One step synthesis of pure cubic and monoclinic HfO2 nanoparticles:

Correlating the structure to the electronic properties of the two polymorphs

P. Rauwel, E. Rauwel, C. Persson, M. F. Sunding, and A. Galeckas

Citation: J. Appl. Phys. 112, 104107 (2012); doi: 10.1063/1.4766272

View online: http://dx.doi.org/10.1063/1.4766272
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 JOURNAL OF APPLIED PHYSICS 112, 104107 (2012)

One step synthesis of pure cubic and monoclinic HfO2 nanoparticles:

Correlating the structure to the electronic properties of the two polymorphs
P. Rauwel,1,2,a) E. Rauwel,2,3,a) C. Persson,2 M. F. Sunding,2 and A. Galeckas1,2
1
Center for Materials Science and Nanotechnology (SMN), University of Oslo, P.O. Box 1048 Blindern,
N0315 Oslo, Norway
2
Department of Physics, University of Oslo, P.O. Box B 1048 Blindern, 0316 Oslo, Norway
3
Department of Chemistry, University of Oslo, P.O. Box 1033 Blindern, 0315 Oslo, Norway

(Received 16 August 2012; accepted 18 October 2012; published online 21 November 2012)
Hafnium dioxide is a wide band-gap, high-j material, and Hafnium based compounds have already
been integrated into micro-electronic devices. The pure cubic HfO2 phase is promising as it presents a
higher permittivity (j > 25), but needs to be stabilized by addition of divalent or trivalent dopants,
which in turn modify the electronic properties of HfO2. Here, we employ a one-pot synthesis approach
to produce undoped cubic and monoclinic HfO2 nanoparticles by choice of solvent alone. The average
size of these nanoparticles from transmission electron microscopy studies was estimated to be around
2.6 nm. We present a study of the morphology and microstructure and also demonstrate the presence of
a strong visible photoluminescence linked to the nanosize of the particles. Furthermore, the synthesis in
equivalent conditions of these two phases of HfO2 provides means for direct comparison of the
chemical composition and electronic structures of the two polymorphs. This has therefore allowed us to
experimentally elucidate similarities and differences in the valence band, band gap states, and
conduction band of these pure phases seconded by first principles calculations within the density
C 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.4766272]
functional theory. V

I. INTRODUCTION 1700  C and 2700  C, respectively.17,18 A number of studies,

mostly based on thin films, have shown that it is possible to
In recent years, metal oxide and perovskite compounds
stabilize the cubic structure by incorporating an appropriate
have been in the limelight due to their various properties, viz.,
cation and forming a solid solution.19–21 A single, two-step
multiferroicity, optics, and catalysis;1–7 however, these prop-
synthesis of pure cubic HfO2 nanoparticles has also been
erties depend on the structure, dimensions, and the shape of
reported,22 where the authors have demonstrated the impor-
the material.8 This renewed interest now surges from the abil-
tance of the reductive nature of the environment during syn-
ity to control the morphology and the structure by employing
thesis which led to the stabilization of the cubic phase on a
modern synthesis methods for producing thin films and nano-
post-annealing treatment. However, majority of the studies
particles (NPs). Diverse oxides such as Al2O3, Y2O3, and
have required either a divalent or a trivalent dopant that gener-
most of the rare-Earth (RE) oxides have been studied as thin
ates oxygen vacancies and in turn stabilizes the cubic phase.
films for complementary metal oxide semiconductor field
In this work, we have employed synthesis processes that
effect transistors (CMOSFETs)9,10 and metal-insulator-metal
allow the direct precipitation of two HfO2 polymorphs, i.e.,
(MIM) capacitor with high-capacitance-value applications.
monoclinic and cubic. Without any post-synthesis treatment,
Nevertheless, HfO2 has been a preferred candidate11 for the
we are able to directly stabilize each of these phases by
replacement of SiO2 in CMOSFETs,12 and has already been
choice of appropriate solvents. HfO2 nanoparticles, as small
integrated into a new generation of transistors.13 High-j
as 2.5 nm in diameter, were synthesized via non-aqueous
dielectric materials such as HfO2 present high thermal and
sol-gel methods. This process was recently developed23 as
chemical stability, and allow scaling with much larger thick-
an alternative to conventional non-hydrolytic routes.24 An
ness than SiO2. HfO2 has three polymorphs: monoclinic,
important advantage of this method, based on the utilization
tetragonal, and cubic; however, the only stable room tempera-
of a solvent like benzyl alcohol mixed with a metalorganic
ture phase is the monoclinic one. Ab initio calculations
precursor in a sealed autoclave, is the possibility to synthe-
suggest that higher symmetry phases of HfO2 exhibit a higher
size pure and highly crystalline oxide nanoparticles at low
permittivity (j > 25) than the monoclinic structure
temperatures and without surfactants.23 The conventional
(j  15);14,15 it is therefore desirable to synthesize HfO2 in
method based on the utilization of benzyl alcohol enables us
the cubic or tetragonal phases. On the flip side, at atmospheric
to synthesize the monoclinic polymorph in the nanoparticle
pressures, these structures are stable only at high tempera-
form, but as demonstrated by Lu et al., a more reductive
tures; nevertheless, metastable phases of cubic HfO2 have
environment is necessary to stabilize the cubic phase.22 For-
been observed at room temperature.16 The monoclinic to
tunately, benzylamine solvent was sufficiently reductive to
tetragonal and tetragonal to cubic transformations occur at
induce the formation of oxygen vacancies necessary for the
stabilization of the cubic polymorph in the nanoparticle
a)
Authors to whom correspondence should be addressed. Electronic addresses: form. Usually, such oxygen vacancies are produced by the
protima.rauwel@fys.uio.no and erwan.rauwel@kjemi.uio.no and rauwel@ua.pt. insertion of a divalent of trivalent cation in the HfO2

