Directed Self‐Assembly of Liquid‐Crystalline Molecular Building Blocks for Sub‐5 nm Nanopatterning

Nickmans, Koen; Schenning, Aphj Albert

doi:10.1002/adma.201703713

Cited by 67 publications

(66 citation statements)

References 162 publications

(252 reference statements)

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“…Self‐assembly is a very efficient approach to develop complex architectures and materials . The bottom‐up organization of building blocks such as polymers, nanoparticles, and small molecules is an increasingly recognized method to reach length scales considered unattainable so far . However, spontaneous “hierarchical” self‐assembly is still difficult to control and attempts to extend it to multiple length scales typically leads to formation of multidomain structures …”

Section: Introductionmentioning

confidence: 99%

“…[1] The bottom-up organization of building blocks such as polymers, [2] nanoparticles, [3] and small molecules [4][5][6] is an increasingly recognized method to reach length scales considered unattainable so far. [7] However, spontaneous "hierarchical" self-assembly is still difficult to control and attempts to extend it to multiple length scales typically leads to formation of multidomain structures. [8] To overcome these issues, molecular design can be combined to directed self-assembly through control of dynamics and anisotropic nanofibers (≈100 nm scale), 3) nanofibers aligned into shaped patterns (≈5-20 µm scale), and 4) patterns organized on a surface with individually chosen orientation (up to ≈100 µm scale).…”

Section: Introductionmentioning

confidence: 99%

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Photocontrolled Hierarchical Self‐Assembly of Anisotropic Micropatterns of Nanofibers onto Isotropic Surfaces

Vet

Gartzia‐Rivero

Schäfer

et al. 2020

Small

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Hierarchical self‐assembly is achieved using a visible light triggered photoreaction. A pro‐gelator, α‐diketone‐2,3‐didecyloxyanthracene, is photoconverted into a low molecular weight gelator, 2,3‐didecyloxyanthracene (DDOA), that self‐assembles into nanofibers. Spatial confinement and patterns of these nanofibers onto a surface are achieved by localizing initial nucleation with a focused laser and photogenerate subsequent fiber growth with the laser or gentler wide‐field irradiation. Remarkably, collective growth of nanofibers results in anisotropic micropatterns with orientation factors (OF) reaching 79%, resulting in collective emission of linearly polarized light. The OF, distance of collective growth and fiber density, are controlled by the photoirradiation conditions and the balance of interactions between DDOA aggregates and the glass surface. An unprecedented juxtaposition of orthogonally oriented nanofiber patterns on an isotropic surface is achieved with individual control of the fibers' main direction. In perspective, this photochemical method can be extended to a large variety of self‐assembling molecules.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Photocontrolled Hierarchical Self‐Assembly of Anisotropic Micropatterns of Nanofibers onto Isotropic Surfaces

Vet

Gartzia‐Rivero

Schäfer

et al. 2020

Small

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“…Elastomeric polymers have been investigated intensively over the past years for the creation of stimuli‐responsive materials. In particular, the combination of the anisotropic nature of liquid crystals (LCs) and the flexibility of elastomer networks have proven to be an excellent combination for shape memory films, soft actuators, and stimuli‐responsive materials . Having control over the polymerization reaction by controlling crosslink density and molecular weight between crosslinks is highly desired to create optimal functionality, flexibility, and strength in the material …”

Section: Introductionmentioning

confidence: 99%

“…In recent studies, liquid crystalline elastomer films are frequently prepared with siloxane oligomers or by Michael addition chain extension reactions . Especially the latter, involving Michael addition, has received a lot of interest recently, due to the large variety of reactive mesogens that are available . By controlling the network formation, a large variety of stimuli‐responsive shape and color changing materials with desired functional properties can be obtained…”

Section: Introductionmentioning

confidence: 99%

Tunable Photonic Materials via Monitoring Step‐Growth Polymerization Kinetics by Structural Colors

Heeswijk

Yang

Grossiord

et al. 2019

Adv Funct Materials

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The functional and responsive properties of elastomeric materials highly depend on crosslink density and molecular weight between crosslinks. However, tedious analytical steps are needed to obtain polymer network structure–property relationships. In this article, an in situ structure–property characterization method is reported by monitoring the structural color change in a photonic elastomeric material. The photonic materials are prepared in a two‐step polymerization process. First, linear chain extension occurs via Michael addition. Second, photopolymerization ensures crosslinking, resulting in the formation of an elastomeric photonic network. During the first step, the step‐growth polymer process can be monitored by following the photonic reflection band redshift, allowing to program the molecular weight between the crosslinks. During network formation, the crosslink density, chain length between crosslinks, and the colors are “frozen in.” These processes can be locally controlled creating both single‐layered multicolor patterned and broadband reflective coatings at room temperature. The scalability of the coating process is further demonstrated by using a gravure printing technique. Additionally, the final coatings are made responsive toward specific solvents and temperature. Here the modulus, response, and color of the coating are controlled by tuning the crosslink density and molecular weight between crosslinks of the elastomeric material.

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“…[8][9][10][11][12][13][14][15][16][17] Apart from technological applications, LCs provideg reater and deeper insight into the fundamental understanding of self-assembly and self-organization of matter at different hierarchical levels. [18][19][20][21][22][23][24][25][26][27][28] Extreme sensitivity of LCs to different external stimuli of small magnitude qualifies them as functionals timuli-responsive soft materials. [29][30][31][32][33][34][35][36][37][38][39][40][41][42][43][44][45][46][47][48] The critical role of LCs in living systemsh as been well recognized.…”

Section: Introductionmentioning

confidence: 99%

The Halogen Bond: An Emerging Supramolecular Tool in the Design of Functional Mesomorphic Materials

Wang

Bisoyi

Urbas

et al. 2018

Chemistry A European J

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Owing to their dynamic attributes, non-covalent supramolecular interactions have enabled a new paradigm in the design and fabrication of multifunctional material systems with programmable properties, performances, and reconfigurable traits. Recently, the "halogen bond" has become an enticing supramolecular synthetic tool that displays a plethora of promising and advantageous characteristics. Consequently, this versatile and dynamic non-covalent interaction has been extensively harnessed in various fields such as crystal engineering, self-assembly, materials science, polymer chemistry, biochemistry, medicinal chemistry and nanotechnology. In recent years, halogen bonding has emerged as a tunable supramolecular synthetic tool in the design of functional liquid-crystalline materials with adjustable phases and properties. In this Concept article, the use of halogen bond in the field of stimuli-responsive smart soft materials, that is, liquid crystals is discussed. The design, synthesis and characterization of molecular and macromolecular liquid crystalline materials are described and the modulation of their properties has been emphasized. The power of halogen bonding in offering a large variety of functional liquid crystalline materials from readily accessible mesomorphic and non-mesomorphic complementary building blocks is highlighted. The article concludes with a perspective on the challenges and opportunities in this emerging endeavor towards the realization of enabling and elegant dynamic functional materials.

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Directed Self‐Assembly of Liquid‐Crystalline Molecular Building Blocks for Sub‐5 nm Nanopatterning

Cited by 67 publications

References 162 publications

Photocontrolled Hierarchical Self‐Assembly of Anisotropic Micropatterns of Nanofibers onto Isotropic Surfaces

Photocontrolled Hierarchical Self‐Assembly of Anisotropic Micropatterns of Nanofibers onto Isotropic Surfaces

Tunable Photonic Materials via Monitoring Step‐Growth Polymerization Kinetics by Structural Colors

The Halogen Bond: An Emerging Supramolecular Tool in the Design of Functional Mesomorphic Materials

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