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Synthesis and characterisation of zirconium–amido guanidinato complex:

a potential precursor for ZrO2 thin films†
Anjana Devi,*a Raghunandan Bhakta,a Andrian Milanov,a Malte Hellwig,a Davide Barreca,b Eugene Tondello,b
Reji Thomas,c Peter Ehrhart,c Manuela Wintera and Roland Fischera
Received 17th November 2006, Accepted 23rd January 2007
Published on 07 February 2007. Downloaded by Carnegie Mellon University on 22/10/2014 21:47:38.

First published as an Advance Article on the web 7th February 2007

DOI: 10.1039/b616861b

A new zirconium complex, bis-(ethylmethylamido)-bis-(N,N
-diisopropyl-2-ethylmethyl-

amidoguanidinato)-zirconium(IV) {[(Ni Pr)2 C(NEtMe)]2 Zr(NEtMe)2 }, was synthesised by partial
replacement of amide ligands with bidentate guanidinate ligands. The monomeric Zr complex was
characterised by 1 H-NMR, 13 C-NMR, EI-MS, elemental analysis, and single crystal X-ray diffraction
studies. The thermal properties of the compound was studied by thermogravimetric and differential
thermal analysis (TG/DTA). The new Zr compound is thermally stable and can be sublimed
quantitatively which renders it promising for thin film growth using vapor deposition techniques like
chemical vapor deposition (CVD) and atomic layer deposition (ALD). The use of this complex for
CVD of ZrO2 on Si(100) substrates was attempted in combination with oxygen as the oxidant.
Stoichiometric ZrO2 films with preferred orientation at lower growth temperatures was obtained and
the films were almost carbon free. The preliminary electrical characterisation of ZrO2 films showed
encouraging results for possible applications in dielectric oxide structures.

Introduction
Zirconium dioxide (zirconia, ZrO2 ) has drawn much interest for
technological applications, due to its excellent thermal, chemical
and mechanical stability, as well as its interesting optical and
dielectric properties.1,2 In particular, ZrO2 thin and ultra-thin
films have an effective dielectric constant k ∼18,3 a band-gap
higher than 5 eV,4 favorable band-mismatch to silicon5 and
high thermodynamic stability on silicon.6 As a result, they have
recently attracted attention as possible high-k gate oxide dielectrics
in microelectronic metal-oxide semiconductor (MOS) devices,
promising to overcome the tunneling limits of SiO2 and thus
allowing further reduction in device dimensions.7
Chemical vapor deposition (CVD) and atomic layer deposition
(ALD) are preferred techniques for the growth of high quality thin
films for technological applications.8 Both CVD and ALD pro-
cesses strongly rely on the precursors and hence the development
of suitable molecular precursors is of great importance. A wide
variety of compounds have been employed for the CVD/ALD
of ZrO2 thin films, from inorganic salts like (ZrCl4 , Zr(NO3 )4 ) to
metal–organic complexes like alkoxides ([Zr(OR)4 , with R = Pri ,
But ) and b-diketonates ([Zr(acac)4 ], [Zr(thd)4 ]).9,10 The alkoxides
have been frequently employed as precursors for oxide film growth.
a
Inorganic Materials Chemistry Group, Lehrstuhl für Anorganische Chemie
II, Ruhr-University Bochum, Bochum, Germany. E-mail: anjana.devi@
rub.de; Fax: +492343214174; Tel: +492343224150
b
ISTM-CNR and INSTM—Department of Chemistry, Padova University,
Via Marzolo, 1-35131, Padova, Italy
c
IFF—Institut für Festkörperforschung and CNI—Center for Nanoelec-
tronic Systems for Information Technology, Forschungszentrum Jülich, D-
52425, Jülich, Germany
† Electronic supplementary information (ESI) available: Variable tem-
perature 1 H-NMR, HMQC spectrum, EDX, RBS and XPS. See DOI:
10.1039/b616861b
However, they are moisture sensitive and the presence of the
electrophilic Zr(IV) centers often results in the formation of dimeric
species. Therefore, there have been attempts to saturate the metal
centre with bidentate chelating ligands in combination with the
alkoxides.11,12 Another class of compounds that are used for oxide
thin film growth by CVD are the metal alkyl amides in combination
with an oxidising agent. The dialkyl amide compounds are reactive
towards a hydroxylated surface but are not self reactive which
makes them suitable for self-limiting processes such as ALD as
well.13 Nevertheless, their high air and moisture sensitivity poses
a problem especially in terms of handling. We have recently
reported the use of chelating malonate ligands in combination with
metal alkylamides, resulting in stable six-coordinated monomeric
complexes with enhanced stability, which are less sensitive to air
and moisture and possessing adequate thermal properties.14
Another interesting class of ligands that has recently
caught much attention are the, N,N
-dialkyl-2-alkyl-amidinates
[(R
N)2 CR]− which were effectively used as chelating bidentate
ligands, bridging the metal center through M–N bonding. Metal
amidinate complexes are reported to be promising for metal and
metal oxide depositions.15 The related class of bidentate ligand,
N-substituted guanidinate anions [RNC(NR2
)NR

