To fulfil today's requirements, gas sensors have to
become more and more sensitive and selective. Temperature-cycled operation
has long been used to enhance the sensitivity and selectivity of metal-oxide
semiconductor gas sensors and, more recently, silicon-carbide-based,
gas-sensitive field-effect transistors (SiC-FETs). In this work, we present a
novel method to significantly enhance the effect of gate bias on a SiC-FET's
response, giving rise to new possibilities for static and transient signal
generation and, thus, increased sensitivity and selectivity. A tungsten
trioxide (WO3) layer is deposited via pulsed laser deposition as an oxide
layer beneath a porous iridium gate, and is doped with 0.1 AT % of lithium
cations. Tests with ammonia as a well-characterized model gas show a
relaxation effect with a time constant between 20 and 30 s after a gate bias
step as well as significantly increased response and sensitivity at +2 V
compared to 0 V. We propose an electric field-mediated change in oxygen
surface coverage as the cause of this novel effect.
Introduction
Dynamic operation of gas sensors has been known for decades to be able to
increase sensitivity, selectivity, speed, and stability. The most prominent
and abundant mode of operation is, arguably, temperature-cycled operation
(TCO) used with resistive-type metal-oxide semiconductor gas sensors (Baur
et al., 2015; Lee and Reedy, 1999; Leidinger et al., 2014). Fewer
publications investigate the effect of electric fields on the surface
reactions of this sensor type (Kiselev et al., 2011; Liess, 2002). The
situation is similar for silicon-carbide-based gas-sensitive field-effect
transistors (SiC-FETs): the benefits of TCO have recently been demonstrated
in many publications (Bur, 2015), but only a few publications study the
influence of gate bias-cycled operation (GBCO) (Bastuck et al., 2014;
Nakagomi et al., 2005; Pohle et al., 2010). Nevertheless, these studies
suggest interesting effects that could enhance both the sensitivity and
selectivity of SiC-FETs. One promising property is the very quick electric
time constant for GBCO of the order of milliseconds (Bur et al., 2014),
whereas the slow thermal time constant (seconds) is not able to excite
responses based on a thermodynamic equilibrium like in e.g. Baur et al. (2015).
The idea of this work is to introduce tungsten trioxide (WO3) as
an additional, top-most oxide material to enhance electrically mediated surface
reactions on the sensor. WO3 is one of the best-studied cathodic
electrochromic (EC) materials, and nearly all oxide-based EC devices contain
amorphous tungsten oxides (Niklasson and Granqvist, 2007). It has been used
as a highly sensitive material for resistive-type metal-oxide gas sensors
with a broad application range from oxidizing (Kim et al., 2005; Penza et
al., 1998) to reducing gases (Shaver, 1967; Solis et al., 2001). Tungsten
oxide is used in highly sensitive ammonia sensors (Llobet et al., 2000; Wang
et al., 2006) and, recently, some of the authors have shown that volatile
organic compounds (VOCs) like naphthalene can also be detected in the low
ppb (parts per billion) range (Leidinger et al., 2015). Furthermore, WO3
layers with a catalytic material on top have been used as the sensing layer
on top of the gate area of a silicon-carbide field effect transistor
(SiC-FET) sensor structure (Puglisi et al., 2015). SiC is used as a substrate
due to its chemical inertness and resilience to high temperatures, up to
1000 ∘C, without losing its semiconducting properties (Lloyd
Spetz and Andersson, 2012). An area where this is of interest is in the
exhaust stream of diesel combustion engines where quantification of ammonia
helps to monitor the selective catalytic reduction (SCR) (Morimune et al.,
1998), which can be used to lower the concentration of hazardous NOx.
WO3 films show relaxation and polarization effects caused by ion
transport when applying an alternating voltage (Sauerwald et al., 2005;
Varpula et al., 2011). This polarization effect can be used to enhance the
sensitivity and selectivity of metal-oxide gas sensors (Sauerwald et al.,
2007). Alkali cations like Li+ can be added to promote this effect
(Niklasson and Granqvist, 2007). In the case of Li+, up to two ions per W atom can be inserted into the WO3 structure, with the
intercalation being fully reversible up to a ratio of 0.7 (Berggren, 2004).
