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Preparation and characterization of tungsten oxynitride nanowires

Y. M. Zhao,a W. B. Hu,a Y. D. Xia,a E. F. Smith,b Y. Q. Zhu,*a C. W. Dunnillc and D. H. Gregoryc
Received 21st June 2007, Accepted 21st August 2007
First published as an Advance Article on the web 31st August 2007
DOI: 10.1039/b709486h
Published on 31 August 2007. Downloaded by University of Michigan Library on 24/10/2014 23:06:23.

Tungsten oxynitride nanowires were generated by the reaction of ammonia with ultra-thin
tungsten oxide nanowires which were themselves prepared by a simple solvo-thermal treatment of
tungsten chloride in a cyclohexanol solvent. The resulting tungsten oxynitride nanowires exhibited
a high specific surface area of 221 m2 g21, even exceeding that of 151 m2 g21 for the bundled and
ultra-thin tungsten oxide nanowire precursor. The observed weak, temperature-independent
paramagnetism indicates that the tungsten oxynitride nanowires are metallic, but no
superconducting transition was observed above 2 K.

Introduction materials,19,20 with a superconducting transition temperature

Synthesis and characterization of one-dimensional nanostruc-
tures are of great importance because such nanomaterials can
exhibit new physical or chemical properties that corresponding
bulk materials do not usually possess. Tungsten oxide
nanowires have attracted much attention due to their potential
applications, such as in optical devices, gas sensors and photo
catalysts.1–5 Tungsten oxide nanowires have also been used as
precursors to synthesize a new class of tungsten sulfide
nanotubes by reaction with hydrogen sulfide.6,7 Recently,
soft-chemistry methods have been successfully used in the pro-
duction of diverse one-dimensional nanomaterials. Tungsten
oxide nanowires have been synthesized by low temperature
processing of tungsten-containing precursors such as WCl6,
W(CO)6 and WCl4 in solvents that are usually a mixture
of alcohol and water with the addition of acids/bases and
surfactants.8–11 As archetypal refractory transition metal
nitrides, tungsten nitrides are known to offer a number of
important properties, including high hardness, excellent
chemical stability and a high melting point. Furthermore,
electrical conductivity (and even superconductivity) reflects the
metallic behaviour of these materials. In contrast to the
numerous investigations of new nanostructures of tungsten
oxides, there are very few reports of nanostructured tungsten
nitrides, and these are confined to studies of nanoparticles
and thin films.12–17 Tungsten nitride thin films are usually
fabricated by reactive sputtering and metal organic chemical
vapour deposition.13–17 Group 6 nitrides generally possess
unique catalytic behaviour, but relatively low specific surface
areas have hindered their applications in the catalysis industry.
Some research groups have tried to prepare nitride catalysts of
high surface areas via temperature-programmed reactions.18
Meanwhile, many binary transition metal nitrides have
attracted significant attention as hard superconducting
a
The School of Mechanical, Materials and Manufacturing Engineering,
University of Nottingham, University Park, Nottingham, UK NG7 2RD.
E-mail: yanqiu.zhu@nottingham.ac.uk
b
The School of Chemistry, University of Nottingham, University Park,
Nottingham, UK NG7 2RD
c
WestCHEM, Department of Chemistry, Joseph Black Building,
University of Glasgow, Glasgow, UK G12 8QQ
(Tc) of 4.2 K reported for tungsten nitride thin-film samples.21
Here, we report a simple route to the synthesis of ultra-thin
tungsten oxynitride nanowires by processing tungsten oxide
nanowires in an ammonia atmosphere. The tungsten oxide
nanowires were prepared via a solvo-thermal technique at low
temperature using tungsten chloride dissolved in cyclohexanol.
The resultant tungsten oxynitride exhibits a high specific
surface area of 221 m2 g21, which is associated with the high
specific surface area of the tungsten oxide nanowire pre-
cursors. The magnetic susceptibility behaviour of the oxy-
nitride nanowires was also investigated, for the first time.