], have also
been under investigation as ancillary ligands for a variety of metal
complexes.16 It is reported that the guanidinate anion can impart a
similar coordination environment while offering increased stability
due to the possibility of the additional zwitterionic resonance
structure as shown in scheme 1(i). Guanidinate based complexes
are reported to be used as precursors for the CVD of metal nitride
films.17
Extending our strategy of developing amide based group(IV)
complexes with different chelating ligands, bidentate guanidinate
ligand systems are used in this work to form a stable all nitrogen
coordinated Zr(IV) complex. Here we describe the use of a

This journal is © The Royal Society of Chemistry 2007 Dalton Trans., 2007, 1671–1676 | 1671
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diisopropyl-carbodiimide with one equivalent of [Zr(NEtMe)4 ]

at room temperature, and subsequent cooling down to −30 ◦ C
resulted in a pure and crystalline product which could be isolated
in good yields (88%). The new compound is a white crystalline
solid at room temperature and melts at 128 ◦ C. It is much less
sensitive to air and moisture compared to the parent dialkylamide
and is soluble and stable in solvents such as toluene, diethyl ether
etc. This could be of importance for liquid injection (LI-MOCVD)
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applications. The compound could be easily and quantitatively

sublimed at 100 ◦ C under reduced pressure without any residue.
The single crystals could be obtained by recrystallisation of the
product in toluene. Employing single crystal X-ray diffraction, the
molecular structure was determined (Fig. 1). The compound was
found to be a monomer, which can be expected due the presence
of bulky ligands in the Zr(IV) coordination sphere.
Scheme 1 (i) Resonance structures of guanidinate anions (ii) Synthetic
route to [Zr(NEtMe)2 (guanid)2 ].

bidentate guanidinate ligand system together with zirconium

dialkylamide to form a stable six-coordinated Zr(IV) complex, bis-
(ethylmethylamido) - bis - ( N,N
- diisopropyl - 2 - ethylmethyl - ami-
doguanidinato)-zirconium(IV) {[(Ni Pr)2 C(NEtMe)]2 Zr(NEtMe)2 }
which is abbreviated as [Zr(NEtMe)2 (guanid)2 ]. The main goal
was to design and synthesise a stable Zr complex with a cleanly
dissociable ligand system, which could grow high quality ZrO2
films at lower growth temperatures with very less carbon content
in the film. The presence of the complex and bulky guanidinato
ligand in the Zr compound not only stabilizes the reactive metal
center but it also dissociates cleanly without much problems.
Additionally our efforts were directed to the possible use of this
compound for the growth of ZrO2 thin films by MOCVD in
combination with oxygen and some results on the deposition and
characterisation of ZrO2 thin films are reported.

