Appl. Phys.
A55, 523-528 (1992)
Temperature Dependence of the Photoluminescence
and Phosphorescence Time Decay
of Magnesia-Stabilized Zirconia
S.E. Paje and J. Llopis
Departamento de Ffsica de Materiales, Facultad de Ciencias Ffsicas, Universidad Complutense, E-28040 Madrid, Spain
(Fax: +34-1/394-4547)
Received 31 March 1992/Accepted 13 July 1992
Abstract. Temperature dependence of photoluminescence
(PL) spectra and time decay ranging from 90 to 330K are
investigated in magnesia-stabilized zirconia single crystals.
The emission PL spectra can be decomposed into two bands.
The prominent one is centered in the blue-green region of
the spectrum whereas the secondary one is centered in the
yellow-orange region. The temperature dependence of these
bands are analyzed in terms of the so-called configuration
coordinate model. The Huang-Rhys parameter for the promi-
nent band is found near 40 and the effective phonon at about
0.030 eV. Thermal quenching energy is determined to be
0.24 eV from the decreasing part of the I(T) curve. Lumi-
nescent decays were satisfactorily fitted by two exponentials
over the whole temperature range investigated. Total lifetime
temperature dependence can be accounted for by assuming a
radiative decay from two metastable levels with a separation
energy of 0.073 eV. Results are discussed on the basis of the
major defects, oxygen vacancies and complex defects.
PACS: 78.55. Hx
So far, a considerable volume of information has been ac-
cumulated on the mechanical and other physical properties
of stabilized zirconia, in contrast with the relatively little re-
search done in the area of the luminescent properties. The
growing interest in this area partially arises from the poten-
tial usefulness of luminescent techniques in the characteri-
zation of zirconia toughened ceramics [1-3], and from the
possibility to use zirconia single crystals as laser host [4].
In a previous work [5], luminescent experiments have
been performed at room temperature from cubic single crys-
tals of zirconia stabilized with MgO and CaO. Significative
differences have been found in the emission and excitation
spectra of the MgO and CaO stabilized crystals. From the
results of this preliminary study it was tempting to suggest
that the luminescence would be connected with metastable
levels modified by neighbouring defects.
Here, we present the temperature dependence results of
photoluminescence (PL) and phosphorescence (PP) measure-
Applied .o,,..
Physics A ""
Surfaces
© Springer-Verlag 1992
ments performed in magnesia stabilized cubic zirconia single
crystals.
1 Experimental Procedures
The stabilized cubic zirconia single crystals (ZrO2, 8 wt.%
MgO) used in the present work were purchased from Good-
fellow Ltd. The as-received crystals were cut by means of a
SiC wheel-saw and without taking into account any special
crystallographical orientation.
The PL and PP measurements were carded out using a
fluorescence spectrometer Perkin-Elmer LS-5 fitted with a
red sensitive photomultiplier R-928. This spectro-fluorom-
eter provides corrected emission and excitation spectra. The
light source used was a pulse xenon lamp of 8 W with a
width at half peak intensity of less than 0.01 ms. Delay and
gate time could be varied in multiplies of 0.01 ms up to a
maximum of a combined delay and gate time of 13.33 ms. To
study the temperature dependence of the luminescence a con-
ventional liquid-nitrogen cryostat with 1 mm thick Suprasil
windows was used. For temperature control the cryostat
holder was attached to a thennocouple chromel-alumel and
a small resistance heater.
2 Results
2.1 TemperatureDependence.Analysis
Temperature dependence of the photoluminescence in the
90 to 330 K temperature range was studied. Over the whole
range of temperatures the samples showed a blue-green lu-
minescence when excited with ultraviolet (UV) light rang-
ing from 230 to 370 nm (5.4 to 3.35 eV). After UV light
exposition for about one hour, samples exhibited a brown-
ish coloration at the exposed area. Below room tempera-
ture the samples exhibited PL bands with shape and peak
position similar, but not exactly the same, to those pre-
viously reported at room temperature [5]. The excitation
spectra of the blue-green luminescence exhibited a broad
 524 S.E. Paje and J. Llopis

