ZnO and SnO2 one-dimensional sensors for detection
of hazardous gases
C. Baratto, F. Rigoni, G. Faglia, E. Comini, D. Zappa, G. Sberveglieri
Sensor Lab
CNR INO & University of Brescia
Brescia, Italy
Abstract— There is need for reliable, low cost detectors to
continuously monitor the air quality in presence of hazardous
gases, harmful for human health. In this work we demonstrate
how the use of different type of metal oxide one-dimensional
sensors based on ZnO and SnO2 could provide high sensing
capabilities together with differentiated responses to gases. The
sensors can then be used together into a cost-effective portable
sensor systems for quantitative detection of harmful emissions
and contaminations. The gases tested in the present work are H2
a highly explosive gas (4% is the lower explosion limit), H2S, one
of the principal compounds involved in the natural cycle of
sulphur in the environment, and DMMP, a simulant of the nerve
agent Sarin. ZnO and SnO2 nanowires were prepared by
Physical Vapour Deposition and ZnO polycrystalline nanorods
were prepared by RF sputtering. The optimum response to low
concentrations of DMMP at 500°C was observed for ZnO
materials, with respect to SnO2 at 500°C. At 400°C H2 is better
sensed by ZnO. Detection of H2S is better obtained with ZnO
NRs compared to the other sensors.
Keywords- nanowires; ZnO, SnO2; gas sensor; H2; H2S;
DMMP.
I.   INTRODUCTION
The increasing market for sensors is demanding to detect
different dangerous chemical agents, and thus highly sensitive
devices are required. Metal oxide gas sensors can be
developed with the help of unique one-dimensional
nanoarchitectures [1], that can ensure higher stability and
comparable response with respect to polycrystalline thin films.
In the framework of the project NANEOS, financed by NATO
SPS Programme, we are developing a cost-effective portable
sensor system for continuous monitoring and quantitative
detection of harmful emissions and contaminations.
Gases of interest are H2, explosive gas produced in
industrial reactions, that can explode when mixed with
atmospheric oxygen at concentration of 4% (LEL, Lower
Explosive Limit). H2S, which is toxic and bad smelling, and
DMMP which is used as a simulant for Sarin gas used in
terroristic attacks.
978-1-5090-1012-7/17/$31.00 ©2017 IEEE
ZnO and SnO2 nanowires (NWs) are used to specifically
detect the cited gases [2]-[4]. However, to the best of our
knowledge, a comparison of the functional properties of NWs
grown by different mechanisms is lacking.
In the current work we studied the influence of the type of
metal oxide (SnO2, ZnO) and of the preparation conditions, on
functional sensing properties. We thus compared the
performances of single crystalline NWs and polycrystalline
nanorods (NRs) for ZnO and single crystalline NWs for SnO2.
II.   RESULTS AND DISCUSSION
A.   Nanowires preparation
ZnO NWs were prepared by vapor liquid solid (VLS)
growth using a Pt catalyzer to obtain a dense growth of NWs.
Zinc oxide powder was placed on an alumina crucible at a
temperature of 1200 °C at 100 mbar to induce its evaporation.
The substrates are placed at lower temperatures, approximately
in the range 500-600°C. A 100 sccm argon flow remained
constant throughout the deposition process.
ZnO polycrystalline NRs were prepared using an
industrially scalable technique like sputtering deposition. The
alumina substrates were kept at constant 400°C, in an inert
atmosphere, starting from ZnO ceramic target, using Sn as a
seed layer: Sn acts as a catalyst for the subsequent growth of
the ZnO NRs [5]. The diameter and length of NRs can be
tailored by changing the deposition conditions like power
(100W-150W). The Ar pressure during deposition was 10-2
mbar.
SnO2 NWs were prepared starting from SnO2 powder
placed in the crucible and kept at 1200°C for evaporation.
Destination substrates were placed in a colder region of the
furnace (900°C) to promote the condensation of evaporated
material on the substrates.
B.   Sensor characterization
 Fig. 1. (Left) SEM image of ZnO NWs prepred by VLS technique; (Center) SEM image of SnO2 NWs prepred by VLS technique; (Right) ZnO NRs
prepared by RF sputtering at 100W power.
