Sensors and Actuators B 144 (2010) 6772

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Sensors and Actuators B: Chemical

journal homepage: www.elsevier.com/locate/snb

Sensor response formula for sensor based on ZnO nanostructures

Niyom Hongsith a , Ekasiddh Wongrat a , Teerakiat Kerdcharoen b , Supab Choopun a,
a
Department of Physics and Materials Science, Faculty of Science, Chiang Mai University, Chiang Mai 50200 and ThEP Center,
CHE, Bangkok 10400, Thailand
b
Department of Physics, Faculty of Science, Mahidol University, Bangkok 10400, Thailand

a r t i c l e

i n f o

Article history:
Received 4 August 2009
Received in revised form
25 September 2009
Accepted 10 October 2009
Available online 20 October 2009
Keywords:
Gas sensor
ZnO
Sensor response formula
Nanostructure

a b s t r a c t
In this paper, we propose a new and general formula to describe ethanol adsorption mechanism underlying the response enhancement of ZnO nanostructure sensors. The derivation of sensor response formula
based on basic chemical reaction at the sensor surface is presented. The formula can be used to explain
response enhancement due to effect of metal doping, surface-to-volume ratio, and surface depletion
layer. Thus, it can be regarded as a general formula to describe the sensor response characteristics of ZnO
sensors. This general formula is a powerful tool for designing ZnO sensor at any desired sensor response.
Furthermore, it is reasonable to expand this formula to explain other sensing materials and also to explain
for different active gases.
2009 Elsevier B.V. All rights reserved.

1. Introduction
Metal-oxide semiconductor sensors based on materials such
as SnO2 , TiO2 , WO3 or ZnO are widely used for ethanol sensors
[114]. Especially, ZnO is a promising material for gas sensor applications due to feasibility for ultrahigh sensitive sensors or ppb-level
sensors. Recently, various morphologies of ZnO such as belt-like,
wire-like, rod-like or tetrapod for ethanol sensor applications have
been widely investigated [1522]. It was suggested that the sensor response characteristics of these sensors strongly depends on
the morphology of ZnO. Ethanol sensors based on ZnO nanostructure such as nanobelts, nanorods or nanowires usually exhibit high
sensor response and sometime up to a few hundred folds over conventional metal-oxide sensors at moderate concentration [9]. On
the other hand, a sensor based on a larger size of ZnO such as thin
lms or microtetrapods show lower sensor response [14,15]. Many
models have been proposed to explain sensor response characteristic of ZnO sensors and still be a subject of discussion.
Basically, the ZnO ethanol gas sensing was simply observed
on the resistance change under ethanol atmosphere. It can be
explained by the chemical reaction between the active gas and oxygen ion adsorption on the surface of ZnO. In air atmosphere and at
high operating temperature, oxygen molecules are adsorbed onto
the surface of the ZnO sensor to form O or O2 ions by attracting electrons from the conduction band of the ZnO. Under ethanol

Corresponding author. Tel.: +66 53 943375; fax: +66 53 357511.

E-mail address: supab99@gmail.com (S. Choopun).
0925-4005/$ see front matter 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.snb.2009.10.037