260 K 205 K 96 K
100 96 K
lOO
"2".
50

L 50
0"3
-'-:-. 0
25 ,4100 205 K

0 P

4
i

5
I i I

4
~

5
f
J
r I

4
i I

5
o'1
5O

PHOTON EN ,RGY (eV) _

Z
Fig. 1. Normalized PL excitation spectrum at three different tempera-
IO0 26O K
tures for the blue-green emission

50
100 96 K
0 i I i I i I p

1.5 2.0 2.5 5.0 ,3.5

P H O T O N E N E R G Y (eV)
":'. 0 Fig. 3. Solid linedescribe the normalized PL emission spectrum at three
differenttemperatures upon exciting with 254 n m (4.9eV). The dashed
~i 100 2O5 K line bands are the non-Gaussians in which the spectrum is decomposed.
The background is not plotted

r/]
5O
2;

100 260 K_ 0.6

>

50 ~ ~
E.-,
I,,--I
0.5
0 I I i P r I p
,_.q • L_L 1
1.5 2.0 2.5 5.0 ,5.5 100 200

P H O T O N E N E R G Y (eV) 0.4
*
• •
~ a • • (b)
Fig. 2. Solid line describe normalized PL emission spectrum at three
different temperatures upon exciting with 291 nm (4.26 eV). The dashed
line bands are the non-Gaussians in which the spectrum is decomposed 0.2
lO0 2oo 3o0
band centered at 291 nm (4.26 eV) with a shoulder at about
TEMPERATURE (K)
2 5 4 n m (4.90eV), as Fig. 1 shows. Figures2, 3 show the Fig. 4a, b. Full band width at half of maximum as a function of
emission spectra at three different temperatures upon ex- temperature of the (a) blue-green band and (b) yellow-orange band.
Inset shows the evolution using Gaussian bands. Solid line through the
citing with 291 and 2 5 4 n m light, respectively. A decon- experimental data represents a least-squares fit to (1). (m EXC 291 nm;
volution of the spectra using two expressions of the kind • EXC 254 nm)
Ii(E) = A~/({1 + e x p [ a i ( E - E 0 ] } { 1 + e x p [ - b ~ ( E - Ei)]})
as well as by two Gaussian bands were performed. The for-
mer allowed to obtain better results in the fitting procedure. configuration coordinate theory [6-8]. If the formulas are
Full band width at half of maximum (FWHM), and peak po- expressed by
sition of both bands as a function of temperature are given
in Figs. 4 and 5, respectively. At temperatures below 200 K W ( T ) = W(O)[coth(hwo/2kT)] I/2 (1)
the half width (FWHM) and the peak position of the blue- and
green band were fitted satisfactorily to the formulas predicted
by the harmonic approximation of the quantum mechanical Emax = A1 + A2coth(hwo/2kT), (2)
Photoluminescence and Phosphorescence Time Decay of Magnesia-Stabilized Zirconia 525
I I I

100 1.0
2.50

2.50
Z
v
N
Z
50 o.5~
E--,
2.25 ~ - - Z
1 O0 200
2.25
• • • • m m m m m mm (b)
2.1 • A • • • • • • •

L
2.0 0 P ' J ' i 0.0
100 200 300 O0 500
200
TEMPERATURE (K) TEMPERATURE (K)
Fig. 5a, b. Peak position of maximum as function of temperature of Fig. 6. Temperature dependence of the blue-green luminescence of
the (a) blue-green band and (b) yellow-orange band. Inset shows the MgO-ZrO2 crystal for excitation by 291 nm (4.9 eV). Solid line through
evolution using Gaussian bands. Solid line through the experimental the experimental data, ([3), represents a least-squares fit to (4). Dashed
data represents a least-squares to (2). (m EXC 291 nm; • EXC 254 nm) line curve shows an estimation of the luminescent yield