0021-8979/2012/112(10)/104107/8/$30.00 112, 104107-1 C 2012 American Institute of Physics

V

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 104107-2 Rauwel et al.
structure.20,21,25 The aim of this study, rather than presenting
a simple one-pot synthesis, is to study and to provide a better
understanding of the chemical, structural, and electronic
properties of these pure polymorphs, represented by free-
standing nanoparticles without any dopants or impurities, as
the latter has always an effect on, e.g., the dielectric proper-
ties of HfO2.20 In fact, Yang et al. have demonstrated that
substitutional Ta in HfO2 disturbs the local cation distribu-
tion around oxygen, changes bond lengths, which in turn
modifies the metal-oxide polyhedra, and shifts the binding
energy (BE) of the core electrons.26
II. EXPERIMENTAL SECTION
A. Synthesis
The procedure for synthesizing HfO2 NPs was carried out
in a glove box (O2 and H2O < 1 ppm). In a typical synthesis,
hafnium tert-butoxide ((Hf(OtBu)4) precursor (STREM 99.9%)
(0.87 mmol) was added to 20 ml (183 mmol) of benzylamine
(purified by redistillation (99.5%), Aldrich) for the synthesis
of cubic HfO2 nanoparticles and to 20 ml (193 mmol) of benzyl
alcohol (99%, Aldrich) for the synthesis of monoclinic HfO2
nanoparticles. The reaction mixture was transferred into a stain-
less steel autoclave and carefully sealed. Thereafter, the auto-
clave was taken out of the glove box and heated in a furnace at
300  C for 2 days. The resulting milky suspensions were centri-
fuged; the precipitates were thoroughly washed with ethanol
and dichloromethane; and subsequently dried in air at 60  C.
B. Characterization
XRD patterns were obtained using Bruker D5000 XRD
instrument equipped with a Braun position sensitive detector,
both using Cu Ka radiation. High resolution transmission elec-
tron microscopy (HRTEM) and electron energy loss spectros-
copy (EELS) were carried out on two microscopes: an 80–300
FEI Titan, operating at 300 kV, disposing a point to point reso-
lution of 1.4 Å and fitted with a Gatan 865 GIF Tridiem energy
filter. O-K edge spectra were acquired in the TEM mode with
a full width at half maximum (FWHM) 0.7 eV of the zero loss
peak, with collection and convergence angles of 6.3 mrad and
0.3 mrad, respectively. The background has been subtracted by
the power law function fit to an energy window of 10 eV just
before the onset. The other microscope, JEOL-2010FS was
operating at 200 kV and disposed a point to point resolution of
1.9 Å, was used for selected area electron diffraction (SAED)
and HRTEM. The samples were plasma cleaned for 10 min
before EELS analysis in order to exclude the contributions to
the O-K edge energy loss near edge structure (ELNES), from
adsorbed organic species. X-ray photoelectron spectroscopy
(XPS) analysis was carried out on a Kratos Analytical Axis
UltraDLD photoelectron spectrometer, equipped with a mono-
chromated Al Ka x-ray source. The analyzer settings employed
for the narrow scans allow for 0.57 eV energy resolution, as
determined by the full width at half maximum of the Ag 3d5/2
photoelectron peak. Low energy electrons were used for
charge compensation, and the energy scale was calibrated
based on the hydrocarbon related C 1s peak from adventitious
carbon at 284.8 eV BE. Peak fitting was performed using Voigt
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J. Appl. Phys. 112, 104107 (2012)
functions after subtraction of a Shirley type background. A
spin-orbit peak splitting energy of 1.7 eV was used for the Hf
4f peak. Thermogravimetric (TG) analyses were carried out in
flowing O2 atmosphere (15 ml/min) with a heating rate of
5  C/min using a Rheometric Scientific STA 1500 instrument.
Photoluminescence (PL) was investigated by employing
325 nm wavelength of cw He-Cd laser with an output power of
10 mW as an excitation source. The emission was collected by
a microscope and directed to a fiber optic spectrometer (Ocean
