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In the lithography landscape, EUV technology recovered some credibility recently. However, its large adoption remains uncertain. Meanwhile, 193nm immersion lithography, with multiple-patterning strategies, supports the industry preference for advanced-node developments. In this landscape, lithography alternatives maintain promise for continued R&D. Massively parallel electron-beam and nano-imprint lithography techniques remain highly attractive, as they can provide noteworthy cost-of-ownership benefits. Directed self-assembly lithography shows promising resolution capabilities and appears to be an option to reduce multi-patterning strategies. Even if large amount of efforts are dedicated to overcome the lithography side issues, these solutions introduce also new challenges and opportunities for the integration schemes.

High chi organic lamellar-forming block copolymers were prepared with 18 nm intrinsic period Lo value. The BCPs were coated on a neutral layer on silicon substrates and were either thermally annealed or exposed to solvent vapors both in a 300mm track. The effect of lowering the glass transition temperature (Tg) on the high chi BCP was investigated. Process temperatures and times were varied. It was found that the BCP having lower Tg exhibits faster kinetics and is able to reach alignment in a shorter time than a similar BCP having higher Tg. Fingerprint defect analysis also shows that the BCP with lower Tg has lower defects. The results show that fingerprint formation can be achieved with either ether or ester type solvents depending on the BCP used. The results show that a track process for solvent annealing of high-χ BCPs is feasible and could provide the path forward for incorporation of BCP in future nodes. Finally, directed self-assembly was demonstrated by implemented high chi polymers on a graphoepitaxy test vehicles. CD and line width roughness was evaluated on patterns with a multiplication factor up to 7.

PS-b-PMMA block copolymer is a well-known DSA material, and there are many DSA patterning methods that make effective the use of such 1st generation materials. Consequently, this variety of patterning methods opens a wide array of possibilities for DSA application[1-4]. Last year, during the inaugural International DSA Symposium, researchers and lithographers concurred on common key issues for DSA patterning methods such as: defect density, LWR, placement error, etc. Defect density was specifically expressed as the biggest obstacle for new processes. Coat-Develop track systems contribute to the DSA pattern fabrication and also influence the DSA pattern performances[4]. In this study, defectivity was investigated using an atmosphere-controlled chamber on the SOKUDO DUO track. As an initial step for expanding the DSA process window, fingerprint patterns were used for various atmospheric conditions during DSA self-assembly annealing. In this study, we will demonstrate an improved DSA process window, and then we will discuss the mechanism for this atmospheric effect.

DSA patterning is a promising solution for advanced lithography as a complementary technique to standard and future lithographic technologies. In this work, we focused on DSA grapho-epitaxy process-flow dedicated for contact hole applications using polystyrene-b-poly(methyl methacrylate) (PS-b-PMMA) block copolymers. We investigated the impact on the DSA performances of the surface affinity of a guiding pattern design by ArF immersion lithography. The objective was to control and reduce the polymer residue at the bottom of the guiding pattern cavities since it can lead to lower a DSA-related defectivity after subsequent transfer of the DSA pattern. For this purpose, the DSA performances were evaluated as a function of the template surface affinity properties. The surface affinities were customized to enhance DSA performances for a PS-b-PMMA block copolymer (intrinsic period 35nm, cylindrical morphology) by monitoring three main key parameters: the hole open yield (HOY), the critical dimension uniformity (CDU-3σ) and the placement error (PE-3σ). Scanning transmission electron microscopy (STEM) was conjointly carried out on the optimized wafers to characterize the residual polymer thickness after PMMA removal. The best DSA process performances (i.e., hole open yield: 100%, CDU-3σ: 1.3nm and PE-3σ: 1.3nm) were achieved with a thickness polymer residue of 7 nm. In addition, the DSA-related defectivity investigation performed by review-SEM enabled us to achieve a dense (pitch 120nm) contact area superior to 0.01mm2 free of DSA-related defects. This result represents more than 6x105 SEM-inspected valid contacts, attesting the progress achieved over the last years and witnessing the maturity of the DSA in the case of contact holes shrink application.

Directed Self Assembly (DSA) of block-copolymers (BCPs) used as a complementary technique to the 193nm immersion lithography has demonstrated sub-10nm node applications in both via and line/space patterning. We propose however to study the performance of graphoepitaxy which allows DSA with thicker initial BCP layer, higher multiplication factors and stronger orientation control of lamellae. The aim of this work is to use the 300mm pilot line available at LETI and Arkema’s advanced materials to evaluate the performances of a novel graphoepitaxy process based on the work on a 38nm period lamellar PS-b-PMMA (L38) reported before.

