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Highly response CO2 gas sensor based on Au-La2O3 doped SnO2 nanofibers

Kuo-Chin Hsu, Te-Hua Fang, Yu-Jen Hsiao, Ching-An Chan

PII: S0167-577X(19)31776-8
DOI: https://doi.org/10.1016/j.matlet.2019.127144
Reference: MLBLUE 127144

To appear in: Materials Letters

Received Date: 12 August 2019

Please cite this article as: K-C. Hsu, T-H. Fang, Y-J. Hsiao, C-A. Chan, Highly response CO2 gas sensor based on
Au-La2O3 doped SnO2 nanofibers, Materials Letters (2019), doi: https://doi.org/10.1016/j.matlet.2019.127144

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© 2019 Published by Elsevier B.V.

Kuo-Chin Hsu1, Te-Hua Fang1*, Yu-Jen Hsiao2, and Ching-An Chan1

1Department of Mechanical Engineering, National Kaohsiung University of Science and Technology,

*Corresponding author: [email protected] (T.H. Fang)

Abstract

In this study, 5 wt% La2O3 doped SnO2 nanofibers (La2O3/SnO2 NFs) were prepared using an

electrospinning process after annealing at 600°C for 1h. The gas sensor fabricated using the 5 wt%

La2O3/SnO2 NFs was found to effectively improve the responses of many types of gases, especially CO2.

Then, the Au particles with a particle size range of approximately 15-20 nm were sputtered on 5 wt%

La2O3/SnO2 NFs. The Au particles were also shown to effectively enhance the gas sensing properties, which

can improve the response of a gas sensor by 50%.

Keywords: Ceramics; Fibre technology; Sol-gel preparation; Sensors; Sputtering

1. Introduction

Due to advances in technology, gas sensors have evolved to being smaller in size, high sensitivity,

with high stability, and a fast response. There have been a significant number of studies on gas sensors

based on metal oxide materials, such as SnO2, ZnO, TiO2, WO3, and In2O3 [1-5]. The earliest used material

was SnO2, which has been widely used in gas sensors due to its low cost, high conductivity, and high

stability. There are many technologies available to synthesize SnO2 materials, including sol-gel, sputter,

hydrothermal, spray pyrolysis, and electrospinning [6-10]. Among them, electrospinning technology has

recently become an important technology used to produce nanofibers, where the nanofibers have high

specific surface area. The high specific surface area of sensing materials can create a gas sensor device with

high sensitivity and a fast response.

An SnO2-based gas sensor can be used to detect different gases and the incorporation of metals or

metal oxides has been known to be effective in enhancing the sensitivity of SnO2-based sensors [11-14].

To the best of our knowledge, the CO2 sensing concentration of La2O3/SnO2-typed CO2 gas sensors are

about 1000 ppm, and the response values are not high. The main purpose of this study is to prepare Au

sputtered on La2O3/SnO2 NFs for use in CO2 gas sensor and operate with better sensitivity at lower gas

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sensing concentration and lower working temperature.

2. Experimental

1 mmol of SnCl2·2H2O (98%) and 1~9 wt% La(NO3)3‧6H2O (99%) were dissolved in 10 mL

Dimethylformamide (DMF, 99.8%); 1.71g Polyvinylpyrrolidone (PVP, average Mw~1,300,000) was

dissolved in 12 mL ethanol (8.3 wt%) and then subjected to magnetic stirring at room temperature for 2 h.

The two solutions were mixed and stirred and immediately used for electrospinning process. The

electrospinning parameters were set as follows: an applied voltage of 17 kV, a working distance of 15 cm,

and a flow rate of 0.05 mL/min. We used an interdigitated gold electrode as the gas sensor device substrate,

and the electrospinning was done on it. The as-prepared La2O3/SnO2/PVP nanofibers were annealed at

600°C for 1 h to remove PVP, and then Au nanoparticles were sputtered onto the nanofibers. The gas sensor

test system provided a variety of gases and heaters, where a digital source meter (Keithley 2400) was used

to record the resistance or current of the gas response.

