This PDF file contains the front matter associated with SPIE Proceedings Volume 9779, including the Title Page, Copyright information, Table of Contents, Introduction, and the Conference Committee listing.

Inpria continues to leverage novel metal oxide materials to produce high resolution photoresists for EUV lithography with high optical density and etch resistance. Our resists have previously demonstrated 13nm line/space patterns at 35 mJ/cm², with extendibility to 10nm half-pitch.¹ We have continued to improve photospeed and in this work we provide an update on imaging performance. Since practical patterns for EUV layers will be more complicated than line/space patterns, we also expand on our previous work by demonstrating 2D resist performance using N7 (7nm node) contact and block mask patterns on full field scanners. A resist model has been created and using this model comparisons are made between a metal oxide resist and CAR platforms. Based on this physical model, the impact of shot noise is examined in relation to realistic 2D features. Preliminary data on the effect on OPC of using a non-chemically amplified resist are also presented.

Nanoparticles with a variety of organic/inorganic combinations have been investigated and the negative tone patterning was demonstrated using EUV radiation. Zirconium methacrylate (ZrMAA) nanoparticles had sensitivity with EUV exposure as high as 4.2 mJ/cm² with a resolution up to 22 nm, and an LER of 5.6 nm. Meanwhile, the dual-tone behavior of ZrMAA photoresists using e-beam and deep UV exposures is another attractive feature of the nanoparticle photoresists, which may be further applied with EUV lithography. The current study investigates the positive tone patterning of ZrMAA and the process-dependent image reversal. Our proposed patterning mechanism is further illustrated and optimized based in a positive tone behavior study.

Metal-based photoresists are appealing for use in EUV lithography due to their improved etch resistance and absorption compared with organic resists, and due to their resolving power demonstrated with 13.53 nm exposures using synchrotron light. Recently imec has started a new project to study novel photoresists for EUV lithography, with particular attention to metal containing materials, in order to explore alternative approaches that may offer superior characteristics in photoresist imaging and etching performance compared with more mature chemically amplified resists. In order to model these novel resists it is mandatory to understand both the optical properties and the electronic response to photon absorption. As in previous experiments on organic materials, some of the optical properties can be determined by merging analysis from high-energy electron scattering models (e.g. CXRO website), X-ray absorption spectroscopy, and DUV spectroscopic ellipsometry. Dispersion curves can be used to calculate the electronic inelastic and elastic mean-free paths; convolved with the expected spectrum at wafer level it is possible to estimate the electron yield and the secondary electron blur of the photoresist. These material properties can be used to modify the physical models currently used to simulate organic photoresist performance in computational lithography software.

Extreme ultraviolet lithography (EUVL) has been recognized as the most promising candidate for the manufacture of semiconductor devices for the 7 nm node and beyond. A key point in the successful introduction of EUV lithography in high volume manufacture (HVM) is the effective EUV dose utilization while simultaneously realizing ultra-high resolution and low line edge roughness (LER). Here we show EUV resist sensitivity improvement with the use of a photosensitized chemically amplified resist PSCARTM system. The evaluation of this new chemically amplified resist (CAR) as performed using EUV interference lithography (EUV-IL) is described and the fundamentals are discussed.

EUV photoacid generation efficiency has been described primarily in terms of the EUV photon absorption by the PAG or the resist matrix and the production of low energy photoelectrons, which are reported as being ultimately responsible for the high quantum efficiencies reported in EUV resists (<1). Such observation led to a number of recent studies on PAGs with variable electron affinity (EA) and reduction potential (Ered) presumably conducive to a differential EUV photoelectron harvesting efficiency. However, such studies either did not disclose the PAG chemical structures, replaced the EUV source with an e-beam source, or lacked a fundamental discussion of the underlying physical mechanisms behind EUV PAG decomposition. In this work, we report the EUV photospeed of a methacrylatebased resist formulated with a battery of openly disclosed isostructural sulfonium PAGs covering a wide range of EA’s and Ered’s, to unveil any preferential photoelectron scavenging effect. In parallel, several iodonium PAGs are also tested in order to compare the direct EUV photon absorption route to the photoelectron-based decomposition path. Contrarily to what has been widely reported, we have found no direct correlation whatsoever between photospeed and the calculated EA’s or experimental Ered’s for the isostructural sulfonium PAGs studied. Instead, we found that iodonium PAGs make more efficient use of the available EUV power due to their higher photoabsorption cross-section. Additionally, we determined a cation size effect for both PAG groups, which is able to further modulate the acid generation efficiency. Finally, we present a formal explanation for the unselective response towards photoelectron harvesting based on the stabilization of the PAG cation by bulky substituent groups, the spatial and temporal range of the transient photoelectron and the differences in electron transfer processes for the different systems studied.

The relative importance of secondary electrons in delivering energy in photoresist films was assessed by performing large area exposures and by quantifying the inelastic mean free path of electrons in a leading chemically amplified positive tone EUV resist. A low energy electron microscope was used to directly pattern large (~15μm x 20μm) features with 15-80 eV electrons followed by analyzing the resulting dissolution rate contrast curve data. In the 40 to 80 eV regime the energy delivery was found to scale roughly proportionally with electron energy. In 15 to 30 eV regime however, this energy scaling did not explain the resist thickness loss data. The dose required to lower the resist thickness down to 20 nm was found to be 2-5X larger for 15 eV electrons than for 20, 25 and 30 eV electrons. Using scattering models from the literature including phonon scattering and optical data deduced electron energy loss spectroscopy and optical reflectometry, the inelastic mean free path values at energies between 10 eV and 92 eV range between about 2.8 and 0.6 nm respectively.

Optimizing the photochemistry of extreme ultraviolet (EUV) photoresists should provide faster, more efficient resists which would lead to greater throughput in manufacturing. The fundamental reaction mechanisms in EUV resists are believed to be due to interactions with energetic electrons liberated by ionization. Identifying the likelihood (or cross section) of how these photoelectrons interact with resist components is critical to optimizing the performance of EUV resists. Chemically amplified resists utilize photoacid generators (PAGs) to improve sensitivity; measuring the cross section of electron induced decomposition of different PAGs will provide insight into developing new resist materials. To study the interactions of photoelectrons generated by EUV absorption, photoresists were exposed to electron beams at energies between 80 and 250 eV. The reactions between PAG molecules and electrons were measured using a mass spectrometer to monitor the levels of small molecules produced by PAG decomposition that outgassed from the film. Comparing the cross sections of a variety of PAG molecules can provide insight into the relationship between chemical structure and reactivity to the electrons in their environments. This research is a part of a larger SEMATECH research program to understand the fundamentals of resist exposures to help in the development of new, better performing EUV resists.

