Fluorescence Switchable Conjugated Polymer Microdisk Arrays by Cosolvent Vapor Annealing

Yamagishi, Hiroshi; Matsui, Tokiya; Kitayama, Yusuke; Aikyo, Yusuke; Tong, Lewei; Kuwabara, Junpei; Kanbara, Takaki; Morimoto, Masakazu; Irie, Masahiro; Yamamoto, Yohei

doi:10.3390/polym13020269

Cited by 7 publications

(7 citation statements)

References 24 publications

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“…Also, several host matrices with varied dielectric constants and polarities could be employed, into which the current 2EHO‐TPA‐CNPE molecule could be doped to yield tuned excitonic properties and emissive electronic transitions. Finally, solvent annealing [ 69 ] can also be used to facilitate the dewetting of organic materials for room temperature fabrication of PUFs.…”

Section: Discussionmentioning

confidence: 99%

Organic Light‐Emitting Physically Unclonable Functions

Kayacı

Özdemir

Kalay

et al. 2021

Adv Funct Materials

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The development of novel physically unclonable functions (PUFs) is of growing interest and fluorescent organic semiconductors (f‐OSCs) offer unique advantages of structural versatility, solution‐processability, ease of processing, and great tuning ability of their physicochemical/optoelectronic/spectroscopic properties. The design and ambient atmosphere facile fabrication of a unique organic light‐emitting physically unclonable function (OLE‐PUF) based on a green‐emissive fluorescent oligo(p‐phenyleneethynylene) molecule is reported. The OLE‐PUFs have been prepared by one‐step, brief (5 min) thermal annealing of spin‐coated nanoscopic films (≈40 nm) at a modest temperature (170 °C), which results in efficient surface dewetting to form randomly positioned/sized hemispherical features with bright fluorescence. The random positioning of molecular domains generated the unclonable surface with excellent uniformity (0.50), uniqueness (0.49), and randomness (p > 0.01); whereas the distinctive photophysical and structural properties of the molecule created the additional security layers (fluorescence profile, excited‐state decay dynamics, Raman mapping/spectrum, and infrared spectrum) for multiplex encoding. The OLE‐PUFs on substrates of varying chemical structures, surface energies and flexibility, and direct deposition on goods via drop‐casting are demonstrated. The OLE‐PUFs immersed in water, exposed to mechanical abrasion, and read‐out repeatedly via fluorescence imaging showed great stability. These findings clearly demonstrate that rationally engineered solution‐processable f‐OSCs have a great potential to become a key player in the development of new‐generation PUFs.

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Section: Discussionmentioning

confidence: 99%

Organic Light‐Emitting Physically Unclonable Functions

Kayacı

Özdemir

Kalay

et al. 2021

Adv Funct Materials

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“…Accordingly, the optical memory array provides a physically uncloneable function (PUF) and can be utilized as an anti-counterfeiting two-step authentication system; the first step is a micrometer-scale QR code and the second step is reading of the WGM fingerprint from each hemisphere pixel. The surface self-assembly process for the fabrication of microdisk arrays is applicable for other organic materials such as PS and π-conjugated polymers …”

Section: Functions Of Micro-photoemitters Made By Self-assemblymentioning

confidence: 99%

“…The surface self-assembly process for the fabrication of microdisk arrays is applicable for other organic materials such as PS and π-conjugated polymers. 33 Photoswitchable microresonators can be utilized in allorganic, all-optical logic gate operations. As described in section 3.1, a cavity-mediated energy transfer cascade occurs efficiently between multiple coupled microspheres.…”

Section: Lasers Memories and Logic Gates From π-Conjugated Polymer Mi...mentioning

confidence: 99%

Molecular and Supramolecular Designs of Organic/Polymeric Micro-photoemitters for Advanced Optical and Laser Applications

