Journal of Materials Science: Materials in Electronics (2018) 29:6129–6148

https://doi.org/10.1007/s10854-018-8606-2

REVIEW

Capacitive gas and vapor sensors using nanomaterials

P. Bindra1 · A. Hazra1 

Received: 18 October 2017 / Accepted: 14 January 2018 / Published online: 29 January 2018
© Springer Science+Business Media, LLC, part of Springer Nature 2018

Abstract
An immense number of sensors has been reported in the literature employing various methods for the detection of different
gases and vapors. This article summarizes those sensors whose sensing layer is made up of nanostructured materials and a
change in capacitance value of device is the key parameter for detecting a gas or vapor. Now-a-days, capacitive sensors are
emerging as they consume less power, operate well at room temperature and show decent response and recovery time. The
sensing principles, configurations, mechanisms and performances of capacitive sensors based on different nanostructures are
summarized and discussed in the current article. Emerging carbon based nanomaterials like carbon nanotube and graphene
are also highlighted for capacitive mode detection of gases and vapors. Finally, an outlook of primary challenges in this field
are identified and discussed at the end of the review.

1 Introduction transfer of charges between sensing layer and contact elec-

The growing awareness of environmental problems has
accelerated the research and development in gas and vapor
sensing field and thus many high performing gas and vapor
detection techniques have been developed [1]. Essentially,
a gas/vapor sensor has an element that converts amount of
adsorbed gas/vapor into an electronic signal. These sen-
sors have different categories including resistive type that
tracks change in resistance [2] of sensing layer, capacitive
type that monitors change in dielectric property of sensing
layer [3–5] and mechanical type that detects change in mass
of sensor [6, 7] etc. Among these, capacitive sensors have
gained a great interest owing to their unique properties like
less temperature dependency that offers thermal stability [8],
linear response and low power requirement [9]. The general
structure of capacitive sensor includes two electrodes and
a dielectric layer sandwiched in between them. Electrodes
of capacitive sensors can have two type of geometries: (i)
two parallel plate electrodes and (ii) interdigital electrodes
(IDE) [10, 11].
Capacitive gas/vapor sensors have also specific advan-
tages over resistive devices. Resistive sensors rely on the
* A. Hazra
arnabhazra2013@gmail.com
1
Department of Electrical and Electronics Engineering, Birla
Institute of Technology and Science (BITS)-Pilani, Vidya
Vihar, Pilani, Rajasthan 333031, India
trodes that is susceptible to flicker (1/f) noise and incomplete
recovery of charges [12]. However, detection mechanism
in a capacitive sensor is principally dominated by tracking
change in dielectric property of sensing layer and does not
involve any transportation of charges. Thus, it provides more
sensitivity and reliability for chemical detection [13]. Also,
capacitive sensors consume no static power and thus are very
much in demand in energy constrained environment [14].
Also, in past few decades, there has been growing inter-
est in fabricating gas and vapor sensors using different
nanomaterials like metal oxide nanostructures [15], carbon
nanotubes [16], organic/inorganic composite materials [17,
18], polymers [19] etc. Nanomaterials offer large effective
surface area [20], high quality crystal lattice [21], high car-
rier mobility [22] etc. Sensors incorporating nanomaterials
significantly improve the thermal and chemical stability, sen-
sitivity and selectivity performance [23–25]. Different nano-
materials like ZnO nanorods [26], carbon nanotubes (CNT)
[27], ­TiO2 nanotubes [28], silicon nanowires (Si-NW) [29],
Silicon nanopillar arrays (Si-NPA) [30], Cu-BTC nanopar-
ticles [31], ­SnO2 nanofibers [32] etc. were used as sensing
material in capacitive sensors. However, miniaturization
in nanometers regime exhibited many technical challenges
where reliable and consistent fabrication of nanostructured
materials are difficult [33].
Capacitive sensors were demonstrated to sense many
gases like H­ 2, ­O2, ­NH3, ­NO2 [34–40], ­NH3, volatile organic
compounds (VOCs) like ethanol, methanol, formic acid

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Vol.:(0123456789)

