Jeanne E. Pemberton

Bio: Jeanne E. Pemberton is an academic researcher from University of Arizona. The author has contributed to research in topics: Raman spectroscopy & Raman scattering. The author has an hindex of 41, co-authored 202 publications receiving 6567 citations. Previous affiliations of Jeanne E. Pemberton include University of North Carolina at Chapel Hill & Georgia Institute of Technology.

Air Stability of Alkanethiol Self-Assembled Monolayers on Silver and Gold Surfaces

Abstract: Surface Raman spectroscopy, electrochemistry, and X-ray photoelectron spectroscopy have been used to study the effects of air exposure on the stability of self-assembled monolayers (SAMs) formed from alkanethiols on mechanically polished, smooth Ag and Au surfaces. Raman spectra exhibit oxidized sulfur modes after only hours of air exposure. X-ray photoelectron spectroscopy of the S 2p region provides additional evidence for sulfur oxidation. Cyclic voltammetry of Ru(NH3)63+ indicates that oxidized alkanethiol SAMs retain blocking characteristics toward electron transfer, even after exposure of the oxidized SAM-surface to a solubilizing solvent. Control experiments suggest ozone as the primary oxidant in ambient laboratory air which causes rapid oxidation of the thiolate moiety. These results have important ramifications for the general use of SAMs in many proposed applications.

Surface Raman scattering of self-assembled monolayers formed from 1-alkanethiols : behavior of films at Au and comparison to films at Ag

Abstract: Surface Raman scattering is used to study self-assembled monolayers formed from a series of 1-alkanethiol s, CH3(CH2)^SH, where n = 3-5, 7, 8,11, and 17, at mechanically polished and electrochemically roughened Au surfaces. Defect structure in these films is investigated by use of the relative intensities of peaks due to trans and gauche conformations in the v(C-S) and P(C-C) frequency regions. Surface selection rules for Raman spectroscopy are used to estimate orientation of the alkanethiol layers at Au. The orientation proposed on the basis of the Raman spectral data is consistent with those previously reported on the basis of other measurements at Au surfaces. This orientation is compared to that previously determined for these films at Ag. Alkanethiols at Ag are found to have a chain tilt from the surface normal less than the 30° previously reported for Au. The C-S bond is found to be perpendicular to the Ag surface while it is largely parallel to the surface at Au. Differences in the spectra of short-chain alkanethiols from smooth and rough surfaces are attributed to disordering of the film at the roughened Au surface which occurs predominantly near the S end of the molecule on rough Au surfaces.

Surface Raman Scattering of Self-Assembled Monolayers Formed from 1-Alkanethiols at Ag

Abstract: Surface Raman scattering is used to study self-assembled monolayers formed from a series of 1-alkanethiols (1-butanethiol, 1-dodecanethiol, 1-octadecanethiol) at both electrochemically roughened and mechanically polished polycrystalline Ag electrodes

Phosphonic Acid Modification of Indium−Tin Oxide Electrodes: Combined XPS/UPS/Contact Angle Studies†

Abstract: Indium−tin oxide (ITO) electrodes have been modified with both fluorinated alkyl and aryl phosphonic acids [n-hexylphosphonic acid (HPA) and n-octadecylphosphonic acid (ODPA); 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl phosphonic acid (FHOPA), pentafluorobenzyl phosphonic acid (PFBPA), and tetrafluorobenzyl-1,4-diphosphonic acid (TFBdiPA)]. These are modifiers designed to control both wetting properties toward nonpolar molecular solids and to provide a wide range of tunability in effective surface work function. The molecular nature of surface attachment and changes in electronic and wetting properties were characterized by X-ray photoelectron spectroscopy (XPS), UV-photoelectron spectroscopy (UPS), photoelastic modulation infrared reflection−absorption spectroscopy (PM-IRRAS), and contact angle measurements using both water and hexadecane. Interface dipoles from the PA modifiers contribute to shifts in the low kinetic energy regions of UPS spectra (local vacuum level shifts, which translate into change...

Phosphonic Acids for Interfacial Engineering of Transparent Conductive Oxides

Abstract: Transparent conducting oxides (TCOs), such as indium tin oxide and zinc oxide, play an important role as electrode materials in organic-semiconductor devices. The properties of the inorganic–organic interface—the offset between the TCO Fermi level and the relevant transport level, the extent to which the organic semiconductor can wet the oxide surface, and the influence of the surface on semiconductor morphology—significantly affect device performance. This review surveys the literature on TCO modification with phosphonic acids (PAs), which has increasingly been used to engineer these interfacial properties. The first part outlines the relevance of TCO surface modification to organic electronics, surveys methods for the synthesis of PAs, discusses the modes by which they can bind to TCO surfaces, and compares PAs to alternative organic surface modifiers. The next section discusses methods of PA monolayer deposition, the kinetics of monolayer formation, and structural evidence regarding molecular orientati...

Formation and Structure of Self-Assembled Monolayers.

