화학공학소재연구정보센터
Journal of Physical Chemistry B, Vol.106, No.24, 6234-6247, 2002
Film growth of ice by vapor deposition at 128-185 K studied by Fourier transform infrared reflection-absorption spectroscopy: Evolution of the OH stretch and the dangling bond with film thickness
The polycrystalline and noncrystalline ice films vapor-deposited at 128-185 K were investigated by grazing-angle Fourier transform Infrared Reflection-Absorption Spectroscopy (RAS). In particular, the polycrystalline ice phase was found above 155 K, whereas the noncrystalline phase was formed below 145 K. The nature of the polycrystalline and noncrystalline ice phases can be differentiated by comparing the respective RA spectra with spectral simulations based on the Fresnel reflection and Mie scattering methods. Furthermore, the OH stretching band (3800-2800 cm(-1)) exhibits complex behavior as a function of film thickness (from less than 10 nm to 1500 nm), which can be simulated and attributed primarily to the physics of absorption-reflection based on the Fresnel equations for reflection coefficients for parallel-and perpendicular-polarized light in a vacuum-dielectric film-metal system. The spectral evolution of the OH stretch with the film thickness is found to be similar for both polycrystalline and noncrystalline phases. In addition, spectral features of the incompletely coordinated OH groups at 3700-3690 cm(-1) have been observed for a majority of noncrystalline and polycrystalline ice samples grown under different conditions (e.g., at 185 K), which shows that these OH dangling bonds are an integral part of the surfaces of both noncrystalline and polycrystalline ice phases. For thin films less than 200 nm thick, both kinds of ice are found to have a comparable amount of OH dangling bonds. In contrast, the thicker films (with thicknesses greater than 700 nm) of the noncrystalline phase contain a noticeably larger amount of CH dangling bonds than the polycrystalline films of comparable thickness. This thickness dependence of the OH dangling bond feature suggests that the OH dangling bonds are located most likely on the external surfaces of the crystalline grains and/or of the ice film itself at larger thicknesses for polycrystalline phase and on the tracery external surface in the case of noncrystalline phase.