Results and discussion

There have been reports in the literature on the insertion of
a carbodiimide ligand into the Zr–N bond of [Zr(NMe2 )4 ].18,19
Fig. 1 Molecular structure of [Zr(NEtMe)2 (guanid)2 ].
In the case of [Zr(NEtMe)2 (guanid)2 ] complex, electron dona-
tion from the guanidinate ligand is expected to stabilize the
The coordination geometry around the zirconium center is a dis-
Zr(IV) charge.20 This could be of some advantage because the
torted octahedron, having an approximate C 2 symmetry with two
[Zr(NEtMe)2 (guanid)2 ] complex combines the reactivity essential
guanidinate groups and two ethylmethylamido groups adopting a
for ALD processes and the use of chelating/stabilizing ligands
cis configuration. The bite angles subtended by the guanidinate
required for stability in the case of CVD application.
ligands on the Zr center are 58.0◦ and 58.2◦ , respectively (Fig. 1).
The trans influence induced from the ethylmethylamido group
Precursor synthesis and characterisation makes the Zr(1)–N(11) bond length slightly longer than Zr(1)–
In order to obtain the [Zr(NEtMe)2 (guanid)2 ] complex, the most N(13) (2.349 Å against 2.255 Å, respectively) (Table 1). One of the
convenient method was followed and reported in Scheme 1. guanidinate moiety defined by N(11)–C(12)–N(13) is positioned
It enables the in-situ formation of the guanidinate ligand by
Table 1 Selected bond lengths (Å) and bond angles (◦ ) for
the insertion of the carbodiimide moiety into the M–N bond.
[Zr(NEtMe)2 (guanid)2 ]
The [Zr(NEtMe)2 (guanid)2 ] complex can be obtained easily by
a convenient synthetic route (Scheme 1(ii)), amenable for syn- C(12)–N(12) 1.393 N(41)–Zr(1)–N(31) 91.5
thesis scale up. In the present work, tetrakis-ethylmethylamido- Zr(1)–N(13) 2.255 N(23)–Zr(1)–N(11) 91.8
zirconium [Zr(NEtMe)4 ] was chosen because of its chemical Zr(1)–N(11) 2.349 N(11)–C(12)–N(13) 114.8
C(12)–N(13) 1.337 N(41)–Zr(1)–N(31) 91.5
reactivity and favorable vapor pressure and it is also one of the C(12)–N(11) 1.315 C(33)–N(31)–C(32) 109.9
widely used parent dialkylamides for vapor deposition processes.21 N(13)–C(131) 1.480 C(122)–N(12)–C(121) 115.6
The ligand diisopropylcarbodiimide was employed due to its N(31)–C(32) 1.466 C(222)–N(22)–C(221) 116.4
N(31)–C(33) 1.458 N(11)–Zr(1)–N(13) 58.0
tunable steric protection around the metal center and it is also
Zr(1)–N(31) 2.093 N(21)–Zr(1)–N(13) 141.78
relatively easily available. The reaction of two equivalents of

1672 | Dalton Trans., 2007, 1671–1676 This journal is © The Royal Society of Chemistry 2007

