William J. Durand

Polarity-Switching Top Coats Enable Orientation of Sub–10-nm Block Copolymer Domains

Thermally Transforming Thin Films Nanoscale features can be created by the phase separation that occurs in block copolymers that join together polymer segments with different wetting properties. For applications such as lithography, it is useful to generate small features and to orient them through simple processing steps. Top-layer coatings should be able to help drive alignment, but it is difficult to coat a layer that also has strong enough interactions to influence assembly. Bates et al. (p. 775) developed a water-soluble polymer that can top-coat lamellaforming block copolymers and that transforms during thermal annealing into a neutral wetting layer that helps drive the formation of vertically oriented lamellae. A chemical reaction in a thin polymer film imposes orientational ordering of lamellar domains in an underlying film. Block copolymers (BCPs) must necessarily have high interaction parameters (χ), a fundamental measure of block incompatibility, to self-assemble into sub–10-nanometer features. Unfortunately, a high χ often results from blocks that have disparate interfacial energies, which makes the formation of useful thin-film domain orientations challenging. To mitigate interfacial forces, polymers composed of maleic anhydride and two other components have been designed as top coats that can be spin-coated from basic aqueous solution in the ring-opened, acid salt form. When baked, the anhydride reforms and switches polarity to create a neutral layer enabling BCP feature alignment not possible by thermal annealing alone. Top coats were applied to the lamella-forming block copolymers poly(styrene-block-trimethylsilylstyrene-block-styrene) and poly(trimethylsilylstyrene-block-lactide), which were thermally annealed to produce perpendicular features with linewidths of 15 and 9 nanometers, respectively.

Directed Self-Assembly of Silicon-Containing Block Copolymer Thin Films

The directed self-assembly (DSA) of lamella-forming poly(styrene-block-trimethylsilylstyrene) (PS-PTMSS, L0=22 nm) was achieved using a combination of tailored top interfaces and lithographically defined patterned substrates. Chemo- and grapho-epitaxy, using hydrogen silsesquioxane (HSQ) based prepatterns, achieved density multiplications up to 6× and trench space subdivisions up to 7×, respectively. These results establish the compatibility of DSA techniques with a high etch contrast, Si-containing BCP that requires a top coat neutral layer to enable orientation.

Interactions between plasma and block copolymers used in directed self-assembly patterning

The directed self-assembly (DSA) of block copolymers offers a promising route for scaling feature sizes below 20 nm. At these small dimensions, plasmas are often used to define the initial patterns. It is imperative to understand how plasmas interact with each block in order to design processes with sufficient etch contrast and pattern fidelity. Symmetric lamella forming block copolymers including, polystyrene-b-poly(methyl methacrylate) and several high-χ silicon-containing and tin-containing block copolymers were synthesized, along with homopolymers of each block, and exposed to various oxidizing, reducing, and fluorine-based plasma processes. Etch rate kinetics were measured, and plasma modifications of the materials were characterized using XPS, AES, and FTIR. Mechanisms for achieving etch contrast were elucidated and were highly dependent on the block copolymer architecture. For several of the polymers, plasma photoemissions were observed to play an important role in modifying the materials and forming etch-resistant protective layers. Furthermore, it was observed for the silicon- and tin-containing polymers that an initial transient state exists, where the polymers exhibit an enhanced etch rate, prior to the formation of the etch-resistant protective layer. Plasma developed patterns were demonstrated for the differing block copolymer materials with feature sizes ranging from 20 nm down to approximately 5 nm.

High chi block copolymer DSA to improve pattern quality for FinFET device fabrication

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.

Directed self assembly of block copolymers using chemical patterns with sidewall guiding lines, backfilled with random copolymer brushes

Recently, alignment of block copolymer domains has been achieved using a topographically patterned substrate with a sidewall preferential to one of the blocks. This strategy has been suggested as an option to overcome the patterning resolution challenges facing chemoepitaxy strategies, which utilize chemical stripes with a width of about half the period of block copolymer to orient the equilibrium morphologies. In this work, single chain in mean field simulation methodology was used to study the self assembly of symmetric block copolymers on topographically patterned substrates with sidewall interactions. Random copolymer brushes grafted to the background region (space between patterns) were modeled explicitly. The effects of changes in pattern width, film thicknesses and strength of sidewall interaction on the resulting morphologies were examined and the conditions which led to perpendicular morphologies required for lithographic applications were identified. A number of density multiplication schemes were studied in order to gauge the efficiency with which the sidewall pattern can guide the self assembly of block copolymers. The results indicate that such a patterning technique can potentially utilize pattern widths of the order of one-two times the period of block copolymer and still be able to guide ordering of the block copolymer domains up to 8X density multiplication.

