Optical Materials 24 (2003) 51–57

www.elsevier.com/locate/optmat

Annealing and doping effects on the structure of

europium-doped HfO2 sol–gel material
nez a, C. Le Luyer a, O. Marty b, J. Mugnier
M. Villanueva-Iba~ a,*

a
Laboratoire de Physico-Chimie des Materiaux Luminescents, CNRS-UMR 5620, Universit e Claude Bernard Lyon I, B^at. A. Kastler,
10 rue Ampere, Domaine Scientifique de la Doua, 69622 Villeurbanne Cedex, France
b
Laboratoire d’Electronique, Nanotechnologies, Capteurs, JE CNRS 2266, Universite Claude Bernard Lyon I, B^
at. A. Kastler,
10 rue Ampere, Domaine Scientifique de la Doua, 69622 Villeurbanne Cedex, France
Received 8 December 2002; accepted 24 February 2003

Abstract

Powders and waveguiding films of europium-doped hafnium oxide (Eu3þ :HfO2 ) are prepared by a sol–gel process.
The material is synthesized using hafnium tetra-ethoxide and europium (III) nitrate pentahydrate which are dissolved in
ethanol and mixed with acatylacetone. The powders and the films present structural changes depending on Eu3þ
concentration and annealing temperature. The monoclinic stable phase appears at low annealing temperatures and is
preferentially crystallised for low doping concentrations. The tetragonal phase appears at high annealing temperatures
and is the predominant phase for high doping concentrations. Differential thermal analysis, X-ray diffraction, Raman
spectroscopy and transmission electron microscopy are used to characterize the powders and the films.
 2003 Elsevier B.V. All rights reserved.

Keywords: HfO2 :Eu3þ ; Sol–gel; Powder; Waveguiding films

1. Introduction more particularly when crystallized into to te-

Hafnium oxide has excellent physical and
chemical properties. HfO2 is high optical index
(2) and low absorption material used in partic-
ular for optical coatings operating between the
near UV (below 300 nm) and IR (10 lm) regions.
Furthermore, it presents a great hardness (the te-
tragonal phase is comparable with the diamond
[1]), a high chemical stability and good dielectric
properties. Moreover, the high density of HfO2 ,
*
Corresponding author. Tel.: +33-4-72-431453; fax: +33-4-
72-431130.
E-mail address: mugnier@pcml.univ-lyon1.fr (J. Mugnier).
tragonal phase (density around 10 g/cm3 ), makes
this compound attractive for host lattice activated
by rare earth for applications as scintillating ma-
terials. Indeed, high density of a material and high
atomic numbers of its constituents are character-
istics for scintillator applications [2]. However, no
efficient dopant for this material has been found
up to now. In this study, our attention is paid on
europium ions for doping, as it has successfully
been used with gadolinium and lutetium oxide
prepared by sol–gel process and exhibiting scin-
tillations properties [3].
This paper presents a fundamental study of
the microstructure of Eu-doped HfO2 for future

0925-3467/$ - see front matter  2003 Elsevier B.V. All rights reserved.
doi:10.1016/S0925-3467(03)00104-6
52 M. Villanueva-Iba~nez et al. / Optical Materials 24 (2003) 51–57

applications in scintillation field. Indeed, the

spectroscopic and optical properties of this mate-
rial strongly depend on its microstructure. For this
intention, a structural analysis based on the do-
pant concentration and thermal treatment is con-
ducted on two kinds of samples: powders and
films.
The samples are prepared using sol–gel process.
The sol–gel method arises as a elaboration method
of high quality oxide materials and is well adapted
for the preparation of high quality thin films used
as planar waveguides [4]. It presents many well-
know advantages such as high purity of precur-
sors, high homogeneity of material, low processing
temperatures, no need of vacuum and high flexi-
bility and feasibility over a good ability to homo-
geneous rare earth doping [5].