The intercalation of Li+ ions increases the electrical conductance by
orders of magnitude (Berggren et al., 2004). Moreover, Li+ ions are
very mobile in the WO3 lattice. The diffusion coefficient for Li+
in WO3 at room temperature (RT) is approximately 10-12 cm2 s-1, with
an ion mobility of approximately 4×10-11 cm2 V-1 s-1 (Niklasson and
Granqvist, 2007; Strømme Mattsson, 2000). Both positive and negative
charge carriers are available in the material, but the gate electrode only
conducts electrons and is impermeable for the Li+ ions. It is well
known that the catalytic effect of surfaces can be changed with ionic
polarization, i.e. the electrochemical potential of the surface. This
effect is known as electrochemical promotion of catalysis (EPOC) or
non-Faradaic electrochemical modification of catalytic activity (NEMCA)
(Katsaounis, 2010). As indicated in the term NEMCA, the mobile ions are not
necessarily part of the catalytic reaction itself, allowing a steady-state
reaction on the gate electrode.
In this work, we aim at the preparation of dense WO3 thin films with
a predominant epsilon (ε) phase. Tungsten oxide in ε phase has been used by some of the authors in a prior investigation
(Leidinger et al., 2016) as there is evidence it might have a positive
effect on sensitivity to reducing gases reported at least for silicon- and
chromium-doped ε-WO3 (Righettoni et al., 2010; Wang et
al., 2008). The WO3 layer was deposited on top of the native gate
oxide, SiO2, of a SiC-FET gas sensor and doped with Li+. The
effects observed with the thusly prepared sensor are analysed and discussed
compared to a non-doped sensor based on ammonia as a well-characterized
model gas.
Experimental detailsSensor preparation
The FET transducer samples were supplied by SenSiC AB, Kista, Sweden, with
80 nm SiO2 as a native gate oxide and without any gate electrode. The detailed
manufacturing process is described by Andersson et al. (2013); 20 nm
HfO2 was deposited on the native gate oxide by thermal evaporation
(2×10-6 mbar background pressure) in order to prevent Li+ ions
diffusing in the SiO2. To ensure good quality of the amorphous HfO2
film with high stoichiometry, the samples were post-annealed in an oxygen
atmosphere at 300 ∘C for 16 h using an alumina-lined tube
furnace (LabStar 600, ENTECH, Ängelholm, Sweden).
Subsequently, WO3 was deposited onto the HfO2 with pulsed laser
deposition (PLD), an efficient method for producing metal-oxide films with
well-defined properties (Eason, 2007; Willmott and Huber, 2000). The
deposition and its pre- and post-treatments were done at the
Microelectronics and Material Physics Laboratory at Oulu University,
Finland. The utilized nanosecond laser is a Lambda Physik Compex 201 xenon
chloride (XeCl) excimer laser with a wavelength of 308 nm and a pulse length
of 25 ns. The beam fluence for a spot area of 0.05 cm2 is approximately
1.25 J cm-2 with a laser pulse frequency of 5 Hz. Before deposition, the
pressure in the chamber is pumped down to between 2×10-5 and
5×10-5 mbar and the oxygen partial pressure is held at
5×10-2 mbar throughout the deposition to ensure a dense layer and to
oxidize the tungsten; 60 nm of WO3, corresponding to 1000 laser pulses,
was deposited on the sensor's gate area. The sensor samples were heated to
550 ∘C during the deposition.
In a final step, a 20 nm thin, porous iridium film was deposited as
a conductive gate electrode on top of the WO3 by DC magnetron sputtering.
The deposition rate was 0.67 nm s-1, the background pressure 6×10-8 mbar,
and the argon pressure 7×10-2 mbar, and the power supply was set to 300 V
with 480 mA.
For the intercalation of Li+ ions into the tungsten oxide film, a
solution of 1 µL deionized water containing the amount of LiCl
corresponding to a ratio of 0.1 AT % Li+ ions per W atom for the used
geometry is dispersed on top of the FET structure. The sample is dried in
an oven for 2 h at 100 ∘C, with a heating rate of 5 ∘C min-1 to evaporate the water, leaving the Li+ ions to diffuse into the
WO3 layer. Considering the high diffusion coefficient for Li, the annealing
time is sufficient to disperse into the complete tungsten oxide layer. The
successful intercalation was shown by measuring the layer's conductivity
before and after doping and the relaxation effect in alternating electrical
fields (cf. Sect. 3.2). An increase of 1 order of magnitude was determined
for the conductivity of the doped sample. Although deionized water was used
for the solution, a subsequent EDX measurement of the layer showed the
presence of some sodium. Since sodium is also an alkali ion, i.e. similar
to Li, we assume no negative influences from these impurities. No
spectroscopic investigations have been done to crosscheck these results.
