J. Am. Ceram. Soc.

, 96 [5] 1602–1609 (2013)

DOI: 10.1111/jace.12149
© 2013 The American Ceramic Society

Journal
Structural and Optical Properties of Tunable Warm-White Light-Emitting
ZrO2:Dy3+–Eu3+ Nanocrystals
Subrata Das, Che-Yuan Yang, and Chung-Hsin Lu†
Department of Chemical Engineering, National Taiwan University, Taipei, Taiwan

A series of Dy3+ +
–Eu3++
-codoped ZrO2 nanocrystals with Pr3+,11 and Eu3+ 12 results in cubic or tetragonal phase of
tetragonal and cubic symmetry was synthesized via a wet ZrO2 at room temperature. The inclusion of trivalent cation
chemical reaction. When the Eu3+ +
-doping content was fixed, introduces oxygen deficiencies that stabilize the tetragonal or
the crystal structure could be stabilized from the mixed phase cubic phase.7–9 Most importantly, stabilization of the tetrag-
to single cubic phase by simply adjusting the content of Dy3+ +
. onal or cubic phase from monoclinic phase is very crucial as
The cubic ZrO2:Dy3+ +
–Eu3++
nanoparticles exhibited spherical these two phases are considered to be more important in
and nonagglomerated morphology. The effective phonon energy fundamental and technological applications than the low
of cubic ZrO2:5%Dy3+ +
–5%Eu3+ +
was calculated to be temperature phase. Furthermore, the preparation of spherical

1
445 cm , which is lower than the previously reported results. ZrO2 particles with rare-earth ions for photoluminescence
Extensive luminescence studies of ZrO2:Dy3+ +
–Eu3+
+
as a func- applications remains a continuing challenge for materials
3+
+
tion of Dy content demonstrated that the dopant concentra- chemists.
tion and its site symmetry play an important role in the In recent years, there has been considerable interest in
emissive properties. Under 352 nm excitation, the increment of photoluminescent properties of rare-earth-doped ZrO2 nano-
Dy3++
concentration in ZrO2:Dy3+ +
–Eu3++
led to an increase in crystals. The structure and optical gap of ZrO2 is commonly
orange (590 nm) and red (610 nm) emissions of Eu3+ +
ions, affected by the incorporation of trivalent rare-earth ions that
which are attributed to the 5D0?7FJ(J = 1, 2) transitions of generally induce new optical properties in the host materials.
Eu3++
ions. This increment is possibly due to the efficient Moreover, ZrO2 has very low dominant phonon energy of
energy transfer (ET) 4F9/2:Dy3+ +
?5D0:Eu3+ +
. The phosphors about 470 cm
1, which is very small comparative to that of
can generates light from yellow through near white and eventu- other hosts.13 Such low phonon energy decreases the proba-
ally to warm white by properly tuning the concentration of Dy3+ +
bility of nonradiative multiphonon relaxation of excited rare-
ions through the ET and change in site symmetry. These earth dopant ions through the vibrational bands of the host
phosphors may be promising as warm-white-/yellow-emitting lattice.13 This low phonon energy opens up the possibility of
phosphors. more efficient luminescence of active ions incorporated into
the ZrO2 matrix.13 The techniques employed to study the
optical properties of lanthanide ion-doped ZrO2 materials
I. Introduction
include cathodoluminescence, photoluminescence, and ther-