Experimental
The synthesis of tungsten nitride nanowires involves two steps:
the first step is the preparation of the tungsten oxide
nanowires, and the second is the nitriding (ammoniation)
process of the resulting oxide nanowires. 100 mg of WCl6
(Sigma-Aldrich, 99.999%) were slowly dissolved in 50 ml of
cyclohexanol to obtain uniform solution. The solution was
then transferred to a 125 ml Teflon-lined stainless-steel
pressure vessel for reaction at 200 uC for 5 h. After reaction,
the precipitate was centrifuged and washed with deionized
water and acetone several times. Scanning electron microscopy
(SEM) and powder X-ray diffraction (XRD) were used to
characterize the blue tungsten oxide products. Synthesis of
tungsten nitride nanowires was carried out by thermal reaction
of the tungsten oxide nanowires in an NH3 (CK gas products,
99.98% pure) atmosphere in a conventional tube furnace
at 923 K for 3 h, with a NH3 flow rate of 400 sccm min21.
The structural change from oxide to nitride nanowires was
appraised by XRD and transmission electron microscopy
(TEM, Jeol, JEM-2000Fx). Average nitrogen content within
the tungsten nitride nanowires was measured using a CHNS
analyzer (Fishons EA 1108). The surface nitrogen content was
characterized by X-ray photoelectron spectroscopy (XPS),
using a Kratos AXIS ULTRA with a monochromated Al kR
X-ray source (1486.6 eV) operating at an emission current of
10 mA with an anode potential of 15 kV. The analysis chamber
pressure used was better than 1029 Torr. Nitrogen sorption
isotherm measurements were conducted on a Micromeritics

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ASAP2020 sorptometer. Prior to analysis, the samples were
oven dried at 150 uC and evacuated for 12 h at 200 uC under
vacuum. Photoluminescence (PL) spectrophotometry of the
tungsten oxide nanowires was performed on a Cary Eclipse
fluorescence spectrophotometer using a Xe lamp as the
excitation light source (excitation at 270 nm) at room
temperature. The magnetic susceptibility of the samples was
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investigated using a Quantum Design MPMS-XL 5T SQUID
magnetometer. Accurately weighed samples were loaded into
gelatine capsules and measurements were taken from 2 to
290 K using fields of 10 and 100 Oe under zero-field cooling
conditions from room temperature and then under field
cooling conditions over the same range. The data were
corrected for the gelatine capsule and the diamagnetic con-
tributions from the elemental constituents. All samples were
loaded in a nitrogen-filled recirculating glovebox.
Results and discussion
Fig. 1 shows the SEM images and XRD patterns of tungsten
oxide nanowire precursor and the resulting tungsten nitride
nanowires. In comparison with the SEM image of the tungsten
oxide nanowire precursor (Fig. 1a) it can be seen that there is
no evidence of major changes in the morphology of the
ammoniated nanowires (Fig. 1c). Both precursor and product
exhibit uniform nanowires with large aspect ratios. XRD
patterns confirm that the tungsten oxide nanowires have been
converted to (oxy)nitride nanowires. All of the peaks in Fig. 1b
are indexed to monoclinic W18O49 (JCPDS No.71-2450).
The XRD pattern of the ammoniated nanowires (Fig. 1d)
matches well with either cubic WN (JCPDS No.75-1012) or
W0.62(N0.62O0.38) (JCPDS No. 25-1254). A lower temperature,
reduced ammonia flow rate and/or shorter reaction time than
the parameters reported in the experimental section resulted in
incomplete nitriding of the tungsten oxide with products of
Fig. 1 SEM images and XRD patterns of: (a) and (b) bundled
tungsten oxide nanowires; (c) and (d) bundled tungsten oxynitride
nanowires.
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even lower N content. For example, the XRD pattern of
materials after a treatment at 700 uC for 30 min under a NH3
flow rate of 100 sccm matches well with either cubic W3N4
(JCPDS No.75-1002) or W3(N,O)4 (JCPDS No. 25-1255) with
a lower N content than that of cubic WN (JCPDS No.75-1012)
or W0.62(N0.62O0.38) (JCPDS No. 25-1254). The two potential
matches (No. 75-1012 and 25-1254) have almost identical
lattice structures and hence diffraction peaks in the XRD
pattern. The N concentration was measured to be about
5.5 wt% using a CHNS analyzer, which is close to that in
W0.62(N0.62O0.38) (6.7 wt%) than that in WN (7.1 wt%). From
the XRD pattern and the elemental analysis results, the
nanowires are not pure tungsten nitride but actually tungsten
oxynitride with about 5–7 wt% oxygen. As is apparent from
the similarity of the XRD patterns WN (JCPDS No.75-1012)
or W0.62(N0.62O0.38) (JCPDS No. 25-1254) above and given the
size and X-ray scattering power of oxygen vs. nitrogen, O
doping in tungsten nitride makes little changes to the crystal
structure. Therefore one would expect almost no difference in
the XRD pattern between pure tungsten nitride and tungsten
oxynitride.
