Matthew R. Linford

Metallosupramolecular thin polyelectrolyte films.

Molecular recognition and electrostatic interaction of oppositely charged polyelectrolytes are combined in the fabrication of ultrathin metallosupramolecular multilayers [shown schematically in the picture, PEI=polyethyleneimine, PSS=poly(styrene sulfonate)]. The layers between the PSS layers are composed of an iron(II) bis(terpyridine) coordination polymer.

Determination of the bonding of alkyl monolayers to the Si(111) surface using chemical-shift, scanned-energy photoelectron diffraction

The bonding of alkyl monolayers to Si(111) surfaces has been studied by conventional x-ray photoelectron spectroscopy (XPS) and chemical-shift, scanned-energy photoelectron diffraction (PED) using synchrotron radiation. Two very different wet-chemical methods have been used to prepare the alkyl monolayers: (i) olefin insertion into the H–Si bond on the H–Si(111) surface, and (ii) replacement of Cl on the Cl–Si(111) surface by an alkyl group from an alkyllithium reagent. In both cases, XPS has revealed a C 1s signal chemically shifted to lower binding energy, which we have assigned to carbon bonded to silicon. PED has shown that both preparative methods result in carbon bonded in an atop site with the expected C–Si bond length of 1.85±0.05 A. Chemical-shift, scanned-energy photoelectron diffraction is a particularly valuable probe of local structure at surfaces that contain the same element in multiple, chemically distinct environments.

Chemical Vapor Deposition of Three Aminosilanes on Silicon Dioxide: Surface Characterization, Stability, Effects of Silane Concentration, and Cyanine Dye Adsorption

Covalently bonded monolayers of two monofunctional aminosilanes (3-aminopropyldimethylethoxysilane, APDMES, and 3-aminopropyldiisopropylethoxysilane, APDIPES) and one trifunctional aminosilane (3-aminopropyltriethoxysilane, APTES) have been deposited on dehydrated silicon substrates by chemical vapor deposition (CVD) at 150 °C and low pressure (a few Torr) using reproducible equipment. Standard surface analytical techniques such as x-ray photoelectron spectroscopy (XPS), contact angle goniometry, spectroscopic ellipsometry, atomic force microscopy, and time-of-flight secondary ion mass spectroscopy (ToF-SIMS) have been employed to characterize the resulting films. These methods indicate that essentially constant surface coverages are obtained over a wide range of gas phase concentrations of the aminosilanes. XPS data further indicate that the N1s/Si2p ratio is higher after CVD with the trifunctional silane (APTES) compared to the monofunctional ones, with a higher N1s/Si2p ratio for APDMES compared to that for APDIPES. AFM images show an average surface roughness of 0.12- 0.15 nm among all three aminosilane films. Stability tests indicate that APDIPES films retain most of their integrity at pH 10 for several hours and are more stable than APTES or APDMES layers. The films also showed good stability against storage in the laboratory. ToF-SIMS of these samples showed expected peaks, such as CN(-), as well as CNO(-), which may arise from an interaction between monolayer amine groups and silanols. Optical absorption measurements on adsorbed cyanine dye at the surface of the aminosilane films show the formation of dimer aggregates on the surface. This is further supported by ellipsometry measurements. The concentration of dye on each surface appears to be consistent with the density of the amines.

Alkyl-terminated Si(111) surfaces: A high-resolution, core level photoelectron spectroscopy study

The bonding of alkyl monolayers to Si(111) surfaces has been studied with high-resolution core level photoelectron spectroscopy (PES). Two very different wet-chemical methods have been used to prepare the alkyl monolayers: (i) Olefin insertion into the H–Si bond of the H–Si(111) surface, and (ii) replacement of Cl on the Cl–Si(111) surface by an alkyl group from an alkyllithium reagent. In both cases, PES has revealed a C 1s component shifted to lower binding energy and a Si 2p component shifted to higher binding energy. Both components are attributed to the presence of a C–Si bond at the interface. Along with photoelectron diffraction data [Appl. Phys. Lett. 71, 1056, (1997)], these data are used to show that these two synthetic methods can be used to functionalize the Si(111) surface.

Core-shell diamond as a support for solid-phase extraction and high-performance liquid chromatography.

We report the formation of core-shell diamond particles for solid-phase extraction (SPE) and high-performance liquid chromatography (HPLC) made by layer-by-layer (LbL) deposition. Their synthesis begins with the amine functionalization of microdiamond by its immersion in an aqueous solution of a primary amine-containing polymer (polyallylamine (PAAm)). The amine-terminated microdiamond is then immersed in an aqueous suspension of nanodiamond, which leads to adsorption of the nanodiamond. Alternating (self-limiting) immersions in the solutions of the amine-containing polymer and the suspension of nanodiamond are continued until the desired number of nanodiamond layers is formed around the microdiamond. Finally, the core-shell particles are cross-linked with 1,2,5,6-diepoxycyclooctane or reacted with 1,2-epoxyoctadecane. Layer-by-layer deposition of PAAm and nanodiamond is also studied on planar Si/SiO(2) surfaces, which were characterized by scanning electron microscopy (SEM), Rutherford backscattering spectrometry (RBS), and nuclear reaction analysis (NRA). Core-shell particles are characterized by diffuse reflectance infrared Fourier transform spectroscopy (DRIFT), environmental scanning electron microscopy (ESEM), and Brunauer-Emmett-Teller (BET) surface area and pore size measurements. Larger (ca. 50 microm) core-shell diamond particles have much higher surface areas and analyte loading capacities in SPE than nonporous solid diamond particles. Smaller (ca. 3 microm), normal and reversed-phase, core-shell diamond particles have been used for HPLC, with 36,300 plates/m for mesitylene in a separation of benzene and alkyl benzenes and 54,800 plates/m for diazinon in a similar separation of two pesticides on a C(18) adsorbent.

