Growth of Eshelby twisted ZnO nanowires through nanoflakes & nanoflowers: A room temperature ammonia sensor
Graphical abstract
Introduction
Design and development of nanoscale architectures create new pathways in the fabrication of sensors and devices with fascinating figure of merits [[1], [2], [3]]. Fabrication of two [4], one and zero-dimensional nanostructures offers properties like quantum confinement, quantum transport and enhanced surface to volume ratio. Among these nanostructures, one-dimensional nanowire/nanorods signify their importance in the fabrication of electrodes for batteries [5], touch screens, display devices [6], electrochromics [7], magnetic devices [8,9] flexible electronics [10], photo detector [11], gas sensor [1,12,13], photovoltaic cell [14], supercapacitor [15] and dye-sensitized solar cell [16]. In particular, the one-dimensional nanostructures of metal oxides namely TiO2 [17], Fe2O3 [18], SnO2 [19], ZnO [20], WO3 [21] have been synthesized and employed for various applications. In this group of widely exploited metal oxides, ZnO has been on the center of attraction over the past several decades due to its wide band gap, enhanced exciton binding energy, chemical stability, tunable transport characteristics and visible region transparency [22]. Among the 1D ZnO nanostructures, nanowire morphology has been preferred for the fabrication of chemical/gas sensors owing to its switching like transient response in the presence of target gas [23].
ZnO nanowires can be grown through popular mechanisms like vapor-liquid-solid (VLS), solution-liquid-solid (SLS) and vapor-solid-solid (VSS) [24]. However, these growth modes are highly relying on the need for metal nanoparticles as catalysts in the anisotropic growth. At the same time the growth of nanowires through axial screw dislocation mechanism [[24], [25], [26], [27]] does not require any metal catalyst for the unidirectional growth. Stephen et al. [27] have reported the epitaxial growth of ZnO nanowires in GaN substrate through screw dislocations and realizing the Eshelby twist. Bierman et al. [24] have synthesized screw dislocated pine tree like fashioned lead sulphide nanowires through CVD and observed the Eshelby twist. Zhu et al. [26] have demonstrated the formation of chiral lead selenide nanowires through combined VLS and screw dislocated mechanisms. Further, they have presented the growth mechanisms of chiral and branched nanowires through Eshelby twist. Senthil Kumar et al. [28] have reported the formation of ZnO nanowires, and hexagonal stacking from screw dislocations on a diamond substrate through nanoparticle assisted pulsed laser deposition technique. Also, the influence of growth velocity in the formation of these nanostructures were extensively reported [28]. In this context, SILAR technique has been preferred to grow ZnO nanowires adapting dislocation driven Eshelby twist growth model by controlling the deposition cycles. To observe the dislocation driven Eshelby twist phenomena, growth patterns of ZnO nanostructures synthesized using four different zinc precursors were considered. Based on the controlled growth features, ZnO nanostructures (nanoflowers to nanowires) synthesized using zinc sulphate precursor alone were taken in to account for the detailed investigation.
On the other hand, there is a massive demand for chemical sensors, which can work in the real-time ambient environment. The excessive presence of toxic gases or volatile organic compounds (VOCs) above the permissible human limits in the living environment result in adverse effects. One such lethal VOC is ammonia, and its presence in industries is familiar due to its significant production and usage [29]. According to Occupational Safety and Health Administration (OSHA), the short-term human permissible limits towards ammonia is 25–35 ppm as a weighted time average [30,29,31]. If this permissible limit exceeds in concentration or long-term exposure, it leads to the respiratory system impairment and even causes fatality [29]. As an impact of regular interactions with other air pollutants, it will also lead to sun blocking effects [32]. In this context, the present work highlights the use of ZnO nanowire to fabricate ammonia sensor with enhanced response characteristics.
Section snippets
Synthesis of ZnO nanowires
All the chemicals used for the synthesis were of analytical reagents and purchased from Merck, India. ZnO nanostructures were synthesized on the glass substrates using SILAR technique. Initially, glass substrates were sequentially ultrasonicated with diluted H2SO4, acetone, ethanol and deionized water. Cationic solutions were prepared by dissolving 0.1 M of four different zinc precursors namely zinc acetate ((Zn (CH3COO)2·2H2O, 98.5% purity), zinc chloride (ZnCl2, >98.5% purity), zinc nitrate
Structure and morphology
X-ray diffraction patterns of the SILAR grown nanostructures prepared using four different zinc precursors are shown in Fig. 2. These patterns revealed the formation of primitive hexagonal wurtzite phase of ZnO with polycrystalline nature. Diffraction peaks such as (1 0 0), (0 0 0 2), (1 0 1), (1 0 2), (1 1 0), (1 0 3), (2 0 0), (1 1 2) and (2 0 1) were observed for all the nanostructures deposited at both 50 and 100 deposition cycles. All the diffraction planes of ZA (1
Conclusion
A series of growth process involved in the formation of cationic assimilated twisted ZnO nanowires via SILAR deposition cycles have been highlighted. A conceptual framework for the growth transformation process from nanoflakes to nanoflowers and Eshelby twisted nanowires was formulated. Twisted tail in the nanowire confirmed the presence of screw dislocations and revealed the controlled dislocation growth features, which can be attained through engineering the cationic assimilation effect.
Acknowledgments
Authors wish to express their sincere thanks to the Department of Science & Technology, New Delhi, India for their financial support IDP/IND/2012/41 (General), ECR/2016/001805 and SR/FST/ETI-284/2011(C)). One of the author, Parthasarathy Srinivasan wish to expresses his sincere thanks to Council of Scientific and Industrial Research (HRDG- 09/1095/0016/2016-EMR-I) for the financial support. Authors thank Nano Mission, DST (SR/NM/PH-16/2007 and SR/NM/PH-04/2015) for their financial support. The
Parthasarathy Srinivasan received his M.Tech. degree in Nanoelectronics from SASTRA Deemed University, Thanjavur, India in the year 2015 and received his B.E. degree in Electronics and Communication Engineering from Arasu Engineering College, Kumbakonam, India, in the year 2013. He is currently working as a CSIR Senior Research Fellow and pursuing his Ph.D. in SASTRA Deemed University, Thanjavur, India. His current research includes development of Low dimensional metal oxide nanostructures as
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Parthasarathy Srinivasan received his M.Tech. degree in Nanoelectronics from SASTRA Deemed University, Thanjavur, India in the year 2015 and received his B.E. degree in Electronics and Communication Engineering from Arasu Engineering College, Kumbakonam, India, in the year 2013. He is currently working as a CSIR Senior Research Fellow and pursuing his Ph.D. in SASTRA Deemed University, Thanjavur, India. His current research includes development of Low dimensional metal oxide nanostructures as gas/chemical sensors for food quality assessment
John Bosco Balaguru Rayappan received his M.Sc. and Ph D. degrees in Physics from St. Joseph’s College, Bharathidasan University, Tiruchirapalli, India in 1996 and 2003, respectively. He is currently working as Associate Dean (Research) in the School of Electrical & Electronics Engineering and Centre for Nanotechnology & Advanced Biomaterials (CeNTAB) of SASTRA Deemed University, Thanjavur, India. His current research interests include development of gas/chemical sensors, biosensors for food & water quality and healthcare applications. He is also working in the field of embedded systems and steganography. He has published more than 220 research articles in peer reviewed international journals and filed six patents including a US patent.