- Nano Express
- Open Access
Promotion on Acetone Sensing of Single SnO2 Nanobelt by Eu Doping
© The Author(s). 2017
- Received: 16 May 2017
- Accepted: 31 May 2017
- Published: 12 June 2017
SnO2 nanobelts (NBs) have unique structural and functional properties which attract great attention in gas detecting. In this work, Eu doping is adopted to improve the gas sensitivity of pure SnO2, especially to enhance the response to one single gas. The Eu-doped SnO2 NBs, pure-SnO2 NBs, and their single NB devices are fabricated by simple techniques. The sensing properties of the two sensors have been experimentally investigated. It is found that the two sensors possess long-term stability with rapid response performance, and Eu doping improves the electronic performance and the gas-sensing response, particularly to acetone. In addition, the effects aroused by Eu have been theoretically calculated, which indicates that Eu doping enhances the sensing performance of SnO2. Consequently, Eu-doped SnO2 NBs show great potential applications in the detection of acetone.
- Eu-doped SnO2
- Single nanobelt
- Acetone sensor
With the development of industry, as an important aspect of environmental problems, the leakage of harmful gases becomes more and more eye-catching. Many efforts of improving the gas sensor performance have been made in order to detect and monitor those gases. Excellent accomplishments have been reached in the field of gas sensor due to the remarkable advancement in novel nanomaterials [1–3].
Among various shapes of nanomaterials, nanobelt is a promising choice in gas sensing application [4, 5] since it could bear a large specific surface area, crystallographic perfection, and great electron transport properties. For instance, Khiabani et al. have reported that In2O3 NBs have excellent gas sensitive properties for NO2 . As to metal oxide semiconductors, their susceptibility coupled with stabilization makes it very applicable to the detection of various gases [7–9]. As an n-type wide-bandgap semiconductor, SnO2 with a high gas-sensitive response to a variety of gases has attracted worldwide attention [10–12]. It has been proved by Huang et al. that SnO2 nanorod arrays take the possession of unique performance as a hydrogen sensor . In such materials, rare metal doping is often used to improve the sensitivity, especially to one single gas [14, 15]. As a typical rare earth metal, it has been proved to be effective for Eu to improve the sensing performance of various materials [16–19]. Especially, Hao et al. have testified the positive effects of Eu doping on the sensing and electrical conductivity of Eu-based metal-organic framework . However, to the best of our knowledge, there are still very few studies about Eu doping effects on the gas-sensitive properties so far. Thus, it is a requisite to explore the gas-sensing properties of Eu-doped-SnO2 nanobelts (Eu-SnO2 NBs) to make progress in the sensitivity of pure-SnO2 nanobelts (SnO2 NBs).
In this work, we have made the synthesis of SnO2 NBs and Eu-SnO2 NBs by thermal evaporation method with simple conditions, low cost, and accessibility. The sensitivity of SnO2 NBs and Eu-SnO2 NBs to four gases was measured, and it is demonstrated that the Eu-SnO2 NB sensor owns a higher response, especially to acetone. The conceivable mechanism was proposed on the basis of theoretical calculations. It turns out that Eu-SnO2 NBs reveal great potential in acetone-sensing applications.
The synthesis of NBs was conducted in a horizontal tube furnace (HTF) with an alundum tube. The raw materials which provided Sn element were pure SnO2 powders, and Eu ions were supplied by pure Eu(O2CCH3)3 powders with a mass ratio of 19:1 for the preparation of the doped NBs. Then, the ingredients were filled into a ceramic boat being laid in the middle of the HTF and a silicon wafer plated with 10 nm Au film was positioned downstream 20 cm far away from the vessel. Subsequently, HTF was rinsed by argon, and then the temperature of the central region climbed up to 1355 °C with a ramp-up of 10 °C/min and then was kept at 1355 °C for 120 min. The flow of argon as carrier gas was at 20 sccm in the meantime, and the internal pressure was maintained at 200 torr by means of a mechanical pump. At last, the temperature declined naturally and the required NBs were obtained.
The specimens were characterized by X-ray diffraction (XRD) (D/max-3B Rigaku with Cu-Kα radiation, λ = 0.15406 nm), scanning electron microscopy (SEM) (Quanta 200 FEG, FEI Company), energy dispersive X-ray spectroscopy (EDS) (Octane Super, EDAX), X-ray photoelectron spectroscopy (XPS) (PHI 5000 Versaprobe, UlVAC-PHI), and high-resolution transmission electron microscopy (HRTEM) attached with the selected area electron diffraction (SAED) (Tecnai G2 Transmission Electron Microscope, 200 kV).
As shown in Fig. 4c, XPS spectrum displays that SnO2 NBs contain Sn 3d, O 1s, Eu 4d, and C 1s states. It is indicative of the successful doping of Eu into SnO2. In Fig. 4d, the Eu 4d peak having great symmetry could be well fitted by a Gaussian spectrum. It implies that there is only Eu 4d5/2 located in a 128.9 eV state arising from trivalent Eu, so the main Eu element in Eu-SnO2 NBs is Eu3+.
Figure 5d displays the chemical resistance response of Eu-SnO2 NB and SnO2 NB sensors to different gas concentrations at 210 °C. With the concentration climbing up, the response/recovery time of Eu-SnO2 NB (SnO2 NB) sensor takes the values of 8/9 (5/7), 10/11 (12/14), 11/14 (12/13), 14/16 (14/16), and 15/19 (15/16) s. Their values are actually more or less the same in size. The detection lasted a few months and was repeated over and over again. Although during the period, the humidity ranged from 30 to 70 RH%, there is almost no fluctuation in the response, which could demonstrate that humidity has no effect on the sensor’s performance.
According to Eqs. 4 and 5, more defects will be formed when Eu ions replace the position of Sn atoms in SnO2 lattice, and this could lead to more active reactions at the same time. In addition, Eu doping can trigger the dehydrogenation which can lower down the energy of the redox reactions . Through these ways, Eu realizes the boost of sensor performance.
The Eu-doped and pure SnO2 NBs with regular morphology and great flakiness ratio have been fabricated and the relevant single nanobelt devices have been prepared. Certainly, their electrical- and gas-sensing properties have been investigated and it is found that the conductivity of Eu-SnO2 is higher than that of the pure one. The results of their sensitive measurements show that the optimum working temperatures of them are both 210 °C, and the highest sensitivity of Eu-SnO2 device to 100 ppm of acetone is 8.56, which is 6.29 times as large as that of its pure counterpart (1.36). The response recovery time of the two devices is less than 20 s. The TDL of the Eu-SnO2 NB and SnO2 NB sensors have been calculated, and the results are 131 and 230 ppb, respectively. The theoretical results have proved that Eu doping could improve the electrochemical properties and conductive performance of SnO2. All the results reveal that Eu doping could improve the sensitivity of sensing response of SnO2 NB, especially to acetone gas.
This work was partially supported by the Recruitment Program of Global Experts, China; the 1000 Talents Plan of Sichuan Province, China; and the National Natural Science Foundation of China (Grant no. 11164034).
YLiu and HZS guided the experiments and revised the final edition of the manuscript. WC and ZQ performed the experiments and wrote the manuscript. YZ guided the simulations. YLi, SS, and ZMW improved the manuscript. All authors read and approved the final manuscript.
The authors declare that they have no competing interests.
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