Materials Science and Engineering B 177 (2012) 1423–1429

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Materials Science and Engineering B

journal homepage: www.elsevier.com/locate/mseb

Structural and photoluminescence study of Er–Yb codoped nanocrystalline

ZrO2 –B2 O3 solid solution
P. Salas a , R. Borja-Urby b , L.A. Diaz-Torres b,∗ , G. Rodriguez a , M. Vega c , C. Angeles-Chavez d
a
Centro de Física Aplicada y Tecnología Avanzada, Universidad Nacional Autónoma de México, A.P. 1-1010, Querétaro 76000, Mexico
b
Grupo de Espectroscopia de Materiales Avanzados y nanoestructurados (EMANA), Centro de Investigaciones en Óptica, A. C., Loma del Bosque 115, Col. Lomas del Campestre, C.P.
37150 León, Gto., Mexico
c
Centro de Geociencias, Universidad Nacional Autónoma de México, A.P. 1-1010, Querétaro 76000, Mexico
d
Instituto Mexicano del Petróleo, Programa de Ingeniería Molecular, Eje Central Lázaro Cárdenas 152, A.P. 14-805, 07730 México, DF, Mexico

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

Article history: Codoped Er3+ and Yb3+ nanocrystalline ZrO2 –B2 O3 phosphor obtained by a modified sol–gel method is
Received 30 September 2011 demonstrated. The addition of up to 2.5 mol% B2 O3 to nanocrystalline ZrO2 :Yb(2%), Er(1%) keep the tetrag-
Received in revised form onal rare-earth stabilized ZrO2 phase; whereas higher B2 O3 content destabilize the tetragonal phase,
23 December 2011
leading to the tetragonal to monoclinic transition with no tetragonal ZrO2 phase segregation. Visible
Accepted 15 January 2012
upconversion of the luminescent active ions, Er3+ and Yb3+ , depend strongly on B2 O3 content. The PL
Available online 30 January 2012
intensity is strongly quenched for high B2 O3 content due to increasing multiphonon relaxation processes
related to B O and B O B vibronic modes.
Keywords:
ZrO2 © 2012 Elsevier B.V. All rights reserved.
B2 O3
Upconversion
Phase transition
FTIR

1. Introduction zirconia structure retards the strong segregation of the

Ce0.75 Zr0.25 O2 byproduct for Ce2 O3 concentrations as high
Upconversion photoluminescent properties of rare earth ions as 5 mol%, whereas without boron doping the same level of
in a variety of hosts have been widely studied for their direct Ce0.75 Zr0.25 O2 segregation is reached at concentrations as low
application on the display and the illumination industry [1–4]. as 2.5 mol% Ce2 O3 . Another research conducted by Rui et al., on
Upconversion photoluminescence emissions of rare earth ions borate phosphors, which have low synthetic temperature and low
are directly affected by the structural vibrations of the host that cost, probed Sr3 RE(BO3 )4 :Dy3+ (RE = Y, La, Gd) to be a potential
supports them, diminishing the intensity of the emissions as the candidate for white-light generation for UV-pumped white-LEDs
vibration or phonon frequency of the host increases. Among a wide [1]. Boron oxide introduction into the yttria-stabilized zirconia
variety of hosts, zirconium dioxide (ZrO2 ) is one of the best candi- probed B2 O3 to be a fine additive which benefits the sinterability
dates to support rare earth ions because of its low phonon energy of and densification of the samples. Besides, proper concentrations
470 cm−1 [5]. Yb3+ –Er3+ codoped systems are of particular interest of B2 O3 allow phase tuning of yttria-stabilized zirconia [9]. In the
since the wide absorption and emission bands of Yb3+ , in the range present research, the influence of boron oxide on the structural
of 870–1060 nm, overlap with that of Er3+ (4 I15/2 → 4 I11/2 ), allowing and optical properties of the Yb3+ –Er3+ codoped ZrO2 system is
efficient energy transfer processes to happen between ytterbium conducted. Characterization of samples with different content of
and erbium ions [6,7]. Such interactions in the codoped system B2 O3 is done by XRD, SEM, FTIR and UV–vis absorption. Transition
enhance the conversion efficiency of near infrared (970 nm) to from stabilized tetragonal to monoclinic phase is found at high
visible (540 and 660 nm) light, improving the Er3+ upconversion concentrations of B2 O3 . Upconversion emission of this system is
emissions. Recently, research studies on ZrO2 :Ce3+ conducted by presented as a function of B2 O3 concentration.
Lee et al. achieved optimization of blue–green photoluminescence
emission of this phosphor by addition of B2 O3 during the synthe- 2. Experimental
sis process [8]. They found that boron ions diffusion into the
2.1. Synthesis