This work focuses on the application of a high speed atomic force microscope (HS-AFM) for the in situ visualization / quantification of the resist dissolution process. This technique, as reported in the past, has provided useful pointers on the formation of resist patterns during dissolution. This paper discusses about an investigation made on the quantification of what we refer to as “dissolution unit size” or the basic units of patterning material dissolution. This was done through the establishment of an originally developed analysis method which extracts the difference between two succeeding temporal states of the material film surface (images) to indicate the amount of change occurring in the material film at a specific span of time. Preliminary experiments with actual patterning materials were done using a positive-tone EUV model resist composed only of polyhydroxystyrene (PHS)-based polymer with a molecular weight of 2,500 and a polydispersity index of 1.2. In the absence of a protecting group, the material was utilized at a 50nm film thickness with post application bake of 90°C/60s. The resulting film is soluble in the alkali-based developer even without exposure. Results have shown that the dissolution components (dissolution unit size) of the PHS-based material are not of fixed size. Instead, it was found that aside from one constantly dissolving unit size, another, much larger dissolution unit size trend also occurs during material dissolution. The presence of this larger dissolution unit size suggests an occurrence of "polymer clustering". Such polymer clustering was not significantly present during the initial stages of dissolution (near the original film surface) but becomes more persistently obvious after the dissolution process reaches a certain film thickness below the initial surface.

Understanding of stochastic phenomena is essential to the development of highly sensitive resist for nanofabrication. In this study, we investigated the stochastic effects in a chemically amplified resist consisting of poly(4-hydroxystyrene-co-t-butyl methacrylate), triphenylsulfonium nonafluorobutanesulfonate (an acid generator), and tri-n-octylamine (a quencher). The SEM images of resist patterns were analyzed, using Monte Carlo simulation on the basis of the sensitization and reaction mechanisms of chemically amplified extreme ultraviolet resists. It was estimated that ±0.82σ fluctuation of the number of protected units per polymer molecule led to line edge roughness formation. Here, σ is the standard deviation of the number of protected units per polymer molecule after postexposure baking.

In extreme ultraviolet (EUV) lithography, 92 eV photons are used to expose photoresists. Typical EUV resists are organic-based and chemically amplified using photoacid generators (PAGs). Upon exposure, PAGs produce acids which catalyze reactions that result in changes in solubility. In EUV lithography, photo- and secondary electrons (energies of 10- 80 eV) play a large role in PAG acid-production. Several mechanisms for electron-PAG interactions (e.g. electron trapping, and hole-initiated chemistry) have been proposed. The aim of this study is to explore another mechanism – internal excitation – in which a bound PAG electron can be excited by receiving energy from another energetic electron, causing a reaction that produces acid. This paper explores the mechanism of internal excitation through the analogous process of electron-induced fluorescence, in which an electron loses energy by transferring that energy to a molecule and that molecule emits a photon rather than decomposing. We will show and quantify electron-induced fluorescence of several fluorophores in polymer films to mimic resist materials, and use this information to refine our proposed mechanism. Relationships between the molecular structure of fluorophores and fluorescent quantum yield may aid in the development of novel PAGs for EUV lithography.

We characterized EIDEC metal resist for EUV lithography by various measurement methods. The low-voltage aberration-corrected scanning transmission electron microscopy combined with electron energy-loss spectroscopy showed the morphology of metal resists in nanometer regions and enabled studying the distribution of resist component in the resist film. The zirconium oxide metal resist kept the core-shell structure in the resist films and the titanium oxide metal resist showed the aggregation in the film. X-ray diffractometry and ab initio molecular dynamics simulation showed the amorphous structure with short-range order of the zirconium oxide metal resist. X-ray Photoelectron spectroscopy of the zirconium oxide-methacrylic acid metal resist showed the decomposition of the shell molecules and the increase of electron density at zirconium atoms after the EUV exposure. Infrared (IR) spectra indicated that the shell molecules made the various bindings to the metal core and the specific vibrational mode of shell molecules showed the divergent responsivity to the irradiation wavenumber of the IR Free electron laser.

Challenges of processing metal containing materials need to be addressed in order apply this technology to Behavior of metal containing materials on coater/developer processing including coating process, developer process and tool metal contamination is studied using CLEAN TRACK^TM LITHIUS Pro^TM Z (Tokyo Electron Limited). Through this work, coating uniformity and coating film defectivity were studied. Metal containing material performance was comparable to conventional materials. Especially, new dispense system (NDS) demonstrated up to 80% reduction in coating defect for metal containing materials. As for processed wafer metal contamination, coated wafer metal contamination achieved less than 1.0E10 atoms/cm² with 3 materials. After develop metal contamination also achieved less than 1.0E10 atoms/cm² with 2 materials. Furthermore, through the metal defect study, metal residues and metal contamination were reduced by developer rinse optimization.

Inorganic resists are of interest for nanomanufacturing due to the potential for high resolution, low line width roughness, and high sensitivity. The combination of high absorption coefficient elements and radiation sensitive ligands can improve inorganic resist sensitivity while still allowing high contrast for extreme ultraviolet (EUV) lithography. A prototypical resist is Hf(OH)_4-2x-2y(O₂)_x(SO₄)_y·qH₂O (HafSOx), which has both high absorption coefficient elements (Hf) and radiation sensitive ligands (peroxides). Herein, we evaluate the use of electron stimulated desorption (ESD) to characterize HafSOx. These results indicate that the peroxo species are extremely radiation sensitive, even for low kinetic energy electrons that approximate the range of electron energies expected during EUV exposures. The primary desorption products from HafSOx are O₂ and H₂O, where the time evolution suggest much faster desorption kinetics for O₂. These data provide insight into the radiation-induced changes responsible for the solubility transition upon exposure and dissolution during development, and the role of low kinetic energy electrons in these processes. The following describes our experimental methodology for the ESD studies, and the specific kinetic model used to extract total desorption cross sections from the ESD data.

Metal oxide nanoparticle resists have recently emerged as next generation photoresist materials which exhibit promising performance for extreme ultraviolet lithography. In this present work, we are able to show our ability to synthesize and well characterize small uniform metal oxide nanoparticles, to present stability study of the nanoparticles in the resist solvent over time, to pattern ~20 nm features by electron beam lithography, and to provide an insight into the insolubilization mechanism of the resist system.

