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Microstructural control and selective C2H5OH sensing properties of Zn2SnO4 nanobers prepared by electrospinningw
Seung-Hoon Choi,a In-Sung Hwang,b Jong-Heun Lee,b Seong-Geun Oha and Il-Doo Kim*c
Downloaded by National University of Singapore on 20 May 2011 Published on 18 April 2011 on http://pubs.rsc.org | doi:10.1039/C1CC10707K

Received 6th February 2011, Accepted 30th March 2011 DOI: 10.1039/c1cc10707k Microstructural evolution of spinel Zn2SnO4 nanobers was manipulated via an in situ phase separation process of inorganic precursors and a matrix polymer during electrospinning and calcination. Chemiresistive gas sensors using porous Zn2SnO4 bers exhibited superior C2H5OH sensing response. One dimensional (1D) metal oxide nanostructures, such as wires, tubes, rods and belts, have been explored extensively for potential applications in chemical sensors, catalysts, rechargeable batteries, photonic devices, and transistors.1 The electrical, optical and catalytic properties of these 1D metal oxides are strongly correlated with their shape, size and structures. Among various synthesis methods of 1D metal oxides, electrospinning (e-spin), which utilizes target material precursors and a matrix polymer,2 is one of the simplest, most cost-eective, and versatile techniques for creating ceramic nanobers. Various metal oxide nanobers such as simple binary oxides3 (i.e., ZnO, TiO2, SnO2, and NiO), complex oxides such as LaNiO3,4 and two-phase mixtures of NiO/ZnO5 have been reported. In addition, the morphologies of e-spun metal oxides have been successfully manipulated by controlling processing conditions, leading to dierent geometries such as nanorods on nanobers, belts, hollow bers, cable-like multi-core bers, and bicomponent bers.6 Thus, multiple, superior functions can be incorporated into metal oxide bers to extend their unique functional features for various applications. Zinc stannate (Zn2SnO4) has a cubic inverse spinel structure with a lattice parameter of B8.65 A and is known as a transparent n-type semiconductor (Eg = 3.6 eV) with high electron conductivity (B104 S cm1) and fascinating optical properties.7 Based on zinc stannates high electrical conductivity and low absorption coecient in the visible range, as well as high chemical sensitivity, various Zn2SnO4 nanostructures such as particles, belts, cones, and wires have been considered as potential candidates for ultraviolet photodetectors,8
a b

Department of Chemical Engineering, Hanyang University, Seoul 133-791, Republic of Korea Department of Materials Science and Engineering, Korea University, Anam-Dong, Seongbuk-Gu, Seoul 136-713, Republic of Korea c Department of Materials Science and Engineering, Korea Advanced Institute of Science and Technology, Daejeon 305-701, Republic of Korea. E-mail: idkim@kaist.ac.kr; Fax: +82-42-359-3310; Tel: +82-42-350-3329 w Electronic supplementary information (ESI) available. See DOI: 10.1039/c1cc10707k

photocatalysts for decomposition of organic pollutants,9 working electrodes for dye-sensitized solar cells,10 sensors for moisture and combustible gases,11 and anode materials for Li-ion batteries.12 However, to the best of our knowledge, there have been no reports in the literature on the fabrication of inverse spinel Zn2SnO4 nanobers and in-depth study on the microstructural evolution of Zn2SnO4 precursor/polymer composite bers during the e-spin and calcination process. Although an earlier study has reported on the fabrication of ZnO/SnO2 composite bers via the e-spin technique,13 morphological design of Zn2SnO4 nanobers via the control of in situ phase separation between an inorganic precursor and a matrix polymer has not been investigated. Here, we report on the facile synthesis of porous and dense Zn2SnO4 nanobers and ultra-selective C2H5OH gas sensing characteristics against H2 and CO gases. The formation mechanism of Zn2SnO4 nanobers with dierent morphologies, i.e., porous and dense bers, is described in the ESIw (Experimental section and Fig. S1). The morphologies of e-spun ceramic bers are strongly inuenced by the miscibility between the inorganic precursor and polymer.14 This indicates that miscibility control between the precursor and polymer is one of the key parameters to control the interior morphologies of e-spun metal oxide bers. In order to verify this, we prepared Zn2SnO4 bers using e-spin of the precursor solution containing zinc acetate (Zn(OAc)2), tin(IV) acetate (Sn(OAc)4) and two dierent kinds of polymers, polyvinylacetate (PVAc, Mw: 1 300 000 g mol1) and polyvinylpyrrolidone (PVP, Mw: 1 300 000 g mol1). Fig. 1ad present FE-SEM images of Zn2SnO4 ber mats, which were prepared using a PVAc based polymer and a ZnSn precursor solution. As-spun Zn(OAc)2Sn(OAc)4/PVAc composite bers exhibit randomly oriented bers in the form of nonwoven mats with diameters ranging from 380 to 718 nm and lengths of several hundred micrometres (Fig. 1a). Calcination of the composite bers at 700 1C resulted in the formation of polycrystalline Zn2SnO4 bers due to decomposition of the PVAc matrix and crystallization of Zn(OAc)2Sn(OAc)4 precursors into inverse spinel Zn2SnO4. Diameters of the Zn2SnO4 bers ranged from 352 to 705 nm, which are similar values to those of as-spun bers. The calcined Zn2SnO4 bers exhibited a porous surface and lotus-root-like morphologies (Fig. 1c and d). Highly porous features were clearly observed in the scanning TEM (STEM) analysis (Fig. 1e). Nanocrystallites,
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Fig. 2 TGA curve of Zn(OAc)2Sn(OAc)4/PVAc composite bers; inset shows longitudinal cross-sectional FESEM images of a single ber taken from each calcination step using FIB milling.

