Achieving structural control with thin polystyrene-b-polydimethylsiloxane block copolymer films: The complex relationship of interface chemistry, annealing methodology and process conditions

O'Driscoll, Benjamin M. D.; Kelly, Róisín A.; Shaw, Matthew T.; Mokarian‐Tabari, Parvaneh; Liontos, George; Ντέτσικας, Κωνσταντίνος; Avgeropoulos, Apostolos; Petkov, Nikolay; Morris, Michael A.

doi:10.1016/j.eurpolymj.2013.07.022

Cited by 29 publications

(29 citation statements)

References 32 publications

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“…3a displays large scale coverage of the Fe 3 O 4 nanowires and the TEM inset shows a slightly elliptical structure that may reflect the elliptical form of the cylinders noted before. 34 The inset also shows that what may be a small amount of Fe 3 O 4 material resides across the polymer substrate interface. This might result from a thin PVP wetting layer (as P4VP has a higher affinity to the hydrophilic native oxide layer) 33 in the self-assembled PS-b-P4VP structure.…”

Section: Resultsmentioning

confidence: 95%

“…It should be noted that we have observed that the ideal cylinder structure is compressed in thin films and this somewhat lower value might represent the true ideal thickness. 34 The relatively small increase in film thickness (~ 15%) under SVA is probably due to the limited swelling of the BCP film during annealing as chloroform is a nonselective solvent for pure PS-b-P4VP. 33 Solubility parameters for chloroform, PS and P4VP are 19.0, 18.6 and ~23 MPa 1/2 respectively.…”

Section: Resultsmentioning

confidence: 99%

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Aligned silicon nanofins via the directed self-assembly of PS-b-P4VP block copolymer and metal oxide enhanced pattern transfer

et al. 2015

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'Directing' block copolymer (BCP) patterns is a possible option for future semiconductor device patterning, but pattern transfer of BCP masks is somewhat hindered by the inherently low etch contrast between blocks. Here, we demonstrate a 'fab' friendly methodology for forming well-registered and aligned silicon (Si) nanofins following pattern transfer of robust metal oxide nanowire masks through the directed self-assembly (DSA) of BCPs. A cylindrical forming poly(styrene)-block-poly(4-vinyl-pyridine) (PS-b-P4VP) BCP was employed producing 'fingerprint' line patterns over macroscopic areas following solvent vapor annealing treatment. The directed assembly of PS-b-P4VP line patterns was enabled by electron-beam lithographically defined hydrogen silsequioxane (HSQ) gratings. We developed metal oxide nanowire features using PS-b-P4VP structures which facilitated high quality pattern transfer to the underlying Si substrate. This work highlights the precision at which long range ordered ∼10 nm Si nanofin features with 32 nm pitch can be defined using a cylindrical BCP system for nanolithography application. The results show promise for future nanocircuitry fabrication to access sub-16 nm critical dimensions using cylindrical systems as surface interfaces are easier to tailor than lamellar systems. Additionally, the work helps to demonstrate the extension of these methods to a 'high χ' BCP beyond the size limitations of the more well-studied PS-b-poly(methyl methylacrylate) (PS-b-PMMA) system.

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Section: Resultsmentioning

confidence: 95%

Section: Resultsmentioning

confidence: 99%

Aligned silicon nanofins via the directed self-assembly of PS-b-P4VP block copolymer and metal oxide enhanced pattern transfer

et al. 2015

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“…In the case of silicon substrate, the strong interaction between the PDMS block and the hydroxyl-terminated polar native oxide surface impede the diffusivity of the polymer on the surface, leading to no equilibrium morphologies and the formation of a thin layer of PDMS at the interface substrate/BCP film [13,14]. Indeed, on untreated surfaces, we observe short and disorganized polymer chains as shown in Figure 1 (left).…”

Section: Choice Of the Patterned Substratementioning

confidence: 82%

“…The lower PDMS block surface energy (γ = 19.9 mN m -1 ) compared to the PS block (γ = 40.7 mN m -1 ) leads to a thin PDMS wetting layer at the polymer/air interface [13,14]. This layer, as well as the PS block of the BCP, has first to be removed to allow the observation of the self-assembled morphology.…”

Section: Methodsmentioning

confidence: 98%

Directed self-assembly of PS-b-PDMS into 193nm photoresist patterns and transfer into silicon by plasma etching

