John C. Hemminger

Electron Spectroscopy of Aqueous Solution Interfaces Reveals Surface Enhancement of Halides

It has been suggested that enhanced anion concentrations at the liquid/vapor interface of airborne saline droplets are important to aerosol reactions in the atmosphere. We report ionic concentrations in the surface of such solutions. Using x-ray photoelectron spectroscopy operating at near ambient pressure, we have measured the composition of the liquid/vapor interface for deliquesced samples of potassium bromide and potassium iodide. In both cases, the surface composition of the saturated solution is enhanced in the halide anion compared with the bulk of the solution. The enhancement of anion concentration is more dramatic for the larger, more polarizable iodide anion. By varying photoelectron kinetic energies, we have obtained depth profiles of the liquid/vapor interface. Our results are in good qualitative agreement with classical molecular dynamics simulations. Quantitative comparison between the experiments and the simulations indicates that the experimental results exhibit more interface enhancement than predicted theoretically.

STM investigation of single layer graphite structures produced on Pt(111) by hydrocarbon decomposition

STM has provided new insight into the nucleation, growth and nature of the graphite layer formed on Pt(111) by hydrocarbon decomposition. Annealing an ethylene covered surface to 800 K results in the formation of small (about 20–30 A in diameter) graphite islands which are initially uniformly distributed over the surface. With further annealing above 1000 K, the graphite is observed to accumulate, forming a layer at the lower step edges and also forming large, regularly shaped islands on the terraces. It has been determined that hydrocarbon decomposition at elevated temperatures results in formation of a single layer of graphite on the Pt surface. It is interesting to note that in the STM images of this single layer of graphite only three of the six carbon atoms in the graphite lattice are visible. This result cannot be accounted for by the usual explanation given in terms of inequivalent carbons atoms for the bulk graphite surface. Superstructures with periodicities varying up to 22 A are evident on the graphite areas and are due to a higher order commensurability of the graphite and Pt lattices at different relative rotations.

Getting Specific About Specific Ion Effects

Recent studies are shedding light on the mechanisms that drive the properties of salt solutions.

PbSe Quantum Dot Field-Effect Transistors with Air-Stable Electron Mobilities above 7 cm2 V–1 s–1

PbSe quantum dot (QD) field effect transistors (FETs) with air-stable electron mobilities above 7 cm(2) V(-1) s(-1) are made by infilling sulfide-capped QD films with amorphous alumina using low-temperature atomic layer deposition (ALD). This high mobility is achieved by combining strong electronic coupling (from the ultrasmall sulfide ligands) with passivation of surface states by the ALD coating. A series of control experiments rule out alternative explanations. Partial infilling tunes the electrical characteristics of the FETs.

Smaller is faster and more sensitive: the effect of wire size on the detection of hydrogen by single palladium nanowires.

Palladium nanowires prepared using the lithographically patterned nanowire electrodeposition (LPNE) method are used to detect hydrogen gas (H2). These palladium nanowires are prepared by electrodepositing palladium from EDTA-containing solutions under conditions favoring the formation of β-phase PdHx. The Pd nanowires produced by this procedure are characterized by X-ray diffraction, transmission electron microscopy, scanning electron microscopy, atomic force microscopy, and X-ray photoelectron spectroscopy. These nanowires have a mean grain diameter of 15 nm and are composed of pure Pd with no XPS-detectable bulk carbon. The four-point resistance of 50-100 μm segments of individual nanowires is used to detect H2 in N2 and air at concentrations ranging from 2 ppm to 10%. For low [H2] < 1%, the response amplitude increases by a factor of 2-3 with a reduction in the lateral dimensions of the nanowire. Smaller nanowires show accelerated response and recovery rates at all H2 concentrations from, 5 ppm to 10%. For 12 devices, response and recovery times are correlated with the surface area/volume ratio of the palladium detection element. We conclude that the kinetics of hydrogen adsorption limits the observed response rate seen for the nanowire, and that hydrogen desorption from the nanowire limits the observed recovery rate; proton diffusion within PdHx does not limit the rates of either of these processes.

The nature of water on surfaces of laboratory systems and implications for heterogeneous chemistry in the troposphere

A number of heterogeneous reactions of atmospheric importance occur in thin water films on surfaces in the earths boundary layer. It is therefore important to understand the interaction of water with various materials, both those used to study heterogeneous chemistry in laboratory systems, as well as those found in the atmosphere. We report here studies at 22 °C to characterize the interaction of water with such materials as a function of relative humidity from 0–100%. The surfaces studied include borosilicate glass, both untreated and after cleaning by three different methods (water, hydrogen peroxide and an argon plasma discharge), quartz, FEP Teflon film, a self assembled monolayer of n-octyltrichlorosilane (C8 SAM) on glass, halocarbon wax coatings prepared by two different methods, and several different types of Teflon coatings on solid substrates. Four types of measurements covering the range from the macroscopic level to the molecular scale were made: (1) contact angle measurements of water droplets on these surfaces to obtain macroscopic scale data on the water-surface interaction, (2) atomic force microscopy measurements to provide micron to sub-micron level data on the surface topography, (3) transmission FTIR of the surfaces in the presence of increasing water vapor concentrations to probe the interaction with the surface at a molecular level, and (4) X-ray photoelectron spectroscopy measurements of the elemental surface composition of the glass and quartz samples. Both borosilicate glass and the halocarbon wax coatings adsorbed significantly more water than the FEP Teflon film, which can be explained by a combination of the chemical nature of the surfaces and their physical topography. The C8 SAM, which is both hydrophobic and has a low surface roughness, takes up little water. The implications for the formation of thin water films on various surfaces in contact with the atmosphere, including building materials, soil, and vegetation, are discussed.