∗ Corresponding author. Tel.: +52 477 441 4200; fax: +52 477 441 4209. Nanocrystals were prepared using the sol–gel method [10]. Six
E-mail address: [email protected] (L.A. Diaz-Torres). samples of ZrO2 codoped with 2 mol% Yb3+ , 1 mol% Er3+ , and xB2 O3

0921-5107/$ – see front matter © 2012 Elsevier B.V. All rights reserved.
doi:10.1016/j.mseb.2012.01.009
1424 P. Salas et al. / Materials Science and Engineering B 177 (2012) 1423–1429

(x = 0, 0.5, 2.5, 5, 10 and 20 mol%) were synthesized. The sam-

ples were obtained by mixing zirconium n-propoxide (ZP) in a
solution of ethanol (EtOH), nitric and hydrochloric acid at room
a)
temperature and vigorous stirring according to the molar rate
1/20/0.1/0.3, respectively. Then the corresponding amounts of boric
acid, Er(NO3 )3 ·5H2 O and YbCl3 ·6H2 O were added under vigorous b)
stirring and the obtained solution was stirred during 90 min. Then
CO2 -free distilled water in a molar rate of 1/4 was added drop- c)
wise to manipulate the gel and oxolation processes. Due to the high
reactivity of ZP, it was required a strict handling of the hydrolysis d)
process to control the homogeneity, avoid the opacity and precipi-
tation. All samples were aged at 60 ◦ C for 48 h and then at a 100 ◦ C e)
for 24 h. The product was grounded in an agate mortar to obtain a
fine powder. Afterwards the samples were heat treated at 500 ◦ C for f)
5 h, and another set of samples, under the same synthesis process,
was heat treated at a 1000 ◦ C for 5 h.
30 40 50 60
2θ
2.2. Characterization
Fig. 1. XRD patterns of samples treated at 500 ◦ C show that despite the increment
The X-ray diffraction patterns of annealed samples were mea- of boron oxide concentration: (a) 0 mol%, (b) 0.5 mol%, (c) 2.5 mol%, (d) 5 mol%, (e)
sured in a – Bruker D-8 Advance diffractometer having the 10 mol% and (f) 20 mol%, the crystalline structure is tetragonal; in agreement with
Braggo-Brentano geometry, Cu K␣ radiation, a Ni 0.5% Cu-K␤ filter the JCPDS 50-1089 (bottom lines).
in the secondary beam and a one-dimensional position sensitive
silicon strip detector (Bruker, Lynxeye). Diffraction intensity as a slight decrement of peaks intensities as B2 O3 increases up to
a function of the angle 2 was measured between 20◦ and 110◦ 20 mol%. For samples that undergo heat treatment at a 1000 ◦ C
with a 2 of 0.01946◦ and a counting time of 53 s per point. Crys- it is observed that crystalline structure depends on B2 O3 content
talline phase composition refinement was done via the Rietveld (Fig. 2). Samples with concentrations of 0, 0.5 and 2.5 mol% B2 O3
method and using Fullprof code [11]. Crystalline space groups preserve pure tetragonal phase and have slight increments of their
considered for Rietveld refinement were space group P42/nmc peaks intensity as B2 O3 increases. No additional peaks that might
for tetragonal ZrO2 , space group P21/c for monoclinic ZrO2 , and indicate segregated phases are observed for these low B2 O3 con-
space group P63/mmc for the LnBO3 hexagonal phase. Transmission centrations. Hence there is an enhancement of crystal structure
electron microscopy (TEM) and scanning transmission electron on these samples due to removal of organic materials off their
microscopy (STEM), were performed both in a JEM-2200FS micro- structure after heat treatment. On the other hand, higher con-
scope with an accelerating voltage of 200 kV. The microscope is centration of boron oxide promote the tetragonal to monoclinic
equipped with a Schottky-type field emission gun, and an ultra high phase transition starting from 5 mol% up to 20 mol% of B2 O3 . XRD
resolution configuration (Cs = 0.5 mm; Cc = 1.1 mm; point-to-point patterns of these samples were in agreement to JCPDS 37-1484
resolution = 0.19 nm) and in-column omega-type energy filter. High standard for monoclinic ZrO2 , and to JCPDS 74-1937 standard for
angle annular dark field (HAADF) image was obtained using the
HAADF detector in the STEM mode. The optical absorption spectra
were obtained with a Perkin-Elmer UV–vis–NIR Lambda 900 spec- t
trophotometer in diffuse reflectance mode using a 1.5 in integrating t t
sphere (Labshpere Co.) Photoluminescence characterization mea- t t a)
surements were performed on an Acton Research modular 2300
spectrofluorometer. The excitation source was a CW semiconduc-
tor laser diode centered at 970 nm. The emission was analyzed with
an Acton Spectra Pro 500i monochromator and a R955 Hamamatsu
b)
photomultiplier, connected to an Acton Research Spectra HUB and a
PC that collected all data. Photoluminescence measurements were
done at room temperature. c)
m m
3. Results and discussion t m m m m
m m
* * * * d)
X-ray diffraction (XRD) patterns of samples heat treated at
500 ◦ C (Fig. 1) show that at this temperature concentrations of
B2 O3 as high as 20 mol% do not influence the crystalline struc- * * * * e)
ture of ZrO2 . All samples have the tetragonal phase, according to
JCPDS 50-1089 standard, and there is no detectable segregation of
other phases. All reflection peaks are well resolved and intense, * * * * f)
which is an indication of the good crystalline structure of these
15 20 25 30 35 40 45 50 55 60 65
samples. Besides, Rietveld refinement indicates that the small crys-
tallite sizes are in the range from 14.4 up to 16.2 nm. As it is 2θ
shown by the XRD patterns in Fig. 1, regardless of the B2 O3 con-
Fig. 2. XRD patterns of samples treated at a 1000 ◦ C and B2 O3 content: (a) 0 mol%, (b)
tent the overall fixed concentration of rare earths (2% Yb and 1%
0.5 mol%, (c) 2.5 mol%, (d) 5 mol%, (e) 10 mol% and (f) 20 mol%. (t), (m), and (*) stand
Er) is the reason for the stable tetragonal ZrO2 phase, in agreement for the tetragonal and monoclinic ZrO2 phases, and (*) for the lanthanide borate
with previous reports [12–14]. Introduction of B2 O3 only leads to segregated phase, respectively.
 P. Salas et al. / Materials Science and Engineering B 177 (2012) 1423–1429 1425

