Photo-cleavable perfluoroalkylated copolymers for tailoring quantum dot thin films

Son, Jongchan; Roh, Heebum; Shin, Han Young; Park, Keun-Woo; Park, Chunhee; Park, Hanbit; Lee, Changhee; Kwak, Jeonghun; Jung, Bernhard; Lee, Jin‐Kyun

doi:10.1039/d0py01017k

Cited by 5 publications

(6 citation statements)

References 34 publications

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“…IBOMA is a monomer that has been widely used in the field of coating, pressure‐sensitive adhesives, etc. [ 80–83 ] The glass transition temperature ( T g ) of PIBOMA is ≈153 °C and it is challenging to prepare colloidally stable PIBOMA‐based block copolymer nano‐objects by RAFT‐mediated dispersion polymerization. As a control experiment, we first performed photoinitiated RAFT dispersion polymerization of IBOMA (20% w/w, DP of 200) at 70 °C mediated by PHPMA 31.4 ‐CDPA.…”

Section: Resultsmentioning

confidence: 99%

Preparation of Block Copolymer Nano‐Objects with Embedded β‐Ketoester Functional Groups by Photoinitiated RAFT Dispersion Polymerization

Huang

Liu

Chen³

et al. 2021

Macromol. Rapid Commun.

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Herein, a photoinitiated reversible addition‐fragmentation chain transfer (RAFT) dispersion polymerization of 2‐(acetoacetoxy)ethyl methacrylate (AEMA) in ethanol/water at room temperature for in situ preparation of β‐ketoester‐functionalized block copolymer nano‐objects is reported. AEMA is also copolymerized with isobornyl methacrylate (IBOMA) to improve the colloidal stability of PIBOMA‐based block copolymer nano‐objects prepared by photoinitiated RAFT dispersion polymerization at low temperatures. A series of P(IBOMA‐stat‐AEMA)‐based block copolymer nano‐objects are prepared by changing reaction parameters. Finally, lanthanide‐doped block copolymer nano‐objects with luminescent and magnetic properties are also prepared based on the complexation of various lanthanide ions with the β‐ketoester group. It is expected that the current study will provide a facile platform for the in situ preparation of β‐ketoester‐functionalized block copolymer nano‐objects with different morphologies for specific applications.

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Section: Resultsmentioning

confidence: 99%

Preparation of Block Copolymer Nano‐Objects with Embedded β‐Ketoester Functional Groups by Photoinitiated RAFT Dispersion Polymerization

Huang

Liu

Chen³

et al. 2021

Macromol. Rapid Commun.

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“…They employed a photo‐cleavable fluorinated copolymer as a stencil material for the generation of QD patterns (Figure 3c). [ 63 ] This developed fluoropolymer exhibited notable solubility in a fluorous solvent, introducing the concept of “orthogonal processing” with the underlying QD film. The application of orthogonal processing is prevalent in solution‐processed QD‐LEDs during the formation of multilayer stacks, relying on the orthogonality of solvents (e.g., nonpolar organic solvent, hydroxylic solvent, and fluorous solvent) to minimize dissolution of underlying layers.…”

Section: Prevailing Qd Patterning Technologiesmentioning

confidence: 99%

Recent Progress on Quantum Dot Patterning Technologies for Commercialization of QD‐LEDs: Current Status, Future Prospects, and Exploratory Approaches

Lee,

Jo,

Choi

et al. 2024

Small Methods

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Colloidal quantum dots (QDs) are widely regarded as advanced emissive materials with significant potential for display applications owing to their excellent optical properties such as high color purity, near‐unity photoluminescence quantum yield, and size‐tunable emission color. Building upon these attractive attributes, QDs have successfully garnered attention in the display market as down‐conversion luminophores and now venturing into the realm of self‐emissive displays, exemplified by QD light‐emitting diodes (QD‐LEDs). However, despite these advancements, there remains a relatively limited body of research on QD patterning technologies, which are crucial prerequisites for the successful commercialization of QD‐LEDs. Thus, in this review, an overview of the current status and prospects of QD patterning technologies to accelerate the commercialization of QD‐LEDs is provided. Within this review, a comprehensive investigation of three prevailing patterning methods: optical lithography, transfer printing, and inkjet printing are conducted. Furthermore, several exploratory QD patterning techniques that offer distinct advantages are introduced. This study not only paves the way for successful commercialization but also extends the potential application of QD‐LEDs into uncharted frontiers.

