Self-assembled monolayers of phosphonates (SAMPs) of 11-hydroxyundecylphosphonic acid, 2,6-diphosphonoanthracene, 9,10-diphenyl-2,6-diphosphonoanthracene, and 10,10'-diphosphono-9,9'-bianthracene and a novel self-assembled organophosphonate duplex ensemble were synthesized on nanometer-thick SiO(2)-coated, highly doped silicon electrodes. The duplex ensemble was synthesized by first treating the SAMP prepared from an aromatic diphosphonic acid to form a titanium complex-terminated one; this was followed by addition of a second equivalent of the aromatic diphosphonic acid. SAMP homogeneity, roughness, and thickness were evaluated by AFM; SAMP film thickness and the structural contributions of each unit in the duplex were measured by X-ray reflection (XRR). The duplex was compared with the aliphatic and aromatic monolayer SAMPs to determine the effect of stacking on electrochemical properties; these were measured by impedance spectroscopy using aqueous electrolytes in the frequency range 20 Hz to 100 kHz, and data were analyzed using resistance-capacitance network based equivalent circuits. For the 11-hydroxyundecylphosphonate SAMP, C(SAMP) = 2.6 ± 0.2 μF/cm(2), consistent with its measured layer thickness (ca. 1.1 nm). For the anthracene-based SAMPs, C(SAMP) = 6-10 μF/cm(2), which is attributed primarily to a higher effective dielectric constant for the aromatic moieties (ε = 5-10) compared to the aliphatic one; impedance spectroscopy measured the additional capacitance of the second aromatic monolayer in the duplex (2ndSAMP) to be C(Ti/2ndSAMP) = 6.8 ± 0.7 μF/cm(2), in series with the first.

We report electrical transport measurements made on alkylphosphonate self-assembled monolayers grown on nanometer-thin SiO2 on top of highly p-doped silicon. At small bias direct tunneling is characterized by a decay constant of β ≈ 0.7/carbon. At larger positive bias to the silicon (1.1–1.5 V) the current-voltage traces feature a prominent shoulder, reminiscent of a negative differential resistance. We attribute this feature to a significant reduction in trap-assisted tunneling, as supported by a simulation. Hence, organophosphonate monolayers are excellent model systems to study electrical transport through ordered structures; they also provide highly efficient electrical passivation of the SiO2/Si surface.

Monolayers of alkyl bisphosphonic acids (bisPAs) of various carbon chain lengths (C4, C8, C10, C12) were grown on aluminum oxide (AlO(x)) surfaces from solution. The structural and electrical properties of these self-assembled monolayers (SAMs) were compared with those of alkyl monophosphonic acids (monoPAs). Through contact angle (CA) and Kelvin-probe (KP) measurements, ellipsometry, and infrared (IR) and x-ray photoelectron (XPS) spectroscopies, it was found that bisPAs form monolayers that are relatively disordered compared to their monoPA analogs. Current-voltage (J-V) measurements made with a hanging Hg drop top contact show tunneling to be the prevailing transport mechanism. However, while the monoPAs have an observed decay constant within the typical range for dense monolayers, β(mono)  =  0.85  ±  0.03 per carbon atom, a surprisingly high value, β(bis) =  1.40  ±  0.05 per carbon atom, was measured for the bisPAs. We attribute this to a strong contribution of 'through-space' tunneling, which derives from conformational disorder in the monolayer due to strong interactions of the distal phosphonic acid groups; they likely form a hydrogen-bonding network that largely determines the molecular layer structure. Since bisPA SAMs attenuate tunnel currents more effectively than do the corresponding monoPA SAMs, they may find future application as gate dielectric modification in organic thin film devices.

We report the impact of geometrical constraint on intramolecular interactions in self-assembled monolayers (SAMs) of alkylphosphonates grown on anodically oxidized aluminum (AAO). Molecular order in these films was determined by sum frequency generation (SFG) spectroscopy, a more sensitive measure of order than infrared absorption spectroscopy. Using SFG we show that films grown on AAO are, within detection limits, nearly perfectly ordered in an all-trans alkyl chain configuration. In marked contrast, films formed on planar, plasma-oxidized aluminum oxide or α-AlO (0001) are replete with gauche defects. We attribute these differences to the nanocylindrical structure of AAO, which enforces molecular confinement.

The successful transfer printing of thin metal films onto monolayers of aliphatic bisphosphonic acids (bisPAs) is reported. These monolayers were prepared from solution on plasma-grown aluminum oxide, and were compared with analogous monolayers of alkyl monophosphonic acids (monoPAs) for transfer printing efficacy. Water contact angle and AFM measurements indicated uniform films formed from both classes of phosphonic acids. Evaporated Au/Ti films were prepared using patterned polymeric stamps, and were transfer printed onto the various phosphonate monolayers; this process resulted in close to 100% yield for bisPA monolayers, but only poor results were measured for the monoPAs. We attribute efficient printing onto bisPA monolayers to the formation of strong chemical bonds between distal phosphonic acid groups and the stamp-adhered metal film via its native Ti-oxide termination.

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