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Degradation-induced changes in the structural and optical properties of the polyfluorene-based blue emitting films and LEDs are examined using spectroscopic (FTIR, UV−vis, photo- and electroluminescence), analytical (FTIR and ESCA), and scanning probe microscopy techniques. The materials studied are oligomers (DP ~ 10) of 9,9-di-n-hexylfluorene and its random copolymer with anthracene. In situ FTIR monitoring is used to characterize chemical changes in the active layer of operating LED devices. Two primary mechanisms of degradation are identified. In the first, photooxidation of the polymer matrix leads to the formation of an aromatic ketone, most likely fluorenone at the chain terminating monomer units, which quenches the fluorescence. The second process promotes aggregate formation, which then leads to loss of luminous intensity by exciton transfer and relaxation through excimers.

We report the results of probing adhesion and friction forces between surfaces with functional terminal groups with chemically modified scanning probe microscopy (SPM) tips. Surfaces with terminal groups of CH3, NH2, and SO3H were obtained by direct chemisorption of silane-based compounds on silicon/silicon nitride surfaces. We studied surface properties of the resulting self-assembled monolayers (SAMs) in air and aqueous solutions with different pHs. Work of adhesion, “residual forces”, and friction coefficients was obtained for four different types of modified tips and surfaces. Absolute values of the work of adhesion between various surfaces, Wad, were in the range 0.5−8 mJ/m². The work of adhesion for different modified surfaces correlated with changes of solid−liquid surface energy estimated from macroscopic contact-angle measurements. Friction properties varied with pH in a register with adhesive forces showing a broad maximum at intermediate pH values for a silicon nitride/silicon nitride mating pair. Similar broad maxima were observed in the acid range for a NH2-terminated SAM and in the basic range for a SO3H-terminated SAM. This behavior can be understood considering the changes of the surface charge state determined by the zwitterionic nature of silicon nitride surfaces with multiple isoelectric points.

Composite molecular films of (AB)x type are fabricated by self-assembly of dendritic macromolecules of two adjacent generations using the electrostatic layer-by-layer deposition. Polyamidoamine dendrimers with surface amine groups for generations 4, 6, and 10 (G4, G6, G10) and carboxylic groups for generations G3.5, G5.5, and G9.5 have been used as building units. The molecular films are explored by scanning probe microscopy and X-ray reflectivity. All even generations are observed to form homogeneous, stable monolayers on a silicon surface. The thickness of a single monolayer varies with generation (molecular weight) from 1.8 nm (G4) to 2.8 nm (G6) and 5.6 nm (G10). Average thickness of a molecular layer in multilayer films is much smaller than the diameter of ideal spherical dendritic macromolecules. The model of molecular ordering of dendrimer films assumes compressed dendritic macromolecules of oblate shape with the axial ratio in the range from 1:3 to 1:6. The high interaction strength between “sticky” surface groups along with short range van der Waals forces and long range capillary forces are considered to be responsible for formation of compact monolayer structures. A tendency to higher spreading of high generation dendrimers observed here corresponds to the surface behavior predicted by molecular dynamic simulations.

Scanning probe microscope observations of monolayers of a classic boundary lubricant, stearic acid (STA), reveal long-range dynamics of wear and reconstruction of monomolecular films under the shear forces caused by the sliding tip. The STA monolayer in a fluid state displays a flow of material from the worn area and its redistribution resulting in multilayer formation within the range of 80 μm. Surface diffusion of mobile organic material is responsible for the observed long-range effects of the local shear stresses produced within the contact area. Solid and fluid monolayers have very different velocity dependencies of the friction forces. For solid monolayers, we observe a monotonic increase of the friction forces with velocity rising from 0.02 to 1000 μm/s. In contrast, for the fluid STA monolayers the friction forces behave nonmonotonically with a maximum value around 0.2 μm/s. We observe significant compression of the STA monolayers under the tip reaching 35% of initial thickness before the fatal damaging. The observed compression can be related to the collective tilting of the molecules under normal loads due to a formation of gauche conformers in alkyl chains. Estimated Young's modulus is in the range of 0.2−0.7 GPa for very small deformations (<3% of thickness compression). However, the elastic modulus decreases sharply to tens of MPa at higher deformations.