Ex Situ Photoelectron Emission Microscopy of Polycrystalline Bismuth and Antimony Telluride Surfaces Exposed to Ambient Oxidation.

The surfaces of textured polycrystalline N-type bismuth telluride and P-type antimony telluride materials were investigated using ex situ photoelectron emission microscopy (PEEM). PEEM enabled imaging of the work function for different oxidation times due to exposure to air across sample surfaces. The spatially averaged work function was also tracked as a function of air exposure time. N-type bismuth telluride showed an increase in the work function around grain boundaries relative to grain interiors during the early stages of air exposure-driven oxidation. At longer time exposure to air, the surface became homogenous after a ∼5 nm-thick oxide formed. X-ray photoemission spectroscopy was used to correlate changes in PEEM imaging in real space and work function evolution to the progressive growth of an oxide layer. The observed work function contrast is consistent with the pinning of electronic surface states due to the defects at a grain boundary.

Determination of Hafnium Zirconium Oxide Interfacial Band Alignments Using Internal Photoemission Spectroscopy and X-ray Photoelectron Spectroscopy.

Doped ferroelectric HfO2 is highly promising for integration into complementary metal-oxide semiconductor (CMOS) technology for devices such as ferroelectric nonvolatile memory and low-power field-effect transistors (FETs). We report the direct measurement of the energy barriers between various metal electrodes (Pt, Au, Ta, TaN, Ti/Pt, Ni, Al) and hafnium zirconium oxide (Hf0.58Zr0.42O2, HZO) using internal photoemission (IPE) spectroscopy. Results are compared with valence band offsets determined using the three-sample X-ray photoelectron spectroscopy (XPS) as well as the two-sample hard X-ray photoelectron spectroscopy (HAXPES) techniques. Both XPS and IPE indicate roughly the same dependence of the HZO barrier on metal work function with a slope of 0.8 ± 0.5. XPS and HAXPES-derived barrier heights are on average about 1.1 eV smaller than barrier heights determined by IPE, suggesting the presence of negative charge in the HZO.

Engineering the Microstructure and Morphology of Explosive Films via Control of Interfacial Energy.

Physical vapor deposition of organic explosives enables growth of polycrystalline films with a unique microstructure and morphology compared to the bulk material. This study demonstrates the ability to control crystal orientation and porosity in pentaerythritol tetranitrate films by varying the interfacial energy between the substrate and the vapor-deposited explosive. Variation in density, porosity, surface roughness, and optical properties is achieved in the explosive film, with significant implications for initiation sensitivity and detonation performance of the explosive material. Various surface science techniques, including angle-resolved X-ray photoelectron spectroscopy and multiliquid contact angle analysis, are utilized to characterize interfacial characteristics between the substrate and explosive film. Optical microscopy and scanning electron microscopy of pentaerythritol tetranitrate surfaces and fracture cross sections illustrate the difference in morphology evolution and the microstructure achieved through surface energy modification. X-ray diffraction studies with the Tilt-A-Whirl three-dimensional pole figure rendering and texture analysis software suite reveal that high surface energy substrates result in a preferred (110) out-of-plane orientation of pentaerythritol tetranitrate crystallites and denser films. Low surface energy substrates create more randomly textured pentaerythritol tetranitrate and lead to nanoscale porosity and lower density films. This work furthers the scientific basis for interfacial engineering of polycrystalline organic explosive films through control of surface energy, enabling future study of dynamic and reactive detonative phenomena at the microscale. Results of this study also have potential applications to active pharmaceutical ingredients, stimuli-responsive polymer films, organic thin film transistors, and other areas.

Effects of Surface Chemistry and Topology on the Kinesin-Driven Motility of Microtubule Shuttles.