We present a comprehensive study of the roughness metrics of different resists. Dense line/space (L/S) images of polymethyl methacrylate (PMMA), hydrogen silsesquioxane (HSQ), different chemically amplified resists (CARs), and metal oxide based resists have been patterned by extreme ultraviolet interference lithography (EUV-IL). The three line width roughness metrics: r.m.s. value σ_LWR, correlation length ξ and roughness exponent α, were measured by metrological analysis of top down SEM images and compared for the different resists imaged here. It was found, that all metrics are required to fully describe the roughness of each resist. Our measurements indicate that few of the state-of-the- art resists tested here can meet the International Technology Roadmap for Semiconductors (ITRS) requirements for σ_LWR. The correlation length ξ has been found to be considerably higher in polymer-based materials in comparison to non-polymers. The roughness exponent α, interpreted using the concept of fractal geometry, is mainly affected by acid diffusion in CARs where it produces line edges with a higher complexity than in non-CAR resists. These results indicate that different resists platforms show very different LWR resist metrics and roughness is not only manifested in the σ_LWR but in all parameters. Therefore, all roughness metrics should be taken into account in the performance comparison of the resist, since they can have a substantial impact on the device performance.

The continuously scaling of complex device geometries is driving by the self-aligned multiple patterning techniques. Depending on such simplified LS scaling, FinFET design rule has been accelerated to unidirectional design layout. ^[1] In particular Fin, Gate and Metal layers are based on grating with cutting/blocking scheme, these process have become high volume manufacturing techniques in N14 and beyond.^[2,3] On the other hand, immersions based pitch scaling of contact hole, via and cutmask processes are required multiple lithography and etching passes.^[4] Overlay management is not only the overlay accuracy of layer to layer, to determine the placement error and patterning fidelity in single layer. In this work, focusing on the placement in hole pattern, total placement error budget will be discussed from the viewpoints of metrology, inspection, Mask, OPC and wafer processing. In addition, hole shrink and hole healing techniques have more significant factors in terms of design-process technology co-optimization for N7 and beyond.^[5]

This paper demonstrates that another class of three-dimensional integrated circuits (3D-ICs) exists, distinct from through silicon via centric and monolithic 3D-ICs. Furthermore, it is possible to create devices that are 3D at the device level (i.e. with active channels oriented in each of the three coordinate axes), by performing standard CMOS fabrication operations at an angle with respect to the wafer surface into high aspect ratio silicon substrates using membrane projection lithography (MPL). MPL requires only minimal fixturing changes to standard CMOS equipment, and no change to current state-of-the-art lithography. Eliminating the constraint of 2D planar device architecture enables a wide range of new interconnect topologies which could help reduce interconnect resistance/capacitance, and potentially improve performance.

Negative tone imaging (NTI) process is a method for obtaining a negative-tone reversal pattern by developing with an organic solvent. As NTI process can break-through the resolution limit of a conventional positive tone development (PTD) process at specific pattern such as trenches and contact holes, it have been applied for a mass production in 20nm and 14nm nodes devices. In NTI system, because a developer is changed from a hydrophilic aqueous solution to a hydrophobic organic solvent, it is possible to review the common resist stack which is optimized for a PTD process. In this paper, we examined the possibility of a bi-layer process using a Si-containing NTI resist. Etching selectivity between the Si-NTI resist and a SOC improved by raising Si-content of the Si-NTI resist, but resolution deteriorates as a trade-off. By suppressing swelling behavior of the Si-NTI resist with a polymer structure control, we overcame this trade-off. As a result, in sub-90 nm pitch L/S and CH patterns, the resolution of the Si-NTI resist achieved comparable level to a conventional NTI resist. In addition, SOC etching was successfully carried out by using the Si-NTI resist pattern as an etching hard mask.

We developed the novel process and material which can prevent the pattern collapse issue perfectly. The process was Dry Development Rinse (DDR) process, and the material used in this process was DDR Material (DDRM). DDRM was containing siloxane polymer which could be replaced the space area of the photo resist pattern. And finally, the reversed pattern would be created by dry etching process without any pattern collapse issue.

This novel process was useful not only in positive tone development (PTD) process but also in negative tone development (NTD) process. We newly developed DDRM for NTD process. Novel DDRM consist of special polymer and it used organic solvent system. So, new DDRM showed no mixing property with NTD photo resist and it has enough etch selectivity against NTD photo resist.

Image reversal was successfully achieved by combination of NTD process and DDR process keeping good pattern quality. Tone reverse pattern below hp 18nm was obtained without any pattern collapse issue, which couldn’t be created by just using normal NTD process.

Enormous advances have been made in recent years to design sub 40nm dense contact hole pattern with local CD uniformity (CDU) that the process can tolerate. Negative tone development process (NTD) on 193nm photoresists has achieved this to a large extent without the requirement of additional processing steps on the patterned layer. With further shrinking of size of the subsequent nodes, the demand to produce smaller patterns with wider process window, low defectivity, and improved CDU is increasing, and reaching beyond what can be achieved through NTD alone. A number of techniques are in practice today to achieve this, most notably, implementation of a collar of Atomic Layer Deposited SiO₂ (ALD) on photoresist or substrate. However, in recent years, various material suppliers have also proposed shrink chemistries to achieve this. In this paper, we have provided fundamental characterization of shrink via application of spin-on agents (organic as well as aqueous) on the post-imaged pattern. We have also compared them for their shrink capacity, defect tendency, dry etch capability and ease of implementation in the process flow. In addition, we have provided recommendations on which technique is suitable for a given set of process prerequisites.

Directed Self Assembly (DSA) has gained increased momentum in recent years as a cost-effective means for extending lithography to sub-30nm pitch, primarily presenting itself as an alternative to mainstream 193i pitch division approaches such as SADP and SAQP. Towards these goals, IMEC has excelled at understanding and implementing directed self-assembly based on PS-b-PMMA block co-polymers (BCPs) using LiNe flow [1]. These efforts increase the understanding of how block copolymers might be implemented as part of HVM compatible DSA integration schemes. In recent contributions, we have proposed and successfully demonstrated two state-of-the-art CMOS process flows which employed DSA based on the PS-b-PMMA, LiNe flow at IMEC (pitch = 28 nm) to form FinFET arrays via both a ‘cut-last’ and ‘cut-first’ approach [2-4]. Therein, we described the relevant film stacks (hard mask and STI stacks) to achieve robust patterning and pattern transfer into IMEC’s FEOL device film stacks. We also described some of the pattern placement and overlay challenges associated with these two strategies. In this contribution, we will present materials and processes for FinFET patterning and integration towards sub-20 nm pitch technology nodes. This presents a noteworthy challenge for DSA using BCPs as the ultimate resolution for PS-b-PMMA may not achieve such dimensions. The emphasis will continue to be towards patterning approaches, wafer alignment strategies, the effects of DSA processing on wafer alignment and overlay.