Abstract: The field of self-assembled monolayers (SAMs) has witnessed tremendous growth in synthetic sophistication and depth of characterization over the past 15 years.1 However, it is interesting to comment on the modest beginning and on important milestones. The field really began much earlier than is now recognized. In 1946 Zisman published the preparation of a monomolecular layer by adsorption (self-assembly) of a surfactant onto a clean metal surface.2 At that time, the potential of self-assembly was not recognized, and this publication initiated only a limited level of interest. Early work initiated in Kuhn’s laboratory at Gottingen, applying many years of experience in using chlorosilane derivative to hydrophobize glass, was followed by the more recent discovery, when Nuzzo and Allara showed that SAMs of alkanethiolates on gold can be prepared by adsorption of di-n-alkyl disulfides from dilute solutions.3 Getting away from the moisture-sensitive alkyl trichlorosilanes, as well as working with crystalline gold surfaces, were two important reasons for the success of these SAMs. Many self-assembly systems have since been investigated, but monolayers of alkanethiolates on gold are probably the most studied SAMs to date. The formation of monolayers by self-assembly of surfactant molecules at surfaces is one example of the general phenomena of self-assembly. In nature, self-assembly results in supermolecular hierarchical organizations of interlocking components that provides very complex systems.4 SAMs offer unique opportunities to increase fundamental understanding of self-organization, structure-property relationships, and interfacial phenomena. The ability to tailor both head and tail groups of the constituent molecules makes SAMs excellent systems for a more fundamental understanding of phenomena affected by competing intermolecular, molecular-substrates and molecule-solvent interactions like ordering and growth, wetting, adhesion, lubrication, and corrosion. That SAMs are well-defined and accessible makes them good model systems for studies of physical chemistry and statistical physics in two dimensions, and the crossover to three dimensions. SAMs provide the needed design flexibility, both at the individual molecular and at the material levels, and offer a vehicle for investigation of specific interactions at interfaces, and of the effect of increasing molecular complexity on the structure and stability of two-dimensional assemblies. These studies may eventually produce the design capabilities needed for assemblies of three-dimensional structures.5 However, this will require studies of more complex systems and the combination of what has been learned from SAMs with macromolecular science. The exponential growth in SAM research is a demonstration of the changes chemistry as a disciAbraham Ulman was born in Haifa, Israel, in 1946. He studied chemistry in the Bar-Ilan University in Ramat-Gan, Israel, and received his B.Sc. in 1969. He received his M.Sc. in phosphorus chemistry from Bar-Ilan University in 1971. After a brief period in industry, he moved to the Weizmann Institute in Rehovot, Israel, and received his Ph.D. in 1978 for work on heterosubstituted porphyrins. He then spent two years at Northwestern University in Evanston, IL, where his main interest was onedimensional organic conductors. In 1985 he joined the Corporate Research Laboratories of Eastman Kodak Company, in Rochester, NY, where his research interests were molecular design of materials for nonlinear optics and self-assembled monolayers. In 1994 he moved to Polytechnic University where he is the Alstadt-Lord-Mark Professor of Chemistry. His interests encompass self-assembled monolayers, surface engineering, polymers at interface, and surfaces phenomena. 1533 Chem. Rev. 1996, 96, 1533−1554

Biosensing with plasmonic nanosensors

Abstract: Recent developments have greatly improved the sensitivity of optical sensors based on metal nanoparticle arrays and single nanoparticles. We introduce the localized surface plasmon resonance (LSPR) sensor and describe how its exquisite sensitivity to size, shape and environment can be harnessed to detect molecular binding events and changes in molecular conformation. We then describe recent progress in three areas representing the most significant challenges: pushing sensitivity towards the single-molecule detection limit, combining LSPR with complementary molecular identification techniques such as surface-enhanced Raman spectroscopy, and practical development of sensors and instrumentation for routine use and high-throughput detection. This review highlights several exceptionally promising research directions and discusses how diverse applications of plasmonic nanoparticles can be integrated in the near future.

Surface-Enhanced Raman Spectroscopy

Abstract: The ability to control the size, shape, and material of a surface has reinvigorated the field of surface-enhanced Raman spectroscopy (SERS). Because excitation of the localized surface plasmon resonance of a nanostructured surface or nanoparticle lies at the heart of SERS, the ability to reliably control the surface characteristics has taken SERS from an interesting surface phenomenon to a rapidly developing analytical tool. This article first explains many fundamental features of SERS and then describes the use of nanosphere lithography for the fabrication of highly reproducible and robust SERS substrates. In particular, we review metal film over nanosphere surfaces as excellent candidates for several experiments that were once impossible with more primitive SERS substrates (e.g., metal island films). The article also describes progress in applying SERS to the detection of chemical warfare agents and several biological molecules.

Surface-enhanced Raman spectroscopy.

Abstract: The ability to control the size, shape, and material of a surface has reinvigorated the field of surface-enhanced Raman spectroscopy (SERS). Because excitation of the localized surface plasmon resonance of a nanostructured surface or nanoparticle lies at the heart of SERS, the ability to reliably control the surface characteristics has taken SERS from an interesting surface phenomenon to a rapidly developing analytical tool. This article first explains many fundamental features of SERS and then describes the use of nanosphere lithography for the fabrication of highly reproducible and robust SERS substrates. In particular, we review metal film over nanosphere surfaces as excellent candidates for several experiments that were once impossible with more primitive SERS substrates (e.g., metal island films). The article also describes progress in applying SERS to the detection of chemical warfare agents and several biological molecules.