where hen0 is the energy of the "effective phonon", k is the
Boltzmann's constant and T is the temperature then, the fit
by the non-Gaussian expressions gives W(0) = 0.46eV,
A1 = 2.26eV, A2 = 0.14eV, and hwo = 0.030eV for
2 9 1 n m excitation and W(0) = 0.50eV, A1 = 2.15eV,
A2 = 0.22 eV, and hey0 = 0.034 eV for 254 nm excitation.
In addition, the Huang-Rhys parameter S was found to be
near 40 which indicates a strong electron-lattice coupling.
For Gaussian decomposition the W(0) and hen0 are about
15% higher than the above reported.
2.2 Thermal Quenching
Figure 6 shows the temperature dependence of the blue-green
luminescent intensity for excitation by 291 nm (4.26eV)
light. As can be seen, the blue-green emission exhibits a
maximum in intensity at temperatures near 200 K. Previ-
ously, Sarver [9] reported a similar dependence of the lu-
minescence intensity on temperature in Ti-activated zirconia
with 254 nm excitation. From the decreasing part of the full-
line curve shown in Fig. 6 and by using the criterium given
by Kr6ger [10] the quenching range was determined to be
A T ---- 104K and A T / T = 0.38. These are smaller than
those reported previously by Kr6ger [10] in ZrO2 activated
with Ti, probably due to differences in the sample compo-
sition and the low excitation intensity source used (8 W) in
the present work. If the luminescence takes place in a single
recombination centre, as it has been proposed recently [11],
the Mott's formula is applicable in the quenching range.
Therefore, the temperature dependence of the intensity was
fit to
Io
I(T) = 1 + Cexp(-Eqo/kT) '
was found to be Eq0 = 0.24 eV. A second attempt to fit the
temperature dependence of the blue-green intensity over the
whole temperature range was made by
I(T) = Z°
1 + C t exp(-E'qt/kT )
x
( 1- '
I+C 2exp(-E2/kT)
)' (4)
where the second factor in (4) may be regarded as the
effectiveness of a trapping process. The best fit of intensity
data by (4), full-line curve in Fig. 6, is given for Eql =
0.20 eV and E 2 = 0.043 eV.
2.3 Luminescence Decay
Over the whole range of temperatures the decay curves
were fitted quite well by two exponentials. However, at
about room temperature and above the curve fitting by
two exponentials is not as good as at lower temperatures
but still satisfactory enough. Figure7 shows some decay
curves taken at different temperatures in which the solid
line represents the curve fit. No significant differences were
found in the shape of the decay curves upon exciting with
291 or 254nm light, except a faster decay in the first 0.1 ms
upon exciting with 254nm light at T < 200 K. The time
variation of the blue-green intensity when there was an
overlapping with the flash lamp, for delay times between
0.01 and 0.05 ms, is plotted in the inset of Fig. 7a. At about
200 K the maximum in intensity of the blue-green emission
was shifted to 0.02 ms.
The temperature dependence of the two components ~-1
and ~'2 is shown in Fig. 7. The total lifetime -r-tot, was calcu-
(3) lated by

where I0, C and Eq0 are parameters. The latter, Eq0, deter- 1 1 1
-- + --. (5)
mined the activation energy of the thermal quenching which "/-tot 7"1 3-2
 526 S.E. Paje and J. Llopis
I b ~ h
,,, ',,
d" "ca 1.0

0.5
d
0.0
[D

v
0.2
z
0.1
k 175 K
0.0
0 1 2 5 4 5 0.2 Trot
TIME ( m s )
0.1

d
!vv~
_
•QO

205 K
0.0

00
i ;

150
TEMPERATURE (K)
r ;

200
i

250
I i

300
v
Fig. 8. Temperature dependence of the time constants T1, ~2 and Trot.
Solid curves through the experimental data represents a least-squares
02 fit to Ti = T0~/[1 ÷ ai exp(-E~/kT)] and to (9), respectively
Z