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etc. [11, 12, 41] and relative humidity (RH) [30]. Since, the
review is about sensing of both gases and vapors, a brief
difference between these two terms is important to mention
here. Critical temperature, ­Tc, is defined as the tempera-
ture above which a gas can’t be liquefied by applying pres-
sure and this temperature is generally used to differentiate
between a gas and a vapor. In general, gas is a state of matter
that has a single and stable thermodynamic state crossing
its critical temperature [42]. As the critical temperature of
­H2 and O ­ 2 is much lower than room temperature, they are
considered as pure gases at room temperature. However, the
term “vapor” is used to describe a state of substance which
has not crossed its critical temperature yet and its gaseous
phase is in equilibrium with its liquid phase [42]. As an
example, critical temperature of water is much higher than
room temperature and thus water molecules in gaseous state
at room temperature is known as vapor. Also, RH is defined
as the ratio of actual vapor pressure to the saturated vapor
pressure at a given temperature and usually denoted in terms
of percentage [43].
This review article discusses the current status of capaci-
tive gas and vapor sensors employing various nanomaterials.
Firstly, the basic device structures and sensing mechanisms
of capacitive sensors are described and then an overview of
different nanomaterials for capacitive sensor is presented.
Various performance parameters of sensor devices are criti-
cally analysed for each nanomaterial considering the tech-
nological advancement, limitations and future prospects. At
the end of the review, a comparative sensing performance of
multiple capacitive sensors in tabular form is represented to
get an overview of their strengths and weaknesses.
Fig. 1  Basic device structure for capacitive sensing: a MOS structure, b MOM structure
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2 Device structures and working principle
of capacitive sensors
In gas and vapor sensor devices, some of its intrinsic proper-
ties vary as a function of concentration of gas and vapor. For
capacitive sensors, capacitance value of the device changes
in the exposure of different gases and vapors [35]. Capaci-
tive sensor offers simple structure with high reliability, low
fabrication cost and better selectivity [44–47].
Two types of device structures i.e. metal–oxide–semicon-
ductor (MOS) and metal–oxide–metal (MOM) were reported
mostly for capacitive mode gas/vapor sensing [27–30].
Figure 1a, b shows the schematic of both MOS and MOM
structure respectively. In general, capacitive mode sensors
follow the formula of parallel plate capacitance as expressed
in Eq. 1 [46]:
𝜀 0 𝜀r
C= A (1)
d
where, ε0 = 8.8541878176 × 10−12 F/m is the vacuum permit-
tivity, εr is the relative permittivity of the dielectric layer, A
is the plate area, and d is the distance between two paral-
lel plates that can be treated as thickness of the dielectric
layer [46]. For capacitive sensing, target gas and vapor must
induce any variation in εr, A, or d value of the sensor. Capac-
itance of a sensor device principally increases or decreases
depending on the dielectric properties of sensing layer and
target vapor. Humidity is omnipresent in the atmosphere and
can severely affects the capacitive sensor performance in
terms of sensitivity, response and recovery time. In general,
dielectric constant of water and dry air at room temperature
Journal of Materials Science: Materials in Electronics (2018) 29:6129–6148 6131
are 80 and 1 respectively [48] and it is observed that die-
lectric constant of the sensing layer increases as moisture/
humidity level increases for any operating frequency.
Major dependency on the dielectric property of the target
vapors make the capacitive device more selective towards
particular target species [49]. Apart from dielectric property
of target vapor, structural properties of the sensing layer also
play a significant role. As the effective surface area or sur-
face to volume ratio (SVR) increases towards lower dimen-
sions, capacitive sensing improves significantly in case of
nanostructured materials. Porous nanostructures offer large
free space which enhances the accumulation possibility
of target vapor on the sensing layer surface enhancing the
capacitive response of the sensor device [50]. Thus, nano-
structured materials like nanotubes, nanowires, nanorods,
nanopillar arrays, nanoparticles etc. were reported as the
promising sensing layer in capacitive mode sensor devices
[15, 19, 26]. The impact of these nanostructures in capaci-
tive mode sensing is discussed in Sect. 3.
Sensing mechanism of capacitive sensors can be
explained with two different approaches i.e. (i) ‘pure capaci-
tive approach’ where only change of device capacitance is
considered in the exposure of different gases and vapors; and
(ii) ‘impedance analysis approach’ where both resistive and
capacitive changes are considered in presence of gases and
vapors in form of an equivalent circuit model.
2.1 Pure capacitive approach
In MOS sensor structure, device capacitance may change
due to the physisorption/chemisorption of gas/vapor mol-
ecules at metal interface and thus changing the work func-
tion of metal plate. So, the flat band voltage of the device
may change which alters the thickness of depletion layer in
semiconductor from oxide–semiconductor interface. Thus,
capacitance of device changes which can be observed from
the capacitance–voltage (C–V) plot. Figure 2 shows a C–V
plot for Ni/SiO2/Si, MOS sensor device towards ­H2 concen-
tration from 50 to 1000 ppm [51].
Usually, noble metals are preferred for the metal plates
to avoid any oxidation possibility at the metal surface. Pd,
Pt and Au are the most commonly used top metals as these
metals can adsorb gases like H ­ 2, ­NO x, ­S O x, ­C H 4, ­S iH 4
etc. [52–54]. Also, due to the catalytic property of metal
atoms, gas molecules get easily dissociate into atoms.
These atoms get dissolved into the noble metal surface
and become polarized to form a dipole layer which results
in the shift of flat band voltage of the MOS device. For
the detection of ­H2, Pt and Pd are the two most commonly
used metal plates. However, Pd is used more often for
detecting ­H2 at low concentration and Pt at high concen-
tration [52].
Fig. 2  C–V plot of Ni/SiO2/Si device for ­H2 detection. Reproduced
from Ref. [51] with permission from Elsevier
Conventionally, MOS capacitance is considered as the
series combination of oxide capacitance ­(Cox) and deple-
tion capacitance ­( C d). ­C ox principally depends on the
dielectric property of the sensing layer (oxide layer) that
can be modulated in presence of target gas/vapor (Eq. 1).
Depletion capacitance ­( C d) can be represented in Eq. 2
as a function of surface potential (ΨS) that may also be
modulated by the metal work function in the exposure of
target gas/vapor [55].
√
𝜀 0 𝜀s q𝜀0 𝜀s ND
Cd = A= A (2)
W 2𝜓S
where W is the depletion width and N ­ D is the doping density
of semiconductor layer.
Another Ni/SiO2/Si MOS structure was reported in ref-
erence [56] for capacitive mode detection of H ­ 2 as shown
in Fig. 3. Detection range was 50–1000 ppm of ­H2 mixed
with ­N 2 (as a carrier gas) at 140  °C and 100  kHz fre-
quency [56]. However, sensor response was decreased with
increase in oxide thickness as the trap state density reduces
with increase in oxide thickness. Since, most of the trap
states present only in the surface of S ­ iO2 and bulk trap
density decreases from S ­ iO2 surface to bulk. So, increase
of oxide thickness has less contribution in providing trap
states [56].
In MOM sensor structures, oxide layer is directly
responsible for the capacitive changes. In presence of tar-
get gas/vapor, dielectric property of the sensing layer var-
ies changing the overall device capacitance. In one mech-
anism, high dielectric (greater than dry air) vapors are
incorporated in the free space (pore region) of the sensing
layer, adsorbed to sensing layer surface and enhance the
dielectric value of the medium between two electrodes.
In another mechanism, vertical filed applied between two
