Synthesis and Characterization of Mixed Methyl/Allyl Monolayers on Si(111)

The formation of mixed methyl/allyl monolayers has been accomplished through a two-step halogenation/alkylation reaction on Si(111) surfaces. The total coverage of alkylated Si, the surface recombination velocities, and the degree of surface oxidation as a function of time have been investigated using X-ray photoelectron spectroscopy, Fourier-transform infrared spectroscopy, and microwave conductivity measurements. The total coverage of alkyl groups, the rate of oxidation, and the surface recombination velocities of Si(111) terminated by mixed monolayers were found to be close to those observed for CH_3−Si(111) surfaces. Hence, the mixed-monolayer surfaces retained the beneficial properties of CH_3−Si(111) surfaces while allowing for convenient secondary surface functionalization

Repeated epitaxial growth and transfer of arrays of patterned, vertically aligned, crystalline Si wires from a single Si(111) substrate

Multiple arrays of Si wires were sequentially grown and transferred into a flexible polymer film from a single Si(111) wafer. After growth from a patterned, oxide-coated substrate, the wires were embedded in a polymer and then mechanically separated from the substrate, preserving the array structure in the film. The wire stubs that remained were selectively etched from the Si(111) surface to regenerate the patterned substrate. Then the growth catalyst was electrodeposited into the holes in the patterned oxide. Cycling through this set of steps allowed regrowth and polymer film transfer of several wire arrays from a single Si wafer

Passivation and Secondary Functionalization of Allyl-Terminated Si(111) Surfaces

Synthesis of passivated silicon surfaces with tunable properties requires formation of a monolayer that includes a synthetically useful functional group, such as an alkene. Thus, Si(111) surfaces have been chemically and electrically passivated by attachment of an allyl monolayer. The structure of the monolayer was confirmed using infrared spectroscopy. The allyl-functionalized surface exhibited resistance to oxidation and had a low density of surface trap states. Metal-catalyzed reactions, in particular, Heck coupling and ruthenium-catalyzed olefin cross-metathesis, allowed attachment of small molecules despite the steric constraints of the dense surface-bound layer. Allyl-terminated silicon surfaces thus offer a means of attaching a variety of chemical moieties to a silicon surface through a short linking group, enabling applications in energy conversion, catalysis, and sensing

Electrical Junction Behavior of Poly(3,4-ethylenedioxythiophene) (PEDOT) Contacts to H‑Terminated and CH_3‑Terminated p‑, n‑, and n^+‑Si(111) Surfaces

The electronic and photovoltaic properties of junctions between the conducting polymer poly(3,4-ethylenedioxythiophene) (PEDOT) and Si(111) surfaces have been investigated for a range of doping types, doping levels, and surface functionalization of the Si. PEDOT–poly(styrenesulfonate) (PSS) formed ohmic, low resistance contacts to H-terminated and CH_3-terminated p-type Si(111) surfaces. In contrast, PEDOT formed high barrier height (0.8–1.0 V) contacts to n-Si(111) surfaces, with CH_3-terminated n-Si(111)/PEDOT contacts showing slightly higher barrier heights (1.01 eV) than H-terminated n-Si(111)/PEDOT contacts (0.89 V). PEDOT contacts to CH_3-terminated and H-terminated n-Si(111) surfaces both produced photovoltages under illumination in accord with the Shockley diode limit based on bulk/recombination diffusion in the semiconductor. Such devices produced solar energy-conversion efficiencies of 5.7% under 100 mW cm^(–2) of simulated air mass 1.5 illumination. The electrical properties of PEDOT contacts to CH_3-terminated Si surfaces were significantly more stable in an air ambient than the electrical properties of PEDOT contacts to H-terminated Si surfaces. PEDOT films produced a low resistance, tunnel-barrier type of ohmic contact to n^+-Si(111) surfaces. Hence, through various combinations of doping type, doping level, and surface functionalization, the PEDOT/Si contact system offers a wide range of opportunities for integration into monolithic photovoltaic and/or artificial photosynthetic systems

Effect of the Presence of Iodide on the Electron Injection Dynamics of Dye-Sensitized TiO_2-Based Solar Cells

The electron injection dynamics of dye-sensitized TiO_2-based solar cells have been investigated to determine the effects of replacing the I_3^−/I^− redox system by non-redox-active supporting electrolytes. TiO-2 films were sensitized with Ru(dcbpy)_2(NCS)_2, where dcbpy = 4,4′-dicarboxylic acid-2,2′-bipyridine (the “N3” dye), and placed in contact with either M(ClO_4) or M(I_3−/I−) solutions (M = Li^+ or (n-C_4H_9)_4N^+); cells that contained I_3−/I− were fully functional solar cells whose steady-state photocurrents were directly measured. In (n-C_4H_9)_4N^+-containing solutions, significant differences were observed between the measured kinetics when ClO_4^− was replaced by the redox-active I3^−/I^− system. In particular, a ps time scale loss of the metal-to-ligand charge-transfer excited-state of the N3 dye, associated with electron injection, that was observed in cells containing either LiClO_4 or [(n-C_4H_9)4N]ClO_4 was absent in fully functional solar cells that contained [(n-C_4H_9)_4N]I/I_2. These results underscore the importance of performing kinetics measurements on this class of solar cells under operational conditions if one is to obtain reliable correlations between the dynamics data and the steady-state performance metrics of the solar cell devices

