We have developed strongly-segregating chemically tailored block copolymers (BCPs), a series of post-functionalized polystyrene-b-polymethacrylates that can form sub-10 nm perpendicular lamellae on thin films by thermal annealing. The desired BCPs successfully synthesized by thiol-epoxy reaction of poly(glycidyl methacrylate)s, a partial component of polystyrene-b-polymethacrylates, with trifluoroethane thiol. Microdomains in the obtained BCP thin films were vertically oriented by tuning the Neutral Layer, and highly aligned and distinct vertical lamellae with L0=15.1 nm were successfully obtained on the guide pattern substrate for DSA.
We have developed strongly-segregating chemically tailored block copolymers (BCPs), a series of post-functionalized polystyrene-b-polymethacrylates capable of forming sub-10 nm perpendicular lamellae on thin films with ease by thermal annealing. The desired block copolymers based on polystyrene-b-polymethacrylates were successfully synthesized by the post-functionalization of poly(glycidyl methacrylate)s and thiol derivatives via thiol-epoxy reaction. To work towards clarifying the essential key to the perpendicular orientation of microdomains, we studied the correlation between the primary structures based on the new concept of molecular design and microphase-separated nanostructures in bulk and thin films.
KEYWORDS: Carbon, Silicon, Etching, Polymers, System on a chip, Scanning electron microscopy, Silicon carbide, Oxides, Reactive ion etching, Optical lithography
For self-aligned multiple patterning, higher etch selectivity between mandrel and spacer is desired to lessen roughness, and thereby prevent pitch walk. We selected dual carbon layers as mandrels and silicon oxide films as spacers for a new self-aligned quadruple patterning process since they potentially provide infinite etch selectivity. We gained insolubility and etch selectivity between two carbon layers by infiltrating trimethylsilyldimethylamine into one of the carbon layers under the ambient atmosphere. Significantly, neither necking nor recess were observed when the spin-on-glass antireflective coating was removed. Thus, a SAQP scheme was developed and successfully demonstrated a sub15-nm halfpitch pattern. Additionally, this scheme improves affordability since all the processes can be performed in the ambient pressure within a coater module.
Directed self-assembly (DSA) of block copolymers (BCPs) with conventional lithography is being thought as one of the potential patterning solution for future generation devices manufacturing. New BCP platform is required to obtain resolution below 10nm half pitch (HP), better roughness, and defect characteristics than PS-b-PMMA. In this study, we will introduce the newly developed Si-containing high chi BCP which can apply perpendicular lamellar orientation with topcoat free, mild thermal annealing under nitrogen process conditions. It will be also shown in experimental results of graphoepitaxy demonstration for L/S multiplication using new high chi BCP.
Directed self-assembly (DSA) of block copolymers (BCPs) is one of candidate for next generation patterning technique. Many good demonstrations of DSA have been reported using polystyrene-block-poly(methyl methacrylate) (PS-b- PMMA) these days. On the other hands, BCPs which show high chi parameter are being developed because the BCPs can be formed smaller features than PS-b-PMMA. Si-containing BCPs are one of them. Moreover Si-containing BCPs show higher etch selectivity than PS-b-PMMA because of higher etch resistance of Si-containing block. Unfortunately, while Si-containing BCPs can be aligned by solvent annealing, they but cannot be aligned perpendicular to the substrate by thermal annealing. Because Si-containing block which has low surface energy achieves maximum interaction with air interface by forming a top parallel wetting layer to the substrate. One solution to control of surface energy on top surface is the use of Top-Coat (TC). It has been already demonstrated that TC with Si-containing BCP could form perpendicular pattern. The challenges are TC coating onto BCP film and TC stripping after annealing. In order to solve these problems, polarity-changeable type TC has been developed. The effect of TC materials to generate finger print of BCP has been reported. However, this TC process should combine with DSA process to form aligned patterns. Graphoepitaxy is one of the DSA technique to align BCP pattern using guide pattern. In this technique, the characteristic of guide pattern side wall is very important to control BCP pattern alignment for the Graphoepitaxy process. Also, in order to establish the process, there are two key parameters for the materials. One is BCP and guide pattern should have enough resistance to TC solvent through TC coating process. The other is TC can be removed easily with basic aqueous solution before BCP patterning. In this report, a detail of examination for TC Graphoepitaxy process will be discussed.
Pitch division lithography (PDL) with a photobase generator (PBG) allows printing of grating images with twice
the pitch of a mask. The proof-of-concept has been published in the previous paper and demonstrated by
others. Forty five nm half-pitch (HP) patterns were produced using a 90nm HP mask, but the image had line
edge roughness (LER) that does not meet requirements. Efforts have been made to understand and improve the
LER in this process. Challenges were summarized toward low LER and good performing pitch division.
Simulations and analysis showed the necessity for an optical image that is uniform in the z direction in order for
pitch division to be successful. Two-stage PBGs were designed for enhancement of resist chemical contrast. New
pitch division resists with polymer-bound PAGs and PBGs, and various PBGs were tested. This paper focuses on
analysis of the LER problems and efforts to improve patterning performance in pitch division lithography.
In current optical lithography, resolution is required to reach for 45 nm half-pitch and a chemically amplified resist
(CAR) is used for a wide variety of applications. For ArF lithography beyond the 45 nm half-pitch, it is important to
control pattern quality. The molecular design of a photo acid generator (PAG) is very important in the study to
control not only acid strength but also acid diffusion length. Various novel PAGs that have different characteristics
were synthesized for resist performance improvement. Acid molecular size was determined by molecular orbital
(MO) calculation, and the acid diffusion coefficients (D) of these PAGs were evaluated by a bilayer method. As a
result, it was found that acid diffusion coefficient (D) could not be controlled simply by adjusting anion molecular size.
It may be presumed that the molecular interaction between acid generated by the exposure and polymer matrix areas is
one of the most important key factors for controlling acid diffusion.
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