Fig. 1 Morphologies and crystal structures of Zn2SnO4 bers using dierent polymer matrixes: (a) SEM image of as-spun ZnSn precursor/ PVAc composite bers; (b) SEM image of Zn2SnO4 bers calcined at 700 1C (PVAc matrix); (c) magnied SEM image of (b); (d) cross sectional image of (c); (e) scanning TEM (STEM) image of (c); (f) and (g) TEM image and EDS elemental mapping of Zn, Sn; (h) HR-TEM image and lattice fringe of selected area (the values in parentheses correspond to the theoretical results); (i) SEM image of Zn2SnO4 bers calcined at 700 1C (reference, PVP matrix); (j) XRD pattern of Zn2SnO4 bers.

which are smaller than 20 nm, are clearly visible in Fig. 1f. The composition prole of Zn2SnO4 bers revealed that the Zn/Sn chemical composition ratio was approximately 2 : 1 (Fig. 1g). Careful examination of HR-TEM images (Fig. 1h) revealed cubic inverse spinel structures. Interplanar distances of 3.08 A, 2.64 A, and 5.02 A were observed with angles of 31.21 and 581 between the respective planes. These planes correspond to the (220), (311), and (111) planes of Zn2SnO4. On the contrary, in the case of Zn2SnO4 bers prepared from a PVP polymer and ZnSn precursor solution, the resultant bers exhibited a smooth surface and a dense inner structure composed of ne particles (Fig. 1i). The X-ray diraction patterns of both Zn2SnO4 bers displayed similar polycrystalline diraction peaks of the cubic inverse spinel phase characterized by 2y peaks = 29.21, 34.41, 35.951, 41.781, 45.71, 51.71, and 55.11, which represent the (220), (311), (222), (400), (331), (422), and (511) planes, respectively (corresponding to PDF 24-1470) (Fig. 1j). Fig. 2 shows a representative TGA curve of Zn(OAc)2 Sn(OAc)4/PVAc composite bers and longitudinal cross-sectional images of a focussed ion beam (FIB)-cut single ber at each calcination step of 10 min. As-spun Zn(OAc)2Sn(OAc)4/PVAc composite bers are composed of an inhomogeneous mixture of two distinctive phases (Fig. 2a), i.e., a Zn(OAc)2Sn(OAc)4-rich
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domain and a PVAc-rich domain (see ESIw, Fig. S2). Below 300 1C, residual N,N 0 -dimethylformamide (DMF) and water in the as-spun bers are slowly vaporized (region I in Fig. 2). The degradation process of the composite bers exhibits two main distinctive regions (II-1 and II-2 regions in Fig. 2). In the rst step, the composite bers begin to lose weight at 300 1C and this weight loss continues up to 325 1C (region II-1 in Fig. 2). This indicates the creation of the thermal decomposition of the organic group mostly associated with acetate groups of Zn(OAc)2 Sn(OAc)4 and deacetylation of VAc (vinylacetate) groups in PVAc to form polyacetylene segments in the backbone.3,13 When the polymer decomposition temperature (300 1C) is rst reached, inner ber morphologies composed of solidstate ZnSn precursor domains maintained their initial shape (Fig. 2b). As the temperature was increased up to 450500 1C, the unsaturated carbon backbone and organic composites burned out (region II-2 in Fig. 2) and ZnSn precursors were crystallized, retaining their highly porous inner morphology (Fig. 2c). The lotus-root-like morphology remains unchanged after heat-treatment at 700 1C (region III in Fig. 2 and Fig. 2d). In contrast, as-spun Zn(OAc)2Sn(OAc)4/PVP composite bers exhibited no apparent interface between the precursors and PVP (middle upper image in Fig. 2), leading to the formation of dense bers after calcination at 700 1C (see ESIw, Fig. S3). This indicates that Zn(OAc)2Sn(OAc)4/PVP