Ashley A. Ellsworth

Partially fluorinated oxo-alkoxide tungsten(VI) complexes as precursors for deposition of WOx nanomaterials

The partially fluorinated oxo-alkoxide tungsten(VI) complexes WO(OR)4 [4; R = C(CH3)2CF3, 5; R = C(CH3)(CF3)2] have been synthesized as precursors for chemical vapour deposition (CVD) of WOx nanocrystalline material. Complexes 4 and 5 were prepared by salt metathesis between sodium salts of the fluoroalkoxides and WOCl4. Crystallographic structure analysis allows comparison of the bonding in 4 and 5 as the fluorine content of the fluoroalkoxide ligands is varied. Screening of as a CVD precursor by mass spectrometry and thermogravimetric analysis was followed by deposition of WOx nanorods.

Role of the Reducing Agent in the Electroless Deposition of Copper on Functionalized SAMs

Metallized organic layer constructs have a wide range of technological applications. Electroless deposition is an attractive technique by which to deposit metal overlayers because it is inexpensive and can be performed at low temperatures, compatible with organic materials. Amine borane reducing agents are versatile and are capable of depositing metals, semiconductors, and even insulators. We have investigated the role of amine borane reducing agents in the electroless deposition of copper on -CH3-, -OH-, and -COOH-terminated SAMs adsorbed on gold using time-of-flight secondary ion mass spectrometry, optical microscopy, and complementary MP2 calculations. Three reducing agents were studied: amine borane, dimethylamine borane, and trimethylamine borane. At pH >9, -COOH-terminated SAMs form copper-carboxylate complexes, which serve as nucleation sites for subsequent copper deposition. The rate of copper deposition is dependent on the strength of the B-N bond of the amine borane reducing agent. Similarly, if the terminal group is nonpolar such as a -CH3 functionality, then the rate of copper deposition is dependent on the amine borane B-N bond strength. However, in contrast to -COOH-terminated SAMs, copper deposition does not begin immediately. If the terminal group contains polar bonds, such as the C-OH bond of -OH-terminated SAMs, deposition is dominated by the interaction of the reducing agent with the terminal group rather than the relative bond strengths of the amine borane reducing agents.

Effect of Ethanolamines on the Electroless Deposition of Copper on Functionalized Organic Surfaces

Electroless deposition (ELD) is widely used in industry to deposit metals because it is inexpensive and compatible with organic materials. The deposition rate and deposited film properties critically depend on the reducing agent, complexing agent, and bath pH and temperature as well as bath additives. We have investigated the role of ethanolamine additives in the ELD of copper using the reducing agent dimethylamine borane on -CH3- and -OH-terminated self-assembled monolayers (SAMs) adsorbed on gold. Three additives were studied: ethanolamine (EOA), diethanolamine (DEOA), and triethanolamine (TEOA). Both the chemical identity and concentration of the ethanolamine significantly affect the deposition process. We show that the Cu deposition rate is faster on -CH3-terminated surfaces than on -OH-terminated SAMs because of the stronger interaction of the ethanolamines with the hydroxyl terminal group. In contrast to physical vapor deposition and other ELD processes, Cu deposits atop methyl-terminated SAMs using TEOA. However, using EOA and DEOA, copper penetrates through -CH3-terminated SAMs to the Au/S interface. For -OH-terminated SAMs, copper is observed to penetrate through the SAM for all ethanolamines investigated. The amount of copper penetration through the SAM to the Au/S interface increases with ethanolamine concentration. These effects are attributed to an adsorption-inhibition mechanism and differences in the chelation of Cu2+ in the deposition bath.

Application of visible-light photosensitization to form alkyl-radical-derived thin films on gold

Visible-light irradiation of phthalimide esters in the presence of the photosensitizer [Ru(bpy)3]2+ and the stoichiometric reducing agent benzyl nicotinamide results in the formation of alkyl radicals under mild conditions. This approach to radical generation has proven useful for the synthesis of small organic molecules. Herein, we demonstrate for the first time the visible-light photosensitized deposition of robust alkyl thin films on Au surfaces using phthalimide esters as the alkyl radical precursors. In particular, we combine visible-light photosensitization with particle lithography to produce nanostructured thin films, the thickness of which can be measured easily using AFM cursor profiles. Analysis with AFM demonstrated that the films are robust and resistant to mechanical force while contact angle goniometry suggests a multilayered and disordered film structure. Analysis with IRRAS, XPS, and TOF SIMS provides further insights.

From Nanowires to Nanopores: A Versatile Method for Electroless Deposition of Nanostructures on Micropatterned Organic Substrates

We demonstrate a fast, flexible, parallel, and highly controllable method by which to synthesize a variety of nanoscale and mesoscale structures. This method addresses one of the most significant challenges in nanoscience: the in situ parallel placement and synthesis of nano-objects over the mesoscale. The method is based on electroless nanowire deposition on micropatterned substrates (ENDOM). In ENDOM nanostructures are produced at the boundary between two unlike materials if two conditions are met: (a) deposition is kinetically preferred on one of the materials while (b) transport of reactants is favored on the other. In this study, copper structures were deposited on patterned -OH/-CH3-terminated alkanethiolate self-assembled monolayers (SAMs) by exploiting the different reaction rates of electroless deposition on these using the reducing agent dimethylamine borane (DMAB). We demonstrate production of nanowires (width < 100 nm), mesowires (100 nm < width < ∼3000 nm), nanorings, nanopores, and nanochannels. We show that a variety of experimental conditions can be employed, making this method compatible with many substrates. We have also studied the nucleation and growth kinetics of the ENDOM process. The width of the deposit grows exponentially with deposition time and can be modeled using classical nucleation theory. Although the deposit width increases, the height and grain size of the copper deposit is constant (to within experimental uncertainty) with deposition time. These observations indicate that the minimum deposit width is controlled by the nanoparticle dimensions and so can be controlled using the reaction conditions.