Z IRCONIUM oxide have been extensively investigated due

to its superior hardness, high melting point, chemical
stability, photo-thermal stability, high thermal expansion
coefficient, low thermal conductivity, and high thermo-
mechanical resistance.1–4 This material has been found
sophisticated in many applications such as electrolyte materi-
als for solid oxide fuel cells,2 hard materials,3 and thermal
barrier coating materials.4 This material finds applications
also in the field of photonics due to its advanced perfor-
mance in active waveguide and highly efficient thermolumi-
nescence response.5,6
Zirconia has three crystalline phases viz., monoclinic,
tetragonal, and cubic. Among these, cubic zirconia is consid-
ered to be the most stable and symmetric.7–9 The tetragonal
and cubic phases are hard to be quenched at room tempera-
ture. In fact, the crystal lattice tends to transform into a
more symmetrical structure with the addition of trivalent rare
earths into zirconia lattice, which is stable at room tempera-
ture.7–9 In addition, the crystal lattice tends to transform into
a structure with high symmetry as crystallite size decreases,
owing to the lower free surface energy of the tetragonal or
cubic phase than the monoclinic phase.7–12 It is reported that
the incorporation of trivalent rare-earth ions such as Y3+ + 10
, this type of white light has poor color rendering caused by
B. Dunn—contributing editor
Manuscript No. 31698. Received July 4, 2012; approved December 4, 2012.
†
Author to whom correspondence should be addressed. e-mail: chlu@ntu.edu.tw
1602
moluminescence spectroscopies. The reported results of the
optical studies include the photoluminescence of sol–
gel-derived ZrO2 nanophosphors doped with Pr3+,11 Eu3+,12
Sm3+,13 Er3+,14 Ce3+,15 and Dy3+ 16 systems. Few reports
have been devoted to the physical understanding of the
relationship between the luminescence properties of the
dysprosium and europium centers and structural modifica-
tions of zirconia, focusing on information about the chemical
environment of Dy3+ and Eu3+ ions.12,16 However, no
detailed studies have been carried out concerning the white
light emission from rare-earth-codoped ZrO2 nanocrystals
with cubic symmetry prepared by wet chemical reaction.
Nowadays, white light LEDs (W-LEDs), considered as
one of the most promising general illumination sources, are
attracting significant attention because of their high bright-
ness, long lifetime, small volume, low power consumption,
and free of mercury.17–19 One of the most popular methods
to generate white light is by combining a blue InGaN chip
with a yellow-emitting Y3Al5O12:Ce3+(YAG) phosphor.
However, this material lacks thermal stability at elevated
temperatures around 200°C and suffers a low color rendering
index (Ra) when pumped by a blue LED chip. Furthermore,
the color deficiency in the blue, red, and green regions.20–22
Another alternative to achieve white light by a single host fit-
ted with near UV-LEDs, and this type of white LEDs offers
superior color uniformity with a high Ra.23,24 Recent efforts
to develop new single host white light-emitting phosphors
include oxide,25,26 oxyfluoride,27,28 nitride,29,30 oxynitride,31,32
sulfide,33,34 and halide hosts.35,36 Among several host materi-
als, zirconia oxide has good potentialities to become efficient
May 2013 Structural and Optical Properties of ZrO2:Dy3+–Eu3+ Nanocrystals 1603

