Enhanced Lateral Ordering in Cylinder Forming PS-<i>b</i>-PMMA Block Copolymers Exploiting the Entrapped Solvent

Seguini, Gabriele; Zanenga, Fabio; Giammaria, Tommaso Jacopo; Ceresoli, Monica; Sparnacci, Katia; Antonioli, Diego; Gianotti, Valentina; Laus, Michele; Perego, Michele

doi:10.1021/acsami.6b00360

Cited by 22 publications

(61 citation statements)

References 62 publications

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“…Moreover, in a vacuum environment, the polymer swelling kinetics can be distinguished from the slow vapor pressure build-up (minutes) in a standard ambient SVA cell. Other approaches include SVA at elevated temperatures [146,198] and the use of a solvent-trapping layer underneath the block copolymer thin film during thermal annealing [212]. Chavis et al [218] reported a real-time in-situ SVA on a symmetric PHEMA-b-PMMA DBCP using a methanol and THF mixture (THF and methanol are selective for PMMA and for PHEMA, respectively).…”

Section: New Approaches To Svamentioning

confidence: 99%

Restructuring in block copolymer thin films: In situ GISAXS investigations during solvent vapor annealing

Posselt

Zhang

Smilgies

et al. 2017

Progress in Polymer Science

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Block copolymer (BCP) thin films have been proposed for a number of nanotechnology applications, such as nanolithography and as nanotemplates, nanoporous membranes and sensors. Solvent vapor annealing (SVA) has emerged as a powerful technique for manipulating and controlling the structure of BCP thin films, e.g.,, by healing defects, by altering the orientation of the microdomains and by changing the morphology. Due to high time resolution and compatibility with SVA environments, grazing-incidence small-angle X-ray scattering (GISAXS) is an indispensable technique for studying the SVA process, providing information of the BCP thin film structure both laterally and along the film normal. Especially, state-of-the-art combined GISAXS/SVA setups at synchrotron sources have facilitated in-situ and real-time studies of the SVA process with a time resolution of a few seconds, giving important insight into the pathways and mechanisms of SVA induced restructuring. We give a short introduction to the GISAXS method and review recent theoretical studies, experimental techniques such as sample preparation and in-situ chambers together with SVA protocols, and we review and discuss experimental results. We conclude by giving an outlook on emerging developments of the in-situ real-time GISAXS scattering technique in combination with new approaches to control BCP thin film structures using SVA.

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Section: New Approaches To Svamentioning

confidence: 99%

Restructuring in block copolymer thin films: In situ GISAXS investigations during solvent vapor annealing

Posselt

Zhang

Smilgies

et al. 2017

Progress in Polymer Science

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“…To promote perpendicular orientation of the domains in the PS-b-PMMA BCP thin films, poly (styrene-random-methyl methacrylate) (P(S-r-MMA)) random copolymer (RCP) (molecular weight, Mn = 69 kg/mol, Styrene fraction, fs = 0.61, polydispersity index, PDI = 1.19) was grafted (RTA: T = 310 °C, t = 60 s) on hydroxyl terminated Si surface to form a neutral ≈ 19 nm thick brush layer. This thick RCP brush layer provides a reservoir of embedded solvent [29,30,33] able to sustain the ordering process in the phase separated PS-b-PMMA film over several decades of time during the SARTA treatment. [29] The all-organic PS-b-PMMA BCP exhibits S-MMA parameter that is weakly dependent on T, because the entropic contribution (0.021) is much larger than the enthalpic one (3.2/T).…”

Section: Textmentioning

confidence: 99%

“…The measured  value can be treated following the time-Temperature superposition (tTS) procedure, to describe the ordering kinetics. [29,32]  as a function of tA for different TA are collected in a master curve at the reference TA (Table 1) Table 1). Interestingly  is not constant within the cylindrical morphology but it is N-dependent, that is, basically, it depends on the driving force for the phase separation.…”

Section: Textmentioning

confidence: 99%

Ordering kinetics in two-dimensional hexagonal pattern of cylinder-forming PS- b -PMMA block copolymer thin films: Dependence on the segregation strength

Seguini¹,

Zanenga

Laus

et al. 2018

Phys. Rev. Materials

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This paper reports the experimental determination of the growth exponents and activation enthalpies for the ordering process of standing cylinder-forming all-organic polystyrene-block-poly (methyl methacrylate) (PS-b-PMMA) block copolymer (BCP) thin films as a function of the BCP degree of polymerization (N). The maximum growth exponent of 1/3 is observed for the BCP with the lowest N at the border of the order disorder transition. Both the growth exponents and the activation enthalpies exponentially decrease with the BCP segregation strength (•N) following the same path of the diffusivity.

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“…As the vertical orientation of the nanofeatures occurs for a wide range of DBC film thickness [33,[41][42][43] these DBCs represent interesting scaffolds for the synthesis of lithographic masks with stripes or vertical pillars having tailored characteristic dimensions and heights. The lateral order within the nanodomains is controlled by the annealing time and temperature, eventually exploiting the residual solvent trapped in the polymeric film [44,45]. Topographical [46][47][48] or chemical pre-pattering [49,50] of the substrate allows registering the in-plane orientation of the nanodomains thus further improving the lateral order.…”

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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Enhanced Lateral Ordering in Cylinder Forming PS-b-PMMA Block Copolymers Exploiting the Entrapped Solvent

Cited by 22 publications

References 62 publications

Restructuring in block copolymer thin films: In situ GISAXS investigations during solvent vapor annealing

Restructuring in block copolymer thin films: In situ GISAXS investigations during solvent vapor annealing

Ordering kinetics in two-dimensional hexagonal pattern of cylinder-forming PS- b -PMMA block copolymer thin films: Dependence on the segregation strength

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

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