Thickness effects on the optical properties of layer-by-layer poly(p-phenylene vinylene) thin films and their use in energy-modulated structures

Poly(p-phenylene vinylene) (PPV) thin films were produced by layer-by-layer (LbL) method, using soluble PPV-precursor and dodecylbenzenesulfonate salt (DBS). The amount of deposited layers strongly influences the optical properties of the thermally converted PPV film. The absorbance and luminescence spectra of ultra-thin films (consisting of only two or three PPV layers) are shifted to smaller wavelengths with respect to spectra of thicker films. This is related to the smaller average conjugation length of polymer chains, resulting in a higher HOMO–LUMO gap energy of the material. However, if a thick film is produced by repeating the deposition process and thermal conversion of ultra-thin layers, the optical spectra are still displaced to higher energies in comparison with those of thicker films produced by the conventional continuous deposition of layers. This result enabled the production of multilayered polymeric films with modulated energy profile, taking the number of deposited layers as the only variable in the manufacturing process of the structure. The aim is to guide the excitation to specific regions of the material through the Förster-type energy transfer processes. Such systems can be used at interfaces electrode/polymer and/or electrode/polymeric active layers in order to improve the performance of organic optoelectronic devices.

► Layer-by-layer PPV ultra-thin films presented higher HOMO–LUMO gap than thicker films.
► Thick films could be formed by superimposed deposition of ultra-thin films.
► The films composed by several superimposed ultra-thin films presented higher bandgap.
► The films composed by several continuously deposited layers presented lower bandgap.
► Step-like structures were made by superimposing films with lower and higher bandgap.