atmosphere, the ethanol gas reacts with oxygen ion molecule on the
surface and gives back electrons into the conduction band, thereby
lowering the resistance of ZnO sensors. The ratio between two
resistances is then calculated as the sensor response. Typically, the
sensor response of the oxide semiconductor gas sensor can usually
be empirically represented as [1,5]: S = aCb , where C is the target gas
partial pressure, which is direct proportion to its concentration, and
the sensor response is characterized by the parameter a and exponent b. The value of b may have some rational fraction value usually
1 or 0.5 depending on the charge of the surface species [1,5].
Wang and co-workers have proposed a contact controlled model
[7] and surface-depletion controlled model [8] that can explain
the improvement of sensor response based on nanostructure. Chen
et al. [9] have used space-charge model to explain ultrahigh sensor response of ethanol sensor based on ower-like ZnO nanorods
with diameters less than 15 nm. Recently, Zhao and co-workers [10]
have used density functional theory (DFT) to reveal the gas-sensing
mechanism of ZnO and provided an exponentially formula of sensor response. However, there is still no general model or formula
to explain all circumstances of ethanol sensor based on ZnO. Thus,
it is interesting to generalize a simple model or formula in order to
describe the sensor response characteristics of ZnO sensor.
In this work, the sensor response formula based on ethanol
adsorption mechanism has been developed and obtained from
basic chemical reaction between ethanol molecule and oxygen ions
by including surface depletion layer. The sensor response formula
can be used to explain response enhancement due to effect of metal
doping, surface-to-volume ratio, and surface depletion layer. This
sensor response formula can be regarded as a general formula to

68

N. Hongsith et al. / Sensors and Actuators B 144 (2010) 6772

describe the sensor response characteristics of ZnO sensors or any

metal-oxide sensors.

and air atmosphere, carrier concentration n and n0 can be considered as a constant with time. Thus, Eq. (10) can be rewritten
as

2. Theory

b
n = t kEth (T )[Oion
ads ] [CH3 CH2 OH] + n0

2.1. Ethanol adsorption mechanism

where  t is a time constant. The carrier concentration is dened

as n = /R, where R is a resistance and is a proportional constant,
and can be substituted in Eq. (11) as

Normally, the ethanol vapor gas sensor based on ZnO semiconductor has an operating temperature at high temperature (about
250350 C). When the ZnO semiconductor is heated at lower temperature about 100200 C, oxygen molecules in the atmosphere
are adsorbed on the surface of ZnO and form oxygen ion molecules
as shown in Eq. (1).
O2 (gas) + e O
2 (adsorb)

(low temperature)

(1)

At higher temperature about of 250350 C, the oxygen ion

molecules are dissociated into oxygen ion atoms with singly or
doubly negative electric charges by attracting an electron from the
conduction band of ZnO as shown in Eqs. (2) and (3).
k

1
O
2 2

Oxy
+ e
Oads

1
O
2 2

Oxy 2
+ 2e
Oads

(2)

(3)

The oxygen ions on the surface of ZnO are active with the ethanol
molecule and give up the electrons from the surface back to the
conduction band of ZnO semiconductor. The chemical reaction
between ethanol molecule and oxygen ions is shown in Eqs. (4)
and (5) for O and O2 , respectively.
k

Eth
CH3 CH2 OHads + O

C2 H4 O + H2 O + 1e
ads

(4)

or
kEth
CH3 CH2 OHads + O2
C2 H4 O + H2 O + 2e
ads

These cause an increasing in the conductivity and thus the decreasing resistance of the sensor.
2.2. Sensor response of ZnO sensor
From Eqs. (4) and (5), rate equation of electron density can be
written as Eqs. (6) and (7), respectively, which can then be combined to Eq. (8).
dn
1
= kEth (T )[O
] [CH3 CH2 OH]1
ads
dt
or

(6)

1/2
dn
] [CH3 CH2 OH]1/2
= kEth (T )[O2
ads
dt

(7)

b
dn
b
= kEth (T )[Oion
ads ] [CH3 CH2 OH]
dt

(8)

kEth (T ) = A exp


Ea

kB T

(9)

where Ea is the activation energy of reaction, kB is the Boltzmann

constant and T is absolute temperature. Integrating Eq. (8) leads to
the solution as
b

b
n = kEth (T )[Oion
ads ] [CH3 CH2 OH] t + n0

(10)

where n0 is the electron concentration of sensor at an operating

temperature in the air atmosphere. At equilibrium under ethanol

(12)

The sensor response, Sg , of the sensor is dened as Ra /Rg where

Ra is the electrical resistance of the sensor in air, and Rg is the electrical resistance of the sensor in ethanolair mixed gas. Therefore,
the sensor response relation can be obtained as
b