Table 1
Band gap estimations, phase composition: (t) for tetragonal ZrO2 , (m) for monoclinic ZrO2 and (h) for hexagonal LnBO3 , crystallite size and lattice constants from the Rietveld
refinement of samples treated at 500 ◦ C and at a 1000 ◦ C.

B2 O3 Band gap [eV] Composition [wt%] Crystallite size [nm] Lattice constants

500 ◦ C
0 mol% 4.65 100 (t) 14.41 a = 3.6092; c = 5.1752
0.5 mol% 4.77 100 (t) 15.6 a = 3.6086; c = 5.1767
2.5 mol% 4.62 100 (t) 16.1 a = 3.6085; c = 5.1783
5 mol% 4.59 100 (t) 15.4 a = 3.609; c = 5.1832
10 mol% 4.78 100 (t) 16.2 a = 3.6090; c = 5.1835
20 mol% 4.92 100 (t) 15.6 a = 3.6101; c = 5.1840

1000 ◦ C
0 mol% 4.83 100 (t) 54.1 a = 3.6072; c = 5.1782
0.5 mol% 4.83 100 (t) 66.3 a = 3.6056; c = 5.1805
2.5 mol% 4.86 100 (t) 66.7 a = 3.6055; c = 5.1823
13.43 (t) 66.0 a = 3.6052; c = 5.1866
5 mol% 4.89 81.54 (m) 29.1 a = 5.1673; b = 5.2185; c = 5.3221
5.04 (h) 39.0 a = 3.759; c = 8.743
0 (t) – –
10 mol% 4.99 90.87 (m) 53.0 a = 5.1578; b = 5.2119; c = 5.3294
9.13 (h) 36.0 a = 3.7585; c = 8.746
0 (t) – –
20 mol% 5.02 88.68 (m) 65.0 a = 5.1553; b = 5.2127; c = 5.3276
11.32 (h) 36.0 a = 3.7575; c = 8.746

hexagonal Lanthanide borate. In spite that these samples have the elements are more intense than the electrons dispersed by the
well defined reflection peaks of the ZrO2 monoclinic phase, there lighter elements producing brighter dots in a HAADF image. As
can be seen some other reflection peaks at 20.5◦ , 27.58◦ , 34.65◦ can be observed in the HAADF image, the particles show similar
and 41.56◦ , which do not belong to the monoclinic ZrO2 phase. contrast suggesting only presence of ZrO2 particles. Less bright or
Rietveld refinement of these XRD patterns was performed to know dark particles that could correspond to lighter compounds B2 O3 or
the tetragonal and monoclinic phase percentages. In addition, since LnBO3 were not observed in the HAADF image. Subsequently, the
some peaks were identified as reflections corresponding to the crystal structure of less bright particles in the HAADF image (Fig. 3a)
hexagonal phase of segregated lanthanide borates, LnBO3 (Ln = Yb3+ was studied by obtaining images of atomic resolution. Fig. 3b dis-
or Er3+ ) [15], such lanthanide borate phase was also included in the plays a HRTEM image corresponding to a thin section of one of such
Rietveld refinements. Rietveld results are summarized in Table 1. particles and the crystal lattice of the particle is clearly revealed. In
There, it is observed that segregated tetragonal phase exist only the HRTEM image, the crystal planes show a discontinuity in the
at the 5 mol% B2 O3 sample corresponding to 13.4 wt% of this sam- direction indicated by the white arrow. The discontinuity indicates
ple composition, whereas for samples with 10 mol% and 20 mol% an increase in the thickness in the direction of the arrow. There-
B2 O3 , the tetragonal ZrO2 phase is absent, suggesting that transi- fore, crystal structure was analyzed in a thinner region, indicated
tion to the monoclinic phase is complete. From Table 1 it is clear by the inset A in Fig. 3b. The determination of the crystal struc-
that lanthanide borate segregation increases from 5.04 to 11.32 wt% ture was performed on the Fast Fourier Transform (FFT), Fig. 3c;
as the B2 O3 content increases from 5 to 20 mol% of B2 O3 respec- it was obtained for the inset A of Fig. 3b. Interplanar distances of
