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phys. stat. sol. (c) 4, No. 3, 1270– 1275 (2007) / DOI 10.1002/pssc.

200673801

Magnetism due to defects/oxygen vacancies in HfO2 thin films


Nguyen Hoa Hong*
Laboratoire LEMA, UMR 6157 CNRS/CEA, Université F. Rabelais, Parc de Grandmont, 37200 Tours,
France

Received 8 July 2006, revised 14 September 2006, accepted 8 November 2006


Published online 9 March 2007

PACS 75.60.Ej, 75.70.Ak


Room temperature ferromagnetism with a large magnetic moment was observed in un-doped HfO2 films
grown on Yttrium Stabilized Zirconia substrates. It is known that neither Hf4+ nor O2– is magnetic. On the
other hand, HfO2 bulk is clearly diamagnetic. Since it is certain that there is no contamination in any sub-
strate, it is not possible to attribute such a large magnetic moment to impurities. Certainly thin film form,
which might create necessary defects and/or oxygen vacancies, must be the main reason for this un-doped
insulating oxide to become ferromagnetic. Filling up oxygen vacancies can reduce the magnetic moment
enormously, and at some critical point, can destroy the ferromagnetic ordering completely. This confirms
the assumption that magnetism in HfO2 thin films originates from defects and/or oxygen vacancies. De-
fects seem to be mostly located at the interface between the film and the substrate.

© 2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

1 Introduction Searching for high temperature ferromagnetic compounds based on semiconducting


or insulating oxides is actually one of the main research topics of many physics and chemistry laborato-
ries. By doping transition – metals into TiO2, ZnO, SnO2, In2O3 or HfO2, room temperature ferromagnet-
ism (FM) could be obtained [1–5] as theory suggested [6]. However, in 2004, Venkatesan et al. reported
about the unexpecxted magnetism in HfO2 thin films on sapphire or silicon substrates, as well as our
results of other types of oxide thin films on various substrates have attracted the attention of the magnet-
ism community about a new phenomenon so-called d0 magnetism [7–9]. Thin film form supports an
formation of defects and/or oxygen vacancies that may lead to magnetism. Many groups have made a lot
of efforts to verify this issue: While theory predicted that Mn-doping alone in ZnO does not produce any
room temperature FM [10], experimentally it has been proven that Mn-doped ZnO films can be room
temperature ferromagnetic [11] Growth conditions must play an important role since they help to create
oxygen vacancies, that are similar to an n-type doping. Many reports have shown that defects could tune
FM in diluted magnetic oxide thin films. It was found that defects could introduce FM into non-magnetic
ZnO [12] while in other cases, filling up oxygen vacancies can improve the crystallinity remarkably, but
silmutaneously degrades the magnetic ordering of the oxide films [13]. A recent theoretical report on the
HfO2 system has pointed out that isolated cation vacancies in HfO2 could form high-spin defect states,
and therefore, they could be ferromagnetically coupled with a rather short-range magnetic interaction
resulting in a ferromagnetic ground state [14]. However, from experimental data, Coey et al. have dis-
cussed that there must be some mechanism by which oxygen vacancies could produce oxygen holes and
it is more likely that lattice defects should be the source for magnetism in HfO2 [8]. All of these contro-
versial issues have urged us to examine the role that oxygen vacancies actually play in tailoring FM in
HfO2 thin films. Moreover, the question whether a transition-metal doping is important or not in shaping
up the magnetic properties of this type of oxide will also be discussed.

*
Corresponding author: e-mail: nguyen.hoahong@univ-tours.fr, Phone: +33 2 47 36 73 36, Fax: +33 2 47 36 71 21

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phys. stat. sol. (c) 4, No. 3 (2007) 1271

