The structure of perhydropolysilazane (PHPS)-derived silica (PDS) waterproof thin layers synthesized by curing at 60 °C for 1 h and allowed to stand for 48 h at 20 °C on various kinds of substrates was studied. Neutron reflectivity (NR) analysis suggested that uniform PDS thin layers were synthesized on the substrates, and the density of the layers varied depending on the type of substrate. Additionally, since the change in PDS density is correlated with the pK_a value of the OH group on the substrate, it can be suggested that the acidity of the substrate would be one of the main factors determining the density of the coated PDS thin layers. For the water penetration structure study, NR analysis revealed that the depth of water penetration into the PDS layers was below 500 Å, and the hydration number of the SiO₂ molecule was estimated to be 8.0–9.0. From these results, we concluded that water penetration occurred by the formation of water-pool structures in the PDS layers, and the randomly formed nano-air holes lead to a reduction in the probability of water penetration into the deep regions of the PDS layers.

A large background scattering originating from the sample matrix is a major obstacle for fine-structure analysis of a nanometric layer buried in a bulk material. As polarization analysis can decrease undesired scattering in a neutron reflectivity (NR) profile, we performed NR experiments with polarization analysis on a polypropylene (PP)/perhydropolysilazane-derived SiO₂ (PDS)/Si substrate sample, having a deep-buried layer of SiO₂ to elucidate the fine structure of the nano-PDS layer. This method offers unique possibilities for increasing the amplitude of the Kiessig fringes in the higher scattering vector (Q_z) region of the NR profiles in the sample by decreasing the undesired background scattering. Fitting and Fourier transform analysis results of the NR data indicated that the synthesized PDS layer remained between the PP plate and Si substrate with a thickness of approximately 109 Å. Furthermore, the scattering length density of the PDS layer, obtained from the background subtracted data appeared to be more accurate than that obtained from the raw data. Although the density of the PDS layer was lower than that of natural SiO₂, the PDS thin layer had adequate mechanical strength to maintain a uniform PDS layer in the depth-direction under the deep-buried condition.

We found a “buffer layer” between the tightly bound layer (which does not swell) and bulk-like swollen layer by means of neutron reflectometry, which was manifested by the sorption of toluene with different scattering length density contrasts.