Directed self-assembly of block copolymers is a promising candidate to address grand challenges towards new generations of low-cost, high-resolution nanopatterning technology. Over the past decade, poly(styrene-b-methyl methacrylate) (PS-b-PMMA) has been the most popular block copolymer applied in this area. However, further scaling towards pitches below 20 nm is hindered by its relatively low segregation strength between constituent blocks, characterized by a low Flory-Huggins interaction parameter, χ (~ 0.038 at r.t). To reach sub-10 nm feature dimensions, many high- χ block copolymer materials and processes are currently being studied. Here we investigate the DSA of PSb- PMMA with blended ionic liquid (IL) on chemically-patterned substrates via thermal annealing with a free surface. In this materials system, by adding low volume fraction of IL, a substantially higher χ than the pure block copolymer is achieved with manageable change in surface and interfacial properties so that poly(styrene-random-methyl methacrylate) brushes may be used to control substrate wetting behavior, and the blend could be assembled using thermal annealing with a free surface. In other words, PS-b-PMMA/IL may serve as a high- χ drop-in replacement for PS-b-PMMA. In this work, we provide key DSA results to determine if PS-b-PMMA/IL blends would offer a solution for sub-10 nm lithography.

The overall quality and processing capability of lithographic materials are critical for ensuring high device yield and performance at sub-20nm technology nodes in a high volume manufacturing environment. Insufficient process margin and high line width roughness (LWR) cause poor manufacturing control, while high defectivity causes product failures.

In this paper, we focus on the most critical layer of a sub-20nm technology node LSI device, and present an improved method for characterizing both lithographic and post-patterning defectivity performance of state-of-the-art immersion photoresists. Multiple formulations from different suppliers were used and compared. Photoresists were tested under various process conditions, and multiple lithographic metrics were investigated (depth of focus, exposure dose latitude, line width roughness, etc.). Results were analyzed and combined using an innovative approach based on advanced software, providing clearer results than previously available. This increased detail enables more accurate performance comparisons among the different photoresists. Post-patterning defectivity was also quantified, with defects reviewed and classified using state-of-the-art inspection tools.

Correlations were established between the lithographic and post-patterning defectivity performances for each material, and overall ranking was established among the photoresists, enabling the selection of the best performer for implementation in a high volume manufacturing environment.

Gridded design rules[1] is major process in configuring logic circuit used 193-immersion lithography. In the scaling of grid patterning, we can make 10nm order line and space pattern by using multiple patterning techniques such as self-aligned multiple patterning (SAMP) and litho-etch- litho-etch (LELE)^[2][3][5] . On the other hand, Line cut process has some error parameters such as pattern defect, placement error, roughness and X-Y CD bias with the decreasing scale. Especially roughness and X-Y CD bias are paid attention because it cause cut error and pattern defect. In this case, we applied some smoothing process to care hole roughness[4]. Each smoothing process showed different effect on X-Y CD bias. In this paper, we will report the pattern controllability comparison of trench and block + inverse. It include X-Y CD bias, roughness and process usability. Furthermore we will discuss optimum method focused on X-Y CD bias when we use additional process such as smoothing and shrink etching .

In this paper we report on our studies of the dynamic process of resist development in real time. Using High Speed – Atomic Force Microscopy (HS-AFM) in dilute developer solution, changes in morphology and nanomechanical properties of patterned resist were monitored. The Bruker Dimension FastScan AFM^TM was applied to analyze 193 nm acrylic-based immersion resists in developer. HS-AFM operated in Peak Force mapping mode allowed for concurrent measurements of image topography resist stiffness, adhesion to AFM probe and deformation during development. In our studies we focused on HS-AFM topography data as it readily revealed detailed information about initial resist morphology, followed by a resist swelling process and eventual dissolution of the exposed resist areas. HS-AFM showed potential for tracking and understanding development of patterned resist films and can be useful in evaluating the dissolution properties of different resist designs.

Strong resist shrinkage effects have been widely observed in resist profiles after negative tone development (NTD) and therefore must be taken into account in computational lithography applications. However, existing lithography simulation tools, especially those designed for full-chip applications, lack resist shrinkage modeling capabilities because they are not needed until only recently when NTD processes begin to replace the conventional positive tone development (PTD) processes where resist shrinkage effects are negligible. In this work we describe the development of a physical resist shrinkage (PRS) model for full-chip lithography simulations and present its accuracy evaluation against experimental data.

Directed self-assembly (DSA) with block-copolymers (BCP) is a promising lithography extension technique to scale below 30nm pitch with 193i lithography. Continued scaling toward 20nm pitch or below will require material system improvements from PS-b-PMMA. Pattern quality for DSA features, such as line edge roughness (LER), line width roughness (LWR), size uniformity, and placement, is key to DSA manufacturability. In this work, we demonstrate finFET devices fabricated with DSA-patterned fins and compare several BCP systems for continued pitch scaling. Organic-organic high chi BCPs at 24nm and 21nm pitches show improved low to mid-frequency LER/LWR after pattern transfer.

We report the synthesis and characterization of novel block copolymer (BCP) materials for the directed self-assembly (DSA) nanolithography applications. Specifically, the poly(t-butyl acrylate) (PtBA) block in the styrenic block copolymers have been chemically modified to a fluorinated block for the enhancement of the BCP χ-parameters. dPSb- PtBA had been first synthesized by anionic polymerization to prepare a well-defined BCP precursor with narrow polydispersity for the fluorination of PtBA block. Then, the precursor BCP was chemically modified by transalcoholysis of the PtBA-block with 2,2,2-trifluoroethanol. This strategy offers the advantage of flexibility and controllability to tailor the χ-parameter, while maintaining the narrow molecular weight distribution of the BCP materials for the advanced lithography applications. The transmission electron microscopy/small angle x-ray scattering (TEM/SAXS) characterization results of the modified BCP consisting of poly(fluoroalkylate) and PS supported the development of highly ordered lamellar domains in bulk.

Properties of new block copolymers systems, specifically designed to reach large periods for the features, are compared to the ones exhibited by classical PS-b-PMMA materials of same dimensions. Conducted studies, like free-surface defects analysis, mild-plasma tomography experiments, graphoepitaxy-guided structures, etch-transfer… indicate much better performances, in terms of achievable film-thicknesses with perpendicular features, defects levels, and dimensional uniformities, for the new system than for the classical PS-b-PMMA. These results clearly highlight unique and original solutions toward an early introduction of DSA technology into large lithographic nodes.

