Photolithographic Approaches for Fabricating Highly Ordered Nanopatterned Arrays
© to the authors 2008
Received: 16 August 2008
Accepted: 9 October 2008
Published: 30 October 2008
In this work, we report that large area metal nanowire and polymer nanotube arrays were successfully patterned by photolithographic approach using anodic aluminum oxide (AAO) templates. Nanowires were produced by electrochemical deposition, and nanotubes by solution-wetting. The highly ordered patterns of nanowire and nanotube arrays were observed using scanning electron microscopy (SEM) and found to stand free on the substrate. The method is expected to play an important role in the application of microdevices in the future.
KeywordsPattern AAO Photolithographic approach Nanowire arrays Nanotube arrays
Recent innovations in the areas of micro- and nanofabrication have created a unique opportunity for patterning surfaces with features, the lateral dimensions of which span over the nano- to millimeter range. Micro- and nanometer scale patterns can be obtained by photolithography [1–4], electron beam lithography [5, 6], soft lithography , micro-contact printing (μCP) [8–11]. These techniques above have partially the same process: they can transfer patterns onto the surface of a substrate. With the development of nanotechnology, a variety of industries, such as biosensor , proteomic arrays , and multifunctional coatings , have focused on obtaining patterns with the smallest possible lateral dimensions . Photolithography is one of the most successful techniques available in large-scale microfabrication . The method is effective, of low cost, simple to implement, and suitable for patterning various nanomaterials [17, 18].
Herein, we report an effective procedure for the fabrication of patterned nanostructure arrays with micro scale features. This process starts with the fabrication of patterned anodic aluminum oxide (AAO) templates. An AAO template was spin-coated with a layer of photoresist to seal the pores of the AAO template, and then “soft baked” at low temperature to remove the solvents from the photoresist and improve photoresist–AAO template adhesion. This composite was covered with a photolithographic mask and exposed to UV, and then “hard baked” at higher temperature to further active cross-linking processes and improve the mechanical stability of the pattern ; it was subsequently developed in a developer to make the pores of AAO selectively open only in those exposed areas.
Then the designed template was used for a secondary template to synthesize metal, semiconductor, and polymer one-dimensional nanoarrays. We explain this useful method by an example of patterning copper (Cu) nanowire and polystyrene (PS) nanotube arrays.
Electrodeposition of Cu Nanowires
The same side of the secondary template was sputtered with a layer of Au and regarded as a work electrode. In a tri-electrode system, the electrodeposition was carried out using platinum as the anode and a calomel electrode as the reference electrode, and the Cu nanowires were selectively deposited into the open pores. Finally, the patterned nanowire arrays were revealed by the removal of AAO in a sodium hydroxide solution.
Solution-Wetting of Polymer Nanotubes
A drop of PS solution was placed on a microscope slide, and then an AAO membrane with patterned side downward was quickly placed on it. The solution entered completely into the template pores along their inner wall. Then the composite was placed in a sodium hydroxide solution to dissolve the template after the solvent completely evaporated. PS nanotube arrays were obtained.
The pattern was tilted to reveal the length of the vertical nanowires. From Fig. 1b, the length is measured to be approximately 50 μm (the depth of AAO is 60 μm), and can be controlled to satisfy application by controlling the deposition time. The line width of the patterns is about 15 μm, and can also be changed by changing the line width in the masks. The diameter of a single wire is about 300 nm, the same as the pores of AAO template, which are well proportioned in diameter (Fig. 1c).
Figure 2b shows that the length of the PS nanotubes is about 45 μm, and can be controlled by controlling the synthesis time or polymer solution amount. The line width of the patterns is the same as Fig. 1b.
Figure 2c shows the characteristic of nanotubes more clearly, from which we can see their open mouths. The free standing nanotubes have very strong mechanical temperament, and an outer diameter of about 300 nm and a wall thickness of about 50 nm. The outer diameter is a bit larger than that of the AAO pores, because PS nanotubes may be swollen when AAO template is removed in the sodium hydroxide solution .
The explanation for forming nanotubes is as follows. Because the inner surfaces of the template nanopores have a very high surface energy, when polymeric solution goes through the open nanopores, it will wet the nanoporous wall first and form a wetting layer. The wetting layer extends along the porous wall to cover the whole template surface. The wetting process is carried on repeatedly and does not stop until the solvent completely evaporated . Thus the nanotubes are formed.
In summary, we obtained highly ordered free standing patterns of metal nanowire and polymer nanotube arrays with secondary templates at room temperature. They have uniform structures and can be applied in microdevices and integrated circuits in the future. Various patterns can be made using this method according to demands. Different kinds of materials, such as metal nanowires, semiconductor, and polymer one-dimensional nanoarrays, can be also fabricated. In addition, our group has made Ni and other polymer non-patterned nanowire arrays by the AAO template [20–23], and further research in the field of photolithography is under way. Our group is trying to use the photolithographic method to combine metal nanowires with polymer nanotubes to synthesize patterned coaxial nanocables, which can be used in microdevices, and will report the application of the method in microdevices in our next work.
This work was supported by the National Natural Science Foundation of China (No. 50473012) and the Provincial Natural Science Foundation (No. Z2005F03).
