Per- and polyfluoroalkyl substances (PFAS) have been identified by various regulatory bodies as substances of concern. In line with the objective of safer and sustainable by design, a comprehensive program has been initiated to address these concerns. Part of this program includes the development of non -fluorinated photoacid generators (PAGs) without introducing new chemicals with unintended consequences. Using computational chemistry and synthetic organic chemistry , several scaffolds amenable to PAG library design have been realized. These novel PAGs offer facile tunability and advantages in many critical design parameters such as pKa, diffusion, absorption, shelf-life stability, and scalability. These early generation non-fluorinated PAGs show competitive and similar lithographic performance compared to fluorinated PAGs in i-line, krypton fluoride (KrF) laser, argon fluoride (ArF) laser and extreme ultraviolet (EUV) lithography.
To maximize value in integrated circuit manufacturing, semiconductor manufacturers continually seek materials that enable processing with higher throughput and which provide higher yield. 193nm immersion lithography (193i) has been a mainstay in semiconductor manufacturing for many years. However, 193i throughput is constrained by topcoat layers necessitating additional processing steps, and yield is impacted by defectivity resulting from water droplet interactions with wafer surfaces. To overcome these limitations, a platform of high contact angle embedded barrier layer (EBL) materials was developed and EBL polymers were incorporated directly into advanced photoresist formulations, obviating the need for topcoat, permitting faster wafer scan speeds, and lowering defectivity from water droplet rupture or water leakage during immersion processing. These EBL materials were designed with a built-in solubility switch such that they maintain a hydrophobic surface during scanning but can rapidly solubilize in aqueous base developer and rinse away during development, significantly outperforming previous generation designs. This report will detail the development, evaluation, and optimization of new EBL materials with substantially higher contact angles than previous materials for next-generation 193i applications.
Miniaturization of lithographic feature sizes via shrink technologies is under development in order to extend 193nm immersion lithographic capabilities and achieve sub-20nm critical dimensions (CD) in integrated circuit manufacturing before extreme ultraviolet lithography comes online. It was found that precisely controlled polymers comprising a grafting unit and a shrink unit are capable of reducing pattern dimensions formed in negative tone development (NTD) photoresists. Fundamental studies were pursued regarding the type of grafting chemistry, the shrink monomer and polymer backbone choice, and differences between polymer architectures. Mechanistic studies demonstrated that shrink amount could be tuned by choice of monomer, polymer molecular weight, and choice of grafting unit. These studies permitted the development of several generations of grafting polymer platforms to meet a range of desired CD shrink targets from less than 10nm shrink to 30nm shrink on contact hole or line/space patterns. The shrink technology further exhibits improved process window compared to optical lithography at the same CD and low defectivity, highlighting the use of this technology in advanced semiconductor processing nodes.
In this paper, we will describe some of our efforts on various leaving group designs and their impacts on resist performance, mainly focusing on the leaving group polarity, activation energy and molecular volume. The EUV lithographic performances of the newly designed leaving groups are evaluated on a standard methacrylate polymer bound photoacid generator (PBP) platform. With our low activation energy and hydrophobic leaving group PBP, we report good line and space and contact hole performance using the Albany eMET and LBNL BMET tool.
James Cameron, Jim Thackeray, Jin Wuk Sung, Suzanne Coley, Vipul Jain, Owendi Ongayi, Mike Wagner, Paul LaBeaume, Amy Kwok, David Valeri, Marie Hellion, Béatrice Icard, Bernard Dal'zotto, Claire Sourd, Laurent Pain
Prompted by the fact that the International Technology Roadmap for Semiconductors (ITRS) has declared no proven
optical solutions are available for sub 22nm hp patterning, we have investigated e-Beam and Extreme Ultraviolet (EUV)
resist performance with a view to High Volume Manufacturing (HVM) at these design rules. Since these patterning
technologies are considered the leading candidates to replace Immersion ArF (ArFi) multilevel patterning schemes, it
was deemed prudent to assess the readiness of these imaging options. We review the advantages and disadvantages of
each patterning method and highlight general technology challenges as well as resist specific challenges. In terms of
resist specific challenges, we primarily focus on Resolution, Linewidth roughness and Sensitivity (RLS) tradeoffs for
both e-Beam and EUV patterning. These metrics are of particular relevance as the industry continues to contend with
the well known tradeoffs between these performance criteria. The RLS relationship is probed for both line space and
contact hole patterns with each exposure wavelength. In terms of resist selection, we focus on our advanced Polymer
Bound PAG (PBP) resist platform as it has been designed for high resolution applications. We also assess resist
outgassing during EUV exposure as it is a potential barrier to adoption of EUV for HVM.
Resolution, line edge roughness, sensitivity and low
outgassing are the key focus points for extreme ultraviolet (EUV) resist
materials. Sensitivity has become increasingly important so as to address
throughput concerns in device manufacturing and compensate for the
low power of EUV sources. Recent studies have shown that increasing
the polymer linear absorption absorption coefficient in EUV resists
translates to higher acid generation efficiency and good pattern
formation. In this study, novel high absorbing polymer platforms are
evaluated. The contributing effect of the novel absorbing chromophore to
the resultant chemically amplified photoresist is evaluated and compared
with a standard methacrylate PAG Bound Polymer (PBP) platform. We
report that by increasing EUV absorption, we cleanly resolved 17 nm 1:1
line space can be achieved at a sensitivity of 14.5 mJ/cm2, which is
consistent with dose requirements dictated by the ITRS roadmap. We
also probe the effect of fluorinated small molecule additives on acid
yield generation (Dil C) at EUV of a PBP platform.
Vipul Jain, Suzanne Coley, Jung June Lee, Matthew Christianson, Daniel Arriola, Paul LaBeaume, Maria Danis, Nicolas Ortiz, Su-Jin Kang, Michael Wagner, Amy Kwok, David Valeri, James Thackeray
Several approaches have been used to minimize LWR in advanced resists. Various polymer and matrix properties, such
as polymer molecular volume and free volume fraction, polymer dissolution, impact of activation energy of the deprotection
reaction and distribution of small molecules in the polymer matrix have been shown to influence the
functional behavior of the resist. We have developed polymerization methods to improve the incorporation and
homogeneity of monomers, including PAG monomer, in an EUV resist polymer. Further, we report on use of a new
cation which imparts reduced OOB character and a 30% improvement in LWR for a 28nm L/S feature with sensitivity of
10mJ/cm2 versus a control containing the TPS cation. Additionally this new material is capable of 21nm resolution. We
also tested the new cation for outgassing by RGA and observed a 60% reduction in outgassing versus a TPS control.
When patterning critical layers at hyper NA, a multilayer antireflectant system is required in order to control
complex reflectivity resulting from various incident angles. Multilayer antireflectants typically consist of an
organic antireflectant and inorganic substrates. However, there are still some applications which need a single
organic antireflectant over high reflective substrates. A 2P2E application in double patterning is one of them.
Even though the pitch for double patterning is relatively loose, the reflectivity control is still challenging in terms
of profiles and overall process window. The optical constants and thickness of antireflectants should be well
optimized depending on applications. We have investigated several organic antireflectants for a single
antireflectant over high reflective substrates. The organic films differ in terms of n, k, thickness to cover both the
1st minimum and the 2nd minimum applications. The overall patterning performance including profiles and
process window has been evaluated. ASML 1900i was used to perform lithography. Simulation was performed
using ProlithTM software.
Via fill performance of AR7 (KrF anti-reflectant) and a prototype 193nm anti-reflectant were measured for 600 and 1000 nm deep vias in thermal oxide. Simple fitting functions were found which gave good agreement with experimental data (Rsq over 0.84). The most important factors were AR thickness, via duty ratio and via depth. The importance of these factors was different for the different anti-reflectants.
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