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Fig. 3  Ni/SiO2/Si MOS structure for capacitive mode H
­ 2 detection.
Reproduced from Ref. [56] with permission from Elsevier
electrodes are varied because of horizontal filed originated
by the surface adsorption and desorption of the gas and
vapor molecules and overall device capacitance changes.
Thus, nanostructured materials offer high effective surface
area, gas/vapor incorporation possibility and horizontal
field effect which extensively enhances the potential of
capacitive sensing.
To make capacitive sensors more sensitive towards
the target gas/vapor, digitized metal electrode can also be
employed at the top of MOM structure as shown in Fig. 4.
Capacitive sensors based on digitized metal electrode exhibit
high sensitivity as vapor/gas gets extra surface area for the
interaction with sensing layer [11, 57]. Though the digitized
electrode structure is complicated to design but could offer
significant improvement in capacitive sensing especially for
the nanoporous sensing layer [53].
Fig. 4  Capacitive sensor with digitized top metal electrode
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2.2 Impedance analysis approach
To understand the mechanism involved in capacitive gas/
vapor sensor, the knowledge of physics of dielectric mate-
rial is essential. This section of article overviews the gen-
eral mechanism of capacitive sensor correlated with sensor
structure, equivalent electrical circuit model and impedance
analysis. Relative permittivity of a material has a complex
value having real part (εre) due to dielectric permittivity and
imaginary part (εim) due to dielectric loss and is given by
Eq. (3a) and (3b) [56].
ε = εre + jεim (3a)
𝜎
= εre + j (3b)
𝜔ε0
√
where j = −1 , σ is conductance of the material, ω is
angular frequency of signal, and ε0 is dielectric permittiv-
ity of vacuum. Dielectric loss measures electrical energy
loss in dielectric medium when an alternating electric field
is applied. Since capacitive sensor generally measures the
change in dielectric constant value for sensing purpose thus
impedance analysis technique is usually adapted to measure
the real and imaginary components of dielectric constant at
various frequencies [56, 58]. Device impedance can be rep-
resented by a series or parallel combination of capacitance
and resistance and the equivalent circuit (Fig. 5a) can be
modeled by measuring the frequency response of the device.
Cole–cole plot in Fig. 5b helps in determining the discrete
values of resistance and capacitance [22]. In most of the
capacitive sensor, a semicircle plot of impedance exists as
shown in Fig. 5b and it can be interpreted as an electrical
circuit shown in Fig. 5a.
In Fig. 5a, ­R1 is the contact resistance between sens-
ing layer and electrode, R­ 2 represents resistance of sensing
layer and ­C1 represents capacitance of sensing layer. At low
Journal of Materials Science: Materials in Electronics (2018) 29:6129–6148 6133
Fig. 5  a Equivalent electrical circuit model and b corresponding cole–cole plot of the equivalent circuit
frequency, ω→0 and thus reactance part tends to infinity.
Thus, capacitor branch of the circuit behaves as an open
circuit and the net impedance of device become maximum
­(R1 + R2) which is plotted at ω = 0 i.e. the right most inter-
cept of impedance value on x-axis. At very high frequency,
ω→∞ and thus reactance part tends to zero and capacitor
branch behaves as short circuit. Thus, the net impedance
of device become minimum ­(R1) which is plotted at ω = ∞
i.e. the left most intercept of impedance value on x-axis. To
measure the capacitance of device (C), the relation ωr = 1/
R2C is used where ωr is that value of angular frequency
where magnitude of imaginary impedance is maximum
[59]. In some other reports, this semicircle is connected with
another line or semicircle which represents addition of other
electrical components in equivalent circuit [60]. To under-
stand this concept more precisely, complex impedance plots
for ­ZrO2 nanoparticles under various RH levels have been
represented in Fig. 6 and its mechanism can be explained by
using concepts of interfacial space charge polarization [61].
Impedance plots in Fig. 6a–e envisage that when RH level
is less, only one semicircle is observed on the cole–cole
plot and as RH level increases, this semicircle starts getting
smaller and in addition to that a liner response of imped-
ance with frequency is observed. At low RH, conduction
process is principally governed by electrons injected from
sensing layer and charged carriers due to H­ 3O+ ions [61]. As
RH level increases, more water gets adsorbed to the sens-
ing layer surface which decreases the resistance of sensing
layer ­(R2) and hence lowering the diameter of semicircle.
At the same time, increased RH level in the void regions of
sensing layer enhances the sensor capacitance (C). Incre-
ment in adsorbed water hydrated ­H3O+ ions and thus a large
amount of ­H+ ions are available for the conduction. These
ions dominate the conduction process over injected electrons
and hence another semicircle gets appear in cole–cole plot
as shown in in Fig. 6b–e [22, 54, 61].
3 Nanostructured materials in capacitive
sensing
Nanostructured materials are widely used in capacitive gas
and vapor sensor devices [29, 61–79]. Nanomaterials offer
(i) very high surface to volume ratio (SVR) and (ii) free
porous region in it. High SVR accelerate the physisorption/
chemisorption process that helps to accumulate gas/vapor
molecules inside the nanomaterial. This phenomenon also
changes the dielectric property of free space inside the nano-
material which alters the device capacitance significantly.
Potentiality of different nanomaterials in capacitive gas/
vapor sensing is represented in this section.
3.1 Nanopillar arrays
Nanopillar array (NPA) has a unique hierarchical structure
which is suitable for capacitive sensor devices as shown
in Fig. 7 [62]. Due to the array like structure, vapors can
easily enter and exit through valleys and device can offer
improvised response and recovery time [59]. In this nano-
structure, valley is formed around nano pillars which are
well connected to each other and make a channel network.
Thus, transport of gas/vapor molecules become faster lead-
ing towards higher adsorption and desorption of target gas/
vapor molecules [59]. Silicon NPA is one of the most popu-
lar nanostructure because of its porous and spongy structure
that makes it more suitable for capacitive type gas/vapor
sensor [63].
X.J. Li et al. reported Si-NPA based capacitive sensor
devices where Si-NPA was used as the dielectric layer over
p-Si substrate with comb like Al as top electrode and Al
layer as bottom electrode as shown in Fig. 8a [50]. Sen-
sor was used for ethanol vapor detection at room tem-
perature in capacitive mode. Capacitance as a function of
ethanol concentration is represented in Fig. 8b showing the
monotonic increment of device capacitance with ethanol
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Fig. 6  Complex impedance plots for various relative humidity (RH) levels for ­ZrO2 nanoparticle based sensor. Reproduced from Ref. [61] with
permission from Elsevier
concentration (0–500 pm). Proposed mechanism suggested
that the change of dielectric value was responsible for the
capacitive response. However, ethanol molecules can inter-
act with dielectric layer in two ways (i) chemisorption and
(ii) physisorption where chemisorption requires high energy
to overcome the adsorption activation energy. As the experi-
ments were performed at room temperature, possibility of
chemisorption was limited because of insufficient thermal
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Journal of Materials Science: Materials in Electronics (2018) 29:6129–6148
energy. Thus, physisorption of ethanol vapors in the voids
and pore walls of Si-NPA might be the dominant factor for
the change of dielectric value as well as the sensor response
[50].
However, Si-NPA alone is seldom used in gas/vapor
sensor because of it gets oxidized easily in the presence
of air and humidity and hence offers poor device stability
[64]. Therefore, various layers of different materials were
Journal of Materials Science: Materials in Electronics (2018) 29:6129–6148 6135