- Li F, Zhu M, Liu C, Zhou WL, Wiley JB: J. Am. Chem. Soc.. 2006, 128: 13342. COI number [1:CAS:528:DC%2BD28XpvVGmtbc%3D] COI number [1:CAS:528:DC%2BD28XpvVGmtbc%3D] 10.1021/ja0647856View ArticleGoogle Scholar
- Gates BD, Xu QB, Stewart M, Ryan D, Willson CG, Whitesides GM: Chem. Rev.. 2005, 105: 1171. COI number [1:CAS:528:DC%2BD2MXhvVSitrc%3D] COI number [1:CAS:528:DC%2BD2MXhvVSitrc%3D] 10.1021/cr030076oView ArticleGoogle Scholar
- Rothschild M: Mater. Today. 2004, 8: 18. 10.1016/S1369-7021(05)00698-XView ArticleGoogle Scholar
- Ziaie B: Langmuir. 2004, 20: 21.Google Scholar
- Elsner H, Meyer HG: Microelectron. Eng.. 2001, 291: 57.Google Scholar
- Yamazaki K, Namatsu H: Microelectron. Eng.. 2004, 85: 73.Google Scholar
- Denoual M, Griscom L, Toshiyoshi H, Fujita H: Jpn. J. Appl. Phys. 2003,42(Part 1):4598. COI number [1:CAS:528:DC%2BD3sXlvVOkurk%3D] COI number [1:CAS:528:DC%2BD3sXlvVOkurk%3D] 10.1143/JJAP.42.4598View ArticleGoogle Scholar
- Goetting LB, Deng T, Whitesides GM: Langmuir. 1999, 15: 1182. COI number [1:CAS:528:DyaK1MXis1Kgsg%3D%3D] COI number [1:CAS:528:DyaK1MXis1Kgsg%3D%3D] 10.1021/la981094hView ArticleGoogle Scholar
- Schmid H, Michel B: Macromolecules. 2000, 33: 3042. COI number [1:CAS:528:DC%2BD3cXhvFWktrg%3D] COI number [1:CAS:528:DC%2BD3cXhvFWktrg%3D] 10.1021/ma982034lView ArticleGoogle Scholar
- St. John PM, Craighead HG: Appl. Phys. Lett.. 1996, 68: 1022. COI number [1:CAS:528:DyaK28XhtVahsbY%3D] COI number [1:CAS:528:DyaK28XhtVahsbY%3D] 10.1063/1.116216View ArticleGoogle Scholar
- Györvary ES: Nano. Lett.. 2003, 3: 315. 10.1021/nl025936fView ArticleGoogle Scholar
- Kuwabara K, Ogino M, Motowaki S, Miyauchi A: Microelectron. Eng.. 2004, 752: 73.Google Scholar
- Christman KL, Requa MV, Enriquez-Rios VD, Ward SC, Bradley KA, Turner KL, Maynard HD: Langmuir. 2006, 22: 7444. COI number [1:CAS:528:DC%2BD28XmvFGjt7s%3D] COI number [1:CAS:528:DC%2BD28XmvFGjt7s%3D] 10.1021/la0608213View ArticleGoogle Scholar
- Lee H, Dellatore SM, Miller WM, Messersmith PB: Science. 2007, 318: 426. COI number [1:CAS:528:DC%2BD2sXhtFOjtb%2FO] COI number [1:CAS:528:DC%2BD2sXhtFOjtb%2FO] 10.1126/science.1147241View ArticleGoogle Scholar
- Wallraff GM, Hinsberg WD: Chem. Rev.. 1999, 99: 1801. COI number [1:CAS:528:DyaK1MXjvFams7g%3D] COI number [1:CAS:528:DyaK1MXjvFams7g%3D] 10.1021/cr980003iView ArticleGoogle Scholar
- Erika S, Alan O’Riordan G, Quinn AJ, Redmond G, Pum D, Sleytr UB: Nano. Lett.. 2003, 3: 315. 10.1021/nl025936fView ArticleGoogle Scholar
- Zhang X, Pham JQ, Ryza N, Green PF, Johnston KPJ: Vac. Sci. Technol. B. 2003, 22: 818. 10.1116/1.1676502View ArticleGoogle Scholar
- Sato H, Houshi Y, Shoji S: Microsyst. Technol.. 2004, 10: 440. COI number [1:CAS:528:DC%2BD2cXot1Ojsrs%3D] COI number [1:CAS:528:DC%2BD2cXot1Ojsrs%3D] 10.1007/s00542-004-0400-9View ArticleGoogle Scholar
- del Campo A, Arzt E: Chem. Rev.. 2008, 108: 911. COI number [1:CAS:528:DC%2BD1cXitlCnt7c%3D] COI number [1:CAS:528:DC%2BD1cXitlCnt7c%3D] 10.1021/cr050018yView ArticleGoogle Scholar
- Song G, Chen D, Peng Z, She X, Li J, Han P: J. Mar. Sci. Technol.. 2007, 23: 427. COI number [1:CAS:528:DC%2BD2sXnslSnt7s%3D] COI number [1:CAS:528:DC%2BD2sXnslSnt7s%3D]Google Scholar
- She X, Song G, Li J, Han P, Yang S, Wang S, Peng Z: Polym. J.. 2006, 38: 639. COI number [1:CAS:528:DC%2BD28XnvFWrsbk%3D] COI number [1:CAS:528:DC%2BD28XnvFWrsbk%3D] 10.1295/polymj.PJ2005208View ArticleGoogle Scholar
- She X, Song G, Li J, Han P, Yang S, Peng Z: J. Mater. Res.. 2006, 21: 1209. COI number [1:CAS:528:DC%2BD28Xks1Skurg%3D] COI number [1:CAS:528:DC%2BD28Xks1Skurg%3D] 10.1557/jmr.2006.0161View ArticleGoogle Scholar
- She X, Song G, Peng Z, Li J, Lim CT, Tan EPS, Lv L, Zhao XS: Polym. J.. 2007, 39: 1025. COI number [1:CAS:528:DC%2BD2sXhsVWrsrjM] COI number [1:CAS:528:DC%2BD2sXhsVWrsrjM] 10.1295/polymj.PJ2007008View ArticleGoogle Scholar