Controllable fabrication of highly ordered thin AAO template on Si substrate for electrodeposition of nanostructures Khaled M.Chahrour, Naser M.

Ahmed, M.R.Hashim, Nezar G.Elfadill & M.A.Qaeed

Applied Physics A Materials Science & Processing ISSN 0947-8396 Appl. Phys. A DOI 10.1007/s00339-014-8242-5

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Appl. Phys. A DOI 10.1007/s00339-014-8242-5

Controllable fabrication of highly ordered thin AAO template on Si substrate for electrodeposition of nanostructures
Khaled M. Chahrour Naser M. Ahmed M. R. Hashim Nezar G. Elfadill M. A. Qaeed

Received: 30 November 2013 / Accepted: 8 January 2014 Springer-Verlag Berlin Heidelberg 2014

Abstract In this work, simple fabrication of hexagonally highly ordered porous anodic aluminum oxide (AAO) of Al thin lm (1 lm) on Si substrate is described using two-step anodization method for electrochemical synthesis of nanostructures. In this method, the templates were prepared under the controllable conditions of the parameters, which give rise to the possibility of highly ordered nanopore arrays with a well aspect ratio. Pore widening was then fullled in 5 wt% phosphoric acid solution at 25 C. The pore diameter and spacing are proportional to the applied voltage, which is due to the mechanical stress associated with the volume expansion of the aluminum during the anodization according to the mechanical stress model. Pore-widening solution adjusted the pore diameter and thinned the AAO barrier layer at room temperature under the control of etching time. As an application, Cu nanorods arrays embedded in anodic alumina (AAO) template were fabricated by dc electrodeposition. The characterization of the AAO templates and the Cu nanorods produced was made by X-ray diffraction, eld emission scanning microscope, energy dispersive X-ray spectroscopy and atomic force microscope (AFM). The images of AFM show that porous AAO template under constant voltage is 40 V which presents the optimum ordering.

1 Introduction Template technique is one of the most successful approaches for obtaining size-controllable nanomaterials [1]. Recently, porous anodic aluminum oxide (AAO) templates have received considerable attention in synthetic nanostructure materials due to particular characters such as controllable pore diameter and periodicity [2]. The porous AAO template fabrication process and mechanisms of pore formation have been studied [3, 4]. Using porous AAO templates for nanostructure deposition needs no costly nanolithography. There are two major kinds of porous AAO templates, the rst-type of porous AAO template is grown on a bulk pure aluminum foil [5], while the second-type is grown on a substrate such as silicon [3]. The second-type of the template is preferable due to fact that this silicon substrate usually functions as an electrode as well as a mechanical support [6]. Most of the developed methods for producing porous AAO templates generally yield highly ordered arrays on bulk Al foil [7]. Until now, the fabrication of highly ordered thin lms of porous AAO on Si substrate is difcult to be formed mainly due to the complicated surface states (roughness and crystallite sizes) and nonuniformity of the deposited Al lm [8, 9] and still remains a major challenge from the scientic and technological point of review [10]. In spite of the wide range of promising applications of the AAO templates, the biggest problem remains is the barrier layer formed at the bottom of the AAO pores, which prevents direct physical and electrical contact to the substrate [11]. To remove the barrier layer, various techniques such as pore widening, cathodic polarization, voltage drop, plasma assisted etching, etc. were employed [1214]. However, there are some challenges posed by the thin lm AAO templates, including achieving highlyordered AAO templates with open-through pore structure.

K. M. Chahrour (&) N. M. Ahmed M. R. Hashim N. G. Elfadill M. A. Qaeed Nano-Optoelectronics Research and Technology Laboratory, School of Physics, Universiti Sains Malaysia, 11800 Penang, Malaysia e-mail: skhaled_66@yahoo.com

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In this work, we show that highly ordered thin porous AAO templates can be grown on Si substrate under controllable condition sets of anodizing process with thin Al lms using two-step anodizing process [15], leading to perfect hexagonal pore structure, since the ordering of the pore arrangement of porous AAO templates control the regularity of further nanostructures fabricated using AAO templates as host material [16]. This work focused on the inuence of voltage and pore-widening time on the structure, order of thin porous AAO template. The advantages of our work over the past studies are that we used a simple pore-widening solution for adjusting the pore diameter and thinning the AAO barrier layer at room temperature under control of etching time for only few minutes to prepare nanostructures scaffolds with desirable pore diameters that we need.

