J Mater Sci: Mater Electron (2024) 35:1425

Pyramid‑like zinc oxide microstructures as humidity

sensor
Punam Tiwary1,2,* , Rajat Mahapatra1, and Amit K. Chakraborty2,*

1
Department of Electronics and Communication Engineering, NIT Durgapur, Durgapur 713209, India
2
Carbon Nanotechnology Lab, Department of Physics, NIT Durgapur, Durgapur 713209, India

Received: 28 February 2024 ABSTRACT

Accepted: 23 June 2024 Detection of humidity is essential for human health monitoring, environmen-
Published online: tal control systems and various industries, including aviation and automobile
18 July 2024 industry. Herein, a facile, single-step method to synthesize pyramid-shaped ZnO
microstructures is reported, which shows sensitivity as high as 480 against expo-
© The Author(s), under sure to 70% relative humidity with a fast response and recovery times of 16 s
exclusive licence to Springer and 7 s, respectively. The sensor shows good repeatability to several cycles and
Science+Business Media, LLC, durability against aging over one month. When tested against different volatile
part of Springer Nature, 2024
organic compounds, the sensor is found sensitive to relative humidity and almost
insensitive to non-alcoholic VOCs. Electron microscopy and X-ray diffraction
analysis revealed uniformly distributed pyramid-like microstructures that are
made of crystalline wurtzite phase of ZnO. UV–visible absorption spectroscopy
revealed the existence of a strong absorption band at 375 nm, corresponding to
a band gap of 3.32 eV as estimated from the Tauc plot. The sensing mechanism
is described with the help of the formation of a favorable conduction pathway
upon exposure to humid air leading to an increase in the electrical conductivity.

1 Introduction called relative humidity (RH) defined by the percent-

age ratio of the quantity of moisture in a particular
Humidity is nothing but the moisture content pre- water–air mixture compared to its saturation value at
sent in the atmospheric air around us. The health of a given temperature. Some reports suggest that mid
humans, other animals even plants are strongly influ- range RH (40–50%) is good for prevention of drying of
enced by change in the humidity of air. While too wet mucous membrane and ciliary acrivities [5]. At higher
air (high humidity) can cause growth of molds, fun- RH values (above 70%), all the pathogens like bacte-
gus, dust mites, and other pests leading to trigger dis- ria, viruses as well as fungi growth rate increases to
eases such as asthma [1] and allergy in human beings, maximum, and thus cause various respiratory diseases
too dry air (low humidity) can cause dryness of the such as asthma, pneumonia, Tuberculosis, etc. [1, 6].
nose, throat and skin [2, 3] leading to diseases such as Thus, humidity levels of the indoor air should be mon-
eczema. Extreme low humidity may cause eye irrita- itored for preventive measures in homes for people
tion [4]. Humidity is generally measured as a quantity with illnesses [7]. The service life of many household

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1425 Page 2 of 8 J Mater Sci: Mater Electron (2024) 35:1425

appliances, furniture, and laboratory equipments or

products can also be influenced by humidity of its
surrounding air and hence in addition to domestic
use, humidity sensors find their applications in sev-
eral industries such as, aviation industry [8], vehicle
equipment industry [9], air conditioning systems [10],
as part of home heating [11] and weather prediction
[12].
Humidity sensors can be designed by suitable selec- Fig. 1  Synthesis of zinc oxide
tion of materials which undergo sharp change in one
of its physical properties upon exposure to humid air
performed using a Carl-Zeiss Sigma field emission
such that by measuring the change in the magnitude
scanning electron microscope (FESEM).
of this property one can estimate the level of RH in air.
Metal oxide semiconductors (MOS) have been widely
explored for sensing applications as they exhibit sharp
2.2 Fabrication of sensor with sensing set‑up
change in electrical resistance when exposed to spe-
cific environment (gases, VOCs, etc.). MOS humidity
The sensor was fabricated by drop-casting a solu-
sensors often operate by responding to the change in
tion of 5 mg ZnO in 2 ml of ethanol on a glass slide
electrical resistance upon exposure to humid air of
to form a film. The ZnO coated glass was then kept
specifc RH. Among various MOS ZnO has been a very
overnight in open air for natural drying to get the
popular choice for resistive-sensing of several analytes
final sensor device which was introduced into a cus-
including Ethanol [13–15], Toluene [16] due to its low-
tom built sensing chamber made of stainless steel as
cost and ease to produce with different size and shape
shown in Fig. 2. Relative changes in current flow-
[17–19].
ing across the ZnO film upon exposure to humid air
Herein, we report the humidity sensing property
were measured by a Keithley 2450 source measure
of pyramid-like ZnO microstructures synthesized
unit. The electrical leads of the source meter were
by a facile single-step thermal decomposition of zinc
introduced into the sensing chamber through an
nitrate. To the best of our knowledge, such a system-
electrical feedthrough to connect to the ZnO film.
atic study on the humidity-sensing property of ZnO
The sensing chamber was first evacuated by a rotary
has not been reported yet. The ZnO sensor thus fabri-
vane pump and the sensor current was measured (Iv)
cated, demonstrates good repeatability and selectivity
when stabilized after which atmospheric air (with a
towards humidity compared to several other polar and
fixed RH) was introdued to the chamber by opening
non-polar volatile organic compounds (VOCs), show-
the air inlet valve. As air fills the chamber, the cur-
ing its potential use as an affordable humidity sensor.
rent across the sensor rises and eventually saturates
(Ia). The instantaneous RH of the air was measured
using a HTC humidity sensor and matched with that
2 Experimental reported by www.​accuw​eather.​com.
The sensitivity (S) of the sensor was defined as
2.1 Synthesis and characterization of materials follows:

