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Supporting Information

Highly Ordered Nanoporous Alumina on Conducting Substrates with

Enhanced Adhesion by Surface Modification:
Universal Templates for Ultrahigh Density Array of Nanorods
Jinseok Byun, Jeong In Lee, Seungchul Kwon, Gumhye Jeon and Jin Kon Kim*

National Creative Research Initiative Center for Block Copolymer Self-Assembly,

Department of Chemical Engineering and Polymer Research Institute,
Pohang University of Science and Technology, Pohang, Kyungbuk 790-784, Korea

S1. Placement of AAO on a surface-modified conducting substrate

ITO-coated glass was cleaned by using chloroform for 30 min, sonicated in the mixture of

an isopropyl alcohol and acetone solution for 30min, and finally rinsed with DI water. The

cleaned ITO-coated glass was flattened for 15 min with a microwave-generated plasma

reactor (Plasma System Inc., PLASMATIC_PREENII, 24. GHz), and exposed to ozone

environment (UV/ozone cleaner, GCS-1700) for 20 min at room temperature.

Anodized aluminum oxide (AAO) was prepared by well-established two step

anodization.[1] Prior to anodization, a highly pure aluminum foil (99.999%, 1-mm thickness)

was degreased with acetone and electrochemically polished to decrease the roughness and

remove irregularities of the surface. Electropolishing was carried out in the mixture of

perchloric acid and ethanol (1:4 v/v) at 7°C and 20V for 30 min twice. After electropolishing,

the aluminum sheet was washed with ethanol and DI water. First anodization was performed

in oxalic acid (0.3M) with a platinum cathode at 15°C and 40V for 12h for obtaining the

perfect hexagonal pore arrangement over the large area.[2] For AAO with 20nm pore size, the

anoidization was carried out in oxalic acid (0.3M) at 1°C and 40V for 16h. Thick oxide layer

with irregular pores was etched by immersing the aluminum into a mixture of chromic

acid/phosphoric acid (1.8wt% H2CrO4/6wt% H3PO4) at 65°C for over 5 h, and a dimple layer

remained. The second-anodization was performed at 15°C and 40V for 6min. Finally, the pore

diameter was controlled by pore-widening step in 0.1M H3PO4 aqueous solution at 30°C.

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Figure S1 shows the schematic of the placement of AAO on the surface-modified

conducting substrate. After two-step anodization, pores of AAO were filled with the nail

polish and dried in the air for 1 h. The nail polish prevents mechanical damage (such as

folding and cracking) of AAO and maintains the pore diameter during the removal of the

barrier layer in addition to easy handling (Figure S1a). Next, the sample was immersed into

saturated aqueous solution of HgCl2 to detach the aluminum (Figure S1b). After being washed

by DI water, AAO was floated on 5 wt% of H3PO4 solution at 30°C for 35 min to remove the

barrier layer (Figure S1c). Then, AAO was immersed in acetone at 40°C to completely

remove the nail polish (Figure S1d). After the acetone was removed, the mixture of DI water

and acetone (1:1 v/v) was added carefully to AAO (Figure S1e). Finally, AAO was floated on

a surface-modified conducting substrate and annealed at 120°C for 20min (Figure S1f).

Figure S2 shows the SEM image of the bottom of AAO after removal of the nail polish,

which indicates the hexagonal ordering and uniformity were well maintained even if after

removal of Al and the barrier layer.

Figure S1. Schematic for the placement of AAO on the surface-modified conducting

substrate.

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Figure S2. SEM image of the bottom of AAO prepared by two-step anodization.

S2. AAO template with pore size of 20nm on various substrates

Figure S3(a-c) are top and cross sectional SEM images of AAO template with a diameter

of 20 nm on two different substrates (Au and ITO-coated glass), indicating that the adhesion

of AAO with smaller diameter was also excellent. This shows that the characteristics of the

pores of the template can be easily tuned by controlling anodization conditions regardless of

the substrates.

Figure S3. Top (a) and cross-sectional (b,c) SEM images of AAO template with a pore size

of 20 nm on two different conducting substrates ((b) ITO-coated glass, (c) Au).

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S3. Peel test

We quantitatively measured the adhesion between AAO and the substrate without and
with surface modification using peel test. The 180° peel test was conducted by texture

analyzer (Stable Micro System TA-XT2i) at a peel speed of 1 mm s-1. The sample dimension

was 10 mm (length) x10 mm (width). Figure S4 shows the work of peel (N/m) with peeling

time of AAO on the surface-modified and bare ITO glasses, respectively. The adhesion force

for the surface-modified substrate was ~ 20 times higher than that of unmodified substrate.

This indicates that the surface treatment on the conducting substrate allows excellent adhesion

between AAO and the substrate.

Figure S4. Work of peel versus peeling time for (a) surface-modified ITO-glass and (b) bare

ITO. The first and second arrows represent the starting and the end of peeling test,

respectively.

