Rapid thermal processing of self-assembling block copolymer thin films

Lupi, Federico Ferrarese; Giammaria, Tommaso Jacopo; Ceresoli, Monica; Seguini, Gabriele; Sparnacci, Katia; Antonioli, Diego; Gianotti, Valentina; Laus, Michele; Perego, Michele

doi:10.1088/0957-4484/24/31/315601

Cited by 71 publications

(70 citation statements)

References 28 publications

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“…To promote perpendicular orientation of the cylinders during the phase segregation step of the DBC self‐assembly, a surface neutralization is required (Figure ‐a1 and b1). Surface neutralization in this work was performed using a P(S‐ r ‐MMA) random copolymer (RCP), following the procedure described in literature . Finally, the non‐grafted RCP chains were removed in an ultrasonic bath of Toluene and a 3.4 ± 0.1 nm thick, as determined by SE, grafted RCP layer was obtained (Figure ‐a2 and b2).…”

Section: Methodsmentioning

confidence: 99%

Development and Synchrotron‐Based Characterization of Al and Cr Nanostructures as Potential Calibration Samples for 3D Analytical Techniques

Dialameh

Lupi

Hönicke

et al. 2017

Physica Status Solidi (a)

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The continuous and aggressive scaling in semiconductor technology results in the integration of increasingly complex 3D architectures and new materials. The realization of these downscaled 3D structures requires also further improvement in 3D characterization techniques. In this work, a potential route to improve the accuracy and reliability of the quantitative analysis of 3D nano-devices is investigated. 3D organic and inorganic reference nanostructures with dimensions and structural ordering resembling those utilized in industrial applications are fabricated and characterized in detail. The 3D organic nanostructures are fabricated exploiting the selfassembly capability of di-block copolymers. Subsequent deposition of a thin Al film lead to the formation and realization of nanostructured Al. In addition, different inorganic nanostructures are fabricated using electron beam lithography. The various nanostructures are characterized with respect to their dimensions as well as composition using various analytical techniques namely reference-free grazing incidence X-ray fluorescence, grazing incidence small angle X-ray scattering, scanning electron microscopy, and spectroscopic ellipsometry. status solidi physica a Di-Block Copolymers www.pss-a.com

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Section: Methodsmentioning

confidence: 99%

Development and Synchrotron‐Based Characterization of Al and Cr Nanostructures as Potential Calibration Samples for 3D Analytical Techniques

Dialameh

Lupi

Hönicke

et al. 2017

Physica Status Solidi (a)

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“…These formations, while periodic, are prone to defects such as dislocations and grain boundaries that detract from their utility in some applications. A variety of strategies have been developed to extend defect-free uniformity during self-assembly including solvent annealing 18 , shear alignment 19 , epitaxy 20–23 , zone casting 24 , and field alignment 25–29 . Studies of domain morphologies have shown that directional quenching and/or annealing of a BCP film can considerably enhance the order within the system, whereby the orientation of the periodic structures is dependent on the direction and the velocity of a moving thermal gradient field 30 .…”

Section: Introductionmentioning

confidence: 99%

Numerical Simulations of Directed Self-Assembly in Diblock Copolymer Films using Zone Annealing and Pattern Templating

Hill

Millett

2017

Sci Rep

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Bulk fabrication of surface patterns with sub-20 nm feature sizes is immensely desirable for many existing and emerging technologies. Directed self-assembly (DSA) of block copolymers (BCPs) has been a recently demonstrated approach to achieve such feature resolution over large-scale areas with minimal defect populations. However, much work remains to understand and optimize DSA methods in order to move this field forward. This paper presents large-scale numerical simulations of zone annealing and chemo-epitaxy processing of BCP films to achieve long-range orientational order. The simulations utilize a Time-Dependent Ginzburg-Landau model and parallel processing to elucidate relationships between the magnitude and velocity of a moving thermal gradient and the resulting BCP domain orientations and defect densities. Additional simulations have been conducted to study to what degree orientational order can be further improved by combining zone annealing and chemo-epitaxy techniques. It is found that these two DSA methods do synergistically enhance long-range order with a particular relationship between thermal gradient velocity and chemical template spacing.The ability to accurately produce nanoscale surface patterns has become a driving factor for research in many fields. As the need for nanoscale manufacturing increases, new processing technologies must be developed in order to meet industry needs. A number of different patterning methods have shown progress in decreasing feature size beyond the capabilities of traditional lithography 1 . These methods include extreme ultraviolet lithography, nanoimprinting, maskless lithography, and directed self-assembly (DSA) of block copolymers (BCP) 2-7 . BCPs can form very monodisperse periodic domains with domain sizes that can be tailored as small as 5 nm. The domain sizes in a microphase separated BCP matrix correspond with the molecular lengths of each section of the copolymer chain 8 . Linear BCPs are commonly used for patterning research and applications, although other chain architectures are also being explored 9-11 . The phase-separated morphologies of linear BCPs are dependent on the interaction parameter χ, degree of polymerization N, and the ratio of the length of each block f. Stable and meta-stable morphologies include ordered spheres, cylinders, lamellae, and gyroid structures [12][13][14][15][16] . The variety, regularity, and small size of these structures make BCPs highly attractive for many nano-manufacturing applications.The microphase separation of BCP thin films has been broadly studied and shown to be useful for surface patterning and membrane applications 17 . These formations, while periodic, are prone to defects such as dislocations and grain boundaries that detract from their utility in some applications. A variety of strategies have been developed to extend defect-free uniformity during self-assembly including solvent annealing 18 , shear alignment 19 , epitaxy [20][21][22][23] , zone casting 24 , and field alignment [25][26][27][28][29] . Studies...

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“…These RCPs were identified with the acronym R n where n is the M n of the sample in kg mol −1 . The ‘grafting to’ process was performed at 250 °C using a rapid thermal processing (RTP) apparatus . For each RCP, the layer thickness was controlled by varying the grafting time from 10 to 900 s. It was demonstrated that two distinct substrate neutralization regimes occur.…”

Section: Introductionmentioning

confidence: 99%

High temperature surface neutralization process with random copolymers for block copolymer self‐assembly

Sparnacci

Antonioli

Perego³

et al. 2016

Polymer International

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Hydroxyl terminated poly(styrene-r-methyl methacrylate) (P(S-r-MMA)) random copolymers (RCPs), with molecular weight (M n ) spanning from 1700 to 69 000 g mol −1 and equal styrene unit content, were grafted at different temperatures onto a silicon oxide surface and subsequently used to study the orientation of nanodomains with respect to the substrate, in cylinder forming polystyrene-b-poly(methyl methacrylate) (PS-b-PMMA) block copolymer thin films. When the grafting temperature increases from 250 to 310 ∘ C, a substantial increase in the grafting rate is observed. In addition, an increase in the surface neutralization efficiency occurs thus resulting in an increase in the robustness of the surface neutralization step. These data revealed that the neutralization of the substrate is the result of a complex interplay between RCP film characteristics and underlying substrate properties that can be finely tuned by properly adjusting the temperature of the grafting process.

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Rapid thermal processing of self-assembling block copolymer thin films

Cited by 71 publications

References 28 publications

Development and Synchrotron‐Based Characterization of Al and Cr Nanostructures as Potential Calibration Samples for 3D Analytical Techniques

Development and Synchrotron‐Based Characterization of Al and Cr Nanostructures as Potential Calibration Samples for 3D Analytical Techniques

Numerical Simulations of Directed Self-Assembly in Diblock Copolymer Films using Zone Annealing and Pattern Templating

High temperature surface neutralization process with random copolymers for block copolymer self‐assembly

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