IJCSNS International Journal of Computer Science and Network Security, VOL.19 No.8, August 2019 135 Controlled Growth of Zinc Oxide Nanowire Arrays by Chemical Vapor Deposition (CVD) Method Waseem A. Bhutto1, Abdul Majid Soomro1, Altaf H. Nizamani1, Hussain Saleem2*, Murad Ali Khaskheli1, Ali Ghulam Sahito3, Roshan Das1, Usman Ali Khan1, Samina Saleem2,4 1Institute of Physics, University of Sindh, Jamshoro, Pakistan. 2Department of Computer Science, UBIT, University of Karachi, Karachi, Pakistan. 3Centre for Pure & Applied Geology, University of Sindh, Jamshoro, Pakistan. 4Karachi University Business School, KUBS, University of Karachi, Pakistan. *Corresponding Author: [email protected] Abstract The Nanostructured materials like nanotubes, nanowires, sensors [11], Resistive-switching Random Access Memory nanorods, and nanobelts etc. have remained the subject of interest (RRAM) [12][13], nano-generators [14][15], nano- these days because of its unique thermal, mechanical and optical capacitors [16], and gas sensors [17][18]. properties. Zinc Oxide (푍푛푂), is the most attractive material due to its unique properties and availability of a variety of growth The performance of 푍푛푂 based devices strongly depend methods. At nanostructured level, the properties of 푍푛푂 can be on their dimensions and morphologies [19][20][21][22][23] altered by controlling the growth process, such as the shape, size, [24][25][26]. Therefore, the investigation of 푍푛푂 nano- morphology, aspect ratio and density control. In this work, structures in highly oriented, aligned and ordered arrays is of Aligned 푍푛푂 Nanowires (NWs) were successfully synthesized by critical importance for the development of novel devices. Chemical Vapor Deposition (CVD) on Aluminum doped Zinc Different methods have been used to synthesize 푍푛푂 Oxide (AZO) substrate. The effects of different growth parameters nanowire arrays, such as metal organic CVD, laser ablation such as growth temperature, flow rate of oxygen and distance of and solution phase method. Most of them are expensive or substrate from source on growth of aligned 푍푛푂 NWs have been environmentally un-attractive [27][28][29]. In this work, we investigated and discussed in detail. Morphologies and structures synthesize the 푍푛푂 nanowires by CVD method to overcome of grown nanowire arrays were characterized by Scanning these issues. In order to achieve vertically well aligned 푍푛푂 Electron Microscopy (SEM) and X-ray diffraction (XRD). Optical nanowires, different parameters have been adapted, properties were optimized by UV-visible transmittance spectra, including growth temperature, flow rate of oxygen and and photo luminescence (PL). distance of substrate from source. Morphologies, structures Key words: and optical properties were characterized by scanning Chemical Vapor Deposition; Controlled Growth; Nano Structure; electron microscopy (SEM), X-ray diffraction (XRD), UV- Nanotubes; Nanowire Arrays; Optics; visible transmittance spectra, and photo luminescence (PL). 1. Introduction 2. Experimental Procedure The nanostructure materials are currently the most popular research targets because of their relatively high surface area There are many possible methods to synthesize 푍푛푂 nano- to volume ratio, high crystallinity, great stoichiometry, and materials, however, the observed properties depend mainly low impurity concentrations [1][2][3][4]. Zinc Oxide (푍푛푂), on the preparation conditions. Since we know that the in its nanostructured form, is the most appealing material substrate material has a significant effect on the morphology because of its direct band gap of 3.37 푒푉 and high exciton of 푍푛푂 nanowires [30]. Therefore, it is convenient to use binding energy of 60 푚푒푉 . Recently, 1퐷 , 2퐷 and 3퐷 푍푛푂 thin layer as a seed layer for nucleation of nanowires nanostructures, which show a diversity of morphologies, growth. In this work, we prepared the substrate using such as nanowires (NWs), nanorods (NRs), nanobelts, and transparent conductive glass coated with an aluminum zinc nanotubes, have received increasing attention due to their oxide (AZO) layer, which have high electrical conductivity unique physical properties, which differ from bulk materials, and optical transmittance value. The growth of vertically especially nanowires (NWs) can provide effective well-aligned 푍푛푂 nanowire arrays on AZO substrate was conduction paths for electrons [5][6] due to their high carried out in a horizontal quartz tube furnace with three crystallinity compared to a thin-film structure which makes heating zones. Zinc powder (5푁, 1푔) was used as the source it suitable for applications in photovoltaic, electrical, material and placed at the central heating zone of the quartz piezoelectric, opto-electrical and electrochemical devices, tube. Three pieces of AZO substrate with the dimensions of such as ultraviolet (UV) sensors [7], photodetectors [8], (1 푐푚 × 1 푐푚) were placed at a distance of 7~9 푐푚 Light-Emitting Diodes (LED) [9], solar cells [10], photo downstream of the 푍푛 powder. Before heating, the system Manuscript received August 5, 2019 Manuscript revised August 20, 2019 136 IJCSNS International Journal of Computer Science and Network Security, VOL.19 No.8, August 2019 Table-1. The Growth Parameters of 푍푛푂 Nanowire Arrays. Variations in Growth Temperature (°퐶). Distance between Growth S. 