strongly related to the site symmetry of Eu3+ in the host
648 T. López-Luke et al.

lattice. The strong band at 600–640 nm (5 D0 →7 F2 ) is split

into four peaks but dominated by two strong peaks, the high-
est one centered at 606 nm and a smaller one centered at
612 nm, see Fig. 6. Such characteristic emission peaks have
been attributed to Eu3+ occupying D2h or D4h symmetry
sites in the cubic phase of ZrO2 nanocrystals [18]. Con-
sidering that the crystalline field strength for Eu3+ in the
tetragonal phase is similar to that in the cubic phase, it is
reasonable to assume that dopant ions occupy the same sites
in tetragonal phase, the dominant phase observed in all sam-
ples under study. However, the peak centered at 612 nm is
the highest one for samples prepared with EtOH and Mrp =
0.0082 presenting 80% of belts, see Fig. 6b. This result is
attributed to Eu3+ ions occupying C1 or Cs symmetry sites
in the monoclinic structure of ZrO2 nanocrystals [18], and Fig. 7 The integrated signal as a function of the molar ratio
is in agreement with the high content of monoclinic phase Pluronic/ZrO2 . The integrated signal error margin is 1.5%
(50 wt%) calculated from XRD patterns. Such conclusion
was confirmed reducing the monoclinic phase content by the
No structural changes on the emission spectra were ob-
increment of hydrothermal temperature to 140 and 200◦ C,
served on samples prepared with different surfactant con-
as was discussed above. In both cases, the intensity of the
centrations. However, an increment of the emitted signal
peak centered at 612 nm is lower than the peak centered
was observed with an optimum concentration of Pluronic
at 606 nm as is shown in Fig. 6d. Interestingly, changes in
F-127, see Fig. 7. The addition of low Pluronic concentra-
the Rf 2 = I (612 nm)/I (606 nm) ratio can be used as an
tion (Mrp = 0.0041) induces a reduction of 44% ± 1.5%
indicator of the symmetry of the coordination polyhedron
of the integrated signal compared with samples prepared
of Eu3+ ion, and consequently the tetragonal/monoclinic
in EtOH without surfactant. Nevertheless, the increment on
structural composition. Rf 2  1 indicates a dominance of
the Pluronic concentration enhances the emitted signal being
612 nm peak and Rf 2  1 a dominance of 606 nm peaks.
the maximum 26% ± 1.5% higher for Mrp = 0.0082. Incre-
Rf 2 = 1.55 for 50 wt% of monoclinic phase and decreases
ment to Mrp = 0.01 and 0.03 induce an increment of the
to 1.00 and 1.39 by increasing the hydrothermal tempera- emitted signal of only 25% ± 1.5% and 15% ± 0.05%, re-
ture to 140 and 200◦ C and monoclinic phase was reduced to spectively. Therefore, the emitted signal was reduced above
20 wt% and 40 wt%, respectively. Furthermore, this ratio de- and below of the optimal molar ratio Mrp = 0.0082. The
creases 66% for the sample prepared with EtOH but without increment could be associated to the reduction of OH’s rad-
surfactant, see Fig. 6c, in which case the monoclinic phase icals and the decrement is probably due to the excess of or-
is only 30 wt%. Belts are also present with the increment ganic materials arising from the use of surfactant, as was re-
of hydrothermal temperature although in lower concentra- ported recently [20, 32, 41]. Little variations were observed
tion and only for 80◦ C Rf 2 > 1. This confirms that Rf 2 is on the integrated emitted signal for samples prepared with
determined by the phase composition and not arising from different solvents, but the highest emitted signal was ob-
the belt formation. Both emission peaks, the one centered tained from samples prepared with the mixture H2 O/EtOH
at 606 nm associated to the tetragonal phase, and the one (50/50 vol%), annealed at 1000◦ C. In this case, an incre-
centered at 612 nm associated to the monoclinic phase, have ment of 50% ± 1.5% was obtained compared with sam-
been reported [18, 25]. However, in either of those cases ples prepared in H2 O and in EtOH. And it is 85% ± 1.5%
were the peaks comparable to what is reported here. From larger than samples prepared in EtOH without surfactant,
Speghini et al. it was estimated Rf 2 ∼ 3.3 for ZrO2 :Eu3+ see Figs. 6a–e. This enhancement of the emitted signal is
doped at 1 mol% presenting 50 wt% of monoclinic phase the result of OH’s reduction due to the combination of both
[24], contrary to the Rf 2 ∼ 1.55 reported here. For the dom- solvents, as was corroborated by the FTIR spectroscopy dis-
inant 606 nm peak reported there, Speghini et al. estimated cussed above, and also confirmed by reducing the anneal-
Rf 2 ∼ 0.4, smaller than Rf 2 ∼ 0.7 as reported here. Thus, ing temperature to 800◦ C. In this case, there is 25% more
in our case, the Rf 2 -value close to one suggest that the Eu3+ OH’s than samples annealed at 1000◦ C and the signal was
ions are occupying the D2h and C1 site positions. Site de- 20% lower, see Fig. 6f. Furthermore, the crystallite size is
pendence of the emission band confirms the substitution of half (17 nm) of the size presented for samples annealed
Zr4+ by Eu3+ with the presence of some defects associated at 1000◦ C and present a higher surface area with probably
to the charge compensation. larger concentration of defects. In addition, the emitted sig-
Solvent and surfactant effect on the self-assembly and luminescence properties of ZrO2 :Eu3+ nanoparticles 649