tively. Affinity between boron and rare earth ions and yttrium 0.295, 0.289 and 0.255 nm were obtained in the FFT. These values
ions has been previously reported [9,15]. de Florio et al. conducted match very well with the interplanar spacing of tetragonal zirconia
experiments on Yttria-stabilized zirconia and used boron oxide as phase reported in the (Join committee Powder Diffraction Stan-
an additive. Their results showed that phase composition tuning dard) JCPDS card no 50-1089. The d-spacing correspond to (0 1 1),
(cubic + monoclinic) is possible by proper addition of B2 O3 . Boron (0 −1 1), and (0 0 2) planes of the tetragonal zirconia phase viewed
ions destabilize the cubic phase by removal of yttrium ions from along the crystallographic axis [1 0 0]. The corresponding inverse
the YZrO2 lattice to form the YBO3 segregated phase. Such desta- FFT image is illustrated in Fig. 3d, displaying clearly the crystal
bilization in turns induced a strong transition to monoclinic phase lattice in the [1 0 0] direction.
[9]. Thus, Rietveld refinements of XRD patterns in Fig. 2 suggest The presence of absorption bands corresponding to transitions
that boron ions diffuse well into the rare earth stabilized tetrago- from the ground state to corresponding excited states of Yb3+ and
nal phase of the host (ZrO2 :Yb3+ , Er3+ ) but do not lead to enough Er3+ ions are patent in the absorption spectra of samples annealed
amounts of LnBO3 compounds as to induce destabilization of the at 1000 ◦ C. The corresponding final exited states are indicated
tetragonal ZrO2 phase. Whereas for B2 O3 concentrations of 5 mol% in Fig. 4a for the sample with 5 mol% B2 O3 content. Evidence of
B2 O3 and higher, up to 20 mol%, boron ions interact strongly with occluded H2 O within the crystallites is observed at the 1386 nm
rare earth ions. Extracting these from the tetragonal structure to absorption band for all samples after the annealing treatment at
form lanthanide borate crystallites of considerable size, around a 1000 ◦ C (Fig. 4a). It is observed a red shift of the UV edge of
36 nm, see Table 1. After rare earth ions extraction, the tetrago- the absorption spectra of Er–Yb codoped ZrO2 as B2 O3 content
nal ZrO2 crystalline structure is destabilized allowing in turn the increases. In particular for the 20 mol% B2 O3 sample a very clear
transition to the monoclinic ZrO2 phase. broad band centered on 400 nm can be observed. That band and
The morphological and structural characteristics of the sample increased absorption for short wavelengths could be a consequence
with 5 mol% of B2 O3 were analyzed by TEM and the results obtained of increasing defects within the crystallites induced by the seg-
are displayed in Fig. 3. The sample is composed by particles of dif- regation of the lanthanide borate phase, in correspondence with
ferent sizes and very well faceted as displayed in HAADF image the XRD patterns of highly doped samples. Introduction of B2 O3
of Fig. 3a. The HAADF detector collects electrons dispersed by the enhance the absorption properties of the rare earth ions in these
nucleus of atoms and its intensity is approximately the squared samples. As B2 O3 content increases, it is observed an increment in
of atomic number. Therefore, electrons dispersed by the heavier intensity and a better definition of the absorption bands of Er3+ in
1426 P. Salas et al. / Materials Science and Engineering B 177 (2012) 1423–1429

