Dependence of the Metal-Insulator-Semiconductor Schottky Barrier Height on Insulator Composition.

The effects of different high-κ tunnel oxides on the metal-insulator-semiconductor Schottky barrier height (ΦB) were systematically investigated. While these high-κ interlayers have been previously observed to affect ΦB, there has never been a clear consensus as to why this ΦB modulation occurs. Changes in ΦB were measured when adding 0.5 nm of seven different high-κ oxides to n-Si/Ni contacts with a thin native silicon oxide also present. Depending on the high-κ oxide composition and ΦB measurement technique, increases in ΦB up to 0.4 eV and decreases up to 0.2 eV with a high-κ introduction were measured. The results were compared to several different hypotheses regarding the effects of tunnel oxides on ΦB. The experimental data correlated most closely with the model of a dipole formed at the SiOx/high-κ interface due to the difference in the oxygen areal density between the two oxides. Knowledge of this relationship will aid in the design of Schottky and ohmic contacts by providing criteria to predict the effects of different oxide stacks on ΦB.

High-Sensitivity Low-Energy Ion Spectroscopy with Sub-Nanometer Depth Resolution Reveals Oxidation Resistance of MoS2 Increases with Film Density and Shear-Induced Nanostructural Modifications of the Surface.

For decades, density has been attributed as a critical aspect of the structure of sputter-deposited nanocrystalline molybdenum disulfide (MoS2) coatings impacting oxidation resistance and wear resistance. Despite its importance, there are few examples in the literature that explicitly investigate the relationship between the density and oxidation behaviors of MoS2 coatings. Aging and oxidation are primary considerations for the use of MoS2 coatings in aerospace applications as they inevitably experience prolonged storage in water and oxygen-rich environments prior to use. Oxidation that is either limited to the first few nanometers or through the bulk of the coating can result in seizure due to high initial coefficients of friction or component failure from excessive wear. High-sensitivity low-energy ion spectroscopy (HS-LEIS) and Rutherford backscattering spectrometry (RBS) are both used to understand the extent of oxidation throughout the first ∼10 nanometers of the surface of pure sputtered nanocrystalline MoS2 coatings after high-temperature aging and how it is impacted by the density of coatings as measured by RBS. Results show that low-density coatings (ρ = 3.55 g/cm3) exhibit a more columnar microstructure and voiding, which act as pathways for oxidative species to penetrate and interact with edge sites, causing severe surface and subsurface oxidation. Furthermore, HS-LEIS of surfaces sheared prior to oxidation reveals that the oxidation resistance of low-density MoS2 coatings can be significantly improved by shear-induced reorientation of the surface microstructure to a basal orientation and elimination of pathways for oxygen into the bulk through compaction of surface and subsurface voids.

Atomic-Layer-Deposited Aluminum Oxide Thin Films Probed with X-ray Scattering and Compared to Molecular Dynamics and Density Functional Theory Models.

A better understanding of amorphous aluminum oxide's structure and electronic properties is obtained through combined experimental and computational approaches. Grazing incidence X-ray scattering measurements were carried out on aluminum oxide thin films grown using thermal atomic layer deposition. The corresponding pair distribution functions (PDFs) showed structures similar to previously reported PDFs of solid-state amorphous alumina and molten alumina. Structural models based on crystalline alumina polymorphs (PDFgui) and amorphous alumina (molecular dynamics, MD) were examined for structural comparisons to the experimental PDF data. Smaller MD models were optimized and verified against larger models to allow for quantum chemical electronic structure calculations. The electronic structure of the amorphous alumina models yields additional insight into the band structure and electronic defects present in amorphous alumina that are not present in crystalline samples.

cm2-Scale Synthesis of MoTe2 Thin Films with Large Grains and Layer Control.

Owing to the small energy differences between its polymorphs, MoTe2 can access a full spectrum of electronic states from the 2H semiconducting state to the 1T' semimetallic state and from the Td Weyl semimetallic state to the superconducting state in the 1T' and Td phase at low temperature. Thus, it is a model system for phase transformation studies as well as quantum phenomena such as the quantum spin Hall effect and topological superconductivity. Careful studies of MoTe2 and its potential applications require large-area MoTe2 thin films with high crystallinity and thickness control. Here, we present cm2-scale synthesis of 2H-MoTe2 thin films with layer control and large grains that span several microns. Layer control is achieved by controlling the initial thickness of the precursor MoOx thin films, which are deposited on sapphire substrates by atomic layer deposition and subsequently tellurized. Despite the van der Waals epitaxy, the precursor-substrate interface is found to critically determine the uniformity in thickness and grain size of the resulting MoTe2 films: MoTe2 grown on sapphire show uniform films while MoTe2 grown on amorphous SiO2 substrates form islands. This synthesis strategy decouples the layer control from the variabilities of growth conditions for robust growth results and is applicable to growing other transition-metal dichalcogenides with layer control.