In this work, we present completely industry adapted processes for high-chi PS-PDMS block copolymers. DSA was performed on trenches fabricated within standard photolithography stacks and pattern transfer was made by using etching processes similar to those used for gate etching in industry. We propose the alignment of two different PS-PDMS (45.5kg/mol, 16kg/mol) solely by thermal annealing. By adding plasticizer molecules in the high molecular weight BCP (45.5k), we have not only avoided solvent vapor annealing but also reduced significantly the processing time. The properties of the guiding lines and the quality of the final BCP hard mask (CD uniformity, LWR, LER) were investigated.

Directed Self-Assembly (DSA) is a well-known candidate for next generation sub-15nm half-pitch lithography. [1-2] DSA processes on 300mm wafers have been demonstrated for several years, and have given a strong impression due to finer pattern results. [3-4] On t he other hand, specific issues with DSA processes have begun to be clear as a result of these recent challenges. [5-6] Pattern placement error, which means the pattern shift after DSA fabrication, is recognized as one of these typical issues. Coat-Develop Track systems contribute to the DSA pattern fabrication and also influence the DSA pattern performance. [4] In this study, the placement error was investigated using a simple contact-hole pattern and subsequent contact-hole shrink process implemented on the SOKUDO DUO track. Thus, we will show the placement error of contact-hole shrink using a DSA process and discuss the difference between DSA and other shrink methods.

A simple and common practice to evaluate Block copolymers (BCP) self-assembly performances, is on a free surface wafer. With no guiding pattern the BCP designed to form line space pattern for example, spontaneously rearranges to form a random fingerprint type of a pattern. The nature of the rearrangement is dictated by the physical properties of the BCP moieties, wafer surface treatment and the self-assembly process parameters. Traditional CDSEM metrology algorithms are designed to measure pattern with predefined structure, like linespace or oval via holes. Measurement of pattern with expected geometry can reduce measurement uncertainty. Fingerprint type of structure explored in this dissertation, poses a challenge for CD-SEM measurement uncertainty and offers an opportunity to explore 2D metrology capabilities. To measure this fingerprints we developed a new metrology approach that combines image segmentation and edge detection to measure 2D pattern with arbitrary rearrangement. The segmentation approach enabled to quantify the quality of the BCP material and process, detecting 2D attributes such as: CD and CDU at one axis, and number of intersections, length and number of PS fragments, etched PMMA spaces and donut shapes numbers on the second axis. In this paper we propose a 2D metrology to measure arbitrary BCP pattern on a free surface wafer. We demonstrate experimental results demonstrating precision data, and characterization of PS-b-PMMA BCP, intrinsic period L 0 = 38nm (Arkema), processed at different bake time and temperatures.

For sub-10nm technologies, the semiconductor industry is facing the limits of conventional lithography to achieve narrow dimensions. DSA (Directed Self-Assembly) of Block Copolymers (BCP) is one of the most promising solutions to reach sub-10nm patterns with a high density. One challenge for DSA integration is the removal of PMMA selectively to PS. In this paper, we propose to study PMMA removal selectively to PS by screening different plasma etch chemistries. These chemistries developed on blanket wafers have been tested on cylindrical and lamellar patterned wafers.

In this paper, we focus on the directed-self-assembly (DSA) application for contact hole (CH) patterning using polystyrene-b-poly(methyl methacrylate) (PS-b-PMMA) block copolymers (BCPs). By employing the DSA planarization process, we highlight the DSA advantages for CH shrink, repair and multiplication which are extremely needed to push forward the limits of currently used lithography. Meanwhile, we overcome the issue of pattern densityrelated- defects that are encountered with the commonly-used graphoepitaxy process flow. Our study also aims to evaluate DSA performances as function of material properties and process conditions by monitoring main key manufacturing process parameters: CD uniformity (CDU), placement error (PE) and defectivity (Hole Open Yield = HOY). Concerning process, it is shown that the control of surface affinity and the optimization of self-assembly annealing conditions enable to significantly enhance CDU and PE. Regarding materials properties, we show that the best BCP composition for CH patterning should be set at 70/30 of PS/PMMA total weight ratio. Moreover, it is found that increasing the PS homopolymer content from 0.2% to 1% has no impact on DSA performances. Using a C35 BCP (cylinder-forming BCP of natural period L0 = 35nm), high DSA performances are achieved: CDU-3σ = 1.2nm, PE-3σ = 1.2nm and HOY = 100%. The stability of DSA process is also demonstrated through the process follow-up on both patterned and unpatterned surfaces over several weeks. Finally, simulation results, using a phase field model based on Ohta-Kawasaki energy functional are presented and discussed with regards to experiments.