luminescent media due to its wide band gap with high (f)
transparency, refractive index, and low vibrational energy
cutoff.37–40
Herein, the synthesis, structural, and photoluminescence (e)
properties of a novel material, ZrO2:Dy3+–Eu3+ is reported
for the first time, which can act as an excellent single-
component warm-white-light phosphor for use in near
UV-based white LEDs. Its excitation wavelength at around (d)
350 nm fits well with the characteristic emission of near
UV LED chips. In addition, to examine the potentialities
of the material as a tunable white light source, the energy (c)
transfer between the Dy3+ and Eu3+ ions has also been
investigated intensively.
(b)
II. Experimental Details
The samples were prepared via wet chemical reaction fol- (a)
lowed by controlled heating. All chemicals were reactive
grade and supplied by Aldrich. Pure ZrO2 was obtained by
mixing appropriate amount of zirconyl nitrate hydrate (ZrO
(NO3)2.xH2O) as a precursor in a solution of ethanol, nitric,
and hydrochloric acid at room temperature according to the
molar ratio of 1/20/0.1/0.3, respectively. ZrO2:Ln3+ (Ln = Fig. 1. Room-temperature X-ray diffraction pattern of (a) undoped
Dy, Eu) samples were prepared by adding various molar ZrO2, (b) ZrO2:1% Dy3+, (c) ZrO2:5% Eu3+, (d) ZrO2:1% Dy3+–5%
concentrations of rare-earth nitrates as precursors. The Eu3+, (e) ZrO2:2.5% Dy3+–5% Eu3+, and (f) ZrO2:5% Dy3+–5%
obtained solution was stirred for at least 3 h and then kept Eu3+ nanocrystals.
at rest for overnight. In the next step, the solution was con- system increased the cubic symmetry of the host lattice
tinuously stirred at 150°C until the liquid totally evaporated significantly, which is clearly visible from Fig. 1(d). With
and only gray white powders were left. Then, the powders further increment of Dy3+ content in the ZrO2:Dy3+–Eu3+,
were grinded properly and annealed at 1000°C for 12 h. the crystal structure was found to be stabilized toward more
Finally, the samples were collected and ground to obtain the symmetrical cubic phase as indicated in the XRD patterns
fine mesh powders. The crystal structures of the prepared from Fig. 1(d)–(f).
powders were identified via X-ray diffraction (XRD, Philips Unfortunately, it is very difficult to unambiguously resolve
X’pert /MPD, Amsterdam, the Netherlands) using CuKa between ZrO2 tetragonal and cubic phase, due to the instru-
radiation at room temperature. The morphology and particle mental angular resolution (0.03°). However, a shift of the
sizes of the as-prepared powders were examined using trans- peaks in the diffraction pattern to lower 2h values with the
mission electron microscopy (TEM; JEM-3010, JEOL, incorporation of Ln3+ ion (Ln = Dy, Eu) was observed, which
Tokyo, Japan) with a point to point and lattice resolution of may benefit the understanding of the phase transformation
0.17 and 0.14 nm, respectively. The photoluminescence spec- phenomena. With an increment in rare-earth ion content, the
tra of the synthesized phosphors were recorded by using a main tetragonal peak in the pattern of ZrO2:1%Dy3+, located
fluorescence spectrophotometer (F-4500, Hitachi, Tokyo, at 30.16° (1 0 1), shifted continuously and finally stabilized in
Japan) with a Xenon lamp operated at 150 W as an excita- its pure cubic form of ZrO2:5%Dy3+–5%Eu3+ at 30.02° (1 1 1)
tion source. The Commission International de I’Eclairage as depicted in Fig. 2.
(CIE) coordinates were recorded using a fluorescence It has been demonstrated in the previous studies that, with
spectrophotometer (Hitachi F-4500) with an Ocean optics a decrease in crystallite size, the crystal lattice tends to trans-
spectrometer model no. USB-2000. form into a structure with more symmetrical cubic phase.41,42
Therefore, Scherrer equation 12 is employed to determine the
III. Results and Discussion crystallite sizes, the resultant particle sizes are tabulated in
Table I. As expected, the crystallite sizes are found to
(1) X-ray Diffraction Studies decrease with an increase in Ln3+ (Ln = Dy, Eu) concentra-
Figure 1(a)–(f) show room-temperature XRD patterns of tion (Table I). This can also be visualized from the broadness
zirconia as a function of different Ln3+ (Ln = Dy, Eu) con- of XRD patterns as shown in Fig. 2. That is, the uniform
centrations. The (hkl)Phase of each peak has been appropri- expansion in the broadness indicates a systematic decrease in
ately assigned and indicated in the figure. The XRD pattern
for undoped ZrO2, presented as Fig. 1(a), shows multiple
peaks associated with a polycrystalline structure composed
by two crystalline phases: monoclinic (M) and tetragonal (T),
being monoclinic in major quantity [JCPDS 88-2390]. Due to
the incorporation of 1 mol% of Dy3+ in the undoped ZrO2
lattice, the monoclinic phase is drastically reduced or even
absent, and the crystal structure is almost stabilized in the
form of tetragonal crystallographic phase [JCPDS 81-1544]
as shown in Fig. 1(b). While, some minor monoclinic phase
[JCPDS 88-2390] also exists [Fig. 1(b)]. As shown in the
XRD pattern of 1 mol% of Dy3+-doped sample, the charac-
teristic XRD peak of tetragonal structure centered at 30.16°
(101) has generated [Fig. 1(b)], suggesting that the more sym-
metrical tetragonal structure is achieved with the addition of
1 mol% of Dy3+ into the undoped host. The sample doped
with 5 mol% of Eu3+ shows the coexistence of major cubic Fig. 2. Magnified XRD patterns in the region between 29° and 30°
phase and minor tetragonal phase as depicted in Fig. 1(c). for ZrO2:1% Dy3+ and ZrO2:x% Dy3+–5% Eu3+ (x = 0, 1, 2.5, 5)
The incorporation of 1 mol% of Dy3+ into the ZrO2:5% Eu3+ nanocrystals.
1604 Journal of the American Ceramic Society—Das et al. Vol. 96, No. 5

Table I. The Crystallite Sizes, Yellow-to-Blue (Y/B) and (a)

Red-to-Orange (R/O) Integrated Ratios and Chromaticity
Coordinates of ZrO2:5%Eu3+ and ZrO2: xDy3+,5%Eu3+
(x = 0, 1, 2.5, 5) Phosphors (kexc = 352 nm)
CIE
Ln3+ Doping Crystallite sizes
(mol.%) from XRD (nm) Y/B R/O X Y

Undoped 83 – – – –
1%Dy3+ 78 1.97 – 0.417 0.389
5%Eu3+ 77 – 1.18 0.494 0.344
1%Dy3+ 62 2.04 0.56 0.424 0.358
–5%Eu3+
2.5%Dy3+ 48 1.78 0.51 0.402 0.355
–5%Eu3+
5%Dy3+ 44 1.45 0.50 0.343 0.325 (b)
–5%Eu3+

the crystallite size which directly supports the transformation

mechanism from tetragonal to cubic structure of the doped
samples. It is worth noting that the reflections in the XRD
patterns of all the samples are sharp and intense, implying
sufficiently higher crystallinity of the sample. Moreover, shift-
ing of diffraction peaks to the lower 2h side established the
successful incorporation of Dy3+ and Eu3+ ions into the Zr4+
sites of ZrO2 and the subsequent creation of oxygen vacan-
cies for charge compensation. The disordered nature of
ZrO2 structure favors the high doping even up to 10 mol%
of Ln3+ (5%Dy3+ + 5%Eu3+) in concentration.