Optics USB4000, spectral resolution 2 nm).
C. Calculations
The density functional theory (DFT) analysis of mono-
clinic HfO2 was based on a full-potential atomistic calculation
employing the fully relativistic augmented plane-wave method
with local orbitals (APW þ LO) method.27 Hf 4f145d26s2 and
O 2s22p4 orbitals were treated as valence states. The
exchange-correlation interaction was described by the Perdew-
Burke-Ernzerhof generalized gradient approximation (GGA)
plus the onsite Coulomb interaction Ud(Hf) ¼ 2 eV and
Uf(Hf) ¼ 7.5 eV to correct the Hf d- and f-states.28,29 Experi-
mental lattice constants were used, and the ion positions were
relaxed by minimizing the forces on the atoms to an accuracy
of 0.5 meV/Å. The ELNES O-K spectra were calculated by
means of a supercell approach (48 atoms body-centered struc-
ture) and the Slater transition state formula. We calculate the
O-K spectrum for bulk oxygen atoms, and we do not therefore
model nanoparticle structure or analyze O-K spectrum for sur-
face oxygen. We present the results with only a small 0.2 eV
Lorentzian broadening, but also broadening to better simulate
the experimental setup: 0.7 eV FWHM, 0.1 eV core-hole life-
time, 300 keV beam energy, and the collection and conver-
gence angles of 6.3 mrad and 0.3 mrad, respectively. The two
ELNES spectra from O3 and O4 co-ordinated sites, respec-
tively, were aligned through the Hf 1s core states, which also
aligned the VB maximum within 5 meV. The charge density
with the partially excited core electron was obtained self-
consistently using Bl€ochl’s tetrahedral integration method with
a 7  5  4 k-mesh (71 k-points in the irreducible Brillouin
zone) and with a plane wave cutoff RmtKmax ¼ 6. The muffin-
tin radius of the oxygen atoms was set to Rmt ¼ 0.9 Å; corre-
sponding radius for Hf was 1.15 Å.
III. RESULTS AND DISCUSSION
A. Atomic arrangement of cubic and monoclinic HfO2
A precise knowledge of the atomic arrangement in the
two structures (cubic and monoclinic) is imperative for our
study. Several theoretical works on the structure and chemical
properties have been published,12,30 but none of them, to the
best of our knowledge, directly compare the chemical proper-
ties of two different structures grown by similar synthesis
routes. The unit cell of the face centered cubic structure of
HfO2 is made up of two atoms, i.e., Hf at (0, 0, 0) and O
located at (1=4, 1=4, 1=4). The oxygen is coordinated to four
Hf-atoms, and is at the center of a regularly shaped tetrahe-
dron (Fig. 1(a)). In comparison, the monoclinic structure of
the HfO2 phase, which is the most stable at room temperature,
 104107-3 Rauwel et al.
FIG. 1. (a) Tetrahedrally coordinated O in the cubic structure, (b) 3-fold and
4-fold coordinated O in the monoclinic structure of HfO2.
has an asymmetric unit cell composed of one Hf atom and two
oxygen atoms, coordinated differently to Hf: the 3 fold coordi-
nated O indicated as “3” in Figure 1(b) and the 4-fold coordi-
nated O indicated as “4”. Compared to the 4-fold coordinated
O atom in the HfO2 cubic structure, the 4-fold coordinated O
atom in the monoclinic structure is centered within a distorted
tetrahedron. These differences play an important role in the
electronic structure of the two polymorphs, as highlighted by
XPS and EELS.
B. X-rays diffraction and thermogravimetric analysis
In the present study, no signs of secondary phases of Hf
metal or carbonates are detected on the XRD pattern. Figure
2 exhibits the XRD patterns for HfO2 nanoparticles synthe-
sized with benzylamine (a) and the benzyl alcohol (b) sol-
vents and suggests that in both cases, the HfO2 nanoparticles
are highly crystalline. The analysis of the XRD pattern illus-
trates that in the case of the benzylamine solvent, the HfO2
nanoparticles possess the cubic crystal structure (Fm-3m,
a ¼ 0.509 nm, JCPDS-ICDD 00-053-0550); while for those
synthesized with benzyl alcohol, the monoclinic crystal
