A Molecular Architectural Approach to Self-Assembled Monolayers as NLO Materials

ABSTRACTSelf-assembled molecular architechtures of nonlinear optical (NLO) chromophores and their super-chromophores are discussed. The chromophores are derivatives of azobenzene sulfonates and the super chromophores are derivatives of calix[4]stilbazole and calix[4]stilbazolium. The studies of azobenzene sulfonates are aimed at understanding the surface coverage and molecular orientation in polar self-assembled monolayers (SAMs). The optimized molecular orientation was found to be 32±3 degree and the maximum surface coverage is approximately 2–4 molecules per nm2 depending on the molecular cross-section. The calixarene chromophores are macrocyclic compounds consisting of four simple D-π-A units bridged by methylene groups. These molecules were synthesized such that four D-π-A units of the calix[4]arene were aligned along the same direction with the calixarene in a cone conformation. Both simple and super-chromophores were subsequently fabricated into covalently bound selfassembled monolayers on the surfaces of fused silica and silicon. Spectroscopic second harmonic generation (SHG) measurements were carried out to determine the absolute value of the dominant element of the second-order nonlinear susceptibility, d33 = 60 pm/V at a fundamental wavelength of 890 nm. Furthermore, SHG imaging was employed to investigate the pattemed SAMs of NLO super chromophores.