Fig. 3. Morphology and structure of the sample with 5 mol% B2 O3 : (a) HAADF image of different size polyhedral nanoparticles very well dispersed, (b) HRTEM image, (c)
crystal structure of the box A in HRTEM image (b), and its Fourier transform pattern (d).

the visible as well as the band related to the 4 I11/2 (Er3+ ) and 2 F5/2 Upon boron introduction this principal band at 490 cm−1 shifts
(Yb3+ ) excited states near 970 nm. The information of the absorp- to longer wavenumbers at 500 cm−1 , this change allows higher
tion spectra was transformed to Munk–Kubelka units to estimate phononic energy to happen in the samples (x ≤ 2.5 mol%), and it
the optical bang gap energy (Eg). The estimations were based on the is the first indication of boron ions inside the structure, see Fig. 6a.
relation: (˛h)2 = C(h − Eg); where ˛ is the absorption coefficient, As boron ions increases, the main band sharps itself and shifts to
h is the photon energy in eV and C is a constant. These spectra are longer wavenumbers. Also, new well defined bands at 418, 580
displayed in a Wood and Tauc plot [12] in Fig. 5. Extrapolation of and 740 cm−1 become distinguishable as B2 O3 increases. Such new
a straight line from the band edge to the intersection with h axis bands are related to B2 O bonds and bending vibration of BO3 [17].
gives the band gap estimation. It was found the Eg grows as boron Particularly, the new band at 418 cm−1 though it is narrow, it
oxide concentration increases in the samples annealed to 1000 ◦ C, gains considerable intensity. For samples with higher concentra-
see Table 1. Despite being crystalline, samples of tetragonal phase tions of B2 O3 (x ≥ 5 mol%) and annealing treatment at 1000 ◦ C, the
(x ≤ 2.5 mol%) have lower band gap energy (Eg = 4.83 eV) because of main band continue shifting towards bigger wavenumbers up to
more incomplete metal oxygen (M O) bonds in their less ordered 530 cm−1 for the 20 mol% B2 O3 content, see Fig. 6b. The bend-
structure [16], in comparison with the more ordered structures of ing vibrations of B O B triangles (740 cm−1 ) gain importance in
the monoclinic phase samples (x ≥ 5 mol%) with higher band gap these systems, becoming a highly probable path for deexcitation
energy (Eg = 5.02 eV). processes to happen. Effects of boron ions in the highly doped sam-
Taking in to account that the phononic energy of pure ZrO2 ples become clear as many resonant vibration bands appear in the
is around 470 cm−1 , which place it as one of the best host to FTIR spectra, mainly in the range from 880 to 1200 cm−1 , related
insert rare earth ions for upconversion photoluminescence (PL) to stretching vibration of BO4 . Similar bands were also present on
applications [5], FTIR was performed to look for boron bonds a study conducted by Cheng et al., over the influence of rare earth
inside the crystalline structure, and see how boron introduc- ions on Bi2 O3 –B2 O3 glasses [17]. Such an increment of vibration
tion affects the phononic energy distribution of these materials. bands increases the probability for the system to lose its excited
For the sample without B2 O3 , annealed at 1000 ◦ C, the principal energy via multiphononic vibrations.
transmittance band is centered at 490 cm−1 , which includes the The typical green (4 S3/2 → 4 I15/2 ) and red (4 F9/2 → 4 I15/2 ) upcon-
reported 470 cm−1 value for bulk ZrO2 , see curve (i) in Fig. 6a. version emissions of the Yb3+ –Er3+ codoped ZrO2 system are
 P. Salas et al. / Materials Science and Engineering B 177 (2012) 1423–1429 1427