Nanoscale transport using the kinesin-microtubule system has been successfully used in applications ranging from self-assembly, to biosensing, to biocomputation. Realization of such applications necessitates robust microtubule motility particularly in the presence of complex sample matrices that can affect the interactions of the motors with the surface and the transport function. In the present work, we explored how the chemical nature and nanoscale topology of various surfaces affected kinesin-microtubule transport. Specifically, we characterized microtubule motility on three distinct interfaces: (i) surfaces modified with self-assembled monolayers (SAMs) displaying three different terminal groups, (ii) SAM-modified surfaces with adsorbed fetal bovine serum (FBS) proteins, and (iii) surfaces where the FBS layer was silicified to preserve an underlying surface topology. The composition and topology of each surface was confirmed with a number of techniques including X-ray photoelectron spectroscopy (XPS), water contact angle, atomic force microscopy (AFM), and scanning electron microscopy (SEM). The majority of surfaces, with the exception of those with the hydrophobic SAM, supported gliding motility consistent with the glass control. Differences in the displacement, velocity, and trajectory of the leading tip of the microtubule were observed in relation to the specific surface chemistry and, to a lesser extent, the nanoscale topology of the different substrates. Overall, this work broadens our understanding of how surface functionality and topology affect kinesin-based transport and provides valuable insights regarding future development of biosensing and probing applications that rely on biomolecular transport.

Intrinsic Properties of Individual Inorganic Silicon-Electrolyte Interphase Constituents.

Because of the complexity, high reactivity, and continuous evolution of the silicon-electrolyte interphase (SiEI), "individual" constituents of the SiEI were investigated to understand their physical, electrochemical, and mechanical properties. For the analysis of these intrinsic properties, known SiEI components (i.e., SiO2, Li2Si2O5, Li2SiO3, Li3SiOx, Li2O, and LiF) were selected and prepared as amorphous thin films. The chemical composition, purity, morphology, roughness, and thickness of prepared samples were characterized using a variety of analytical techniques. On the basis of subsequent analysis, LiF shows the lowest ionic conductivity and relatively weak, brittle mechanical properties, while lithium silicates demonstrate higher ionic conductivities and greater mechanical hardness. This research establishes a framework for identifying components critical for stabilization of the SiEI, thus enabling rational design of new electrolyte additives and functional binders for the development of next-generation advanced Li-ion batteries utilizing Si anodes.

Cubic SnGe nanoalloys: beyond thermodynamic composition limit.

Tin-germanium alloys are increasingly of interest as optoelectronic and thermoelectric materials as well as materials for Li/Na ion battery electrodes. However, the lattice incompatibility of bulk Sn and Ge makes creating such alloys challenging. By exploiting the unique strain tolerance of nanosized crystals, we have developed a facile synthetic method for homogeneous SnxGe1-x alloy nanocrystals with composition varying from essentially pure Ge to 95% Sn while still maintaining the cubic structure.

Adsorption and fusion of hybrid lipid/polymer vesicles onto 2D and 3D surfaces.

We investigated the formation of hybrid lipid/polymer (1,2-dioleoyl-sn-glycero-3-phosphocholine and poly(ethylene oxide-b-butadiene); DOPC/EO22Bd37) films onto planar silica surfaces. Using laser scanning confocal microscopy, atomic force microscopy, and quartz crystal microbalance analysis, we monitored the adsorption and fusion of hybrid lipid/polymer vesicles onto planar borosilicate glass cleaned via chemical etching or RF/air plasma treatment. In addition we used cryo-electron microscopy to characterize film formation on mesoporous silica nanoparticles. As the polymer content in the vesicles increased, the resulting hybrid lipid/polymer films on borosilicate glass - cleaned by chemical etching or plasma treatment - were more heterogeneous, indicating a large number of adsorbed vesicles rather than continuous bilayer films at higher polymer loadings. The observed lateral fluidity of both DOPC and hybrid lipid/polymer films also decreased substantially with increasing polymer fraction and was found to be relatively insensitive to changes in pH. Films prepared from vesicles with higher polymer loadings were completely immobile. We also found that polymer vesicles did not interact with clean plasma-treated glass surfaces, which may be due to elevated OH and Si-OH on plasma-treated surfaces. Conformal hybrid lipid/polymer coatings consistent with bilayers could be formed on mesoporous silica nanoparticles and imaged via cryo-electron microscopy. These results expand the library of biocompatible materials that can be used for coating silica-based materials and nanoparticles.