2 Experimental method P-type (100) Si substrate with area of (1.5 cm 9 1.5 cm) was cleaned with (RCA) method prior to deposit 20 nm of Ti lm using RF sputtering, subsequently an Al (purity 99.99 %) was evaporated by e-beam on Ti lm with thickness of 1 lm. All samples were annealed at 500 C for 2 h in a conventional furnace under nitrogen ambient.

Our experimental results show that the use of a Ti adhesion layer prevented the pealing-off the Al lm from the Si wafer during anodization. The anodizing process was performed in a special design electrochemical cell using a platinum rod as a cathode. The electric contact was made at the backside of the Si substrate. The samples were anodized in acidic aqueous solution of 0.3 M oxalic acid under different voltages for a certain time. After the nishing of the rst anodizing, an aluminum oxide layer was removed by wet etching in aqueous solution of 6 wt% phosphoric acid and 1.8 wt% chromic acid at 60 C for 30 min. The second anodizing was carried out with the same controllable conditions of the rst anodizing until all of the residual aluminum was oxidized. Pore widening is controlled by immersing the AAO template into 5 wt% phosphoric acid solution at 25 C for different times. The electrochemical cell was cooled with circulating water bath system to ensure a constant temperature below 20 C. During anodizing process, the electrolyte was vigorously stirred. Some as-synthesized AAO templates are further annealed at 800 C for 5 h in atmosphere. As an application, copper nanorods were deposited potentiostatically, with AAO template serving as working electrode, platinum rod and Ag/AgCl(sat) as the counter and reference electrodes, respectively, using a EDAQ Model potentiostat. The electrolyte was 0.45 M of CuSO2

Fig. 1 a FESEM images show top view and a cross-sectional view of the AAO templates. AAO templates were prepared under parameter conditions; time of rst anodization is 10 min and anodizing voltage

40, 45, 50 V, respectively. Pore-widening time is 20 min, b curve correlating mean pore diameter with voltage, and c AFM images (i ) AAO prepared under 50 V and (ii) AAO prepared under 40 V

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dissolved in 3 M lactic acid. The solutions PH was adjusted to 9 using sodium hydroxide. The electrodeposition was performed at an applied potential of -1 V for 5 min. The temperature was maintained at 60 C, with constant stirring throughout electrodeposition. Upon completion, the AAO template was rinsed by deionized water and dried. The surface morphology and structure of the fabricated AAO templates and the deposited Cu nanorods were studied using FESEM, EDX, AFM and XRD.

3 Results and discussion The morphology of the fabricated AAO templates was characterized by FESEM and AFM images. Figure 1a shows typical top view and a cross-sectional view of the AAO templates under 40, 45 and 50 V, respectively. The results show distinctly that an ordered honeycomb structure with uniformity in pore diameter and spacing can be fabricated with two-step anodization under controllable conditions; also Fig. 1a illustrates that the pore diameter and interpore distance increase with increasing voltage. The mean of pore diameter is 65 nm and mean of interpore

distance is 110 nm for AAO template prepared under 40 V. AAO template prepared under 45 V has a mean pore size of 70 nm and a mean interpore distance of 115 nm, while AAO template prepared under 50 V has a mean pore size of 85 nm and a mean interpore distance of 128 nm. A curve correlating mean pore diameter with anodizing voltage described in Fig. 1b illustrates that the mean pore diameter is increased with increasing the voltage. In addition, AAO sample prepared under lower voltage is more regular as shown in AFM images (Fig. 1c). The mechanism of selforganization is not fully understood, even though it can be explained by the mechanical stress model proposed by Jessensky et al. [4]. Pores are rst formed at certain microrough region where the current density is concentrated on after the formation of steady oxide layer and then the pores grow vertically to surface with equilibrium of eldenhanced oxide dissolution at the oxide/electrolyte interface and oxide growth at the metal/oxide interface, and the horizontal growth is performed simultaneously. In this process, the compressive stress between the pores which are associated with the volume expansion of the aluminum during anodization impulses the structural adjustment to form honeycomb like pore arrays. With the enhancement of