To extend directed self-assembly (DSA) of poly(styrene-b-methyl methacrylate) (PS-b-PMMA) for higher resolution, placement accuracy and potentially improved pattern line edge roughness (LER), we have developed a next-generation material platform of organic high-χ block copolymers (“HC series”, AZEMBLY^TM EXP PME-3000 series). The new material platform has a built-in orientation control mechanism which enables block copolymer domains to vertically selforient without topcoat/additive or delicate solvent vapor annealing. Furthermore, sub-10 nm lines and spaces (L/S) patterning by two major chemoepitaxy DSA, LiNe and SMART^TM processes, was successfully implemented on 12” wafer substrates by using the PME-3000 lamellar series. The results revealed that the new material platform is compatible with the existing PS-b-PMMA-based chemical prepatterns and standard protocols. We also introduced the built-in orientation control strategy to the conventional PS-b-PMMA system, producing a new generation of PS-b-PMMA materials with facile orientation control. The modified PS-b-PMMA (m-PS-b-PMMA) performed LiNe flow DSA yielding a comparable CD process window with improved LER/LWR/SWR after the L/S patterns were transferred into a Si substrate.

In this study, we have successfully synthesized polystyrene-b-poly(4-hydroxystyrene) (SH) with molecular weight of 14k and with narrow molecular weight distribution by living anionic polymerization, and the obtained SH diblock copolymer has formed the definite alternative lamellar structure with the half pitch of 10.4nm. In order to achieve narrow half pitch pattern, diblock copolymer (XY) with stronger segregated polymer components with high chi (X and Y) was used, and it was confirmed that the high-chi XY diblock copolymer having molecular weight of 6k showed the clear lamellar structure with the half pitch of 5.5nm. Furthermore syntheses of multiblock copolymers with high chi such as YXY (where X is Si contained polymer) triblock and XYXY (where XYXY is Si contained high χ polymer) tetrablock copolymers were attempted to achieve the narrower half pitch pattern less than 5 nm, and the multiblock copolymers with aimed molecular weight and narrow molecular weight distribution have been successfully obtained. From the highchi multiblock copolymers, it was confirmed that the formation of the definite microphase-separated structure with the half pitch of 4.8nm was observed by TEM and SAXS measurements. Moreover we have developed a large-scale living anionic polymerization apparatus for the preparation of well-defined block copolymers scaled over 3kg.

In recent years, as next-generation lithography, various exposure techniques have been studied such as Extreme Ultraviolet Lithography (EUVL), Directed Self Assembly (DSA) and multiple patterning processes. In particular, EUVL is the most promising candidate for the high volume manufacturing below N7 node. However, there are many problems to be solved such as materials, through put of the exposure tool and mask defect. With respect to the DSA, the fine patterning with block copolymer has been studied. But the DSA process also has the several problems such as the complicated process flow in chemo process, quality of the block copolymer and defect. On the other hand, although the multiple patterning has been applied the device manufacturing for several years, there are some problems such as significant increase in cost due to increasing of the process steps and the overlay accuracy at the multiple process steps. Therefore, Pattern Trimming Materials (PTM) and Pattern Shrink Materials (PSM) were developed for miniaturization using the current exposure technology. The PTM is applied on a resist pattern produced in a Positive Tone Development (PTD) process and trim the resist pattern. It is possible to control the trimming amount by changing the formulation and the baking process. It has been confirmed that the effectiveness of PTM is not only for the L/S pattern, but also for the 2D pattern like pillar pattern. At the same time, it is confirmed that the PTM can improve the Line Width Roughness (LWR) and Local Critical Dimension Uniformity (LCDU). On the other hand, the PSM is applied on the pattern prepared in a Negative Tone Imaging (NTI) process and then it can shrink the resist pattern after baking. We adopted the new concept for pattern shrinkage process which dramatically improved LCDU with the hole shrinkage. In this paper, we demonstrated the L/S and pillar pattern trimming by PTM and the C/H shrink by PSM with ArF immersion (ArF im) condition and EUV condition. In the future, PTM and PSM are expected to be applied in not only ArF im patterning process but also in EUVL.

The application of phasefluid based intelligent fluids® in the field of photoresist stripping was studied. Due to their highly dynamic inner structure, phasefluids penetrate into the polymer network of photoresists and small gaps between resist layer and substrate and lift off the material from the surface. These non-aggressive stripping fluids were investigated regarding their efficiency in various resist stripping applications including initial results on copper metallization. Furthermore intelligent fluids® have been evaluated on an industry standard high volume single wafer cleaner. A baseline process on 300 mm wafers has been developed and characterized in terms of metallic and ionic impurities and defect level. Finally a general proof of concept for removal of positive tone resist from 300 mm silicon wafers is demonstrated.

ArF lithography is still major process to develop N7/N5 devices. Especially in resist materials, DOF, roughness and CD uniformity are the biggest key parameters in fine pitches. To improve these issues, we newly propose to apply Dry Development Rinse Process (DDRP) and Materials (DDRM) as the ArF extension approach. In EUV lithography, DDRP is already one of the approaches to achieve high resolution. However, the performance of DDRP for ArF lithography was never demonstrated in detail. In this paper, we especially focus to improve DOF, CD uniformity and roughness by applying DDRP for ArF generation. Finally we succeeded to enhance every parameter at the same time by controlling DDRM etching condition. This new DDRP technology can be the promising approach for ArF extension stages in N7/N5 and beyond.

The lithographic performance of photoresists is a function of the vertical distribution of formulation components, such as photoacid generator (PAG) molecules, in photoresist thin films and how these components undergo chemical modification and migrate within the film during the lithography processing steps. This paper will discuss how GCIB-SIMS depth profiles were used to monitor the PAG and quencher base distributions before and after exposure and post-exposure bake processing steps for different PAG/photoresist formulations. The authors show that the use of surface active quencher in an NTD photoresist leads to better resist profiles, superior DOF and better OPC performance.

In the presented work solvent-free film preparation from molecular glass resists, the evaluation of the patterning performance using thermal scanning probe lithography (tSPL) and an efficient etch transfer process are demonstrated. As the presented materials have a high tendency to crystallize and thus form crystalline films of bad quality when processed by solution casting, two component mixtures prepared by coevaporation were investigated. Stable amorphous films were obtained by selecting compatible material pairs for the coevaporation. One optimized material pair is based on trissubstituted, twisted resist materials with a distinct difference in molecular design. Here a high resolution tSPL prepared pattern of 18 nm half pitch in a 10 nm thick film is demonstrated.

A further optimization is reported for “small” cubic silsequioxane molecules. Again single component films show independent to applied film preparation techniques bad film forming properties due to the high crystallinity of the symmetric cubic silsequioxane molecules. But coevaporation of the phenyl substituted octaphenylsilsequioxane combined with the fully aromatic 2,2',7,7'-tetraphenyl-9,9'-spirobi[fluorene] results in stable amorphous thin films. tSPL investigations demonstrate the patternability by writing high resolution line features of 20 nm half pitch. An important advantage of such a silicon rich resist material is that it can be directly converted to SiO₂, yielding to a patterned hardmask of SiO₂. This proof of principle is demonstrated and an efficient pattern transfer of 60 nm half pitch line into the underlying HM8006 is reported.