(2) Raman Spectroscopic Studies Fig. 3. (a) Raman spectrum of (i) undoped ZrO2, (ii) ZrO2:1% Dy3+,
The systematic transformation from the monoclinic phase to (iii) ZrO2:5% Eu3+, (iv) ZrO2:5% Dy3+–5% Eu3+ nanocrystals.
the cubic phase due to the incorporation of rare-earth ions into (b) Example Raman spectrum of ZrO2:1%Dy3+ with Lorentzian
the ZrO2 host is clearly visible in the room-temperature fitting for the estimation of phonon energy.
Raman spectra as presented in Fig. 3(a). As shown in the
Raman spectra, major bands appear at 179, 191, 222, 308, 339,
380, 476, 534, 560, and 632 cm
1 for the undoped ZrO2 sam-
was calculated to be 406, 443, and 445 cm
1 for ZrO2:1%
ple. These Raman bands are assigned to the Raman-active
Dy3+, ZrO2:5%Eu3+, and ZrO2:5%Dy3+–5%Eu3+, respec-
modes for monoclinic ZrO2.43,44 In addition, there are two
tively. The resultant phonon energies for the present samples
weak bands at 260 and 640 cm
1 for the tetragonal ZrO2.43,44
are lower than that previously reported for ZrO2 matrix
Obviously, the undoped ZrO2 sample is mainly composed of
(470 cm
1).48 Thus, present nanocrystals can be ideal host
monoclinic ZrO2 together with a minor proportion of tetrago-
materials for photonic applications, as its low phonon energy
nal ZrO2, and this finding agrees with the XRD results. For the
decreases the probability of nonradiative multiphonon relax-
ZrO2:1%Dy3+ sample, the spectra become simpler, in which
ation of excited rare-earth activator ions throughout the
strong tetragonal bands at 265, 319, 463, and 645 cm
1 45
vibrational bands of the host lattice.47,48
together with weak bands at 185 and 625 cm
1 belonging to
monoclinic phase are observed.43,44 This indicates the transfor-
mation of monoclinic to tetragonal phase due to rare-earth ion
(3) TEM Studies
doping, which again agrees with the XRD results. Finally, ZrO2
To evaluate the exact morphology and particle size of the
nanocrystals codoped with 5%Dy3+–5%Eu3+ only showed
prepared nanoparticles, the transmission electron microscopy
broad band with a maximum at around 540 cm
1 which is the
(TEM) was used. Figure 4(a)–(c) represent the TEM images
characteristic Raman peak of cubic ZrO2 phase, suggesting the
of undoped ZrO2, ZrO2:1% Dy3+, and ZrO2:5% Dy3+
5%
complete formation of cubic phase.46
Eu3+ nanocrystals, respectively. The synthesized nanoparti-
To estimate the phonon energy for the present samples,
cles are almost equiaxed, nonagglomerated and clearly fac-
the Lorentzian fitting was incorporated and a representative
eted, which in turn is a good indication of their crystallinity.
example figure for the ZrO2:1%Dy3+ phosphor has been
The average diameters approximated from TEM for the und-
depicted in Fig. 3(b). The Lorentzian fitting of the spectrum
oped ZrO2, ZrO2:1% Dy3+, and ZrO2:5% Dy3+–5% Eu3+
revealed six phonon bands centered at 185, 265, 319, 463,
nanocrystals were found to be 98, 52, and 48 nm, respec-
625, and 645 cm
1. Taking into account the positions (x),
tively. The particle size estimation from TEM and XRD
FWHMs (wi) and the intensities (A) of the corresponding
results were found to be in close agreement for the present
Lorentzian subbands, the effective phonon energy for the
nanocrystals. Moreover, TEM results revealed that the nano-
present phosphors could be estimated by using the following
particles are almost spherical in nature, which is very impor-
equation47:
tant in the field of display as spherical phosphor particles
P would increase the screen-film brightness and improve the
xi wi Ai
image resolution due to lower light scattering of the evolved
Eph ¼ P
i
(1) light and a higher packing density, as compared with irregu-
wi Ai
i larly shaped phosphor particles.
In the high-resolution transmission electron microscopy