a) a)
5 mol% B2O3 1.0
4
G11/2 2

Transmittance (a.u.)
H11/2
Intensity (a.u.)

0.8
4
F7/2 2 4
4
F5/2 I11/2 4
4 F9/2 I13/2
S3/2 4 0.6
I9/2 H2O
2
H9/2 iv)
4 0.4 iii)
F3/2
ii)
400 800 1200 1600
i)
0.2
Wavelength (nm) 500 750 1000 1250 1500
-1
Wavenumber (cm )
b)
b)
0.5
1.0
0.4
0.8

Transmittance (a.u.)
Intensity (a.u.)

0.3 1440
vi) iii)
v) 0.6 BO4
0.2 ii)
iv)
iii) 0.4 i)
0.1
ii) 418 B-O-B
0.0 i) 0.2
B2O
400 600 800 1000 1200 500 - 530
0.0
Wavelength (nm)
500 750 1000 1250 1500
-1
Fig. 4. (a) Absorption band transitions of Er3+ and Yb3+ from ground states to respec- Wavenumber (cm )
tive excited energy levels for ZrO2 :Er, Yb sample with 5 mol% content of B2 O3 . (b)
Absorption spectra of ZrO2 :Yb3+ Er3+ xB2 O3 samples treated at 1000 ◦ C: (i) x = 0 mol%, Fig. 6. FTIR spectra of Yb3+ , Er3+ codoped ZrO2 + xB2 O3 treated at 1000 ◦ C: (a)
(ii) x = 0.5 mol%, (iii) x = 2.5 mol%, (iv) x = 5 mol%, (v) x = 10 mol% and (vi) x = 20 mol%. samples with boron oxide concentration of: (i) x = 0 mol%, (ii) x = 0.5 mol%, (iii)
x = 2.5 mol% and (iv) x = 5 mol%; and (b) samples with (i) x = 5 mol%, (ii) x = 10 mol%
and (iii) x = 20 mol%.
observed in all samples under 970 nm diode laser excitation.
Fig. 7 depicts the upconversion emission spectra for samples
upconversion emission is strongly quenched. While being all of
annealed at 500 ◦ C, and Fig. 8 depicts the upconversion spectra
them of tetragonal phase, it is observed that the increment on
for samples annealed at 1000 ◦ C. The red emission is predom-
upconverted emissions is not linear with B2 O3 content. The main
inant in all samples treated at 500 ◦ C, see Fig. 7. The overall
vibronic band of the 20 mol% B2 O3 sample at 1330 cm−1 becomes
upconversion emission intensity presents around a six fold incre-
wider and more intense than the band at 500 cm−1 allowing mul-
ment with the addition B2 O3 in comparison with sample without
tiphononic vibrations of B O bonds at 1330 cm−1 that lead to very
B2 O3 , with exception of the 20 mol% B2 O3 sample for which its
strong multiphonon relaxation processes in all Er3+ excited levels,
see the nonradiative relaxation processes Wi (i = 1, 2, 3, 4) depicted
8 in Fig. 9. As a consequence the overall upconversion emission of
0%
such sample is strongly quenched.
0.5%
In the case of samples treated at a 1000 ◦ C, the overall upcon-
2.5%
6 version emission increases as B2 O3 content increases up to 5 mol%
5%
10%
(Fig. 8), and then is strongly quenched for higher B2 O3 contents.
20% Sample with 5 mol% B2 O3 presents the highest increment in overall
4 upconversion emission with around 70% more integrated emission
2
(αhν)