structure (P21/c, a ¼ 0.51 nm, b ¼ 0.52 nm, c ¼ 0.53 nm,
b ¼ 99.19 , JCPDS-ICDD 00-043-1017) is obtained. The
more reductive character of benzylamine solvent has cer-
tainly promoted oxygen vacancies (VO) in the structure and,
in consequence, has stabilized the cubic phase. In practice,
the cubic phase of HfO2 is stabilized by the incorporation of
FIG. 2. XRD patterns of (a) cubic HfO2 nanoparticles and (b) monoclinic
HfO2 nanoparticles.
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J. Appl. Phys. 112, 104107 (2012)
oxygen vacancies generated by doping with divalent or triva-
lent cations. This method was intensively investigated for
thin films aimed at CMOS-FET applications.20,21,25 Alterna-
tively, by using an appropriate solvent, it is also possible to
create VO without dopants to stabilize the cubic polymorph.
Thermogravimetric analyzes (TGA) were performed on
samples of both polymorphs in order to evaluate their purity.
In principle, organic species usually remain adsorbed on the
surface of the nanoparticles when synthesized by non-aqueous
methods, without hydrate species in the metalorganic precur-
sor.31 The probable nature of these organic species is linked to
residual benzylamine, benzyl alcohol or reaction by-products
like benzoate species, depending on the synthesis method
employed and the nature of organic species resulting from the
reaction synthesis. Consequently, the amount of these organic
species on the nanoparticle surface along with the possible
presence of carbonate species was analyzed by TGA. In
the case of cubic HfO2 nanoparticles (Fig. S1, benzylamine
solvent42), a total weight loss of about 14% was estimated up
to 800  C, speaking for the organic species adsorbed on the
surface of the nanoparticles. Furthermore, the weight loss that
may correspond to water desorption was estimated to be about
1.55%. In the case of monoclinic HfO2 nanoparticles (Fig. S1,
benzyl alcohol solvent), a total weight loss of about 12.9%
was measured, implying a lower amount of organic species
adsorbed on the surface of the nanoparticles; the weight loss
that may correspond to water desorption was estimated to be
about 3.2%. Finally, in both cases, TGA does not show any
presence of carbonate species, usually highlighted by a
shoulder at high temperatures.
C. High resolution transmission electron microscopy
The overview of the nanoparticles in Figures 3(a) and
3(b) shows a high level of monodispersion. A closer look at
the higher magnification image of Figure 3(b) confirms the
monodispersed nature of the particles synthesized with ben-
zyl alcohol as almost no overlapping nanoparticles are visi-
ble. The SAED pattern from a region of these nanoparticles
can be completely indexed to the monoclinic phase of HfO2
(Fig. 3(c)). Nanoparticles with different orientations were
studied using HRTEM. In Figure 3(d), the nanoparticle is
oriented along the [101] zone axis and presents a twin
boundary, commonly observed in the monoclinic polymorph,
as it helps to relieve the shearing forces at the edges of the
nanoparticle, due to the asymmetrical monoclinic structure.
However, these planar defects were not systematically
observed in the nanoparticles. Figures 3(e) and 3(f) present
monoclinic HfO2 nanoparticles oriented along the [100] and
[011] zone axes. With regards to the shape of the nanopar-
ticles, one can observe in all three HRTEM images that the
nanoparticles are oblong; consequently, the size distribution
histograms estimate an average size of 3.5 nm along the long
axis and 2.5 nm along the short axis (Fig. S2(a)) with a stand-
ard deviation of 0.8 nm. These data were obtained from
TEM images for more than 80 nanocrystals.
Cubic HfO2 synthesized using benzylamine as a solvent
is represented as free-standing nanoparticles (Figs. 4(a) and
4(b)) of 2.6 nm average size (Fig. S2(b)) with a standard
 104107-4 Rauwel et al. J. Appl. Phys. 112, 104107 (2012)

