Materials Research Express

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Influence of growth temperature and duration on different properties of

ultra-long ZnO nanorods grown by modified chemical bath deposition
method
To cite this article before publication: Sabah M. Mohammad et al 2018 Mater. Res. Express in press https://doi.org/10.1088/2053-1591/aad76b

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Page 1 of 18 AUTHOR SUBMITTED MANUSCRIPT - MRX-109212.R1

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4 Influence of growth temperature and duration on different
5 properties of ultra-long ZnO nanorods grown by modified
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7 chemical bath deposition method
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9 Sabah M. Mohammad1*, Nabeel M. Abd-Alghafour2,3, Rawnaq A. Talib4, Z.
10 Hassan1*, Naser M. Ahmed2, A.A. Abuelsamen2 and Naveed Afzal5
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12 1
Institute of Nano Optoelectronics Research and Technology (INOR), Universiti Sains
13 Malaysia, 11800 USM, Penang, Malaysia.

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School of Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia.
15 3
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University of Al-Anbar, College of Science, Al-Anbar, Iraq
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17 Polymer Research Centre, University of Basra, Iraq
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18 Centre for Advanced Studies in Physics, GC University, Lahore, Pakistan
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20 *Corresponding authors at: Institute of Nano Optoelectronics Research and

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21 Technology (INOR), Universiti Sains Malaysia, 11800 USM, Penang, Malaysia.
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E-mail addresses:
24 zai@usm.my (Zainuriah Hassan), Tel: +604-653 5638; Fax: +604-6535639
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26 sabahaskari14@gmail.com, (Sabah M. Mohammad) Tel.: +60147256871
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ABSTRACT
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31 In this work, ultra-long ZnO nanorods (NRs) were grown on ZnO buffered Si
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substrates by using direct heat substrate-modified chemical bath deposition (DHS-
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36 MCBD) method. Initially, the growth temperature was varied in the range 140 oC to
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38 250 oC while keeping the time fixed at 4h. In the second stage, the growth
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40 temperature was kept fixed at 220 oC and the time was changed from 4h to 8h. The
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43 morphological, structural and optical properties of ZnO NRs at different growth
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45 temperatures were investigated by using field emission scanning electron microscope
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47 (FESEM), x-ray diffraction (XRD) and photoluminescence (PL) spectroscopy
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50 techniques. The surface morphology results revealed the formation of hexagonal-
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52 shaped, ultra-long and vertically-aligned ZnO NRs. The average length of the NRs
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54 was increased from 5.7 µm to 24.5 µm by increasing the growth temperature from
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140 oC to 250 oC. The XRD results specified the formation of c-axis oriented
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59 diffraction peak corresponding to hexagonal ZnO NRs in all the samples. The
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 AUTHOR SUBMITTED MANUSCRIPT - MRX-109212.R1 Page 2 of 18

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3 intensity of this peak was increased by increasing the growth temperature up to 220
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6 C, however, on further increasing the temperature to 250 oC, the c-axis peak intensity
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8 was decreased. The PL analysis indicated higher UV to deep level emission intensity

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10 ratio (IUV/IDLE) of the NRs grown at 220 oC as compared to the others. Similarly, by
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changing the growth time from 4h to 8h, the length of ZnO NRs was also increased.

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15 The results obtained were correlated and the chemical reactions for ZnO NRs growth
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17 were discussed in this paper.
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20 Keywords: Ultra-long NRs, ZnO, Direct heat, Modified, CBD.

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1. Introduction
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30 Among various metal-oxide semiconductors, ZnO nanostructures especially
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32 ZnO nanorods (NRs) exhibit a tremendous interest of researchers due to their
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34 remarkable properties and applications in various devices such as light emitting
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37 devices (LEDs), UV detectors, solar cells, pH sensors, chemical sensors, biosensors
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39 etc. [1, 2].
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41 A nanorod or nanowire is obtained when the growth is constrained in two
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dimensions. Several techniques have been used for the growth of ZnO
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46 films/nanostructures that include, hydrothermal, chemical bath deposition (CBD)
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48 [3-5], metal–organic chemical vapour deposition (MOCVD) [6, 7], physical vapor
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50 deposition (PVD) [8, 9], molecular beam epitaxy (MBE) [10], pulsed laser deposition
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53 (PLD) [11], sputtering [12], top-down approaches by etching [13], electro-spinning
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55 [14, 15] etc. In addition to this, Andrés-Vergés et al. [16] proposed an aqueous
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57 solution growth method in 1990 that was used to fabricate high-quality ZnO micro-
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60 rods on conducting glass and Si substrates [17].

