Reversible Photoswitching of the Interfacial Nonlinear Optical Response.

Incorporating photochromic molecules into organic/inorganic hybrid materials may lead to photoresponsive systems. In such systems, the second-order nonlinear properties can be controlled via external stimulation with light at an appropriate wavelength. By creating photochromic molecular switches containing self-assembled monolayers on Si(111), we can demonstrate efficient reversible switching, which is accompanied by a pronounced modulation of the nonlinear optical (NLO) response of the system. The concept of utilizing functionalized photoswitchable Si surfaces could be a way for the generation of two-dimensional NLO switching materials, which are promising for applications in photonic and optoelectronic devices.

Formation of carboxy- and amide-terminated alkyl monolayers on Silicon(111) investigated by ATR-FTIR, XPS, and X-ray scattering: construction of photoswitchable surfaces.

We have prepared high-quality, densely packed, self-assembled monolayers (SAMs) of carboxy-terminated alkyl chains on Si(111). The samples were made by thermal grafting of methyl undec-10-enoate under an inert atmosphere and subsequent cleavage of the ester functionality to disclose the carboxylic acid end-group. X-ray photoelectron spectroscopy (XPS) and grazing incidence X-ray diffraction (GIXD) indicate a surface coverage of about 50% of the initially H-terminated sites. In agreement, GIXD implies a rectangular unit mesh of 6.65 and 7.68 Å side lengths, containing two molecules in a regular zigzag-like substitution pattern for the ester- and carboxy-terminated monolayer. Hydrolysis of the remaining H-Si(111) bonds at the surface furnished HO-Si(111) groups according to XPS and attenuated total reflection Fourier-transform infrared spectroscopy (ATR-FTIR) studies. The amide-terminated alkyl SAM on Si(111) assembled in a 2-(6-chloro-1H-benzotriazol-1-yl)-1,1,3,3-tetramethyluronium hexafluorophosphate (HCTU)-mediated one-pot coupling reaction under an inert atmosphere, whereby the active ester forms in situ prior to the reaction with an amino-functionalized photoswitchable fulgimide. ATR-FTIR and XPS studies of the fulgimide samples revealed closely covered amide-terminated SAMs. Reversible photoswitching of the headgroup was read out by applying XPS, ATR-FTIR, and difference absorption spectra in the mid-IR. In XPS, we observed a reversible breathing of the amide/imide C1s and N1s signals of the fulgimide. The results demonstrate the general suitability of HCTU as a reagent for amide couplings to carboxy-terminated alkyl SAMs and the on-chip functionalization toward photoswitchable Si(111) surfaces.