Directed self-assembly (DSA) of block copolymers has gained much attention for its potential as a low-cost, high-throughput patterning tool to supplement existing lithographic techniques, and in particular for its ability to easily pattern vertical interconnect accesses (VIAs).¹ Single-hole shrink has been extensively explored, but the continued push towards higher-resolution patterns requires more efficient, less space-consuming approaches. The lithographic resolution limits the minimum distance between two features, and the single-hole templates take up valuable real estate on the wafer.² To accommodate denser features and relax the resolution requirements of the lithographic techniques, it is prudent to move to multi-VIA configurations in which two or more features are assembled in a single guiding template (such as a peanut,³ or a rounded rectangle⁴). This allows considerably denser feature patterning, but comes at the cost of more plentiful and complicated defect modes than those found in single-hole shrink features. Most systems contain persistent horizontal structures (eg. rings, U-defects, or bars as shown in Figure 1) that prove detrimental to the etch process and yield undesirable configurations. Largely unexplored is the tandem use of chemoepitaxy and graphoepitaxy to suppress defect modes in multi- VIA templates. Specifically, chemically selective patterning of the substrate beneath a template could act synergistically with the template's lateral guidance to lower defectivity.

In this study, we use three-dimensional self-consistent field theory (SCFT) simulations to investigate the equilibrium and metastable defective configurations of di-block copolymer DSA systems in the presence of chemically selective or neutral template sidewalls and preferentially attractive striped substrates. We identify chemo-patterning schemes that maximize defect energies, including sidewall interaction strength and chemical preference. In addition, we discuss chemo-patterning schemes that backfire, creating even more complicated and persistent defect modes such as horizontal half-cylinders on the system substrate.

Overcoming the optical limitations of 193nm immersion lithography can be achieved using Directed Self Assembly (DSA) of block-copolymers (BCPs) as a low-cost and versatile complementary technique. The goal of this paper is to investigate the potential of DSA to address line and space (L/S) high resolution patterning by performing the density multiplication of lines with the graphoepitaxy approach. As surface affinity is a key parameter in self-assembly, three variations, or "flavors", of DSA template affinity are investigated regarding several success criteria such as morphology control or defectivity. More precisely, both the methodology to register DSA defects and the impact of process parameters on defectivity are detailed. Using the 300mm pilot line available in LETI and Arkema’s advanced materials, we investigate process optimization of DSA line/space patterning of a 38nm period lamellar PS-b-PMMA BCP (L38). For this study, our integration scheme, depicted in figure 2-1, is based on BCP self-assembly inside organic hard mask guiding patterns obtained using 193i nm lithography. Defect analysis coupled with the fine tuning of process parameters (annealing, brush material) provided the optimum conditions for the L38 self-assembly. Using such conditions, DSA using the three affinity flavors is investigated by means of SEM top-view and cross-section review. Lithographic performances of one selected flavor are then evaluated with the comparison of Process Windows (PWs) function of either commensurability, morphology or LWR. This work is a first step in finding the best process for an industrial graphoepitaxy approach.

Directed self-assembly (DSA) of block copolymers (BCP) is considered a promising patterning approach for the 7 nm node and beyond. Specifically, a grapho-epitaxy process using a cylindrical phase BCP may offer an efficient solution for patterning randomly distributed contact holes with sub-resolution pitches, such as found in via and cut mask levels. In any grapho-epitaxy process, the pattern density impacts the template fill (local BCP thickness inside the template) and may cause defects due to respectively over- or underfilling of the template. In order to tackle this issue thoroughly, the parameters that determine template fill and the influence of template fill on the resulting pattern should be investigated. In this work, using three process flow variations (with different template surface energy), template fill is experimentally characterized as a function of pattern density and film thickness. The impact of these parameters on template fill is highly dependent on the process flow, and thus pre-pattern surface energy. Template fill has a considerable effect on the pattern transfer of the DSA contact holes into the underlying layer. Higher fill levels give rise to smaller contact holes and worse critical dimension uniformity. These results are important towards DSA-aware design and show that fill is a crucial parameter in grapho-epitaxy DSA.

Spin-on-carbon hard mask (SOC HM) has been used in semiconductor manufacturing since 45nm node as an alternative carbon hard mask process to chemical vapor deposition (CVD). As advancement of semiconductor to 2X nm nodes and beyond, multiple patterning technology is used and planarization of topography become more important and challenging ever before. In order to develop next generation SOC, one of focuses is planarization of topography. SOC with different concepts for improved planarization and the influence of thermal flow temperature, crosslink, film shrinkage, baking conditions on planarization and filling performance are described in this paper.

We describe a lithographic approach – Nanocrystal Plasma Polymerization (NPP)-based lithography (Figure 1) – where colloidal nanocrystal assemblies (CNAs) are used as the resist and, potentially, the active material. The patterning process is based on a change in the dispersibility of the CNAs in solvents as a result of the exposure to plasmas. Plasmas can etch the capping ligands from the exposed area. During the development step, the unexposed area of CNAs are redispersed leaving behind the patterned area.

In this paper, we report the development of a new polyphenol, NF7177, applied to the Spin-On Carbon Hardmask and the thermosetting properties. The new polyphenol derivatives were easily synthesized by the condensation of aldehydes and dihydroxybiphenyl compounds. We found new polyphenol NF7177 was showed the good applicability to the raw material for the Spin-On Carbon Hardmask [1]. It was indicated that the heat resistance of NF7177 was due to cross-linking based on dehydration reaction. Furthermore the thermosetting properties seem to be depend on the number and position of OH group.

Novolak resists have been widely used in IC production and are still used in the production of flat panel displays (FPDs) and MEMS. However, with the advent of high-definition products, FPDs increasingly face requirements for finer dimensions. These trends have generated requirements for higher sensitivity, higher resolution, and wider process margin for novolak resists. Using a lithography simulator with the goal of improving the performance of novolak resists, we examined various approaches to improving resist materials. This report discusses efforts to improve resolution and sensitivity using highly fractionated novolak resins and adding low molecular weight phenol resins.

Metal oxide or metal nitride films are used as hard mask materials in semiconductor industry for patterning purposes due to their excellent etch resistances against the plasma etches. Chemical vapor deposition (CVD) or atomic layer deposition (ALD) techniques are usually used to deposit the metal containing materials on substrates or underlying films, which uses specialized equipment and can lead to high cost-of-ownership and low throughput. We have reported novel spin-on coatings that provide simple and cost effective method to generate metal oxide films possessing good etch selectivity and can be removed by chemical agents. In this paper, new spin-on Al oxide and Zr oxide hard mask formulations are reported. The new metal oxide formulations provide higher metal content compared to previously reported material of specific metal oxides under similar processing conditions. These metal oxide films demonstrate ultra-high etch selectivity and good pattern transfer capability. The cured films can be removed by various chemical agents such as developer, solvents or wet etchants/strippers commonly used in the fab environment. With high metal MHM material as an underlayer, the pattern transfer process is simplified by reducing the number of layers in the stack and the size of the nano structure is minimized by replacement of a thicker film ACL. Therefore, these novel AZ^® spinon metal oxide hard mask materials can potentially be used to replace any CVD or ALD metal, metal oxide, metal nitride or spin-on silicon-containing hard mask films in 193 nm or EUV process.