deposited over Si-NPA for better response and stability. But,

Fig. 7  Field emission scanning electron micrograph (FESEM) of Sili-
con Nanopillar arrays (Si-NPA). Reproduced from Ref. [62] with per-
mission from Elsevier
faster response and recovery time offered by Si-NPA sensor
was somehow sacrificed.
In one approach, S­ nO2:Sn composite was deposited on Si-
NPA (Fig. 9a) using vapor-liquid-solid (VLS) technique for
capacitive mode humidity sensing at room temperature [65].
Use of ­SnO2: Sn composite on Si-NPA offered response/
recovery time of 20/20 s at 1 kHz (Fig. 10a) that was compa-
rable with response/recovery time of Si-NPA only (5/15 s).
Unique surface morphology of ­SnO2: Sn/Si-NPA provided
higher surface area and the valleys surrounding by the pillars
offered easy transportation of vapors inside the nanostruc-
ture. Therefore, adsorption and desorption rate of vapor get
increased which leads to faster response and recovery time
[65–67].
In an another structure, nanowire silicon carbide (NW-
SiC) was deposited on Si-NPA through chemical vapor dep-
osition (Fig. 9b) for analyzing capacitive humidity response
[68]. NW-SiC as a dielectric material introduced high ther-
mal and chemical stability, large surface area and high aspect
ratio [68–72] that makes the sensor suitable for use in harsh

Fig. 8  a Schematic of capacitive sensor devices by using Silicon nanopillar array (Si-NPA) and b capacitance as a function of ethanol concentra-
tion. Reproduced from Ref. [50] with permission from Elsevier

Fig. 9  FESEM images of other material decorated Si-NPA: a ­SnO2:Sn/Si-NPA [65], b nanowires silicon carbide (NW-SiC)/Si-NPA [68], c ZnO
cauliflowers decorated Si-NPA (ZnO/Si-NPA) [59]. Reproduced from Ref. [59, 65, 68] with permission from Elsevier

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Fig. 10  Repeated cycle characteristics of a ­SnO2: Sn/Si-NPA [65], b NW-SiC/Si-NPA [68], c ZnO/Si-NPA [59] based capacitive sensor. Repro-
duced from Ref. [59, 65, 68] with permission from Elsevier

chemical conditions and at high operating temperature.

This type of structure also showed highly stable capacitive
response towards humidity with insignificant response varia-
tion of 0.7 and 0.9% for 6 and 12 months, respectively. At the
same time, NW-SiC/Si-NPA based humidity sensor offered
moderate response/recovery time of 105/85 s as shown in
repeated cycle characteristics in Fig. 10b [68].
Response and recovery time were improved significantly
in ZnO cauliflowers decorated Si-NPA based capacitive
mode humidity sensor where ZnO cauliflowers were depos-
ited by CVD method on Si-NPA as shown in Fig. 9c [59].
Response/recovery time was recorded for ZnO/Si-NPA [59]
as 20/3 s (Fig. 10c) which showed better performance than
other nanostructures involving ZnO like ZnO nanotetrapads
(36/17 s) [73], ZnO colloidal nanocrystal (50/6 s) [74] and
ZnO naorods (5/10 s) [75] etc. However, ZnO/Si-NPA struc-
ture was suffered from instability issue as there was a varia-
tion of 3.78% in response of capacitive sensor after 50 days
of storage in ambient air having RH of 11.35% [59].

3.2 Nanowires

Nanowires are one of the important nanostructure, reported

largely for capacitive mode gas/vapor sensing [76]. Si
nanowire (SiNW) and SiNW coated by other materials were
reported mostly for capacitive mode detection [29, 76–79].
Top and sectional view of SiNW are shown in Fig. 11a, b,
respectively.
SiNW offers few specific advantages like high surface to
volume ratio, good wettability and chemisorption proper-
ties [8]. Also, well established growth techniques, biocom-
patibility and controllable physical and electrical proper-
ties make SiNW suitable for efficient capacitive sensing
[79]. High density and doped SiNW were also used for
enhancing the sensitivity of capacitive sensors. For various
RH values, capacitance (C) of sensor was measured and
it was found that C increased monotonically with RH for
high density SiNW sensor [68]. For doped SiNW sensor,
Fig. 11  FE-SEM image of Silicon Nanowires (SiNWs): a top view,
b sectional view. Reproduced from Ref. [76] with permission from
Elsevier
C was increased non-linearly showing the capacitive sen-
sitivity of 20.88% at RH level of 45 and 54.20% at RH
level of 95%. On the other hand, sensor response time
was increased from low density SiNW (~ 150 s) to high
density SiNW (300 s) and get further increased for doped
SiNW (1500 s) [8].
SiNW surface is hydrophilic in nature due to the presence
of hydroxyl group (Si–OH) at SiNW interface which dete-
riorates the performance of sensor. Therefore, in one of the

