Growth of a Surface-Tethered, All-Carbon Backboned Fluoropolymer by Photoactivated Molecular Layer Deposition

Closser, Richard G.; Lillethorup, Mie; Bergsman, David S.; Bent, Stacey F.

doi:10.1021/acsami.9b03462

Cited by 13 publications

(16 citation statements)

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“…Most published MLD processes feature relatively simple reaction mechanisms such as nucleophilic acyl substitutions with precursors that consist almost exclusively of an electrophilic acyl derivative and nucleophilic amine or alcohol, and the thermodynamic favorability means that the formation of the product goes to completion provided that the kinetics allow it. These simpler reaction mechanisms are often concerted in the gas phase or consist of few steps, and do not involve large changes in reaction coordinate, with limited possibilities for branching pathways in the mechanism that would lead to unwanted side-reaction products. , Since most of the MLD processes reported to date lead to a single dominant product, reaction selectivity in typical MLD has not been the subject of much study, with some notable exceptions. ,, …”

Section: Resultsmentioning

confidence: 99%

“…In recent years, molecular layer deposition (MLD) has been the subject of significant research effort for applications that require ultrathin organic materials, such as photolithography, − lithium batteries, − and microelectronics. − The molecular analogue of atomic layer deposition (ALD), MLD is a vapor-phase vacuum deposition technique that utilizes alternating self-limiting surface reactions to grow a film on a solid substrate, incorporating entire molecular motifs with each surface reaction. The self-limiting nature of each reaction allows for molecular control of film thickness and deposition of conformal films over even high-aspect-ratio surfaces.…”

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confidence: 99%

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Bridging the Synthesis Gap: Ionic Liquids Enable Solvent-Mediated Reaction in Vapor-Phase Deposition

Shi

Bent

2021

ACS Nano

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Molecular layer deposition (MLD) is an attractive, vapor-phase deposition method for applications requiring ultrathin organic materials, such as photolithography, lithium batteries, and microelectronics. By using sequential self-limiting surface reactions, MLD offers excellent control over thickness and conformality, but there are also challenges such as a limited range of possible film compositions and long deposition times. In this study, we introduce a modified technique, termed ionic liquid assisted MLD (IL-MLD), that can overcome these barriers. By performing the surface reactions inside of an ultrathin layer of a compatible ionic liquid (IL), solvent effects are replicated inside a vacuum system, broadening the possible reactions to a much wider suite of chemistries. Using this strategy, the MLD of polyetherketoneketone, an industrially and research-relevant, high-performance thermoplastic, is reported. With this proof-of-concept, we demonstrate that IL-MLD can enable the synthesis of polymers via solvent-or catalyst-mediated reactions and establish an approach that may allow solution chemistries to be accessed in other vapor deposition techniques as well.

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Section: Resultsmentioning

confidence: 99%

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confidence: 99%

Bridging the Synthesis Gap: Ionic Liquids Enable Solvent-Mediated Reaction in Vapor-Phase Deposition

Shi

Bent

2021

ACS Nano

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“…New organic components have also been developed for the purely organic MLD processes; the MLD material library already includes, besides the initially introduced polyimides [ 15,17–22,137–143 ] and polyamides, [ 15,23–28,144–149 ] many other polymers: polyurea, [ 29,30,37,38,51,150–164 ] polythiourea, [ 52 ] polyurethane, [ 165,166 ] polyazomethine, [ 167–172 ] poly(3,4‐ethylenedioxy‐thiophene), [ 173–177 ] polyimide–polyamide, [ 141 ] poly(ethylene terephthalate) (PET), [ 50,178–180 ] and others. [ 31,32,39–44,176,181–200 ] In recent years, the organic precursor library has been rapidly expanding. We have collected in Table 1 the organic precursors so far used in ALD/MLD processes, together with the heating temperatures employed for their evaporation in the corresponding process conditions; [ …”

Section: Organic Precursors In Ald/mldmentioning

confidence: 99%

Atomic/Molecular Layer Deposition for Designer's Functional Metal–Organic Materials

Multia

Karppinen

2022

Adv Materials Inter

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organic ligands act as bridges between the metal centers to form infinite 1D, 2D, or 3D structures. These materials are often referred to as coordination polymer (CP) [1] or metal-organic framework (MOF) [2] materials; the latter term is used when the metal-organic material is crystalline and highly porous. [3] The research field of CP-and MOF-type materials has grown tremendously over the last two decades. The structural and chemical diversity of these materials has served as a continuous source of scientific excitement; the same diversity has also triggered huge technological interest as these materials possess enormous potential to be tailored for a wide variety of applications ranging from gas capture, storage, and separation to sensing, catalysis, optics, electronics, and energy storage. [4][5][6][7] Most of the targeted application breakthroughs of metal-organics require that these materials can be produced as highquality thin films and coatings, which can be integrated with the other components in the actual device configuration. The possibility to deposit such thin films in an industry-feasible manner on the substrate types needed, would be a major step forward in the field. [8] Traditionally, solvent-based processes such as liquid-phase epitaxy, Langmuir-Blodgett, layer-by-layer, and electrochemical deposition techniques have been used for metal-organic thin films. [9][10][11] These are, however, incompatible with the requirements set by the possible integration of the materials in microelectronics. This is due to corrosion and contamination risks, and the problems in patterning and precise deposition on high-aspect-ratio features. Hence, it is vital to develop solventfree thin-film deposition routes for the metal-organic material family. In the optimal case, these deposition methods should allow conformal coatings on large-area and high-aspect-ratio substrates.The currently strongly emerging ALD/MLD technique is uniquely suited to address the challenge in a scientifically elegant yet industrially feasible way. This technique is derived from the two parent gas-phase thin-film techniques: ALD for inorganic materials (mostly binary metal oxides, sulfides, and nitrides), [12][13][14] and its counterpart MLD for purely organic thin films (e.g., polyimides and polyamides). [15] In both cases, the attractive film growth characteristics are derived from the unique way of separating the different precursor gas pulses. Currently, ALD is the standard thin-film technology in many Atomic layer deposition (ALD) for high-quality conformal inorganic thin films is one of the cornerstones of modern microelectronics, while molecular layer deposition (MLD) is its less-exploited counterpart for purely organic thin films. Currently, the hybrid of these two techniques, i.e., ALD/MLD, is strongly emerging as a state-of-the-art gas-phase route for designer's metal-organic thin films, e.g., for the next-generation energy technologies. The ALD/MLD literature comprises nearly 300 original journal papers covering most of the alkali...