3. Results and discussion

Figure 1 shows SEM images of (a) 1, (b) 3, (c) 5, (d) 7, and (e) 9 wt% La2O3/SnO2 NFs after annealing

at 600°C for 1h. It can be observed that the surface morphology of the 1 and 3 wt% La2O3/SnO2 NFs appear

to be a sticky band structure, while the 5, 7, and 9 wt% La2O3/SnO2 NFs are more uniform and smooth. The

5 wt% La2O3/SnO2 NFs have the minimum average diameter about 85 nm. The 7 wt% La2O3/SnO2 NFs

have a slightly larger average diameter and a more bead-like structure, while the 9 wt% La2O3/SnO2 NFs

have an average diameter greater than that of the 7 wt% La2O3/SnO2 NFs, the structure of which appears to

be fragile. The 5 wt% La2O3/SnO2 NFs electrospun onto interdigitated gold electrode after annealing at

600°C for 1h was shown in Figure 1(f). The XRD pattern of 5 wt% La2O3/SnO2 NFs after annealing at 400,

500, and 600°C was shown in Figure 1(g). When the annealing temperature is 400°C, the crystallinity was

poor. While annealing over 500°C, the crystallinity was better, and the peak was more obvious. It can be

observed that the lattice planes of (110), (101), (200), (211), (220), and (310) conform to the JCPDS card

(No. 41-1445) as a highly crystalline SnO2 structure. However, the crystal phase of La2O3 cannot be

observed in the XRD pattern, which was presumed to be due to the lower doping concentration.

The 5 wt% La2O3/SnO2 NFs were annealed at 600°C and then analyzed using TEM, as shown in Figure

2(a). The fiber diameter was approximately 70 nm, and the fiber was composed of many nanoparticles

which were obviously polyhedrons located close together within the fibers. This is because the PVP

polymer decomposed after high temperature calcination, causing the fiber to have a porous structure [15,

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16]. Figure 2(b) and (c) show the EDS analysis, where it can be seen that the element La appeared in the

analysis, and the element ratios of Sn : La : O were 29.35 : 3.09 : 67.56, respectively. Figure 2(d) is a single

fiber mapping diagram, which confirms that the La2O3 was evenly distributed throughout the fiber. The

chemical state of elements was measured by XPS as illustrated in Figure 2(e). The survey scan spectra

indicate the appearance of La 3d, Sn 3d, and O 1s from La2O3/SnO2 NFs and C 1s caused by the PVP

polymer remaining in the NFs. The above results prove that the La element is uniformly doped in the SnO2

nanofiber.

Figure 3(a) and (b) show the response diagram for the 1, 3, 5, 7, and 9 wt% La2O3/SnO2 NFs with and

without Au particles sensing with 100 ppm C2H6O (ethanol), TVOC (total volatile organic compounds),

CO, and CO2 at 300°C. The sputter times of Au particles are 0, 20, 30, and 40 s. It can be observed that as

the concentration of La2O3 increased, the response to various gases also increased. However, the gas sensing

response of the nanofiber doping of more than 5 wt% La2O3 was gradually reduced. The highest response

values of 5 wt% La2O3/SnO2 NFs with Au particles for all the sensing gases were C2H6O = 102, TVOC =

6.8, CO = 4.9, and CO2 = 10.1, respectively. Based on the above results, it can be seen that the 5 wt%

La2O3/SnO2 NFs and Au particles sputtered for 30 s improved the response of the above four gases, and

thus enhanced the response by about 50%.

