We measure silane density and Sulfo-EMCS cross-linker coupling efficiency on aminosilane films by high-resolution X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM) measurements. We then characterize DNA immobilization and hybridization on these films by (32)P-radiometry. We find that the silane film structure controls the efficiency of the subsequent steps toward DNA hybridization. A self-limited silane monolayer produced from 3-aminopropyldimethylethoxysilane (APDMES) provides a silane surface density of ~3 nm(-2). Thin (1 h deposition) and thick (19 h deposition) multilayer films are generated from 3-aminopropyltriethoxysilane (APTES), resulting in surfaces with increased roughness compared to the APDMES monolayer. Increased silane surface density is estimated for the 19 h APTES film, due to a ∼32% increase in surface area compared to the APDMES monolayer. High cross-linker coupling efficiencies are measured for all three silane films. DNA immobilization densities are similar for the APDMES monolayer and 1 h APTES. However, the DNA immobilization density is double for the 19 h APTES, suggesting that increased surface area allows for a higher probe attachment. The APDMES monolayer has the lowest DNA target density and hybridization efficiency. This is attributed to the steric hindrance as the random packing limit is approached for DNA double helices (dsDNA, diameter ≥ 2 nm) on a plane. The heterogeneity and roughness of the APTES films reduce this steric hindrance and allow for tighter packing of DNA double helices, resulting in higher hybridization densities and efficiencies. The low steric hindrance of the thin, one to two layer APTES film provides the highest hybridization efficiency of nearly 88%, with 0.21 dsDNA/nm(2). The XPS data also reveal water on the cross-linker-treated surface that is implicated in device aging.

The amine density of 3-aminopropyldimethylethoxysilane (APDMES) films on silica is controlled to determine its effect on DNA probe density and subsequent DNA hybridization. The amine density is tailored by controlling the surface reaction time of (1) APDMES, or (2) n-propyldimethylchlorosilane (PDMCS, which is not amine terminated) and then reacting it with APDMES to form a mixed monolayer. High-resolution X-ray photoelectron spectroscopy (XPS) is used to quantify silane surface coverage of both pure and mixed monolayers on silica; the XPS data demonstrate control of amine density in both pure APDMES and PDMCS/APDMES mixed monolayers. A linear correlation between the atomic concentration of N atoms from the amine and Si atoms from the APDMES in pure APDMES films allows us to calculate the PDMCS/APDMES ratio in the mixed monolayers. Fluorescence from attached DNA probes and from hybridized DNA decreases as the percentage of APDMES in the mixed monolayer is decreased by dilution with PDMCS.

We present a method for grafting silanes onto low-temperature-plasma synthesized silicon quantum dots. The resulting solution of dots is characterized with Fourier transform infrared spectroscopy and transmission electron microscopy, and determined to be a colloidal suspension. The silane is attached at a single point on the quantum dot surface to avoid cross-linking and multilayer formation, and photoluminescence spectroscopy shows the colloidal suspension of dots is stable for over two months in air. The hydroxyl-terminated surfaces required for silanization are created by wet chemical etch, which can be used to tune the luminescence of the silicon dots in the green- to red-wavelength range. We find, however, that the wet etch cannot move the emission into the blue-wavelength range and discuss this observation in terms of the nature of etching process and origin of the emission. In addition, we discuss the photoluminescence quantum yield in the context of other passivation and synthetic techniques.

Semiconductor quantum dots (QDs) have been the subject of intense research interest due to novel experimentally observed properties, such as tunable bandgap, phonon bottleneck, and a variety of surface effects. The control of these properties makes quantum dots a candidate for revolutionizing a variety of fields, including photovoltaics. Because silicon is such a well characterized PV material in its bulk form, it would be a good choice for QD research for application in solar cells. In addition, there is recent theoretical evidence that its indirect gap may become more direct as size decreases, allowing for a fine-tuning of the absorption characteristics for photovoltaics.We present a method for grafting silanes onto lowtemperature-plasma synthesized silicon quantum dots. The resulting solution of dots is characterized with Fourier transform infrared spectroscopy and transmission electron microscopy, and determined to be a colloidal suspension. The silane is attached at a single point on the quantum dot surface to avoid cross-linking and multilayer formation, and photoluminescence spectroscopy shows the colloidal suspension of dots is stable for over two months in air. The hydroxyl-terminated surfaces required for silanization are created by wet chemical etch, which can be used to tune the luminescence of the silicon dots in the green-to redwavelength range.Unpassivated Si quantum dots show vastly different behaviors in electron paramagnetic resonance than wet-chemically oxidized, silane-functionalized particles. The dangling bond density of unpassivated Si quantum dots is large and changes over time, while the dangling bond density of the silanized dots is unchanged and undetectable. This suggests silanized dots will be better for solution-processed PV devices since transport will not be hindered by dangling bonds.Finally, we perform PL excitation (PLE) spectroscopy on both ensembles of dots, and discuss the way such spectra are represented in the literature, especially in comparison with absorption. This discussion is critical to the success of Si QDs in optoelectronic devices, since absorption and luminescence play critical roles.

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