2. Sol–gel processing

2.1. Chemical process

Hafnium tetra-ethoxide, 99.9% (ABCR) and

europium (III) nitrate pentahydrate, 99.9% (Ald-
rich) are used to elaborate Eu3þ :HfO2 material by
sol–gel process. The chemical procedure is de-
scribed on Fig. 1. As hafnium tetra-ethoxide
(Hf(OC2 H5 )4 ) is highly hygroscopic, it is first dis-
solved in ethanol under controlled atmosphere of
nitrogen flux (2% RH) before strongly stirring
during 1 h at 100 C. A mixture of acetylacetone
(acac) and ethanol is then added to the solution
with a Hf(OC2 H5 )4 /acac ¼ 1 mol ratio, to chemi-
cally stabilized the alcoxide. The resulting solution
is hydrolyzed under water saturated atmosphere
by mixing and heating at 120 C. The final con-
centration of hafnium oxide is 60 g/l. Eu(NO3 )3 ,
5H2 O is introduced after the hydrolysis of the so-
lution. The solution remains transparent and
keeps a constant viscosity for more than 6 months.
2.2. Powder preparation
Europium-doped hafnia sol–gel powders are
obtained by drying the sol during 24 h at 95 C.
Solutions with doping concentration varying from
1 at.% up to 25 at.% are elaborated and studied.
Fig. 1. Experimental procedure of preparation of Eu-doped
HfO2 powders and films.
The powders are sintered at different temperatures
between 650 and 1000 C for 3 h under air.
2.3. Film deposition
The solution is filtered using a 0.2 lm Millipore
filter and is deposited onto carefully cleaned pure
silica (Herasil from Heraeus) substrates using the
dip-coating technique. The substrates are im-
mersed into the solution with a withdrawal speed
of 90 mm/min. Three different solutions containing
europium, with concentrations 0.1, 1 and 10 at.%,
are prepared. After each coating, the films are
dried for 10 min at 100 C to allow evaporation of
the more volatile solvent and at 350 C in a tubular
 M. Villanueva-Iba~nez et al. / Optical Materials 24 (2003) 51–57 53

oven under flow of oxygen to remove the organic

compounds. Then, the resulting films are heat-

(1,1,1)
treated at temperatures varying from 400 to 800
C. Four coatings are required to obtain mono-
mode waveguiding films (200 nm thick).

(2,2,0)

(3,1,1)
Intensity (a.u.)

(2,0,0)

(2,2,2)
3. Results and discussion (b)

(-1,1,1)

(1,1,1)
3.1. Powder analyses

The existing phases of the europium-doped

HfO2 powders (see Section 2.2) are investigated in

(0,2,2)

(3,1,0)
(-1,1,2)
(1,1,0)
detail through both X-ray diffraction and micro-

(0,3,2)
Raman spectroscopy techniques conducted at (a)
room temperature. The micro-Raman experiments
use the 514.5 nm exciting wavelength of an Argon 10 20 30 40 50 60 70

laser (Spectra-Physics, 250 mW). The powder is 2θ

excited through a microscope objective (50) that Fig. 2. X-ray diffractions patterns of HfO2 powders heat-trea-
directly focuses the laser beam onto the sample. ted at 900 C and doped with 1 at.% (a) and 25 at.% (b) of Eu3þ .
The backscattered light from the powder is anal-
ysed by a Dilor XY micro-Raman spectrometer
equipped with a N2 cooled charged coupled device
multichannel detector.
As an example, the XRD spectra obtained of a
(b)
25 and 1 at.%. doped Eu3þ :HfO2 powders heat-
treated at 900 C are shown on Fig. 2a and b re-
Intensity (a.u.)

spectively. The complete series of Bragg reflections

observed on Fig. 2a correspond to the HfO2
monoclinic phase (referenced JCPDS 43-1017),
and those observed on Fig. 2b are identified as
HfO2 tetragonal phase (referenced JCPDS 08-
0342). These observations are confirmed by micro-
Raman experiments conducted on a 1 at.% (Fig. (a)
3a) and 25 at.% (Fig. 3b) doped Eu3þ :HfO2 pow-
ders. The Raman spectrum recorded on sample
heat-treated at 900 C and doped with 1 at.%. of
europium, indicates that the powder is crystallized 100 200 300 400 500 600

in monoclinic phase (Fig. 3a). The corresponding Raman shift (cm-1)

Raman spectrum presents narrow bands at 110,
133, 146, 163, 242, 256, 335, 381, 397, 497, 521,
550, 580 and 640 cm1 . These bands are assigned
to the monoclinic phase of single crystal of haf-
nium oxide studied at atmospheric pressure [6].
The Raman spectrum obtained for sample heat-
treated at the same temperature but doped with 25
at.% of europium exhibits three broad bands
around 280, 460 and 656 cm1 , and a small one at
Fig. 3. Micro-Raman spectra (k ¼ 514 nm) of HfO2 powders
heat-treated at 900 C and doped with 1 at.% (a) and 25 at.%
(b) of Eu3þ .
110 cm1 . Those bands also appear on Raman
spectrum of tetragonal single crystal of hafnium
oxide recorded at pressure higher than 28 GPa [6].
The results obtained for various concentration of
54 M. Villanueva-Iba~nez et al. / Optical Materials 24 (2003) 51–57

