Fabricating Nanogaps by Nanoskiving

There are several methods of fabricating nanogaps with controlled spacings, but the precise control over the sub-nanometer spacing between two ...

This paper compares the structural and electrical characteristics of self-assembled monolayers (SAMs) of n-alkanethiolates, SCn (n = 10, 12, 14), on two types of silver substrates: one used as-deposited (AS-DEP) by an electron-beam evaporator, and one prepared using the method of template-stripping. Atomic force microscopy showed that the template-stripped (TS) silver surfaces were smoother and had larger grains than the AS-DEP surfaces, and reflectance-absorbance infrared spectroscopy showed that SAMs formed on TS substrates were more crystalline than SAMs formed on AS-DEP substrates. The range of current densities, J (A/cm2), measured through mercury-drop junctions incorporating a given SAM on AS-DEP silver was, on average, several orders of magnitude larger than the range of J measured through the same SAM on TS silver, and the AS-DEP junctions failed, on average, 3.5 times more often within five current density-voltage (J-V) scans than did TS junctions (depending on the length of the alkyl chains of the molecules in the SAM). The apparent log-normal distribution of J through the TS junctions suggests that, in these cases, it is the variability in the effective thickness of the insulating layer (the distance the electron travels between electrodes) that results in the uncertainty in J. The parameter describing the decay of current density with the thickness of the insulating layer, beta, was either 0.57 A-1 at V = +0.5 V (calculated using the log-mean of the distribution of values of J) or 0.64 A-1 (calculated using the peak of the distribution of values of J) for the TS junctions; the latter is probably the more accurate. The mechanisms of failure of the junctions, and the degree and sources of uncertainty in current density, are discussed with respect to a variety of defects that occur within Hg-drop junctions incorporating SAMs on silver.

Influence of defects on the electrical characteristics of mercury-drop junctions: self-assembled monolayers of n-alkanethiolates on rough and smooth silver.

Eutectic gallium-indium (EGaIn): a moldable liquid metal for electrical characterization of self-assembled monolayers.

This paper describes the electrical characteristics of junctions composed of three-dimensional arrays of colloidal CdSe quantum dots (QDs) with tin-doped indium oxide (ITO)/poly(3,4-ethylenedioxy-thiophene):poly(styrenesulfonate) (PEDOT:PSS) and eutectic Ga-In (EGaIn) electrodes. It focuses on a comparison of junctions containing QDs of one size to those of arrays containing QDs of multiple sizes. This comparison makes it possible to estimate the relative contributions of transport across various interfaces (e.g., between the QDs and between the QDs and the electrodes) to the observed electrical characteristics of the junction and to evaluate the dependence of these contributions on the locations of various sizes of QDs within the junction. The junctions were diodes, and their turn-on voltage depended on the size of the QDs next to the PEDOT:PSS. We describe this dependence using a Marcus model to estimate the barrier for charge transfer induced by the difference in energies between the orbitals of the QDs and the valence band of PEDOT:PSS.

Size-dependent charge collection in junctions containing single-size and multi-size arrays of colloidal CdSe quantum dots.

This paper describes a study of the generation and flow of photocurrent through junctions containing three-dimensional arrays of colloidal CdSe quantum dots (QDs) of either a single size or multiple sizes. The electrodes were indium tin oxide (ITO) covered with a thin layer of poly(3,4-ethylenedioxy-thiophene):poly(styrenesulfonate) (PEDOT:PSS) and a eutectic alloy of Ga and In (EGaIn). We measured the current-voltage characteristics of the junctions in the dark and under illumination, with various sources and wavelengths of excitation, and their photocurrent action spectra. Size-selective photoexcitation of the arrays of multiple sizes of QDs helped to determine (i) the location of the interface at which photoinduced separation of charge occurred, (ii) whether the energy absorbed by the QDs was redistributed before separation of charge, and (iii) the dependence of the photovoltage on the locations of various sizes of QDs within the junction. This research is a step toward the use of QDs for harvesting light and for transporting energy and charge in devices-for example, solar cells and photodetectors-that operate at zero bias.

The use of size-selective excitation to study photocurrent through junctions containing single-size and multi-size arrays of colloidal CdSe quantum dots.