2 Experiment Films of HfO2, Ni-doped HfO2, and Fe-doped HfO2 with a Fe concentration of 0.01
and 0.05, were deposited by a pulsed-laser deposition (PLD) system (KrF-248 nm, 5 Hz, 1.8 J/cm2) from
ceramic targets on (100) Yttrium Stabilized Zirconia (YSZ) substrates. The substrate temperature was
800oC and an oxygen partial pressure (PO2) of 10–6 Torr was used during deposition. The typical thick-
ness of Ni-doped HfO2 is about 190-220 nm, of Fe-doped HfO2 films is 130-140 nm. The typical thick-
ness of the undoped HfO2 films is 200 nm, however some films with a special thickness of 5-10 nm were
also made in order to examine the thickness dependence as well as defects’ location. All films are color-
less and transparent. After deposition, films of HfO2 were annealed in an oxygen atmosphere at 800 oC
for 2 hrs and 10 hrs, as well as heated in vacuum at the same temperature for 2 hours. Fe0.01Hf0.99O2 and
Fe0.05Hf0.95O2 were treated by different heating processes. One as-deposited film of Fe0.01Hf0.99O2 was re-
fixed into the chamber and annealed in vacuum at 800 oC during 2 hrs. Then finally that vacuum-
annealed film was put into the furnace and annealed at 500 oC for 12 hrs in an oxygen atmosphere with
the pressure as of 760 Torr. As for the Fe0.05Hf0.95O2 films, the process applied is somewhat different:
after deposition, one film of Fe0.05Hf0.95O2 was annealed in air at 800 oC for 30 minutes, then finally re-
fixed into the chamber to be heated in high vacuum at 800 oC for 2 hrs. After each single step, structural
and magnetic properties of films were checked by an X-ray diffractometer and a magnetometer, respec-
tively. Basically the magnetic moment was measured with the field applied parallel to the film plane
from 0 to 0.5 T in the range of temperature from 5 up to 400 K. Some measurements were also carried
out in the magnetic field applied perpendicular to the film plane in order to check the anisotropy of the
samples.

3 Results and discussions In general, ferromagnetic insulators (FI) are rare since in insulating com-
pounds, most probably, spins tend to couple with each other antiferromagnetically. With the shed light
from the finding of room temperature ferromagnetism by doping transition - metals into semiconducting
oxides such as TiO2, ZnO, or SnO2 [1–3] doping Ni in HfO2 under the thin film form was also done in
order to verify if such a transition-metal doping can create some kind of insulating ferromagnets. It was
expected that Ni as a magnetic impurity can play a role as an intermediate to help the isolated spins in
HfO2 to interact one to the other ferromagnetically through the Ruderman-Kittel-Kasuya-Yoshida
(RKKY) interaction.
One can see from Fig. 1 that the Ni-doped HfO2 films have a large magnetic moment of about 12
emu/cm3 (or about 2.7 µB/Ni, by using the number of Ni atoms determined by Rutherford backscattering
measurements, and supposing that all the Ni atoms in the films contribute to the magnetism). This ob-

15
200 nm-thick-Ni0.05Hf0.95O2 film
Magnetization (emu/cm )
3

10

5 Fig. 1 Magnetization versus magnetic field at 300 K


for a 200 nm-thick-Ni0.05Hf0.95O2 film.
0

-5
H//, at 300 K
-10

-15
-0.4 -0.2 0.0 0.2 0.4
Field (T)

served magnetic moment is too large to attribute to any precipitation of grains of pure Ni, so that it is
more likely comes from the doped matrix.

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1272 Nguyen Hoa Hong: Magnetism due to defects/oxygen vacancies in HfO2 thin films

As for diluted magnetic semiconductors (DMS) and diluted magnetic insulators (DMI) compounds, re-
cently, it has been discussed recently that oxygen treatments could make the samples to be ferromagnetic
or reversibly be switched to a diamagnetic state and vice versa [13]. Thus, we have to judge carefully if
the dopant is the main reason for the observed magnetism in this type of insulating oxide thin films, or in
these oxide families, FM can stem from defects and/or oxygen vacancies.

H//, 0.5 T
30
Magnetization (emu/cm )
3

HfO2 bulk
Fig. 2 Magnetization versus temperature at
0.002
20 0.5 T for a 200 nm-thick-HfO2 film. The
M(emu/g)

inset shows the magnetization versus mag-


0.000
H//, at 300 K
netic field taken at 300 K for a piece of
HfO2 bulk. The field was applied parallel to
-0.002
10 the film plane.
-0.4 -0.2 0.0 0.2 0.4
H(T)

0
100 200 300 400
Temperature (K)

