Liquid Manipulation Lithography to Fabricate a Multifunctional Microarray of Organosilanes on an Oxide Surface under Ambient Conditions

Authors

  • Naoto Shirahata,

    Corresponding author
    1. International Center for Materials Nanoarchitectonics (MANA)1-1 Namiki, Tsukuba, Ibaraki 305-0044 (Japan)
    2. National Institute for Materials Science (NIMS)1-2-1 Sengen, Tsukuba, Ibaraki 305-0047 (Japan)
    • International Center for Materials Nanoarchitectonics (MANA)1-1 Namiki, Tsukuba, Ibaraki 305-0044 (Japan).
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  • Jun Nakanishi,

    1. International Center for Materials Nanoarchitectonics (MANA)1-1 Namiki, Tsukuba, Ibaraki 305-0044 (Japan)
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  • Yoshitaka Echikawa,

    1. Department of Pure and Applied Chemistry Tokyo University of Science 2641 Yamasaki, Noda, Chiba 278-8510 (Japan)
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  • Atsushi Hozumi,

    1. National Institute of Advanced Industrial Science and Technology (AIST)2266-98 Anagahora, Shimoshidami, Moriyama, Nagoya 463-8560 (Japan)
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  • Yoshitake Masuda,

    1. National Institute of Advanced Industrial Science and Technology (AIST)2266-98 Anagahora, Shimoshidami, Moriyama, Nagoya 463-8560 (Japan)
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  • Shigeru Ito,

    1. Department of Pure and Applied Chemistry Tokyo University of Science 2641 Yamasaki, Noda, Chiba 278-8510 (Japan)
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  • Yoshio Sakka

    1. International Center for Materials Nanoarchitectonics (MANA)1-1 Namiki, Tsukuba, Ibaraki 305-0044 (Japan)
    2. National Institute for Materials Science (NIMS)1-2-1 Sengen, Tsukuba, Ibaraki 305-0047 (Japan)
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  • We thank the Bio-Organic Materials Facility and the Nanotechnology Innovation Center for the use of the fluorescence microscope. This work was, in part, supported by the World Premier International (WPI) Research Center Initiative, MEXT, Japan. N. S. is grateful for financial support from the Iketani Science and Technology Foundation, and the Grant-in-Aid from the Ministry of Education, Science, Sports and Culture, Japan.

Abstract

A novel method to produce a multifunctional microarray in which different types of self-assembled monolayers (SAMs) are positioned on predefined surface sites on an oxide-covered silicon substrate is described. To achieve this, a liquid-transportation system called “liquid manipulation lithography” (LML) is developed. This system allows the delivery of different varieties of molecular inks, trialkoxysilanes, onto each predefined surface position of the given substrate even under ambient conditions. Under optimum conditions, the transferred trialkoxysilane inks first form one-molecule-thick microstructures at each surface position through the hydrolysis of the reactive silanes with surface water adsorbed on the substrate, followed by a condensation reaction. Three types of trialkoxysilanes with long alkyl-chains, specifically triethoxysilylundecanal (TESUD), N-(6-aminohexyl)-3-aminopropyltrimethoxysilane (AHAPS), and octadecyltrimethoxysilane (OTS), are used as model molecular inks due to their high-end group-functionalities in biological and electronic applications. The precise positioning of the ink with sub-micrometer edge resolution is performed by carefully controlling a femtoliter-scale liquid-injection micromanipulator under a microscope. To ensure that the prepared SAM microarray is available for parallel analysis of biomolecular interactions, the area-selective immobilization of a protein molecule is explored. Successful observation of the area-selective biomolecular attachment confirmed a high industrial potential for the method as a lithography-free process for the miniaturization of a multifunctional SAM array on an oxide substrate.

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