A dithiocarbamate anchoring group as a flexible platform for interface engineering.

The molecular organization and electronic properties of dithiocarbamate (DTC) anchored self-assembled monolayers (SAMs) linked to Au(111) substrates are studied by a combination of X-ray photoelectron spectroscopy (XPS), near-edge X-ray absorption fine structure (NEXAFS) spectroscopy, and state-of-the-art density functional theory calculations. For that, several piperidine/piperazine precursors with different architecture and substitution patterns are selected. The presented data show that the DTC anchor provides a useful building block for monomolecular self-assembly on coinage metals with both sulfur atoms bonded to the substrate in a way similar to what is usually observed for the more commonly applied thiolate docking group. The combination of the DTC group with the quite flexible piperidine/piperazine cyclic linkers results in a dense molecular packing with an upright orientation of the terminal moieties. The latter comprise phenyl rings bearing various substituents, which enables tuning the interfacial dipole over a wide range. Simulations on two prototypical DTC-docked SAMs help to better understand the experimental observations and provide insight into the local origin of the SAM-induced shifts in the electrostatic energy. In particular, a comparison of measured and simulated XP spectra reveals the significant contribution of the DTC group to the interfacial dipole.

Built-In Potentials Induced by Molecular Order in Amorphous Organic Thin Films.

Many molecules used to fabricate organic semiconductor devices carry an intrinsic dipole moment. Anisotropic orientation of such molecules in amorphous organic thin films during the deposition process can lead to the spontaneous buildup of an electrostatic potential perpendicular to the film. This so-called giant surface potential (GSP) effect can be exploited in organic electronics applications and was extensively studied in experiment. However, presently, an understanding of the molecular mechanism driving the orientation is lacking. Here, we model the physical vapor deposition process of seven small organic molecules employed in organic light-emitting diode applications with atomistic simulations. We are able to reproduce experimental results for a wide range of strength of the GSP effect. We find that the electrostatic interaction between the dipole moments of the molecules limits the GSP strength and identify short-range van der Waals interactions between the molecule and the surface during deposition as the driving force behind the anisotropic orientation. We furthermore show how the GSP effect influences the energy levels responsible for charge transport, which is important for the design of organic semiconductors and devices.

Structural origins of the cohesive energy in metal-terpyridine oligomer thin-films.

FeII-terpyridine based oligomers have attracted considerable interest as key constituents for the realization of highly robust, ultra-thin ordered layers of metal center oligomers (MCOs) for organic electronics applications. By using molecular simulations and nanotribology investigations, we report on the origins of the surprisingly high mechanical and thermal stability in this type of MCO layers, which finds its expression in nanowear resistance values of up to 1.5 µN for the MCO films, as well as in a thermal stability of two-terminal MCO junctions to temperatures up to ∼100 °C under electrical load. A theoretical analysis of the fundamental cohesive forces among the constituents within the context of an electrostatic model reveal that the cohesive energy is essentially based on Coulomb interactions among the ionic constituents of the oligomers, leading to an estimated cohesive energy per molar mass of 0.0132 eV mol g-1 for MCO layers that advantageously compare to the 0.0061 eV mol g-1 reported for pentacene crystals.

Photoswitchable Sn-Cyt c Solid-State Devices.

Electron transfer across proteins plays an important role in many biological processes, including those relevant for the conversion of solar photons to chemical energy. Previous studies demonstrated the generation of photocurrents upon light irradiation in a number of photoactive proteins, such as photosystem I or bacteriorhodopsin. Here, it is shown that Sn-cytochrome c layers act as reversible and efficient photoelectrochemical switches upon integration into large-area solid-state junctions. Photocurrents are observed both in the Soret band (λ = 405 nm) and in the Q band (λ = 535 nm), with current on/off ratios reaching values of up to 25. The underlying modulation in charge-transfer rate is attributed to a hole-transport channel created by the photoexcitation of the Sn-porphyrin.

Surface Energy and Work Function Control of AlOx/Al Surfaces by Fluorinated Benzylphosphonic Acids.

