Celia Nicolet

Optimization of the Bulk Heterojunction Composition for Enhanced Photovoltaic Properties: Correlation between the Molecular Weight of the Semiconducting Polymer and Device Performance

Herein we propose an approach toward the optimization of the photovoltaic performance of bulk heterojunctions by tuning the composition of the active layer with respect to the molecular weight of the semiconducting polymer. We used a poly(3-hexylthiophene):[6,6]-phenyl-C61-butyric acid methyl ester (P3HT:PCBM) blend as a typical system and varied the molecular weight of the P3HT semiconducting polymer in order to determine its influence on the bulk heterojunction morphology as well as on the optoelectronic characteristics of the device. We have systematically mapped out the phase diagram for different molecular weight P3HTs blended with PCBM and observed the presence of a eutectic composition, which shifts to higher content of P3HT for lower molecular weight P3HTs. This shift inherent to the P3HT molecular weight is also apparent in the photovoltaic performance as the eutectic composition corresponds to the best of the photovoltaic properties. The P3HT molecular weight dependence of the eutectic composition is due to the molecular weight dependence of the P3HT crystallization behavior, which leads to dramatic morphological changes of the bulk heterojunction.

Scaling-down lithographic dimensions with block-copolymer materials: 10-nm-sized features with poly(styrene)-block-poly(methylmethacrylate)

Abstract. Poly(styrene)-block-poly(methylmethacrylate) (PS-b-PMMA) block-copolymers (BCP) systems synthesized on an industrial scale and satisfying microelectronic’s requirements for metallic contents specifications are studied in terms of integration capabilities for lithographic applications. We demonstrate in particular that this kind of polymer can efficiently achieve periodic features close to 10 nm. These thin films can be transferred in various substrates through dry-etching techniques. The self-assembly optimization for each polymer is first performed on freesurface, leading to interesting properties, and the changes in self-assembly rules for low molecular-weight polymers are investigated and highlighted through different graphoepitaxy approaches. The improvements in self-assembly capabilities toward low periodic polymers, as well as the broad range of achievable feature sizes, make the PS-b-PMMA system very attractive for lithographic CMOS applications. We conclude by showing that high-χ polymer materials developed in Arkema’s laboratories can be efficiently used to reduce the pattern’s size beyond the ones of PS-b-PMMA based BCP’s capabilities.

Assessing the Local Nanomechanical Properties of Self-Assembled Block Copolymer Thin Films by Peak Force Tapping

The mechanical properties of several types of block copolymer (BCP) thin films have been investigated using PeakForce quantitative nanomechanical mapping. The samples consisted of polystyrene/poly(methylmethacrylate) (PS/PMMA)-based BCP thin films with different pitches both randomly oriented and self-assembled. The measured films have a critical thickness below 50 nm and present features to be resolved of less than 22 nm. Beyond measuring and discriminate surface elastic modulus and adhesion forces of the different phases, we tuned the peak force parameters in order to reliably image those samples, avoiding plastic deformation. The method is able to detect the changes in mechanical response associated with the orientation of the PMMA cylinders with respect to the substrate (parallel versus vertical). The nanomechanical investigation is also capable of recognizing local stiffening due to the preferential growth of alumina deposited by atomic layer deposition on BCP samples, opening up new possibilities in the field of hard mask materials characterization.

Etch challenges for DSA implementation in CMOS via patterning

This paper reports on the etch challenges to overcome for the implementation of PS-b-PMMA block copolymer’s Directed 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 steps: a) DSA of block copolymers inside guiding patterns, b) PMMA removal, c) brush layer opening and finally d) PS pattern transfer into typical MEOL or BEOL stacks. All results presented here have been performed on the DSA Leti’s 300mm pilot line. The first etch challenge to overcome for BCP transfer involves in removing all PMMA selectively to PS block. In our process baseline, an acetic acid treatment is carried out to develop PMMA domains. However, this wet development has shown some limitations in terms of resists compatibility and will not be appropriated for lamellar BCPs. 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 compared 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 optimized 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 shrinking by DSA. A study of CD uniformity has been addressed to evaluate the capabilities of DSA approach after graphoepitaxy and after etching.

Improvements of self-assembly properties via homopolymer addition or block-copolymer blends

The properties of cylindrical poly(styrene-b-methylmethacrylate) (PS-b-PMMA) BCPs self-assembly in thinfilms are studied when the pure BCPs are blended either with a homopolymer or with another cylindrical PS-b-PMMA based BCP. For both of these approaches, we show that the period of the self-assembled features can be easily tuned and controlled, and that the final material presents interesting characteristics, such as the possibility to achieve thicker defects-free films, as compared to pure block-copolymers having the same period. Moreover, a statistical defectivity study based on a Delaunay triangulation and Voronoi analysis of the self-assemblies made with the different blends is described, and prove that despite their high value of polydispersity index, these blends exhibit also improved selfassembly properties (bigger monocrystalline arrangements and enhanced kinetics of defects annihilation) as compared to pure and monodisperse block-copolymers. Finally, the behavior of the blends is also compared to the ones their pure counter-part in templated approach like the contact-hole shrink to evaluate their respective process-window and response toward this physical constrain for lithographic applications.

Contact holes patterning by directed self-assembly of block copolymers: process window study

Abstract. Contact hole (CH) patterning by directed self-assembly (DSA) of polystyrene-b-polymethylmethacrylate (PS-b-PMMA) block copolymers (BCPs) is extensively studied. Based on statistical analysis of defectivity and CD measurements after DSA, a process window (PW) for CH shrink is experimentally determined as a function of guiding pattern dimensions and BCP molecular weights corresponding to BCP natural periods. This PW permits to define the suitable BCP molecular weight and the best guiding CD ranges required to achieve a desired DSA hole CD within a specific tolerance. As an 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 35-nm-natural-period cylindrical BCP. Furthermore, it is shown that the CH shrink PW is also dependent on the guiding pattern density and the DSA process conditions such as the self-assembly annealing and the spin coating conditions. The study also highlights an interesting property of commensurability between guiding pattern dimensions and BCP’s natural period that governs the DSA CH patterning for both CH shrink and CH doubling configurations. This permits one to predict the guiding pattern dimensions needed for CH patterning by DSA using a given BCP of known natural period.

Process highlights to enhance directed self-assembly contact patterning performances

Abstract. We focus on the directed self-assembly (DSA) for contact hole (CH) patterning application 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 density-related defects that are encountered with the commonly used graphoepitaxy process flow. Our study also aims to evaluate the DSA performances as functions 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 significant enhancement of CDU and PE. Regarding material 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=35  nm), good DSA performances are achieved: CDU-3σ=1.2  nm, PE-3σ=1.2  nm, and HOY=100%. Finally, the stability of DSA process is also demonstrated through the process follow-up on both patterned and unpatterned surfaces over several weeks.

DSA planarization approach to solve pattern density issue

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.

Contact holes patterning by Directed Self-Assembly of block copolymers: what would be the Bossung plot?

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.

Self-assembly of high-resolutions PS-b-PMMA block-copolymers: processes capabilities and integration on 300mm track

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.