There is a rapidly growing need for new materials for extreme ultra-violet, EUV, lithography which incorporate high EUV absorbing atoms. Hybrid resists which are a combination of inorganic and organic moieties are promising as they offer both high EUV sensitivity and high etch resistance. However, there is a glaring lack of methods to examine the uniformity of these important materials at the nanoscale. Here we examine the capabilities of Nano-Projectile Secondary Ion Mass Spectrometry (NP-SIMS) to investigate hybrid resists. NP-SIMS is a mass spectrometry-based technique with high lateral resolution. Using NP-SIMS, a surface is probed stochastically with a suite of individual projectiles, 106−7 in total, separated in time and space. Examining these individual mass spectra allows for nanoscale investigation of the uniformity of the surface. We evaluated the performance NP-SIMS using samples of polymethyl methacrylate, PMMA, infiltrated with varying amounts of InOx via vapor-phase infiltration (VPI). We found that NP-SIMS measurements contained abundant characteristic ions related to both the PMMA and infiltrated In. The intensity of In atomic ions increased linearly with the number of infiltration cycles, however the uniformity of In and PMMA varied with the number of infiltration cycles. After one cycle we found that both the PMMA and In were relatively inhomogeneous. The homogeneity improved with subsequent infiltration cycles. Overall, the results show that NP-SIMS is capable of examining both the inorganic and organic moieties in a hybrid resist and will be an important method for understanding the performance of these materials for use in EUV lithography.
In this study, we focus on examining the stability of Al-based inorganic-organic hybrid thin films deposited through the molecular atomic layer deposition (MALD) process in ambient environment. Our observations reveal an initial reduction in material thickness within the first 3 days, followed by a period of stability. XPS analysis is employed to further investigate the chemical alternations in the aged Al-based hybrid thin films, revealing an increase in C=O species as well as overall oxygen content in the material. We also evaluate the effects of atmospheric exposure on the sensitivity of the Al-based hybrid thin films using electron flood exposure. This study aims to enhance the understanding of the stability of a vapor-phase synthesized hybrid thin film system for advanced resist applications.
High-NA EUV lithography required for continued extreme downscaling of Si devices demands ultrathin photoresists with high EUV patterning performance and etch resistance. This talk briefs our current efforts on synthesizing new organic-inorganic hybrid resists based on atomic layer deposition (ALD) techniques and characterizing their electron beam and EUV patterning characteristics. Two distinctive approaches are discussed–vapor-phase infiltration (VPI) and molecular ALD (MALD), where the former utilizes an infiltration of gaseous inorganic precursors into existing organic resists and the latter a cyclic layering of organic and inorganic moieties. Featured systems include an indium-oxide-infiltrated PMMA and a MALD hybrid resist comprising trimethylaluminum (TMA) and hydroquinone (HQ). Given the facile implementablility and control of resist composition and characteristics, the ALD-based hybrid resist synthesis has a potential for enabling high-performance EUV photoresist systems.
Infiltration synthesis of vapor-phase precursors is ex-situ route of converting established polymeric resists into hybrids. The concept initially modelled over polymethylmethacrylate (PMMA)-AlOx hybrid has been expanded to infiltrating several metal oxide moieties into high sensitivity resist (HSR). Beyond implementing single metal oxide species, alloyed infiltration is explored as a means to limit pattern roughness originating from granular crystallites. Lithography performance of these new generation of hybrid positive tone resists is assessed towards contact-hole patterning.
Herein, we investigated the chemical reactions associated with low-energy electron exposures on an inorganic-organic hybrid thin film system deposited using molecular atomic layer deposition (MALD) for EUV photoresist applications. Using the hybrid thin films consisting of trimethylaluminum (TMA) and hydroquinone (HQ), we determined the critical doses and thickness contrast of the hybrid materials at various electron energies (up to 400 eV). The custom-built in-situ Fourier-Transform Infrared (FTIR) spectroscopy system, equipped with an electron flood gun and gas residual analyzer (RGA), was employed to monitor the chemical changes induced by low-energy electrons in the hybrid thin films. Based on the in-situ FTIR and RGA results, potential chemical reaction mechanisms responsible for the change in solubility of the TMA/HQ material are proposed.
High-NA EUV lithography–scheduled to be implemented in a few years for high-volume manufacturing of extremely downscaled Si devices with 2 nm node and beyond–demands ultrathin organic-inorganic hybrid photoresists with high EUV sensitivity and etch resistance. In this work, we synthesized a positive-tone hybrid photoresist composed of PMMA infiltrated with molecular network of indium oxide by vapor-phase infiltration (VPI), an ex-situ inorganic hybridization method derived from atomic layer deposition, and evaluated its patterning characteristics by electron-beam and EUV lithography (EBL and EUVL). The hybrid resist featured significantly enhanced etch resistance under dry etching but also the critical doses of 300 uC/cm2 for EBL and 60 mJ/cm2 for EUVL, both largely comparable to those of PMMA. Unlike alumina infiltration in PMMA that has been demonstrated previously, it was found that the weak binding nature of trimethyl indium (TMIn), the gaseous precursor used to infiltrate indium oxide in PMMA matrix, to the carbonyl group in PMMA enabled a uniform distribution of the oxide content across the PMMA thickness. However, it also led to undesired residue in the developed regions due to the strong interaction between the Lewis-basic hydroxyl groups on the surface of starting Si substrate with infiltrated TMIn. The residue issue could be mitigated by passivating the Si surface by hexamethyldisilizane (HMDS) and combining the acid/base rinse and oxygen plasma descum. The results not only hint at the potential of VPI-based ex-situ hybridization in developing novel hybrid EUV photoresists but also highlight the technological details that must be addressed to enable high EUVL performance in the infiltrated hybrid resist system.
We investigated the hydroquinone (HQ)/trimethylaluminum (TMA) hybrid thin film synthesized by molecular atomic layer deposition (MALD) as a potential extreme ultraviolet (EUV) photoresist. The patterning characteristics of the resist was studied using electron beam lithography (EBL) and low-energy electron microscopy (LEEM), identifying energy-dependent critical exposure dose and contrast under wet development. Also identified were the reactive ion etching (RIE) characteristics, demonstrating a dry development parameter window, achieving the maximum etch contrast of ~10 nm between the regions with and without electron exposure. The results suggest the MALD approach as a viable synthesis route for developing new hybrid EUV photoresists.
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