TEM images of the tungsten oxynitride nanowires are
illustrated in Fig. 2. Although changes in the nanowire
morphology after nitriding were not detected by SEM,
differences were indeed recognized using TEM. Further
TEM characterization (Fig. 2a) of the tungsten oxide nanowire
precursor has revealed that the structures shown in the SEM
images (Fig. 1a) are actually tungsten oxide nanowire bundles
consisting of ultra-thin individual nanowires with a diameter
of less than 5 nm. These individual nanowires exhibited
orientations mostly parallel to each other. Similar bundles of
Fig. 2 TEM images of (a) tungsten oxide nanowires; (b) tungsten
oxynitride nanowires; and (c) a single tungsten oxynitride nanowire.
(d) HRTEM image of tungsten oxynitride nanowire. The insets in (a)
and (b) are the ED patterns obtained from a corresponding nanowire
bundle (arrowed in the images with the tip pointing to the growth
direction of the nanowires).
J. Mater. Chem., 2007, 17, 4436–4440 | 4437

tungsten oxide nanowires have been previously prepared by
other soft-chemical synthesis techniques.20,21 After ammoniat-
ing, the bundled structure of the oxide nanowires was not
visible any more, and high contrast areas were often present
within each individual nanowire, as shown in Fig. 2b. The
electron diffraction (ED) pattern of the tungsten oxynitride
nanowires exhibits two broadened and strong spots along the
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growth direction of the wires. This can be attributed to the
essentially asymmetric one-dimensional nature of the long and
thin nanowires, and bears a close resemblance to the ED
patterns from the tungsten oxide nanowire bundles. The
disappearance of the initial bundled structure may be due to
that at high temperature (700 uC), crystalline re-arrangement
must have occurred to the neighbouring oxide nanowires
within a bundle via mass transport (diffusion) and subsequent
inter-linking of the wires during nitriding. Indeed, the ultra-
thin diameters (less than 5 nm) of the tungsten oxide nanowires
within the bundles are energetically active so that the
recrystallization took place more easily upon heating in
appropriate sites occasionally, leading to the formation of
oxynitride nanowires with bamboo-like structures and rela-
tively larger diameters. It is noteworthy that such an
incontinuous inter-diffusion of the aligned nanowires within
a bundle would not result in a completely integral single-
crystalline nanowire. As shown in the high resolution TEM
(HRTEM) image of the tungsten oxynitride nanowires, multi-
crystalline characteristic with some cavities or pores can be
recognized within the body of the resultant new nanowires.
This may account for the numerous multi-contrast areas
within the nanowires examined by TEM (Fig. 2b).
Fig. 3a exhibits the XPS surface spectrum of the tungsten
oxynitride nanowires after the sample was etched away about
6 nm in depth by Ar ion bombardment. The etching removed
most of the carbon adsorbed on the surface during washing
with acetone. The O 1s peak (Fig. 3b) is still very strong after
the etching, indicating the presence of oxygen within the
sample. High resolution scanning showed that the N 1s peak is
Fig. 3 XPS spectra of tungsten oxynitride nanowires for (a) surface
survey after etching; (b) O 1s after etching; (c) N 1s after etching; and
(d) W 4f, before and after Ar etching, and the four fitted lines for W 4f.
4438 | J. Mater. Chem., 2007, 17, 4436–4440
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at 397.6–397.9 eV (Fig. 3c), similar to the nitride ion.22 The
etching almost made no change in the peak position of C 1s
and O 1s. However, the oxidation state of W became rather
different, as shown in the high resolution W 4f spectra in
Fig. 3d. Prior to etching, the peaks near binding energy of
36.22 eV (W 4f 7/2) and 38.40 eV (W 4f 5/2) are considered to
be the +6 oxidation state of W in WO3.14–17 The non-
appearance of Bragg peaks for WO3 in the XRD patterns
further suggests that the trioxide forms as a surface layer on
the W(N,O) nanowires. The peaks near the lower binding
energies of 33.53 eV (W 4f 7/2) and 35.71 eV (W 4f 5/2) are
associated with lower oxidation states of W (WO32x) as might
be expected in tungsten oxynitrides.14–17 After etching, the
peaks associated with WO3 became weaker while, conversely,
the W 4f peak associated with tungsten nitride became
stronger and broadened to an even lower binding energy.
This etching experiment has indicated that there is more oxide
at the surface than in the bulk of the ammoniated nanowires.