Impact of Microstructure on MoS2 Oxidation and Friction.

This work demonstrates the role of microstructure in the friction and oxidation behavior of the lamellar solid lubricant molybdenum disulfide (MoS2). We report on systematic investigations of oxidation and friction for two MoS2 films with distinctively different microstructures-amorphous and planar/highly-ordered-before and after exposure to atomic oxygen (AO) and high-temperature (250 °C) molecular oxygen. A combination of experimental tribology, molecular dynamics simulations, X-ray photoelectron spectroscopy (XPS), and high-sensitivity low-energy ion scattering (HS-LEIS) was used to reveal new insights about the links between structure and properties of these widely utilized low-friction materials. Initially, ordered MoS2 films showed a surprising resistance to both atomic and molecular oxygens (even at elevated temperature), retaining characteristic low friction after exposure to extreme oxidative environments. XPS shows comparable oxidation of both coatings via AO; however, monolayer resolved compositional depth profiles from HS-LEIS reveal that the microstructure of the ordered coatings limits oxidation to the first atomic layer.

Byproduct-Free Route to Aminosiloxane Monolayers on Silicon/Silicon Dioxide.

The chemisorption of N-methyl-aza-2,2,4-trimethylsilacyclopentane from either the solution or the vapor phase produces monolayer films on silicon (oxide) substrates. The formation of a covalent siloxane linkage to the surface by this adsorbate is accompanied by ring opening, which produces no byproduct. The resulting secondary amine reacts with maleic anhydride to produce a carboxylic acid-terminated surface, accompanied by the formation of a stable amide bond. These reactions and their products were characterized by a combination of optical ellipsometry, contact-angle goniometry, and X-ray photoelectron spectroscopy.

Use of Mixed CH3-/HC(O)CH2CH2-Si(111) Functionality to Control Interfacial Chemical and Electronic Properties During the Atomic-Layer Deposition of Ultrathin Oxides on Si(111).

Silicon surfaces terminated with a mixed monolayer containing both a propyl aldehyde functionality and methyl groups were prepared and used to control the interfacial chemical and electronic properties of Si(111) surfaces during atomic-layer deposition (ALD) of Al2O3 or MnO. Si(111) surfaces functionalized only with the aldehyde moiety exhibited surface recombination velocities, S, of 2500 ± 600 cm s(-1) whereas the mixed CH3-/HC(O)CH2CH2-Si(111) surfaces displayed S = 25 ± 7 cm s(-1). During the ALD growth of either Al2O3 or MnO, both the HC(O)CH2CH2-Si(111) and CH3-/HC(O)CH2CH2-Si(111) surfaces produced increased metal oxide deposition at low cycle number, relative to H-Si(111) or CH3-Si(111) surfaces. As detected by X-ray photoelectron spectroscopy after the ALD process, the CH3- and mixed CH3-/HC(O)CH2CH2- functionalized Si(111) surfaces exhibited less interfacial SiOx than was observed for ALD of metal oxides on H-Si(111) substrates.

Chemical Stability of Titania and Alumina Thin Films Formed by Atomic Layer Deposition.

Thin films formed by atomic layer deposition (ALD) are being examined for a variety of chemical protection and diffusion barrier applications, yet their stability in various fluid environments is not well characterized. The chemical stability of titania and alumina thin films in air, 18 MΩ water, 1 M KCl, 1 M HNO3, 1 M H2SO4, 1 M HCl, 1 M KOH, and mercury was studied. Films were deposited at 150 °C using trimethylaluminum-H2O and tetrakis(dimethylamido)titanium-H2O chemistries for alumina and titania, respectively. A subset of samples were heated to 450 and 900 °C in inert atmosphere. Films were examined using spectroscopic ellipsometry, atomic force microscopy, optical microscopy, scanning electron microscopy, and X-ray diffraction. Notably, alumina samples were found to be unstable in pure water, acid, and basic environments in the as-synthesized state and after 450 °C thermal treatment. In pure water, a dissolution-precipitation mechanism is hypothesized to cause surface roughening. The stability of alumina films was greatly enhanced after annealing at 900 °C in acidic and basic solutions. Titania films were found to be stable in acid after annealing at or above 450 °C. All films showed a composition-independent increase in measured thickness when immersed in mercury. These results provide stability-processing relationships that are important for controlled etching and protective barrier layers.

Photoelectrochemical behavior of n-type Si(111) electrodes coated with a single layer of graphene.

