Remarkable effect of halogenation of aromatic compounds on efficiency of nanowire formation through polymerization/crosslinking by high-energy single particle irradiation

Horio, Akifumi; Sakurai, Tsuneaki; Kayama, Kazuto; Lakshmi, G. B. V. S.; Avasthi, D.K.; Sugimoto, Masaki; Yamaki, Tetsuya; Chiba, Ayano; Saito, Yuichi; Seki, Shu

doi:10.1016/j.radphyschem.2017.02.052

Cited by 6 publications

(4 citation statements)

References 37 publications

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“…It is noteworthy that the nanowires could be produced from the simple sublimable polyaromatic hydrocarbon 9,10-bis(phenylethynyl)anthracene (BPEA), where the STLiP protocol could induce efficient chain polymerization/cross-linking reactions mediated by the reaction at C–C triple bonds 58 . Much higher enhancement of the reactions could be promoted by dissociative electron attachment onto halogen atoms bound to aromatic rings 59 , 60 , resulting in the successful formation of standing nanowires based on all five starting compounds represented in Fig. 3 .…”

Section: Resultsmentioning

confidence: 99%

Ubiquitous organic molecule-based free-standing nanowires with ultra-high aspect ratios

et al. 2021

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The critical dimension of semiconductor devices is approaching the single-nm regime, and a variety of practical devices of this scale are targeted for production. Planar structures of nano-devices are still the center of fabrication techniques, which limit further integration of devices into a chip. Extension into 3D space is a promising strategy for future; however, the surface interaction in 3D nanospace make it hard to integrate nanostructures with ultrahigh aspect ratios. Here we report a unique technique using high-energy charged particles to produce free-standing 1D organic nanostructures with high aspect ratios over 100 and controlled number density. Along the straight trajectory of particles penetrating the films of various sublimable organic molecules, 1D nanowires were formed with approximately 10~15 nm thickness and controlled length. An all-dry process was developed to isolate the nanowires, and planar or coaxial heterojunction structures were built into the nanowires. Electrical and structural functions of the developed standing nanowire arrays were investigated, demonstrating the potential of the present ultrathin organic nanowire systems.

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Section: Resultsmentioning

confidence: 99%

Ubiquitous organic molecule-based free-standing nanowires with ultra-high aspect ratios

et al. 2021

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“…For example, polystyrene derivatives were extensively studied, and the formation of clear nanowires were confirmed after the development with aliphatic or aromatic hydrocarbon solvents [81,82]. Halogenated derivatives, poly(4-chlorostyrene) and poly(4-bromostyrene), were also irradiated with 129 Xe ion beams, giving thicker nanowires with larger cross-sectional diameters [83,84]. The possible reason for the increase in diameters of nanowires resulted not only from the molecular weight of initial polymers, but also the dissociative electron attachment reactions often observed for halogenated hydrocarbons [85,86].…”

Section: D Nanostructures Based On a Variety Of Polymersmentioning

confidence: 99%

Interactions of Single Particle with Organic Matters: A Facile Bottom-Up Approach to Low Dimensional Nanostructures

Sakaguchi¹,

Kamiya²,

Sakurai³

et al. 2020

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A particle induces a pack of chemical reactions in nanospace: chemical reactions confined into extremely small space provide an ultimate technique for the nanofabrication of organic matter with a variety of functions. Since the discovery of particle accelerators, an extremely high energy density can be deposited, even by a single isolated particle with MeV-ordered kinetic energy. However, this was considered to cause severe damages to organic molecules due to its relatively small bond energies, and lack of ability to control the reactions precisely to form the structures while retaining physico-chemical molecular functionalities. Practically, the severely damaged area along a particle trajectory: a core of a particle track has been simply visualized for the detection/dosimetry of an incident particle to the matters, or been removed to lead nanopores and functionalized by refilling/grafting of fresh organic/inorganic materials. The use of intra-track reactions in the so-called “penumbra” or “halo” area of functional organic materials has been realized and provided us with novel and facile protocols to provide low dimensional nano-materials with perfect size controllability in the 21st century. These protocols are now referred to as single particle nanofabrication technique (SPNT) and/or single particle triggered linear polymerization technique (STLiP), paving the way towards a new approach for nanomaterials with desired functionalities from original molecules. Herein, we report on the extremely wide applicability of SPNT/STLiP protocols for the future development of materials for opto-electronic, catalytic, and biological applications among others.

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“…1). The key factor in the STLiP technique is to achieve gelation with high enough insolubility against successive wet development process with strong solvent for initial target molecules [15][16][17][18], and thus to trigger efficiently the initiation reactions and promote propagation reactions in a charged particle track.…”

Section: Introductionmentioning

confidence: 99%

Highly Efficient Solid-State Intra-Track Polymerization of Ethynyl-Substituted Spirobifluorenes Triggered by Swift Heavy Ion Irradiations

Sakaguchi

Sakurai

Idesaki

et al. 2020

J. Photopol. Sci. Technol.

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Acetylenes are the first monomer to polymerize by the energy deposited by ionizing radiations. Herein we report an extremely efficient solid state polymerization of ethynylsubstituted 9,9'-spirobi[9H-fluorene]s (SBFs) via a unique nano-fabrication technique referred to as Single Particle Trigged Linear Polymerization (STLiP) initiated by high energy charged particles. The resulted nanowires of polymerized/crosslinked SBFs show a gradual transformation from flexible to rigid rod-like with an increase in the reaction efficiency mediated by the ethynyl substitution. The overall efficiency of initiation/propagation/crosslinking reactions is remarkably high even in comparison with the primary yield of ionization events in the radiation chemical processes, marking up to G > 80 (100 eV)-1 , which is suggestive of efficient chain reactions in the propagation steps. The present results demonstrate efficient solid-state polymerization reactions, which are neither topochemical polymerization reactions nor acid/base catalyzed reactions, expand the versatility of STLiP technique to fabricate 1D nanomaterials based on a variety of organic compounds.

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Remarkable effect of halogenation of aromatic compounds on efficiency of nanowire formation through polymerization/crosslinking by high-energy single particle irradiation

Cited by 6 publications

References 37 publications

Ubiquitous organic molecule-based free-standing nanowires with ultra-high aspect ratios

Ubiquitous organic molecule-based free-standing nanowires with ultra-high aspect ratios

Interactions of Single Particle with Organic Matters: A Facile Bottom-Up Approach to Low Dimensional Nanostructures

Highly Efficient Solid-State Intra-Track Polymerization of Ethynyl-Substituted Spirobifluorenes Triggered by Swift Heavy Ion Irradiations

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