The obtained value of the effective phonon energy, which (HRTEM) images of the present nanocrystals, as depicted in
defines the rate of radiation less transitions in a material, Fig. 4(d)–(f), the lattice fringes on the individual nanoparticle
May 2013 Structural and Optical Properties of ZrO2:Dy3+–Eu3+ Nanocrystals
(a) (d)
(b) (e)
(c) (f)
Fig. 4. TEM images of (a) undoped (b) 1% Dy3+-doped and (c)
5% Dy3+–5% Eu3+-codoped ZrO2 nanocrystals. High-Resolution
TEM images of (d) undoped (e) 1%Dy3+-doped and (f) 5%Dy3+–
5%Eu3+-codoped ZrO2 nanocrystals.
are clearly distinguishable, indicating that the prepared nano-
particles are highly crystalline. The distance between the lat-
tice fringes of the undoped sample was measured to be
0.311 nm, which corresponds to the d-spacing of lattice plane
in the crystals of monoclinic ZrO2 [Fig. 4(d)]. This result is
consistent with the calculated d-spacing of the (
1 1 1)
lattice plane of 0.316 nm derived from the XRD results of
monoclinic phased ZrO2 [JCPDS 88-2390]. While the values
of 0.289 and 0.186 nm shown in the image of ZrO2:1%
Dy3+ sample corresponds to the d-spacing of lattice planes
(1 0 1) and (1 1 2), respectively, of tetragonal ZrO2
[Fig. 4(e)], which has been confirmed by the XRD of the
ZrO2:1% Dy3+ sample [JCPDS 81-1544]. As seen in
Fig. 4(f), the distances between the lattice fringes of
ZrO2:5%Dy3+–5%Eu3+ nanocrystals are measured to be
0.299 and 0.261 nm, and these values match well with the
d-values of the cubic ZrO2 [JCPDS 81-1551].
(4) Photoluminescence Studies
The photoluminescence emission spectra of x mol% (x = 1,
2.5, 5) Dy3+-codoped ZrO2:5%Eu3+ samples have been
recorded under near UV excitation at 352 nm, which are
shown in Fig. 5. The spectra of undoped and Dy3+ and Eu3+
individually doped ZrO2 samples are also shown for com-
parison. The undoped ZrO2 nanocrystalline sample exhibited
a broad emission band centered at 490 nm [Fig. 5(a)]. In this
case, electrons promoted to the conductive band decay non-
radiatively to the recombination band (RB). From this meta-
stable band electrons decay to the valence band producing
1605
(f)
(e)
(d)
(c)
(b)
(a)
Fig. 5. Room-temperature PL emission spectra of (a) undoped
ZrO2, (b) ZrO2:1% Dy3+, (c) ZrO2:5% Eu3+, (d) ZrO2:1% Dy3+–
5% Eu3+, (e) ZrO2:2.5% Dy3+–5% Eu3+, and (f) ZrO2:5% Dy3+–
5% Eu3+ nanocrystals (kexc = 352 nm). The Eu3+-based transitions
are indicated by star mark. The emission graphs of all the samples
are represented in same intensity scale.
Fig. 6. Schematic energy levels of Dy3+ and Eu3+ ions in ZrO2
matrix.
the broad emission. The broad bandwidth indicates the pres-
ence of different recombination sites [or the existence of a
recombination band (RB)] within the band gap of the host
(see energy level diagram in Fig. 6). The Dy3+ and Eu3+-
individually doped and codoped ZrO2 samples were excited
with 352 nm wavelength, which matches the corresponding
absorption band of the Dy3+ (6H15/2?6P7/2), and the results
are depicted in Fig. 5(b)–(f). It is shown that, the emissions
at 483, 583, 680, and 750 nm are attributed to the Dy3+
transitions of 4F9/2?6HJ/2(J = 15, 13, 11 and 9) and the
emissions at 579, 590, 610, 645, and 710 nm are correspond-
ing to Eu3+ transitions of 5D0?7FJ(J = 0, 1, 2, 3, and 4),
respectively.
The hypersensitive yellow (583 nm of 4F9/2?6H13/2) in
ZrO2:Dy3+and hypersensitive red (610 nm of 5D0?7F2)
in ZrO2:Eu3+ are the strongest emission lines, as shown in
Fig. 1(b) and (c), respectively. This outcome clearly indicates
that Dy3+ and Eu3+ ions in the Dy3+ and Eu3+singly
doped samples are located at the sites without inversion sym-
metry.49,50 Most importantly, the broad emission generated
from host lattice disappeared in the doped samples, which
clearly indicates efficient energy transfer from host to activators.
1606 Journal of the American Ceramic Society—Das et al. Vol. 96, No. 5