Insights into the spontaneous formation of hybrid PdO x /PEDOT films: electroless deposition and oxygen reduction activity.

Hybrid palladium oxide/poly(3,4-ethylenedioxythiophene) (PdO x /PEDOT) films were prepared through a spontaneous reaction between aqueous PdCl4 2- ions and a nanostructured film of electropolymerized PEDOT. Spectroscopic and electrochemical characterization indicate the presence of mixed-valence Pd species as-deposited (19 ± 7 at% Pd0, 64 ± 3 at% Pd2+, and 18 ± 4 at% Pd4+ by X-ray photoelectron spectroscopy) and the formation of stable, electrochemically reversible Pd0/α-PdO x active species in alkaline electrolyte and furthermore in the presence of oxygen. The elucidation of the Pd speciation as-deposited and in solution provides insight into the mechanism of electroless deposition in neutral aqueous conditions and the electrocatalytically active species during oxygen reduction in alkaline electrolyte. The PdO x /PEDOT film catalyses 4e- oxygen reduction (n = 3.97) in alkaline electrolyte at low overpotential (0.98 V vs. RHE, onset potential), with mass- and surface area-based specific activities competitive with, or superior to, commercial 20% Pt/C and state-of-the-art Pd- and PEDOT-based nanostructured catalysts. The high activity of the nanostructured hybrid PdO x /PEDOT film is attributed to effective dispersion of accessible, stable Pd active sites in the PEDOT matrix.

Kinetics of chemi-ionization reactions of lanthanide metals (Nd, Sm) from 150 to 450 K.

The kinetics of chemi-ionization reactions of neodymium and samarium atoms with an oxygen atom to yield a metal monoxide cation and electron were studied using a flow tube apparatus over a temperature range of 150-450 K. Nd reacts efficiently with O, near the hard-sphere collision limit at all temperatures, with a rate constant of 3 × 10(-10) cm(3) s(-1) at 300 K and a slight positive temperature dependence. No chemi-ionization of Nd with N2O was observed, despite the reaction being exothermic. Chemi-ionization of Sm with O is slow, with a rate constant at 300 K determined to be 7 × 10(-12) cm(3) s(-1), although with large uncertainty. The Sm reaction also shows a slightly positive temperature dependence, described by a small activation energy of 60 meV. Although not definitive, the data suggest that excited states of Sm react efficiently whereas ground state Sm reacts inefficiently.

Electrodeposited Ni(x)Co(3-x)O4 nanostructured films as bifunctional oxygen electrocatalysts.

Nanostructured Ni(x)Co(3-x)O4 films serve as effective electrocatalysts for both the oxygen reduction and oxygen evolution reactions in alkaline electrolyte.

Simple, benign, aqueous-based amination of polycarbonate surfaces.

Polycarbonate is a desirable material for many applications due to its favorable mechanical and optical properties. Here, we report a simple, safe, environmentally friendly aqueous method that uses diamines to functionalize a polycarbonate surface with amino groups. The use of water as the solvent for the functionalization ensures that solvent induced swelling does not affect the optical or mechanical properties of the polycarbonate. We characterize the efficacy of the surface amination using X-ray photo spectroscopy, Fourier transform infrared spectroscopy (FT-IR), atomic force microscopy (AFM), and contact angle measurements. Furthermore, we demonstrate the ability of this facile method to serve as a foundation upon which other functionalities may be attached, including antifouling coatings and oriented membrane proteins.

Controlled nucleation and growth of pillared paddlewheel framework nanostacks onto chemically modified surfaces.

