Self-Assembly in ultrahigh molecular weight sphere-forming diblock copolymer thin films under strong confinement

Cao, Wuteng; Xia, Senlin; Appold, Michael; Saxena, Nitin; Bießmann, Lorenz; Grott, Sebastian; Li, Nian; Gallei, Markus; Bernstorff, Sigrid; Müller‐Buschbaum, Peter

doi:10.1038/s41598-019-54648-3

Cited by 11 publications

(13 citation statements)

References 60 publications

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“…[255][256][257][258][259] In Figure 7b (from left to right), a self-assembled spherical structure of PSPI block copolymer dissolved in toluene is reported after a thermal solvent annealing (below 100°C). Cao et al [259] showed a promising way to fabricate large-sized nanostructures, investigating the influence of the spin coating parameters and solvent vapor annealing on the self-assembly of multi-geometrical ordered structure. Further, Jacucci et al [260] investigated the optimization of the morphology of the scatterer elements rather than the tunability of their refractive index, obtaining silica-based spheroid-cylindrical particles as colloids, thus showing a new class of pigment microsphere for ultrabright coatings.…”

Section: Leucophore As Incoherent Structural Scatterersmentioning

confidence: 99%

“…For example, di-block copolymers show photonic bandgap in the visible range thanks to self-assembled ordered nanostructures. [255][256][257][258][259] In Figure 7b (from left to right), a self-assembled spherical structure of PSPI block copolymer dissolved in toluene is reported after a thermal solvent annealing (below 100°C). Cao et al [259] showed a promising way to fabricate large-sized nanostructures, investigating the influence of the spin coating parameters and solvent vapor annealing on the self-assembly of multi-geometrical ordered structure.…”

Section: Leucophore As Incoherent Structural Scatterersmentioning

confidence: 99%

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A Perspective on Cephalopods Mimicry and Bioinspired Technologies toward Proprioceptive Autonomous Soft Robots

Giordano

Carlotti

Mazzolai

2021

Adv Materials Technologies

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scientific community. [1][2][3][4][5][6][7] Regardless, every time a living being reveals novel adaptive and dynamically reactive mimicry behavior, it inspires and fosters futuristic and unexpected technological outcomes. [8][9][10][11][12] At the biological level, the visual crypsis is the ability of a species to resemble the surroundings by matching the coloration and the geometrical patterns of the habitat. In this sense, a living being can control its appearance optically (thanks to arranged and optimized structures at the mesoscopic scale, by means of pigmentation, or emissive elements) and morphologically (it can show wrinkles and textures on the body to evade detection or observation). [13][14][15][16][17][18] Both these mechanisms are characterized by a time response that ranges from milliseconds to hundreds of seconds. In nature, several species take advantage of cryptic abilities, as, e.g., in cephalopods, [7] crustaceans, [19] reptilians, [1,20,21] insects, [22,23] birds, [24,25] shells, [26,27] plants, [28,29] among many. The biotic color changing and body patterning relate to reproductive, communicative, and defensive and/or predatory strategies. Unfortunately, the nervous or central control-chain system that steers these behaviors in animals and plants, is still somehow fogged for scientists. [7,[30][31][32] A complete knowledge about their central information process systems, can open to astonishing developments in many scientific branches, from neurobiology [33,34] to quantum biology. [35] Undoubtedly, the most debated case of study in the natural world are cephalopods, which not only are highly evolved and specialized in fast adaptive color changing displays, but also are able to actuate their skin to generate 3D patterns, when exposed to specific mechanical, thermal, optical, or chemical stimuli. Soft muscular arrangements, [36][37][38] spatially distributed and expandable absorbing components (namely chromatophores), [39,40] iridescent elements (namely irido phores), [41,42] and bright white scatterers (namely leucophores) [43] are responsible for textural, postural and color changing. Moreover, octopuses are a remarkable intelligent species, able, for example, to open a jar or avoid predators in the order of seconds. [44] Thus, cephalopods are usually regarded as a perfect example of embodied intelligence, [45] thanks to the symbiosis between their body's mechanics and morphology, and the distributed sensory neuro-motor-control system. Their "learning", "mechanical" and "material intelligence" will be our lodestars along this review, resulting in a fascinating connection between Octopus skin is an amazing source of inspiration for bioinspired sensors, actuators and control solutions in soft robotics. Soft organic materials, biomacromolecules and protein ingredients in octopus skin combined with a distributed intelligence, result in adaptive displays that can control emerging optical behavior, and 3D surface textures with rough geometries, with a remarkably high control speed (≈ms). To be able ...

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Section: Leucophore As Incoherent Structural Scatterersmentioning

confidence: 99%

Section: Leucophore As Incoherent Structural Scatterersmentioning

confidence: 99%

A Perspective on Cephalopods Mimicry and Bioinspired Technologies toward Proprioceptive Autonomous Soft Robots

Giordano

Carlotti

Mazzolai

2021

Adv Materials Technologies

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“…ii) The complex molecular topology and conformation of LBCPs in solvent can cause slow self-assembly dynamics. [5,6,95,96] An alternative class of BCP, the brush block copolymer (BBCP), also known as a bottlebrush block copolymer or molecular brush, promises to alleviate these issues, allowing for greater access to photonic materials. BBCPs have densely grafted side chains and the strong steric hindrance of these side chains significantly increases the rigidity of the polymer backbone, which extends the conformation of the BBCP and reduces chain entanglement.…”

Section: Introductionmentioning

confidence: 99%

Recent Advances in Block Copolymer Self‐Assembly for the Fabrication of Photonic Films and Pigments

Wang

Chan

Zhao

et al. 2021

Advanced Optical Materials

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history and recent progress of 1D photonic films, also commonly referred to as photonic multilayer structures. In the third section, recent advances in exploiting confined self-assembly of block copolymers to produce photonic pigments are introduced and the diversity of structures that can be achieved with this method explored, ranging from concentric lamellae to porous particles with correlated disorder. Finally, we conclude by highlighting promising directions for future investigation.