Direct observation of surface reactions by scanning tunneling microscopy : ethylene→ethylidyne→carbon particles→graphite on Pt(111)

We have used variable temperature, ultrahigh vacuum scanning tunneling microscopy (STM), in both static and time‐dependent experiments, to study the chemistry of the ethylene/Pt(111) system. Images of ethylene which exhibit long‐range order have been obtained at a sample temperature of 160 K. The conversion of ethylene to ethylidyne has been observed directly in STM images. This conversion reaction is observed to occur in a ‘‘patchy’’ manner across the surface at saturation coverage. As the reaction proceeds, well‐defined islands of unreacted ethylene continue to be clearly observed. Further dehydrogenation of the ethylidyne formed from ethylene leads to carbon containing particles dispersed randomly across the sample. After annealing the ethylidyne covered sample to 500 K, the surface is uniformly covered with carbon containing particles which exhibit a bimodal distribution of heights (one and two atomic layers) consisting of an average of ten and twenty carbon atoms, respectively. Further annealing to 7...

Iron Pyrite Thin Films Synthesized from an Fe(acac)3 Ink

Iron pyrite (cubic FeS2) is a promising candidate absorber material for earth-abundant thin-film solar cells. Here, we report on phase-pure, large-grain, and uniform polycrystalline pyrite films that are fabricated by solution-phase deposition of an iron(III) acetylacetonate molecular ink followed by sequential annealing in air, H2S, and sulfur gas at temperatures up to 550 °C. Phase and elemental compositions of the films are characterized by conventional and synchrotron X-ray diffraction, Raman spectroscopy, Auger electron spectroscopy, secondary ion mass spectrometry, and X-ray photoelectron spectroscopy (XPS). These solution-deposited films have more oxygen and alkalis, less carbon and hydrogen, and smaller optical band gaps (E(g) = 0.87 ± 0.05 eV) than similar films made by chemical vapor deposition. XPS is used to assess the chemical composition of the film surface before and after exposure to air and immersion in water to remove surface contaminants. Optical measurements of films rich in marcasite (orthorhombic FeS2) show that marcasite has a band gap at least as large as pyrite and that the two polymorphs share similar absorptivity spectra, in excellent agreement with density functional theory models. Regardless of the marcasite and elemental impurity contents, all films show p-type, weakly activated transport with curved Arrhenius plots, a room-temperature resistivity of ~1 Ω cm, and a hole mobility that is too small to measure by Hall effect. This universal electrical behavior strongly suggests that a common defect or a hole-rich surface layer governs the electrical properties of most FeS2 thin films.

Ion spatial distributions at the liquid-vapor interface of aqueous potassium fluoride solutions

X-Ray photoemission spectroscopy operating under ambient pressure conditions is used to probe ion distributions throughout the interfacial region of a free-flowing aqueous liquid micro-jet of 6 M potassium fluoride. Varying the energy of the ejected photoelectrons by carrying out experiments as a function of X-ray wavelength measures the composition of the aqueous-vapor interfacial region at various depths. The F(-) to K(+) atomic ratio is equal to unity throughout the interfacial region to a depth of 2 nm. The experimental ion profiles are compared with the results of a classical molecular dynamics simulation of a 6 M aqueous KF solution employing polarizable potentials. The experimental results are in qualitative agreement with the simulations when integrated over an exponentially decaying probe depth characteristic of an APPES experiment. First principles molecular dynamics simulations have been used to calculate the potential of mean force for moving a fluoride anion across the air-water interface. The results show that the fluoride anion is repelled from the interface, consistent with the depletion of F(-) at the interface revealed by the APPES experiment and polarizable force field-based molecular dynamics simulation. Together, the APPES and MD simulation data provide a detailed description of the aqueous-vapor interface of alkali fluoride systems. This work offers the first direct observation of the ion distribution at an aqueous potassium fluoride solution interface. The current experimental results are compared to those previously obtained for saturated solutions of KBr and KI to underscore the strong difference in surface propensity between soft/large and hard/small halide ions in aqueous solution.

Synthesis of PbTe Nanowire Arrays using Lithographically Patterned Nanowire Electrodeposition

We describe the preparation by electrodeposition of arrays of lead telluride (PbTe) nanowires using the lithographically patterned nanowire electrodeposition (LPNE) method. PbTe nanowires had a rectangular cross-section with adjustable width and height ranging between 60-400 nm (w) and 20-100 nm (h). The characterization of these nanowire arrays using X-ray diffraction, transmission electron microscopy and electron diffraction, scanning electron microscopy, atomic force microscopy, and X-ray photoelectron spectroscopy (XPS) is reported. PbTe nanowires were electrodeposited using a cyclic electrodeposition-stripping technique that produced polycrystalline, stoichiometric, face-centered cubic PbTe with a mean grain diameter of 10-20 nm. These nanowires were more than 1 mm in length and two additional processing steps permitted their suspension across 25 microm air gaps microfabricated on these surfaces. The LPNE synthesis of lithographically patterned PbTe nanowires was carried out in unfiltered laboratory air. Nanowires with lengths of 70-100 microm showed an electrical resistivity comparable to bulk PbTe. XPS reveals that exposure of PbTe nanowires to air causes the formation on the nanowire surface of approximately one monolayer of a mixed lead oxide and tellurium oxide within a few minutes.