Dip‐Pen Nanolithography of Chemical Templates on Silicon Oxide

Abstract

A. Hagfeldt, M. Grätzel, Chem. Rev. 1995, 95, 49. [17] The intensity was determined by comparing the measured J SC with the J SC at 1 sun intensity, which was obtained from the convolution of the spectral response with the solar AM1.5 spectrum, and correcting for the small nonlinearity of the light intensity dependence using I = I(1 sun) [J SC /J SC (1 sun)] The range of material systems to which DPN and related techniques have been applied has rapidly expanded since the first report of depositing thiols on gold surfaces, [2±4] to include patterning of proteins [5] and DNA [6] on gold surfaces, and metal salts, [7,8] metal oxides, [9] silazanes, [10,11] alkoxysilanes, [11,12] organic dyes, [13] dendrimers, [14] and polymers [15] on silicon oxide surfaces. Herein we describe a new functional ink based on trichlorosilane chemistry that is amenable to deposition by DPN onto silicon oxide. Additionally, we show this produces a versatile template that can direct subsequent deposition or growth of a variety of materials. Lithography on insulating substrates at ever-shrinking scales is critical to the future development of electronic and sensor devices. DPN has been shown to provide a facile method for the serial patterning of silicon oxide surfaces. Ivanisevic and Mirkin [10] described the deposition of hexamethyldisilazane (HMDS) on Si and GaAs native oxide surfaces using DPN; however, HMDS is not amenable to further chemical functionalization after patterning. In order to pattern molecules on silicon oxide with DPN, Mirkin and co-workers have also created etch-resists based on self-assembled monolayers. [16,17] In this approach, a thin sacrificial layer of gold is deposited on a silicon oxide substrate, followed by patterning of a thiol on the gold by DPN. A final chemical etching step removes the unpatterned gold areas. More recent papers by Pena et al. [11] and Jung et al. [12] have explored the ability of In our studies, we have chosen 10-undecenyltrichlorosilane (UTCS) as the DPN ink' for several reasons. The choice of UTCS, or trichlorosilanes in general, allows the direct patterning of molecules on silicon oxide without the need for a solvent or elevated temperatures. Our approach results in the direct covalent attachment through only the headgroup of the silane, leaving the olefin-terminated tail (in the case of UTCS) available as a flexible starting point for further chemical modification. Possible modifications include the covalent or noncovalent growth of nanoparticles, conducting polymers, metal films, or biomolecules.Although some authors have proposed that trichlorosilanes and alkoxysilanes would be unsuitable inks' for DPN [10] (due to possible decomposition or polymerization in the water meniscus that forms between the tip and surface), Pena et al. [11] and Jung et al. [12] have both found that deposition is possible in the case of alkoxysilanes. Given careful tip preparation, we have found that trichlorosilanes can also be written under appropriate conditions. Specifically, to ach...

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