FIG. 3. (a), (b) Overview of monoclinic

HfO2 nanoparticles, (c) SAED pattern,
(d) HRTEM of a nanoparticle presenting
a twin boundary indicated by an arrow,
(e) a nanoparticle along the [100] direc-
tion, and (f) particle oriented along the
[011] zone axis.

deviation of 0.9 nm. These data were again obtained from
TEM images for more than 80 nanocrystals. The nanopar-
ticles are not equally well monodispersed as the monoclinic
ones. The indexed SAED pattern can be attributed to the
HfO2 cubic phase (Fig. 4(c)). Figures 4(d) and 4(e) are
HRTEM images of single nanoparticles oriented along the
h001i and h110i zone axis, respectively. Figure 4(f) shows a
nanoparticle exhibiting two different orientations, i.e., h001i
and h111i, with the grain boundary being indicated by an
arrow. This illustrates that even very small particles contain
grain boundaries and are susceptible to planar defects.
D. Photoluminescence properties
An insight into the defect-related luminescent band gap
states of the two types of nanoparticles was attained from photo-
luminescence measurements using UV-laser with hv ¼ 3.8 eV
photon energy as an excitation source. Considering the fact that
the bandgap of HfO2 is around Eg  5.7 eV,12 no luminescence
from hafnia is expected under such below-bandgap (hv < Eg)
photoexcitation conditions. However, recently we have observed
strong visible luminescence from hafnia perovskite nanopar-
ticles, supposed to be equally translucent for the employed exci-
tation.32 The key observations from HfO2 nanoparticles are
summarized in Figure 5, where PL from the two polymorphs
exhibits certain spectral similarity with a dominant emission at
around 2.5 eV. The overall emission yield, on the other hand, is
notably different, indicating by a factor of 3, stronger emission
in the case of monoclinic nanoparticles as compared to cubic.
Since size reduction of a given particle, especially on the nano-
meter scale, leads to a dramatic increase in its surface-to-volume
ratio, the role of luminescent surface-defects in the overall

FIG. 4. (a) Overview of the HfO2 cubic

nanoparticles, (b) higher magnification
image of the nanoparticles, (c) SAED
pattern, (d), (e) HRTEM images of nano-
particles oriented along h001i and h110i
zone axes, respectively, and (f) a nano-
particle showing 2 different orientations;
the grain boundary is indicated by an
arrow.

