Tuning Surface Chemoresistivity of Au Ultrathin Films Using Metal Deposition via Surface-Limited Redox Replacement of the Underpotentially Deposited Pb Monolayer.

The presented work investigates the chemoresistivity of Au ultrathin films, whose surface is modified by deposition of few monolayers of Au, Pd, or AuPd alloy. The model adsorbate in this study was the HS- ion from 0.1 M NaCl solution having concentrations ranging from 0 to 40 ppm. The Au surface modification was carried out using deposition via surface-limited redox replacement of the underpotentially deposited Pb monolayer. Modified Au films have shown higher chemoresistivity than the pristine ones. Our results and analysis suggest that these improvements are due to increased concentration of surface defects and enhanced scattering cross-section per adsorbate induced by chemical modification of the surface by Pd. The significance of our findings is discussed for practical applications shining more light on the importance of surface preparation for chemoresistive sensor design and performance.

Electroless Deposition of Pb Monolayer: A New Process and Application to Surface Selective Atomic Layer Deposition.

The present work demonstrates an electroless (e-less) deposition of Pb monolayer on Au and Cu surface whose morphology and properties resemble its underpotentially deposited counterpart. Our results and analysis show that the e-less Pb monolayer deposition is a surface selective, surface controlled, self-terminating process. Results also show that the electroless Pb monolayer deposition is enabling a phenomenon for new deposition method called "electroless atomic layer deposition" (e-less ALD). Here, the e-less Pb monolayer serves as reducing agent and sacrificial material in surface limited redox replacement reaction with noble metal ions such as Pt n+, i.e., Pt deposition. The e-less ALD is highly selective to the metal substrates at which Pb forms the e-less monolayer. The full e-less ALD cycle leads to an overall deposition of a controlled amount of the noble metal. Repetition of the two-step e-less ALD cycle an arbitrary number of times leads to formation of a highly compact, smooth, and conformal noble metal thin film with applications spanning from catalyst synthesis to semiconductor technology. The process is designed for (but not limited to) aqueous solutions that can be easily scaled up to any size and shape of the substrate, deeming its wide applications.

Finite Size Effects in Submonolayer Catalysts Investigated by CO Electrosorption on PtsML/Pd(100).

A combination of scanning tunneling microscopy, subtractively normalized interfacial Fourier transform infrared spectroscopy (SNIFTIRS), and density functional theory (DFT) is used to quantify the local strain in 2D Pt clusters on the 100 facet of Pd and its effect on CO chemisorption. Good agreement between SNIFTIRS experiments and DFT simulations provide strong evidence that, in the absence of coherent strain between Pt and Pd, finite size effects introduce local compressive strain, which alters the chemisorption properties of the surface. Though this effect has been widely neglected in prior studies, our results suggest that accurate control over cluster sizes in submonolayer catalyst systems can be an effective approach to fine-tune their catalytic properties.

Efficient C-C bond splitting on Pt monolayer and sub-monolayer catalysts during ethanol electro-oxidation: Pt layer strain and morphology effects.

Efficient catalytic C-C bond splitting coupled with complete 12-electron oxidation of the ethanol molecule to CO2 is reported on nanoscale electrocatalysts comprised of a Pt monolayer (ML) and sub-monolayer (sML) deposited on Au nanoparticles (Au@Pt ML/sML). The Au@Pt electrocatalysts were synthesized using surface limited redox replacement (SLRR) of an underpotentially deposited (UPD) Cu monolayer in an electrochemical cell reactor. Au@Pt ML showed improved catalytic activity for ethanol oxidation reaction (EOR) and, unlike their Pt bulk and Pt sML counterparts, was able to generate CO2 at very low electrode potentials owing to efficient C-C bond splitting. To explain this, we explore the hypothesis that competing strain effects due to the Pt layer coverage/morphology (compressive) and the Pt-Au lattice mismatch (tensile) control surface chemisorption and overall activity. Control experiments on well-defined model Pt monolayer systems are carried out involving a wide array of methods such as high-energy X-ray diffraction, pair-distribution function (PDF) analysis, in situ electrochemical FTIR spectroscopy, and in situ scanning tunneling microscopy. The vibrational fingerprints of adsorbed CO provide compelling evidence on the relation between surface bond strength, layer strain and morphology, and catalytic activity.

Development of Pinhole-Free Amorphous Aluminum Oxide Protective Layers for Biomedical Device Applications.

This paper describes synthesis of ultrathin pinhole-free insulating aluminum oxide layers for electronic device protection in corrosive liquid environments, such as phosphate buffered saline (PBS) or clinical fluids, to enable emerging biomedical applications such as biomolecular sensors. A pinhole-free 25-nm thick amorphous aluminum oxide layer has been achieved using ultra-high vacuum DC magnetron reactive sputtering of aluminum in oxygen/argon plasma followed by oxygen plasma post-processing. Deposition parameters were optimized to achieve the best corrosion protection of lithographically defined device structures. Electrochemical deposition of copper through the aluminum oxide layers was used to detect the presence (or absence) of pinholes. FTIR, XPS, and spectroscopic ellipsometry were used to characterize the material properties of the protective layers. Electrical resistance of the copper device structures protected by the aluminum oxide layers and exposed to a PBS solution was used as a metric to evaluate the long-term stability of these device structures.

Close-packed noncircular nanodevice pattern generation by self-limiting ion-mill process.

We describe a self-limiting, low-energy argon-ion-milling process that enables noncircular device patterns, such as squares or hexagons, to be formed using precursor arrays of uniform circular openings in poly(methyl methacrylate) defined using electron beam lithography. The proposed patterning technique is of particular interest for bit-patterned magnetic recording medium fabrication, where square magnetic bits result in improved recording system performance. Bit-patterned magnetic medium is among the primary candidates for the next generation magnetic recording technologies and is expected to extend the areal bit density limits far beyond 1 Tbit/in(2). The proposed patterning technology can be applied either for direct medium prototyping or for manufacturing of nanoimprint lithography templates or ion beam lithography stencil masks that can be utilized in mass production.