All-nanoparticle multilayer films found novel applications in the areas of photonics, catalysis, sensors, and biomaterials. The assembly of nanoparticles into conformal and uniform films with precise control over chemical and physical properties poses a significant challenge. Using time-of-flight secondary ion mass spectrometry (ToF-SIMS), we have investigated the growth behavior in all-nanoparticle multilayer films using a novel indicator layer. The all-nanoparticle multilayer films were prepared by dipping the polyester substrate with electrostatic charges alternatively into solutions containing three different types of nanoparticles (TiO2, Al2O3, and SiO2). Upon the deposition of each layer, ToF-SIMS was employed to determine the surface chemical composition of intermediate products. The intermixing extent of TiO2 indicator layer was used to reveal the stratification of each layer. Combining with zeta-potential measurements, the solvation and deposition of the under-layer species in the aqueous environment during fresh layer formation was proposed as a plausible cause for mutilayers not stratified into well-defined layers but displaying a nonlinear growth behavior. (C) 2008 Elsevier B. V. All rights reserved.