Monitoring the concentration of carbon dioxide by resistance

change of K-doped TiO2 Nanowires

C.J. Lee

Korea International School [Seongnam-si, South Korea]

Cjlee25@student.kis.or.kr

Corresponding author: C.J. Lee, Cjlee25@student.kis.or.kr

SUMMARY
The usage of the gas sensor based on metal oxide semiconductors has been increasing very rapidly
in industry and in daily life for various potential applications due to their inherent physical and
chemical properties. In this study, the K-doped TiO2 nanowires showed the possibility of use as a
sensing material due to their resistance changes to the presence of CO 2 gas. In addition, treatment
with H2 plasma improved the sensitivity of the CO 2 gas sensor made of K-doped TiO2 nanowires. The
sensing mechanism was attributed to electron adsorption to the TiO 2 as a result of CO2 reduction on
the surface of K-doped sites. It reduces the hole accumulation layer due to electron–hole
recombination process, so the surface resistance of K-doped TiO 2 increases depending on the
amount of CO2 adsorption. This development suggests opportunities for the fabrication of simple,
inexpensive CO2 microsensors with low power consumption.

KEYWORDS
Carbon dioxide, Gas sensor, Nanowires

INTRODUCTION
Gas sensors have been developed to monitor the presence of carbon dioxide (CO 2) in the
environment because of its significant role in global warming. Due to the stable chemical properties of
CO2 gas, only a limited number of CO2 sensing materials have been reported. Most existing CO 2
sensors based on potentiometric devices are large, bulky devices that involve complicated fabrication
processes. To overcome the disadvantages of potentiometric CO2 sensors, measurable interaction
has been studied. It is related to a surface reaction caused by adsorption–desorption, which leads to a
change in the electrical conductance (or resistance) of metal oxides as a result of the charge-carrier
transfer. The surface reaction of metal oxide sensors is driven by many factors, such as
semiconducting nature, target gas, size, and morphology.
To achieve a miniaturized CO2 sensor, we have been aggressively exploring new CO2 sensing
materials by measuring electrical conductance in response to exposure to CO2 gas. Thus, we report
the possibility of using nanocrystalline TiO 2 doped with potassium as a resistive CO 2 sensing material,
which we have demonstrated successfully for the detection of CO2 gas. In this work, we investigated
the feasibility of using K-doped TiO2 nanowires for the detection of CO2 gas, and the effect of the H2
plasma treatment of the nanowires on their detection sensitivity.

METHODS
Fabrication of K-doped nanowires
We fabricated TiO2 nanowires by the moisture-assisted, direct oxidation of titanium in the presence of
KOH. Thin films of Ti were prepared by using a DC magnetron sputtering system with 120W DC
power. A thin film of Ti was deposited at 5 mTorr with Ar 45 sccm by heating the substrate to 400 °C.
The thickness of Ti thin film was estimated to be 200 nm.
For the fabrication of the TiO 2 nanowires, one drop (2 mL, area of ~1 cm 2) of a 1 wt% aqueous
solution of KOH was placed at the center of the Ti deposited on the substrate. Then, the substrate
was inserted into a quartz tube and placed in a horizontal tube furnace for the heat treatment. The
heat treatment was conducted by 2 steps, 150 °C for 30 min and then 650 °C for 4hrs in the humidity
60% condition by bubbling Ar gas through DI water at room temperature.
Measurement of sensing characteristics
Sensing tests were performed by attaching Au electrodes and Au lead wires on top of the TiO 2
nanowires on the Al2O3 substrate. The Au electrodes were cured at 500 °C for 1 h. The sensor was
held in a tube furnace and heated from 450 °C at different H2 levels from 2% to 10%, and then CO2
gas was introduced into the furnace. The response of the sensor was observed in the range of 500 to
2500 ppm of CO2, and the change in the resistance was measured at each CO2 concentration.

Condition of H2 plasma treatment

To improve their sensitivity, the K-doped TiO2 nanowires were treated with H2 plasma at 350 °C. H2
Plasma treatments were performed with ICP source frequency 2 MHz and power 30 W. The RF
frequency applied to the chuck was 13.56 MHz, with the chuck power 200W. H2 gas flow rate was 50
sccm.