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Journal of Materials Science: Materials in Electronics (2018) 29:6129–6148 6137
approach, Hexamethyldisilazane (HMDS) was coated over
the surface of SiNW which made the surface hydrophobic
due to the termination of methyl group from HMDS mon-
olayer that improves the adsorption/desorption rate of sen-
sor [78]. Schematic of HMDS coated SiNW based humidity
sensor device with digitized top metal electrode is shown in
Fig. 12 [78].
Figure 13a–c shows FESEM images of modified struc-
tures of SiNW viz, (a) HMDS modified SiNW [78], (b) Ni/
SiNW nanocomposites [76] and (c) nanorods on SiNW [67].
Morphological properties of SiNW were changed by these
modification methods enhancing the sensor performance
towards humidity. Nickel coated SiNW or Ni/SiNWs nao-
composites (Fig. 13b) humidity sensor exhibited high sen-
sitivity and fast response compared to simple SiNW. Due to
Ni coating, distance between SiNWs was decreased effec-
tively and capacitance of sensor increased [76]. Due to the
annealing, Ni ions were started to diffuse on the surface of
Fig. 12  Schematic diagram of HMDS coated SiNW humidity sensor.
Reproduced from Ref. [78] with permission from Elsevier
Fig. 13  FE-SEM of surface modified SiNW: a Hexamethyldisilazane (HMDS) coated SiNW [78]: b Ni/SiNW nanocomposites [76] and c ZnO
nanorods on SiNW [67]. Reproduced from Ref. [67, 76, 78] with permission from Elsevier
SiNW and ­SiNix phases were formed on surface. Therefore,
the surface become rough and more adsorption of vapors
occurred [76].
ZnO nanorod/SiNW nanocomposites (Fig. 13c) were
also synthesized for efficient capacitive mode humidity
sensing where maximum capacitance change was recorded
from 2.4 to 64.4 nF for the RH level change of 11.30 to
97.69% respectively [67]. One of the key advantage of ZnO
modification over SiNW was that it offered large number
of hydroxyl groups which increased the adsorption rate of
water vapors on the sensor surface. Response/recovery time
of 26/7 s for ZnO/SiNW nanocomposites was found to be
the best figures in comparison of other nanowire structures
reviewed in this study [64, 75, 78].
3.3 Nanorods
Zinc oxide (ZnO) nanorods (NR) are frequently used in
capacitive mode gas/vapor detection because of its high ther-
mal stability and well established growth technique [80, 81].
Usually, ZnO nanorods (Fig. 14a, b) has been synthesized by
chemical bath deposition (CBD) method [80, 81].
ZnO nanorods were grown on ITO coated glass substrate
by CBD method and sandwich device was developed by
using two squared Ag electrodes as shown in Fig. 15a [79].
Growth mechanism of ZnO–NR was also studied and it was
found that diameter of NR increased from 200 to 250 nm as
seed layer thickness increased from 50 to 200 nm. Device
having the lowest density of ZnO NRs showed maximum
capacitive response [79].
A device having less density of NRs offers maximum
free space that can be filled with air initially and hence water
molecules (for humidity sensing) can replace the air and thus
change in the capacitance value would be more. In case of
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6138
Fig. 14  FE-SEM image of ZnO naorod by CBD method a surface view, b cross sectional view. Reproduced from Ref. [80] with permission from
Elsevier
Fig. 15  a Schematic drawing of
ZnO nanorods based capaci-
tive sensor devices, b transient
response of the sensor at dif-
ferent RHs. Reproduced from
Ref. [79] with permission from
Elsevier
high density of NRs, most of the space is filled by NRs having
dielectric constant value higher than air but less than water
molecules. So, the baseline capacitance of device having high
density NRs becomes more than the device having less density
of NRs. Thus, the net change of capacitance (∆C) in presence
of water molecules become less in case of high density NRs
because of unavailability of sufficient free space to occupy.
Hence, sensitivity (∆C/C) must be sacrificed in case of high
density NRs. Figure 15b shows the linear increment of sensi-
tivity with increase of RH level for ZnO NRs based capacitive
sensor [81].
Xiaoyan et al. [81] fabricated ZnO nanorods by hydro-
thermal synthesis where Ag paste was used as the electrodes
material. Sensor showed a maximum capacitance change
(∆C/C) of 122% towards 20 ppm ethanol. Furthermore, sen-
sor capacitance was increased with ethanol concentration at
low frequency (below 1 kHz) but no significant change was
observed at high frequency (above 1 kHz) as shown in Fig. 16.
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Journal of Materials Science: Materials in Electronics (2018) 29:6129–6148
The increment of sensor capacitance with ethanol concentra-
tion can be explained by Eq. 4 [81].
)1
(
n 2
(4)
C∝
Vb
where C represents capacitance, n is electron concentra-
tion and V
­ b is barrier potential. Since, fabricated ZnO NRs
were n-type in nature due to native defects, its surface got
depleted in presence of air as oxygen molecules capture free
electrons from the surface. Thus, n value decreased and ­Vb
increased which results in the decrement of device capaci-
tance in presence of air. When reductive ethanol vapor came
in contact of ZnO NR surface, it reduced oxygen molecules
from surface which resulted in the releasing of trapped
electrons and hence n value increased. Since, this process
reduced the depletion width and hence potential barrier, V­ b,
across grain–grain contact also reduced. Thus, according to
Journal of Materials Science: Materials in Electronics (2018) 29:6129–6148 6139
Fig. 16  Capacitance of the ZnO nanorod as a function of ethanol
vapor concentration at different frequencies. Reproduced from Ref.
[81] with permission from Elsevier
Eq. 4, C value increased with increase in ethanol concen-
tration because of increment in n and decrement in ­Vb. No
significant increment of capacitances was observed at higher
ethanol concentration at higher frequency because of insuffi-
cient settling time of polarization of adsorbed vapor [82]. At
high frequency, it became difficult for charges to change the
direction with electric field and thus polarization remained
constant offering almost constant capacitance value [61, 82].
3.4 Nanoparticles, nanofibers and nanotubes
Other nanostructures like nanoparticles [14], nanofibers
[82], nanotubes [83] etc. provide high porosity and high
effective surface area and consequently used in capacitive
mode detection of volatile organic compounds (VOCs) like
methanol, ethanol, isopropanol, acetone, benzene- toluene-
xylene (BTX) etc.
Copper-benzene tricarboxylate ­[Cu 3(BTC) 2], one of
the most studied metal organic frameworks (MOFs) was
reported for capacitive mode humidity sensor [84, 85].
Cu-BTC is non-toxic in nature having regular pores with
material specific adsorption characteristics [84]. Cu-BTC
nanoparticles (Fig. 17a) based sensors were fabricated using
drop casting technique and nanoparticles were sandwiched
between two metallic electrodes: copper as a back electrode
and silver as an upper electrode as shown in Fig. 18a. Capac-
itive change (∆C) towards different VOCs like methanol,
ethanol, isopropanol and acetone was tested below 20% RH
condition where individual VOC concentration was varied
from 250 to 1500 ppm as shown in Fig. 18b. Order of capac-
itive sensitivity decreased from methanol, ethanol, isopro-
panol and acetone [85]. Porous ­TiO2 based capacitive type
humidity sensor was also reported where porous T ­ iO2 was
prepared by using sol–gel template process [86]. Sensor was
suitable to sense humidity level greater than 33% at 100 Hz
with relatively faster response and recovery time of 5 and
8 s, respectively.
SnO2 nanofibers provide rough porous structure in the
fiber network where transfer of sensing mass is faster due to
the one dimensional (1-D) nanostructure [32, 82]. To further
improve the performance of S ­ nO2 based humidity sensor in
terms of sensitivity, KCl doped ­SnO2 nanofibers based sen-
sor (Fig. 17b) was used to get extra sites for adsorbing water
molecules. KCl (source of alkali ions) was doped with ­SnO2
nanofibers using electrospinning technique [82, 87] and then
it was mixed with DI water to form a paste. This paste was
put on a ceramic substrate using screen printing method and
Ag-Pd electrodes were used for the contacts. Impedance of
the sensor was decreased from ­108 to 1­ 03 Ω when RH level
was increased from 11 to 95% at 100 Hz [82].
Anodically grown ­TiO2 nanotubes array (Fig. 17c, d) was
reported for the capacitive mode detection of benzene, tolu-
ene and xylene (BTX) sensing [83]. Capacitive structure
was developed by considering Ti substrate (or Ti foil) as the
bottom electrode and physically deposited Ti metal as the
top electrode [83]. A physical modeling was also developed
by the authors to calculate surface to volume ratio (SVR) of
nanotube and capacitive response magnitude of the sensor
and it was found that the SVR was independent of nano-
tube’s length. Equivalent circuit model shown in Fig. 19 was
constructed with two capacitances; one originated from air/
VOC in the free space of nanotube (i.e. pore and void region)
and another originated from the ­TiO2 solid. These sensors
were used to detect BTX i.e. benzene, toluene and xylene
and showed response magnitude of 14.33, 9.86 and 8.93%
at 150 °C, respectively [83].
4 Carbon based nanomaterials
for capacitive sensing
Carbon nanomaterials are promising materials to be
used as sensing layer in gas/vapor sensor devices as they
exhibit outstanding electrical, thermal and chemical prop-
erties [88–91]. But, one of the most exclusive property
of carbon nanomaterials which make them competitive in
the sensing material community is their high activation
energy. Carbon nanotubes and graphene are the two most
extensively used carbon based nanomaterials in gas/vapor
sensing applications [92, 93] and are discussed in detail
in this section.
13