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 104107-5 Rauwel et al.
emission becomes increasingly dominant. Assuming a common,
most likely oxygen vacancy related origin for the observed PL33
and bearing in mind the average size of the particles, 2.6 nm for
the cubic and 2.5 by 3.5 nm for the monoclinic HfO2, the
observed differences in luminosity can be attributed both to dis-
similar intrinsic defect concentration and to the particular parti-
cle shape, spherical for cubic versus elliptical for monoclinic,
which might affect the affinity to adsorb some organics species
acting as non-radiative recombination centers.
The fact that more organic species are adsorbed on the
surface of cubic HfO2 nanoparticles (See section B) com-
bined with the lower luminescence yield observed in this
case suggests that the adsorbents associated with residual
solvents act as non-radiative recombination centers.34 Refer-
ring to dissimilar shape of the nanoparticles, a somewhat
smaller volume of a cubic HfO2 nano-sphere also means cor-
respondingly larger effective surface area per unit volume,
thus enhancing the abovementioned effects further. Finally,
we note that although some organic adsorbents on the sur-
face of the HfO2 nanoparticles may act as luminescence cen-
ters, the employed 3.8 eV photon energy is insufficient for
excitation of organic species usually exhibiting absorption
thresholds of about 4.2 eV. Since no carbonates were
detected by TGA, no luminescence from these species, oth-
erwise known for their PL response under UV illumination,
is expected. While the origin of luminescence at around
2.5 eV is apparently related to oxygen vacancies, the nature
of the higher energy emission components needs to be fur-
ther examined.
E. X-ray photoelectron spectroscopy
The XPS survey spectra show the presence of Hf, O,
and C, along with a small amount of N for the cubic HfO2
sample (Fig. S3). Nitrogen in the cubic HfO2 sample can be
linked to the remnant organic species originating from the
benzylamine solvent or other organic species resulting from
the reaction synthesis as discussed in the TGA part.31 Fig-
ures 6 and 7 provide the XPS spectra obtained for the Hf 4f,
FIG. 5. Photoluminescence spectra of cubic and monoclinic HfO2 nanopar-
ticles recorded at 300 K in air ambient (Gaussian deconvolution components
are represented by grey curves).
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J. Appl. Phys. 112, 104107 (2012)
O 1s and valence band (VB) energy region, respectively.
The Hf 4f spectra shown in Figures 6(a) and 6(b) could not
be adequately fitted using a single pair of symmetric peaks;
either a pair of asymmetric peaks (not shown) or two pairs of
symmetric peaks were required. Sharp, symmetric Hf 4f par-
tial density of states (PDOS) are obtained from DFT calcula-
tions35,36 and peak broadening from electron shake-up to the
conduction band is not likely in materials with a notable
band gap.37 No peak asymmetry is thus expected and the
presence of two Hf chemical states is therefore probable.
This stems from the fact that the small size of the nanopar-
ticles (2.6 nm) induces a high surface to volume ratio; the
contribution of Hf from the surface of the nanoparticles is
more pronounced here than in thin films. The position of the
low BE Hf 4f7/2 peak, component 1 located at 16.6 6 0.2 eV
BE for both samples, is similar to the few published values
for bulk HfO2.38,39 The higher BE of component 2 located at
17.3 6 0.2 eV BE could be attributed to the Hf atoms from
the surface of the nanoparticles and indicates a more electro-
negative ligand being linked to them like hydroxyl groups or
reduced surface oxygen atoms (O),35,36 see discussion of
the O 1s spectra below. The higher proportion of this high
BE Hf in the monoclinic sample is attributed to the benzyl
alcohol used as solvent compared to the more reductive sol-
vent (benzylamine) used for the synthesis of the cubic
sample.
The O 1s spectra can be deconvoluted into 2 sub-peaks
(Figs. 6(c) and 6(d)), the low BE energy component at
530.2 6 0.3 eV BE corresponds to the O in the lattice and is
in the energy region of bulk HfO2.38,39 The high BE compo-
nent at 531.7 6 0.3 eV BE corresponds to adsorbed O on the
surface. This high BE component is stronger in the mono-
clinic HfO2 sample synthesized using benzyl alcohol. The