Z On the other hand, "/-totcan be rewritten as

1 1 1
~ i 260 ' K " - + --, (6)
(b) Ttot Tr Tnr
I
where ~-r is the radiative lifetime and %r is the nonradia-
0.0 0.1 0.2 0.3 0.4 0.5 tive lifetime of the luminescent process. Assuming that the
TIME ( m s ) radiative lifetime is temperature dependent and follows the
Fig. 7a, b. Luminescence decay curves taken at six different temper- theoretical predictions for the temperature dependence of the
atures. Solid lines through the experimental data represents a least- lifetime associated with two excited states coupled by radi-
squares fit to two exponentials. The curves for different temperatures ationless transitions in thermal equilibrium, then it can be
are displaced arbitrarily along the vertical axis for convenient graphi- expressed by
cal presentation. The inset in (a) shows in detail the decay in the time
range overlapping with the flash lamp 1 + D exp(-AE/kT)
~-r = ~-L , (7)
1 + "rED e x p ( - A E / k T )
Tu
The temperature dependence for the "/-totderived from (5) is where TL and TU are the intrinsic lifetimes of the two states,
plotted in Fig. 8. ~-tot was found to increase as the temper- the lower and the upper, respectively, A E is their energy
ature decreases. If the luminescence decay would be dom- difference, and D is the ratio of the degeneracies of the
inated by the first-order kinetics of a single trap then the two states [13]. Moreover, a Mott-type expression for the
temperature dependence of the decay constants followed nonradiative lifetime can be applied
an exponential law in the form of To e x p ( - E t / k T ) , where 1
Et represents the activation energy of the trap [12]. How- -- = s exp(-Eq/kT), (8)
Tnr
ever, the temperature dependence of the decay constants
scarcely fits to the latter form. In contrast, a good approx- which is in agrement with a strong coupling of the lattice
imation was found when the constants fitted to equation with the centre. From (6), (7) and (8), the temperature de-
r~ = ~-0~/[1 + a~ e x p ( - E * / k T ) ] , where E~ is an activation pendence of Ttot will be expressed by
energy parameter, ~-0i and ai are also fit parameters. Then,
1 + D exp(-AE/kT)
fitting T1 and T2 data to the preceding formula the activation
Tto~ = ~-L1 + ~-LD e x p ( - A E / k T ) + s exp(-Eq/kT). (9)
energies E{ = 0.093 eV and E~ = 0.086 eV were found. For
TU
~-tot the fit gives T0tot = 0.2ms, a0tot/~-0tot = 2.5 × 1 0 6 S - 1
and E* = 0.075eV. Note that the value for E* is far Hence, '/-totexperimental data were fitted quite well by equa-
off the thermal quenching activation energy reported above, tion (9), full line in Fig. 7, given ~-L = 0.20 ms, zu = 0.45 gs,
0.20 _< Eq _< 0.24 eV. A E = 0 . 0 7 3 e V , s--= 1.3 x 106s -1, f o r D = 1 a n d E q =
Photoluminescence and Phosphorescence Time Decay of Magnesia-Stabilized Zirconia
0.24 eV. A quite similar accurate fit is built for D = 3. An
estimation of the luminescent yield ~7 = "E/"Erwas made by
using the former fit parameters, dashed line in Fig. 6.
3 Discussion
The origin and detailed mechanism of the blue-green lumi-
nescence is not yet clear and it has been the subject of con-
troversy. In an earlier work [1] the emission was supposed
to be related to a self-activated origin by the asymmetric
and unusual oxygen coordination of zirconium in the mon-
oclinic zirconia phase. Preceding work [9, 14, 15] assumed
an activated origin by substitutional Ti4+ ions. In particular,
Macke [15] speculated with the possibility that the lumi-
nescence originated from a defect titanate centre. Radiative
recombination via structural defects, such as oxygen vacan-
cies, has also been contemplated [16, 17]. Recently [5, 11],
a plausible origin of the luminescence has been proposed
from metastable levels modified by neighbouring defects. In
the present investigation the latter assumption is partially
confirmed.
The spectral similarities observed under excitation either
for 254 or 291 nm suggest that a similar centre is involved in
the radiative process, this in agreement with the configura-
tion coordinate model assumed for T _< 200 K. In addition,
the decomposition of the emission spectra into broad bands,
the large Stokes shift and the high value of the Huang-Rhys
parameter, indicate a strong interaction of the centre with
the lattice. These facts show great similitude to the lumines-
cent characteristics of the F-type centres in alkaline earth
oxides and alkali halides [8, 18]. In particular, F-centres
with one or two impurities in the nearest-neighbour cation
shell, FA or FB-centre, respectively, could primarily concil-
iate the F-centre features observed with a presumable role
of the Ti4+ ion in the blue-green luminescence. Recently,
PaiVerneker etal. [19] reported that the absorption edge of
4.23 eV (293 nm) in yttria-stabilized cubic zirconia can be
accounted for by the excitation of an FA complex consist-
