Optical effects in Langmuir-Blodgett films of novel organic materials.

The high level of molecular control makes the Langmuir-Blodgett (LB) technique an appealing method of film deposition. The uniform nature of the films produced allows convenient investigation of intermolecular interactions and provides information pertaining to the orientation of molecules within films. LB films of two amphiphilic materials with contrasting molecular structures have been deposited. AmPc5 (a metal-free phthalocyanine (pc)) is a two-dimensional, cyclic molecule, whereas AmAzl (a resorcinol calixarene) possesses a three-dimensional basket-type structure. The amphiphilic nature of both molecules is as a result of functional side-chains.The AmPc5 spreading solution was prepared by dissolving in trichloroethane to a concentration of 0.1 mg/ml. After spreading 500-600 ul, the resulting Langmuir film was found to have a critical pressure of 28 mN/m and an area per molecule of 1.61 nm2 on the water surface. Monolayer deposition onto glass substrates enabled spectroscopic examination of the films and comparison to solution spectra. The solution spectrum shows the split Q-band absorption peaks at 700 nm and 733 nm characteristic of metal-free pc's. The LB film spectrum shows a broadening of both peaks and a red shift of the 733 nm peak, and a blue shift of the 700 nm peak. The 700 nm peak is suppressed as a result of the stack-like packing structure of AmPc5. Absorption spectra of floating AmPc5 monolayers imply that the material does not assume the monomer state at any stage of compression. This is characteristic of rigid molecules that induce order within the floating monolayer.The refractive indices (n) and extinction coefficients (k) were determined across the visible wavelength range. Both the n and k values are shown to increase with monolayer thickness, although the n value tends towards a steady value of 2.1. Deposition onto gold coated glass substrates enabled surface plasmon resonance analysis and determination of n and k at specific film thickness'. The n was found to increase with film thickness, tending towards a steady state value of 2.0. This is in excellent agreement with spectroscopic analysis.Absorption spectra measured using polarised light show AmPc5 exhibits dichroism. The calculations indicate that the pc ring lies almost perpendicular to the substrate.AmAzl was dissolved in chloroform to a concentration of 0.5 mg/ml with 10% ethanol to aid solubility. The optimum solution spreading quantity required to form a floating monolayer was found to be between 50 and 100 ul. The film was shown to have a critical pressure of 30 mN/m and an area per molecule of 1.86 nm2 on the water surface. Both LB film and solution spectra show a single absorbance peak at 454 nm which is due to transitions in the azo functional side chains.Calculation of n and k shows that they tend towards steady values of 1.5 and 2.0, respectively. The n obtained via surface plasmon resonance analysis shows a steady state value of 1.43 on silver coated glass and 1.35 on gold coated glass. This suggests a different type of packing structure on all three substrates. The lack of dichroism exhibited by AmAzl indicates the formation of in-plane amorphous films.AmAzl was deposited in alternating layers with tricosenoic acid. The structure was confirmed by X-ray diffraction studies and investigated using second harmonic generation. The second harmonic signal was shown to be proportional to the square of the number of bilayers.