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3 Previous studies demonstrated that an increase in the aspect ratio of ZnO
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6 nanorods (length/diameter) plays a crucial role in improving their performance in
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8 electrical devices [18, 19], Recent studies have reported that longer ZnO nanorods/

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10 nanowires find potential applications in solar cells [20], hydrophobicity [21, 22],
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piezotronics [23], field emission [24], photodetection [25, 26], LED [27], gas sensing

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15 [25] etc. Therefore, extending the length of ZnO NRs and reducing their diameter
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17 have attracted significant attention in recent times. Most of the synthesis methods for
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ultra-long ZnO NRs growth are complex and these require high growth temperature
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22 [28]. In addition to the above mentioned techniques, other methods such as
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24 polyethyleneimine (PEI)-assisted preheating hydrothermal method (PAPHT) [29],
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continuous flow injection (CFI) hydrothermal [30], anodization [31], carbothermal

[32], vapour phase transport [33] and direct heat substrate-modified chemical bath
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31 deposition (DHS-MCBD) [34] have also been used for the synthesis ultra-long ZnO
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Among various techniques, the growth of ZnO NRs by CBD technique has
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38 been found to be quite effective and inexpensive. Four major parameters, including,
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40 precursor materials, precursor concentration, duration, and temperature have
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significant influence in controlling structure, stability, morphology and optical
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45 properties of ZnO NRs grown by CBD method. Therefore, significant efforts have
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47 been made to investigate the effect of these parameters on dimensions and quality of
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49 ZnO NRs synthesized by CBD method in order to achieve the optimum synthesis
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52 parameters. However, it is important to point out that the growth temperature during
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54 CBD or hydrothermal methods usually refers to solution temperature whereas in this
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56 work, it has been referred to the substrate temperature. This is mainly due to a direct
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supply of heat on the backside of the substrate and not within the solution which is a
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3 feature of DHS-MCBD technique. The effects of growth temperature and time on the
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6 morphological (length and diameter), structural, and optical properties of ultra-long
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8 ZnO NRs arrays obtained from the DHS-MCBD technique have been investigated in

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10 this paper.
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15 2. Experimental procedure
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17 In this study, all sources of chemical materials used were without further
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purification. The synthesis technique has been explained in our earlier work [28]. The
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22 Si was used as a substrate to grow ultra-length ZnO NRs in this work. After removing
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24 contamination from the top of Si substrate by using 2-propanol and acetone, the Radio
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Corporation of America (RCA) cleaning process was utilized to remove any oxide

layer on the Si wafer [35]. Then RF sputtering system was used to deposit 150 nm
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31 thick ZnO buffer layer on the Si substrate. Afterward, the buffered substrate was
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33 inserted in a quartz tube of the furnace for heat treatment in air 350 oC for 0.5h to
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obtain ZnO seeds for the CBD growth of ZnO NRs [36]. In the second stage, the
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38 backside of ZnO-buffered Si substrate was connected tightly on the glass surface of a
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40 Teflon tube and then the tube was placed diagonally in a beaker containing precursor
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solution (see Figure. 1). In this work, the precursor solution containing equimolar
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45 aqueous solution of zinc nitrate Zn (NO3)2 6H2O and hexamethylamine C6H12N4
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47 (HMTA)) was used. The concentration of each chemical was 0.08 M. An AC variable
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49 voltage controller was used to vary the input voltage across the heater of the system.
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52 This enabled us to select a suitable substrate temperature for the experiment.

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54 The growth temperature was varied from 140 °C to 250 °C while fixing the growth
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56 time at 4h, and the growth duration was changed from 4h to 8h with fixing of the
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3 growth temperature at 220 °C. The samples were washed out with deionized water to
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6 remove any remaining salt and finally, these were dried using the nitrogen gas.
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8 The ZnO NRs were characterized by using field emission scanning electron

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10 microscope (FEI-NOVA NANOSEM 450) for morphological analysis. The crystal
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structure of ZnO NRs was studied through high-resolution X-ray diffraction (HR-

