J. Phys. Chem. C, 111 (51), 18871 -18877, 2007. 10.1021/jp074829c S1932-7447(07)04829-7
Web Release Date: November 13, 2007

Copyright © 2007 American Chemical Society

Langmuir-Blodgett Films Constructed from a Charge-Transfer Complex and Gold Nanoparticles

Yoko Tatewaki, Yuki Noda, Tomoyuki Akutagawa,* Ryo Tunashima, Shin-ichiro Noro, Takayoshi Nakamura,* Hiroyuki Hasegawa, Shinro Mashiko, and Jan Becher

Graduate School of Environmental Earth Science, Hokkaido University, Sapporo 060-0810, Japan, Research Institute for Electronic Science, Hokkaido University, Sapporo 060-0812, Japan, CREST, Japan Science and Technology Agency (JST), Kawaguchi 332-0012, Japan, National Institute of Information and Communication Technology (NICT), Kobe 651-2492, Japan, and University of Southern Denmark, Campusvej 55, DK-5230, Odense M, Denmark

Received: June 21, 2007

In Final Form: August 27, 2007

Abstract:

A charge-transfer complex between an amphiphilic bis(tetrathiafulvalene) (bis-TTF) annulated macrocycle (1) and 2,3,5,6-tetrafluoro-7,7,8,8-tetracyano-p-quinodimethane (F4-TCNQ), (12+)(F4-TCNQ-)2, which can form molecular-assembly nanowires by application of the Langmuir-Blodgett (LB) method, was hybridized with gold nanoparticles with an average diameter of 13 nm. LB films of (12+)(F4-TCNQ)2 were transferred onto a substrate surface from a subphase containing gold nanoparticles at concentrations ranging from 10-6 to 10-4 M, based on the number of gold atoms in the subphase (cAu). One-dimensional nanowires and zero-dimensional gold nanoparticles were found to coexist in films transferred onto mica by a single withdrawal from a subphase with cAu less than 1 × 10-5 M, whereas films transferred from a subphase with cAu greater than 1 × 10-4 M formed network structures of gold nanoparticles, which was confirmed by AFM measurements as well as electronic spectroscopy. The room-temperature electrical conductivities of the latter LB films (cAu > 1 × 10-4 M) were 2 or 3 orders of magnitude higher than those of the former (cAu< 1 × 10-5 M). The films, which contained nanoparticle network structures, showed two types of conducting behavior depending on the temperature range (above and below ~150 K). At higher temperatures, conduction was dominated by (12+)(F4-TCNQ-)2, which is an intrinsic semiconductor, whereas collective tunneling charge transport in the gold nanoparticle network structure was observed at lower temperatures. In the prepared films, the gold nanoparticles were randomly connected to each other, and a random single electron tunneling array yielded a finite threshold voltage (Vth) at lower temperatures due to Coulomb blockade behavior and three-dimensional correlation of the conducting paths.


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