The main target of the current work was to develop new polymeric materials for lithographic applications, the main chain of which is cleaved under the influence of photogenerated acid. Acetals have been chosen as functional groups in the main polymer chain since they can be cleaved in the presence of an acid while they remain untouched in alkaline ambient. The synthesized polymers were designed to bear in addition suitable functional groups for the achievement of desirable lithographic characteristics (thermal stability, acceptable glass transition temperature, etch resistance, proper dissolution behaviour). The synthesis was carried out via polyaddition of a vinyloxyl compound and a diol compound to produce novel polymers with acetal repeating units in their backbone. We chose polyaromatic hydrocarbons as diol units to achieve increased etch resistance. In addition, the polyaromatic units allow exposure at 193 nm as well, where the absorption of simple aromatics is prohibitively high. Good solubility and increased surface adhesion were achieved by choosing cycloaliphatic vinyloxyl ethers as the second component for the polyaddition. In addition, the same route can be followed to incorporate chromophores that can tune the resist absorbance in different spectral regions. Furthermore, single component systems can be designed following this approach by the incorporation of suitable PAGs in the main chain.

We explored the metal removal efficiency of Nylon 6,6 and HDPE (High Density Polyethylene) membrane based filters, in solvents of varying degree of polarity such as Cyclohexanone and 70:30 mixture of PGME (Propylene Glycol Monomethyl Ether) and PGMEA (Propylene Glycol Monomethyl Ether), In all the solvents tested, Nylon 6,6 membrane filtration was found to be significantly more effective in removing metals than HDPE membranes, regardless of their respective membrane pore sizes. Hydrophilic interaction chromatography (HILIC) mechanism was invoked to rationalize metal removal efficiency dependence on solvent hydrophobicity.

This paper discusses the integration of nanosphere lithography (NSL) with other fabrication techniques, allowing for nano-scaled features to be realized within larger microelectromechanical system (MEMS) based devices. Nanosphere self-patterning methods have been researched for over three decades, but typically not for use as a lithography process. Only recently has progress been made towards integrating many of the best practices from these publications and determining a process that yields large areas of coverage, with repeatability and enabled a process for precise placement of nanospheres relative to other features. Discussed are two of the more common self-patterning methods used in NSL (i.e. spin-coating and dip coating) as well as a more recently conceived variation of dip coating. Recent work has suggested the repeatability of any method depends on a number of variables, so to better understand how these variables affect the process a series of test vessels were developed and fabricated. Commercially available 3-D printing technology was used to incrementally alter the test vessels allowing for each variable to be investigated individually. With these deposition vessels, NSL can now be used in conjunction with other fabrication steps to integrate features otherwise unattainable through current methods, within the overall fabrication process of larger MEMS devices. Patterned regions in 1800 series photoresist with a thickness of ~700nm are used to capture regions of self-assembled nanospheres. These regions are roughly 2-5 microns in width, and are able to control the placement of 500nm polystyrene spheres by controlling where monolayer self-assembly occurs. The resulting combination of photoresist and nanospheres can then be used with traditional deposition or etch methods to utilize these fine scale features in the overall design.

We discuss edge placement errors (EPE) for multi-patterning of Mx critical layers using ArF lithography. Specific focus is placed on the block formation part of the process. While plenty of literature characterization data exist on spacer formation, only limited published data is available on block processes. We analyze the accuracy of placing blocks relative to narrow spacers. Many publications calculate EPE assuming Gaussian distributions for key process variations contributing to EPE. For practical reasons, each contributor is measured on dedicated test structures. In this work, we complement such analysis and directly measure the EPE in product. We perform high density sampling of blocks using CDSEM images and analyze all feature edges of interest. We find that block placement errors can be very different depending on their local design context. Specifically we report on 2 block populations (further called block A and B) which have a 4x different standard deviation. We attribute this to differences in local topography (spacer shape) and interaction with the plasma-etch process design. Block A (on top of the ‘core space’ S1) has excellent EPE uniformity of ~1 nm while block B (on top of ‘gap space’ S2) has degraded EPE control of ~4 nm. Finally, we suggest that the SOC etch process is at the origin on positioning blocks accurately on slim spacers, helping the manufacturability of spacer-based patterning techniques, and helping its extension toward the 5nm node.

One of the practical candidates to produce 7nm node logic devices is to use the multiple patterning with 193-immersion exposure. For the multiple patterning, it is important to evaluate the relation between the number of mask layer and the minimum pitch systematically to judge the device manufacturability. Although the number of the time of patterning, namely LE(Litho-Etch) ^ x-time, and overlay steps have to be reduced, there are some challenges in miniaturization of hole size below 20nm. Various process fluctuations on contact hole have a direct impact on device performance. According to the technical trend, 12nm diameter hole on 30nm-pitch hole will be needed on 7nm node. Extreme ultraviolet lithography (EUV) and Directed self-assembly (DSA) are attracting considerable attention to obtain small feature size pattern, however, 193-immersion still has the potential to extend optical lithography cost-effectively for sub-7nm node. The objective of this work is to study the process variation challenges and resolution in post-processing for the CD-bias control to meet sub-20nm diameter contact hole. Another pattern modulation is also demonstrated during post-processing step for hole shrink. With the realization that pattern fidelity and pattern placement management will limit scaling long before devices and interconnects fail to perform intrinsically, the talk will also outline how circle edge roughness (CER) and Local-CD uniformity can correct efficiency. On the other hand, 1D Gridded-Design-Rules layout (1D layout) has simple rectangular shapes. Also, we have demonstrated CD-bias modification on short trench pattern to cut grating line for its fabrication.

As the critical dimension of devices is approaching the resolution limit of 193nm photo lithography, multiple patterning processes have been developed to print smaller CD and pitch. Multiple patterning and other advanced lithographic processes often require the formation of isolated features such as lines or posts by direct lithographic printing. The formation of isolated features with an acceptable process window, however, can pose a challenge as a result of poor aerial image contrast at defocus. Herein we report a novel Chemical Trimming Overcoat (CTO) as an extra step after lithography that allows us to achieve smaller feature size and better process window.