The nucleation and growth of metal-organic frameworks onto functional surfaces stands to facilitate the utility of these supramolecular crystalline materials across a wide range of applications. Here, we demonstrate the solvothermal nucleation and growth of a pillared paddlewheel porphyrin framework 5 (PPF-5) onto semiconductor surfaces modified with carboxylic acids. Using versatile diazonium and catechol chemistries to modify silicon and titania surface chemistries, we show that solvothermally grown PPF-5 selectively nucleates and grows as stacked crystalline sheets with preferential (001), (111), and (110) crystallographic orientations. Furthermore, variations in the synthesis temperature produce modified stack morphologies that correlate with changes in the surface-nucleated PPF-5 photoluminescence.

Lithographically defined three-dimensional graphene structures.

A simple and facile method to fabricate 3D graphene architectures is presented. Pyrolyzed photoresist films (PPF) can easily be patterned into a variety of 2D and 3D structures. We demonstrate how prestructured PPF can be chemically converted into hollow, interconnected 3D multilayered graphene structures having pore sizes around 500 nm. Electrodes formed from these structures exhibit excellent electrochemical properties including high surface area and steady-state mass transport profiles due to a unique combination of 3D pore structure and the intrinsic advantages of electron transport in graphene, which makes this material a promising candidate for microbattery and sensing applications.

Large area mosaic films of graphene-titania: self-assembly at the liquid-air interface and photo-responsive behavior.

Photo-responsive graphene-titania composite nanofilms were formed via evaporative induced self-assembly at the air-liquid interface from the UV-photo-reduction of titania-graphene oxide colloidal solutions.

Nanostructured ruthenium oxide electrodes via high-temperature molecular templating for use in electrochemical capacitors.

Ruthenium oxide is a model pseudocapacitive materials exhibiting good electronic and protonic conduction and has been shown to achieve very high gravimetric capacitances. However, the capacitance of thermally prepared ruthenium oxide is generally low because of low protonic conductivity resulting from dehydration of the oxide upon annealing. High-temperature processing, however also produces the electrically conducting ruthenium oxide rutile phase, which is of great interest for electrochemical capacitors. Here, unusual electrochemical characteristics were obtained for thermally prepared ruthenium oxide when fabricated in the presence of alkyl-thiols at high temperature. The performance characteristics have been attributed to enhanced multifunctional properties of the material resulting from the novel processing. The processing method relies on a simple, solution-based strategy that utilizes a sacrificial organic template to sterically direct hierarchical architecture formation in electro-active ruthenium oxide. Thin films of the templated RuO(2) exhibit energy storage characteristics comparable to hydrous ruthenium oxide materials formed under dramatically different conditions. Extensive materials characterization has revealed that these property enhancements are associated with the retention of molecular-sized metal oxide clusters, high hydroxyl concentrations, and formation of hierarchical porosity in the ruthenium oxide thin films.

Oxide contacts in organic photovoltaics: characterization and control of near-surface composition in indium-tin oxide (ITO) electrodes.

The recent improvements in the power conversion efficiencies of organic photovoltaic devices (OPVs) promise to make these technologies increasingly attractive alternatives to more established photovoltaic technologies. OPVs typically consist of photoactive layers 20-100 nm thick sandwiched between both transparent oxide and metallic electrical contacts. Ideal OPVs rely on ohmic top and bottom contacts to harvest photogenerated charges without compromising the power conversion efficiency of the OPV. Unfortunately, the electrical contact materials (metals and metal oxides) and the active organic layers in OPVs are often incompatible and may be poorly optimized for harvesting photogenerated charges. Therefore, further optimization of the chemical and physical stabilities of these metal oxide materials with organic materials will be an essential component of the development of OPV technologies. The energetic and kinetic barriers to charge injection/collection must be minimized to maximize OPV power conversion efficiencies. In this Account, we review recent studies of one of the most common transparent conducting oxides (TCOs), indium-tin oxide (ITO), which is the transparent bottom contact in many OPV technologies. These studies of the surface chemistry and surface modification of ITO are also applicable to other TCO materials. Clean, freshly deposited ITO is intrinsically reactive toward H(2)O, CO, CO(2), etc. and is often chemically and electrically heterogeneous in the near-surface region. Conductive-tip atomic force microscopy (C-AFM) studies reveal significant spatial variability in electrical properties. We describe the use of acid activation, small-molecule chemisorption, and electrodeposition of conducting polymer films to tune the surface free energy, the effective work function, and electrochemical reactivity of ITO surfaces. Certain electrodeposited poly(thiophenes) show their own photovoltaic activity or can be used as electronically tunable substrates for other photoactive layers. For certain photoactive donor layers (phthalocyanines), we have used the polarity of the oxide surface to accelerate dewetting and "nanotexturing" of the donor layer to enhance OPV performance. These complex surface chemistries will make oxide/organic interfaces one of the key focal points for research in new OPV technologies.