Sg =

b
t kEth (T )[Oion
Ra
ads ] [CH3 CH2 OH]
=
+ 1.
Rg
n0

(13)

Usually, temperature dependence of sensor response is controlled by two parameters; reaction rate coefcient kEth (T ) between
adsorbed oxygen ions with ethanol molecules, and electron density
of the sensor n0 . The reaction rate coefcient and electron density
increases exponentially with rising temperature. However, sensor
response is proportional to reaction rate coefcient but inversely
proportional to electron density. These two parameters compete
with each other and result in maximum sensor response at optimum operating temperature. Ethanol gas sensor based on ZnO
material has optimum operating temperature around 300 C [59].
Sometimes, a compact form of the sensor response relation on
ethanol concentration (Cg ) can be rewritten as
(14)

where a is a controllable parameter. At the optimum operating

temperature condition, Eq. (14) can be rewritten as:
log(Sg 1) = log a + b log Cg .

(15)

It can be seen that log(Sg 1) has a linear relation with log Cg having
a slope of b value. Thus, b value which represents oxygen ion species
on the surface of ZnO sensors can be obtained from a slope of a plot
between log(Sg 1) and log Cg .
In the nanostructure regime, the surface-to-volume ratio is an
important parameter and should be included in the sensor response
relation. Generally, this surface-to-volume ratio can be related to
the density of adsorbed oxygen ions. Thus, we propose that the
density of adsorbed oxygen ions can be written in term of surfaceto-volume ratio as
[Oion
ads ] =

In Eq. (8), n is the electron density or electron concentration under

the ethanol atmosphere, b is a charge parameter having value of 1
for O and 0.5 for O2 and kEth (T) is the reaction rate constant or
reaction rate coefcient described as

b
t kEth (T )[Oion
1
1
ads ] [CH3 CH2 OH]
=
+
Rg

Ra

Sg = aCgb + 1.
(5)

(11)

0 Vm
Vs

(16)

where  0 is a number of oxygen ion per unit area, is a ratio of surface area per volume of material (Vm ), and Vs is the system volume.
Thus, substituting Eq. (16) onto Eq. (13) give
b

S =

t kEth (T )(0 (Vm /Vs )) b

Cg + 1.
n0

(17)

2.3. Surface depletion layer models

According to the depletion layer or the space-charge model, Ld
(a Debye length), can be expressed by [9]
Ld =

 k T 1/2
B
q2 n

(18)

where is the static dielectric constant, q is the electrical charge

of the carrier, and n is the carrier concentration. It can be seen that

N. Hongsith et al. / Sensors and Actuators B 144 (2010) 6772

69

Fig. 1. Schematic diagram of the depletion layer on the surface of cylinder with a
thickness of Ld , under condition of D 2Ld and D  2Ld (not in scale).

at steady operating temperature, the depletion layer is dependent

only on the carrier concentration.
In this model, a cylinder, which is one of the most basic geometric shapes in one-dimension, is considered and a conductive
channel is assumed to be along the axis of the cylinder. At an operating temperature, the oxygen ions were adsorbed by attaching an
electron on the surface of the cylinder. Therefore, the depletion
layer is formed on the surface of cylinder with a thickness of Ld ,
and then a size of conductive channel is reduced along the radial
direction as shown in Fig. 1.
When exposed to the ethanol atmosphere, the ethanol gas
reacts with oxygen ions on the surface and gives back electrons to
ZnO sensors resulting in increasing conductive channel (decreasing depletion layer). The conductive channel can be related to the
carrier concentration, and can be written in term of the depletion
layer thickness (Ld ) as
n = n0

(D 2Ld )2
D2

(19)

where n0 is the carrier concentration of intrinsic material, n represents carrier concentration of the Debye length, and D is diameter
of the cylinder. Thus, the depletion layer effects on sensor response
based on cylindrical ZnO nanostructure are given by inserting Eq.
(19) in Eq. (17) and obtained

SLd =

t kEth (T )(0 (Vm /Vs ))

n0

D2 Cg b
(D 2Ld )

+ 1.