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15 XRD) analysis. The HR-XRD was conducted by operating the x-ray diffractometer at
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17 40 kV with 20 mA and by using Cu-Kα radiation having 0.1541 nm wavelength. The
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diffraction patterns were recorded in the 2θ range of 20o–80o. The optical properties
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22 of ZnO NRs were measured at room temperature by photoluminescence (PL)
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24 operating with a He-Cd laser (325 nm) as the excitation source.
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49 Figure 1. Schematic of step-by-step fabrication of the ultra-long ZnO NRs
50 on ZnO/Si substrate
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3 3. Result and Discussion
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3.1 Morphology Characterization by FESEM
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10 Figure 2 shows FESEM cross-sectional images of ultra-long ZnO NRs grown
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12 on ZnO/Si substrates at various growth temperatures: (a) 140 °C, (b) 180 °C, (c) 220
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14 °C, and (d) 250 °C for 4h. It is seen that the ZnO NRs for all the samples were
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crystallized in vertical directions. The average length of the NRs was found to be
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19 about 5.7 µm, 7 µm, 15.5 µm and 24.5 µm at 140 °C, 180 °C, 220 °C and 250 °C
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21 respectively. The figure clearly indicates that the length of ZnO NRs increases with
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increase in the growth temperature from 140 °C to 250 °C. This increase in length is
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26 attributed to an increase in the energy supplied from the external heater to the
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substrate [37]. The calculated growth rate of ZnO NRs was found to be 19, 23, 52,
30 and 82 nm/min respectively. These results show the length of ZnO NRs can be made
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35 direct supply energy on the substrate. The FESEM images show high growth
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37 distribution density of ultra-long ZnO NRs on Si for all the samples that is due to a
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high temperature which is provided from the backside of the Si substrate. The DHS-
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42 MCBD synthesis technique leads to an activation of a large number of grains of ZnO
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44 buffer layer that finally increases the density of the NRs [36, 38].
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30 Figure 2. FESEM cross-sectional images of ultralong ZnO NRs grown onto ZnO
31 seeds/silicon substrate at various temperatures: (a) 140 °C, (b) 180 °C, (c) 220 °C, and
32 (d) 250 °C for 4h.
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3.2 Structural Characterization
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39 Figure 3 displays XRD patterns of ZnO NRs grown on ZnO/Si substrate at
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41 different temperatures. These patterns show a high intensity ZnO diffraction peak
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relating to (002) plane (JCPDS Card No. 01-080-0074) and a Si (111) peak (JCPDS
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46 Card No. 01-077-2111) in all the samples. The (002) diffraction peak of ZnO shows
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48 its hexagonal wurtzite nature. A variation in the intensity of (002) peak with growth
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50 temperature is also shown in the inset of Figure. 3. The intensity of (002) peak
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53 increases with increase of the growth temperature to 220 °C, however, on further
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55 increasing the temperature, the intensity is decreased. The full width at half maximum
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57 (FWHM) of (002) diffraction peak for all samples is found to be quite low. The
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FWHM values are noticed to be 0.245o, 0.237o, 0.217o and 0.333o at 140 oC, 180 oC,

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3 220 oC and 250 oC respectively. The strong intensity and narrow FWHM of ZnO NRs
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6 demonstrate that the NRs have grown perpendicularly on Si substrate (along the c-
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8 axis) with good crystalline quality [39]. The (222) and (004) oriented peaks represent

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10 second order diffraction of Si and ZnO NRs respectively.
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47 Figure. 3. X-ray diffraction pattern of ultra-long ZnO NRs at various growth
48 temperatures (a) 140 °C, (b) 180 °C, (c) 220 °C, and (d) 250 °C with 4h growth time.
49 The figure inset is the (002) peak intensity of ZnO NRs was plotted as a function of
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the growth temperature.
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3 3.2 Optical Characterizations
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7 The room-temperature photoluminescence (PL) spectra of ultra-long ZnO NRs
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9 formed on ZnO/Si substrate at various growth temperatures are shown in Fig. 4. The
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high intensity UV emission peaks for ZnO NRs are located at 376 nm to 382 nm that
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14 corresponds to the ZnO band gap. In addition, some peaks are also observed in the
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16 visible region of the electromagnetic spectrum containing the wavelength range
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18 between 460 nm (2.70 eV) and 730 nm (1.70 eV). These peaks are associated with
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deep energy levels’ emission (DLE) of ZnO. These peaks arise due to the presence of

