The Role of Adhesion Promoters on the Molecular and Mesoscopic Structure of the Interphase

Abstract

New experimental results are described from Near Edge X-Ray Absorption Fine Structure (NEXAFS) spectroscopy, X-ray photoelectron spectroscopy (XPS) and Atomic Force Microscopy (AFM) on the molecular orientation, chemical composition, and topography of PMDA/ODA Polyimide (PI) deposited by the Langmuir-Blodgett (LB) technique onto Si (100) surfaces covered with a native oxide (SiO _x ) and onto SiO _x substrates pre-treated with a variety of alkylsilanes. The alkylsilane monolayers used as adhesion promoters were found to be chemically and structurally stable during temperature treatments used to imidize the polymer precursor films. On both the oxidized silicon surface and on the silane-treated surfaces, we find a thickness-dependent, preferential orientation of the pyromellitimide unit in PI, but randomly-oriented oxydianiline fragments. We can not identify any specific chemical bonds between the polymer and the aminosilane film or, in the case of the untreated surface, the SiO _x substrate. However, a quantitative analysis of the NEXAFS data reveals a pronounced deficit in oxydianiline in the monolayer (ML) films, which decreases with film thickness, and a higher degree of imidization on the 3-aminopropyltrimethoxysilane (APS) surface indicating that imide linkages are formed between the polymer and the aminosilane. The AFM images show a heterogeneous surface topography with nucleation of PI polycondensates on both the SiO _x and aminosilane-treated surfaces. On the aminosilane surface additional nuclei are detected, believed to be polycondensates of aminosilane formed during imidization of the PI precursor. Nucleation of aminosilane polycondensates is not observed in the absence of polyamic acid. As suggested by a comparison of Lateral Force Microscopy (LFM) and Atomic Force Microscopy measurements, these aminosilane nuclei are covered by PI with increasing film thickness and, hence, provide mechanical connections between the polymer and substrate on a mesoscopic scale. Delamination experiments of 2 μm thick PI films spun onto ω-amino and methyl terminated alkylsilanes indicate that bond fracture always occurs in the aminosilane/PI and alkylsilane/PI and interphase. We conclude that the adhesion promotion effect of LB-deposited polyimide films by aminosilanes can be explained by chemical stabilization of the interface against decomposition and mechanical interlinking surface via polycondensates of aminosilane on a mesoscopic length scale. Our study is not conclusive as to whether covalent bonding of the polymer to the substrate via the silane is important for macroscopic adhesion.

Key Words:

• Adhesion promoters
• AFM
• aminosilanes
• interphase
• NEXAFS
• polyimide
• silanes
• XPS