additional intensity of this peak in the HfO2 monoclinic sam-
ple relative to the cubic sample synthesized using benzyl-
amine could be associated with the presence of hydroxyl
groups or benzoate ligands produced during the reaction syn-
thesis using the benzylalcohol solvent. The properties of a
material are largely determined by the outer layer valence
electrons, and similar profiles of the upper valence band
have been obtained from XPS for the two polymorphs in Fig-
ure 7. Our results are consistent, considering the similarity of
the VB PDOS of both crystal structures reported by other
groups.35,36,40 This therefore implies that the Hf 4f orbital
lying between the O 2p and O 2s orbitals, being completely
occupied, has a very small influence on the latter, and in turn
does not affect dramatically the density of states profile of
the upper valence band of both polymorphs.
F. Energy loss near edge structure
EELS provides the energy distribution of electrons
transmitted through a sample. Some of these electrons will
have lost energy through inelastic scattering in the sample,
by exciting core electrons from their ground state. These
excitations involve transitions of electrons from the occupied
core levels into empty states above the Fermi level. Since the
initial core levels are highly localized in energy, these transi-
tions following the dipole selection rules are mainly sensitive
 104107-6 Rauwel et al.
FIG. 7. Valence band XPS spectrum obtained on the (A) cubic and (B)
monoclinic HfO2 nanoparticles.
to final-state effects. The occupancy of these final states may
change due to bonding through charge transfer or hybridiza-
tion, and this will be reflected in the shape of the ELNES.
Thus, using ELNES in EELS, we probe the local density of
empty states of the material and obtain information on the
bonding and the crystal structure. O-K edge ELNES provides
qualitative differences between cubic and monoclinic HfO2
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J. Appl. Phys. 112, 104107 (2012)
FIG. 6. Hf 4f XPS spectrum obtained on
the cubic HfO2 synthesized using ben-
zylamine (a) and monoclinic HfO2 syn-
thesized using benzyl alcohol (b). O 1s
XPS spectrum obtained on the cubic
HfO2 synthesized using benzylamine (c)
and monoclinic HfO2 synthesized using
benzyl alcohol (d). See text for the iden-
tification of the spectral components 1
and 2.
due to charge transfer and hybridization effects, in turn,
causing a change in the d-character of the valence electrons.
The energy loss mechanism of excitation of the 1s electrons
to the 2p-orbitals respecting the selection rules provides
direct access to the density of the O 2p state. The O-K edge
ELNES for the cubic and monoclinic phases is presented in
Figure 8. Contrary to the cubic phase of HfO2, O-K edge
ELNES of the monoclinic phase has been well studied in the
literature. Typically, both phases have 2 peaks dominating
the O-K edge ELNES (“a” and “b”). Peak “a” is less intense
than peak “b” in both cases.
For the monoclinic structure the maxima of the peaks
“a” and “b” are at 532 eV and 536.5 eV; whereas, for the
cubic phase, the maxima for peaks “a” and “b” are at 532 eV
and 536 eV. PDOS calculations of unoccupied bands of
HfO2 by other groups have concluded that peaks “a” and “b”
are direct indications of local hybridizations of the oxygen p
components and Hf d-eg and d-t2g states, respectively, and
therefore, depend on the local symmetry of the oxygen
atoms.36 The broadening of peaks “a” and “b” in the mono-
clinic phase is due to the overlapping of d-eg and d-t2g with
O p components of the O3 and O4 coordination of oxygen.
On the other hand, the peaks “a” and “b” of the cubic phase
 104107-7 Rauwel et al.
are sharper as oxygen is always 4-fold coordinated. The
other less intense peak “c” in the cubic phase is more promi-
nent than in the monoclinic phase with a maximum at
540 eV, and relates to the O p component hybridization
with the Hf s component. Once again, the better defined
peaks of the HfO2 cubic phase in the O-K edge ELNES are
attributed to the Oh point symmetry; whereas, in the mono-
clinic structure, the O3 and O4 coordinated oxygen distort
the HfO2 structure and are responsible for the broadening of
the peaks.
Our experimental ELNES for the cubic phase agrees
very well with calculated ELNES reported by Mizoguchi
et al. However, reports have suggested a split in peak “a” for
