We demonstrate the method of a rapid covalent modification of silicon oxide surfaces with alcohol-containing compounds with assistance by microwave reactions. Alcohol-containing compounds are prevalent reagents in the laboratory, which are also relatively easy to handle because of their stability against exposure to atmospheric moisture. The condensation of these alcohols with the surfaces of silicon oxides is often hindered by slow reaction kinetics. Microwave radiation effectively accelerates this condensation reaction by heating the substrates and/or solvents. A variety of substrates were modified in this demonstration, such as silicon oxide films of various thicknesses, glass substrates such as microscope slides (soda lime), and quartz. The monolayers prepared through this strategy demonstrated the successful formation of covalent surface modifications of silicon oxides with water contact angles of up to 110° and typical hysteresis values of 2° or less. An evaluation of the hydrolytic stability of these monolayers demonstrated their excellent stability under acidic conditions. The techniques introduced in this article were successfully applied to tune the surface chemistry of silicon oxides to achieve hydrophobic, oleophobic, and/or charged surfaces.
Alcohol-based monolayers were successfully formed on the surfaces of silicon oxides through reactions performed in polar aprotic solvents. Monolayers prepared from alcohol-based reagents have been previously introduced as an alternative approach to covalently modify the surfaces of silicon oxides. These reagents are readily available, widely distributed, and are minimally susceptible to side reactions with ambient moisture. A limitation of using alcohol-based compounds is that previous reactions required relatively high temperatures in neat solutions, which can degrade some alcohol compounds or could lead to other unwanted side reactions during the formation of the monolayers. To overcome these challenges, we investigate the condensation reaction of alcohols on silicon oxides carried out in polar aprotic solvents. In particular, propylene carbonate has been identified as a polar aprotic solvent that is relatively nontoxic, readily accessible, and can facilitate the formation of alcohol-based monolayers. We have successfully demonstrated this approach for tuning the surface chemistry of silicon oxide surfaces with a variety of alcohol containing compounds. The strategy introduced in this research can be utilized to create silicon oxide surfaces with hydrophobic, oleophobic, or charged functionalities.
Transparent conductive oxides serve a critical function in many devices, such as organic light emitting diodes (OLEDs) and organic photovoltaics (OPVs). To optimize the performances of these devices, it is desirable to tune the interface between the transparent conductive oxide (TCO) and the next functional layer of these devices. Self-assembled monolayers prepared from phosphonic acids and silanes are commonly used to tune the properties and performance of this interface, including its surface energy, work function, and durability. Here, we report a new form of self-assembled monolayers for modifying indium tin oxide (ITO), a standard TCO used in OLEDs and OPVs. The ITO surfaces were modified with a series of distinct alcohol reagents.Stabilities of these alcohol based monolayers were compared with modifications derived from silanes and phosphonic acids, which are commonly used in the literature and industrial processes. Work functions and surface energies of these modified substrates were determined using ultraviolet photoelectron spectroscopy and contact angle measurements. Stability of these monolayers were assessed using cyclic voltammetry, X-ray photoelectron spectroscopy, and transmission spectroscopy techniques. Based on the results of these studies, alcohol based monolayers are promising candidates to modify ITO substrates for use in OLEDs and OPVs.
Alcohol-based reagents provide a versatile platform to covalently functionalize the surfaces of silica coated iron oxide nanoparticles through a silanol–alcohol condensation.
We demonstrate the formation of mixed monolayers derived from a microwave-assisted reaction of alcohols with silicon oxide surfaces in order to tune their surface oleophobicity. This simple, rapid method provides an opportunity to precisely tune the constituents of the monolayers. As a demonstration, we sought fluorinated alcohols and aliphatic alcohols as reagents to form monolayers from two distinct constituents for tuning the surface oleophobicity. The first aspect of this study sought to identify a fluorinated alcohol that formed monolayers with a relatively high surface coverage. It was determined that 1H,1H,2H,2H-perfluoro-1-octanol yielded high quality monolayers with a water contact angle (WCA) value of ∼110° and contact angle values of ∼80° with toluene and hexadecane exhibiting both an excellent hydrophobicity and oleophobicity. Tuning of the oleophobicity of the modified silicon oxide surfaces was achieved by controlling the molar ratio of 1H,1H,2H,2H-perfluoro-1-octanol within the reaction mixtures. Surface oleophobicity progressively decreased with a decrease in the fluorinated alcohol content while the monolayers maintained their hydrophobicity with WCA values of ∼110°. The simple and reliable approach to preparing monolayers of a tuned composition that is described in this article can be utilized to control the fluorocarbon content of the hydrophobic monolayers on silicon oxide surfaces.
We demonstrate the use of microwave radiation as a tool to accelerate the formation of perfluoroalkylsilane based self-assembled monolayers (SAMs) on silicon oxide surfaces. Surface coverage of these SAMs of monoreactive perfluoroalkylsilanes increased in proportion to the duration over which the solutions were heated by microwave radiation.
We demonstrate an alternative route to synthesize functionalized silica nanoparticles through incorporation of alcohol compounds in the Stöber process. The Stöber process has been widely utilized for the synthesis of silica nanoparticles due to its simplicity and reliability. Silane based compounds have been incorporated in this process in order to tailor surface properties of the silica nanoparticles. These compounds do, however, have limitations in their utility due to side reactions with water and intermolecular polymerization. In this article, we report the incorporation of alcohol based reagents in the Stöber process as an alternative means of synthesis and functionalization of silica nanoparticles. In particular, choline chloride was chosen as an exemplary alcohol to be incorporated in the process for tuning overall surface charge of the silica nanoparticles. These silica nanoparticles with incorporated choline chloride were characterized by atomic force microscopy (AFM), zeta potential measurements, and X-ray photoelectron spectroscopy (XPS) in comparison with silica nanoparticles synthesized from the traditional Stöber process. While the size and shape of the nanoparticles exhibited little difference between the two synthetic routes, the zeta potential of the choline chloride incorporated nanoparticle was ∼10 mV higher than that of the traditional silica nanoparticles. Composition of the choline chloride containing silica nanoparticles was verified by XPS with the observation of strong N1s and C1s signals. The methods introduced in this article could be expanded to incorporate a range of alcohol containing compounds including choline chloride for the synthesis of silica nanoparticles with a tuned surface chemistry.
The thickness of alcohol based monolayers on silicon oxide surfaces were investigated using angle-resolved X-ray photoelectron spectroscopy (ARXPS). Advantages of using alcohols as building blocks for the formation of monolayers include their widespread availability, ease of handling, and stability against side reactions. Recent progress in microwave assisted reactions demonstrated the ease of forming uniform monolayers with alcohol based reagents. The studies shown herein provide a detailed investigation of the thickness of monolayers prepared from a series of aliphatic alcohols of different chain lengths. Monolayers of 1-butanol, 1-hexanol, 1octanol, 1-decanol, and 1-dodecanol were each successfully formed through microwave assisted reactions and characterized by ARXPS techniques. The thickness of these monolayers consistently increased by ~1.0 Å for every additional methylene (CH2) within the hydrocarbon chain of the reagents. Tilt angles of the molecules covalently attached to silicon oxide surfaces were estimated to be ~35° for each type of reagent. These results were consistent with the observations reported for thiol based or silane based monolayers on either gold or silicon oxide surfaces, respectively. The results of this study also suggest that the alcohol based monolayers are uniform at a molecular level.
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