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“…SVA involves the uptake of solvent into a BCP film, resulting in increased polymer chain mobility, a lower effective value of T g , and the avoidance of any thermal degradation of the material. − There are multiple interdependent variables that influence the SVA process, including pressure, temperature, and humidity. Nonetheless, previous work has shown that it can be performed with a very simple strategy known as “static” SVAthis consists of a BCP sample placed inside a sealed chamber containing a reservoir of solvent, which is then left for a predetermined period of time. − Moreover, SVA can be performed at room temperatures or below and has been proven to effectively induce self-assembly in a number of UHMW BCP systems. ,− Kim et al successfully obtained phase separation of lamellar and gyroid UHMW polystyrene- block -poly(methyl methacrylate) (PS- b -PMMA) BCP films with periods of ∼200 nm using tetrahydrofuran (THF) as a neutral solvent for SVA, followed by a 12 h thermal annealing step. , Phase separation of a UHMW spherical PS- b -PMMA system was also demonstrated by Cao et al again using THF as the annealing solvent of choice . Additionally, Takano et al developed a novel instrumentation technique to monitor the phase separation of UHMW lamellar PS- b -PMMA using in situ atomic force microscopy (AFM) under high swelling conditions during SVA .…”

Section: Introductionmentioning

confidence: 99%

“…achieved the phase separation of a high molecular weight PS-P2VP system ( M n = 430 kg/mol) in a time period of 1 h using an uncontrolled “static” SVA strategy . Despite the relative success of these previous studies for the induction of phase separation in UHMW systems, the required timescales often extended from several hours to daysthereby severely hindering the industrial applicability of such processes. ,− The acceleration of the SVA process is therefore critical for the future development of this field. Here, we demonstrate a procedure for ultrafast self-assembly of UHMW BCP systems by controlling the swelling kinetics during SVA, reducing the required annealing time to minutes.…”

Section: Introductionmentioning

confidence: 99%

Optimization and Control of Large Block Copolymer Self-Assembly via Precision Solvent Vapor Annealing

et al. 2021

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The self-assembly of ultra-high molecular weight (UHMW) block copolymers (BCPs) remains a complex and timeconsuming endeavor owing to the high kinetic penalties associated with long polymer chain entanglement. In this work, we report a unique strategy of overcoming these kinetic barriers through precision solvent annealing of an UHMW polystyrene-blockpoly(2-vinylpyridine) BCP system (M w : ∼800 kg/mol) by fast swelling to very high levels of solvent concentration (ϕ s ). Phase separation on timescales of ∼10 min is demonstrated once a thickness-dependent threshold ϕ s value of ∼0.80−0.86 is achieved, resulting in lamellar feature spacings of over 190 nm. The threshold ϕ s value was found to be greater for films with higher dry thickness (D 0 ) values. Tunability of the domain morphology is achieved through controlled variation of both D 0 and ϕ s , with the kinetically unstable hexagonal perforated lamellar (HPL) phase observed at ϕ s values of ∼0.67 and D 0 values of 59−110 nm. This HPL phase can be controllably induced into an order−order transition to a lamellar morphology upon further increase of ϕ s to 0.80 or above. As confirmed by grazing-incidence small-angle X-ray scattering, the lateral ordering of the lamellar domains is shown to improve with increasing ϕ s up to a maximum value at which the films transition to a disordered state. Thicker films are shown to possess a higher maximum ϕ s value before transitioning to a disordered state. The swelling rate is shown to moderately influence the lateral ordering of the phase-separated structures, while the amount of hold time at a particular value of ϕ s does not notably enhance the phase separation process. These large period self-assembled lamellar domains are then employed to facilitate pattern transfer using a liquid-phase infiltration method, followed by plasma etching, generating ordered, high aspect ratio Si nanowall structures with spacings of ∼190 nm and heights of up to ∼500 nm. This work underpins the feasibility of a room-temperature, solvent-based annealing approach for the reliable and scalable fabrication of sub-wavelength nanostructures via BCP lithography.

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Self-Assembly in ultrahigh molecular weight sphere-forming diblock copolymer thin films under strong confinement

Cited by 11 publications

References 60 publications

A Perspective on Cephalopods Mimicry and Bioinspired Technologies toward Proprioceptive Autonomous Soft Robots

A Perspective on Cephalopods Mimicry and Bioinspired Technologies toward Proprioceptive Autonomous Soft Robots

Recent Advances in Block Copolymer Self‐Assembly for the Fabrication of Photonic Films and Pigments

Optimization and Control of Large Block Copolymer Self-Assembly via Precision Solvent Vapor Annealing

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