RESULTS AND DISCUSSION

Figure 1 shows the resistance changes to the CO2 concentration from 500 ppm to 2500 ppm at 500
°C on as-grown, K-doped TiO2 nanowires. The sensing test temperature was 500 °C, and the level of
the H2 background gas varied from 2% to 10%. Since the as-grown K-doped TiO2 nanowires were p-
type semiconductors and CO2 was categorized as a reducing species, the resistance of the nanowires
increases when they are exposed to CO2. Adsorption of gases on the surface of TiO 2 results in the
transfer of carrier charges between the gas and the TiO 2, which permits tuning of the electrical
resistance. As TiO2 is exposed to air, oxygen usually can be adsorbed in three forms: molecular O2 ,
atomic O and O 2 species. Once oxygen ions are chemisorbed, the concentration of free charge
carriers (holes) increases in p-type materials. Chemisorbed oxygen species can form a hole-
accumulating layer near the TiO2 surface. When a targeting gas, CO2, is introduced after
chemisorption of O2, it reacts with adsorbed oxygen and may chemisorb by transferring electrons to
the TiO2. Accordingly, the recombination of electron holes increases, narrowing the accumulation
layer. Hence, the resistance of resistance increases depending on the concentration of a targeting
gas.

Figure 1. Resistance changes of K-doped TiO2 nanowires from CO2 concentration at 450 °C and with
the different levels of H2 background gas.

Figure 2(a) shows the sensitivity changes of the K-TiO 2 nanowire sensor at sensing temperatures for
different levels of H2 background gas. Although the sensitivity at a CO 2 concentration of 500 ppm did
not depend significantly on the levels of background H2 gas, the sensitivity was improved by
increasing the level of H2 background gas at high concentrations of CO 2. According to this result,
hydrogen on the surface of TiO2 nanowires played an important role in the absorption of CO 2. Figure
2(b) shows the sensitivity at post H2 plasma treatment with different times. The sensitivity of the as-
grown nanowires was 6.6% at a CO2 concentration of 500 ppm. After treatment with the H2 plasma for
5 min, the sensitivity increased from 6.6% to 9.5% at the CO 2 concentration of 500 ppm. After the H2
plasma treatments for times ranging from 5 to 20 min, the improvements were similar. This
improvement might be due to physical and chemical effects from ion bombardment, surface charges,
and etching by the H2 plasma. Hydrogen ion bombardment might modify the surfaces of the
nanowires and create dangling bonds that can react easily with CO 2 on the nanowires. The H2 plasma
treatment on TiO2 is related to the number of oxygen vacancies and Ti 3+. The H2 plasma treatment
might create electron-hole separation in TiO2 and then enhances the surface-active states of TiO 2 by
changing its electronic structure from TiO2 (Ti4+) to Ti2O3 (Ti3+). This behavior makes a positive
contribution to absorbing O2 ions on TiO2 exposed to air, the sensitivity of the sensor can be
enhanced by increasing the hole accumulation layer on the surface of TiO2.

Figure 2. (a) The sensitivity changes at different levels of H 2 background gas and (b) the sensitivity
changes at post H2 plasma treatment with different times.

CONCLUSIONS
Transition metal oxides, such as TiO2 and SnO2, have been used extensively in gas sensor
applications for reactive gases such as CO and H 2 because of the changes in their electrical
conductivities in the presence of a target gas. However, to date, limited research about a CO 2 sensor
that uses transition metal oxide has been reported. K-doped TiO2 nanowires are promising as
potential CO2 gas sensors. After treatment with H2 plasma, the sensor showed better sensitivity to
CO2 gas. Although additional research is needed to detect the variable range of CO 2 concentration,
and to stabilize the baseline by investigating the interference with other gases including humidity, the
results of this study indicate that the K-doped TiO 2 nanowires provide a promising opportunity for the
development and use of simple, inexpensive CO2 microsensors.

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