Nevertheless, the XPS analyses indicate that the resultant
nanowires are not pure tungsten nitride (WN), but tungsten
oxynitride (WN12xOx), which is consistent with the XRD
results. Furthermore, previous studies of various tungsten
nitride nanostructures (in the form of thin films or nano-
particles), almost all report materials containing a certain
amount of oxygen (from XPS and/or elemental analysis),
although some authors claimed that their materials are pure
tungsten nitride based only on XRD patterns.13–17 Hence,
from the balance of evidence it seems likely that the wires are
polycrystalline W(N,O) formed with a passivating layer of
WO32x at the surface. From the lack of evidence to the
contrary in the selected area ED (SAED) patterns, it can be
assumed that this surface oxide layers is amorphous. Shen
and co-workers have also proposed that O is important in
stabilizing the tungsten nitride structure and prevents the
desorption of N from the nitride structure.14
Brunauer–Emmett–Teller (BET) gas-sorption measurements
were employed to evaluate the specific areas and porous
features of the nanowires. The calculated BET specific surface
area of the tungsten oxynitride nanowires is 221 m2 g21 based
on the absolute adsorption. Conventional powder-metallurgy
methods usually yield very low surface-area metal nitrides and
limit their application in catalysis. The highest surface area of
tungsten nitride achieved to date through the ammoniation of
a tungsten oxide precursor is 79 m2 g21,23 although meso-
structured tungsten nitride using tungstic acid as a precursor
can be produced with a surface area of 89 m2 g21.24 The
significantly increased surface areas of the present nanowires,
by ca. 250%, result from the high surface area of the tungsten
oxide nanowire precursor. After the reaction with NH3, the
resulting nanowires ostensibly retained the original shape and
porous structures of the bundled precursors, in spite of some
diffusion (mass transport) between neighbouring nanowires
within the bundle. The nitrogen adsorption–desorption iso-
therms for the tungsten oxide nanowires also exhibited a type
IV feature, as shown in Fig. 4a. The BET specific surface area
of the oxide samples calculated from the absolute adsorption is
151 m2 g21, and to the best of our knowledge surpasses the
specific surface area of any reported form of tungsten trioxide.
The specific surface areas of our oxide nanowires are higher
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Fig. 4 Nitrogen sorption isotherms (a) tungsten oxide nanowires and
(b) tungsten oxynitride nanowires.
than both mesoporous WO3 (125 m2 g21)25 (prepared from
WCl6 and surfactant) and mesoporous WO3 thin films
(143 m2 g21).26 Furthermore, our value of 151 m2 g21 is
about two orders of magnitude better than typical commercial
WO3 powder (1.7 m2 g21),27 and exceeds the reported surface
area for nano-sized monoclinic WO3 powders (,25 m2 g21)
prepared by organic ligands and emulsion-based methods
by a factor of five.27 The current high specific surface areas of
the oxide nanowires may be due in part to a combination of
the small diameters of individual nanowires comprising the
bundles and the unique packing characteristic of the bundles
themselves. However, the high specific surface areas of the
oxide nanowires are also undoubtedly associated with the sizes
and distribution of the pores. The pores are considered to arise
from two possible mechanisms; (1) direct formation within
nanowires during the solvo-thermal preparation at low
temperature, and (2) indirect formation via the inter-nanowire
spaces within a bundle. The enhanced surface areas of the
oxynitride nanowires over the bundled oxide nanowires
possibly arises from the formation of additional pores during
the ammoniation, as shown by the severe contrast in the TEM
images (Fig. 2). The inter-linking of the oxide nanowires
during heating eventually leads to partial nanowire re-
arrangement, generating extra pores between the points of
contact of the reacting wires. In addition, the multi-crystalline
features and the high surface roughness of the oxynitride
nanowires (Fig. 2) both contribute to further increase the
surface area of the oxynitride nanowires when compared with
their bundled oxide precursors. As has been previously
demonstrated, there is a linear relationship between the
specific surface area and sensitivity of SnO2-based sensors.28,29
Potentially, the high surface areas of these oxide and
oxynitride nanowires could be enormously beneficial in their
application as sensors for the detection of toxic gases such as
H2S and NO2. Indeed, this hypothesis has been preliminarily
verified for the bundled oxide nanowires as sensors for NH3;
an ultra low 20 ppb detection level has been recorded, which
will be reported separately later.