ZnO was synthesized by thermal decomposition of I a − Iv

(Zn(NO3)2⋅6H2O) at 800 °C for 3 h in a muffle furnace,
%S = × 100 (1)
Iv
as shown in Fig. 1. The material synthesized was taken
out and ground in powder form with the help of a where, Iv and Ia are the electrical current across the
mortar pestle. sensor in vacuum and in humid air, respectively.
Structural characteristics were achieved using a
Rigaku TTRXA III X-ray diffractometer irradiating
with Cu Kα X-rays (wavelength 1.54 Å), Optical
characteristics were recorded using a JASCO (V-750)
spectrophotometer, and morphological analysis was
J Mater Sci: Mater Electron (2024) 35:1425 Page 3 of 8 1425

Fig. 2  Schematic for the cus-

tomized gas sensing set-up

3 Results and discussions 70% are plotted in Fig. 4b, which confirms good
reproducibility at all RH values.
3.1 Characterization of ZnO Figure 4c plots a single cycle at 70% RH to demon-
strate the process of estimation of the response and
The analysis of synthesized ZnO by X-ray diffrac- recovery times. From Fig. 4a–c it is evident that the
tion pattern shows (Fig. 3a) several sharp peaks sensitivity of the ZnO sensor at 70% RH is as high
indicating its high degree of crystallinity. All the as 480% and its response and recovery times are 16 s
peaks were matched to hexagonal wurtzite phase of and 7 s, respectively.The variation of sensitivity of the
ZnO in accordance with JCPDS card No. 00-036-145. sensor as a function of RH value of the atmosphere
Using the Scherrer equation, the average crystal- is plotted in Fig. 4d in which the exact nature of the
lite size of 49.4 nm is obtained for the most intense dependence is shown by fitting the experimental data
peak at 36.7° corresponding to (101) planes of ZnO points with an exponential function given by the fol-
[14]. UV–vis absorbance spectrum shows a peak at lowing equation:
380 nm (Fig. 3b) corresponding to Π–Π* transition. −x
Assuming ZnO as a direct bandgap semiconduc- y = y0 + A1 e t (2)
tor, its bandgap was estimated to 3.32 eV as can be
where, y0 is the offset, A1 is the amplitude, and t is the
seen from the Tauc plot (inset of Fig. 3b) [20, 21].
time constant. The value of the ­R2 COD (R square coef-
The FESEM images recorded at two different mag-
ficient of determination) for the fitted graph is 96.7%
nifications, shown in Fig. 3c, d, where one can see a
indicating it as a good fit of the data.
homogenously distributed pyramid-like microstruc-
The inset in Fig. 4d plots the variation of response
tures with an edge length of 270 µm. Each pyramid
and recovery times with increasing RH where one
encompasses hundreds of multifaceted plates, each
can see that both response and recovery times shows
100 µm long and 50 µm wide.
an initial decrease between 40 and 50% RH above
which these remain almost constant showing no
significant rise/fall with increase in RH. The I–V
3.2 Gas sensing measurements
plots of the sensor (Fig. 4e) at different atmospheric
The dynamic sensitivity plot of the ZnO sensor at conditions, i.e., in vacuum, dry Nitrogen, and in air
different RH (Fig. 4a) shows that the sensitivity of varying RH shows straight lines confirming the
increases with increase in RH. The repeatability of ohmic contacts. Figure 4f displays the sensitivity of
the sensor response (expressed in current) for five the sensor at 50% RH recorded at different intervals
consecutive cycles at RH 50%, 55%, 60%, 65%, and of days over a period of one month. It is evident
from the plot that the sensor is preety stable against
1425 Page 4 of 8 J Mater Sci: Mater Electron (2024) 35:1425