et al. 2023

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Metrics & MoreArticle Recommendations CONSPECTUS: For optical and electronic applications of supramolecular assemblies, control of the hierarchical structure from nano-to micro-and millimeter scale is crucial. Supramolecular chemistry controls intermolecular interactions to build up molecular components with sizes ranging from several to several hundreds of nanometers using bottom-up self-assembly process. However, extending the supramolecular approach up to a scale of several tens of micrometers to construct objects with precisely controlled size, morphology, and orientation is challenging. Especially for microphotonics applications such as optical resonators and lasers, integrated optical devices, and sensors, a precise design of a micrometer-scale object is required. In this Account, we review the recent progress on precise control of microstructures from π-conjugated organic molecules and polymers, which work as micro-photoemitters and are suitable for optical applications.After the introduction on the importance of the control of the hierarchical structures from molecular assembly, we review supramolecular methodology for assembling molecules and supramolecules to form microstructures such as spheres and polygons with precisely controlled morphology and molecular orientations. The resultant microstructures act as anisotropic emitters of circularly polarized luminescence. We report that synchronous crystallization of π-conjugated chiral cyclophanes forms concave hexagonal pyramidal microcrystals with homogeneous size, morphology, and orientation, which clearly paves the way for the precise control of skeletal crystallization under kinetic control. Furthermore, we show microcavity functions of the self-assembled micro-objects. The self-assembled π-conjugated polymer microspheres work as whispering gallery mode (WGM) optical resonators, where the photoluminescence exhibits sharp and periodic emission lines. The spherical resonators with molecular functions act as long-distance photon energy transporters, convertors, and full-color microlasers. Fabrication of microarrays with photoswitchable WGM microresonators by the surface self-assembly technique realizes optical memory with physically unclonable functions of WGM fingerprints. All-optical logic operations are demonstrated by arranging the WGM microresonators on synthetic and natural optical fibers, where the photoswitchable WGM microresonators act as a gate for light propagation via a cavity-mediated energy transfer cascade. Meanwhile, the sharp WGM emission line is appropriate for utilization as optical sensors for monitoring the mode shift and mode splitting. The resonant peaks sensitively respond to humidity change, absorption of volatile organic compounds, microairflow, and polymer decomposition by utilizing structurally flexible polymers, microporous polymers, nonvolatile liquid droplets, and natural biopolymers as media of the resonators. We further construct microcrystals from π-conjugated molecules with rods and rhombic plates, which act as WGM laser ...

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“…This is especially advantageous due to its superior visco-elastic and mechanical properties, which aid in the manufacturing of new devices [ 14 , 15 , 16 , 17 , 18 , 19 ]. FPs, similar to small fluorescent molecules, have a wide range of uses for sensing [ 20 , 21 ] and imaging [ 22 , 23 , 24 , 25 , 26 , 27 ], optoelectronics [ 28 ], fluorescent bioprobes [ 29 ], molecular imaging [ 30 ], photodynamic treatments [ 31 ], OLEDs [ 32 ], storage data security [ 33 ], encryption [ 34 ], anti-counterfeiting materials [ 35 ], and other fields [ 27 , 36 , 37 , 38 , 39 , 40 , 41 , 42 , 43 ].…”

Section: Introductionmentioning

confidence: 99%

Fluorescent Polymers Conspectus

Ahumada

Borkowska

2022

Polymers

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The development of luminescent materials is critical to humankind. The Nobel Prizes awarded in 2008 and 2010 for research on the development of green fluorescent proteins and super-resolved fluorescence imaging are proof of this (2014). Fluorescent probes, smart polymer machines, fluorescent chemosensors, fluorescence molecular thermometers, fluorescent imaging, drug delivery carriers, and other applications make fluorescent polymers (FPs) exciting materials. Two major branches can be distinguished in the field: (1) macromolecules with fluorophores in their structure and (2) aggregation-induced emission (AIE) FPs. In the first, the polymer (which may be conjugated) contains a fluorophore, conferring photoluminescent properties to the final material, offering tunable structures, robust mechanical properties, and low detection limits in sensing applications when compared to small-molecule or inorganic luminescent materials. In the latter, AIE FPs use a novel mode of fluorescence dependent on the aggregation state. AIE FP intra- and intermolecular interactions confer synergistic effects, improving their properties and performance over small molecules aggregation-induced, emission-based fluorescent materials (AIEgens). Despite their outstanding advantages (over classic polymers) of high emission efficiency, signal amplification, good processability, and multiple functionalization, AIE polymers have received less attention. This review examines some of the most significant advances in the broad field of FPs over the last six years, concluding with a general outlook and discussion of future challenges to promote advancements in these promising materials that can serve as a springboard for future innovation in the field.

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Fluorescence Switchable Conjugated Polymer Microdisk Arrays by Cosolvent Vapor Annealing

Cited by 7 publications

References 24 publications

Organic Light‐Emitting Physically Unclonable Functions

Organic Light‐Emitting Physically Unclonable Functions

Molecular and Supramolecular Designs of Organic/Polymeric Micro-photoemitters for Advanced Optical and Laser Applications

Fluorescent Polymers Conspectus

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