Directed Self-Assembly (DSA) of Block Copolymers (BCP) is one of the most promising solutions for sub-10 nm nodes. However, some challenges need to be addressed for a complete adoption of DSA in manufacturing such as achieving DSA-friendly design, low defectivity and accurate pattern placement. In this paper, we propose to discuss the DSA integration flows using graphoepitaxy for contact-hole patterning application. DSA process dependence on guiding pattern density has been studied and solved thanks to a new approach called “DSA planarization”. The capabilities of this new approach have been evaluated in terms of defectivity, Critical Dimension (CD) control and uniformity before and after DSA etching transfer.

There has been significant research in the area of modeling self-assembling molecular systems. Directed self-assembly (DSA) has proven to be a promising candidate for cost reduction of processes which use double patterning and an enabler of new technology nodes. Self-consistent field theory and Monte Carlo simulators have the capability to probe and explore the mechanisms driving the different phases of a diblock copolymer system. While such methods are appropriate to study the nature of the self-assembly process, they are computationally expensive and they cannot be used to perform mask synthesis operations nor full chip verification. In this case we focus our effort in establishing the minimum set of conditions that a compact model for the manufacture of contact holes using a grapho epitaxy process for a PS-b-PMMA diblock copolymer system needs. The compact model’s main objectives are to find the guiding pattern that produces the lowest possible placement error, as well as verifying that the intended target structures are present after processing. Given that masks are not perfect, and lithographic process variations are not negligible, it is necessary to understand the mask requirements and the types of Optical Proximity Correction techniques that will be used to build guiding patterns. This paper explores the guiding pattern conditions under which proper assembly is achieved, and how the compact model formulation is able to determine placement of reliably assembling structures as well as identification of the guiding patterns which lead to improper assembly. The research leading to these results has been performed in the frame of the industrial collaborative consortium IDeAL focused on the development of Directed Self-assembly technique by block copolymers.

Ordered microstructures with nanometrically defined periodicity offer promising opportunities in microelectronic applications for the production of advanced CMOS digital logic circuits. To produce the features and arrays inherent to such technologies, the combination of the “bottom-up” block copolymer self-assembly with “top-down” guiding templates has been successfully introduced leading to new technological breakthroughs. Among the materials used in the direct self-assembly methodology, poly(styrene-b-methylmethacrylate) systems have reached an unprecedented level of maturity which will lead to their introduction into the next technological nodes. However, this system suffers from deficiencies such as a low Flory Huggins parameter (X = 0.04 at 25°C) and a low chemical contrast as regards to the etching processes which could be problematic for targeting sub-22 nm features. Consequently we have developed new systems based on Si-containing block copolymers which are characterized by high segregation strength as well as strong chemical etching contrast. In this contribution, we focus on a poly(lactic acid) / poly(dimethylsiloxane) system exhibiting a cylindrical mesostructure. By controlling the surface energy at the interface between the substrate and the block copolymer domains, we show the possibility to control the orientation of the mesostructure with a methodology comparable to the one used for poly(styrene) / poly(methyl methacrylate) system but with random copolymers having distinct monomers than the block copolymers.

Contact hole (CH) patterning by directed-self-assembly (DSA) of polystyrene-b-polymethylmethacrylate (PS-b-PMMA) block copolymers (BCPs) is extensively studied in this paper. Based on statistical analysis performed on 300mm wafers, a process window (PW) for CH shrink is experimentally evaluated in terms of hole open yield and critical dimension (CD) variation after DSA as a function of BCPs of different natural periods and guiding patterns of different dimensions. The PW allowed us to define the suitable BCP molecular weight with the best guiding CD ranges required to achieve a desired DSA hole CD within a specific tolerance. As example, for a DSA hole CD targeted at 19.5 nm with 10% tolerance, circular guiding patterns of 52 nm CD with 20% guiding CD latitude are needed using a 35nm-natural-period BCP. It is also shown that the CH shrink PW is dependent on guiding pattern pitch and on DSA process conditions such as the self-assembly annealing and spin coating conditions. In addition, the study highlights an interesting property of commensurability between guiding pattern dimensions and BCP’s natural period that governs the CH patterning by DSA for both CH shrink and CH doubling configurations. This permits to predict the guiding pattern dimensions needed for CH patterning by DSA using a given BCP of known natural period.