Table 1 ready been described elsewhere [4]. This high sen-

Microstructure of Eu3þ :HfO2 sol–gel powders for different Eu3þ sitive and non destructive technique is extremely
concentrations and heat-treated at different annealing temper-
atures (t: HfO2 tetragonal phase, JCPDS 08-0342, m: HfO2
powerful, especially for sol–gel waveguide analy-
monoclinic phase, JCPDS 43-1017) sis. Briefly, a Krypton laser beam (k ¼ 647:1 nm,
T (C) at.%
500 mW) is focused at room temperature near the
corner of a prism coupler used to launch the light
1 3 5 7 10 25
into the film. The scattered light is analyzed by a
650 m m mþt mþt mþt t Jobin-Yvon double monochromator (U-1000
750 m m m mþt mþt t
900 m m m m mþt t
model) and a photocounting system. At tempera-
1000 m m m m m mþt tures higher than 800 C, the films loss their
waveguiding properties and WRS measurements
cannot be carried out.
europium-doped HfO2 powders and heat-treated As an example, the Raman spectra obtained on
at different temperatures (from 650 C) are sum- the 1 at.% doped film for different annealing tem-
marised on Table 1. The powders heat-treated at peratures are shown on Fig. 4. The film crystallises
temperature below 650 C are amorphous. Ac- at 500 C from the amorphous phase into the pure
cording to XRD and Raman data at room tem- monoclinic phase. The Raman bands assigned to
perature, concentrations of europium 1 and 3 at.%
show monoclinic phase at all annealing tempera-
tures. After 650 C heat treatment, hafnia Eu3þ
doped at 5, 7 and 10 at.% is composed by a mix-
ture of monoclinic and tetragonal phases. Twenty-
five at.% Eu3þ -doped HfO2 is crystallized in pure
tetragonal phase from 650 C up to 900 C. A
mixture of tetragonal and monoclinic phases ap-
pears for this concentration only after an anneal-
800°C
ing treatment at 1000 C.

3.2. Film analyses

Intensity (a.u.)

The films are analyzed by waveguide Raman

spectroscopy (WRS) and conventional trans-
mission electron microscopy (CTEM). These tech-
niques are well adapted and are two complementary 650°C
approaches for thin films analyses [4]. WRS pro-
vides a mean and non destructive results from the
layers although CTEM allows local and destruc- 500°C
tive observations of the films.
The microstructure of europium-doped HfO2
films is studied for annealing temperatures ranging
from 400 C up to 800 C and for europium con-
400°C
centrations varying from 0.1 to 10 at. %. The de-
posited sol–gel films present planar waveguiding
0 100 200 300 400 500 600 700 800
properties which are a proof of their optical
quality. This feature allows to study their micro- Raman shift (cm-1)
structure by Raman spectroscopy in waveguiding Fig. 4. Room temperature waveguide Raman spectra of 1 at.%
configuration conducted at room temperature. Eu3þ -doped HfO2 sol–gel films heat-treated for 15 min at dif-
Details of the WRS experimental set-up have al- ferent temperatures from 400 C up to 800 C.
 M. Villanueva-Iba~nez et al. / Optical Materials 24 (2003) 51–57 55