6140 Journal of Materials Science: Materials in Electronics (2018) 29:6129–6148

Fig. 17  FE-SEM image of a nanoparticle Cu-BTC layer [31], b KCl-doped ­SnO2 nanofibers [82], c top view of ­TiO2 nanotubes [28], d side view
of ­TiO2 nanotubes [29]. Reproduced from Ref. [28] with permission from IEEE and from Ref. [31, 82] with permission from Elsevier

Fig. 18  a Schematic of Cu-BTC based capacitive sensor, b transient characteristics of Cu-BTC sensor for methanol, ethanol, isopropanol and
acetone (RH below 20%). Reproduced from Ref. [31] with permission from Elsevier

13
Journal of Materials Science: Materials in Electronics (2018) 29:6129–6148 6141
Fig. 19  Equivalent circuit model of T­ iO2 nanotube based capacitive
sensor for VOCs detection; εr(vap): dielectric value of vapor and εr(nt):
dielectric value of nanotubes. Reproduced from Ref. [83] with per-
mission from Elsevier
4.1 Graphene
Graphene is an allotrope of carbon having a two-dimensional
monolayer of ­sp2-bonded carbon atoms exhibiting high
chemical stability, good thermal conductivity, ballistic trans-
port, large surface area and hollow geometry which increase
the adsorption of gas/vapor [94]. Sensors using graphene as
sensing material with high sensitivity were reported for vari-
ous gases including O ­ 2, ­SO2, ­CO2, ­N2O, NO, N
­ O2, ­NH3 etc.
[93, 95]. Functional chemical groups used in vapor sensing
applications can be divided into two groups i.e. hydrophilic
(tendency to mix with water) and hydrophobic (incapable
to mix with water). Gas sensor having hydrophilic group as
Fig. 20  Humidity sensing mechanism at graphene oxide films. Reproduced from Ref. [96] with permission from Nature
sensing material is used to detect acidic, basic and water/
humidity environment whereas hydrophobic group is used
to detect volatile organic compounds [48]. Graphene oxide
(G-O) film has better hydrophilic property due to the pres-
ence of oxygen containing functional group on its surface
and larger interlayer space which increase the adsorption and
desorption of water molecules [96]. Thus, G-O film is used
widely for sensing humidity, also in capacitive mode with
high sensitivity, fast response and recovery, small humidity
hysteresis and larger stability [97].
In reference [96], in-plane capacitor having G-O films
as sensing layer and two sets of interdigital electrodes
were fabricated. Capacitance of sensor increased mono-
tonically with increase of RH. The effect of frequency on
capacitance was also examined and it was observed that
capacitance decreased with increase in frequency up to
10  kHz and saturated afterwards. The reason of satura-
tion was explained as polarization of adsorbed water get
enough time to change direction with electric field at lower
frequency but at higher frequency, it become difficult to
change the direction with electric field and thus polariza-
tion remain constant and almost no change in capacitance
was observed [61, 96]. Numerically, relative changes in
capacitance value were 8000, 37,800, 32,200% for 100 Hz,
1 and 10 kHz respectively when RH varied from 15 to 95%.
Thus, graphene oxide showed excellent humidity sensing
behavior due to the presence of various hydrophilic groups
like carboxyl, hydroxyl etc. Fig. 20 shows the schematic of
physisorbed water layers on G-O sensing film. This sche-
matic was used to explain the sensing mechanism which
discusses the dependency of dielectric constant value (and
hence capacitance) on the humidity/moisture content [96].
13