A schematic drawing of the resulting device is shown in Fig. 1. Note that
the WO3 layer is associated with the dielectric stack of the FET
structure despite its high conductivity in its doped state. The polarization
effect is shown for a positive gate bias VGS, with the result that the
Li+ ions move to the lower part of the WO3 film and accumulate
there since further movement is inhibited by the HfO2 diffusion
barrier.
Schematic of the used FET structure adapted from Andersson et
al. (2013) highlighting the dielectric stack and the polarization effect
with a positive VGS. The schematics are not to scale.
The as-deposited, both doped and undoped, sensor chips of approximately
2×2 mm2 in size, each containing two FET structures,
were attached to a heater substrate (Heraeus Sensor-Nite GmbH, Kleinostheim,
Germany) for the electrical and gas characterizations, along with a Pt100
temperature sensor (Heraeus Sensor-Nite GmbH), using a high-temperature,
non-conducting ceramic adhesive (AREMCO 571). The heater substrate was then
mounted on a 16-pin TO8 header and electrically contacted together with the
Pt100 temperature sensor by spot welding to pins on the TO8 header. The
SiC-FET device was electrically connected to the pins of the TO8 header by
gold wire bonding. Before the first measurement, each sensor was burned in
using the internal heater for at least 24 h at 400 ∘C.
Hardware and electronics
The electronic measurement equipment for setting the operation parameters
(temperature and gate bias voltage) and read-out of the sensor signals was
developed by 3S GmbH, Saarbrücken, Germany. It can adjust the sensor
temperature between 70 and 400 ∘C with a resolution of
1 ∘C and controls the drain-source (VDS), gate-source
(VGS), and substrate-source (or bulk) (VBS) voltages. The drain
current ID was measured as a sensor signal within the range from 0 to
500 µA at a constant VDS of +4 V. During the measurement, the
sensors were kept at 300 ∘C.
A gas mixing system using dynamic dilution was utilized to expose the
sensors to defined gas concentrations similar to the system described in
Helwig et al. (2014). A commercial gas cylinder with 500 ppm ammonia gas
was diluted into a carrier gas stream of dry zero air. The total flow over
the sensor was kept at 100 mL min-1.
Results and discussionMorphological and structural characterization
The average roughness of the WO3 layer, calculated as the root mean
square deviation (RMSD) of a 1×1µm2 AFM
micrograph, was 3 nm, indicating a very flat layer. The grain size of
approximately 24 nm was determined from an XRD spectrum of the columnar
layer. Further details about how these results have been achieved as well as
more information about the following Raman measurements can be found in the Supplement.
The heat treatment has a strong influence on the layer morphology and
distribution and orientation of crystalline phases. In the Raman spectra
(Fig. 2), the change from amorphous (blue, as-deposited) to more oriented
(black, in situ annealed) WO3 can be seen. The ε peaks at Raman
shifts of 268 and 425 cm-1 as well as the γ peaks at 71 and
134 cm-1 are clearly visible, whereas the ε peak at
372 cm-1 and the γ peak at 187 cm-1 are not pronounced
much (Cazzanelli et al., 1999). As most of the ε and γ peaks are very close to each other and the peaks are mostly broad, it is
difficult to determine which orientation is dominating. The peak at a Raman
shift of 521 cm-1 obviously belongs to the silicon substrate and
exceeds the intensity measured for tungsten oxide by 1 order of magnitude.
Above a shift of 600 cm-1, W–O stretching from the amorphous phase
is observed for the as-deposited (RT) sample as a wide hump (Baserga et al.,
2007). It has been stated in the literature that the ε phase
has a Raman mode at 678 cm-1, while the γ phase has a distinct
peak at 717 cm-1 (Cazzanelli et al., 1999; Righettoni et al., 2010).
Thus, the Raman measurement indicates that the in situ annealed sample
contains more of the ε phase.
Raman spectra for undoped WO3 layers deposited at room
temperature (blue, dashed) and at 550 ∘C (black, solid).
