The main target of the current work was to develop new sensitive polymeric materials for lithographic applications, focusing in particular to EUV lithography, the main chain of which is cleaved under the influence of photogenerated acid. Resist materials based on the cleavage of polymer main chain are in principle capable to create very small structures, to the dimensions of the monomers that they consist of. Nevertheless, in the case of the commonly used nonchemically amplified materials of this type issues like sensitivity and poor etch resistance limit their areas of application, whereas inadequate etch resistance and non- satisfactory process reliability are the usual problems encountered in acid catalysed materials based on main chain scission. In our material design the acid catalyzed chain cleavable polymers contain very sensitive moieties in their backbone while they remain intact in alkaline ambient. These newly synthesized polymers bear in addition suitable functional groups for the achievement of desirable lithographic characteristics (thermal stability, acceptable glass transition temperature, etch resistance, proper dissolution behavior, adhesion to the substrate). Our approach for achieving acceptable etch resistance, a main drawback in other main chain cleavable resists, is based on the introduction of polyaromatic hydrocarbons in the polymeric backbone, whereas the incorporation of an inorganic component further enhances the etch resistance. Single component systems can also be designed following the proposed approach by the incorporation of suitable PAGs and base quencher molecules in the main chain. Resist formulations based on a random copolymer designed according to the described rules evaluated in EUV exhibit ultrahigh sensitivity, capability for high resolution patterning and overall processing characteristics that make them strong candidates for industrial use upon further optimization.
In this work, direct-write, high-resolution multiphoton photolithography using doped random methacrylic co-polymer thin films is demonstrated, using a continuous wave ultraviolet (UV) 375 nm diode laser source. The random copolymers are specifically designed for enhancing resolution and addressing issues arising from laser ablation processes, such as the berm-formation around the created holes in the film, which can be accessed by tuning the polymeric material properties including Tg, surface adhesion etc. The methacrylic copolymer is composed of monomers, each of them especially selected to improve individual properties. The material formulations comprise perylene molecules absorbing at the exposure wavelength where the polymeric matrix is transparent. It was found that if the radiation intensity exceeds a certain threshold, the perylene molecules transfer the absorbed light energy to the acrylate polymer matrix leading to polymer degradation and ablation of the exposed areas. The non-linear nature of the light absorption and energy transfer processes resulted in the creation of holes with critical dimensions well below the used wavelength reaching the sub 50 nm domain. Arrays of holes having various dimensions were fabricated in the laser ablation experiments using a directwrite laser system developed specifically for the purposes of this project.
The main target of the current work was to develop new polymeric materials for lithographic applications, the main chain of which is cleaved under the influence of photogenerated acid. Acetals have been chosen as functional groups in the main polymer chain since they can be cleaved in the presence of an acid while they remain untouched in alkaline ambient. The synthesized polymers were designed to bear in addition suitable functional groups for the achievement of desirable lithographic characteristics (thermal stability, acceptable glass transition temperature, etch resistance, proper dissolution behaviour). The synthesis was carried out via polyaddition of a vinyloxyl compound and a diol compound to produce novel polymers with acetal repeating units in their backbone. We chose polyaromatic hydrocarbons as diol units to achieve increased etch resistance. In addition, the polyaromatic units allow exposure at 193 nm as well, where the absorption of simple aromatics is prohibitively high. Good solubility and increased surface adhesion were achieved by choosing cycloaliphatic vinyloxyl ethers as the second component for the polyaddition. In addition, the same route can be followed to incorporate chromophores that can tune the resist absorbance in different spectral regions. Furthermore, single component systems can be designed following this approach by the incorporation of suitable PAGs in the main chain.