in the equatorial plane of the distorted octahedra. Another
guanidinate moiety defined by N(21)–C(22)–N(23) binds to the
metal center with N(23) occupying the axial position and N(21)
occupying the equatorial position of the distorted octahedra.
The distortion of the geometry can be inferred from the angle
between two ethylmethylamido groups N(41)–Zr(1)–N(31) which
is 91.5◦ . The –NEtMe moieties of guanidinato ligands are not in
the same plane of the four-membered ring consisting of Zr(1)–
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N(11)–C(12)–N(13). The dihedral angles subtended by –NEtMe
groups and the four-membered ZrNCN rings are 50.7◦ and 48.1◦ ,
respectively. The shortened C(12)–N(11) bond length of 1.315 Å
(typical C–N single-bond length 1.42–1.45 Å) indicates some
double-bond character between these atoms. These observations
are consistent with results for similar zirconium guanidinate
complexes.22
The thermal properties of the complex [Zr(NEtMe)2 (guanid)2 ]
were analysed in detail to evaluate its suitability for CVD and
ALD applications. It was found from the TG/DTA studies that
the compound possesses promising thermal properties with a
sufficient temperature window between sublimation (∼100 ◦ C)
and decomposition (∼250 ◦ C). Isothermal TG studies carried
out on the [Zr(NEtMe)2 (guanid)2 ] complex at ambient pressure
revealed its sublimation at a constant and appreciable rate for
long periods of time (>200 min in the temperature range 80–
120 ◦ C (Fig. 2). From the isothermal curves, the constant weight
loss indicates only sublimation and no signs of decomposition.
This result is of much relevance for a CVD/ALD precursor, since
it ensures reproducibility in constant vapor supply during the film
deposition process. Thus a compound which is stable, a monomer,
less sensitive to air and moisture, and having promising thermal
characteristics makes it interesting for CVD and ALD. The use
of [Zr(NEtMe)2 (guanid)2 ] as CVD precursor for ZrO2 thin film
growth was tested in a home-built horizontal cold wall reactor.
The film deposition was carried out in nitrogen (carrier gas) and
oxygen (oxidant) atmosphere on Si(100) substrates in the substrate
temperature range 350–600 ◦ C. The threshold temperature for
the CVD of ZrO2 thin films using [Zr(NEtMe)2 (guanid)2 ] was
350 ◦ C. The growth rate increased as a function of temperature
and the maximum growth rate of ∼7 nm min−1 could be achieved
at a substrate temperature of 500 ◦ C. The possibility to grow
ZrO2 thin films at reduced substrate temperatures with appreciable
Fig. 2 Isothermal studies carried at different temperatures for
[Zr(NEtMe)2 (guanid)2 ].
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growth rates could be of technological importance in dielectric
applications.
The films grown at temperatures below 400 ◦ C were amorphous
and begin to crystallise above 400 ◦ C. ZrO2 may exist in the
form of four basic crystalline polymorphs: monoclinic, tetragonal,
cubic and orthorhombic.23–25 XRD measurements indicate an
increase in film crystallinity with substrate temperature (Fig. 3).
The films grown at 400 ◦ C were monoclinic (JCPDS Card 00-037-
1484) indicating some degree of preferred orientation in the (002)
direction. Increasing the substrate temperature to 500 ◦ C resulted
in highly textured (002) films (Fig. 3). At 600 ◦ C, the films were
polycrystalline, with reflections corresponding to both monoclinic
(predominantly) and the orthorhombic phases detected. The
variation of oxygen flow showed no significant change in resulting
film properties. The flow was changed to 100 sccm and films began
to crystallize above 400 ◦ C with some degree of orientation in
the (002) direction. At 600 ◦ C the films were polycrystalline as
observed in the case of lower oxygen flow.
Fig. 3 XRD pattern of the ZrO2 films deposited as a function of substrate
temperature.
The surface morphology of the ZrO2 thin films was analysed by
scanning electron microscopy (SEM) and atomic force microscopy
(AFM). The SEM micrograph of a ZrO2 film grown on Si(100)
at 500 ◦ C shows the formation of uniformly and densely packed
grains (Fig. 4a). The inset in Fig. 4b shows the cross section of the
film which displays columnar growth and a lateral size of 65 nm.
From the AFM analysis, the films grown at 400 ◦ C were smooth
with an average rms roughness of 0.8 nm. The increase in the
substrate temperature resulted in the development of a globular
surface texture. A representative AFM image of a ZrO2 film grown
on Si(100) at 500 ◦ C is shown in Fig. 4b. The root mean square
(rms) roughness was estimated to be 6 nm (for a film thickness of
250 nm).
Compositional analyses performed by EDXS confirmed the
presence of Zr and oxygen in the films (see ESI, Fig. 3†). Fur-
ther investigation was carried out by Rutherford back-scattering
(RBS), which confirmed the occurrence of a Zr/O atomic ratio
very close to the stoichiometric ratio of 1 : 2 (see ESI, Fig. 4†).
The films were subjected to a detailed XPS analysis. The surface
Zr 3d5/2 binding energy (BE) (see ESI, Fig. 5a†) was in excellent
agreement with that expected for Zr(IV) oxide (BE = 182.2 eV).26
Dalton Trans., 2007, 1671–1676 | 1673