Magnetization as a function of temperature of a 200 nm-thick-HfO2 film is shown in Fig. 2. One can see
clearly that the undoped HfO2 film is ferromagnetic with Curie temperature (TC) above 300 K. The satu-
rated magnetic moment of about 30 emu/cm3 is quite large, and it is really surprising since HfO2 is
known as a non-magnetic oxide. This value seems to be even larger than what Venkatesan et al. reported
for their HfO2 films on Al2O3 and Si substrate (as of 0.15 µB/HfO2 formula unit) [7]. What can be the
source for magnetism here if neither Hf 4+ nor O–2 is magnetic? An easy question arises if the observed
magnetism is due to some impurities. As regards to the purity of the target, we must say that such possi-
bility is very little, since the impurity of less than 10–2 wt% could not bring such a huge magnetic mo-
ment. From the viewpoint of structural properties of the HfO2 films, no trace of impurities that could be
seen from XRD and films are well single phase. The result implies that defects and/or oxygen vacancies
might be the main source for the observed ferromagnetism as suggested in Refs. [8] and [9]. We should
note here that the YSZ substrate that was measured under the same sequences as for the film shows
clearly diamagnetic behavior [9]. Additionally, all the pieces of straws used for measurements were also
checked carefully and all of them gave no magnetic signal. Therefore, any assumption for an existence of
contamination is ruled out. It is very likely that the FM that was found in HfO2 films is unique for thin
film form. As one can see from the inset of Fig. 2, the HfO2 bulk (i.e. a piece cut from the corresponding
target) is diamagnetic. At the moment, we have not been able yet to claim strongly that such remarkable
FM at such high temperatures is due to defects on the Hf site (as accorded to the calculations in Ref.
[14]); or defects at the interface between the films and the substrates; or oxygen [9] However, this sur-
prising discovery gives a serious feedback to the theoreticians to find a more suitable model to explain
correctly the mechanism that governs magnetic properties in undoped insulating oxide films. If our as-
sumption about the origin of the magnetism in these systems as of defects/oxygen vacancies is correct,
there must be some evidence or that could be seen from oxygen treatments on the samples. From Fig. 3,
one can see clearly that annealing in oxygen atmosphere for 4 hrs could reduce the magnetic moment of
HfO2 films up to one order. When we prolong the annealing time to 10 hrs, the film can return to the
diamagnetic state as that of the bulk.

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phys. stat. sol. (c) 4, No. 3 (2007) 1273

as-grown HfO2
HfO2 annealed in O2 for 4 hrs
30
Magnetization (emu/cm )

HfO2 annealed in O2 for 10 hrs


3

15
Fig. 3 Magnetization versus magnetic
field at 300 K for as-deposited, 4 hrs-
0
annealed, and 10 hrs-annealed HfO2
films. Field was applied parallel to the
-15 film plane.
H//, at 300 K

-30
-0.4 -0.2 0.0 0.2 0.4
Field (T)

These results prove that the magnetism in HfO2 films really originates from oxygen vacancies: filling up
vacancies degrades magnetic moments, and at some critical point, it even can destroy completely the
ferromagnetic ordering of the system.
This finding of room temperature FM in HfO2 thin films has drawn our attention to a new phenomenon:
magnetism due to defects/oxygen vacancies. Obviously, the role that 3d element doping indeed could
play in introducing FM must be re-judged carefully: Does the doping of TM really introduce FM, or in
fact it can only enhance the magnetism that already exists in the host under a thin film form? In order to
Magnetization (emu/cm3)

8 as-deposition
vacuum-annealing
O2-annealing
4 Fig. 4 Magnetization versus magnetic
field at 300 K for as-deposited, vacuum-
annealed, and oxygen–annealed
0
Fe0.01Hf0.99O2 films. Field was applied
parallel to the film plane.
-4 Fe0.01Hf0.99O2 film

-8
-0.4 -0.2 0.0 0.2 0.4
Field (T)

clarify this issue, we return to another typical case of doping a magnetic element in HfO2: Fe-doped
HfO2 thin films.
Fe-doped HfO2 thin films are room temperature ferromagnetic. In comparison with results of the un-
doped HfO2 films, it seems that the Fe doping is not the main cause for the FM, but only acts as a cata-
lyst. Experimental results of oxygen annealing and vacuum heat treatments have proved that in this fam-
ily of compounds, magnetism might originate from oxygen vacancies or defects: Removing oxygen
enhances the magnetic moment, while reversibly filling up oxygen vacancies can destroy the ferromag-
netic ordering of the system. Results on the films doped with 1% and 5% Fe are quite similar. The data
of Fe0.01Hf0.99O2 films with different heat treatments are given in Fig. 4 as an example. As-deposited
films of Fe0.01Hf0.99O2 are ferromagnetic at room temperature with a saturated magnetization (Ms) of
about 6 emu/cm3. Basically, a vacuum annealing should give an effect as of removing oxygen from the