(20)

Let consider a diameter of cylinder D compared to Debye length

(Ld ). Since Debye length is in the order of nanometer, it can be
divided into three conditions.
(1) Under condition D  2Ld , Eq. (20) turns in to Eq. (17)
In this condition, a diameter of cylinder is much larger than
micrometer which is the case of microstructure or bulk materi-

Fig. 2. Plot of sensor response (Sg 1) and ethanol concentration in log scale for
ethanol sensor based on different ZnO morphologies. The linear line in the graph
has a slope of 0.5.

als. The depletion layer thickness is very small compared with

the cylindrical diameter (D  2Ld ) and Eq. (20) can be approximated to Eq. (17) which is an equation that has no depletion
layer effect.
(2) D > 2Ld , Eq. (20) can be approximated to Eq. (17)
When a diameter of cylinder is in the order of nanometer
but still larger than Debye length (D > Ld ), Eq. (20) again can be
approximated to Eq. (17) with no depletion layer effect. However, sensor response strongly depends on oxygen ion density
due to the surface-to-volume ratio, , parameter.
(3) D 2Ld , sensor response strongly depends on D.
When a cylindrical diameter decreases down to the order of
nanometer and is comparable to Debye length (D 2Ld ), the
depletion layer has strong effect and the sensor response is
strongly dependent on a cylindrical diameter. Thus, Eq. (20) can
be used to explain sensor response of all structural sizes from
nanometer to bulk and can be considered as a general form of
sensor response.
3. Results and discussion
3.1. Oxygen ion species on the surface of ZnO sensors
Recently, the ethanol gas sensing based on different ZnO morphologies and various sizes have been widely investigated, for
examples, nanorods [79], nanobelts [4] and nanowires [5,11] and
the sensor response of sensors were listed in Table 1. As aforementioned, a slope value of a plot between log (Sg 1) and log Cg can
represent the oxygen ion species. The plots between log (Sg 1)
and log Cg of some previous works as listed in Table 1 are displayed
in Fig. 2.

Table 1
Sensor response of ZnO sensor with different morphologies.
Sensor response

Ethanol concentration (ppm)

Morphology

D (nm)

Nanowires [5]
Nanorods [7]
Nanorods [8]
Nanorods [9]
Au-doped nanorods [23]
Nanobelts [4] a
Nanowires [11] a

25 5
150
15
<15
15 5
50150
60180

Our previous work.

5
8
4.4

16.4

b value

10

50

100

200

300

500

1000

15
5.8
10
20.5
20.1

11.4
18
104.9
41.8
7.3

32.5
14.6
30
176.8
89.5
11.8
5.07

47

224.2

55
258
193.6

25.2
72
267.7
250
21.1
9.79

30.1
100

23.2
14.14

2000

46.5
14.19

0.504
0.496
0.512
0.677
0.630
0.500
0.504

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N. Hongsith et al. / Sensors and Actuators B 144 (2010) 6772