Metalloporphyrin assemblies on pyridine-functionalized titanium dioxide.

Porphyrin adsorption on TiO2 nanoparticles has been achieved for multiple porphyrins, and in mixed porphyrin assemblies, via axial ligation to surface-bound pyridine anchored by either para carboxylic or phosphonic functionalizations. Homogenous assemblies were prepared and characterized, while mixed metalloporphyrin assemblies were demonstrated by controlling the concentration ratios of respective porphyrins in the modifying solution. Evaluation of the assemblies using spectroscopic techniques and electrochemistry confirms high porphyrin retention, while exhibiting their surface bound optical and electrochemical properties. A thorough study is discussed where several metalloporphyrins have been evaluated (Ru(CO)OEP, Ru(CO)TPP, and ZnTPP) for relative comparisons and relationships to pyridyl axial binding strengths. The systematic study evaluates multiple background cases using either H2TPP, TiO2 modification with benzoic acid, or unmodified TiO2 to confirm the high affinity of Ru and Zn porphyrins for surface-anchored pyridyl sites. The simple method of step-by-step coordinative anchoring of porphyrins to TiO2 using small, commercially available molecules is highly adaptable for use in dye-sensitized solar cells (DSSC) where intimate contact between the absorbing dye and the semiconductor is required. DSSC devices with novel mixed porphyrin assemblies were shown to give higher power performance than DSSCs utilizing sensitization with only one type of porphyrin.

Organic/Organic' heterojunctions: organic light emitting diodes and organic photovoltaic devices.

Heterojunctions created from thin films of two dissimilar organic semiconductor materials [organic/organic' (O/O') heterojunctions] are an essential component of organic light emitting diode displays and lighting systems (OLEDs, PLEDs) and small molecule or polymer-based organic photovoltaic (solar cell) technologies (OPVs). O/O' heterojunctions are the site for exciton formation in OLEDs, and the site for exciton dissociation and photocurrent production in OPVs. Frontier orbital energy offsets in O/O' heterojunctions establish the excess free energy controlling rates of charge recombination and formation of emissive states in OLEDs and PLEDs. These energy offsets also establish the excess free energy which controls charge separation and the short-circuit photocurrent (J(SC) ) in OPVs, and set the upper limit for the open-circuit photopotential (V(OC) ). We review here how these frontier orbital energy offsets are determined using photoemission spectroscopies, how these energies change as a function of molecular environment, and the influence of interface dipoles on these frontier orbital energies. Recent examples of heterojunctions based on small molecule materials are shown, emphasizing those heterojunctions which are of interest for photovoltaic applications. These include heterojunctions of perylenebisimide dyes with trivalent metal phthalocyanines, and heterojunctions of titanyl phthalocyanine with C(60) , and with pentacene. Organic solar cells comprised of donor/acceptor pairs of each of these last three materials confirm that the V(OC) scales with the energy offsets between the HOMO of the donor and LUMO of the acceptor ($E_{{\rm HOMO}^{\rm D} } - E_{{\rm LUMO}^{\rm A} }$).

Surface composition and electrical and electrochemical properties of freshly deposited and acid-etched indium tin oxide electrodes.

