Nanocrystals Assembled by the Chemical Reaction of the Dispersion Solvent

Nakanishi, H.; Kawabata, Yasujiro; Tsujiai, Shogo; Tanaka, Hisataka; Teraji, Satoshi; Holló, Gábor; Lagzi, István; Norisuye, Tomohisa; Tran‐Cong‐Miyata, Qui

doi:10.1002/anie.202005827

Cited by 7 publications

(15 citation statements)

References 37 publications

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“…Of note, this mechanism is not specific to this system as migration generally occurs in various systems of different nanocrystals (e.g., Al 2 O 3 and TiO 2 nanoparticles) and monomers (e.g., acrylates). 22 The increase in the difference in light intensity (ΔI) provides the mixture with a large transient concentration difference and thus with a greater thermodynamic driving force, thereby favoring the migration of AgNWs.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…Such a migration mechanism based on the imbalanced chemical potentials enhanced by the Trommsdorff−Norrish effect can be reproduced using a reaction−diffusion model. 22 Briefly, the system can be described in one dimension (along the perpendicular direction to the line-shaped mask) according to the following set of reaction−diffusion equations…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…Another interesting approach, albeit less wellknown, is photopolymerization of monomers under illumination with patterned light such as interference fringes of lasers 21 or intensity-modulated light using a photomask. 22 Such inhomogeneous light illumination transiently produces a nonuniform distribution of the product (polymer) concentration during the formation of polymer films via photopolymerization, which results in a local increase in the concentration of nanocrystals dispersed in the monomer solution along the light patterns via the uphill transport (diffusion) 23 of the nanocrystals. The underlying mechanism for the uphill diffusion of nanocrystals is proposed to be thermodynamically driven on the basis of differences in the chemical potentials due to compositional differences in the reaction mixture.…”

Section: ■ Introductionmentioning

confidence: 99%

“…The underlying mechanism for the uphill diffusion of nanocrystals is proposed to be thermodynamically driven on the basis of differences in the chemical potentials due to compositional differences in the reaction mixture. 21,22 Such a mechanism is intuitive and likely effective for patterning nanocrystals in polymer films because it constitutes a simple method for the simultaneous formation of films and patterning of nanocrystals. However, the relationship between light irradiation and resulting nanocrystal patterns has been much less studied than the mechanisms of other patterning techniques, which limits the practical application of patterning nanocrystals using photopolymerization induced by the patterned light.…”

Section: ■ Introductionmentioning

confidence: 99%

“…A typical example is the use of block copolymers as a template in which nanocrystals are localized in one of the phases (or at the interface) formed via microphase separation of block copolymers. , In this localization process, the chemistry of the ligands bound to the nanocrystals influences the thermodynamics of the nanocrystal–block copolymer systems, thus determining the location of the nanocrystals in block copolymers. Another interesting approach, albeit less well-known, is photopolymerization of monomers under illumination with patterned light such as interference fringes of lasers or intensity-modulated light using a photomask . Such inhomogeneous light illumination transiently produces a nonuniform distribution of the product (polymer) concentration during the formation of polymer films via photopolymerization, which results in a local increase in the concentration of nanocrystals dispersed in the monomer solution along the light patterns via the uphill transport (diffusion) of the nanocrystals.…”

Section: Introductionmentioning

confidence: 99%

See 4 more Smart Citations

Patterning Silver Nanowires by Inducing Transient Concentration Gradients in Reaction Mixtures