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1274 Nguyen Hoa Hong: Magnetism due to defects/oxygen vacancies in HfO2 thin films

samples. One can see that after heating in vacuum, the magnetic moment of the films is enhanced to
some extent. Most probably, the oxygen atoms inside the sample were so well located after deposition
that removing them in this condition is not very easy. If oxygen vacancies are really source of magnet-
ism, then we must observe a clear difference in magnetic properties of the films after the oxygen anneal-
ing. From Fig. 4, one can see clearly that the film turns to be diamagnetic after oxygen annealing. Thus,
we must say that filling up oxygen vacancies destroy the ferromagnetic ordering in the sample. Another
test is to apply a vacuum heating after an air annealing to see more clearly the enhancement of magnet-
ism in those samples. Compared to the as-deposited films, the air-annealed films have more oxygen, so
that it is easier to remove them. Removing oxygen by a vacuum heating could also restore the FM of the
films [15].
Comparing the two absolute values of saturated magnetization of the undoped HfO2 film (Fig. 3) and the
Fe-doped HfO2 film (Fig. 4), we can see that the Ms of undoped HfO2 film is much larger that that of the
doped one, or in other words, we must say that the doping is not the main reason for the samples to be
ferromagnetic or not, but the base of undoped HfO2 films is more essential. It is obvious that oxygen
treatments give very the same influence on the magnetic properties of both undoped and TM-doped
HfO2, or undoubtly, oxygen vacancies and/or defects must play more important role in introducing FM
in HfO2 thin films. We must also say that if the magnetism in the HfO2 system is due to defects, then the
defects must be at the O site, but not Hf site.

600
Magnetization (emu/cm )
3

10 nm thick HfO2
400

200
Fig. 5 Magnetization versus magnetic
0 field taken at 300 K for a 10 nm-thick-
HfO2 film. Field was applied parallel to
-200 the film plane.
at 300 K, H//
-400

-600
-4 -2 0 2 4
Field (T)

Another point that is important to emphasize in here is that there is a strong thickness dependence of the
magnetic moment in undoped HfO2 thin films: the 10 nm-thick films have a magnetization of about 15
times larger than that of the 200 nm –thick- films (comparing the data shown in Fig. 3 and the data in
Fig. 5). One can directly interpret that if the observed magnetism is due to defects, then those defects
must be localized mostly near the interface between the films and the substrates. On the other hand, if
defects/oxygen vacancies are a possible source for magnetism in those types of films, a strong anisotropy
is also well expected [8]. The data that have shown above are for magnetic fields that were applied paral-
lel to the film plane. We must say that basically in HfO2 films, FM is in - plane, since as magnetic fields
applied perpendicular to the film plane, magnetic moments are much smaller (one can see from Fig. 6
that in that configuration, there is a mixed state of diamagnetism and a small component of paramagnet-
ism for HfO2 films). Thus, all of these facts strongly support the assumptions that were given earlier.

4 Conclusions The finding of room temperature FM in laser ablated HfO2 thin films has called our
attention to a new phenomenon: magnetism due to defects and/or oxygen vacancies. We must re-
consider carefully the role that a transition-metal doping indeed plays in introducing FM in oxide hosts:
Does the doping really introduce FM, or in fact it just enhances the magnetism that already exists in the
oxide hosts under a thin film form? Additionally, the actual role that the growth conditions could play in

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phys. stat. sol. (c) 4, No. 3 (2007)
Magnetization (emu/cm )
3 1275

200 nm thick HfO2


2
Fig. 6 Magnetization versus magnetic field taken
at 300 K for a 200 nm-thick-HfO2 film. Field was
0
applied perpendicular to the film plane.

H perpendicular
-2
at 300 K

-0.4 -0.2 0.0 0.2 0.4


Field (T)

creating necessary defects /oxygen vacancies must be clarified, with an expectation that we can exploit it
in order to tune precisely the magnetic properties of the system to usefully bring it into real applications.

Acknowledgements The author would like to sincerely thank J. Sakai (JAIST) and N. Poirot (LEMA) for their
fruitful co-work on this subject. The support of F. Gervais is also acknowledged.

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