Laser spike annealing was applied to PS-b-PDMS diblock copolymers to induce short-time (millisecond time scale), high-temperature (300 to 700 °C) microphase segregation and directed self-assembly of sub-10 nm features. Conditions were identified that enabled uniform microphase separation in the time frame of tens of milliseconds. Microphase ordering improved with increased temperature and annealing time, whereas phase separation contrast was lost for very short annealing times at high temperature. PMMA brush underlayers aided ordering under otherwise identical laser annealing conditions. Good long-range order for sub-10 nm cylinder morphology was achieved using graphoepitaxy coupled with a 20 ms dwell laser spike anneal above 440 °C.

The solubility behavior of Hf and Zr based hybrid nanoparticles with different surface ligands in different concentrations of photoacid generator as potential EUV photoresists was investigated in detail. The nanoparticles regardless of core or ligand chemistry have a hydrodynamic diameter of 2-3 nm and a very narrow size distribution in organic solvents. The Hansen solubility parameters for nanoparticles functionalized with IBA and 2MBA have the highest contribution from the dispersion interaction than those with tDMA and MAA, which show more polar character. The nanoparticles functionalized with unsaturated surface ligands showed more apparent solubility changes after exposure to DUV than those with saturated ones. The solubility differences after exposure are more pronounced for films containing a higher amount of photoacid generator. The work reported here provides material selection criteria and processing strategies for the design of high performance EUV photoresists.

Previous studies of methacrylate based nanoparticle have demonstrated the excellent pattern forming capability of these hybrid materials when used as photoresists under 13.5 nm EUV exposure. HfO 2 and ZrO 2 methacrylate resists have achieved high resolution (~22 nm) at a very high EUV sensitivity (4.2 mJ/cm 2 ). Further investigations into the patterning process suggests a ligand displacement mechanism, wherein, any combination of a metal oxide with the correct ligand could generate patterns in the presence of the suitable photoactive compound. The current investigation extends this study by developing new nanoparticle compositions with transdimethylacrylic acid and o-toluic acid ligands. This study describes their synthesis and patterning performance under 248 nm KrF laser (DUV) and also under 13.5 nm EUV exposures (dimethylacrylate nanoparticles) for the new resist compositions.

The interaction of 91.6eV EUV photons with photoresist is very different to that of optical lithography at DUV wavelength. The latter is understood quite well and it is known that photons interact with the resist in a molecular way through the photoacid generator (PAG) of the chemically amplified resist (CAR). In EUV however, the high energy photons interact with the matter on atomic scale, resulting in the generation of secondary electrons. It is believed that these secondary electrons in their turn are responsible in chemical modification and lead to switching reactions that enable resist local dissolution. However, details of the interaction are still unclear, e.g. which reaction an electron with a given energy can initiate.In this work we have introduced a method to measure the chemical interaction of the secondary electrons with the EUV resist. The method is based on electron gun exposures of low energy electrons (range ~1eV to ~80eV) in the photoresist. The chemical interaction is then measured by Residual Gas Analysis (RGA), which can analyze out of the outgassing which and how much reaction products are generated. In this way a 'chemical yield' can be quantified as function of electron energy. This method has been successfully applied to understand the interaction of secondary electrons on the traditional CAR materials. The understanding was facilitated by testing different compositions of an advanced EUV CAR, where resp. polymer only, polymer+PAG, and polymer+PAG+quencher are tested with the electron gun. It was found that lowenergy electrons down to ~3-4eV can activate PAG dissociation, which can lead to polymer deprotection. However it was observed too that energy electrons of ~12eV and higher can do direct deprotection even in absence of the PAG. In addition, testing suggests that electrons can generate also other chemical changes on the polymer chain that could lead to cross-linking.