Tanaka

Morinaga

Tran‐Cong‐Miyata

et al. 2021

ACS Appl. Mater. Interfaces

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Patterning nanocrystals in polymer films is essential for the widespread use of nanocrystals in various fields from optics to electronics; therefore, the development of patterning methods for nanocrystals is an important task. Here, we report a unique approach for patterning silver nanowires (AgNWs) using a thermodynamic driving force induced by transient concentration gradients in reaction mixtures. The procedure starts with the preparation of a photocurable monomer solution containing homogeneously dispersed AgNWs. Ultraviolet illumination through a straight-line mask reduces the polymerization rate of monomers in the masked area, decreasing the polymer concentration in comparison with that in the unmasked area. Such transient polymer concentration gradients yield imbalances in the chemical potentials of AgNWs, inducing the migration of AgNWs to form a straight-line pattern of AgNWs. The pattern of AgNWs was visualized via photoluminescence imaging under a laser scanning confocal microscope and compared with the light patterns applied to the mixture. These observations revealed that the magnitude of the AgNW migration is enhanced as the transient concentration gradient increases by thickening the mask to decrease the intensity of light passing through the mask. The structural features of the AgNW pattern were reproduced using numerical simulations based on a set of reaction−diffusion equations, which suggested the key role of the polymerization kinetics characterized by the Trommsdorff−Norrish effect. Moreover, as the AgNW pattern becomes clearer, the electrical resistance along the patterns decreases and more complex patterns can be produced, indicating the potential of the method. Overall, the present patterning method constitutes a simple approach that only requires illumination through a mask to generate the AgNW pattern, which renders it a promising alternative for patterning nanocrystals in polymer films.

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Section: ■ Results and Discussionmentioning

confidence: 99%

Section: ■ Results and Discussionmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Patterning Silver Nanowires by Inducing Transient Concentration Gradients in Reaction Mixtures

Tanaka

Morinaga

Tran‐Cong‐Miyata

et al. 2021

ACS Appl. Mater. Interfaces

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Photo‐Directed Growth of Surface Micro‐Patterns on Photosensitive Semicrystalline Polymers

Yan,

Chen,

Deng

et al. 2024

Adv Funct Materials

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Patterning polymeric materials with controllable microstructures can meet diversified requirements and realize promising applications. Exploring micro‐/nano‐pattern methodology offers possibilities for future techniques, however, the self‐organized growth of polymeric materials has some limitations and the development of direct and noncontact patterning processes is still challenging. In this work, the study presents a facile strategy for endowing polymers with spatially regulated microstructures by direct photo‐printing, which incorporates both advantages of typical top‐down and bottom‐up approaches. By employing the photodimerization of anthracene‐containing semi‐crystallized polymers, the gradient crosslinking results in a mismatch of thermal expansion coefficients between the crosslinked surface and the uncrosslinked bottom layer. After heating treatment, constrained by the crosslinked surface, the uncrosslinked bottom polymer of the molten state in the exposed region tends to flow and migrate toward the unexposed region, similar to a volcanic eruption, which accurately determines the height and morphology of pattern. Besides, the well‐defined patterns can controllably grow upon thermal treatment due to phase transformation and migration. The versatility of the proposed strategy not only provides a brand‐new reliable platform to pattern functional materials with photo‐regulated and reversible microstructures, but also promotes the development of smart materials that can find applications in information safety, reversible microfluidics, and electronic devices.

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In Situ Observation of Perovskite Quantum Dots Driven by Photopolymerization Controlled Using a Digital Micromirror Device

Tanaka,

Lagzi,

Nakanishi

2023

Advanced Optical Materials

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Perovskite quantum dots (PQDs) are inherently unstable under environmental conditions, making it difficult to form patterns using conventional techniques. Herein, a unique approach is reported for patterning PQDs by the nonuniform photopolymerization of the liquid monomer. The demonstrated approach employs a PQD‐dispersed photocurable liquid, which is illuminated with the patterned light formed using a digital micromirror device (DMD). As the monomers are photopolymerized, the PQDs in the solution are patterned by diffusion (migration), and eventually, their pattern is imprinted on the film after photopolymerization. The migration process of the PQDs is in situ observed using an inverted‐type confocal microscope, and the patterning principle is examined by fine‐tuning the spatial distribution of the light intensity using the DMD. These findings will promote the generation of clear nanocrystal patterns with high contrasts and narrow line widths on films.

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Nanocrystals Assembled by the Chemical Reaction of the Dispersion Solvent

Cited by 7 publications

References 37 publications

Patterning Silver Nanowires by Inducing Transient Concentration Gradients in Reaction Mixtures

Patterning Silver Nanowires by Inducing Transient Concentration Gradients in Reaction Mixtures

Photo‐Directed Growth of Surface Micro‐Patterns on Photosensitive Semicrystalline Polymers

In Situ Observation of Perovskite Quantum Dots Driven by Photopolymerization Controlled Using a Digital Micromirror Device

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