6142
In general, electronic polarization is observed when charges
oscillate or reorient with applied field. At low RH level,
water molecules adsorbed through double H-bonding. Thus,
first layer of water molecules was tightly bound with surface
grains and was not free to reorient with the external electric
field. Hence, less polarization results in less increment in
capacitance value. As RH level increased, second layer of
water molecules adsorbed through single H-bonding on the
hydroxyl group. This second layer of water molecules was
loosely bound and hence become free to reorient with the
external electric field. Thus, polarization and capacitance of
the sensor increased significantly at higher level of RH [96].
4.2 Carbon nanotubes
Carbon nanotubes are members of fullerene structure and is
made up of wrapped graphite sheet in the shape of tube [37].
If only one layer of graphite is rolled into tube, then single
layer tube is formed and is known as single-walled carbon
nanotube (SWCNT) and if more than one layer is rolled, the
result is multi concentric tubes and hence structure is known
as multi-wall carbon nanotube (MWCNT). Single and multi-
walled CNT films demonstrated excellent sensing towards
­H2, ­NH3, ­NO2 and O ­ 2 gases [37]. But one of the problem
of this type of sensors is that individual CNT is difficult to
fabricate and CNT bundle has a long recovery time. Thus,
it is required that CNT should have an ordered structure for
better performance [12].
In reference [12], capacitive sensor having highly ordered
CNT arrays as sensing layer was used to detect ammonia
and formic acid at room temperature. Ordered CNT array
Fig. 21  Capacitive response of CNT sensor towards, a ­NH3 gas, b HCOOH vapour. Reproduced from Ref. [12] with permission from Elsevier
13
Journal of Materials Science: Materials in Electronics (2018) 29:6129–6148
was synthesized in nanopores of the aluminum anodized
oxide (AAO) template by flowing a mixture of 9% acetone
in Ar at a rate of 6 sccm at 750 °C for 1 h. The role of AAO
was to catalyze the reaction of breaking acetone into CNT
arrays. Capacitive response increased as gas concentration
­(NH3 and HCOOH both) increased (Fig. 21). However, it
was found that response and recovery time of N ­ H3 was more
than that of HCOOH and detection limit of N ­ H3 was less
than that of HCOOH (Fig. 21). In the proposed mechanism
of this behavior, the sensor capacitance was modeled as two
parallel plate capacitors, one having CNT arrays as dielectric
material and other has air. The complete circuit constituted
rows of these capacitances in parallel as represented in Eq. 5
[12, 79].
𝜀1 A1 + 𝜀2 A2
C= 𝜀0 (5)
d
where C is the effective capacitance, ε0 is the free space
permittivity, ­A1 is the total area of the plate occupied by
CNTs, ε1 is the dielectric constant of CNT, ε2 is the dielec-
tric constant of air and A­ 2 is the total area of the parallel
plate exposing to air. When a new gas molecule is adsorbed
to the surface of CNT, polarization of absorbate is changed.
Debye equation, as shown in Eq. 6 gives the relationship
between polarizabiltiy and dielectric constant [98].
𝜇2
( )
𝜀 = 1 + 4𝜋N1 𝛼0 + (6)
3kT
where ε is the dielectric constant of gas or vapor, N ­ 1 is the
number of molecules per c­ m3 which is proportional to the
gas concentration, α0 is the intrinsic molecular polarizability,
Journal of Materials Science: Materials in Electronics (2018) 29:6129–6148 6143
µ is the dipole moment, k is the Boltzmann’s constant, and
T is the temperature in Kelvin. Adsorption of gas molecule
primarily depends on the number of active sites available
on sensing layer surface. Responses of ­NH3 and HCOOH
were different because of their different adsorption mecha-
nism [99]. It was found out that value of dipole moment and
polarizability of HCOOH molecules were larger than that
of ­NH3. Thus, HCOOH molecules showed better capacitive
sensing compared to ­NH3.
Yeow et al. demonstrated the use of multi-wall carbon
nanotubes (MWCNTs) as capacitive humidity sensor [48].
The MWCNT based sensors network was formed by ran-
domly aligned porous nano-structure on a stainless steel
substrate. Not only high surface area was provided by the
MWCNT sensing layer but also capillary condensation was
induced offering amplified capacitive response. Capillary
condensation is a process by which water vapor become
condensed into liquid water within pores at a lower humid-
ity level. When water molecules and surface of MWCNT
is confined in a very small volume, due to incremental Van
dar wall forces between them, water vapor condensed into
liquid [100]. Since relative dielectric constant of water is
much higher than that of water vapor and thus capillary con-
densation increases effective dielectric constant of system
even at low RH level [48]. Thus, this approach enables to
fabricate a humidity sensor with high sensing resolution.
Capillary condensation mechanism is valid for any other
nanostructures that significantly enhance the sensing per-
formance of capacitive vapor sensors even at very low vapor
concentration.
5 Comparative sensing performance
of capacitive type sensor devices
Table 1 reviews the performance of gas, VOC and RH sen-
sors which measure capacitance change in the device for
sensing. Sensing layers are mostly nanomaterials which
include SiNWs, CNT, G-O, ZnO NRs, ­TiO2 NTs, Si-NPA,
­SnO2 nanoparticles etc.
Capacitive sensors were reported mostly in humidity
detection as water has a very high value (~ 80) of relative
permittivity [48] which increases the capacitance of the
device to a large value and hence sensitivity of device is
large. Various capacitive sensor has been reported in Table 1
where ZnO cauliflowers on Si-NPA [59] and graphene oxide
[96] showed excellent sensitivity for humidity detection. The
best response time of 5 s for humidity sensing was observed
for porous T­ iO2 based sensor [86] and best recovery time
of 3 s was observed for ZnO cauliflowers on Si-NPA based
sensor [59].
6 Summary and prospects
In this review, the versatile capabilities of capacitive gas
and vapor sensor with different nanomaterials are demon-
strated. To realize the capacitive sensing, possible sensor
structures and their gas/vapor sensitive parameters are dis-
cussed in both (i) pure capacitive mode and (ii) impedance
mode approach. To assess the impact of structural and mor-
phological parameters on capacitive sensing performance
towards different VOCs, gases, relative humidity etc., vari-
ous nanostructures like nanowires, nanopillar arrays, nano-
tubes etc. are reviewed in this article. The sensing mecha-
nism of these type sensors are straightforward and sensitivity
can be tuned by optimally selecting the dielectric material,
frequency, amplitude of applied alternating voltage and
operating temperature.
Capacitive sensors are usually used to sense relative
humidity because of large change in dielectric constant value
in sensor leading to high sensitivity. These type of sensors
are slightly more suitable for selective detection of vapors/
gases. Moreover, these type of devices are simple to fab-
ricate and operate at relatively low temperature and hence
consume low power.
However, despite of all these developments in gases and
VOCs detection by using different nanomaterials, there
are many issues where capacitive type sensors are lagging
behind its counterparts. Capacitive sensors have practically
low selectivity for a number of gases and vapors because
humidity is always present in real time environment that
hinders the performance of capacitive sensors. To over-
come these major issues, few approaches can be employed
by which capacitive type sensor can be improved further.
Nanomaterial based capacitive sensors can be modeled by
an equivalent electrical circuit and the circuit parameters can
be tuned to get the best sensing performance. The selectivity
of capacitive sensor for gases and VOCs can be enhanced
by using porous functionalized nanomaterials. Selectivity
may also improve by choosing a dielectric material which is
sensitive and stable towards a particular gas/vapor molecule.
However, the review exhibits the possibilities to vary multi-
ple parameters of the devices to achieve improvised sensing
performance in nanomaterial based capacitive sensors.
13