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23 inherent defects in the ZnO NRs such as oxygen interstitials, oxygen vacancies, zinc
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25 vacancies, and interstitials. The emissions at 540 nm (2.30 eV) and 588 nm (2.10 eV)
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are attributed to the transitions of electrons from oxygen vacancy (Vo) site to the

30 valence band [40, 41]. On the other hand, the emission bands localized in the spectral
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32 range 650-680 nm (1.90-1.82 eV) correspond to the red bands. The red emission is
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ascribed to defect levels that are associated with oxygen vacancies or Zn interstitials
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37 [42-44]. In fact, the PL emission from ZnO defect levels is difficult to understand
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39 completely. However, from a theoretical point of view, the positions of zinc
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41 interstitial (Zni), zinc vacancy (VZn), Vo and oxygen interstitials (Oi) are located at
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44 0.22 eV, 2.28 eV, 2.47 eV and 3.06 eV below the conduction band respectively [34].
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47 However, it is reasonable to expect the presence of defects in the ultra-long
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49 ZnO NRs synthesized by DHS-MCBD technique [45]. From the Fig. 4, it is clear that
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52 the intensity of UV peak at 220 oC is higher than that of the other samples. Therefore,
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54 the ultra-long ZnO NRs prepared at 220 °C show the highest IUV/I DLE ratio (5.7)
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56 whereas those NRs prepared at 140 °C exhibit lowest IUV/IDLE ratio (1.75) as shown
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59 inside Fig. 4. This large difference in intensity (IUV/IDLE) suggests that the ultra-long
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3 ZnO NRs grown on ZnO/Si substrate at 220 oC exhibit high crystalline quality that is
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6 in accordance with the XRD analysis as described above [46]. The PL peaks related to
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8 deep level defects for the sample d (which was prepared at 250 °C) have a higher

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10 intensity as compared to the other samples. The increased length of ZnO NRs in the
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case of sample d compared with other samples (see Figure 2) suggests that sample d

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15 has the highest surface area to volume ratio, therefore, we believe that the ZnO NRs
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17 prepared at 250 °C have higher level of surface and sub-surface oxygen vacancies and
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other defects under the current environment [8].
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49 Figure 4. Room-temperature PL spectra of ultra-long ZnO NRs at various
50 temperatures: (a) 140 °C, (b) 180 °C, (c) 220 °C, (d) 250 °C, grown on ZnO/Si for 4h
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The figure inset shows IUV/IDLE ratio as a function of the growth temperature.
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55 The second study in this work was the investigation of deposition time effects
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58 on the growth of ultra-long ZnO NRS on ZnO/Si substrate. The growth time was
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3 was found to be the optimum growth temperature as described above. Figure 2c and
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6 Figure 5 (C2 and C3) show FESEM images of the ultra-long ZnO NRs fabricated at
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8 different growth time 4h, 6h, and 8h at 220 °C. The length of ZnO NRs was

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10 significantly increased from approximately 15.5 µm to 28 µm and their average
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diameter also was increased from approximately 800 nm to 1800 nm by increasing the

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15 growth time from 4 h to 8 h. This shows that by extending the growth time, the length
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17 and diameter of the ZnO NRs could be increased. [47].
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40 Figure 5. FESEM cross-sectional images of ultra-long ZnO NRs grown on
41 ZnO/Si substrate at various growth time: (C2) 220 °C and (C3) at 250 °C. The inset is
42 a schematic of polar faces, perpendicular to the [0001] direction, and non-polar faces,
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parallel to the [0001] direction.

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47 In this experimental method, as like CBD method (or hydrothermal method),
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49 in order to grow the units of ZnO NRs, two ions are needed, namely, Zn2+ and OH-.
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These ions play a significant role in producing colloidal Zn (OH)2 clusters. The Zn2+
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54 ions are provided by the zinc nitrate salt that are used to grow ZnO NRs. On the other
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56 hand, the O2− ions are provided by the water molecules. Although, the exact role of
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58 HMTA for the ZnO NRs growth is under investigation, however, it is considered to
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3 serve as a weak base and it slowly hydrolyse in the water solution to supply OH- ions
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6 [48, 49]. The chemical reactions for the growth of ZnO NRs can be summarized into
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8 the following four equations: decomposition reaction (Eq.1), hydroxyl supply reaction

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10 (Eq.2), super saturation reaction (Eq. 3-4) and ZnO nanowire growth reaction (Eq. 5)
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[50-52]:

