Two commercial thermoplastic block copolymer elastomers with a high stiffness were investigated as
stamp materials for microcontact printing and compared to conventional poly(dimethylsiloxane) (PDMS).
Stamps with a relief structure were produced by hot embossing techniques, utilizing the thermoplastic
properties of these rubberlike block copolymers. It is shown that the stamps based on these copolymers
are able to transfer a thiol ink to a gold substrate. After printing, the thiol ink acts as an etch resist, which
indicates that a coherent self-assembled monolayer is formed. Like PDMS stamps, specific copolymer
stamps can be used for repeated printing without re-inking. Moreover, the higher stiffness of the
thermoplastic stamps increases the load above which structural collapse occurs by a factor of 10−15 in
comparison to that of identical PDMS stamps, which is potentially useful in the reproduction of structures
which are sensitive to sagging, buckling, or pairing. An example is presented of relief structures, which
are accurately reproduced with the thermoplastic elastomers, in contrast to identical chemically cross-linked PDMS stamps.
A moderately hydrophilic, thermoplastic elastomer (poly(ether-ester)) was investigated as a stamp material for microcontact printing of a polar ink: pentaerythritol-tetrakis-(3-mercaptopropionate). Stamps with a relief structure were produced from this polymer by hot embossing, and a comparison was made with conventional poly(dimethylsiloxane) (PDMS) and oxygen-plasma-treated PDMS. It is shown that the hydrophilic stamps can be used for the repetitive printing (without re-inking) of at least 10 consecutive patterns, which preserve their etch resistance, and this in rather sharp contrast to conventional and oxygen plasma-treated PDMS stamps. It is argued that these enhanced printing characteristics of the hydrophilic stamps originate from an improved wetting and solubility of polar inks in the hydrophilic stamp.
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