The orientation of functional groups, side chains, and repeat units at the surface of a liquid crystal (LC) alignment layer (AL) polyimide was changed by rubbing with a cotton velvet cloth. It was discovered that rubbing induced polar functional groups and repeat units to reorient out-of-the-plane of the surface, and it made nonpolar aliphatic side chains partially reorient inward, toward the bulk of the film. The polar AL surface provided relatively small LC pretilt angles while polyimides with long alkyl side chains gave relatively large LC pretilt angles. The results suggest that LC pretilt angles are greatly affected by both electronic interaction and steric repulsion between LC molecules and an alignment layer polyimide surface.

A mechanistic picture of the effects of rubbing on polyimide alignment layer (AL) surfaces and nematic liquid crystal (LC) pretilt angles (ΘP), leading to establishing a mechanism of determination of ΘP’s, was proposed on the basis of the study of the change in surface polarity of a polyimide AL with the rubbing force and density, and the subsequent changes in the ΘP and the azimuthal anchoring energy. In the regime of relatively weak rubbing where inhomogeneous, patchy surface modification (the microscopic reorientation of polymer functional groups and the orientation of polymer backbones) occurs, the surface polarity, the anchoring energy, and the ΘP all increase monotonically with rubbing strength. These increases correlate to an increase in the area fraction of the reoriented/oriented AL surface which generates in-plane orientation of the first LC monolayer at the surface and subsequently bulk alignment. Beyond this region in which the AL surface gets modified sufficiently to induce fully developed in-plane orientation of the LC monolayer, the surface chemistry and roughness have dominant effects on the ΘP and the anchoring energy. The increase in surface polarity and the generation of a larger reoriented surface area by high-force rubbing, which enhances the attractive interaction between the LC monolayer and the rubbed surface, contribute to increases in both the anchoring energy and the thermal stability of ΘP and to a decrease of ΘP. This decrease of ΘP with increasing AL surface polarity was verified by studying the relationship between ΘP and surface polarity under constant rubbing conditions by manipulating the surface polarity via the degree of imidization of a poly(amic acid) AL.

The pretilt angle (Θ p) of nematic liquid crystals (LCs) could be controlled with alignment layer (AL) polyimides (PIs) and/or LCD processes in the case that a cell gap and a rubbing condition are fixed. Θ p was increased by introducing long, linear alkyl side chains and/or other nonpolar groups to the AL polyimide. On the other hand, Θ p was decreased by modifying the polyimide surfaces (with UV exposure or O2 plasma) and LCD processes such as heating or cleaning the rubbed polyimide and annealing the LC-filled cell. Thus, the AL polyimide and the LCD process can be designed so as to obtain a desired pretilt angle, which is important in applications. In the UV-type two-domain twisted nematic approach for wide-viewing angle LCDs, two different Θ ps were obtained in one pixel and a mechanism for modifying the Θ p was discovered. Upon UV-exposing the PI films, aromatic or conjugated radicals with long lifetimes (greater than 2 weeks) were generated and some side chains were removed, and these PI surfaces subsequently became more polar since polar functional groups such as OH were introduced. The Θ p of ZLI-5080 on the UV-exposed/rubbed PI film decreased by 4.5°–8.8° in comparison with that on the rubbed film probably because the lower steric repulsion and greater electronic attraction would decrease the Θ p.

Four different structure polyimide thin films based on 1,4-phenylene diamine (PDA) and 4,4 0 -oxydianiline (ODA) were synthesized by using two different dianhydrides, pyromellitic dianhydride (PMDA) and 3,3 0 ,4,4 0 -biphenyltetracarboxylic dianhydride (BPDA), and their residual stress behavior and mechanical properties were investigated by using a thin film stress analyzer and nanoindentation method. The residual stress behavior and mechanical properties were correlated to the morphological structure in polyimide films. The morphological structure of polyimide thin films was characterized by X-ray diffraction patterns and refractive indices. The residual stress was in the range of À5 to 38 MPa and increased in the following order: PMDA-PDA < BPDA-PDA < PMDA-ODA < BPDA-ODA. The hardness of the polyimide films increased in the following order: PMDA-ODA < BPDA-ODA < PMDA-PDA < BPDA-PDA. The PDA-based polyimide films showed relatively lower residual stress and higher hardness than the corresponding ODA-based polyimide films. The in-plane orientation and molecularly ordered phase were enhanced with the increasing order as follows: PMDA-ODA < BPDA-ODA < BPDA-PDA $ PMDA-PDA. The PDA-based polyimides, having a rigid structure, showed relatively better-developed morphological structure than the corresponding ODA-based polyimides. The residual stress behavior and mechanical properties were correlated to the morphological structure in polyimide films.