this phase are observed at 500 and 650 C. At low

annealing temperature, the film presents good
waveguiding properties and the Raman spectrum
is well resolved. After a 800 C heat treatment, the
film presents lower waveguiding properties and, as
consequence, the Raman spectrum is more noisy.
The main bands of the monoclinic phase, located
at 133, 145 and 497 cm1 , are still observed, but
the tetragonal phase is more difficult to identify
due to the broad shape of the associated bands (see
Fig. 3b). CTEM observations are then carried out
for high annealing temperature to complete WRS
results.
The film is peeled off from the substrate and put
onto a microscope grid. CTEM studies have been
performed on a TOPCON EM-002B working at
200 kV. The observations are conducted on films
heat-treated at 800 C and containing different
concentrations of europium i.e.: 0.1 at.% (Fig. 5a),
1 at.% (Fig. 5b) and 10 at.% (Fig. 6a). All the
structure are dense and fully crystallized, with
grains size lower than 50 nm for 0.1 and 1 at.%
doping concentration and with grain sizes higher
than 70 nm for 10 at.% of europium. This large
size of the crystallites size directly explains that the
signal to noise ratio of the WRS intensity de-
creases at 800 C, as observed and discussed be-
fore. The electron diffraction patterns of the 0.1
and 1 at.% europium-doped HfO2 films are similar
(Fig. 5c) and exhibits mainly rings associated to
(1 0 0), (0 1 1), ()1 1 1), (1 1 1) and (0 0 2) planes of
HfO2 monoclinic phase, which confirmed WRS
analyses. Rings characteristics of tetragonal phase
are not observed. However, selected nanodiffrac-
tion patterns (Fig. 7) conducted on the films,
whatever the concentration of europium, is in- Fig. 5. CTEM observations conducted on HfO2 films heat-
dexed for the HfO2 tetragonal phase. Moreover, treated at 800 C and doped with 0.1 at.% (a) and 1 at.% (b) of
the diffraction pattern of the 10 at.% europium- Eu3þ , (c) is the electron diffraction pattern obtained on both (a)
and (b) samples.
doped HfO2 films (Fig. 6b) indicates the presence
of both the monoclinic and the tetragonal phases.
This two phases are then simultaneously present
into the layers annealed at 800 C, for the three 3.3. Discussion
different doping concentrations, but probably their
ratio is Eu3þ concentration dependent. Hafnia (HfO2 ) has three polymorphisms of
All the results obtained on the films are sum- monoclinic, tetragonal and cubic phases with the
marized in Table 2. The films heat-treated at 400 crystal structures similar to those of zirconia at
C are amorphous whatever the concentration of atmospheric pressure. The transition and melting
Eu3þ in HfO2 . points in hafnia are higher than those of zirconia.
56 M. Villanueva-Iba~nez et al. / Optical Materials 24 (2003) 51–57
Fig. 6. CTEM observation of HfO2 films heat-treated at 800 C
and doped with 10 at.% of Eu3þ (a) and the corresponding
electron diffraction pattern (b).
Fig. 7. Selected nanodiffraction patterns of Eu3þ :HfO2 films
heat-treated at 800 C whatever europium concentration.
Pure HfO2 tends to appear in the monoclinic
phase, which transforms to tetragonal phase on
Table 2
Microstructure of Eu3þ :HfO2 sol–gel films for different Eu3þ
concentrations and heat-treated at different annealing temper-
atures (t: HfO2 tetragonal phase, JCPDS 08-0342, m: HfO2
monoclinic phase, JCPDS 43-1017)
T (C) at.%
0.1 1 10
500 m m mþt
600 m m mþt
700 m mþt mþt
800 mþt mþt mþt
heating between 1510 and 2000 C. The cubic
phase crystallises at temperature higher than 2700
C [7].
The low concentration Eu3þ -doped HfO2 films
elaborated in this study present a similar behaviour
(see Table 2). The monoclinic phase crystallises at
low annealing temperature from amorphous phase
and tetragonal phase seems to crystallise from
monoclinic phase. For high doping concentrations
(10 at.%), the film crystallises from amorphous
phase into a mixed phase of monoclinic and te-
tragonal structures.
The sol–gel Eu3þ :HfO2 powders do not present
the same structural behaviour as the sol–gel
Eu3þ :HfO2 films (see Table 1) although the pure
monoclinic phase appears, in both the powders
and the films, from amorphous phase at low an-
nealing temperature and for low doping concen-
tration. Nevertheless, in the powder with Eu3þ
concentration from 5 to 10 at.%, the samples are
crystallized into both monoclinic and tetragonal
phases and the pure monoclinic phase appears at
high annealing temperature. The pure tetragonal
phase can even been formed from amorphous
phase for 25 at.% doped powder heat-treated be-
low 1000 C.
Andrievskaya et al. [8] have studied the struc-
ture of stabilized HfO2 –Eu2 O3 solid solution, but
the mechanisms of stabilisation of the tetragonal
form have never been studied onto Eu3þ -doped
sol–gel HfO2 material. Nevertheless, it has already
been discussed and presented on rare earth doped
ZrO2 sol–gel films [9,10] and on undoped ZrO2
materials prepared by different method [11,12].
More generally, ours observations confirm that
europium doping may stabilize HfO2 tetragonal
 nez et al. / Optical Materials 24 (2003) 51–57
M. Villanueva-Iba~
phase. As the physical and chemical properties of
HfO2 are similar to those of ZrO2 , we assume that
the nature of the phase is linked to three main
parameters, as suggested by Bouvier et al. on ZrO2
studies [13]:
• the crystallite size and its surface energy,
• the effect and the concentration of dopant,
• the internal compressive stress generated during
the growth process and depending on the shape
of the material.
The total understanding of all the structural
change phenomena is very complex as it is due to
the coupled effects of all those parameters. The
study of the effects of annealing temperature and
Eu3þ concentration on the grain size and on the
stress into the sol–gel HfO2 films and powders will
be presented in details in a future paper.
4. Conclusion
In this work, we performed Eu3þ -doped HfO2
powders and films by sol–gel technology. We
present the structural evolutions of this material as
function of the annealing temperature and of the
concentration of doping element. It is noted that
the films and the powders do not present similar
structural behaviour. The determination of the
ratio of each phase depending on the doping
concentration and the annealing temperature is in
progress. The formation of the phase that is en-
ergetically favoured is attributed to a combined
effect of stress and grain size. More details about
this very complex study and preliminary results of
scintillation properties will be presented in a future
publication. More particularly, further investiga-
tions of the average crystallites size calculated onto
the powder by the broadness of diffraction peak
and by Scherrer formula, and onto the films by
57
WRS conducted in the very low frequency range,
will be detailed.
Acknowledgements
The authors are grateful to CONACyT-SFERE
Program 2001 for M.V.-I. scolarship. The authors
would like to thank Dr. C. Bovier and Dr. S. Pa-
rola for stimulating discussions.
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