Our mirror-based lithographic technique achieves 5 nm half-pitch patterning with EUV light. This breakthrough pushes EUV lithography boundaries beyond the high-NA specifications and serves as a benchmarking platform for novel photoresists.

We report on the extreme ultraviolet (EUV) patterning performance of tin-oxo cages. These cage molecules were already known to function as a negative tone photoresist for EUV radiation, but in this work, we significantly optimized their performance. Our results show that sensitivity and resolution are only meaningful photoresist parameters if the process conditions are optimized. We focus on contrast curves of the materials using large area EUV exposures and patterning of the cages using EUV interference lithography. It is shown that baking steps, such as postexposure baking, can significantly affect both the sensitivity and contrast in the open-frame experiments as well as the patterning experiments. A layer thickness increase reduced the necessary dose to induce a solubility change but decreased the patterning quality. The patterning experiments were affected by minor changes in processing conditions such as an increased rinsing time. In addition, we show that the anions of the cage can influence the sensitivity and quality of the patterning, probably through their effect on physical properties of the materials.

Resists that enable high-throughput and high-resolution patterning are essential in driving the semiconductor technology forward. The ultimate patterning performance of a resist in lithography is limited because of the trade-off between resolution, line-width roughness, and sensitivity; improving one or two of these parameters typically leads to a loss in the third. As the patterned feature sizes approach angstrom scale, the trade-off between these three metrics becomes increasingly hard to resolve and calls for a fundamental rethinking of the resist chemistry. Low-molecular-mass monodispersed metal-containing resists of high atom economy can provide not only very high resolution but also very low line-width roughness without sacrificing sensitivity. Here we describe a modular metal-containing resist platform (molecular mass <500 Da) where a molecular resist consists of just two components: a metal and a radical initiator bonded to it. This simple system not only is amenable to high-resolution electron beam lithography (EBL) and extreme ultraviolet lithography (EUVL) but also unites them mechanistically, giving a consolidated perspective of molecular and chemical processes happening during exposure. Irradiation of the resist leads to the production of secondary electrons that generate radicals in the initiator bonded to metal. This brings about an intramolecular rearrangement and causes solubility switch in the exposed resist. We demonstrate record 1.9-2.0 nm isolated patterns and 7 nm half-pitch dense line-space features over a large area using EBL. With EUVL, 12 nm half-pitch line-space features are shown at a dose of 68 mJ/cm². In both of these patterning techniques, the line-width roughness was found to be ≤2 nm, a record low value for any resist platform, also leading to a low-performance trade-off metric, Z factor, of 0.6 × 10^-8 mJ·nm³. With the ultimate resolution limited by instrumental factors, potential patterning at the level of a unit cell can be envisaged, making low-molecular-mass resists best poised for angstrom-scale lithography.

Background:Inorganic resists show promising performances in extreme ultraviolet (EUV) lithography. Yet, there is a need for understanding the exact chemical mechanisms induced by EUV light on these materials. Aim:To gain knowledge on the EUV chemistry of inorganic resists, we investigate hybrid inorganic–organic molecular compounds, metal oxoclusters (MOCs). Their molecular nature allows for the monitoring of specific structural changes by means of spectroscopy and thus for the elucidation of the mechanisms behind pattern formation. Approach:We compare the sensitivity of MOCs based on Zr and Hf, and methacrylate ligands as EUV resists. The chemical and structural changes causing the solubility switch were investigated by ex situ x-ray spectroscopy, infrared spectroscopy, ultraviolet–visible spectroscopy, and grazing incidence x-ray scattering. Results:Higher sensitivity was detected for the Hf-based material, in line with its higher absorptivity. A small fraction of the carboxylate ligands is lost at doses that yield solubility contrast, whereas aggregation of the inorganic clusters was not observed. Conclusions:These results provide evidence that, although the mechanism of solubility switch in these materials starts with decarboxylation reactions, it mainly proceeds through cross linking of the organic shells instead of aggregation of the inorganic clusters.