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“…A modified photolithography protocol that uses less-damaging highly fluorinated or fluorous solvents has been proposed to overcome this compatibility hurdle. − In this process, a fluorous solution of a fluorinated photoresist is cast into a thin film on top of the organic active layer, and then, it is used to produce a stencil with a fluorous developing solvent following UV irradiation. The physical and chemical integrity of the underlying organic layer can be preserved during the stencil-making process due to the orthogonality between the fluorous and organic materials.…”

Section: Introductionmentioning

confidence: 99%

“…Recently, we reported that benzil monoxime moieties could be used as side units on a fluoroalkylated polymethacrylate backbone to produce a positive-tone photoresist. 19 UVtriggered cleavage reactions of the bulky nonfluorinated benzil monoximes led to an increase in solubility in nonpolar fluorous media. This success encouraged us to explore another chemical route, which revealed an interesting motif with spiropyranyl compounds (Figure 1a).…”

Section: Introductionmentioning

confidence: 99%

Photoinduced Solubility Modulation in the Copolymers of Fluoroalkyl, Spiropyranyl, and Isobornyl Methacrylates

Park

Choi

et al. 2023

ACS Appl. Polym. Mater.

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This article reports photoinduced solubility modulation in copolymer thin films derived from spiropyranyl, perfluoroalkyl, and isobornyl methacrylates. A random copolymer of spiropyranyl methacrylate (SPMA) and 1H,1H,2H,2H-perfluorooctyl methacrylate (FOMA) was first prepared in the absence of isobornyl methacrylate (IBMA). The resulting as-prepared thin film could be dissolved in highly fluorinated or fluorous solvents but became insoluble following exposure to UV light (λ = 365 nm) via the photoisomerization transformation of spiropyran units into merocyanine moieties. On the other hand, the incorporation of IBMA into the copolymer structure above a certain threshold resulted in copolymers exhibiting the opposite dissolution behavior. UV–vis spectroscopic measurements on the copolymer films and solutions indicated that dipolar attraction between the photoisomerized merocyanine moieties contributed to the decrease in solubility. The incorporation of IBMA into the copolymer chains diluted the merocyanine moieties and increased their glass-transition temperature, resulting in the disruption of the intermolecular attraction and an increase in the solubility of the UV-exposed polymer chains. These results suggested that stencils could be developed without additives to generate strong acid molecules or free radicals in polymer thin films. The proposed processing technique for fluoroalkylated copolymers was thus tested in the fabrication of orthogonal copolymer stencils and demonstrated to be a useful tool for the pixel patterning of chemically vulnerable organic light-emitting diodes.

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Photo-cleavable perfluoroalkylated copolymers for tailoring quantum dot thin films

Abstract: We report the synthesis, operating mechanism, and application of a copolymer that reveals increasing solubility in fluorous solvents by photolysis. The copolymer, PFBI, was prepared by polymerizing perfluorooctyl methacrylate (FOMA),...

Cited by 5 publications

References 34 publications

Preparation of Block Copolymer Nano‐Objects with Embedded β‐Ketoester Functional Groups by Photoinitiated RAFT Dispersion Polymerization

Preparation of Block Copolymer Nano‐Objects with Embedded β‐Ketoester Functional Groups by Photoinitiated RAFT Dispersion Polymerization

Recent Progress on Quantum Dot Patterning Technologies for Commercialization of QD‐LEDs: Current Status, Future Prospects, and Exploratory Approaches

Photoinduced Solubility Modulation in the Copolymers of Fluoroalkyl, Spiropyranyl, and Isobornyl Methacrylates

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