Fig. 5 shows the PL spectra of the tungsten oxide nanowires
under Xe lamp excitation with a wavelength of 270 nm. The
ultraviolet (UV) emission peak at 369 nm (3.36 eV) is assigned
to be due to band–band transition of the wide band gap
tungsten oxide. The blue emission peak at 423 nm (2.94 ev) is
generally attributed to oxygen vacancies that are often implicit
in the preparation of oxide semiconductors.30,31 The strong
blue emission is indicative of the existence of a high degree of
oxygen vacancies in the tungsten oxide nanowire samples. We
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Fig. 5 Photoluminescence spectrum of the tungsten oxide nanowires.
have recently reported the PL spectra of tungsten oxide
nanorods prepared by the thermal oxidation of tungsten
disulfide nanowires with a mean diameter .100 nm,32 which
exhibited a UV emission at 359 nm (3.45 eV) and a blue
emission at 422 nm (2.94 eV). The UV emission peak for the
present tungsten oxide nanowires prepared by the solvother-
mal method is about 10 nm red-shifted; however the blue
emission peak is very close to that of the large nanorods
produced by the thermal oxidation technique. The red-shifted
UV emission seems to imply a reduced band gap in the present
tungsten oxide nanowires, which is probably related to the
quantum-confinement effect on the band structure if the ultra-
fine diameters (,5 nm) of individual nanowires within each
bundle are considered. A decrease of the band gap in tungsten
oxide nanowires due to the quantum-confinement effect has
been reported previously.30
As shown in Fig. 6, the magnetic susceptibility of the
tungsten oxynitride nanowires is weak and almost independent
of temperature in the examined temperature range of 2–50 K,
suggesting the Pauli paramagnetic behaviour expected for
a metallic compound. The magnetism thus suggests that
tungsten oxynitride nanowires exhibit a metallic behaviour
below 50 K, but no superconducting transition was found for
the sample above 2 K. The theoretically predicted Tc for WN,
with the cubic rock salt (RS) structure, is around 15.8 K.20 The
Tc of transition metal nitrides is considered to depend upon
the crystal structure, impurity concentration and nitrogen to
metal ratio33 and the reported Tc values for transition metal
nitrides are generally much lower than those predicted by
Fig. 6 Magnetic susceptibility vs. temperature for the tungsten
oxynitride nanowires under an applied field of 10 Oe.
J. Mater. Chem., 2007, 17, 4436–4440 | 4439

electron–phonon coupling calculations.19,33–36 Tc tends to a
maximum for a 1 : 1 metal–nitrogen stoichiometry for the
majority of the RS transition metal nitrides that exhibit a
superconducting transition.33 Matthias and Hulm found that
RS W2N was not superconducting down to 1.28 K.37 Kilbane
and Habig found that W2N thin films with a nitrogen
concentration of 5–20 at% exhibited a Tc of 4.85 K, and films
with nitrogen concentrations greater than 20 at% were not
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superconducting down to 4.2 K.21 The origin of the suppres-
sion of the superconductivity and the inconsistency of the Tc
values are still not fully understood. For our tungsten
oxynitride nanowires, the possible quantum effect originating
from the very narrow diameters may play an important role,
and the occurrence of a significant amount of oxygen in
the sample may also suppress the superconductivity.19,33–37
Further detailed investigations of the relationships between
crystal structure, composition, impurity, shape/size and the
superconducting properties of nanostructured transition metal
nitrides are in progress.
Conclusions
In summary, tungsten oxynitride nanowires have been
generated by using ultra-thin semiconducting tungsten oxide
nanowires as a precursor which were, in turn, prepared by
a simple solvothermal process. The ultra-thin and bundled
features of the tungsten oxide nanowire precursors, with a high
surface area of 151 m2 g21, lead to the oxynitride nanowires
exhibiting even larger specific surface areas of 221 m2 g21. The
tungsten oxynitride nanowires retain many of the original
shape and porous structural features of the bundled oxide
nanowire precursor. Compositional analyses by XPS and
nitrogen concentration measurements indicate that following
ammoniation the resulting tungsten-containing nanowires are
in fact tungsten oxynitride, WN12xOx. The weak temperature-
independent magnetic susceptibility in the temperature range
of 2–50 K indicates that the tungsten oxynitride nanowires are
metallic. The significantly high specific surface areas of both
the oxynitride nanowires and the oxide precursors show great
potential for catalysis and sensor applications.
Acknowledgements
We thank the EPSRC and the Royal Society (UK) for
financial support.
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