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“…Over the past few years, fluoropolymers [1][2][3][4] have attracted much attention due to their many advantages, such as weather resistance, heat resistance, and solvent resistance [5,6]. As the C-F bonds are particularly strong (bond energy of 485 kJ mol −1 ) and the fluorine atoms exhibit low polarizability and strong electronegativity [7], polymers containing a significant fraction of fluorine atoms usually possess excellent chemical and thermal stability [8].…”

Section: Introductionmentioning

confidence: 99%

Preparation of UV-Curable Low Surface Energy Polyurethane Acrylate/Fluorinated Siloxane Resin Hybrid Coating with Enhanced Surface and Abrasion Resistance Properties

et al. 2020

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Low surface energy coatings have gained considerable attention due to their superior surface hydrophobic properties. However, their abrasion resistance and sustainability of surface hydrophobicity are still not very satisfactory and need to be improved. In this work, a series of utraviolet (UV)-curable fluorosiloxane copolymers were synthesized and used as reactive additives to prepare polyurethane acrylate coatings with low surface energy. The effect of the addition of the fluorinated graft copolymers on the mechanical durability and surface hydrophobicity of the UV-cured hybrid films during the friction-annealing treatment cycles was investigated. The results show that introducing fluorosiloxane additives can greatly enhance surface hydrophobicity of the hybrid film. With addition of 2 wt.% fluorosiloxane copolymers, the water contact angle (WCA) value of the hybrid film was almost tripled compared to that of the pristine PU film, increasing from 58 • to 144 • . The hybrid film also showed enhanced abrasion resistance and could withstand up to about 60 times of friction under a pressure of 20 kPa. The microstructure formed in the annealed film was found to contribute much to achieve better surface hydrophobicity. The polyurethane acrylate/fluorinated siloxane resin hybrid film prepared in this study exhibits excellent potential for applications in the low surface energy field.Especially, some pioneering studies demonstrated that the robust and self-healing ability of the fluorinated materials contribute significantly to the performance of superhydrophobic coatings. For example, Lin et al. [15] prepared superhydrophobic fabrics under 12 KPa and 28,000 cycles of abrasion with wool felt by using a fluoroalkyl silane and crosslinked polydimethylsiloxane (PDMS). Their results showed that the water contact angle of the fabrics remained above 150 • , indicating that the superhydrophobic surface character was retained. They also utilized fluorinated-decyl polyhedral oligomeric silsesquioxane (FD-POSS) and hydrolyzed fluorinated alkyl silane (FAS) to prepare superhydrophobic fabrics, which still exhibited superhydrophobic surface even under ten plasma-and-heat cycles [16]. Zhang et al. [17] combined thiol-ene fluorinated siloxane (T-FAS) and hydrophobic fumed silica nanoparticles to prepare superhydrophobic coatings that could withstand approximately 100 abrasion cycles at 45 KPa [18]. It should be noted that, in these examples, the materials were surface-modified materials rather than pure fluoropolymers.Incorporation of fluorinated groups into acrylate copolymers could bring several desirable properties to the polyacrylate coatings. Depending on their chain length, the contribution of the introduced fluoroalkyl-containing moieties to the material surface properties can be tailored. If the molecular chain of the moieties are too short, they may be buried within the polymer matrix, thus mitigating their contribution [19]. In this aspect, Koji Honda et al. [9] studied the effects of side chain length on the molecular ag...

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Growth of a Surface-Tethered, All-Carbon Backboned Fluoropolymer by Photoactivated Molecular Layer Deposition

Cited by 13 publications

References 68 publications

Bridging the Synthesis Gap: Ionic Liquids Enable Solvent-Mediated Reaction in Vapor-Phase Deposition

Bridging the Synthesis Gap: Ionic Liquids Enable Solvent-Mediated Reaction in Vapor-Phase Deposition

Atomic/Molecular Layer Deposition for Designer's Functional Metal–Organic Materials

Preparation of UV-Curable Low Surface Energy Polyurethane Acrylate/Fluorinated Siloxane Resin Hybrid Coating with Enhanced Surface and Abrasion Resistance Properties

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