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Fig. 4 (a) SEM micrograph with cross section (inset) and (b) AFM top
view of the ZrO2 films deposited at 500 ◦ C (rms roughness = 6 nm).
Two contributing bands, at BE = 530.3 and 531.8 eV, were found
for the O1s peak (see ESI, Fig. 5b†). While the former was in good
agreement with the value reported for zirconia, the latter, which
disappeared after sputter etching, was due to surface –OH groups
arising from atmospheric exposure.27,28
Fig. 5 XPS depth profile of a ZrO2 film deposited at 500 ◦ C.
In order to investigate the presence of contaminants such as
carbon that can arise from incomplete precursor decomposition,
the film composition was investigated by XPS depth profiling.
As displayed in Fig. 5, the ZrO2 film deposited at 500 ◦ C on
Si(100) substrate displays a very uniform composition with an
average O/Zr ratio of 1.9, in agreement with the value expected
1674 | Dalton Trans., 2007, 1671–1676
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for stoichiometric ZrO2 . The disappearance of the carbon signal-
to-noise level after sputter etching the surface indicated that it
arose from atmospheric contamination, thus indicating a very
clean decomposition pattern of the proposed precursor under the
adopted process conditions.
Finally, electrical properties of the films were studied in terms of
the C–V characteristics to investigate their suitability for potential
application in Pt/ZrO2 /SiOx /Si capacitor structures for high-k
application. C–V curve (Fig. 6), shows small counter clockwise
hysteresis and could be related to the charging and de-charging
of interface traps on sweeping the bias voltage between positive
and negative values and back.29 The observed hysteresis, DV fb
(difference in the flatband voltage, V fb for backward and forward
voltage sweep) was less than 20 mV; suggesting very low (1.5 ×
10−10 per cm2 ) rechargeable trap states at the interface and bulk of
the film. The calculated dielectric constant from the capacitance
at accumulation of the ZrO2 film deposited at 500 ◦ C was k ∼25
which is within the range of values given in the literature: between
20 and 31.30 Thin films of ZrO2 show a dielectric constant that
is dependent on the method of deposition.31 It has been reported
that pure ZrO2 deposited using different oxygen sources like O2 ,
H2 O and N2 O with b-diketonate complexes of zirconium showed
a dielectric constant of ∼18.32 These results suggest that (high
dielectric constant and low hysteresis) the ZrO2 films grown from
the new precursor are attractive for dielectric oxide applications.
Fig. 6 C–V characteristics of the Pt/ZrO2 /SiOx /Si capacitor obtained
for a ZrO2 specimen grown at 500 ◦ C.
Conclusions
The present work has focused on (i) the synthesis of a monomeric
six-coordinated bis-(ethylmethylamido)-bis-(N,N
-diisopropyl-2-
ethylmethylamidoguanidinato) zirconium(IV) complex and (ii) its
use as a potential precursor for the CVD of ZrO2 thin films.
The precursor is easy to synthesize, and its stability and lower
sensitivity to air and moisture compared to the parent alkylamide
system is found to be advantageous. The promising thermal
properties can be an added value for CVD and ALD applications.
As demonstrated, the growth of ZrO2 films was achieved at low
substrate temperatures and films grown at temperatures as low as
This journal is © The Royal Society of Chemistry 2007