It was found that the value b of all sensors is close to 0.5 suggesting that the adsorbed surface oxygen species on ZnO sensor is O2
[3]. In addition, this suggests that the oxygen adsorption species
on the surface is independent on the grain size of ZnO regardless of
bulk, microstructure or nanostructure.
However, the value b of ZnO sensor which has diameter close to
Debye length (2Ld ) was not that close to 0.5, for example, the value
b of nanorods [9,24] with diameter size <15 nm is equal 0.677 and
0.630. Such deviation arises because the surface depletion layer
has some small effect on the oxygen adsorption species at ZnO
surface.
3.2. The effect of metal doping
From previous report, doping on semiconductor can modify
resistance [20] that also affect the sensor response. There have
been several reports on sensor response enhancement due to metal
doping effect such as Au-doped [11,23,24], Pd-doped [13,25] and
Pt-doped [26,27] sensors. However, the reason for sensor response
enhancement is still not clear. The metal doping effect can be simply
explained in our model by using Eq. (13).
From Eq. (13), it can be seen that the sensor response is proportional to the reaction rate constant, kEth (T) and kOxy (T), through
oxygen density. Basically, the reaction rate constant can be affected
by noble metals (such as Au, Pd, and Pt) in oxide semiconductor
sensor due to the catalytic effect. Thus, metal doping causes an
increasing of reaction rate constant and resulting in enhancement
of sensor response. The increase of reaction rate constant (or oxygen density) can be conrmed by observation of an increasing of
resistance in air due to metal doping [24]. The increasing resistance
in air suggests that the gold metal catalytically activates the dissociation of molecular oxygen due to higher reaction rate that results
in increasing quantity of oxygen adsorption. Therefore, an electron
in ZnO nanostructure was captured by oxygen adsorption to form
oxygen ion and hence ZnO nanostructure loses more electrons and
caused the larger depletion layer at ZnO surface resulting in higher
resistance.

Fig. 3. (a) Ethanol sensor based on ZnO thin lms with an area of 1 cm2 , (b) ethanol
sensor based on vertical alignment ZnO nanorods with diameter D and length L and
(c) sensor response ratio as a function of diameter where L = 10 m.

by decreasing the diameter due to increasing of surface-to-volume

ratio.
S (B) 1
=
S (A) 1

 b
B

(21)

3.4. The effect of depletion layer for ultrahigh sensor response

Recently, several works has been reported on ultrahigh sensor response of ZnO sensors [8,9] and explained qualitatively by
surface depletion layer. In our model, we shall consider the two
cases of ethanol sensors based on microstructure (D  2Ld and
limitD SLd = Sg ) and nanostructure (D > 2Ld and D 2Ld ). Since
only the effect of depletion layer is considered, we neglect the effect
of surface-to-volume ratio by taking into account that the surface
area of sensor is the same in both cases. The sensor response in
Eq. (20) can be rewritten as the ratio between the two cases of
microstructure and nanostructure as

3.3. The effect of surface-to-volume ratio

From earlier reports on conductometric ZnO sensor, it is quite
amazed that ZnO nanostructures which are not aligned in the conductive direction exhibited sensor response higher than the bulk
[16,19]. This can be simply explained, based on our model, by the
effect of the surface-to-volume ratio as shown in Eq. (17). Under
condition of ZnO sensor (D > 2Ld and D  2Ld for nanostructure,
microstructure and bulk) with no depletion layer effect, the sensor response strongly depends on the surface-to-volume ratio
as discussed earlier. For example, let consider a thin lm with an
area of 1 cm2 as shown in Fig. 3(a). Then, given cylindrical nanostructures of 10 m in length with various diameters are grown on
this area, as shown in Fig. 3(b). The surface-to-volume ratio can
be calculated and put in Eq. (21) for the sensor response ratio. The
sensor response ratio as a function of diameter can be plotted as
shown in Fig. 3(c). It can be seen that sensor response is enhanced

SLd 1
Sg 1

D2
(D 2Ld )2

(22)

The value of Ld can be obtained in Eq. (18) by using the electron density of about 1017 1018 cm3 [21,22] T = 573 K (optimum
temperature), = 7.9 8.85 1012 F m1 and then, give Ld of about
5 nm (for n = 8 1017 cm3 ).
Eq. (22) is plotted as shown in Fig. 4 by varying the rods diameter. It can be seen that the sensor response of nano-sensor is
increasing when the diameter steps down below 50 nm, wherein
the sensor response dramatically surging when the diameter is

Table 2
List of sensor response formula for ethanol sensor based on ZnO.
Sensor response formula