Chemomechanical surface patterning and functionalization of silicon surfaces using an atomic force microscope

Surface modification and patterning at the nanoscale is a frontier in science with significant possible applications in biomedical technology and nanoelectronics. Here we show that an atomic force microscope (AFM) can be employed to simultaneously pattern and functionalize hydrogen-terminated silicon (111) surfaces. The AFM probe was used to break Si–H and Si–Si bonds in the presence of reactive molecules, which covalently bonded to the scribed Si surface. Functionalized patches and patterned lines of molecules were produced. Linewidths down to 30 nm were made by varying the force at the tip.

Stable, Microfabricated Thin Layer Chromatography Plates without Volume Distortion on Patterned, Carbon and Al2O3-Primed Carbon Nanotube Forests

Some of us recently described the fabrication of thin layer chromatography (TLC) plates from patterned carbon nanotube (CNT) forests via direct infiltration/coating of the CNTs by low pressure chemical vapor deposition (LPCVD) of silicon from SiH₄, followed by high temperature oxidation of the CNTs and Si. Herein we present an improved microfabrication process for the preparation of these TLC plates. First, a few nanometers of carbon and/or a thin film of Al₂O₃ is deposited on the CNTs. This method of priming the CNTs for subsequent depositions appears to be new. X-ray photoelectron spectroscopy confirms the presence of additional oxygen after carbon deposition. After priming, the plates are coated by rapid, conformal deposition of an inorganic material that does not require subsequent oxidation, i.e., by a fast pseudo atomic layer deposition (ψ-ALD) of SiO₂ from trimethylaluminum and tris(tert-butoxy)silanol. Unlike devices described previously, faithful reproduction of the features in the masks is still observed after oxidation. A bonded, amino phase on the resulting plates shows fast, highly efficient separations of fluorescent dyes (plate heights in the range of 1.6-7.7 μm). Extensive characterization of the new materials by TEM, SEM, EDAX, DRIFT, and XPS is reported. A substantially lower process temperature for the removal of the CNT scaffold is possible as a result of the already oxidized materials used.

Reactivity of the HSi (1 1 1) surface

Abstract The HSi (1 1 1) surface has been well characterized [Hricovini et al., Phys. Rev. Lett. 70 (1993) 1992], so the reactivity of this surface was studied. HSi (1 1 1) surfaces exposed to Cl 2 , Br 2 , and 1-alkenes were studied with photoemission spectroscopy. These particular compounds were chosen because of their importance in semiconductor processing and surface functionalization. The observation of the growth of a Si 2p component at high binding energy, characteristic of halogen reactivity, confirmed that bromine and chlorine gases both reacted with the HSi (1 1 1) surface. Reactions with 1-alkenes were confirmed by measuring both the Si 2p and the C 1s core level spectra. The C 2s-based molecular orbitals in the valence band revealed the identity of the alkyl monolayer on the Si (1 1 1) surface. Therefore, we found that the HSi (1 1 1) surface, under certain conditions, was reactive.

Amino-Modified Diamond as a Durable Stationary Phase for Solid-Phase Extraction

We report the formation of a highly stable amino stationary phase on diamond and demonstrate its use in solid-phase extraction (SPE). This process consists of spontaneous and self-limiting adsorption of polyallylamine (PAAm) from aqueous solution onto oxidized diamond. Thermal curing under reduced pressure or chemical cross-linking with a diepoxide was shown to fix the polymer to the particles. The resulting adsorbents are stable under even extreme pH conditions (from at least pH 0-14) and significantly more stable than a commercially available amino SPE adsorbent. Coated diamond particles were characterized by X-ray photoelectron spectroscopy (XPS) and diffuse reflectance Fourier transform-infrared spectroscopy (DRIFT). Model silicon surfaces were characterized by spectroscopic ellipsometry and wetting. Solid-phase extraction was demonstrated using cholesterol, hexadecanedioic acid, and palmitoyloleoylphosphatidylcholine as analytes, and these results were compared to those obtained with commercially available materials. Breakthrough curves indicate that, as expected, porous diamond particles have higher analyte capacity than nonporous solid particles.

Silicon (100)/SiO2 by XPS

Silicon (100) substrates are ubiquitous in microfabrication and, accordingly, their surface characteristics are important. Herein, we report the analysis of Si (100) via X-ray photoelectron spectroscopy (XPS) using monochromatic Al Kα radiation. Survey scans show that the material is primarily silicon and oxygen with small amounts of carbon, nitrogen, and fluorine contamination. The Si 2p region shows two peaks that correspond to elemental silicon and silicon dioxide. Using these peaks the thickness of the native oxide (SiO2) is estimated using the equation of Strohmeier. The oxygen peak is symmetric. These silicon wafers are used as the substrate for subsequent growth of templated carbon nanotubes in the preparation of microfabricated thin layer chromatography plates.