ing of an y3+ ion and an F + oxygen vacancy.
For temperatures above 200 K the experimental data can-
not be well fitted by the predicted formulas of the configu-
rational coordinates model. A possible explanation may be
given by trapping effects on the intensity and the shape of
the luminescent spectrum against temperature of active traps.
In fact, thermoluminescent glow peaks have been reported
ranging from 100 to 350K in ZrO2 crystals [9, 14, 16,20].
In particular, the reported glow peak, near 200 K, display a
single maximum in the blue-green region of the spectrum
and it has been ascribed to a electron trap presumably con-
stituted by an oxygen vacancy and a Ti4+ ion [14]. This trap
is assigned to an energy of about 0.36 eV. A similar energy
trapping of 0.4 eV has been estimated recently from a centre
consisting of an electron localized at a cation site near an
oxygen vacancy [21,22]. The presence of traps absorbing
at about 480-500nm is also consistent with the brownish
coloration observed at the UV exposed areas of our crys-
tals. This coloration effect has been previously described
in electroreduced and thermally reduced stabilized zirconia
composites and supposed to be associated with empty levels
of an oxygen vacancy-type defect [23-26].
527
The value of thermal quenching activation energy found
at about 0.24 eV is the same that those reported by Batigov
etal. [27] and tentatively attributed to the energy of mi-
gration of self-localized excitons in ZrO2-Y203 crystals. In
addition, they give a second activation energy of 0.055 eV
applicable for temperatures below 200 K, which is very close
to the E2 -- 0.043 eV obtained fitting our data to (4).
Accepting a single centre, the decay curves fitted by
means of the two exponentials can be explained by the flu-
orescence decay of at least a four-levels system [13]. Then,
the radiative lifetime will be a weighted combination of the
lifetimes "E3t = "E~ and 7-21 "EL,and will vary with tempera-
=
ture as the populations of the two states change. At low tem-
peratures "Er tends to be 0.2ms = "EL = "E2~,whereas above
room temperature the total lifetime tends to be controlled
by nonradiative rather than radiative processes. Bogan et al.
[28] firstly used this mixed-state model to give a consistent
explanation for the temperature dependence of F-centre ra-
diative lifetimes in alkali halides. In another way, some few
analogies with the decay time and energy level schemes of
titanate complexes [14, 29] may justify to keep in mind a
defect titanate centre in the blue-green luminescence origin.
The increase in intensity at about 200 K, for 0.02 ms after
the flash lamp rise, can be accounted for by the presence of
a electron trap associated with a glow peak near 200 K. As
mentioned above, this sort of trap is likely connected to
oxygen vacancies, which would be relatively abundant in
our crystals owing to electrical neutrality reasons. This is
also on good agreement with the observable small increase
of the time constants "El, "E2 and consequently in "Etotat about
200 K shown in Fig. 8.
Luminescence in the yellow-orange range of the visible
spectrum has already been reported in stabilized cubic (full
or partially) zirconia [3-5, 17, 19, 20, 30] and in ZrO2 com-
posites [3, 11]. In the PL emission spectrum of the yttria-
stabilized zirconia crystals the yellow-orange luminescence
usually appears as a prominent band upon exciting in the
302 to 330nm light range. This differs with the secondary
appearance upon exciting with 291 or 254 nm light observed
in the present and prior investigations in pure and stabilized
zirconia [3, 5, 11,20]. Although the nature of this band is
not yet fully clear, some proposals have been done. Some
of them assumed an activated origin presumably related to
impurities [4, 20] whereas others tentatively ascribed the lu-
minescence to color centres [5, 17, 30]. In the present study
the observed broad character of the emission similar to the
blue-green band sustain the latter. In addition, the fact that
the excitation peaks were found common for the yellow-
orange and the blue-green luminescence may be explained
as due to a similar but not necessarily the same defect ori-
gin, since differences in the temperature dependence of the
PL emission spectrum were found.
Finally, we can conclude that it is very likely that com-
plex defects constituted by anoin vacancies and any major
impurity including titanium, are involved in the lumines-
cence of zirconia.
Acknowledgements.We are grateful to Dr. M. Jimrnez de Castro, Dr. A.
Ibarra and R. Vila for the useful suggestions and facilities given in the
construction of the cryostat. The financial support of Direccidn General
de Investigacidn Cientfficay Trcnia, DGICYT, project No. PB90-0250
is also acknowledged.
528
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