Sensors morphology and phase was characterized using
SEM, photoluminescence and micro-Raman techniques. Fig. 1
reports the SEM image of ZnO and SnO2 NWs prepared by
VLS technique, showing that they are composed by a mats of
single crystalline NWs with diameters in the range of tenths of
nanometers. ZnO NRs prepared by sputtering are
polycrystalline [5] and shorter, with a diameter similar to that
prepared by VLS. PL emission was observed to be present
from single crystalline NWs and polycrystalline NRs (results
not shown).
Samples of ZnO NWs and NRs and SnO2 NWs were tested
in the temperature range 300-500° towards H2 (300, 500, 700
ppm), DMMP (3, 5, 7 ppm), H2S(10, 20, 30 ppm) gases at
different temperatures. Relative humidity was set to 30%.
Gases come from certified bottles.
Fig. 2 compares the dynamic response of sensors to H2 gas
(300, 500, 700 ppm) at 400°C, which is the optimum operating
temperature for this gas: ZnO NWs prepared in the furnace
(ZNOF_2); ZnO NWs prepared by sputtering (ZNOS10_B);
SnO2 NWs prepared in the furnace (SNO2F_B).
Fig. 2. (Left) Relative response of ZnO NWs (blue triangles), ZnO NRs (grey
circles) and SnO2 NWs (red squares) sample to H2 at 400°C working temperature.
(Right) Dynamic responses to H2 300 ppm at 400°C, for the three sensors
analyzed. RH=30%.
All sensors showed quite good current stability, fast and
high response to H2, with a full recovery of the signal after H2
exposure. For H2 detection, ZnO NWs and SnO2 NWs are
better than ZnO NRs. Among the two single crystalline
nanowire sensors, the ZnO material showed higher response at
400°C.
For DMMP sensing, the optimum working temperature was
observed to be 500°C for all tested sensors. Fig. 3 shows the
normalized dynamic response of different sensors tested
towards 7 ppm of DMMP. All sensors are capable of reversible
detection of the gas, but ZnO based sensors performed better.
Two samples are shown for ZNO nanorods, ZNOS10 and
ZNOS12, which differs for preparation power (100W and 150
W respectively): ZNOS10 is composed of nanorods with
smaller diameter than for ZNO12. The response of ZNOS10 is
better than the one of ZNOS12, and comparable to the one of
ZnO nanowires prepared by furnace.
The data collected experimentally, can be fitted by a power
law R=A*[C]B to obtain a calibration curve. The B coefficient
allows to differentiate between the material: it is higher (from
1.4 to 2) for ZnO NWs and lower for SnO2 NWs (0.4).
Fig. 4 shows the response of sensors towards H2S at 500°C:
the relative response of ZNO NRs prepared by sputtering is
better to that of ZnO NWs prepared by furnace, with a change
of three orders of magnitude towards 20 ppm of this gas.
Saturation at higher concentration is observed, so tests at lower
Fig. 3. Normalized current variation of tested sensors towards 7 of
DMMP at 500°C
concentration range are on the way. Instead for SnO2 NWs
sensors a stable and reversible response is observed, but the
current variation is much lower than that observed with ZnO.
 III.   CONCLUSIONS
In the current work we prepared and characterized SnO2
and ZnO single crystalline NWs together with ZnO
Fig. 4. Relative response to H2S (10-20-30) at 500°C.
polycrystalline NRs. This allows to select the proper sensors to
be used into a cost-effective portable sensor systems for
quantitative detection of harmful gases like H2, H2S and
DMMP. As a general trend, ZnO seems to be better material
for detection for these gases. ZnO nanowires prepared by VLS
are better in terms of current stability and relative response for
H2 detection at 400°C. For DMMP detection at 500°C, the
difference between ZnO NWs and ZnO NRs is small. SnO2
NWs showed comparable performance to that of thin films
towards DMMP, but we expect higher sensor stability due to
single crystalline nature. For H2S detection ZnO NRs showed
higher sensor response.
ACKNOWLEDGMENT
The current work was partially supported by project
NANEOS, financed by NATO SPS Programme under grant N°
9085043,.
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