Archambault

Girardot²,

Delalande³

et al. 2014

SPIE Proceedings

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Block CoPolymer (BCP) self-assembly creates periodical patterns with feature sizes eventually below 10 nm. On plain substrates, ordering is only obtained in grains not larger than a few micrometers but self-assembly in trenches of a pattern (using so-called graphoepitaxy technique) can create long-range order between the polymer micro-domains. As a result, such directed self-assembly (DSA) approaches may be used as ultra-high resolution patterning schemes in the microelectronics industry.Due to its ease of processing, a large majority of the lithographic BCP work reported so far concerned polystyreneblock-polymethylmethacrylate (PS-b-PMMA). Researchers show now an increased interest to polystyrene-blockpolydimethylsiloxane (PS-b-PDMS) block copolymers due to its improved resolution.In the present study, typical industry-like photolithography stacks are patterned by combining graphoepitaxy with cylindrical PS-b-PDMS BCP and state of the art plasma etching technologies. The industry like photolithography stack is fabricated on 300 mm diameter silicon wafers, and composed of three layers: Spin-On-Carbon (SOC), Siliconcontaining Anti-Reflective Coating (SiARC) and 193 nm photolithography resist. About 60 nm deep trenches are first patterned by plasma etching in the SiARC/SOC stack using the 193 nm photolithography resist mask. These trenches are then used to confine the BCP and guide the self-assembly of horizontal PDMS cylinders. Wetting conditions allows avoiding the interfacial PDMS wetting layer at the bottom and lateral interfaces after the solvent annealing step.Finally, dedicated pulsed plasma etching conditions were developed in order to reveal the BCP patterns, transfer them into the remaining SOC layer under the trenches and finally into the underlying silicon substrate. 15 nm half-pitch dense line/space features are formed with a height up to 105 nm.In conclusion, long-range order line/space features could be produced by using horizontal cylindrical high FloryHuggins parameter (χ) BCPs combined with industry-type photolithography stacks.

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“…These hydroxyl groups permits proper balancing of the incompatibility between modified PDMS and PS blocks preventing the preferential wetting at the free surface of one of the two blocks and consequently leading to a perpendicular orientation of the nanostructures with respect to the substrate. Apart from these few examples of perpendicular orientation of the nanofeatures, foreseeing the development of complex experimental setup, most studies focus on PS-b-PDMS systems where PDMS cylinders lie parallel to the substrate (Figure 3 [69,70]. In this context, Ross and coworker developed a method to easily control the in plane orientation of PS-b-PDMS cylindrical microdomains parallel oriented with respect to the substrate by designed post arrays to generate complex integrated circuits with the stripes geometries shown in Figure 2(a)-(g) [71,72].…”

Section: Bcps Backgroundmentioning

confidence: 99%

Technological strategies for self-assembly of PS-b-PDMS in cylindrical sub-10 nm nanostructures for lithographic applications

Giammaria

Laus

Perego³

2018

Advances in Physics: X

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The continuous demand for small portable electronics is pushing the semiconductor industry to develop novel lithographic methods to fabricate the elementary structures for microelectronics devices with dimensions below 10 nm. Topdown strategies include multiple patterning photolithography, extreme ultraviolet lithography (EUVL), electron beam lithography (EBL), and nanoimprint lithography. Bottom-up approaches mainly rely on block copolymers (BCPs) self-assembly (SA). SA of BCPs is extremely appealing due to its excellent compatibility with conventional photolithographic processes, high-resolution patterns, and low process costs. Among the various BCPs, the polystyrene-b-polydimethylsiloxane (PS-b-PDMS) represents the most investigated material for the fabrication of sub-10 nm structures. However, PS-b-PDMS cannot be easily processed by conventional thermal treatments due to its slow SA kinetic coupled with a relatively low thermal stability. This review focuses on the available annealing methods to promote the SA PS-b-PDMS in parallel-oriented cylindrical sub-10 nm structures. Moreover, literature data regarding the annealing time, defects density, line edge roughness (LER) and line width roughness (LWR) are discussed with reference to the stringent requirements of semiconductor technology.

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Achieving structural control with thin polystyrene-b-polydimethylsiloxane block copolymer films: The complex relationship of interface chemistry, annealing methodology and process conditions

Cited by 29 publications

References 32 publications

Aligned silicon nanofins via the directed self-assembly of PS-b-P4VP block copolymer and metal oxide enhanced pattern transfer

Aligned silicon nanofins via the directed self-assembly of PS-b-P4VP block copolymer and metal oxide enhanced pattern transfer

Directed self-assembly of PS-b-PDMS into 193nm photoresist patterns and transfer into silicon by plasma etching

Technological strategies for self-assembly of PS-b-PDMS in cylindrical sub-10 nm nanostructures for lithographic applications

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