Tunable Chiral Second-Order Nonlinear Optical Chromophores Based on Helquat Dications

Fourteen new dipolar cations have been synthesized, containing methoxy or tertiary amino electron donor groups attached to helquat (Hq) acceptors. These Hq derivatives have been characterized as their TfO^– salts by using various techniques including NMR and electronic absorption spectroscopies. UV–vis spectra show intense, relatively low energy absorptions with λ_(max) ≈ 400–600 nm, attributable to intramolecular charge-transfer (ICT) excitations. Single-crystal X-ray structures have been solved for two of the chromophores, one as its PF_6^– salt, revealing centrosymmetric packing arrangements (space groups Pbca and P1̅). Molecular quadratic nonlinear optical (NLO) responses have been determined directly by using hyper-Rayleigh scattering (HRS) with a 800 nm laser, and indirectly via Stark (electroabsorption) spectroscopy for the low energy absorption bands. The obtained static first hyperpolarizabilities β_0 range from moderate to large: (9–140) × 10^(–30) esu from HRS in MeCN and (44–580) × 10^(–30) esu from the Stark data in PrCN. The magnitude of β_0 increases upon either extending the π-conjugation length or replacing a methoxy with a tertiary amino electron donor substituent. Density functional theory (DFT) and time-dependent DFT calculations on selected tertiary amino chromophores confirm that the low energy absorptions have ICT character. Relatively good agreement between the simulated and experimental UV–vis absorption spectra is achieved by using the CAM-B3LYP functional with the 6-311G(d) basis set. The β_(tot) values predicted by using DFT at the same level of theory are large ((472–1443) × 10^(–30) esu in MeCN). Both the theoretical and experimental results show that para-conjugation between Hq and electron donor fragments is optimal, and enlarging the Hq unit is inconsequential with respect to the molecular quadratic NLO response

Heck Coupling of Olefins to Mixed Methyl/Thienyl Monolayers on Si(111) Surfaces

The Heck reaction has been used to couple olefins to a Si(111) surface that was functionalized with a mixed monolayer comprised of methyl and thienyl groups. The coupling method maintained a conjugated linkage between the surface and the olefinic surface functionality, to allow for facile charge transfer from the silicon surface. While a Si(111) surface terminated only with thienyl groups displayed a surface recombination velocity, S, of 670 ± 190 cm s^(–1), the mixed CH_3/SC_4H_3–Si(111) surfaces with a coverage of θ_(SC_4H_3) = 0.15 ± 0.02 displayed a substantially lower value of S = 27 ± 9 cm s^(–1). Accordingly, CH_3/SC_4H_3–Si(111) surfaces were brominated with N-bromosuccinimide, to produce mixed CH_3/SC_4H_2Br–Si(111) surfaces with coverages of θ_(Br–Si) < 0.05. The resulting aryl halide surfaces were activated using [Pd(PPh_3)_4] as a catalyst. After activation, Pd(II) was selectively coordinated by oxidative addition to the surface-bound aryl halide. The olefinic substrates 4-fluorostyrene, vinylferrocene, and protoporphyrin IX dimethyl ester were then coupled (in dimethylformamide at 100 °C) to the Pd-containing functionalized Si surfaces. The porphyrin-modified surface was then metalated with Co, Cu, or Zn. The vinylferrocene-modified Si(111) surface showed a linear dependence of the peak current on scan rate in cyclic voltammetry, indicating that facile electron transfer had been maintained and providing evidence of a robust linkage between the Si surface and the tethered ferrocene. The final Heck-coupled surface exhibited S = 70 cm s^(–1), indicating that high-quality surfaces could be produced by this multistep synthetic approach for tethering small molecules to silicon photoelectrodes

Use of Mixed CH_3−/HC(O)CH_2CH_2−Si(111) Functionality to Control Interfacial Chemical and Electronic Properties During the Atomic-Layer Deposition of Ultrathin Oxides on Si(111)

Silicon surfaces terminated with a mixed monolayer containing both a propyl aldehyde functionality and methyl groups were prepared and used to control the interfacial chemical and electronic properties of Si(111) surfaces during atomiclayer deposition (ALD) of Al_2O_3 or MnO. Si(111) surfaces functionalized only with the aldehyde moiety exhibited surface recombination velocities, S, of 2500 ± 600 cm s^(−1) whereas the mixed CH_3−/HC(O)CH_2CH_2−Si(111) surfaces displayed S = 25 ± 7 cm s^(−1). During the ALD growth of either Al_2O_3 or MnO, both the HC(O)CH_2CH_2−Si(111) and CH_3−/HC(O)CH_2CH_2−Si(111) surfaces produced increased metal oxide deposition at low cycle number, relative to H−Si(111) or CH_3−Si(111) surfaces. As detected by X-ray photoelectron spectroscopy after the ALD process, the CH_3− and mixed CH_3−/HC(O)CH_2CH_2− functionalized Si(111) surfaces exhibited less interfacial SiO_x than was observed for ALD of metal oxides on H−Si(111) substrates

