Preparation
and
room
temperature
methane
sensing
properties
of
platinum-decorated
vanadium
oxide
films
Jiran
Liang
*
,
Junfeng
Liu,
Wenjiao
Li,
Ming
Hu
School
of
Electronics
and
Information
Engineering,
Tianjin
University,
Tianjin
300072,
PR
China
A
R
T
I
C
L
E
I
N
F
O
Article
history:
Received
28
February
2016
Received
in
revised
form
11
August
2016
Accepted
13
August
2016
Available
online
16
August
2016
Keywords:
A.
Oxides
B.
Sputtering
A.
Thin
films
A.
Nanostructures
A.
Semiconductors
A
B
S
T
R
A
C
T
Room
temperature
methane
(CH
4
)
response
characteristics
of
vanadium
oxide
(VO
x
)
thin
films
loaded
with
platinum
(Pt)
nanoparticles
were
investigated
for
detection
of
CH
4
.
The
Pt/VO
x
thin
films
have
been
prepared
on
sapphire
substrate
by
means
of
dc-magnetron
sputtering
of
V
metal,
followed
by
deposition
of
Pt
nanoparticles,
and
then
rapid
thermal
annealing
(RTA)
in
O
2
atmosphere
from
450
C
to
470
C.
SEM
and
XRD
were
used
to
investigate
the
morphology
and
crystal
structure
of
the
films.
The
results
showed
that
irregular
rod-shaped
particles
with
size
on
the
average
of
100
nanometers
and
the
monoclinic
vanadium
dioxide
(VO
2
)
were
obtained.
The
property
of
metal
to
insulator
transition
(MIT)
was
a
confirmation
of
the
prepared
VO
2
.
The
sensor
annealed
at
460
C
showed
the
largest
response
value
which
was
18.2
toward
methane
(CH
4
)
at
room
temperature
with
the
concentration
of
500
ppm.
The
optimal
operating
concentration
for
CH
4
detection
is
1500
ppm.
ã
2016
Elsevier
Ltd.
All
rights
reserved.
1.
Introduction
CH
4
is
a
kind
of
strong
absorbed,
flammable
and
explosive
substances
as
a
major
constituent
of
mash
gas,
firedamp
and
rock
gas.
It
is
well
known
that
a
small
spark
can
cause
violent
explosion
and
do
great
damage
to
human
beings
if
the
concentration
of
CH
4
reaches
a
critical
limit
(5%–15%).
Up
to
now,
there
are
various
semiconductor
oxide
nanostructured
materials
used
for
the
detection
of
CH
4
,
for
instance,
including
tin
oxide
[1,2],
zinc
oxide
[3,4]
etc.
However,
these
materials
sensors
operate
at
high
temperature
greater
than
100
C
to
get
good
response
sensitivity
toward
CH
4
,
which
could
cause
a
series
of
problems,
such
as
higher
power
consumption
and
a
reduction
in
their
stability.
Therefore,
it
is
of
great
importance
to
develop
a
convenient
and
applied
gas
sensor
which
can
be
operated
at
a
low
temperature
for
CH
4
detection.
Among
extensive
research
for
nanostructure
sensitive
materi-
als,
VO
x
has
been
studied
as
a
new
type
of
gas
sensitive
materials.
The
VO
x
family
consists
of
more
than
ten
kinds
of
compounds
with
vanadium
valence
from
+2
to
+5,
such
as
VO,
V
2
O
3
,
VO
2
and
V
2
O
5
etc.
In
the
meantime,
the
vanadium
dioxide
(VO
2
)
and
vanadium
pentoxide
(V
2
O
5
)
cause
intensive
research
interest
due
to
the
property
of
metal
to
insulator
transition.
The
transition
temperature
T
C
of
VO
2
is
around
68
C
[5]
with
a
reversible
change
from
monoclinic
structure
at
low
temperature
to
a
high-
temperature
tetragonal
rutile
structure
with
a
band
gap
about
0.7
eV
[6].
The
transition
temperature
T
C
of
V
2
O
5
is
around
250
C
[7].
They
have
been
successfully
applied
to
storage
devices
[8,9],
switching
circuit
[10,11]
and
smart
windows
[12,13].
There
are
several
commonly
used
methods
to
synthesize
nanostructured
thin
films,
such
as
sputtering
[14–17],
chemical
vapor
deposition
[18,19],
sol-gel
[20]
and
pulsed
laser
deposition
[21,22].
To
the
best
of
our
knowledge,
there
are
only
few
available
articles
reported
VO
x
is
associated
with
detection
of
CH
4
.
A.K.
Prasad’s
team
[23]
firstly
reported
the
single
VO
2
thin
film
for
detection
of
CH
4
by
sputtering
in
2014.
Recent
efforts
have
been
concentrated
on
enhancing
the
sensitivity
and
decreasing
the
operating
tempera-
ture
of
methane
sensor.
More
contact
surface
area
such
as
nanorods
and
nanowire
are
preferred
for
improving
sensitivity
for
CH
4
.
On
the
other
hand,
many
reports
available
claimed
adding
noble
metal
[24–26]
could
enhance
the
response
characteristics
of
gas
sensor
attributed
to
a
selective
promotion
of
the
desired
molecule
reaction
at
different
adsorbed
locations.
In
this
paper,
we
have
deposited
Pt
nanoparticles
on
the
nanostructured
VO
x
thin
films
for
the
detection
of
CH
4
at
room
temperature.
The
Pt/VO
x
films
sensor
structures
have
been
successfully
prepared
using
dc
magnetron
sputtering
for
the
deposition
of
metal
vanadium
thin
films,
adding
bit
of
Pt
particles,
and
then
RTA
to
obtain
nanostructured
VO
x
films
with
desired
composition
and
morphology.
*
Corresponding
author
at:
School
of
Electronics
and
Information
Engineering,
Tianjin
University,
92
Weijin
Road,
Nankai
District,
Tianjin
300072,
PR
China.
E-mail
address:
liang_jiran@tju.edu.cn
(J.
Liang).
http://dx.doi.org/10.1016/j.materresbull.2016.08.024
0025-5408/ã
2016
Elsevier
Ltd.
All
rights
reserved.
Materials
Research
Bulletin
84
(2016)
332–339
Contents
lists
available
at
ScienceDirect
Materials
Research
Bulletin
journa
l
homepage:
www.elsevier.com/locate/matresbu
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