400 ◦ C showed some preferred orientation. In addition, the films
were stoichiometric and carbon free. Preliminary results from the
electrical characterisation of the ZrO2 films showed encouraging
electrical properties interesting for technological applications such
as high-k dielectrics. In summary, the approach of tailoring
parent alkyl amides in combination with the bidentate guanidinate
as chelating ligands resulted in a new compound of Zr. This
monomeric compound [Zr(NEtMe)2 (guanid)2 ] shows potential
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both for CVD and ALD related applications as it combines both
stability and reactivity. We are currently investigating the use of this
precursor for ZrO2 thin film deposition by ALD in a commercial
reactor (F-120; ASM).
Experimental
General comments
All reactions were performed using a conventional vacuum/argon
line with standard Schlenk techniques. Samples for all analysis
were prepared in argon filled glove boxes. Elemental analysis
was performed by the analytical service center at faculty of
Chemistry at Ruhr University Bochum (CHNSO Vario EL 1998).
1
H- and 13 C-NMR-spectra were recorded on the Bruker Advance
DRX-400. TG/DTA analysis was carried out using a Seiko
TG/DTA 6300S11 at ambient pressure (Sample weight ∼15 mg).
ZrCl4 (Alfa Aesar), n-BuLi (Merck), HNEtMe (Fluka) and
N,N
-diisopropylcarbodiimide (Aldrich) were used as received.
The zirconium amide compound [Zr(NEtMe)4 ] was synthesized
according to a previously reported procedure.33 Crystallographic
data were collected on a Xcalibur 2 Oxford using graphite
monochromated Mo-Ka radiation (k = 0.71073 Å, T = 150 K).
The structure was solved using the SHELXL-97
R software
package and refined by full matrix least-squares methods based
on F 2 with all observed reflections.
Synthesis of {[(Ni Pr)2 C(NEtMe)]2 Zr(NEtMe)2 }.
Two equivalents of N,N
-diisopropylcarbodiimide (1.54 ml,
10 mmol) in 20 ml hexane were added dropwise over a period
of 1 h to a solution of [Zr(NEtMe)4 ] (1.54 ml, 5 mmol) in
20 ml of hexane. During the addition, a slight increase in the
temperature was observed. After stirring for 24 h at ambient
conditions, the solvent was removed under reduced pressure
yielding a white solid. The resulting solid was extracted into
toluene, concentrated and kept at −30 ◦ C for 24 h to afford
colorless crystals suitable for single crystal X-ray analysis. In-
creasing the excess of the ligand to 3 : 1 or 4 : 1 did not result
in the formation of higher-coordinated complexes, probably due
to the steric hindrance of the amide and carbodiimide ligands.
The [Zr(NEtMe)2 (guanid)2 ] complex was found to be highly
soluble in toluene and diethyl ether. Yield 2.54 g {88% based on
[Zr(NEtMe)4 ]}. Melting point: 128 ◦ C. Elemental analysis: calc.
for C26 H60 N8 Zr: C 54.21%, H 10.5%, N 19.45%; found: C 54.15%,
H 9.84%, N 19.35%; 1 H–NMR (room temp., 400 MHz, toluene-
d8): d H 0.9 (6H, t, CN(CH2 CH 3 ), 1.2 (6H, t, ZrN(CH2 CH 3 ),
1.3 (24H, d, NCH(CH 3 )2 ), 2.5 (6H, s, CNCH 3 ), 2.9 (4H, q,
CNCH 2 CH3 ), 3.2 (6H, s, ZrNCH 3 ), 3.6 (overlapping, 4H+
4H, sept + q, NCH(CH3 )2 + ZrN(CH 2 CH3 )). 13 C-NMR (room
temp., 400 MHz, toluene-d8 ): d C 13.73 (CN(CH2 CH 3 ), 14.80
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(ZrN(CH2 CH 3 )), 25.53 (NCH(CH 3 )2 ), 36.91 (CNCH 3 ), 41.58
(CNCH 3 ), 46.09 (CN(CH 2 CH3 ), 47.32(ZrN(CH 2 CH3 ), 50.43
(NCH(CH3 )2 ), 172.38 (N3 C). As additional evidence for the purity
of [Zr(NEtMe)2 (guanid)2 ], NMR spectra at different temperatures
are included (see ESI, Fig. 1 and 2†). EI-MS (70 eV) 576 <
1% (complex); 516, 15% (complex-NEtMe); 390, 20% (complex-
guanidinate); 264, 4% (Zr(NEtMe)3 ); 185, 10% ({(CH3 )2 CHN}2 –
C–NEtMe); 128, 15% ((CH3 )2 CHN=C=NCH(CH3 )2 ); 58, 65%