The performance of organic electronic devices can be significantly improved by modifying metal electrodes with organic monolayers, which alter the physical and chemical nature of the interface between conductor and semiconductor. In this paper we examine a series of 12 phosphonic acid compounds deposited on the native oxide layer of aluminum (AlOx/Al), an electrode material with widespread applications in organic electronics. This series includes dodecylphosphonic acid as a reference and 11 benzylphosphonic acids, seven of which are fluorinated, including five newly synthesized derivatives. The monolayers are experimentally characterized by contact angle goniometry and by X-ray photoemission spectroscopy (XPS), and work function data obtained by low-intensity XPS are correlated with molecular dipoles obtained from DFT calculations. We find that monolayers are formed with molecular areas ranging from 17.7 to 42.9 Å(2)/molecule, and, by the choice of appropriate terminal groups, the surface energy can be tuned from 23.5 mJ/m(2) to 70.5 mJ/m(2). Depending on the number and position of fluorine substituents on the aromatic rings, a variation in the work function of AlOx/Al substrates over a range of 0.91 eV is achieved, and a renormalization procedure based on molecular density yields a surprising agreement of work function changes with interface dipoles as expected from Helmholtz' equation. The ability to adjust energetics and adhesion at organic semiconductor/AlOx interfaces has immediate applications in devices such as OLEDs, OTFTs, organic solar cells, and printed organic circuits.

Ultrarobust Thin-Film Devices from Self-Assembled Metal-Terpyridine Oligomers.

Ultrathin molecular layers of Fe(II) -terpyridine oligomers allow the fabrication of large-area crossbar junctions by conventional electrode vapor deposition. The junctions are electrically stable for over 2.5 years and operate over a wide range of temperatures (150-360 K) and voltages (±3 V) due to the high cohesive energy and packing density of the oligomer layer. Electrical measurements reveal ideal Richardson-Shottky emission in surprising agreement with electrochemical, optical, and photoemission data.

Organic dipole layers for ultralow work function electrodes.

The alignment of the electrode Fermi level with the valence or conduction bands of organic semiconductors is a key parameter controlling the efficiency of organic light-emitting diodes, solar cells, and printed circuits. Here, we introduce a class of organic molecules that form highly robust dipole layers, capable of shifting the work function of noble metals (Au and Ag) down to 3.1 eV, that is, ∼1 eV lower than previously reported self-assembled monolayers. The physics behind the considerable interface dipole is elucidated by means of photoemission spectroscopy and density functional theory calculations, and a polymer diode exclusively based on the surface modification of a single electrode in a symmetric, two-terminal Au/poly(3-hexylthiophene)/Au junction is presented. The diode exhibits the remarkable rectification ratio of ∼2·10(3), showing high reproducibility, durability (>3 years), and excellent electrical stability. With this evidence, noble metal electrodes with work function values comparable to that of standard cathode materials used in optoelectronic applications are demonstrated.

Alkylation of gold surface by treatment with C18H37HgOTs and anodic Hg stripping.

Treatment of a gold surface with a solution of C18H37HgOTs under ambient conditions results in the formation of a covalently adsorbed monolayer containing alkyl chains attached directly to gold, Hg(0) atoms, and no tosyl groups. It is stable against a variety of chemical agents. When the initial deposition is performed at a positive applied potential and is followed by oxidative electrochemical stripping, the mercury can be completely removed, leaving a gold surface covered only with alkyl chains. The details of the attachment structure are not known. The conclusions are based on infrared spectroscopy, X-ray and UV photoelectron spectroscopy, ellipsometry, contact angle goniometry, differential pulse polarography, and measurements of electrode blocking and electrochemical admittance.

Conductance modulation in tetraaniline monolayers by HCl-doping and by field-enhanced dissociation of H2O.

Oligoanilines are interesting candidates for organic electronics, as their conductivity can be varied by several orders of magnitude upon protonic doping. Here we demonstrate that tetraaniline self-assembled monolayers exhibit an unprecedented conductance on/off ratio of ∼710 (at +1 V) upon doping of the layers from the emeraldine base to the emeraldine salt form. Furthermore, a pronounced asymmetry in the current-voltage characteristics indicates dynamic doping of the tetraaniline layer by protons generated through field-enhanced dissociation of water molecules, a phenomenon known as the second Wien effect. These results point toward oligoanilines as promising substitutes for polyaniline layers in next-generation thin film devices.

Fabrication of asymmetric molecular junctions by the oriented assembly of dithiocarbamate rectifiers.

The oriented assembly of molecules on metals is a requirement for rectification in planar metal-molecule-metal junctions. Here, we demonstrate how the difference in adsorption kinetics between dithiocarbamate and thioacetate anchor groups can be utilized to form oriented assemblies of asymmetric molecules that are bound to Au through the dithiocarbamate moiety. The free thioactate group is then used as a ligand to bind Au nanoparticles and to form the desired metal-molecule-metal junction. Besides allowing an asymmetric coupling to the electrodes, the molecules exhibit an asymmetric molecular backbone where the length of the alkyl chains separating the electrodes from a central, para-substituted phenyl ring differs by two methylene units. Throughout the junction fabrication, the layers were characterized by photoelectron spectroscopy, infrared spectroscopy, and scanning tunneling microscopy. Large area junctions using a conducting polymer interlayer between a mercury-drop electrode and the self-assembled monolayer prove the relationship between electrical data and molecular structure.