Fig. 3  a XRD plot; b UV–vis absorbance spectra with the Tauc plot in the inset; c, d FESEM images of ZnO at different magnifications

ageing at 50% RH as the sensitivity remained almost O2 atmosphere + e− (ZnO CB) → O−

( )
2 (ZnO surface)
unchanged from day 1 to day 30. (3)
The selectivity of the sensor was tested by measur-
When exposed to humid air water molecules present
ing its response upon exposure to several VOCs. The
in the humid air may form hydrogen bonds with the
sensor shows (Fig. 5a) no response against exposure
active sites on the ZnO surface by chemisorption, which
to 100 ppm of Toluene and Hexane and 10 ppm of
forces other water molecules to be physically adsorbed
Methanol, Ethanol, and Propanol-2 indicating excel-
to the chemisorbed hydroxyl layer through hydrogen
lent selectivity of the sensor against humidity.
bonds to neighboring hydroxyl groups. The neighbor-
ing hydroxyl group interaction is determined using
hydrogen bonds and van der wall forces for physical
3.3 Gas sensing mechanism
attachment [25–27]. Thus, the favorable path for elec-
tron transport increases with an increase in RH, which
Figure 5b shows a schematic representation of the
contributes to the increased current response of the
humidity sensing mechanism for the ZnO sensor.
MOS sensor upon increase in RH. Another possibility
MOS sensing mehanism is often explained [21–24]
of humidity sensing is based on the polaron conduction
by the existence of pre-adsorbed oxygen molecules
mechanism and water protonation (Eq. 4, 5)
on their active surface which captures electrons from
the conduction band (CB) of the MOS as shown H2 O + O2− → H3 O+ (4)
below:
J Mater Sci: Mater Electron (2024) 35:1425 Page 5 of 8 1425

Fig. 4  a Dynamic response of the ZnO sensor at various RH; b function (variation of response time and recovery times with RH
Repeatability plot at varying RH; c Dynamic response curve at in the Inset); e I–V characteristics; and f stability of the sensor
70% RH demonstrating the estimation of response and recovery against ageing at 50% RH
times; d Experimental data vs RH plot fitted with an exponential
1425 Page 6 of 8 J Mater Sci: Mater Electron (2024) 35:1425

Fig. 5  a Selectivity test plot of the sensor against some VOCs and; b Schematic ofhumidity sensing mechanism

Table 1  Comparison of
S. No. Morphology of ZnO RH Sensitivity Response time References
performance parameters
of reported ZnO humidity 1 Nanosheet 96 R12%
= 220 600/3 [28]
R96%
sensors with the present 2 Nanowire 30 Rdry 60/3 [29]
= 88
pyramid-like ZnO sensor R30%

3 Film by screen printing 70 𝜎g−𝜎a

× 100 =61% 89/175 [30]
technique
𝜎a

4 Film 90 Rdry
= 226 8/25 [31]
R90%

5 Pyramid-like 70 Rv −Ra
× 100 = 480% 16/7 This work
Rv

H2 O + H3 O+ → H3 O+ + H2 O (5) exhibited good sensitivity to humid air at room

temperature. The ZnO sensor exhibited sensitivity
In order for the reader to assess how good is the as high as 480 to 70% RH, along with fast response
ZnO humidity sensor developed in this work, a table time of 16 s and recovery time of 7 s. The sensor
(Table 1) has been compiled by listing the major per- also showed good repeatability over several cycles
formance parameters of our ZnO sensor along with and maintained its performance against aging over
those obtained from previous reports of ZnO humid- a period of one month. When tested against various
ity sensor. VOCs, the sensor also showed high degree of selec-
tivity to humid air as it showed almost negligible
sensitivity when exposed to non-alcoholic VOCs.
4 Conclusion Thus, the simplicity of the synthesis combined with
excellent sensing performance makes the ZnO micro-
To conclude, this paper reports a cost-efficient and structures a very good choice for practical humidity
straightforward single-step method that can be easily sensor applications.
scaled up for synthesizing zinc oxide (ZnO) micro-
structures by thermal decomposition of zinc nitrate.
The microstructure analysis of the synthesized ZnO Acknowledgements
confirmed formation of pyramid shaped micro-struc-
tures of crystalline wurtzite phase whereas the opti- The authors gratefully acknowledge MHRD (TEQIP-II,
cal absorption studies revealed that the material has April 2013), Govt. of India funded Centre of Excel-
a moderate energy band gap of 3.32 eV. Flims made lence in Advanced Materials at NIT Durgapur for the
of these ZnO microstructures on glass substrate experimental resources.
J Mater Sci: Mater Electron (2024) 35:1425 Page 7 of 8 1425

Author contributions experiments. Ann. Occup. Hyg.Hyg. 21, 177–190 (1978).

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