The CO2 sensing mechanism taking place at the Au adsorbed La2O3/SnO2 NFs is illustrated in Figure

3(c). When the average size of about 15-20nm Au NPs is uniformly adsorbed on La2O3/SnO2 NFs, it can

promote active oxygen as a chemical sensitizer, which is very beneficial for oxygen spillover and thus

facilitate the sensing reaction between surface oxygen ions and sensing gas. Therefore, the spillover effect

is the mechanism most likely to lead to improved sensor response. Furthermore, there is catalytic synergy

effect between Au and metal oxide phase. Au NPs act as a gas sensing reactive site under this effect and

play an excellent medium to provide nanochannels for electron transfer during sensing process. In summary,

the gas sensing performance of the Au adsorbed 5 wt% La2O3/SnO2 NFs sensor has been significantly

improved, indicating that it has a promising application in detecting CO2.

The gas sensor discussed in this study can be used to sense many types of gases. It was also found that

the response toward CO2 gas was significantly improved as compared with previous reports, as shown in

Table 1 [17-21]. This work can obtain a higher response CO2 gas sensor at relatively lower concentrations

and lower temperatures. This is a positive outcome for the future development of CO2 sensors.

4. Conclusion

We successfully prepared 5 wt% La2O3/SnO2 NFs onto interdigitated gold electrode using an

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electrospinning process and then Au nanoparticles with a particle size of approximately 15-20 nm were

sputtered onto the nanofibers. The gas sensor fabricated using Au adsorbed 5 wt% La2O3/SnO2 NFs can

effectively increase the gas response values for many types of gases. The device in this study demonstrated

potential for improved responses about 50% of many types of gas, especially CO2.

Acknowledgments

The authors acknowledge the support in part by the Ministry of Science and Technology, Taiwan

under grant number MOST 106-2221-E-992-333-MY3 and 106-2221-E-992-343-MY3.

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Declaration of interests

The authors declare that they have no known competing financial interests or personal relationships

that could have appeared to influence the work reported in this paper.

Conflict of interest: none.

Table 1. Comparison of the properties of the La2O3 doped SnO2-based CO2 sensors.

Materials CO2 gas Operating temperature Response Reference

La2O3/SnO2 1100 400 1.5 [17]

La2O3/SnO2 1000 400 1.2 [18]

La2O3/SnO2 1000 400 1.52 [19]

La2O3/SnO2 1000 225 0.005 [20]

1% Pt-La2O3/SnO2 1000 225 0.32 [20]

3% Pt-La2O3/SnO2 1000 225 4.38 [20]

La2O3/SnO2 1000 350 2.9 [21]

La2O3/SnO2 100 300 5.1 This work

Au-La2O3/SnO2 100 300 10.1 This work

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Figure 1: SEM image of (a) 1, (b) 3, (c) 5, (d) 7, and (e) 9 wt% La2O3/SnO2 NFs after annealing at 600°C

for 1h; (f) 5 wt% La2O3/SnO2 NFs electrospun onto interdigitated gold electrode after annealing at 600°C

for 1h; (g) XRD pattern of the 5 wt% La2O3/SnO2 NFs after annealing at 400, 500, and 600°C.

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Figure 2: (a) LR-TEM, (b)(c) EDS analysis, (d) elemental mapping, and (e) XPS analysis of 5 wt%

La2O3/SnO2 NFs after annealing at 600°C.

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Figure 3: The response diagram of (a) 1, 3, 5, 7, and 9 wt% La2O3/SnO2 NFs; (b) Au on 5 wt% La2O3/SnO2

NFs sputtered for 0, 20, 30, and 40 s sensing 100 ppm ethanol, TVOC, CO, and CO2 at 300°C; (c) CO2 gas

sensing mechanism of Au adsorbed La2O3/SnO2 NFs.

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Highlights:

1. Highly response CO2 sensor of Au-La2O3/SnO2 NFs were prepared.

2. The CO2 gas response is 10.1 with Au particle adsorption.

3. The CO2 gas sensor mechanism is also displayed.

Conflict of interest: none

Declaration of interests

☒ The authors declare that they have no known competing financial interests or
personal relationships that could have appeared to influence the work reported in this
paper.

☐The authors declare the following financial interests/personal relationships which may be
considered as potential competing interests: