Extreme ultraviolet lithography (EUVL) enables integrated circuit (IC) industry to manufacture chips with increased transistor density per volume unit, so the Moore's law remains true to date. To support the endless requirement of reducing critical dimension (CD), chemically amplified resist (CAR) has been designed to address the resolution, line width roughness, and sensitivity (RLS) in nanoscale level. However, a good Litho performance from an EUV photoresist may not always be transferred into a good etch performance, limiting the stochastic defects after patten transfer is the key to achieve a good after etch inspection (AEI) defectivity. In this paper, we report the EUV photoresist design strategies to acquire good AEI defectivity with the understanding of CAR's property in a defined pattern transfer scheme with special focus on small molecule in photoresist. The CAR's Litho performance and the corelated etch performance will be discussed, the component etch rate and its correlation to photoresist etch performance will be covered.

We report on the relationship between resist make-up, filtration process & CH AEI defectivity for an advanced CAR resist with fast dose. In particular, the effect of a pattern transfer scheme on a resist platform with formulation & filtration variation is examined. Resist design & manufacturing strategies for continuous improvement of EUV CAR lithographic performance will be discussed.

For designing high-resolution integrated circuits, extreme ultraviolet (EUV) lithography using 13.5-nm light is indispensable; however, stochastic issues which can result in pattern roughness and stochastic defects have yet to be resolved. Many of these issues can relate to the low photon density when compared to DUV lithography. To resolve stochastic concerns in chemically amplified (CA) photoresists, it is important to use appropriate photoacid generator (PAG). EUV PAGs are designed to capture secondary electrons that originate from EUV irradiation to the photoresists. Herein, we focused on in silico analysis of C-S bond cleavage of sulfonium cation series, which is a well-known mechanism in production of photogenerated acids. Change in cation types or substituted functional groups directly affect electron affinities of PAG cations, as well as the efficiency of C-S bond cleavage reaction. Finally, the correlation between actual lithographic performance and calculated properties was carried out to understand the factors that influence efficiency of photoacid generation.

The drive toward tighter pitch and higher density integrated circuits requires continual advancement in lithography. Advanced photolithography tools use extreme ultraviolet (EUV) light with a wavelength of 13.5nm. The high energy nature of EUV light generates secondary electrons in the photoresist that are responsible for the photochemistry that induces the solubility switch. This distinct mechanism has provided the driving force for the development of new photoresists that are sensitive to EUV and highly reactive toward secondary electrons. Despite the considerable change in acid generation mechanism going from DUV to EUV, chemically amplified photoresists continue to be leading photoresist candidates for new process nodes at low NA EUV (0.33 NA) and their use is expected to extend into early high NA (0.55 NA). Herein the after-developer defects (ADI) and EUV P36 LS trench printing performance of a series of chemically amplified photoresists (CAR) with distinct chemistry developed specifically for EUV lithography are compared. In particular, the relationship of different leaving group chemistries and polymer manufacturing processes on stochastic defectivity is explored as well as the connection to photoresist polymer hydrophobicity and homogeneity. The insights gained from this study guide design strategies for improvement of advanced chemically amplified photoresists for EUV lithography.

Chemically amplified resists (CAR) enable the transition of extreme ultraviolet (EUV) lithography to high-volume manufacture (HVM). Novel photoresists continue to be designed to meet the simultaneous improvement of resolution, line width roughness, and sensitivity (RLS) trade-off. The absorption of EUV photons in the photoresist film leads to emission of primary electrons to form secondary electrons by inelastic scattering events which in turn leads to the activation of the photoacid generator compound. A unique challenge for the use of CAR in EUV lithography is their poor absorption at 13.5nm wavelength. Understanding the photoresist EUV absorption impact on lithographic performance parameters is critical for photoresist design. In this study, we designed photoresist polymers with tuned EUV absorption coefficients by incorporating EUV absorption group(s) onto different CAR polymers. The effect of the EUV absorption increase on polymer properties as well as on resist lithographic performance will be presented.

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.

Chemically amplified resist (CAR) materials are widely used in advanced node patterning by extreme ultraviolet lithography (EUVL). To support the continuous requirement of reducing critical dimension (CD), CAR has been designed to process at tens of nanometer coating thickness while taking into consideration film roughness, aspect ratio, and etch transfer challenge. In this study, we investigated the impact of the photoresist’s different spin speed for same film thickness on resolution, line width roughness, and sensitivity (RLS) trade-off for Line and Space (L/S) patterns. We selected photoresists with identical chemical composition that differed only in total wt solid% in the solution. Photoresist films at constant thickness were investigated for the spin speed impacts on photoresist film density, hydrophobicity on the film surface, and film surface roughness. The corresponding EUV lithographic performance will be presented.

Conventional chemically amplified resists for extreme ultraviolet (EUV) lithography are comprised of three fundamental components: a photoreactive, acid-generating species (PAG), an acid reactive polymer for solubility switching, and a basic component for acid diffusion control. The PAG component is typically derived from an organic onium salt, wherein the cation's capacity to capture secondary electrons generated upon EUV irradiation of the resist underscores their reactivity in lithographic applications. Thus, effective rational design of these materials is critical for controlling both sensitivity of the resist and feature regularity. Herein, we describe a robust method for in silico prediction of fundamental properties of onium cations including electron affinity, LUMO energy, and relative charge distribution. We correlate these theoretical values to experimental measurements and further to the influence of PAG cation properties on resist performance under EUV exposure. In addition to the reactive properties of these cations, we analyze these lithographic data in the context of the physicochemical properties of the cations, particularly polarity. In all, the results of this study suggest that while electron affinity of the PAG cation may drive reactivity in response to EUV exposure, multiple factors must be considered in the design of cations for optimal overall resist performance.

Extreme ultraviolet (EUV) lithography technology empowers integrated circuit industry to mass produce chips with smaller pitches and higher density. Along with EUV tool advancement, significant progress has also been made in the development and advancement of EUV chemically amplified resist (CAR) materials, which allows for the improvement of resolution, line edge roughness, and sensitivity (RLS) trade-off. The scarce number of EUV photons has triggered the development of resist material with high absorption at 13.5 nm. However, a review of open literature reveals very limited reports on the effect of high EUV absorption elements on etch properties of advanced EUV resist. To ensure Moore's Law continues to move forward, further resist performance improvement is required. In this regard, stochastic defects originating from photon shot noise, materials, and processing variabilities present a unique challenge for the extension of CAR platform for the patterning of smaller nodes. Notably, less attention has been paid to defects formed during the etching process used for pattern transfer. In this paper, we report on the relationship between resist make-up and etch properties. In particular, the effect of incorporation of EUV high absorbing elements are examined. New resist material design strategies for continuous improvement of EUV CAR lithographic performance will be discussed.

Further increasing integrated circuit storage capacities while reducing the cost has led to the development of stacked 3D structures for NAND application. The 3D NAND structures can be enabled by using KrF photoresist coated at high thickness, and a staircase pattern can be generated through multiple etch steps. Pushing KrF lithography to high coating thickness creates several challenges for the materials and formulation design, such as lack of film transparency, as well as film cracking and delamination. The photoresist used in KrF lithography is based on poly(hydroxystyrene) (PHS) type polymers, which is associated with unique technical challenges for printing 10s microns scale features due to its high absorbance at 248 nm and its high glass transition temperature, T-g. Here we report the development of novel KrF photoresist materials for 3D NAND application with sufficient film transmittance, which forms desired straight profile with no footing. Our results also indicate that the film cracking could be mitigated by additive and process condition optimization, and film delamination could be addressed by adding an adhesion promotion layer.

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 the semiconductor manufacturing industry, photoresist materials are used for transferring an image to one or more underlying layers. To increase the integration density of semiconductor devices and reduce cost of ownership, continuous development efforts towards advanced lithography processes, such as multiple patterning methods, have been devoted to reduce critical dimension. Multiple patterning processes, however, often encounter challenges to obtain an appreciable process window due to the poor aerial image contrast at the defocus region, not to mention the complexity in process and high cost. Herein, we report a novel CTO (TM) photoresist trimming solution as a post-lithography spin-on method to enhance photoresist performance in not only effectively reducing critical dimension, but also enabling larger process window, lower line width roughness, less scum and lower defectivity. This is a versatile process that is compatible with both acrylic and polyhydroxystyrene types of photoresists, therefore allowing it to become a general process for a wide range of applications across ArF, KrF and EUV lithography.

Directed self-assembly (DSA) of block copolymers (BCPs) is a promising technology for advanced patterning at future technology nodes, but significant hurdles remain for commercial implementation. The most widely studied material for DSA is poly(styrene-block-methyl methacrylate) (PS-PMMA), but the relatively weak segregation strength of PS-PMMA results in some limitations. This paper reports on these limitations for PS-PMMA and highlights a path to success through use of more strongly segregated "high-chi" block copolymers. In general, stronger segregation is predicted to lower defectivity at equilibrium, but unfortunately, kinetics of self assembly also becomes much slower as segregation strength increases. Recognizing diffusion is much faster for cylinder morphologies than lamellar ones, we have investigated new cylinder-forming BCPs that enable defect elimination with thermal annealing processes. In addition, a formulation strategy is presented that further improves the kinetics of the assembly process, enabling tremendous improvements in defectivity over simple BCP systems. Excitingly, successful chemoepitaxy DSA with a high-chi lamellar BCP is also demonstrated using a thermal annealing process and no top coat. These technologies hold promise to enable DSA with thermal annealing processing across pitches from 40 - 16 nm.

Directed self- assembly (DSA) of block copolymers (BCPs) is a promising technology for advanced patterning at future technology nodes, but significant hurdles remain for commercial implementation. The most widely studied material for DSA is poly(styrene-block-methyl methacrylate) (PS-PMMA), but the relatively weak segregation strength of PS-PMMA results in some limitations. This paper reports on these limitations for PS-PMMA and highlights a path to success through use of more strongly segregated "high-chi" block copolymers. In general, stronger segregation is predicted to lower defectivity at equilibrium, but unfortunately, kinetics of self assembly also becomes much slower as segregation strength increases. Recognizing diffusion is much faster for cylinder morphologies than lamellar ones, we have investigated new cylinder-forming BCPs that enable defect elimination with thermal annealing processes. In addition, a formulation strategy is presented that further improves the kinetics of the assembly process, enabling tremendous improvements in defectivity over simple BCP systems. Excitingly, successful chemoepitaxy DSA with a high-chi lamellar BCP is also demonstrated using a thermal annealing process and no top coat. These technologies hold promise to enable DSA with thermal annealing processing across pitches from 40 - 16 nm.