Electrical characterization
The drain current ID was measured in zero air at different gate-source
voltages VGS (Fig. 3a). The IV curve shows, for both doped and
undoped devices, the expected behaviour of a normally on, n-type FET, i.e.
significant current flow at VGS=0 V and an increase in current with
the gate bias. When the gate bias is changed abruptly (Fig. 3b), the
undoped sensor shows the expected behaviour of an n-type FET; i.e. the
current increases, almost instantaneously, with the gate bias. The same
effect is observed for the doped sensor (solid blue line) with an additional
overshoot, marked with a circle, right after every gate bias step, followed
by a relaxation effect. This is exemplarily shown for a switch from 0 to
±0.5 V. Another measurement with voltages up to ±2 V is shown
in the Supplement (Fig. S3).
One possible explanation for this behaviour can be the following: a positive
gate bias pushes the lithium cations down, i.e. away from the surface, so
that more free electrons are available close to the surface. With the
abundance of electrons, the surface coverage with oxygen anions increases
over time (Sauerwald et al., 2007), partly compensating for the positive gate
bias and lowering the measured current until the oxygen surface coverage has
reached its new equilibrium. The opposite happens for negative gate biases:
lithium cations partly bind electrons close to the surface, resulting in a
decreasing oxygen surface coverage and an increasing current. Alternatively,
or additionally, this observation could also be explained by an
electrochemical variation of the surface reactions similar to the EPOC
effect, which creates an effective double layer of Li+ ions hindering
oxygen adsorption to the sensor surface when a negative bias is applied
(Katsaounis, 2010).
(a) IV curves at different gate biases for doped and undoped
sensors with indication of the measurement set point of VDS=4 V and
(b) drain current ID at different gate biases for doped and undoped
samples annealed in situ with a circle exemplarily highlighting one
overshoot for the doped sensor. The different gate potentials -0.5, 0, and
+0.5 V are shown in the lower subplot. The measurements in (a) and (b) were done some time apart, so that the slight baseline shift can be
explained by sensor drift.
The relaxation after the initial peak was fitted over 300 s to gain
information about the time constant τ using the following exponential
equation:
It=I0-A⋅exp-t-t0τ.
The fit parameters are the terminal current, I0, the amplitude, A, and
the time constant, τ. The parameter t0 is the starting point of
the fit in time. The relaxation exhibits time constants between 20 and 30 s.
The high mobility of Li+ in WO3 (Niklasson and Granqvist, 2007)
disqualifies ionic movement as the sole explanation for the observed
relaxation – the time constant estimated from mobility and the electric field
is already at room temperature one order of magnitude below the measured effect,
supporting the slower oxygen surface coverage as an explanation. This would,
at the same time, explain the lower transconductance, i.e. change in
ID with UGS, observed in Fig. 3.
Gas response
The FET sensor samples were exposed to two different ammonia concentrations
(10 and 100 ppm) in dry air at a sensor temperature of 300 ∘C.
Ammonia was selected as a model gas to investigate the influence of the gate
bias: it is one of the most studied gases for SiC-FETs in particular and was
shown to interact well with WO3 as a sensing material (Wang et al.,
2006). Each concentration was offered for 30 min with 60 min of zero air
after each gas exposure to allow relaxation to the baseline. Figure 4 shows
the different responses ΔID, i.e. the difference
between the measured drain current with and without gas exposure, of the
doped (a) and undoped (b) sensors for gate biases of 0, +1, and
+2 V. The quantization error of the response is ±60 nA.
Both sensors exhibit a clearly concentration-dependent response. The higher
response of the undoped sensor at 0 and 1 V is, most likely, due to
variations in the manufacturing process of the transistor structure. It has
been reported that the threshold voltage of these FET devices may vary
within the same batch, influencing the sensitivity baseline (Andersson et
al., 2013). The undoped sensor's response is independent of the applied gate
bias and is approximately 12 and 20 µA for 10 and 100 ppm NH3,
respectively. In contrast, the doped sensor's response is strongly
influenced by the gate bias. While the response is 3 and 6 µA at 0 V,
it increases to 9 and 28 µA, at 2 V for 10 and 100 ppm, respectively.
Sensor response at different gate biases of 0, 1, and 2 V for a
doped (a) and an undoped (b) sensor at 10 and 100 ppm NH3.