S4. Laterally long-range ordering of nanorods

To check the laterally long-range ordering in hexagonal packing of the fabricated
nanorods, we employed the Voronoi diagram. We used the ultrahigh density array of CdSe

nanorods on ITO-coated glass. Figure S5(a) gives top view of CdSe nanorods with a diameter
of 40 nm and a height of 200 nm. Figure S5(b) gives the Voronoi diagram corresponding to

the white box region of Figure S5(a), from which we could not see any defect within this area.

That is, an excellent long-range ordering of the CdSe nanorods is achieved even though they

are on a rigid substrate.

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Figure S5. (a) Top view SEM image of CdSe nanorods on the ITO-coated glass (b) Voronoi

diagram corresponding to the white box in Figure S4(a).

S5. XRD patterns of CdSe nanorod array

Figures S6(a) and S6(b) show XRD patterns of CdSe nanorods array in a wide area on Au and

ITO-coated glass substrates, respectively. Diffraction peaks at 2θ=25.4° (d=3.505Å) and

2θ=42.04° (d=2.147Å) correspond to the (111) and (220) planes of cubic phase of CdSe.[3]

Figure S6. XRD patterns of the ultrahigh density array of CdSe nanorods on (a) Au and (b)

ITO-coated glass.

S6. Characterization of cobalt nanorods

Figures S7(a) and S7(b) give top and cross-sectional SEM images of ultrahigh density

array of Co nanorods on ITO-coated glass. Highly ordered Co nanorod array with a diameter

of 60 nm and height of 300 nm was obtained after removal of the AAO template. Figures

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S7(c) and S7(d) show TEM images of Co nanorods at lower and higher magnifications,

respectively. From Figure S7(d) and the SAED pattern given in the inset of Figure S7(d), Co

nanorods showed single crystal structure. XRD patterns of Co nanorod arrays on Au and

ITO-coated glass substrates are shown in Figures S7(e) and S7(f), respectively. Two peaks of

(100) and (002) are observed at 2θ=41.7° (d=2.165Å) and 2θ=44.62° (d=2.030Å), suggesting

that Co nanorods show hexagonally closed packed (hcp) cubic structure.

Figure S7. SEM images of top (a) and cross-sectional (b) Co nanorod array. (c) TEM image

and (d) HRTEM image of the Co nanorods. The inset in (d) is the SAED pattern. XRD pattern

of the Co nanorod arrays on (e) Au and (f) ITO-coated glass substrates.

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S7. Preparation of PAR film with the conducting surface

Polyarylate (PAR, AryLiteTM, A200HC) film with a thickness of 200 µm was used as a

flexible substrate. The eletrode was prepared by a thermal deposition of Ti with 5 nm,
followed by Au with 50 nm at a deposition rate of 0.1 Å s-1 under 2 ×10-6 Torr. Ti layer was

used to improve the adhesion between the PAR film and Au layer. A root-mean square (rms)

of the surface roughness of Au-coated PAR film was 1.2 nm, which is similar to that of bare

PAR film (1.7nm), as shown in Figure S8(a) and S8(b), respectively.

Figure S8. (a) and (b) AFM height images and height profiles of the surface of neat PAR film

and Au-coated PAR film

S8. Surface modification of Au substrate

For the surface modification of Au substrate, we used thiol terminated polystyrene (PS-

SH) with Mw of 7700 g mol-1. After the thiol groups were anchored to the Au surface and

annealed at 120°C, un-anchored PS-SH chains were washed out with cyclohexane. The

resultant thickness of anchored PS-SH layer was very thin (~1.5 nm). This layer was further

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exposed to ozone enviroment to make OH-rich hydrophilic surface. Figure S9 shows water-

contact angles on a bare Au (~85°) and surface-modified Au (infinite contact angle). The

increased hydrophilicity of the surface provides an enhanced adhesion with AAO through the

favorable interaction between the hydroxyl groups in the Au surface and AAO.

Figure S9. Water contact angle on a bare Au (left) and surface-modified Au substrate (right)

S9. Electrodeposition of CdSe and Co, and electropolymerization of P3HT

Electrodeposition of CdSe was performed potentiostatically at 0.6V from 0.01M selenium

dioxide (SeO2, 99.9+%, Aldrich), 0.01M H2SO4, and 0.2M cadmium sulfate (CdSO4,

99.99+%, Aldrich) in DI water. Cobalt nanorods were fabricated potentiostatically at -0.9V

from 1M CoSO4·6H2O and 45g L-1 boric acid (H3BO3, 99.5%, KANTO CHEMICALS) in DI

water. P3HT nanorods were fabricated by electropolymerization potentiostatically at 1.8V

from 0.1M 3-hexylthiophene (3HT, 99+%, Aldrich) and 0.02M lithium perchlorate (LiClO4,

Aldrich) in acetronitrile.

References
[1] S. K. Hwang, S. H. Jeong, H. Y. Hwang, O. J. Lee, K. H. Lee, Korean J. Chem. Eng. 2002,
19, 467
[2] F. Li, L. Zhang, R. M. Metzger, Chem. Mater. 1998, 10, 2470
[3] R. B. Kale, C. D. Lokhande, Semicond. Sci. Technol. 2005, 20, 1