(NEtMe); 44, 100% (NEt). Crystal data for (1): C26 H60 N8 Zr,
M = 575.2, Orthorhombic, space group Pbca, a = 10.8201(18),
b = 17.638(2), c = 33.626(5) Å, V = 6417.3(16) Å3 , Z = 8, q =
1.184 Mg m−3 , l = 0.369 mm−1 , Refl. collected = 45330, Refl.
unique = 5629, R1[I > 2r (I)] = 0.0662, wR2 = 0.1032.
CCDC reference number 279876.
For crystallographic data in CIF or other electronic format see
DOI: 10.1039/b616861b
ZrO2 film deposition and characterisation.
Preliminary CVD experiments were performed using a home built,
horizontal cold wall CVD-reactor, details of which have been
reported earlier.34 Nitrogen (purity: 6.0, flow rate: 50 sccm) and
oxygen (purity: 4.8, flow rate: 50–100 sccm) were used as carrier
and reactive gases, respectively. The substrate temperature was
varied between 350 and 600 ◦ C, while the precursor vaporizer
temperature was maintained at 120 ◦ C. Depositions were carried
out for 1 h at a total pressure of 1 mbar on 1 × 1 cm2 p-type
Si(100) substrates which were pre-cleaned using standard methods.
The native oxide was not removed prior to deposition. For each
deposition, approximately 100 mg of fresh precursor were weighed
into the bubbler. XRD analyses were performed on Bruker D8
Advance AXS Diffractometer with Cu-Ka radiation (1.5418 Å)
with position sensitive detector (PSD). All films were analyzed in
the h–2h geometry. The morphology of the film was analyzed using
a LEO Gemini SEM 1530 electron microscope and EDX analysis
was carried out using an Oxford ISIS EDX system at the central
facility at Ruhr University, Bochum. A multimode scanning probe
microscope from Digital Instruments was used for AFM studies in
tapping mode. RBS measurements were carried out with a 2 MeV
He beam of the Dynamitron-Tandem accelerator in Bochum with
beam intensities of about 10 nA. A silicon surface barrier detector
with an energy resolution of 15 keV was placed at an angle of 170◦
with respect to the beam axis. The spectra were analyzed with
the program RBX.35 using the stopping powers of the program
SRIM. XPS spectra were recorded on a Perkin Elmer U 5600ci
spectrometer at a pressure lower than 10−9 mbar, using an Al-Ka
excitation source (1486.6 eV). The spectrometer was calibrated by
assigning the Au4f7/2 line to the BE of 84.0 eV with respect to the
Fermi level. The BE shifts were corrected assigning to the C1s line
of adventitious carbon a value of 284.8 eV. The estimated standard
deviation for BEs was ±0.2 eV. The atomic compositions were
evaluated using sensitivity factors provided by U V5.4A software.
Depth profiling was carried out by Ar+ sputtering at 3 kV and
0.5 mA cm−2 beam current density, with an argon partial pressure
of 5 × 10−8 mbar. Under these conditions, the sputtering rate
was estimated to be in the range 1–3 nm × min−1 . Samples were
introduced directly into the analysis chamber by a fast entry lock
system. The deposition of the Pt top electrode was performed by
sputtering and patterning by lift-off process. Thickness of the films
Dalton Trans., 2007, 1671–1676 | 1675

used for this study was around 200 nm and this higher thickness
preferred to minimise the effect of the interlayer capacitance from
the SiOx between Si and ZrO2 films. In this case the measured
effective capacitance at the accumulation is almost equal to the
capacitance of the ZrO2 films and gives the dielectric constant.
Acknowledgements
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The authors are grateful for financial support from the Deutsche
Forschungsgemeinschaft (DFG, CVD-SPP-1119, DE-790/3-3)
and the Italian Research Program FISR-MIUR “Inorganic and
hybrid nanosystems for the development and innovation of fuel
cells”.
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