Luz M. Ballesteros

Preparation of nascent molecular electronic devices from gold nanoparticles and terminal alkyne functionalised monolayer films

A metal–molecule–GNP assembly has been fabricated using an acetylene-terminated phenylene–ethynylene molecular monolayer, namely 4-((4-((4-ethynylphenyl)ethynyl)phenyl)ethynyl)benzoic acid (HOPEA), sandwiched between a gold substrate bottom electrode and gold nanoparticle (GNP) top contact electrode. In the first stage of the fabrication process, a monolayer of directionally oriented (carboxylate-to-gold) HOPEA was formed onto the bottom electrode using the Langmuir–Blodgett (LB) technique. In the second stage, the gold-substrate supported monolayer was incubated in a solution of gold nanoparticles (GNPs), which resulted in covalent attachment of the GNPs on top of the film via an alkynyl carbon–Au σ-bond thereby creating the metallic top electrode. Adsorption of the GNPs to the organic LB film was confirmed by both UV-vis absorption spectroscopy and X-ray photoemission spectroscopy (XPS), whilst the contact angle showed changes in the physical properties of the film surface as a result of top-coating of the LB film with the GNPs. Importantly, surface-enhanced Raman scattering (SERS) confirmed the covalent attachment of the metal particles to the LB film by formation of Au–C σ-bonds via a heterolytic cleavage of the alkyne C–H bond. Electrical properties of these nascent metal–molecule–GNP assemblies were determined from I–V curves recorded with a conductive-AFM in the Peak Force Tunneling AFM (PF-TUNA™) mode. The I–V curves obtained from these structures rule out the formation of any significant number of short-circuits due to GNP penetration through the monolayer, suggesting that this strategy of self-assembly of GNPs to alkyne-terminated monolayers is an effective ‘soft’ procedure for the fabrication of molecular junctions without damaging the organic layer.

Towards the Fabrication of the Top-Contact Electrode in Molecular Junctions by Photoreduction of a Metal Precursor

Langmuir films of 4-{[4-({4-[(trimethylsilyl)ethynyl]phenyl}ethynyl)phenyl]ethynyl} benzenaminium chloride ([1 H]Cl) undergo anion metathesis when assembled on an aqueous auric acid (HAuCl4 ) subphase. Subsequent transfer to solid supports gives well-formed Langmuir-Blodgett (LB) monolayers of [1 H]AuCl4 in which the trimethylsilyl group serves as the surface contacting group. Photoreduction of the aurate on these monolayers leads to the formation of metallic gold nanoislands, which were distributed over the surface of the film. Electrical properties of these nascent devices were determined by recording current-voltage (I-V) curves with conductive atomic force microscopy (c-AFM) using the PeakForce tunneling AFM (PF-TUNA) mode. This gives consistent sigmoidal I-V curves that are indicative of well-behaved junctions free of metallic filaments and short circuits. The photoreduction of a metal precursor incorporated onto monomolecular films is therefore proposed as an effective method for the fabrication of molecular junctions.

Nanofabrication techniques of highly organized monolayers sandwiched between two electrodes for molecular electronics

Abstract It is expected that molecular electronics, i.e., the use of molecules as critical functional elements in electronic devices, will lead in the near future to an industrial exploitable novel technology, which will open new routes to high value-added electronic products. However, despite the enormous advances in this field several scientific and technological challenges should be surmounted before molecular electronics can be implemented in the market. Among these challenges are the fabrication of reliable, robust and uniform contacts between molecules and electrodes, the deposition of the second (top) contact electrode, and development of assembly strategies for precise placement of molecular materials within device structures. This review covers advances in nanofabrication techniques used for the assembly of monomolecular films onto conducting or semiconducting substrates as well as recent methods developed for the deposition of the top contact electrode highlighting the advantages and limitations of the several approaches used in the literature. This contribution also aims to define areas of outstanding challenges in the nanofabrication of monomolecular layers sandwiched between two electrodes and opportunities for future research and applications.