We compare the near-surface composition and electroactivity of commercial indium tin oxide (ITO) thin films, activated by plasma cleaning or etching with strong haloacids, with ITO films that have been freshly deposited in high vacuum, before and after exposure to the atmosphere or water vapor. Conductive-tip AFM, X-ray photoelectron spectroscopy (XPS), and the electrochemistry of probe molecules in solution were used to compare the relative degrees of electroactivity and the near-surface composition of these materials. Brief etching of commercial ITO samples with concentrated HCl or HI significantly enhances the electrical activity of these oxides as revealed by C-AFM. XPS was used to compare the composition of these activated surfaces, focusing on the intrinsically asymmetric O 1s line shape. Energy-loss processes associated with photoemission from the tin-doped, oxygen-deficient oxides complicate the interpretation of the O 1s spectra. O 1s spectra from the stoichiometric indium oxide lattice are accompanied by higher-binding-energy peaks associated with hydroxylated forms of the oxide (and in some cases carbonaceous impurities) and overlapping photoemission associated with energy-loss processes. Characterization of freshly sputter-deposited indium oxide (IO) and ITO films, transferred under high vacuum to the surface analysis environment, allowed us to differentiate the contributions of tin doping and oxygen-vacancy doping to the O 1s line shape, relative to higher-binding-energy O 1s components associated with hydroxyl species and carbonaceous impurities. Using these approaches, we determined that acid activation and O2 plasma etching create an ITO surface that is still covered with an average of one to two monolayers of hydroxide. Both of these activation treatments lead to significantly higher rates of electron transfer to solution probe molecules, such as dimethyferrocene in acetonitrile. Solution electron-transfer events appear to occur at no more than 4x10(7) electroactive sites per cm2 (each with diameters of ca. 50-200 nm) (i.e., a small fraction of the geometric area of the electrode). Electron-transfer rates correlate with the near-surface tin dopant concentration, suggesting that these electroactive sites arise from near-surface tin enrichment.

Modification of indium-tin oxide electrodes with thiophene copolymer thin films: optimizing electron transfer to solution probe molecules.

We describe the modification of indium-tin oxide (ITO) electrodes via the chemisorption and electropolymerization of 6-{2,3-dihydrothieno[3,4-b]-1.4-dioxyn-2-yl methoxy}hexanoic acid (EDOTCA) and the electrochemical co-polymerization of 3,4-ethylenedioxythiophene (EDOT) and EDOTCA to form ultrathin films that optimize electron-transfer rates to solution probe molecules. ITO electrodes were first activated using brief exposure to strong haloacids, to remove the top approximately 8 nm of the electrode surface, followed by immediate immersion into a 50:50 EDOT/EDOTCA co-monomer solution. Potential step electrodeposition for brief deposition times was used to grow copolymer films of thickness 10-100 nm. The composition of these copolymer films was characterized by solution depletion studies of the monomers and atomic force microscopy (AFM), X-ray photoelectron spectroscopy, and Fourier transform infrared spectroscopy (reflection-absorption infrared spectroscopy (RAIRS)) of the product films. The spectroscopic data suggest that the composition of the copolymer approaches 80% EDOTCA when electropolymerization occurs from concentrated (10 mM) solutions. AFM characterization shows that electrodeposited poly(EDOT)/poly(EDOTCA) (PEDOT/PEDOTCA) films are quite smooth, with texturing on the nanometer scale. RAIRS studies indicate that these films consist of a combination of EDOTCA units with noninteracting -COOH groups and adjacent hydrogen-bonded -COOH groups. The EDOTCA-containing polymer chains appear to grow as columnar clusters from specific regions, oriented nearly vertically to the substrate plane. As they grow, these columnar clusters overlap to form a nearly continuous redox active polymer film. ITO activation and formation of these copolymer films enhances the electroactive fraction of the electrode surface relative to a nonactivated, unmodified "blocked" ITO electrode. Outer-sphere solution redox probes (dimethylferrocene) give standard rate coefficients, kS > or = 0.4 cm.s-1, at 10 nm thick copolymer films of PEDOT/PEDOTCA, which is 3 orders of magnitude greater than that on the unmodified ITO surface and approaches the values for kS seen on clean gold surfaces.