The behavior of graphene-coated n-type Si(111) photoanodes was compared to the behavior of H-terminated n-type Si(111) photoanodes in contact with aqueous K3[Fe(CN)6]/K4[Fe(CN)6] as well as in contact with a series of outer-sphere, one-electron redox couples in nonaqueous electrolytes. The n-Si/Graphene electrodes exhibited stable short-circuit photocurrent densities of over 10 mA cm(-2) for >1000 s of continuous operation in aqueous electrolytes, whereas n-Si-H electrodes yielded a nearly complete decay of the current density within ~100 s. The values of the open-circuit photovoltages and the flat-band potentials of the Si were a function of both the Fermi level of the graphene and the electrochemical potential of the electrolyte solution, indicating that the n-Si/Graphene did not form a buried junction with respect to the solution contact.

Electrochemically mediated atom transfer radical polymerization.

Atom transfer radical polymerization is a versatile technique for exerting precise control over polymer molecular weights, molecular weight distributions, and complex architectures. Here, we show that an externally applied electrochemical potential can reversibly activate the copper catalyst for this process by a one-electron reduction of an initially added air-stable cupric species (Cu(II)/Ligand). Modulation of polymerization kinetics is thereby tunable in real time by varying the magnitude of applied potential. Application of multistep intermittent potentials successfully triggers initiation of polymerization and subsequently toggles the polymerization between dormant and active states in a living manner. Catalyst concentrations down to 50 parts per million are demonstrated to maintain polymerization control manifested in linear first-order kinetics, a linear increase in polymer molecular weight with monomer conversion, and narrow polymer molecular weight distributions over a range of applied potentials.

In situ photopolymerization of pyrrole in mesoporous TiO2.

We examined mesoporous TiO(2) as a photosensitizer and template for creating hybrid TiO(2)-polypyrrole materials. Optical excitation of mesoporous TiO(2) was used to generate the electronic potential necessary for the oxidation and polymerization of the pyrrole monomer. The photopolymerization process was monitored by the quartz crystal microbalance, nitrogen sorption, and thermogravimetric techniques. In situ generation of polypyrrole was observed to be self-limiting after approximately 20-30% filling of the mesoporous TiO(2) network. In situ generation of a complementary phase by means of charge transfer from an active host phase represents an alternative means of assembling hybrid inorganic-organic materials with potential applications ranging from electrocatalysis to photovoltaics.

Ionic ligand mediated electrochemical charging of gold nanoparticle assemblies.

We demonstrate that ionic surface functionalization is well-suited for controlling the electrochemical charging of nanoparticle assemblies. Gold nanoparticles approximately 2 nm in diameter were functionalized with between 0 and approximately 3.3 cationic thiols per particle and the coupled motion of ions and electrons during redox cycling (charging) was followed in situ using an electrochemical quartz-crystal microbalance. When the electrochemistry is performed using a polycation electrolyte too large to penetrate the nanoparticle film, the degree of reduction possible was found to be dictated by the number of cationic ligands on the particle surface available for charge compensation. This route to reduced particles might be useful for electronic device fabrication, since the negative electronic charge is precisely compensated by immobile cationic ligands.

One- and two-photon induced polymerization of methylmethacrylate using colloidal CdS semiconductor quantum dots.

The development of one- and two-photon induced polymerization using CdS semiconductor quantum dots (QDs) and amine co-initiators to promote radical generation and subsequent polymerization is presented. Two-photon absorption (TPA) cross-section measurements, linear absorption, and transmission electron microscopy are used to characterize the QDs. The effectiveness of the co-initiators in increasing the efficiency of photopolymerization (polymer chains formed per excitation) is examined. Triethylamine was observed to be most effective, yielding quantum efficiencies of initiation of >5%. The interactions between the co-initiators and QDs are investigated with steady-state photoluminescence and infrared spectroscopies. Possible initiation mechanisms are discussed and supported by electrochemical data. Making use of the surface chemistry developed here and the large QD TPA cross-sections, two-photon induced polymerization is demonstrated. The large TPA cross-sections coupled with modest quantum efficiencies for initiation reveal the unique potential of molecularly passivated QDs as efficient two-photon photosensitizers for polymerization.

Tunable electronic interfaces between bulk semiconductors and ligand-stabilized nanoparticle assemblies.

Interfaces between nanoscale and bulk electroactive materials are important for the design of electronic devices using solution-processed nanoparticles. We report that thin films of hexanethiolate-capped gold nanoparticles with a core diameter of 2.1+/-0.4 nm deposited onto n-InP wafers form Schottky contacts whose barrier height can be actively tuned from 0.27+/-0.03 to 1.11+/-0.09 eV by electrochemically adjusting the nanoparticle Fermi level. This result is remarkable because interfacial barriers at conventional metal-semiconductor contacts are largely insensitive to the initial Fermi level of the metal. Furthermore, it highlights two general features of solution-processed nanoparticle assemblies in comparison with traditional bulk electronic materials: (1) the ability of ions to permeate the nanoparticle assembly enables the electrochemical injection of charges and hence active control of the Fermi level, and (2) ligand passivation of nanoparticle surfaces prevents interfacial reactions with the semiconductor that could otherwise lead to strong Fermi-level pinning.