The reason might be that the incorporation of Ln3+

(Ln = Dy or Eu) ions into the host matrix gives rise to a
substantial number of oxygen vacancies. These oxygen
vacancies might act as a sensitizer for the effective energy
transfer from the host to activators.13,16,51,52
The host lattice-independent magnetic-dipole transition at
590 nm (5D0?7F1:Eu3+) was found stronger compare with
other transitions in all Dy3+–Eu3+-codoped samples
[Fig 5(d)–(f)]; while in ZrO2:Eu3+, red (610 nm of 5D0?7F2)
is the strongest emission line. The structural results proved
that adding Dy3+ in ZrO2:Eu3+ improved the lattice symme-
try. Because of this reason, Eu3+ ions moved to the sites with
inversion symmetry during the synthesis of Dy3+–Eu3+-
codoped ZrO2 nanophosphors. Due to this phenomenon, the
orange emission (590 nm of 5D0?7F1:Eu3+) was found to be
stronger than the red emission (610 nm of 5D0?7F2:Eu3+) in Fig. 7. Room-temperature PL emission spectra of ZrO2:5% Eu3+
all Dy3+–Eu3+-codoped ZrO2 nanophosphors. This discus- and ZrO2:1% Dy3+–5% Eu3+ nanocrystals (kexc = 280 nm).
sion is extended further in the later section. Moreover, the
orange (590 nm) and red (610 nm) emission intensities of
Eu3+ show systematic enhancement with the codoping of (a)
Dy3+ up to 2.5 mol%, which could be possibly due to partial
energy transfer (ET) from Dy3+ to Eu3+ ions.49 As the Dy3+
concentration reached beyond 2.5 mol%, a decrease in the
emission intensity is observed in the codoped sample due to
concentration quenching.
The Schematic energy diagram for electronic transitions as
well as energy-transfer processes in Dy3+–Eu3+-codoped
ZrO2 is shown in Fig. 6. The energy level diagram indicates
that some of the excited Dy3+ ions transferred partial energy
to Eu3+ ions, possibly due to a dipole–dipole interaction as
a result of the magnetic-dipole transition of both Eu3+ and
Dy3+ in the host matrix. Although the energy level 4F9/2 of
Dy3+ (21.14 9 103 cm
1) is slightly higher than the energy
level 5D0 of Eu3+ (17.29 9 103 cm
1), the energy transfer
(ET) is possible due to the phonon-aided nonradiative relaxa- (b)
tion from 4F9/2 level of Dy3+ to the 5D0 level of Eu3+.
Hence, in the ZrO2:Dy3+–Eu3+ host lattice, the dipole tran-
sitions of Dy3+ ions should be quenched due to the energy
transfer from Dy3+ ions to the neighboring Eu3+ ions. To
establish the ET between Dy3+ and Eu3+ ions, it is desirable
to demonstrate the Eu3+ emission from Eu–O charge-trans-
fer excitation. Upon excitation at 280 nm, the emission peaks
belonging to Eu3+ were observed (Fig. 7). From the corre-
sponding emission spectral features, it is shown that the Eu3+
emission intensity increased almost 148% with the incor-
poration of Dy3+ ions into the host, suggesting energy
transfer from Eu–O charge-transfer band and from Dy3+ to
Eu3+.
To clearly demonstrate the origin of photoluminescence in
these codoped systems, the excitation spectra of the 5%
Dy3+–5% Eu3+-codoped ZrO2 sample were studied and Fig. 8. Room-temperature PL excitation spectra of (a) ZrO2:5%
depicted in Fig. 8, in which the corresponding transitions are Eu3+, ZrO2:5% Dy3+–5% Eu3+ monitored at 610 nm and (b)
appropriately assigned and indicated. Respective excitation ZrO2:5% Dy3+, ZrO2:5% Dy3+–5% Eu3+ monitored at 583 nm.
spectra for undoped, 5%Dy3+ and 5%Eu3+singly doped Inset in (a): excitation spectra of the undoped ZrO2 recorded at
phosphors are also included for comparison. As depicted in 490 nm.
Fig. 8(a), the spectra of the ZrO2:5%Dy3+–5%Eu3+ moni-
tored at 610 nm Eu3+ emission exhibit two distinct regions. to the various excited states of Eu3+, the codoped system
The first region is associated with a broad band in the range shows an additional excitation band at around 352 nm,
of 225–300 nm generated from charge-transfer state of Eu–O which corresponds to solely Dy3+:6H15/2?6P7/2 excitation
as the band of the Dy–O charge transfer is usually located in transition [Fig. 8(a)]. This is an indication of possible inter-
the vacuum ultraviolet (VUV) region. The second region ion energy transfer between Dy3+ and Eu3+ ions. In general,
involves sharp emission bands at longer wavelengths that the Eu3+ emission in some of the oxide-based phosphors is
characteristic of individual rare earths and the spectral fea- sensitive to the site selectivity of doped rare-earth ions. In
tures are somewhat similar [Fig. 8(a)]. The excitation spec- the codoped system, the excitation peak at around 352 nm
trum monitored at the yellow emission (583 nm) from Dy3+ (Dy3+:6H15/2?6P7/2) is responsible for the two emission
ions, as displayed in Fig. 8(b), indicates several bands in the peaks situate at 483 and 583 nm, belonging to the Dy3+
range of 300–500 nm and consists of the f?f transitions of transitions of 4F9/2?6H15/2 (blue) and 4F9/2?6H13/2 (yellow),
the Dy3+ ion. And the codoped system shows an additional respectively. While the excitation peak at around 394 nm
excitation band at around 394 nm corresponding to exclu- (Eu3+:7F0?5L6) corresponding to the orange (590 nm:
sively Eu3+:7F0?5L6 excitation transition [Fig. 8(b)]. While 5
D0?7F1) and red (610 nm: 5D0?7F2) emissions of Eu3+
the excitation spectra corresponding to the 610 nm emission of ions (Fig. 8). The relative intensities of these emission bands
Eu3+:5D0?7F2 ions show typical transitions from 7F0 and 7F1 vary with the content proportion of Eu3+ and Dy3+ ions in
May 2013 Structural and Optical Properties of ZrO2:Dy3+–Eu3+ Nanocrystals 1607