Plasma and photon interactions with organosilicon polymers for directed self-assembly patterning applications

Silicon (Si)-containing block copolymers (BCPs) are promising candidates for directed self-assembly patterning applications and are able to access structures with critical dimensions less than 10 nm. Significant etch contrast between the blocks is required to integrate BCPs for patterning applications and form an initial topographical mask. For Si-containing BCPs, O2 plasma exposure can give high etch contrast between the blocks by forming a thin etch resistant silicon oxide (SiOx) surface layer from the Si-containing block. The authors have also found that H2 and N2/H2 plasmas can form etch resistant barrier layers from organosilicon polymers (OSPs). Photodegradation of the OSPs induced by H2 plasma-generated vacuum ultraviolet (VUV) photons initiates the formation of this etch barrier layer. Fourier transform infrared transmission spectroscopy measurements show enhanced VUV-induced degradation in polymers with higher Si content due to cleavage of the methylsilyl bonds (Si-CH3) and subsequent carbon depl...

Plasma etch of block copolymers for lithography

To date, the semiconductor manufacturing industry has relied on optical lithography to enable the scaling of devices to ever smaller dimensions. Developers use extreme UV lithography to print very small features, but this technology has suffered numerous technical delays and is still not feasible for highvolume manufacturing. The industry is therefore pursuing new schemes, such as multiple patterning, that are intended to improve 193nm immersion lithography (the technique that uses a liquid with a relatively high refractive index to enhance resolution). These approaches have enabled successful fabrication of features smaller than the resolution limit of the 193nm immersion tools. However, their drawbacks are increased process complexities and higher costs. One potentially lower-cost alternative for generating smaller structures is the directed self-assembly (DSA) of block copolymers (BCPs),1, 2 where a BCP is deposited and aligned and one block is removed to form a pattern. There has been tremendous progress in advancing DSA patterning, yet significant hurdles remain to its commercial adoption. These include the need to reduce patterning defects and to integrate these materials into robust patterning schemes. The BCPs need to show resistance to the reactive ion etch (RIE) plasmas that are used to pattern the underlying materials. Furthermore, at such small dimensions, the initial pattern is often created using a dry RIE plasma (rather than a wet process in order to prevent collapse of the mask from capillary forces during drying). Therefore, it is necessary to have high etch contrast between the individual blocks of the BCP, and because welloriented BCP film thicknesses are typically less than 50nm. Figure 1. Scanning electron microscope (SEM) image of a crosssection of self-assembled poly(styrene-block-methyl methacrylate) (PSb-PMMA) with 21nm domains prior to PMMA removal (a) and post reactive ion etch (RIE) removal of PMMA domains (b). Minimal mask loss of polystyrene was observed.

Self-aligned patterning on a flexible substrate using a dual-tone, thermally activated photoresist

The fabrication of electronic devices on flexible substrates represents an opportunity for the development of flexible display technologies, large area devices, and roll-to-roll manufacturing processes. Traditional photolithography encounters alignment and overlay limitations when applied to flexible substrates. One solution to the overlay challenges is imaging of two device layers in a single lithographic exposure. To enable the simultaneous patterning of two device layers, a new photoresist system was developed. Prior work on dual-tone photoresists introduced formulations capable of storing two independent images, but the reported systems are incompatible with the reactive ion etch processes commonly used today. This paper describes a dual-tone photoresist system that maintains the ability to store two independent latent images, distinguished by the incident exposure light wavelength, simultaneously remaining compatible with reactive ion etch image transfer processes.

Fundamental study of optical threshold layer approach towards double exposure lithography

193 immersion lithography has reached its maximal achievable resolution. There are mainly two lithographic strategies that will enable continued increase in resolution. Those are being pursued in parallel. The first is extreme ultraviolet (EUV) lithography and the second is double patterning (exposure) lithography. EUV lithography is counted on to be available in 2013 time frame for 22 nm node. Unfortunately, this technology has suffered several delays due to fundamental problems with source power, mask infrastructure, metrology and overall reliability. The implementation of EUV lithography in the next five years is unlikely due to economic factors. Double patterning lithography (DPL) is a technology that has been implemented by the industry and has already shown the proof of concept for the 22nm node. This technique while expensive is the only current path forward for scaling with no fundamental showstoppers for the 32nm and 22nm nodes. Double exposure lithography (DEL) is being proposed as a cost mitigating approach to advanced lithography. Compared to DPL, DEL offers advantages in overlay and process time, thus reducing the cost-of-ownership (CoO). However, DEL requires new materials that have a non-linear photoresponse. So far, several approaches were proposed for double exposure lithography, from which Optical Threshold Layer (OTL) was found to give the best lithography performance according to the results of the simulation. This paper details the principle of the OTL approach. A photochromic polymer was designed and synthesized. The feasibility of the material for application of DEL was explored by a series of evaluations.