풁풏 푶 , 푵 Flow Source and ퟐ ퟐ Temp No (품) (풔풄풄풎) Substrate (풄풎) (°푪) 1 1.0 10,100 8 540 2 1.0 10,100 8 560 3 1.0 10,100 8 580 Fig.1. SEM images of 푍푛푂 nanowire arrays at different temperatures: (a) 540 °퐶; (b) 560 °퐶; (c) 580 °퐶. Variations in Growth Temp (°퐶). was evacuated to 1.0 × 10−2 푃푎, and a mixed gas consisting It has been noticed that the 푍푛 source evaporated very of 100 푠푐푐푚 푁2 flow and 8~10 푠푐푐푚 푂2 flow was little at the low growth temperature of 540°퐶, which causes introduced into the tube. Abbreviation 푠푐푐푚 stands for the low 푍푛 vapor pressure. Insufficient 푍푛 vapor pressure “standard cubic centimeters per minute” [34]. Then, the tube slows down the growth rate along all directions [32]. As a was heated to 540°퐶~580°퐶 at a rate of 20°퐶/푚푖푛 and result, the final product is very short 푍푛푂 nanowires or even maintained at this temperature for 30 푚푖푛[35][36][37][38]. a layer of 푍푛푂 thin film, as shown in Fig.1(a). Increasing the temperature to 560°퐶, leads to grow random nanowires, as The diameter and density of nanowires were controlled depicted in Fig.1(b). Further increasing the temperature at by the distance between substrate and source. After the 580°퐶, the more evaporation of the 푍푛 source occurs and growth, the tube furnace was cooled down to room reacts with oxygen. Due to high temperature 푍푛 and 푂 temperature. vapors with high kinetic energy diffuse much more easily to form the 푍푛푂 nanowires and make the orientation of nanowires better, as shown in Fig.1(c). From the Fig.1, it can 3. Results and Discussion be seen that as the temperature rises, the average diameter of nanowires is gradually increased, because the higher 푍푛푂 vapor pressure leads to larger 푍푛푂 seeds during initial 3.1 Effect of Growth Temperature on 푍푛푂 Nanowire growth [39][40][41][42]. Arrays In CVD process, morphology and the structure of a final 3.2 Effect of Oxygen Flow Rate on 푍푛푂 Nanowire product can be controlled by the temperature and the level Arrays of super-saturation. Generally, for the growth of nanowire arrays, the growth direction and rate are two important In order to study the effect of oxygen flow on the growth of factors which determine whether a nanowire can be formed. 푍푛푂 nanowires, we used different flow rates as 8 푠푐푐푚, However, the growth rate mainly depends on the growth 9 푠푐푐푚 and 10 푠푐푐푚 oxygen flows. Growth parameters are temperature [31]. In order to study the effect of temperature listed in Table-2, and the SEM images are shown in Fig.2. on 푍푛푂 nanowire arrays, we used three different From the figure we can see that well aligned nanowires were temperatures i.e. 540°퐶 , 560°퐶 and 580°퐶 . The growth grown for these three parameters, and in this case, the parameters are illustrated in Table-1, and the morphologies oxygen flow has little effect on the diameter and relatively of these samples were analyzed by SEM shown in Fig.1. density. As we know, nanowire diameter and density are IJCSNS International Journal of Computer Science and Network Security, VOL.19 No.8, August 2019 137 Table-2. The Growth Parameters of 푍푛푂 Nanowire Arrays. Variations in 푂2, 푁2 Flow (푠푐푐푚). Distance between Growth S. 풁풏 푶 , 푵 Flow Source and ퟐ ퟐ Temp No (품) (풔풄풄풎) Substrate (풄풎) (°푪) 1 1.0 8,100 8 580 2 1.0 9,100 8 580 3 1.0 10,100 8 580 Fig.2. SEM images of 푍푛푂 nanowire arrays with different oxygen concentration, (a) 8%, (b) 9%, (c) 10%. Variations in 푂2, 푁2 Flow (푠푐푐푚). crucial for coating the shell layer on 푍푛푂 nanowires. If the super saturation level. The high vapor pressure can promote density is too high or the diameter is too large, it will be growth in several directions, which results in the formation difficult to deposit a shell layer around the entire 푍푛푂 of clusters as shown in Fig.3 (a). The increase of 8 푐푚 nanowires. For low density or small diameter, the shell distance away from source decreases the 푍푛 vapor pressure. deposition is easier but it reduces light absorption which At lower 푍푛 vapor pressure, nanowire arrays preferably degrades the efficiency of device. By changing the flow rate grow in good orientation as shown in Fig.3 (b). Further little we can control the density of nanowires, and can get a increase in position of substrate at 9 푐푚 , the density of favorable condition for the growth of coaxial nanowires. nanowires is decreased as shown in Fig.3 (c).