Fig. 2 FESEM images show top view of the AAO templates. AAO templates were prepared under parameter conditions; time of rst anodization is 10 min and anodizing voltage 40 V. Time of pore

widening t = 10, t = 15 and t = 20 min, respectively. Curve correlating mean pore diameter with pore-widening time

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Fig. 3 XRD spectra of AAO template a with annealing and b without annealing

anodizing voltage, the horizontal growth of the pores increases leading to the enlargement of the pore diameter and spacing. At the same time, the arrangement among the pores cannot keep up with the growth velocity of AAO and the ordering of this structure might decrease. Although AAO template prepared after two-step anodization possesses controllable pore diameter and periodicity, further pore adjustment can be actualized by exposure to phosphoric acid, which is called pore widening. The FESEM images of the AAO templates were prepared under 40 V after pore widening for 10, 15 and 20 min at 25 C as shown in Fig. 2a. The pore diameter increases, while the pore spacing almost keeps unchanged.

Fig. 4 a, b FESEM image shows the deposition of Cu inside of AAO template and EDX spectra. c, d FESEM image shows a cross-sectional view of Cu nanorods perpendicular to the Si substrate after removal of AAO template and EDX spectra, respectively

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Controllable fabrication of highly ordered thin AAO template on Si substrate

4 Conclusions Highly ordered pore arrays in AAO templates with uniform pore size and vertically aligned nanotubes with well aspect ratio were successfully fabricated by anodization of thin Al lm on Si wafer. Anodizing voltage and time of pore widening are explored in our experimental conditions. FESEM analysis show that the pore diameter depends on both anodizing voltage and time of pore widening, also the AAO template prepared under 40 V present the optimum ordering as shown in the AFM images. The relation between the ordering of the pore arrays and anodizing voltage is explained by a growthdissolution model. A simple wet etching process is used for thinning the bottom barrier layer of AAO template and widening of any desired pore diameter that we need under a control of etching time. FESEM analysis show that highly orderly self-aligned Cu nanorods have been prepared on AAO template/Si substrate using electrochemical process. Finally, stirring and maintaining the electrolyte below 20 C are critical steps in obtaining ordered pore arrays.
Acknowledgments We gratefully acknowledge the support of the School of Physics, University Saince Malaysia under short term Grant No. 304/PFIZIK/6312076.

Fig. 5 XRD spectra of copper nanorods embedded in AAO template

A curve correlating mean pore diameter with widening time described in Fig. 2b illustrates that the mean pore diameter is monotonously increased with increasing the pore-widening time. The increase of pore diameter after the thinning of the outer and inner surface of AAO template might be due to the wet etching effect of phosphoric acid. This provides a convenient route to prepare AAO template of any desired pore diameter that we need. Then, any desired nanostructure diameter can be grown in its pore. Figure 3 shows XRD spectra of AAO template after annealing, the reection peak of (222) corresponding to the Al2O3 phase appear [17], which implies that the AAO transforms from amorphous to crystalline after annealing at 800 C. With the aid of AAO template and electrodeposition process, highly ordered and vertical arrays of Cu nanorods can be prepared. Figure 4a, b shows the plane view for AAO template on a Si substrate after deposition of Cu, almost all the nanopores were lled by Cu and conrmed with the EDX spectra. The lengths of Cu nanorods grown inside the AAO template were longer than the depth of AAO template whereby all the nanorods showed sign of overgrowth. Figure 4c shows the Cu nanorods remained vertically to the Si substrate and could be observed clearly. It is worth noting that the heights of the nanorods were uniform and remained separated from each other after the removal of the AAO template. The length of the nanorods was 1.25 lm and the approximate diameter was 50 nm. Note that some of the Cu nanorods near the front edge were broken during the splitting process for the preparation of cross-sectional FESEM samples. Figure 4d shows EDX spectra that conrm the compositions of the nanorods on Si substrate after the removal of the AAO template. Figure 5 shows the X-ray diffraction patterns of copper nanorods embedded in AAO template. The nanorods were polycrystalline with cubic structure indicated by the presence of two prominent peaks close to 2h angles of 43.41 and 50.60, corresponding to Cu (111) and Cu (200) diffractions, respectively.

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