This paper describes the fabrication of conjugated polymer nanowires by a three stage process: (i) spin-coating a composite film comprising alternating layers of a conjugated polymer and a sacrificial material, (ii) embedding the film in an epoxy matrix and sectioning it with an ultramicrotome (nanoskiving), and (iii) etching the sacrificial material to reveal nanowires of the conjugated polymer. A free-standing, 100-layer film of two conjugated polymers was spin-coated from orthogonal solvents: poly(2-methoxy-5-(2'-ethylhexyloxy)-1,4-phenylenevinylene) (MEH-PPV) from chloroform and poly(benzimidazobenzophenanthroline ladder) (BBL) from methanesulfonic acid. After sectioning the multilayer film, dissolution of the BBL with methanesulfonic acid yielded uniaxially aligned MEH-PPV nanowires with rectangular cross sections, and etching MEH-PPV with an oxygen plasma yielded BBL nanowires. The conductivity of MEH-PPV nanowires changed rapidly and reversibly by >10 (3) upon exposure to I 2 vapor. The result suggests that this technique could be used to fabricate high-surface-area structures of conducting organic nanowires for possible applications in sensing and in other fields where a high surface area in a small volume is desirable.

Fabrication of conjugated polymer nanowires by edge lithography.

Visible-near infrared absorbing dithienylcyclopentadienone-thiophene copolymers for organic thin-film transistors.

This paper describes a simple technique for fabricating uniform arrays of metal and metal oxide nanotubes with controlled heights and diameters. The technique involves depositing material onto an anodized aluminum oxide (AAO) membrane template using a collimated electron beam evaporation source. The evaporating material enters the porous openings of the AAO membrane and deposits onto the walls of the pores. The membrane is tilted with respect to the column of evaporating material, so the shadows cast by the openings of the pores onto the inside walls of the pores define the geometry of the tubes. Rotation of the membrane during evaporation ensures uniform deposition inside the pores. After evaporation, dissolution of the AAO in base easily removes the template to yield an array of nanotubes connected by a thin backing of the same metal or metal oxide. The diameter of the pores dictates the diameter of the tubes, and the incident angle of evaporation determines the height of the tubes. Tubes up to approximately 1.5 mum in height and 20-200 nm in diameter were fabricated. This method is adaptable to any material that can be vapor-deposited, including indium-tin oxide (ITO), a conductive, transparent material that is useful for many opto-electronic applications. An array of gold nanotubes produced by this technique served as a substrate for surface-enhanced Raman spectroscopy: the Raman signal (per molecule) from a monolayer of benzenethiolate was a factor of approximately 5 x 10(5) greater than that obtained using bulk liquid benzenethiol.

Fabrication of arrays of metal and metal oxide nanotubes by shadow evaporation.

This article describes a self-powered system that uses chemical reactions--the thermal excitation of alkali metals--to transmit coded alphanumeric information. The transmitter (an "infofuse") is a strip of the flammable polymer nitrocellulose patterned with alkali metal ions; this pattern encodes the information. The wavelengths of 2 consecutive pulses of light represent each alphanumeric character. While burning, infofuses transmit a sequence of pulses (at 5-20 Hz) of atomic emission that correspond to the sequence of metallic salts (and therefore to the encoded information). This system combines information technology and chemical reactions into a new area--"infochemistry"--that is the first step toward systems that combine sensing and transduction of chemical signals with multicolor transmission of alphanumeric information.

Infochemistry and infofuses for the chemical storage and transmission of coded information.

This Article reports a systematic study on the formation of self-assembled monolayers (SAMs) of conjugated molecules for molecular electronic (ME) devices. We monitored the deprotection reaction of acetyl protected dithiols of oligophenylene ethynylenes (OPEs) in solution using two different bases and studied the quality of the resulting SAMs on gold. We found that the optimal conditions to reproducibly form dense, high-quality monolayers are 9-15% triethylamine (Et(3)N) in THF. The deprotection base tetrabutylammonium hydroxide (Bu(4)NOH) leads to less dense SAMs and the incorporation of Bu(4)N into the monolayer. Furthermore, our results show the importance of the equilibrium concentrations of (di)thiolate in solution on the quality of the SAM. To demonstrate the relevance of these results for molecular electronics applications, large-area molecular junctions were fabricated using no base, Et(3)N, and Bu(4)NOH. The magnitude of the current-densities in these devices is highly dependent on the base. A value of Î²=0.15 Ã…(-1) for the exponential decay of the current-density of OPEs of varying length formed using Et(3)N was obtained.

Formation of high-quality self-assembled monolayers of conjugated dithiols on gold: base matters.