Careful control and reproducibility of BCP’s synthesis are mandatory parameters to push-down PS-b-PMMA block-copolymer systems toward its lowest dimensions for microelectronic applications. The self-assembly process optimization of different high-resolution cylindrical PS-b-PMMA block-copolymers (i.e. L0 period below 25 nm) is studied to highlight processes-variations as regard to more classical PS-b-PMMA systems while the characterizations of bulk materials provide deeper insights on the parameters addressing the self-assembly of such materials. The integration of a high-resolution BCP on 300 mm track is then studied to check the capabilities of such materials in terms of lithographic applications. CD uniformity measurements in contact hole shrink approach, as well as the transfer of the BCP mask into typical industrial under-layer stacks leading to aggressive features, show that these materials exhibit promising potentials for advanced lithographic nodes.

T his paper reports on the etch challenges to overcome for the implementation of PS -b-PMMA block c oSRO\PHU¶VDirected Self -Assembly (DSA ) in CMOS via patterning level . Our process is based on a graphoepitaxy approach , employing an industrial PS -b-PMMA block copolymer (BCP) from Arkema with a cylindrical morphology . The process consists in the following step s: a) DSA of block copolymers inside guiding patterns, b) PMMA remov al, c) brush layer opening and finally d ) PS pattern transfer into typical MEOL or BEOL stacks . All results presented here KDYHEHHQSHUIRUPHGRQWKH'6$/HWL¶V PPSLORWOLQH The f irst etch challenge to overcome for BCP transfer involves in removing all PMMA selectively to PS block . In our process baseline, a n acetic acid treatment is carried out to develop PMMA domains . However, this wet development has shown some limitations in te rms of resists compatibility and will not be appropriated for lamellar BCP s. That is why we also investigate the possibility to remove PMMA by only dry etching . In this work the potential of a dry PMMA removal by using CO based chemistries is shown and com pared to wet development . The advantages and limitations of each approach are reported . The second crucial step is the etching of brush layer (PS -r-PMMA ) through a PS mask . We have optimize d this step in order to preserve the PS patterns in terms of CD , holes features and film thickness. Several integrations flow with complex stacks are explored for contact shrink ing by DSA. A study of CD uniformity has been addressed to evaluate the capabilities of DSA approach after graphoepitaxy and after etching . Keyw ords: block copolymer, PS -b-PMMA, contact -hole shrink, PMMA removal, CMOS integration , etching

For 11nm and below, several alternatives are still potential candidates to meet the patterning requirements. Spacer patterning, Mask Less Lithography (i.e. Electron beam lithography) and Direct Self Assembly are alternatives under development at CEA-LETI. We have demonstrated the integration of these alternative techniques in front end of line and back end of line levels. Common challenges such as minimum achievable CD, CD control through the integration steps, mask budget and LWR were compared for these techniques.

Directed Self-Assembly (DSA) is today a credible alternative lithographic technology for semiconductor industry [1]. In the coming years, DSA integration could be a standard complementary step with other lithographic techniques (193nm immersion, e-beam, extreme ultraviolet). Its main advantages are a high pattern resolution (down to 10nm), a capability to decrease an initial pattern edge roughness [2], an absorption of pattern guide size variation, no requirement of a high-resolution mask and can use standard fab-equipment (tracks and etch tools). The potential of DSA must next be confirmed viable for high volume manufacturing. Developments are necessary to transfer this technology on 300mm wafers in order to demonstrate semiconductor fab-compatibility [3-7]. The challenges concern especially the stability, both uniformity and defectivity, of the entire process, including tools and Blok Co-Polymer (BCP) materials. To investigate the DSA process stability, a 300mm pilot line with DSA dedicated track (SOKUDO DUO) is used at CEALeti. BCP morphologies with PMMA cylinders in a PS matrix are investigated (about 35nm natural period). BCP selfassembly in unpatterned surface and patterned surface (graphoepitaxy) configurations are considered in this study. Unpatterned configuration will initially be used for process optimization and fix a process of record. Secondly, this process of record will be monitored with a follow-up in order to validate its stability. Steps optimization will be applied to patterned surface configurations (graphoepitaxy) for contact hole patterning application. A process window of contact hole shrink process will be defined. Process stability (CD uniformity and defectivity related to BCP lithography) will be investigated.

Chemically Amplified resists are complex systems. If the main mechanisms implied have already been described, the challenge to even better control and model these formulations remains important as performance requirements become more and more stringent and critical dimensions get smaller and smaller. This paper tries to assess and deconvolute some of the main potential mechanisms involved during the process of a 193 nm chemically amplified resist, before correlating them with the final lithographic results obtained. A formulation was selected in order to offer a large range of film physical properties, thus allowing the resist film to switch from non-annealing to annealing conditions. The use of thermal analysis as the main characterization technique allowed correlation between the variations in physico-chemical properties and process conditions. This investigation also included a study of the behavior of some additives during bake steps. In so doing, it became possible to correlate the variations of the resist properties under different bake conditions to the changes in its final lithographic performance, i.e. contrast, sensitivity and line edge roughness.