The undoped sensor shows the expected logarithmic response dependence of a
FET (Eriksson and Ekedahl, 1998), which can be seen from the ratio of the
response of 1:2 between 10 and 100 ppm. This ratio stays the same for all
applied gate biases and also for the doped sensor at 0 V. For the latter,
it increases, however, up to 1:3 at +2 V. The sensitivity, estimated from
the quotient of response difference and concentration difference, follows
the same pattern: it stays at a constant 96±3 nA per ppm for the undoped
device, but increases from 29 to 198 nA per ppm for the doped device at 0 and
+2 V, respectively. These findings fit the explanation given in Sect. 3.2,
i.e. a changing oxygen surface coverage. Fogelberg et al. (1987) have shown
that oxygen coverage promotes ammonia dissociation, at least for palladium,
which, like iridium, belongs to the platinum metals. For metal-oxide
sensors, a high oxygen coverage, achieved by quick temperature changes,
results in a highly sensitive state (Baur et al., 2015). With the addition
of Li+-doped WO3 in the FET's dielectric stack, a similar state
could then be reached by quick gate bias changes, which give the additional
benefit of much easier control compared to temperature. The increase in
response at a positive gate bias is consistent with the expected increased
catalytic activity due to the removal of lithium cations from the catalytic
sites (Katsaounis, 2010). However, lithium-doped tungsten oxide as a mixed
conductor has additional effects compared to classical EPOC catalysts, which
are pure ionic conductors. The most important difference is that the
electron density in tungsten oxide is increased by lithium doping as well
(Niklasson and Granqvist, 2007). In the surface state trapping model this
leads to an increase in surface oxygen (Ding et al., 2001). This increase in
oxygen coverage is presumably the reason for the higher sensitivity of the
doped sensors.
A second pair of sensors from a second production batch was tested with
similar and different concentrations and gate biases to verify the doping
effect. The results are shown in Figs. S3 and S4 in the Supplement.
Conclusions
Pulsed laser deposition parameters have been successfully optimized to
deposit dense WO3 films on top of SiC-FET devices. The distribution and
orientation of crystalline phases can be adjusted by heat treatment during
the deposition. In situ annealing leads to a more ordered and stable
structure with a comparably high amount of the ε phase. This ordered
layer was deposited as the top-most layer of the dielectric stack of a
SiC-FET and the effect of Li doping of this layer on the sensor response was
studied. The sensor with a doped layer exhibits strong relaxation processes
for GBCO with time constants of the order of 10 s. This effect,
presumably caused by electrochemical polarization, can be utilized to boost
the effect of GBCO as demonstrated by ammonia tests. While the response for
the undoped layer is almost independent of the gate bias, it increases for
the doped layer up to 5-fold between 0 and +2 V gate bias.
Additionally, the doped layer shows increased sensitivity at +2 V gate
bias. We could demonstrate that ionic polarization has a large impact on the
sensor characteristics and that it can be utilized to boost the sensor's
sensitivity. Furthermore, the ionic polarization increases the impact of
gate bias variation on the sensor signal. Therefore, we expect that this
method can result in enhanced performance of GBCO and, consequently,
selectivity.
Data availability
Research data are available upon request to the authors.
The supplement related to this article is available online at: https://doi.org/10.5194/jsss-8-261-2019-supplement.
Author contributions
MR, MB, TS, and MA planned the measurements. JH carried out the Raman
measurements and evaluation and supervised the PLD process. MR carried out
all other measurements and did most of the evaluation. JP performed the XRD
data evaluation. MR, MB, and TS prepared a concept of the manuscript. MR
wrote the manuscript. MB, TS, JL, MA, and AS contributed with substantial
revisions.
Competing interests
The authors declare that they have no conflict of interest.
Acknowledgements
The authors want to thank the technical support of the Center of Microscopy and Nanotechnology of the University of Oulu.
We acknowledge the support by the European Cooperation in Science and Technology (within COST Action TD1105-EuNetAir) and by the Deutsche Forschungsgemeinschaft (DFG, German Research Foundation) within the Open Access Publishing funding programme.
Financial support
We have received support for scientific exchange from the European Cooperation in Science and Technology and support for Open Access Publishing from the Deutsche Forschungsgemeinschaft and Saarland University.
Review statement
This paper was edited by Albert Romano-Rodriguez and reviewed by two anonymous referees.
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