This paper compares the current density (J) versus applied bias (V) of self-assembled monolayers (SAMs) of three different ethynylthiophenol-functionalized anthracene derivatives of approximately the same thickness with linear-conjugation (AC), cross-conjugation (AQ), and broken-conjugation (AH) using liquid eutectic Ga-In (EGaIn) supporting a native skin (~1 nm thick) of Ga(2)O(3) as a nondamaging, conformal top-contact. This skin imparts non-Newtonian rheological properties that distinguish EGaIn from other top-contacts; however, it may also have limited the maximum values of J observed for AC. The measured values of J for AH and AQ are not significantly different (J â‰ˆ 10(-1)A/cm(2) at V = 0.4 V). For AC, however, J is 1 (using log averages) or 2 (using Gaussian fits) orders of magnitude higher than for AH and AQ. These values are in good qualitative agreement with gDFTB calculations on single AC, AQ, and AH molecules chemisorbed between Au contacts that predict currents, I, that are 2 orders of magnitude higher for AC than for AH at 0 < |V| < 0.4 V. The calculations predict a higher value of I for AQ than for AH; however, the magnitude is highly dependent on the position of the Fermi energy, which cannot be calculated precisely. In this sense, the theoretical predictions and experimental conclusions agree that linearly conjugated AC is significantly more conductive than either cross-conjugated AQ or broken conjugate AH and that AQ and AH cannot necessarily be easily differentiated from each other. These observations are ascribed to quantum interference effects. The agreement between the theoretical predictions on single molecules and the measurements on SAMs suggest that molecule-molecule interactions do not play a significant role in the transport properties of AC, AQ, and AH.

Evidence for quantum interference in SAMs of arylethynylene thiolates in tunneling junctions with eutectic Ga-In (EGaIn) top-contacts.

This paper describes the fabrication of electrically addressable, high-aspect-ratio (>10000:1) nanowires of gold with square cross sections of 100 nm on each side that are separated by gaps of 1.7-2.2 nm which were defined using self-assembled monolayers (SAMs) as templates. We fabricated these nanowires and nanogaps without a clean room or any photo- or electron-beam lithographic processes by mechanically sectioning sandwich structures of gold separated by a SAM using an ultramicrotome. This process is a form of edge lithography known as Nanoskiving. These wires can be manually positioned by transporting them on drops of water and are directly electrically addressable; no further lithography is required to connect them to an electrometer. Once a block has been prepared for Nanoskiving (which takes less than one day), hundreds of thousands of nanogaps can be generated, on demand, at a rate of about one nanogap per second. After ashing the organic components with oxygen plasma, we measured the width of a free-standing gap formed from a SAM of 16-mercaptodohexanoic acid (2.4 nm in length) of 2.6 Â± 0.5 nm by transmission electron microscopy. By fitting current-voltage plots of unashed gaps containing three alkanedithiolates of differing lengths to Simmonsâ€™ approximation, we derived a value of Î² = 0.75 Ã…(-1) (0.94 n(C)(-1)) at 500 mV. This value is in excellent agreement with literature values determined by a variety of methods, demonstrating that the gap-size can be controlled at resolutions as low as 2.5 Ã… (i.e., two carbon atoms).

Article	Year
Influence of defects on the electrical characteristics of mercury-drop junctions: self-assembled monolayers of n-alkanethiolates on rough and smooth silver. Journal of the American Chemical Society\| PubMed ID: 17358061	2007
Eutectic gallium-indium (EGaIn): a moldable liquid metal for electrical characterization of self-assembled monolayers. Angewandte Chemie (International ed. in English)\| PubMed ID: 18038438	2008
Size-dependent charge collection in junctions containing single-size and multi-size arrays of colloidal CdSe quantum dots. Journal of the American Chemical Society\| PubMed ID: 18072773	2008
The use of size-selective excitation to study photocurrent through junctions containing single-size and multi-size arrays of colloidal CdSe quantum dots. Journal of the American Chemical Society\| PubMed ID: 18072774	2008
Fabrication of conjugated polymer nanowires by edge lithography. Nano letters\| PubMed ID: 18517256	2008
Visible-near infrared absorbing dithienylcyclopentadienone-thiophene copolymers for organic thin-film transistors. Journal of the American Chemical Society\| PubMed ID: 19049454	2008
Fabrication of arrays of metal and metal oxide nanotubes by shadow evaporation. ACS nano\| PubMed ID: 19206613	2008
Infochemistry and infofuses for the chemical storage and transmission of coded information. Proceedings of the National Academy of Sciences of the United States of America\| PubMed ID: 19470465	2009
Formation of high-quality self-assembled monolayers of conjugated dithiols on gold: base matters. Journal of the American Chemical Society\| PubMed ID: 21384876	2011
Evidence for quantum interference in SAMs of arylethynylene thiolates in tunneling junctions with eutectic Ga-In (EGaIn) top-contacts. Journal of the American Chemical Society\| PubMed ID: 21561156	2011
Directly addressable sub-3 nm gold nanogaps fabricated by Nanoskiving using self-assembled monolayers as templates. ACS nano\| PubMed ID: 22577867	2012

Ryan C. Chiechi

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