A methodology was developed in order to characterize the deprotection mechanisms implied in 193nm chemically amplified (CA) resists. This method is based on resist outgassing measurements as a function of exposure dose and bake temperature using Thermal Desorption-Gas Chromatography - Mass Spectrometry / Flame Ionization Detector (TDGCMS/ FID) technique. This approach allows both quantitative and qualitative studies of the outgassing behaviour and was validated from a 193nm model resist representative of CA formulations. In so doing, the identification of outgassed by-products respectively coming from the PAG, from the polymer as well as from the solvent is made possible. In parallel, quantitative results as a function of exposure dose and temperature allowed us to monitor the deprotection process and the solvent evaporation. The quantitative results obtained by this technique were in good agreement with Thermo-Gravimetric Analysis (TGA) results. Such a methodology can be used not only to characterise 193nm resist outgassing during exposure, but also be extended to monitor resist behaviour during implant, thermal treatment, e-beam exposure.

In this paper we investigate an in situ measurement of polymer and lithographic resist film mechanical properties on a silicon substrate, with a Dynamical Mechanical Analysis tool (DMA). This technique allows the measure of the glass transition temperature (Tg) of the resist film (thickness range: several μm to few nm) and its elastic and viscous modulus variations with a high precision and reproducibility. Indeed, DMA appears to be more sensitive than other thermal analysis methods like Differential Scanning Calorimetry (DSC), to monitor Tg variations induced by film thickness reduction. First we will discuss the performance of the tool and present the variations of the glass transition temperature of a PMMA (PolyMethylMethAcrylate) layer as a function of its thickness: we observe a shift towards higher temperatures up to 30°C when the film thickness decreases from one micrometer to 10nm. This behavior highlights the importance of surface properties versus bulk. We will also discuss the interest of the DMA technique applied to more complex chemistries, as it is the case for lithographic resist formulations, i.e. a blend of polymer with grafted functionalities, photoactive compounds and various additives. We successfully applied this technique to characterize different resist film thicknesses and we observed the effect of the thickness on the thermal events. Such kind of change is important to take into account in the optimization of material performance for thin film applications. This material understanding allows to better define the process conditions and can be applied to different microelectronic topics such as: thermal flow treatment of positive tone photo resists, hot-embossing nanoimprint, cross linking reactions with negative tone resists or so called "hardening" processes.

In this paper, we investigate the capabilities to form small contact holes with various 193nm resists applying a thermal flow process. We first compare the material properties (glass transition temperature Tg and thermal deprotection T D ) of different 193nm resists to our reference process for thermal reflow, namely the 248nm reference resist (RoR). The main difficulty related to 193nm acrylate backbone is the high Tg value, which implies some flow bake temperature closed to or superior to the deprotection temperature. Depending on the resist chemistry, different behaviours have been observed such as acceleration of the flow rate, formation of bubble defects linked to gaseous by-products or even contact hole diameter increase. These results are strongly dependent on the chemical reactions occurring in the resist film at the same time as the film softening. In order to better select the most promising 193nm resist candidates for contact hole reflow technique, we also develop a polymer flow measurement with Dynamic Mechanical Analysis (DMA). By measuring the creep compliance of the resist film spin-coated onto a silicon wafer under various bake temperatures, we are able to define the optimal temperature range for resist flow.

Microlenses arrays are commonly used in CMOS images sensors to focus the incident light onto the photosensitive area of the pixel. These microlenses are fabricated using a thermal reflow method. Currently, due to the fast evolution of CMOS Imager technology, the understanding of the mechanisms involved in microlens formation becomes essential to better control what occurs during the process. We have seen in a previous study that the complexity of the reflow method comes from the competition between two phenomena occurring during the melt bake step: on one hand the surface tension tends to push the resist patterns into a spherical shape, on the other hand the resist crosslinking reaction drastically increases the resist viscosity hindering the microlens formation. In this paper the influence of resist crosslinking, resist volume and resist/substrate interface on the final shape of the microlens has been investigated. It appears that the contact angle between microlens and substrate varies depending on substrate wettability but is the same whatever the resist volume for a given substrate/resist combination. The microlens shape depends also significantly on bake temperature and crosslinking kinetics. In fact the right tuning of process conditions seems to be the key parameter in the control of the final microlens shape because it enables to adjust the kinetics of each mechanism and thus favour the microlens formation with regards to resist crosslinking.