Efficient electronic coupling and improved stability with dithiocarbamate-based molecular junctions.

Molecular electronic devices require stable and highly conductive contacts between the metal electrodes and molecules. Thiols and amines are widely used to attach molecules to metals, but they form poor electrical contacts and lack the robustness required for device applications. Here, we demonstrate that dithiocarbamates provide superior electrical contact and thermal stability when compared to thiols on metals. Ultraviolet photoelectron spectroscopy and density functional theory show the presence of electronic states at 0.6 eV below the Fermi level of Au, which effectively reduce the charge injection barrier across the metal-molecule interface. Charge transport measurements across oligophenylene monolayers reveal that the conductance of terphenyl-dithiocarbamate junctions is two orders of magnitude higher than that of terphenyl-thiolate junctions. The stability and low contact resistance of dithiocarbamate-based molecular junctions represent a significant step towards the development of robust, organic-based electronic circuits.

Structure and conductance of aromatic and aliphatic dithioacetamide monolayers on Au(111).

The structure and electrical properties of self-assembled monolayers of cyclic aromatic and aliphatic dithioacetamides (1,4-bis(mercaptoacetamido)benzene and 1,4-bis(mercaptoacetamido)cyclohexane) and of mixed dithioacetamide/alkanethiol monolayers are characterized by X-ray photoelectron spectroscopy (XPS), scanning tunneling microscopy (STM) and contact angle goniometry. Both dithioacetamides are found to pack densely on Au(111), however the monolayers are poorly ordered as a result of hydrogen bond formation between the amide groups. The coassembly and the insertion method are compared for the formation of mixed dithioacetamide/alkanethiol monolayers. By coassembly, islands of dithioacetamides in a dodecanethiol matrix can only be obtained at a low dithioacetamide/dodecanethiol concentration ratio in solution (1/10) and by thermal annealing of the resulting monolayers. Small and well defined dithioacetamide domains are realized by insertion of dithioacetamides into defect sites of closely packed octanethiol monolayers. These domains are used to determine the molecular conductance by means of STM height profiles and molecular lengths resulting from density functional theory (DFT) calculations. The difference in the tunneling decay constant beta measured for aromatic dithioacetamides (beta = 0.74-0.76/A) and for aliphatic dithioacetamides (beta = 0.84-0.91/A) highlights the influence of the conjugation within the cyclic core on molecular conductance.

Optical and electrical properties of three-dimensional interlinked gold nanoparticle assemblies.

The optical and electrical properties of 11-20 nm thick films composed of approximately 4 nm gold nanoparticles (Au-NPs) interlinked by six organic dithiol or bis-dithiocarbamate derivatives were compared to investigate how these properties depend on the core of the linker molecule (benzene or cyclohexane) and its metal-binding substituents (thiol or dithiocarbamate). Films prepared with the thiol-terminated linker molecules, (1,4-bis(mercaptomethyl)benzene, 1,4-bis(mercaptomethyl)cyclohexane, 1,4-bis(mercaptoacetamido)benzene, and 1,4-bis(mercaptoacetamido)cyclohexane), exhibit thermally activated charge transport. The activation energies lie between 59 and 71 meV. These films show distinct plasmon absorption bands with maxima between 554 and 589 nm. In contrast, the film prepared with 1,4-cyclohexane-bis(dithiocarbamate) has a significantly red-shifted plasmon band ( approximately 626 nm) and a pronounced absorbance in the near infrared. The activation energy for charge transport is only 14 meV. These differences are explained in terms of the formation of a resonant state at the interface due to overlap of the molecular orbital and metal wave function, leading to an apparent increase in NP diameter. The film prepared with 1,4-phenylene-bis(dithiocarbamate) exhibits metallic properties, indicating the full extension of the electron wave function between interlinked NPs. In all cases, the replacement of the benzene ring with a cyclohexane ring in the center of the linker molecule leads to a 1 order of magnitude decrease in conductivity. A linear relationship is obtained when the logarithm of conductivity is plotted as a function of the number of nonconjugated bonds in the linker molecules. This suggests that nonresonant tunneling along the nonconjugated parts of the molecule governs the electron tunneling decay constant (beta(N)(-)(CON)), while the contribution from the conjugated parts of the molecule is weak (corresponding to resonant tunneling). The obtained value for beta(N)(-)(CON) is approximately 1.0 (per non-conjugated bond) and independent of the nanoparticle-binding group. Hence, the molecules can be viewed as consisting of serial connections of electrically insulating (nonconjugated) and conductive (conjugated) parts.