than the sample with no B2 O3 . The gained intensity of the resonant

vibration bands at 740 cm−1 and 1440 cm−1 in the FTIR spectrum,
2 see Fig. 6b, is the reason for strong multiphonon relaxation and con-
sequent upconversion emission quenching for the 10 and 20 mol%
B2 O3 samples. An interesting feature of all samples annealed at
0 1000 ◦ C is the evident change in the red to green emission ratio in
4.83 eV 5.02 eV comparison with samples annealed at 500 ◦ C. The green band emis-
4.0 4.2 4.4 4.6 4.8 5.0 5.2 5.4 sion becomes stronger than the red band emission as B2 O3 content
hν(eV) increases up to 5 mol% B2 O3 . And for the higher B2 O3 contents, in
spite that the overall upconversion emission is strongly quenched,
Fig. 5. Tauc plot for the diffuse reflectance in Kubelka–Munk (k/s) units and esti- the green emission is the dominant one. It is also worth to point
mation of band gaps. Percentages on labels correspond to the mol% content of B2 O3 . out that, a threefold increment in overall upconversion emission is
1428 P. Salas et al. / Materials Science and Engineering B 177 (2012) 1423–1429

0%
x 5.95

0.5%
x 1.0

2.5%
x 1.603

5%
x 1.045

10%
x 1.025

20%
x 63.5

520 560 600 640 680 720

Wavelength (nm)

Fig. 7. Green and red upconversion emissions of ZrO2 :Yb3+ Er3+ xB2 O3 treated at
500 ◦ C, as a function of boron oxide concentrations x = 0, 0.5, 2.5, 5, 10 and 20 mol%. Fig. 8. Green and red upconversion emissions of ZrO2 :Yb3+ Er3+ xB2 O3 treated at a
PL intensities were multiplied by a normalization factor for display purposes to show 1000 ◦ C, as a function of boron oxide concentrations x = 0, 0.5, 2.5, 5, 10 and 20 mol%.
intensity variations between the samples. The normalization factor is in reference PL Intensities were multiplied by a normalization factor for display purposes to show
to the integrated PL of sample with 0.5 mol% content of B2 O3 . intensity variations between the samples. The normalization factor is in reference
to the Integrated PL of sample with 5 mol% content of B2 O3 .