Oxygen ion species

Sg = aCgb + 1
b

Sg =
S =
SLd =

t kEth (T )[Oion ]

ads
Cgb + 1
n0
t kEth (T )(0 (Vm /Vs ))b b
Cg
n0

t kEth (T )(0 (Vm /Vs ))b

n0

+ 1 2

D Cg b

(D2Ld )2

+1

Metal doping

Nanostructure (D > 2Ld )

Nanostructure (D 2Ld )

N. Hongsith et al. / Sensors and Actuators B 144 (2010) 6772

Fig. 4. Sensor response ratio (SLd 1/Sg 1) as a function of rod diameter. The
marked points on the graph are the sensor response of ZnO sensors in Table 1.

close to 15 nm. The experimental results (SLd ) from Table 1 are also
plotted in Fig. 4 by taking diameter of 150 nm as a microstructure
(Sg ) in order to neglect the surface-to-volume ratio effect. Surprisingly, the experimental results are in good agreement with Eq. (22).
Moreover, the sensors having size very close to the value of Debye
length (2Ld ) exhibited ultrahigh sensor response and have potential
to detect for a ppb level of ethanol concentration. This suggests that
the sensor response enhancement is prominent when the nanostructure is close to 15 nm [8,9].
4. Conclusions
In summary, the sensor response formulas for ethanol sensor
based on ZnO nanostructures are listed in Table 2. It can be seen
that the formula of SLd can be used to explain for all circumstances
of ethanol sensors based on ZnO. Thus, it can be regarded as a general formula to describe the sensor response characteristics of ZnO
sensor. This formula is a powerful tool for designing ZnO sensor at
any desired sensor response, especially in ppb level of concentration, and for further application such as designing electronic nose.
Furthermore, it is reasonable to expand this formula to explain
other sensing materials such as SnO2 , TiO2 , MoO3 or WO3 and also,
to explain for different active gases such as CO2 , CO, NOx , NH3 or
H2 S.

71

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Biographies

Acknowledgment
This work was supported by Thailand Research Fund (TRF).
Niyom Hongsith would like to acknowledge the nancial support
via the DPST scholarship, and the Graduate School, Chiang Mai University.

Niyom Hongsith received the B.Sc. degree in physics in

2003 and the M.Sc. degree in applied physics from Chiang Mai University, Chiang Mai, Thailand, in 2006. He
is currently a Ph.D. candidate in Physics at Chiang Mai
University. His current research interests are in the eld
of metal-oxide semiconductor nanostructures including
synthesis, fabrication and application such as ZnO nanostructures for gas sensor and dye-sensitized solar cell.

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Ekasiddh Wongrat received the B.S. degree in physics

in 2003 and the M.S. degree in applied physics in 2006
from Chiang Mai University, Chiang Mai, Thailand. He is
currently a Ph.D. candidate in physics at Chiang Mai University. His current research interests are in the eld of
metal-oxide semiconductor nanostructures such as ZnO
for gas sensor application.

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N. Hongsith et al. / Sensors and Actuators B 144 (2010) 6772

Teerakiat Kerdcharoen received B.Sc. and M.Sc. in
chemistry and physical chemistry from Chulalongkorn
University in 1990 and 1992, respectively. As an exchange
student, he received his PhD in physical chemistry from
University of Innsbruck in 1995. Presently, he is a faculty member of Mahidol University. His research interests
cover the topics of organic electronics ranging from theoretical modeling of materials to fabrication of devices,
such as tactile and chemical sensors, and to applications,
such as electronic skin and electronic nose.

Supab Choopun received a Ph.D. in chemical physics from

University of Maryland College Park in 2002. Currently,
he is an assistant professor at Department of Physics and
Materials Science, Faculty of Science, Chiang Mai University, Thailand. His current research interests are in the eld
of metal-oxide semiconductor nanostructures such as ZnO
for gas sensor and dye-sensitized solar cell applications.