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𝐶6 𝐻12 𝑁4 + 6𝐻2 𝑂 → 6𝐻𝐶𝐻𝑂 + 4𝑁𝐻3 (1)
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23 𝑁𝐻3 + 𝐻2 𝑂 → 𝑁𝐻4+ + 𝑂𝐻 − (2)
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26 𝑍𝑛(𝑁𝑂3 )2 → 𝑍𝑛2+ + 2𝑁𝑂3− (3)
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29 𝑍𝑛2+ + 2𝑂𝐻 − → 𝑍𝑛(𝑂𝐻)2
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32 𝑍𝑛(𝑂𝐻)2 → 𝑍𝑛𝑂 + 𝐻2 𝑂 (5)
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35 In this context, one can see that the diameter of ZnO NRs also increases beside
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38 the increase in their length when either the growth temperature (see Fig 2) or the
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40 growth duration (see Figure 5) becomes longer. The increase in growth temperature
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42 and time accelerates the reaction process for growing ZnO NRs to a greater extent in
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45 the z-direction and a lesser degree for the (a and b)-direction. On the other hand,
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47 longer growth durations leads to the formation of smaller diameter NRs to combine
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49 with each other and ZnO NRs with a larger diameter are obtained [37, 53].
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The ZnO NRs exhibit wurtzite structure consisting of alternating Zn and O

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54 atoms. The oxygen ion (O2− ) is tetrahedrally coordinated with four Zn ions ( 𝑍𝑛2+ ),
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56 whereas the Zn ion is in connection with four oxygen ions. The ZnO crystal structure
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consists of two polar surfaces that are polar Zn (0001) and O (0001) terminated faces.
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3 The non-polar (1120) and (1010) surfaces of ZnO contain an equal number of Zn and
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6 O atoms (shown in the inset of Figure 5) [54, 55]. Finally, we can observe that the
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8 increase in the length of ZnO NRs is larger than the increase in their diameter with

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10 increase of either the growth temperature or the growth time. The ZnO polar surface
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possesses high kinetic energy (K.E) therefore, it plays a crucial role in the column

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15 growth. The cleavage energy of polar {001} surfaces is approximately 60% higher
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17 than that of the nonpolar {100} and {110} faces [56]. As a result, the polar surface
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{001} having higher cleavage energy grows faster as compared to the surface that has
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22 lower energy. This process is repeated during the ZnO crystallization that leads to the
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24 higher growth rate along [100] direction than the other directions [57-59]. This
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explains that the growth of ZnO NRs in the longitudinal direction (length) occurs

more rapidly than in lateral directions (diameter).

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33 4. Conclusion
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36 In conclusion, we proposed a direct heat substrate-modified chemical bath
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38 deposition method to grow vertically ultralong ZnO NRs on the buffered silicon
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40 substrates. The growth temperature and growth time effects on the morphological,
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structural and optical properties of ultralong ZnO NRs were investigated by FE-SEM,
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45 XRD and PL spectroscopy. From the FESEM measurement, the length of as-grown
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47 ZnO NRs was increased with increasing growth temperature and growth time, in
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49 which it has successfully synthesized average length of rods of 24.5 µm for the NRs
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52 grown at 250 oC for 4h and 28 µm for the NRs grown at 8h with growth temperature
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54 of 220 oC. However, all the conditions resulted in the vertical growth of the ultralong
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56 ZnO NRs with good morphological properties for all samples. XRD measurement
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59 results show that the ZnO NRs which prepared at 220 °C have the strongest (002)
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3 peak intensity and the lowest FWHM value. The room temperature PL spectra
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6 revealed that the highest value of IUV/IDLE ratio (5.7) can be obtained when the ZnO
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8 NRs are prepared at 220 °C whereas the lowest IUV/IDLE ratio (1.75) for the ZnO NRs

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10 is obtained at 140 oC. Since, he DHS-MCBD technique does not involve complex
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processes, therefore this method can be effectively be used to fabricate various

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15 nanostructures for applications in electrical devices.
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18 Acknowledgments
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22 The authors would like to thank the Institute of Nano Optoelectronics
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24 Research and Technology (INOR) and School of Physics, Universiti Sains Malaysia
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(USM) for the help extended during the research work. The support of LRGS grant

(203/CINOR/6720013) is gratefully acknowledged.

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