Institute of Chemistry, Center for Nanoscience and Nanotechnology, The Hebrew University of Jerusalem, Jerusalem 91904, Israel.
Langmuir. 2009 Dec 15;25(24):13900-5. doi: 10.1021/la901701u.
A nitrospiropyran (1a) monolayer-modified Au electrode provides an active surface for the photolithographic patterning of an electrode with Ag(0) nanoclusters. Illumination of the monolayer-modified Au surface through a mask yields nitromerocyanine (1b)-patterned domains on the Au electrode that bind Ag(+) ions. The electrochemical reduction of the Ag(+) ions yields stable Ag(0) nanoclusters on the patterned domains, and this enables the SEM imaging of the resulting microstructures. The photoisomerizable and electroactive nitromerocyanine/Ag(0) nanoclusters exhibit several important features: (i) By the electrochemical oxidation of Ag(0) nanoclusters to Ag(+) ions, the patterned metallic nanoclusters are erased but stored in the form of Ag(+) ions, confined to the patterned monolayer. The stored information can be retrieved by the electrochemical reduction of the Ag(+) ions. (ii) The photoisomerization of the nitromerocyanine (1b)-modified domains to the nitrospiropyran (1a) state (lambda > 475 nm) coupled to the electrochemical oxidation of the Ag(0) nanoclusters to Ag(+) enables the removal of Ag(+) from the surface and its restoration for new patterning. (iii) The orthogonal patterning of the Au surface with Ag(0) nanocluster structures is accomplished by the stepwise coupled photochemical/electrochemical patterning of the surface by two (or more) irradiation steps through the mask.
一个硝基亚螺吡喃（1a）单层修饰的金电极提供了一个活性表面，用于通过光刻对电极进行图案化，形成银（0）纳米簇。通过掩模对单层修饰的金表面进行照射，在 Au 电极上得到硝基亚螺吡喃（1b）图案化的区域，这些区域可以结合 Ag(+) 离子。Ag(+) 离子的电化学还原在图案化区域上生成稳定的 Ag(0)纳米簇，这使得可以对所得微结构进行 SEM 成像。光致变色和电活性硝基亚螺吡喃/Ag(0)纳米簇具有几个重要特征：（i）通过电化学氧化 Ag(0)纳米簇为 Ag(+) 离子，可以擦除图案化的金属纳米簇，但以 Ag(+) 离子的形式存储，局限于图案化的单层。存储的信息可以通过 Ag(+) 离子的电化学还原来检索。（ii）硝基亚螺吡喃（1b）修饰区域的光致异构化为硝基螺吡喃（1a）状态（lambda > 475nm）与 Ag(0)纳米簇的电化学氧化耦合，可以将 Ag(+) 从表面去除，并为新的图案化恢复其功能。（iii）通过掩模进行两步（或更多步）辐照，通过两步（或更多步）辐照，分步骤地将表面进行光化学/电化学图案化，从而完成 Au 表面与 Ag(0)纳米簇结构的正交图案化。