nal was also affected by the hydrothermal temperature, di- 9. C.H. Yan, L.D. Sun, C.S. Liao, Y.X. Zhang, Y.Q. Lu, S.H. Huang,
minishing 20% by increasing the temperature from 80◦ C to Appl. Phys. Lett. 82, 3511 (2003)
200◦ C, see Fig. 6d. These results confirm the important role 10. G. Qin, J. Lu, J.F. Bisson, Y. Feng, K.-i. Ueda, H. Yagi, T. Yanag-
itani, Solid State Commun. 132, 103 (2004)
of solvent and annealing temperature on the sample prepa-
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precipitation method with a particle size ranging from 17 to 15. G. Mialon, S. Turkcan, A. Alexandrou, T. Gacoin, J.P. Boilot,
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43 nm. Experimental results suggest that crystallite size and
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crystalline phase composition can be controlled by control- (2007)
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annealing temperature. The use of EtOH strongly affects the 18. B.K. Moon, I.M. Kwon, J.H. Jeong, C.-S. Kim, S.-S. Yi, P.S. Kim,
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20. T. Lopez-Luke, E. De la Rosa, P. Salas, C. Angeles-Chavez, L.A.
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Diaz-Torres, S. Bribiesca, J. Phys. Chem. C 111, 17110 (2007)
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to stabilize the monoclinic phase, increased to 50 wt%, com- Wang, Phys. Rev. B 75, 6 (2007)
pared to the 30 wt% obtained in EtOH without surfactant. 22. P. Salas, C. Angeles-Chavez, J.A. Montoya, E. De la Rosa, L.A.
The use of EtOH promotes the self-assembly of nanopar- Diaz-Torres, H. Desirena, A. Martinez, M.A. Romero-Romo,
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the presence of surfactant. The structural differences of the
J. Majimel, J.P. Manaud, R. Backov, C. Boissiere, D. Grosso,
emitted signal for nanobelts and nanoparticles are associ- C. Sanchez, B. Viana, F. Pelle, Chem. Phys. Chem. 9, 2077 (2008)
ated to different site symmetry occupying Eu3+ in the host 24. A. Speghini, M. Bettinelli, P. Riello, S. Bucella, A. Benedetti,
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emitted signal was obtained for nanoparticles prepared with 25. H.-Q. Liu, L.-L. Wang, S.-G. Chen, B.-S. Zou, J. Alloys Comp.
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content of OH’s and the largest crystallite size. Experimen- 27. C.F. Wu, W.P. Qin, G.S. Qin, D. Zhao, J.S. Zhang, S.H. Huang,
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Acknowledgements Financial support of CONCyTEG through 29. P. Salas, N. Nava, C. Angeles-Chavez, E. De la Rosa, L.A. Diaz-
grant 09-04-K662-072, 09-04-K662-055 and CONACyT scholarship Torres, J. Nanosci. Nanotechnol. 8, 6431 (2008)
for V. Romero is acknowledged. The help of J.C. Borttolucci Aviles 30. Y.H. Zhou, J. Lin, M. Yu, S.M. Han, S.B. Wang, H.J. Zhang,
and M. Olmos in the optical measurement and samples preparation, Mater. Res. Bull. 38, 1289 (2003)
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