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

Martı́n, Santiago; Pera, Gorka; Ballesteros, Luz M.; Hope, Adam J.; Marqués‐González, Santiago; Low, Paul J.; Pérez‐Murano, F.; Nichols, Richard J.; Cea, Pilar

doi:10.1002/chem.201303967

Cited by 13 publications

(18 citation statements)

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“…15,[26][27][28][29][30] A wide variety of techniques to deposit the top metal electrode onto a molecular monolayer have been described in the literature including direct and indirect evaporation, 11,[31][32][33][34][35][36][37][38] use of liquid metals, 11,34,39,40 flip chip lamination, 34,41 electrodeposition, [42][43][44] surface-diffusion-mediated deposition, 44 chemisorption of metal nanoparticles onto surface-functionalised monolayers, 45 thermal induced decomposition of an organometallic monolayer, 46 and photoreduction of a metal precursor. 47,48 The most significant problems in the deposition of the top-contact electrode are those related to damage of the functional molecules during the metallization process of the monolayer or penetration of the growing top-contact through the monolayer, which results in short circuits. In addition, many of the proposed 'soft' methods that avoid penetration of the growing metal electrode through the monolayer result in a relatively low surface coverage of the monolayer by the newly fashioned top contact.…”

Section: Introductionmentioning

confidence: 99%

“…In addition, many of the proposed 'soft' methods that avoid penetration of the growing metal electrode through the monolayer result in a relatively low surface coverage of the monolayer by the newly fashioned top contact. [45][46][47] In this contribution, a simple procedure for the deposition of a metallic top-contact electrode onto a monolayer film of 'wire-like' molecules is presented. A self-assembled monolayer (SAM) of an oligo( phenylene ethynylene) (OPE) derivative, 4-(2-(4-(2-(4-aminophenyl)ethynyl)phenyl)ethynyl)benzenamine, 1, featuring amine functional groups to provide metallic contacts 49,50 has been used as the wire-like molecular component.…”

Section: Introductionmentioning

confidence: 99%

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High surface coverage of a self-assembled monolayer by in situ synthesis of palladium nanodeposits

et al. 2017

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Nascent metal|monolayer|metal devices have been fabricated by depositing palladium, produced through a CO-confined growth method, onto a self-assembled monolayer of an amine-terminated oligo(phenylene ethynylene) derivative on a gold bottom electrode. The high surface area coverage (85%) of the organic monolayer by densely packed palladium particles was confirmed by X-ray photoemission spectroscopy (XPS) and atomic force microscopy (AFM). The electrical properties of these nascent Au|monolayer|Pd assemblies were determined from the I-V curves recorded with a conductive-AFM using the Peak Force Tunneling AFM (PF-TUNA™) mode. The I-V curves together with the electrochemical experiments performed rule out the formation of short-circuits due to palladium penetration through the monolayer, suggesting that the palladium deposition strategy is an effective method for the fabrication of molecular junctions without damaging the organic layer.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

High surface coverage of a self-assembled monolayer by in situ synthesis of palladium nanodeposits

et al. 2017

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“…Charge transfer within ap eptidec an be defined electrochemically as attached to an electrode at one end and ar edox-active moiety at the other,o rm easured across two electrodes at am olecular junction.T he latter technique provides current/ voltage (I-V)c haracteristics of am olecule of interest bridged between the electrodes, through the application of an external potential. [2,7] Recent studies have shown that peptides can be used in the design of am olecular junction [8] using scanning probe techniques such as AFM, [9] and STM, [10] to measure the associated conductance. Significant work has also been reported on studying molecular junctionsb yt heoretical methods, using density functional theory (DFT) and Green's function techniques.…”

Section: Introductionmentioning

confidence: 99%

The Correlation of Electrochemical Measurements and Molecular Junction Conductance Simulations in β‐Strand Peptides

Horsley

2015

Chemistry A European J

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Understanding the electronic properties of single peptides is not only of fundamental importance, but it is also paramount to the realization of peptide-based molecular electronic components. Electrochemical and theoretical studies are reported on two β-strand-based peptides, one with its backbone constrained with a triazole-containing tether introduced by Huisgen cycloaddition (peptide 1) and the other a direct linear analogue (peptide 2). Density functional theory (DFT) and non-equilibrium Green's function were used to investigate conductance in molecular junctions containing peptides 3 and 4 (analogues of 1 and 2). Although the peptides share a common β-strand conformation, they display vastly different electronic transport properties due to the presence (or absence) of the side-bridge constraint and the associated effect on backbone rigidity. These studies reveal that the electron transfer rate constants of 1 and 2, and the conductance calculated for 3 and 4, differ by approximately one order of magnitude, thus providing two distinctly different conductance states and what is essentially a molecular switch. A definitive correlation of electrochemical measurements and molecular junction conductance simulations is demonstrated using two different charge transfer techniques. This study furthers our understanding of the electronic properties of peptides at the molecular level, which provides an opportunity to fine-tune their molecular orbital energies through suitable structural manipulation.

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“…LB films of an organic compound incorporating a metal precursor, AuCl 4 -, from the subphase have been reported [271]. These LB monolayers were subsequently irradiated and photoreduction of the metal precursor results in gold nanoislands on top of the organic monolayer without destruction of the underlying organic film nor penetration of the nanoparticles.…”

Section: Deposition Of the Top Contact Electrodementioning

confidence: 98%

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

2014

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Molecular electronics [1,2] is a promising field of research based on the idea that a single molecule or two dimensional assemblies of molecules (monomolecular films) can work as wires, switches, rectifiers, etc. Molecules are the smallest functional units and therefore it is expected that the use of molecules will permit to catch up with the limits of miniaturization (MM: more Moore), with an increase in device density by a factor of several orders of magnitude compared to today's state of the art. At the same time due to quantum effects novel and remarkable properties of organic and organometallic compounds at the nanoscale devices will result in increased performance (MtM: more than Moore) together with the appearance of new functions not possible with conventional semiconductors, and also cheaper devices due to the non-dependence of expensive materials used today in CMOS (complementary metal-oxide semiconductor) technology such as hafnium oxide. Nowadays, the number of research groups from different disciplines of science contributing to molecular electronics is gradually growing, and this field is becoming of great scientific and technological interest [1,3-8]. Since the seminal work of Aviram and Ratner in 1974 who firstly suggested that a single molecule could function as a rectifier [9], molecules have been experimentally demonstrated to work as switches, molecular wires or rectifiers, and a new field of opportunities is opened due to the understanding of electron transport through single entities or assemblies of molecules and expansion towards work on molecular spintronics, vibronic effects, excitation of the molecular junction with polarized light, quantum interference and decoherence, molecular chirality, molecular stretching and distortion as well as work on thermoelectric response in molecular junctions.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 electro...

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

Cited by 13 publications

References 71 publications

High surface coverage of a self-assembled monolayer by in situ synthesis of palladium nanodeposits

High surface coverage of a self-assembled monolayer by in situ synthesis of palladium nanodeposits

The Correlation of Electrochemical Measurements and Molecular Junction Conductance Simulations in β‐Strand Peptides

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

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