Neutral layer (NL) material is one of the key materials for aligning block-co-polymer (BCP). In this study, NLs were designed and investigated, which have the capability to enhance the photo-lithography performance, a good alignment performance of BCP, and reduce the defectivity after chemo-epitaxy process. In order to enhance the photo-lithography performance, some new polymers were prepared with chromophores to control n/k value and adhesive unit interacted with the photo resist. The surface energy of these materials was adjusted to the neutral for BCP by controlling the ratio of chromophore and adhesion unit. The defects were also investigated and achieved low defectivity by optimized materials. Since this material has the above properties, it shows a good perpendicularly alignment pattern of BCP and a photolithography performance.

Block copolymer self-assembly is a powerful tool for nanoscale patterning which benefits from predictive simulations. Two classes of simulations are self-consistent field theory (SCFT), which is accurate but computationally expensive, and phase field models, which are faster but historically less accurate. We refine a mapping procedure that uses results from SCFT to optimize parameters in a phase field model for diblock copolymers. We validate the performance of this optimized phase field model with regards to accuracy and computational speed in perfect and defective configurations. The optimized phase field model is significantly faster than SCFT and more accurate than previous phase field models, making it a viable design tool for directed self-assembly processes.

In this paper, we presented the filtration effects on block copolymers (BCP) that are commonly used in directed self-assembly lithographic (DSAL) imaging schemes. Specifically we focused on filtration effects on micro-contaminants such as metal ions and metal induced gels.

Gel removal efficiency studies carried out with HDPE, Nylon and PTFE filters pointed out that Nylon 6,6 membrane is the most effective in removing gels in block copolymer (BCP) solutions.

Metal removal efficiency studies were conducted using multistep filtrations such as repetitive filtration of single membrane material and combination of different type of membranes. Results showed that a combination of Nylon-6,6 and ion-exchange filters is highly effective in reducing metals such as Li, Mg and Al to > 99.99% efficiency. The mechanism of metal removal efficiency is discussed in detail.

Block-copolymers (BCPs) offer the potential to meet the demands of next generation lithographic materials as they can self-assemble into scalable and tailorable nanometer scale patterns. In order for these materials to find wide spread adoption many challenges remain, including reproducible thin film morphology, for which the purity of block copolymers is critical. One of the sources of impurities are reaction conditions used to synthesize block copolymers that may result in the formation of homopolymer as a side product, which can impact the quality and the morphology of self-assembled features. Detection and characterization of these homopolymer impurities can be challenging by traditional methods of polymer characterization. We will discuss an alternate NMR-based method for the detection of homopolymer impurities in block copolymers – contrast enhanced diffusion ordered spectroscopy (CEDOSY). This experimental technique measures the diffusion coefficient of polymeric materials in the solution allowing for the ‘virtual’ or spectroscopic separation of BCPs that contain homopolymer impurities. Furthermore, the contrast between the diffusion coefficient of mixtures containing BCPs and homopolymer impurities can be enhanced by taking advantage of the chemical mismatch of the two blocks to effectively increase the size of the BCP (and diffusion coefficient) through the formation of micelles using a cosolvent, while the size and diffusion coefficient of homopolymer impurities remain unchanged. This enables the spectroscopic separation of even small amounts of homopolymer impurities that are similar in size to BCPs. Herein, we present the results using the CEDOSY technique with both first generation BCP system, poly(styrene)-b-poly(methyl methacrylate), as well as a second generation high-χ system.

In this contribution, we present the results of a systematic material variation for the development of a resist material for high resolution positive tone electron beam lithography (EBL). Several acrylic copolymer materials with different compositions, that is varying mass fractions of the comonomers and different molecular weights, were synthesized and – as resist solutions – evaluated in terms of EBL performance at acceleration voltages of 30 kV and 100 kV. The resist material exhibiting the best combination of the desired properties, named mr-PosEBR, is two times more sensitive than PMMA 495k and performs comparably to the known high resolution resist ZEP520A at 30 kV. For example, a grating pattern with 29 nm wide lines with a period of 100 nm could be lithographically generated in films of mr-PosEBR with an area dose of 100 μC/cm². In terms of resolution, single lines of only 35 nm width could be fabricated via metal liftoff. Furthermore, the dry etch stability of mr-PosEBR in a CF₄/SF₆ process is similar to the one of ZEP520A. Consequently, via dry etching nano patterns in mr-PosEBR could be smoothly transferred into the underlying Si substrate with high fidelity. Moreover, mr-PosEBR was evaluated as electron beam grayscale patterning and reflow resist. It was shown that the resist exhibits a good grayscale and reflow performance very similar to PMMA 120k and ZEP520A. Via these well controllable processes the generation of a wide variety of features and applications is possible.

We have developed a range of fullerene containing materials for use as organic hard masks. Recent advances in material development are reported together with some results from external evaluations of the original HM100 series. Initial results for the new HM340-383-010 formulation show it to have a high thermal stability (~5.5 % mass loss at 400°C) and a very high carbon content (at 95.3%), offering high etch durability.

Helium ion beam lithography (HIBL) is a novel alternative lithographic technique with the capacity of fabricating highresolution and high-density features. Only limited research has been performed exploring HIBL to date. HafSOx (Hf(OH)_4–2x−2y(O2)_x(SO₄)_y·qH₂O) is a negative-tone inorganic resist that is one of several candidate resist materials for extreme ultraviolet lithography (EUVL) and e-beam lithography (EBL), and has been demonstrated to show high resolution, moderate sensitivity and low line-edge roughness (LER) in both EUVL and EBL. To date, no ion beam lithography work on HafSOx has been reported. In this study, we tested HafSOx as an HIBL resist and achieved a high sensitivity compared with EBL with a turn-on dose D₁₀₀ ~ 2-4 μC/cm². We obtained sub-10 nm line widths with low LER. A simple Monte Carlo simulation suggests that ionizing excitation accounts for most of the incident He ions’ energy loss.

The validity of our approach of inedible cellulose-based resist material derived from woody biomass has been confirmed experimentally for the use of pure water in organic solvent-free water spin-coating and tetramethylammonium hydroxide(TMAH)-free water-developable techniques of eco-conscious electron beam (EB) and extreme-ultraviolet (EUV) lithography. The water developable, non-chemically amplified, high sensitive, and negative tone resist material in EB and EUV lithography was developed for environmental affair, safety, easiness of handling, and health of the working people. The inedible cellulose-based biomass resist material was developed by replacing the hydroxyl groups in the beta-linked disaccharides with EB and EUV sensitive groups. The 50-100 nm line and space width, and little footing profiles of cellulose-based biomass resist material on hardmask and layer were resolved at the doses of 10-30 μC/cm². The eco-conscious lithography techniques was referred to as green EB and EUV lithography using inedible cellulose-based biomass resist material.