observed in the samples annealed at 1000 ◦ C in comparison with

the ones annealed at 500 ◦ C.
The above results suggest that for the compounds of tetragonal
phase (B2 O3 content ≤ 2.5 mol%) introduction of B2 O3 leads to diffu-
sion of rare earth ions into the surface of the tetragonal compounds;
exposing the RE ions to stronger first neighbors interactions and
hence increasing their upconversion emissions, as can be seen in
Fig. 8. On the other hand, high concentrations of B2 O3 promote the
tetragonal to monoclinic transition by increasing the lanthanide
borate segregation. The rare earth extraction from the monoclinic
ZrO2 phase leads to a very small green upconversion emission
as expected in low Er3+ doped monoclinic ZrO2 [6], whereas the
extracted rare earth that have been incorporated in the lanthanide
borate phase are unable to present upconversion emission due to
high boron phononic vibrations energies, as shown in the FTIR spec-
tra in Fig. 6. Those resonant vibration bands of high energy promote
de-excitation processes of Er3+ excited electrons lo lower excited
states disfavoring upconversion emissions.
A schematic energy level diagram of the Yb3+ –Er3+ codoped
ZrO2 system is shown in Fig. 9, to describe the VIS upconversion
and NIR downconversion emission processes. First, the continu-
ous pumping excitation from the laser diode at 970 nm is mainly
absorbed by Yb3+ ions due to its wide absorption cross section
(2 F7/2 , 2 F5/2 ) [6]. Erbium ions are excited from the ground state
4I 4
15/2 to the I11/2 level through direct non-radiative energy trans-
Fig. 9. Schematic energy level diagram for green and red upconversion and infrared
fer (ET) process from ytterbium Yb(2 F5/2 , 2 F7/2 ) → Er(4 I15/2 , 4 I11/2 ),
emissions of Yb3+ , Er3+ codoped ZrO2 + xB2 O3 under 970 nm diode laser excitation.
as well as by direct laser diode excitation to a much lesser degree. Erbium is excited via energy transfer (ET) processes. Resonant vibration modes of
Electrons in the 4 I11/2 level are then excited to the 4 F7/2 level by boron bonds favor nonradiative relaxation of erbium ions (Wi , curved arrows) to
a second ET process, Yb(2 F5/2 , 2 F7/2 ) → Er(4 I11/2 , 4 F7/2 ). Electrons lower energy levels.
in 4 F7/2 level rapidly relax to the lower levels 4 S3/2 and 2 H11/2
 P. Salas et al. / Materials Science and Engineering B 177 (2012) 1423–1429 1429

from which the green upconversion emission (550 nm) is produced and present a dominant red upconversion emission. Enhancement
when these radiatively relax to the ground state. Also, excited elec- of upconversion emission is observed after boron oxide intro-
trons at 4 I11/2 level decay nonradiatively to the 4 I13/2 level, from duction and heat treatment at a 1000 ◦ C, in particular the green
which NIR emission (1550 nm) of Er3+ ions takes place. Finally, elec- emission becomes comparable to the red emission. The enhanced
trons at 4 I13/2 level could be excited to 4 F9/2 level by a third ET tetragonal crystalline structure is preserved for concentrations as
process Yb(2 F5/2 , 2 F7/2 ) → Er(4 I13/2 , 4 F9/2 ), and the red upconver- high as 2.5 mol% of B2 O3 without other phase segregations. For
sion emission (660 nm) takes place after radiative transitions from higher concentrations of boron oxide, a transition from tetrago-
this level to the ground state 4 I15/2 [7,18]. The wide principal vibra- nal to monoclinic ZrO2 phase was observed along with lanthanide
tion band centered at 610 cm−1 , see FTIR spectra in Fig. 6, enhances borate segregation. This phase transition is ascribed to extraction of
the multiphonon nonradiative relaxation of level 2 H11/2 –4 S3/2 to rare earth ions from the ZrO2 structure by boron ions. More intense
the next lying level 4 F9/2 . That is due to the fact that an increase green emissions of samples with low concentrations of boron oxide
in the maximum phonon energy from 470 to 610 cm−1 will lead to could be due to the presence of rare earth ions on the surface of
need less phonons to bridge the energy gap between consecutive the nanophosphors. A schematic energy level diagram is proposed
energy levels, and in consequence the rate for multiphonon relax- to explain how high concentrations of B2 O3 kill the upconversion
ations will increase. Likewise the excited electrons at 4 F9/2 level emission of the samples after the increment of resonant vibration
will decay more nonradiatively to the 4 I9/2 level, and so on for the bands of boron–oxygen bonds observed in the FTIR spectra.
rest of the lower lying excited levels. Taking in to account that,
the addition of B2 O3 gives place to the important boron related Acknowledgments
FTIR bands at 410, 610, 740, and 1440 cm−1 , it will be expected an
increase in the nonradiative relaxations W1 , W2 , and W3 (Fig. 9) One of the authors, Borja-Urby, thanks to CONACyT for its sup-
between energy levels 4 I9/2 and 4 I11/2 , 4 F9/2 and 4 I9/1 and 4 I11/2 and port through a scholarship grant 173046 for PhD studies at Centro
4I
13/2 , respectively. As a consequence, the decay rate of an excited de Investigaciones en Optica A. C.
electron to the immediate inferior energy level increases, and the
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