Table 1  Comparative sensing performance of nanomaterials-based capacitive sensors for the detection of different gases/volatile organic compounds (VOCs)/relative humidity (RH)
6144

S. no. Sensing layer Other structural Fabrication tech- Sensing gas/vapor Sensitivity formula Sensitivity Response ­timeb Recovery ­timec Ref.
parameters nique

13
a
1 Porous nanocrystal- Pore thickness: – VOCs ∆C = C − C0 0.15 pF (hexane) for – – [1]
line silicon 15 nm 800 ppm
Pore sizes: 5–50 nm 0.1 pF (toulene) for
1000 ppm
2 P doped SiNW Thickness: Vapor–liquid–solid Humidity (∆C/C0) × 100% 54.20% – – [8]
100–150 nm For RH of 95%
3 MWCNT Uniform diameter of Acetone pyrolysis NH3 and HCOOH (∆C/C0) × 100% NH3 100 s for 15 ppm 150 s for 15 ppm [12]
CNT is 40 nm and 2% (1 ppm) ­NH3 ­NH3
average inter-tube 10% (15 ppm) 20 s for 175 ppm 70 s for 175 ppm
distance of the HCOOH HCOOH HCOOH
CNTs is 80 nm 2% (35 ppm) 15%
(175 ppm)
4 Cu-BTC nanopar- Size: 100 nm, Drop casting tech- Methanol (∆C/C0) × 100% 61% (250 ppm) 178 s for 250 ppm 140 s for 250 ppm [31]
ticles Thickness: 8 µm nique 412.5% (1500 ppm) methanol methanol
5 Cu-BTC nanoporous ~ 5 µm of Cu-BTC Electrochemical Ethanol and metha- (∆C/C0) × 100% Methanol: 12% – – [47]
film layer with particle method nol (250 ppm)
size of 2–3 µm 58% (2000 ppm)
Ethanol: 4%
(250 ppm)
20% (2000 ppm)
6 Si-NPA Pillar height: 2.5 µm Hydrothermally Ethanol ∆C% = 430% (500 ppm) at 15 s at 50 ppm 30 s at 50 ppm [50]
Distance between etching of Si (C − C0) × 100 200 Hz
two neighboring
pillars: ∼ 4.0 µm
7 ZnO cauliflowers on Diameter of ZnO Chemical vapor Humidity (∆C/C0) × 100% 21,400% (RH 20 s 3 s [59]
Si-NPA cauliflowers: deposition changed from 11.3
∼3 µm to 94.6%) at 1 kHz
8 SnO2:Sn on Si-NPA Film thickness: Vapor–liquid–solid Humidity (∆C/C0) × 100% 265% at 1 kHz 20 s 20 s [65]
200 nm growth method
9 ZnO/SiNW Length of Water bath process Humidity Slope of C-RH 0.69 nF/RH (%) 26 s (97.69% of 7 s (97.69% of RH) [67]
ZnO NR and RH)
SiNW = 200 nm at
8 µm respectively
10 SiC NW on Si-NPA Diameter: 15 nm CVD Humidity ∆C% = 960% 105 s 85 s [68]
(C − C0) × 100
11 Ni/SiNW Length of SiNWs is Wet chemical etch- Humidity ∆C% = 1900% Minimum: 39 s, Minimum: 24 s, [76]
90 µm and diam- ing (C − C0) × 100 maximum: 101 s maximum: 53 s
eters of SiNWs
ranged from 60 to
300 nm
Journal of Materials Science: Materials in Electronics (2018) 29:6129–6148
 Table 1  (continued)
S. no. Sensing layer Other structural Fabrication tech- Sensing gas/vapor Sensitivity formula Sensitivity Response ­timeb Recovery ­timec Ref.
parameters nique

12 ZnO nanorods – Chemical bath Humidity (∆C/C0) × 100% 25% (for seed layer – – [79]
deposition thickness: 50 nm),
14% (for seed
layer thickness:
200 nm)
13 ZnO nanorods Diameter: Hydrothermal Ethanol (∆C/C0) × 100% 122% for 20 ppm 3 min 4 min [81]
80–150 nm synthesis ethanol
14 TiO2 nanotube array Wall thickness: Electrochemical Benzene, toluene (∆C/C0) × 100% Benzene (14.33%) 69.4, 21.9 and 27.2, 13.5 and [83]
16 nm, inner anodization and xylene toluene (9.86%) 67.9 s for 200 ppm 63.6 s for 200 ppm
radius: 25.2 nm, xylene (8.93%) of benzene, of benzene,
spacing between toluene and xylene toluene and xylene
two nanotubes: respectively respectively
14.4 nm
15 Porous ­TiO2 – Sol–gel template Humidity ∆C% = 120% (RH 11 to 5 s 8 s [86]
(C − C0) × 100 95%) at 50 Hz
16 Graphene oxide – Hummers method Humidity (∆C/∆RH) × 100% 37,800% 10.5 s 41 s [96]
17 Macroporous Si Pore size: 4 µm. Atomic layer depo- Humidity (∆C/C0) × 100% 297.5% at 1 kHz, 300 s (100% RH) – [101]
with ­Ta2O5 Thickness of sition 59.6% at 200 kHz
Journal of Materials Science: Materials in Electronics (2018) 29:6129–6148

­Ta2O5: 95 nm
18 SnO2 nanoparticle Particle size: 10 nm Dip coating process Ethylene ∆C = C − C0 5 pF (100 ppm) 5 min 7 min [102]
to 15 nm
Film thickness:
1300 nm
19 Nickel-silicon Macro-porous of Electrochemical Humidity (∆C/C0) × 100% 700% – – [103]
microchannel plate ∼ 5 µm width etching
20 Amorphous carbon Average grain size: Direct current mag- Humidity (∆C/C0) × 100% 200% (RH changes 3 min 4 min [104]
film/n-Si hetero- 30 nm netron sputtering from 11 to 95%) at
junctions 1 kHz
21 ZnO nanorods Length: 10 µm and Thermal decompo- Humidity Slope of f-RH 52.3 Hz/RH% 90 s 20 s [105]
radius: 200 nm sition technique
a
 Co is initial device capacitance, C is final device capacitance in target vapor ambient
b
 Response time is time taken to reach 90% of saturation response
c
 Recovery time is time taken to come back 90% from saturation response

13
6145

6146
Acknowledgements  This work was supported in part by Early Carrier
Research Grant (Lett. No. ECR/2015/000345) by SERB, Govt. of India.
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