Study of the conformational structure and cluster formation in a Langmuir-Blodgett film using second harmonic generation, second harmonic microscopy, and FTIR spectroscopy


M. S. Johal, A. N. Parikh, Y. Lee, J. L. Casson, L. Foster, B. I. Swanson, D. W. McBranch, D. Q. Li, J. M. Robinson, , Langmuir 15, 1275 (1999)

Nonlinear second harmonic generation (SHG), second harmonic microscopy (SHM), and infrared spectroscopy are used to determine the structural and optical properties of the Langmuir−Blodgett (LB) monolayer assemblies of NLO-active, 4-eicosyloxo-(E)-stilbazolium iodide (4-EOSI) on a glass substrate. The packing characteristics of the pretransferred interfacial films are determined using π−A isotherm measurements. The molecular coverage of the transferred films is determined by ellipsometry. The films formed on both sides of the glass substrate show substantial second harmonic (SH) conversion from p-polarized 1064 nm fundamental excitation. The SHG and FTIR measurements imply that the single LB layer on glass is composed of oriented clusters of 4-EOSI molecules that are laterally discontinuous. Ordered clusters up to 40 μm in diameter are directly observed using SHM. Subsequent LB transfers using the same 4-EOSI molecule or an amphiphile of comparable chain-length (eicosanoic acid) fill in the unoccupied vacancies in the first layer. The magnitude of the dominant element of the nonlinear susceptibility and the average molecular orientation angle of the chromophore are determined by modeling the characteristic SHG Maker fringes.