The combined reactivity of methacrylate and trifluoroacetate ligands make zinc-oxoclusters pattern 22–50 nm lines with high sensitivity by EUV Lithography.

Background: Hybrid inorganic-organic materials have emerged as promising candidates for EUV resists. However, knowledge on their stability when deposited as thin films is essential for their performance in EUV lithography. Aim: We investigate whether the molecular structure of Zn-based metal oxoclusters is preserved upon thin film deposition and study aging processes of the thin film under different atmospheres, since these chemical changes affect the solubility properties of the material. Approach: A hybrid cluster that combines the high EUV photon absorption cross-sections of zinc and fluorine with the reactivity of methacrylate organic ligands was synthesized. The structural modifications upon thin film formation and after aging in air, nitrogen, and vacuum were studied using a combination of spectroscopic techniques. Preliminary studies on the lithographic performance of this material were performed by EUV interference lithography. Results: The Zn-based compound undergoes structural rearrangements upon thin film deposition as compared to the bulk material. The thin films degrade in air over 24 h, yet they are found to be stable for the duration and conditions of the lithography process and show high sensitivity. Conclusions: The easy dissociation of the ligands might facilitate hydrolysis and rearrangements after spincoating, which could affect the reproducibility of EUV lithography.

A general, one-step patterning technique for colloidal quantum dots by direct optical or e-beam lithography. Photons (5.5–91.9 eV) and electrons (3 eV–50 kV) crosslink and immobilize QDs down to tens of nm while preserving the luminescent properties.

Electron-induced reactions make an important contribution to the solubility switch of a novel Zn oxocluster resist in extreme ultraviolet lithography (EUVL). The study also gives direct evidence that chain reactions are involved in this process.

Helium (He) ion lithography is being considered as one of the most promising and emerging technology for the manufacturing of next generation integrated circuits (ICs) at nanolevel. However, He-ion active resists are rarely reported. In this context, we are introducing a new non-chemically amplified hybrid resist (n-CAR), MAPDSA-MAPDST, for high resolution He-ion beam lithography (HBL) applications. In the resist architecture, 2.15 % antimony is incorporated as heavy metal in the form of antimonate. This newly developed resists has successfully used for patterning 20 nm negative tone features at a dose of 60 μC/cm2. The resist offered very low line edge roughness (1.27±0.31 nm) for 20 nm line features. To our knowledge, this is the first He-ion active hybrid resist for nanopatterning. The contrast (γ) and sensitivity (E0) of this resist were calculated from the contrast curve as 0.73 and 7.2 μC/cm2, respectively.

The absorption of extreme ultraviolet (EUV) radiation by a photoresist strongly depends on its atomic composition. Consequently, elements with a high EUV absorption cross section can assist in meeting the demand for higher photon absorbance by the photoresist to improve the sensitivity and reduce the photon shot noise induced roughness. In this work, we enhanced the EUV absorption of the methacrylic acid ligands of Zn oxoclusters by introducing fluorine atoms. We evaluated the lithography performance of this fluorine-rich material as a negative tone EUV photoresist along with extensive spectroscopic and microscopic studies, providing deep insights into the underlying mechanism. UV−vis spectroscopy studies demonstrate that the presence of fluorine in the oxocluster enhances its stability in the thin films to the ambient atmosphere. However, the EUV photoresist sensitivity (D 50 ) of the fluorine-rich oxocluster is decreased compared to its previously studied methacrylic acid analogue. Scanning transmission X-ray microscopy and in situ X-ray photoelectron spectroscopy in combination with FTIR and UV−vis spectroscopy were used to gain insights into the chemical changes in the material responsible for the solubility switch. The results support decarboxylation of the ligands and subsequent radical-induced polymerization reactions in the thin film upon EUV irradiation. The rupture of carbon−fluorine bonds via dissociative electron attachment offers a parallel way of generating radicals. The mechanistic insights obtained here will be applicable to other hybrid materials and potentially pave the way for the development of EUV materials with better performance.

Extreme ultraviolet (EUV) lithography uses 13.5 nm light to reach the sub-20 nm resolution. However, the process of pattern formation induced by this high-energy light is not wellunderstood. In this work, we provide an inorganic EUV photoresist with fluorescence properties by introducing a carbazole derivative as a ligand, and we study its effect on the patterning process. Using the fluorescence properties, changes in the emission of the material after EUV exposure could be tracked by means of spectroscopy and microscopy. The resist sensitivity was substantially reduced by the incorporation of the carbazole benzoate ligands, which is attributed to hole trapping and steric hindrance. After EUV irradiation of the resist films, infrared, UV−visible absorption, and fluorescence spectroscopies showed that the carbazole units were still mostly intact, although their fluorescence intensity was lowered. Our work shows that fluorescent labeling can provide relevant mechanistic insights in the patterning process of resists, potentially with a molecular resolution.

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