3D Orientational Control in Self‐Assembled Thin Films with Sub‐5 nm Features by Light

Nickmans, Koen; Bögels, G.; Sánchez‐Somolinos, Carlos; Murphy, Jeffrey J.; Leclère, Philippe; Voets, Ilja K.; Schenning, Albertus P. H. J.

doi:10.1002/smll.201701043

Cited by 24 publications

(24 citation statements)

References 67 publications

(134 reference statements)

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“…However, in order to utilize these materials, the alignment of these supramolecular structures should be explored. For example, the azobenzene‐containing hierarchical materials reported here could be combined with photo‐alignment processes in order to obtain oriented monodomain structures by exposure to linearly polarized light, or act as photo‐switches ( Figure ) . The directed hierarchical self‐assembly of block copolymers with small molecules could also be explored to create hybrid nanomaterials with well‐defined hierarchical features …”

Section: Discussionmentioning

confidence: 99%

“…To date, however, the self‐assembly of liquid crystalline hybrid organic/inorganic molecules has hardly been explored. We previously reported a series of ODMS liquid crystals (LCs) that formed large‐area ordered sub‐5 nm structures by graphoepitaxy, and photoalignment . The morphology of the structures could be tuned by length of the ODMS tail .…”

Section: Introductionmentioning

confidence: 99%

“…columnar, lamellar, or bicontinuous mesophases, can be formed . The self‐assembly of these materials on the nanometer scale can be manipulated using alignment layers, electric or magnetic fields, shear forces, or light, ][ resulting in materials with a monolithic structure on macroscopic length scales produced with large scale and low cost processes. The generation of such ordered nanostructured materials is comparatively straightforward, in contrast to the self‐assembly of block copolymers .…”

Section: Introductionmentioning

confidence: 99%

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Hydrogen‐Bonded Siloxane Liquid Crystals for Hybrid Nanomaterials

Nickmans

Jansma

Hey

et al. 2018

Helvetica Chimica Acta

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The self‐assembly of molecular inorganic/organic hybrid building blocks into ordered hierarchical nanomaterials with a tunable morphology is an enormous challenge. Here, we describe the synthesis and characterization of a novel liquid crystalline hydrogen‐bonding hepta(dimethylsiloxane) azobenzene carboxylic acid dimer. This inorganic/organic hybrid dimer forms sub‐5 nm lamellar features in the bulk and at the liquid solid interface. When mixed with a complementary hydrogen‐bonding disk‐shaped small molecule, a columnar hexagonal phase is formed. When adding a block copolymer containing hydrogen bond‐accepting moieties, a hierarchical nanostructured material is obtained with a hexagonal columnar arrangement perpendicular to lamellae super structure. Our supramolecular approach shows that hierarchical hybrid nanomaterials can be fabricated with controlled properties which is appealing for applications such as nanoporous materials, organic electronics, and nanolithography.

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Section: Discussionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Hydrogen‐Bonded Siloxane Liquid Crystals for Hybrid Nanomaterials

Nickmans

Jansma

Hey

et al. 2018

Helvetica Chimica Acta

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“…Such morphologies can be aligned in the plane by irradiating the sample with linearly polarized blue light at temperatures just below the isotropization temperature to favor mobility (Figure b). The organic–inorganic hybrid nature that favors etch contrast, together with the possibility to combine top‐down photolithography to micropattern regions with different morphology orientations, turns these systems into an exciting platform for next‐generation nanolithographic processes …”

Section: Molecular Alignment Enabled By Lightmentioning

confidence: 99%

Section: Molecular Alignment Enabled By Lightmentioning

confidence: 99%

Light to Shape the Future: From Photolithography to 4D Printing

Barrio

Sánchez‐Somolinos

2019

Advanced Optical Materials

185

147

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producing increasingly complex patterned films and miniaturized devices, which are required in modern information and communication technologies. [1] In addition to semiconductor device fabrication, a host of applications for patterned thin films and structured polymeric systems have been identified over the last two decades in areas including optics, energy harvesting, biotechnology, and medicine. [2] Our ability to structure polymeric materials has grown tremendously and the palette of materials and techniques to achieve a quick and reliable production of patterns with increasing resolution is quite extensive. This boom has been largely sustained by the development of specific photonic technologies, such as advanced light sources or spatial light modulators, photosensitive materials, and, more importantly, our growing knowledge of the interaction between light and matter. Indeed, the ability to control a chemical reaction with light in a remote fashion is a powerful concept. Light irradiation can initiate a photochemical process that otherwise would not occur at ambient conditions. This property lies at the origin of the temporal control afforded by simply turning the light source on and off. Moreover, patterned illumination or the use of focused light beams enables control of not only when, but also where a photoinduced transformation occurs. The photochemical processes occurring in many polymers and resists can be effectively manipulated by fine-tuning the intensity and frequency of light. However, these are just two of the primary properties of light, and there are specific photoresponsive systems that enable the generation of ordered structures by adjusting the polarization of light, in addition to intensity and frequency.In this review, an overview of photochemical reactions, photosensitive polymers, and light-based structuring techniques is provided. As this field is too broad to be covered in depth in one single article, some recent examples and applications, as well as emerging opportunities and trends, are highlighted throughout the discussion. Section 2 is focused on light-induced reactions and photosensitive materials. The fundamentals of photochemical reactions and their implementation in polymer science have been overviewed in many excellent books and reviews. [3] In Section 2, rather than being comprehensive, emphasis is given to those photochemical processes lying at the basis of those structuring techniques that are later discussed in Section 3. Some of these techniques, including conventional mask lithographies, interference lithographies, direct laser writing (DLW) with one-or two-photon processes, or stereolithographic techniques, make use of light as a structuring tool.There is an additional group of techniques where light is employed to set a structure created beforehand through a Over the last few decades, the demand of polymeric structures with welldefined features of different size, dimension, and functionality has increased from various application areas, including microelectronics, ...

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Sub‐5 nm Dendrimer Directed Self‐Assembly with Large‐Area Uniform Alignment by Graphoepitaxy

Park

Jung

Kwon

et al. 2019

Adv Funct Materials

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Directed self-assembly (DSA) using soft materials is an important method for producing periodic nanostructures because it is a simple, cost-effective process for fabricating high-resolution patterns. Most of the previously reported DSA methods exploit the self-assembly of block copolymers, which generates a wide range of nanostructures. In this study, cylinders obtained from supramolecular dendrimer films with a high resolution (<5 nm) exhibit planar ordering over a macroscopic area via guiding topographical templates with a high aspect ratio (>10) and high spatial resolution (≈20 nm) of guiding line patterns. Theoretical and experimental studies reveal that this property is related to geometrical anchoring on the meniscus region and physical surface anchoring on the sidewall. Furthermore, this DSA of dendrimer cylinders is demonstrated by the non-regular geometry of the patterned template. The macroscopic planar alignment of the dendrimer nanostructure reveals an extremely small feature size (≈4.7 nm) on the wafer scale (>16 cm 2 ). This study is expected to open avenues for the production of a large family of supramolecular dendrimers with different phases and feature dimensions oriented by the DSA approach.

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3D Orientational Control in Self‐Assembled Thin Films with Sub‐5 nm Features by Light

Cited by 24 publications

References 67 publications

Hydrogen‐Bonded Siloxane Liquid Crystals for Hybrid Nanomaterials

Hydrogen‐Bonded Siloxane Liquid Crystals for Hybrid Nanomaterials

Light to Shape the Future: From Photolithography to 4D Printing

Sub‐5 nm Dendrimer Directed Self‐Assembly with Large‐Area Uniform Alignment by Graphoepitaxy

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