Comparison of the Photoelectrochemical Behavior of H‑Terminated and Methyl-Terminated Si(111) Surfaces in Contact with a Series of One-Electron, Outer-Sphere Redox Couples in CH_3CN

The photoelectrochemical behavior of methyl-terminated p-type and n-type Si(111) surfaces was determined in contact with a series of one-electron, outer-sphere, redox couples that span >1 V in the Nernstian redox potential, E(A/A^−), of the solution. The dependence of the current vs potential data, as well as of the open-circuit photovoltage, V_(OC), on E(A/A^−) was compared to the behavior of H-terminated p-type and n-type Si(111) surfaces in contact with these same electrolytes. For a particular E(A/A^−) value, CH_3-terminated p-Si(111) electrodes showed lower V_(OC) values than Hterminated p-Si(111) electrodes, whereas CH_3-terminated n-Si(111) electrodes showed higher V_(OC) values than H-terminated n-Si(111) electrodes. Under 100 mW cm^(−2) of ELH-simulated Air Mass 1.5 illumination, n-type H−Si(111) and CH_3−Si(111) electrodes both demonstrated nonrectifying behavior with no photovoltage at very negative values of E(A/A^−) and produced limiting V_(OC) values of >0.5 V at very positive values of E(A/A^−). Illuminated p-type H−Si(111) and CH_3−Si(111) electrodes produced no photovoltage at positive values of E(A/A^−) and produced limiting V_(OC) values in excess of 0.5 V at very negative values of E(A/A^−). In contact with CH_3CN-octamethylferrocene^(+/0), differential capacitance vs potential experiments yielded a −0.40 V shift in flat-band potential for CH_3-terminated n-Si(111) surfaces relative to H-terminated n-Si(111) surfaces. Similarly, in contact with CH_3CN-1,1′-dicarbomethoxycobaltocene^(+/0), the differential capacitance vs potential data indicated a −0.25 V shift in the flat-band potential for CH_3-terminated p-Si(111) electrodes relative to H-terminated p-Si(111) electrodes. The observed trends in V_(OC) vs E(A/A^−), and the trends in the differential capacitance vs potential data are consistent with a negative shift in the interfacial dipole as a result of methylation of the Si(111) surface. The negative dipole shift is consistent with a body of theoretical and experimental comparisons of the behavior of CH_3−Si(111) surfaces vs H−Si(111) surfaces, including density functional theory of the sign and magnitude of the surface dipole, photoemission spectroscopy in ultrahigh vacuum, the electrical behavior of Hg/Si contacts, and the pH dependence of the current−potential behavior of Si electrodes in contact with aqueous electrolytes

Diquat Derivatives: Highly Active, Two-Dimensional Nonlinear Optical Chromophores with Potential Redox Switchability

In this article, we present a detailed study of structure−activity relationships in diquaternized 2,2′-bipyridyl (diquat) derivatives. Sixteen new chromophores have been synthesized, with variations in the amino electron donor substituents, π-conjugated bridge, and alkyl diquaternizing unit. Our aim is to combine very large, two-dimensional (2D) quadratic nonlinear optical (NLO) responses with reversible redox chemistry. The chromophores have been characterized as their PF_6^− salts by using various techniques including electronic absorption spectroscopy and cyclic voltammetry. Their visible absorption spectra are dominated by intense π → π^* intramolecular charge-transfer (ICT) bands, and all show two reversible diquat-based reductions. First hyperpolarizabilities β have been measured by using hyper-Rayleigh scattering with an 800 nm laser, and Stark spectroscopy of the ICT bands affords estimated static first hyperpolarizabilities β_0. The directly and indirectly derived β values are large and increase with the extent of π-conjugation and electron donor strength. Extending the quaternizing alkyl linkage always increases the ICT energy and decreases the E_(1/2) values for diquat reduction, but a compensating increase in the ICT intensity prevents significant decreases in Stark-based β_0 responses. Nine single-crystal X-ray structures have also been obtained. Time-dependent density functional theory clarifies the molecular electronic/optical properties, and finite field calculations agree with polarized HRS data in that the NLO responses of the disubstituted species are dominated by ‘off-diagonal’ β_(zyy) components. The most significant findings of these studies are: (i) β_0 values as much as 6 times that of the chromophore in the technologically important material (E)-4′-(dimethylamino)-N-methyl-4-stilbazolium tosylate; (ii) reversible electrochemistry that offers potential for redox-switching of optical properties over multiple states; (iii) strongly 2D NLO responses that may be exploited for novel practical applications; (iv) a new polar material, suitable for bulk NLO behavior