ZrO2 host. Because of this reason, the warm-white light was

achieved with appropriate combination of Eu3+ and Dy3+ (a)
excited by near UV light. Overall, the excitation spectra of
these phosphors have rich excitation lines (350–400 nm),
matches well with the emission of near UV chips (350–
420 nm).53 The excitation spectra of the undoped ZrO2 were
also recorded at the 490 nm emission wavelength of the und-
oped sample and the result is presented as the inset of
Fig. 8(a). As can be seen, the excitation spectrum showed a
broad band peaked at about 290 nm, which is close agree-
ment with the results reported previously.54,55
The intensity ratios of the yellow-to-blue (Y/B) (4F9/
2? H13/2/ F9/2? H15/2 of Dy
6 4 6 3+
) and red-to-orange (R/O)
(5D0?7F2/5D0?7F1 of Eu3+) emissions will give insight into
the covalent nature, and site asymmetry effects the local
structure. Such ratios for different Dy3+-codoped ZrO2:Eu3+
samples are estimated and listed in Table I. The asymmetry
ratio Y/B in the mixed phased ZrO2:1% Dy3+ is calculated
to be 1.97, which is larger than that of the Dy3+–Eu3+- (b)
codoped samples having cubic structures. Moreover, this
value is decreased continuously with an increase in Dy3+
content in the ZrO2:Dy3+–Eu3+ host. It is well-known that
the Y/B intensity ratio of Dy3+ greatly depends on the host
lattice structures or more precisely on the local symmetry
around the dopant ions. The decrease in the value of asym-
metry ratios always indicates the increase in symmetry
around the dopant ions.7,49,50 Hence, we can conclude that,
with the change in the host structure from low symmetric
mixed phase (ZrO2:1% Dy3+) to more proportioned cubic
phase (ZrO2:5% Dy3+–5% Eu3+), the local symmetry
around Dy3+ ion in ZrO2 host is also improved. It is shown
in Table I that the trend is preserved in all four concentra-
tions of Dy3+.
On the other hand, it is well-known that the asymmetry
ratio R/O strongly depends on the local symmetry of Eu3+ Fig. 9. (a) CIE chromaticity diagram of ZrO2:x% Dy3+–5% Eu3+
and a higher symmetry of the crystal field around Eu3+ (x = 1, 2.5, 5) nanophosphors. (b) Comparison of relative integrated
results in a lower R/O value.49,50 To evaluate the symmetry photoluminescence intensities of ZrO2:5% Dy3+–5% Eu3+ and
of the present samples, R/O values were also calculated commercial YAG as a function of the temperature (kexc = 360 nm).
(Table I). The R/O value for the ZrO2:5% Eu3+ sample
was found to be 1.18, which is smaller than that of the
reported tetragonal phase 41 and approximate to that of would be potentially used as a white light-emitting source to
the reported cubic phase.12 The estimated R/O values for meet the needs of illumination devices.
the reported tetragonal and cubic phases are 1.4641 and For device applications (such as LEDs), good thermal sta-
1.26,12 respectively. Therefore, the symmetry of Eu3+ site bility of phosphor is essential to prevent any changes in the
in the ZrO2:Eu3+ sample is higher than in tetragonal chromaticity and brightness. The poor thermal quenching
phase. In light of better symmetry in cubic phase than in property of phosphors is one of the important factors for
tetragonal phase,12 it is demonstrated by the obtained val- applying pc-LEDs usually operated at 200°C. Figure 9(b)
ues of R/O that supports ZrO2:5% Eu3+ sample is cubic in shows the temperature dependence of the luminescence inten-
phase. It is observed that both Y/B and R/O ratios give sity for the warm-white light-emitting ZrO2:5%Dy3+–5%Eu3+
different values with varying concentrations of Dy3+. nanophosphor excited at 360 nm near UV wavelength. At
Hence, by appropriate adjustment of Dy3+–Eu3+ ion com- 200°C, the present phosphor can maintain more than 80% of
bination, it is possible to obtain white emission in codoped the intensity that measured at room temperature, which
ZrO2 phosphors. is higher than the commercial YAG phosphor [Fig. 9(b)].
Figure 9(a) depicts the Commission Internationale de Such high thermal stability is good enough for the LED
L’Eclairage (CIE) chromaticity diagram of the ZrO2:Dy3+– applications.
Eu3+ phosphors codoped with different doping contents of
Dy3+ and excited at 352 nm. The resultant CIE coordinates,
IV. Conclusions
as listed in Table I, were calculated based on the correspond-
ing photoluminescence emission spectrum. Interestingly, in Various Dy -codoped ZrO2:Dy3+–Eu3+ nanophosphors
3+