composites have better miscibility than that of Zn(OAc)2Sn(OAc)4/PVAc composites. This is due to the fact that PVP binds with inorganic salts, as compared to PVAc, because a strong withdrawing pyrrolidone group in PVP facilitates the association with salt.15 In order to examine the gas response performance, we measured the response of sensor prototypes comprising networks of porous and dense Zn2SnO4 nanobers, respectively (see Fig. 3ac). Both the porous and dense Zn2SnO4 bers showed typical n-type gas sensing behaviors, i.e., a resistance decrease by reducing gases (100 ppm CO, H2, and C2H5OH). Ra/Rg ratios were used to evaluate the gas responses to reducing gases.16 Here, a maximum sensor response to 100 ppm of C2H5OH was achieved at an operating temperature of 450 1C (Fig. 3dg). The gas sensing transient plots of both Zn2SnO4
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the matrix polymer. We applied porous and dense Zn2SnO4 bers to semiconducting gas sensors. Remarkably high selectivity for C2H5OH against CO and H2 gases was observed in both porous and dense Zn2SnO4 sensors. In particular, the porous Zn2SnO4 sensor exhibited approximately 4-fold higher C2H5OH sensitivity compared to the dense Zn2SnO4 sensor, leading to a new player for application in volatile organic compound sensors. The proposed synthetic method is simple and versatile, providing fascinating opportunities to control the morphology of various complex metal-oxide nanobers, particularly optimized for applications in gas sensors. This work was supported by a grant from the cooperative R&D Program (B551179-10-01-00) funded by the Korea Research Council Industrial Science and Technology, Republic of Korea. The work of J.-H. Lee was supported by the KOSEF NRL Program (R0A-2008-000-20032-0).

Notes and references

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Fig. 3 (a) Confocal laser micrograph of porous Zn2SnO4 bers coated on the Al2O3 substrate with two Au electrodes; SEM image of (b) porous Zn2SnO4 bers in a selected area of (a); (b1) enlarged image of (b); (c) dense Zn2SnO4 bers on the Al2O3 substrate with two Au electrodes; (c1) enlarged image of (c); (d) and (e) dynamic C2H5OH sensing transient of porous and dense Zn2SnO4 bers as a function of C2H5OH concentration at 450 1C; (f) gas responses (Ra/Rg, Ra: resistance in air and Rg: resistance in gas) from 1 ppm to 100 ppm of C2H5OH at 450 1C; (g) gas responses to 100 ppm of CO, H2, and C2H5OH operated at 450 1C.

bers at 1100 ppm of C2H5OH exhibited stable response and recovery characteristics (Fig. 3d and e). The gas response to 100 ppm of C2H5OH of PVAc based porous Zn2SnO4 nanobers (Ra/Rg: 300) was 3.75 times higher than that of PVP based dense Zn2SnO4 nanobers (Ra/Rg: 80) (Fig. 3f). Considering the dierent microstructures of the Zn2SnO4 bers, the enhanced C2H5OH sensing characteristics of porous Zn2SnO4 bers can be attributed to their highly porous structure with a higher surface area (29.02 m2 g1) and larger accessible pore volume than that (11.06 m2 g1) of dense Zn2SnO4 nanobers, which facilitate fast gas transport and eective surface reaction (see ESIw, Fig. S4). In addition, the crossresponses to 100 ppm of CO and H2 were negligible (Fig. 3g). This demonstrated the potential for selective and sensitive detection of C2H5OH at 450 1C using porous Zn2SnO4 nanober networks. In summary, the morphology of Zn2SnO4 bers was strongly aected by the miscibility between Zn(OAc)2, Sn(OAc)2 and

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