the monoclinic phase (but not for the cubic phase) as a result
of the two dissimilar coordination of O.36,41 In fact, our DFT
analysis of the O-K edge ELNES reveals that the O3 and O4
coordinated oxygen have different energy localizations of
their 1s states. The calculated energy level is about 536 eV
below the VB maximum, aligned to the experimental spectra
and O3 (with shorter Hf–O bonds) has 1 s states that are
energetically 0.51 eV higher than those of O4 (with longer
Hf–O bonds). This is due to the oxygen coordination and not
due to core-hole excitation effects, because the correspond-
ing energy difference is also seen in a ground-state calcula-
tion. However, for the excited state, the density of states
from the valance band top for the 2 polymorphs has different
profiles as indicated from their respective O-K edge
ELNES.27 Whereas the energy levels of O3 1s and O4 1s dif-
fer by 0.5 eV, the energy of their corresponding VB and
CB states is more similar. This is because these states are
spatially more delocalized and hybridized with the Hf states.
Thereby, the O3 1s ! O 2p transitions imply 0.5 eV higher
transition energies than those of corresponding O4 1s ! O 2p
transitions, and thus the individual O3 spectrum involves a
shift with respect to the O4 spectrum (Figs. 8(A) and 8(B)).
This effect is evident for the “a” peak for which the calcula-
tion of both the O3 and the O4 K-edges reveals two peaks in
the low-energy region separated by about 1 eV; however, the
peak positions of this double-peak for O3 and O4 are shifted
by 0.5 eV. The measured O-K edge ELNES involves both
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J. Appl. Phys. 112, 104107 (2012)
FIG. 8. O-K ELNES calculated spectra for
the monoclinic phase (A) O4 coordinated,
(B) O3 coordinated, (C) combined O3 and
O4 coordination, and (D) spectra C cor-
rected for a FWHM of 0.7 eV.
Experimental ELNE spectra obtained for
(E) the monoclinic phase and (F) cubic
phase of HfO2. Atom color codes: blue is
Hf and red is O.
types of transitions, and since the O3 and O4-K edge spectra
are shifted by about 0.5 eV the average of the two spectra
smoothens out the double-peak of “a” (Fig. 8(C)). The calcu-
lated average O-K edge spectrum with FWHM ¼ 0.7 eV
broadening (Fig. 8(D)) agrees well with the measured spec-
trum with a single “a” peak (Fig. 8(E)). Moreover, the meas-
ured and calculated energy differences between peaks “a” and
“b” are 4.5 eV for the monoclinic phase, 0.5 eV higher than
the “a” and “b” peak difference of 4 eV for the cubic phase.
Furthermore, experimental and calculated ratios of the “a”
and “b” peak intensities also agree very well. The high-energy
peak “c” contains two structures (around 540 and 540.5 eV)
that are overlapping for the moderate broadening for the
monoclinic phase, contrary to the cubic phase where the peak
is clearly visible.
IV. CONCLUSION
In summary, pure cubic and monoclinic HfO2 nanopar-
ticles with average size of about 2.6 nm were synthesized via
a sol-gel process without evidence of secondary phases, and
the structure and chemical composition as well as electronic
properties were characterized. By the utilization of a more
reductive solvent, it is possible to stabilize the cubic phase.
XPS analysis has provided an insight on the nature of the or-
ganic species present at the surface of the nanoparticles. With
regards to the electronic structure in the ground state, there
seems to be negligible difference between the top of the va-
lence band in the two polymorphs as the contributions from
the O3 and O4 coordinated oxygen overlap and density of the
O 2p states in the monoclinic structure is similar to that of the
cubic structure. Nevertheless, DFT calculations have illus-
trated that the O 1s core state of the monoclinic phase is
affected by the O3 and O4 co-ordination, and in particular, the
O3 1s state is localized 0.5 eV higher in energy than that of
the O4 1s state. This is manifested in the O-K edge ELNES of
the excited state by a broadening of the peaks due to differen-
ces in the energy localizations of O3 2 p and O4 2 p peaks, a
co-ordination phenomenon absent in the cubic HfO2 due to
the high symmetry Oh point group. In this work, we have
 104107-8 Rauwel et al. J. Appl. Phys. 112, 104107 (2012)

16
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