the ZrO2:Dy3+–Eu3+ phosphors, the photoluminescence
color has been modulated from yellow to near white and
eventually to warm white as the Dy3+ content increases from
1 to 5 mol%. Such tuning effects are possible due to the dif-
ferent emission composition of the Eu3+ and Dy3+ ions and
energy transfer between Dy3+ and Eu3+. As seen, the near
white light is achieved for the 2.5 mol% of Dy3+-codoped
systems; whereas codoped ZrO2:5% Dy3+–5% Eu3+ exhibits
warm-white light with CIE coordinates of X = 0.343 and
Y = 0.325. On the other hand, the individually doped Dy3+
and Eu3+ phosphors fall in yellow and red regions, respec-
tively. This adjustability of luminescence color can also
broaden the fields of application, and the present material
have been synthesized for near UV excited white LED appli-
cations. More symmetrical cubic structure has been stabilized
with the doping of rare-earth ions, which subsequently gener-
ated oxygen vacancies that favored the charge compensation.
The particle sizes of the prepared phosphors were observed
to be in the range of 44–83 nm. The particle sizes estimated
from TEM and XRD results were found to be in close agree-
ment for the present nanocrystals. The effective phonon
energy derived from Raman measurements of ZrO2:1%Dy3+,
ZrO2:5%Eu3+, and ZrO2:5%Dy3+–5%Eu3+ were estimated
to be 406, 443, and 445 cm
1, respectively. The resultant pho-
non energies for the present samples were slightly lower than
that previously reported for ZrO2 matrix (470 cm
1), making
1608 Journal of the American Ceramic Society—Das et al.
the present system a very promising candidate in the field of
photoluminescence. Detailed luminescence studies of the
ZrO2:Dy3+–Eu3+ nanoparticles as a function of Dy3+ content
demonstrated that the dopant concentration and the site sym-
metry play an important role in the emissive properties of the
luminescent centers. The emission color was easily modulated
from yellow to near white light, and eventually to warm-white-
light by simply adjusting the content of Dy3+ in the ZrO2:
Dy3+–Eu3+ system. This tunable emission from the single
host is explained on the basis of the change in site symmetry
due to Dy3+ codoping and efficient energy transfer from 4F9/2:
Dy3+ to 5D0:Eu3+. The excitation spectra of these phosphors
have rich excitation lines (300–400 nm) enabling the excitation
from most of the available near UV excitation sources. Partic-
ularly, a warm-white-light emission with CIE coordinates of
X = 0.343 and Y = 0.325 was realized in ZrO2:5% Dy3+–5%
Eu3+ phosphor under 352 nm excitation. Mean while, the
warm-white light-emitting ZrO2:5% Dy3+–5% Eu3+ phos-
phor showed enough thermal stability even at 200°C; this
broadly suggests that the present phosphor could be very suit-
able for LED applications. These findings would certainly
facilitate more studies on the luminescence properties of ZrO2:
Dy3+–Eu3+ phosphor system for simplified white light genera-
tion and its relevant technologies.
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