Radical-triggered cross-linking for molecular layer deposition of SiAlCOH hybrid thin films

Ashurbekova, Kristina; Ashurbekova, Karina; Šarić, Iva; Modin, Evgeny; Petravić, M.; Abdulagatov, Ilmutdin M.; Абдулагатов, А. И.; Knez, Mato

doi:10.1039/d0cc07858a

Cited by 9 publications

(11 citation statements)

References 25 publications

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“…Clearly, trimethylaluminum (TMA), the most widely studied organometallic precursor ,,,,, for VPI, is not suitable for polysiloxanes. The strong Lewis acidity of TMA often leads to a cleavage of the Si–O–Si bonds, thus damaging the siloxane chains and rings. , In comparison, diethylzinc (DEZ) is less aggressive than TMA with regard to preserving the polymer structures. However, the larger molecular size and weaker Lewis acidity of DEZ represent a significant difficulty in diffusion and entrapment in a polymer matrix in general, leading to a small or even negligible Zn loading. , Organosiloxane polymers lack common reactive functionalities for DEZ such as hydroxyl, , amide, amine, and imine groups .…”

Section: Introductionmentioning

confidence: 99%

Vapor-Phase Molecular Doping in Covalent Organosiloxane Network Thin Films Via a Lewis Acid–Base Interaction for Enhanced Mechanical Properties

Qiu

Luo

et al. 2021

ACS Appl. Mater. Interfaces

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Incorporating inorganic components in organosiloxane polymer thin films for enhanced mechanical properties could enable better durability and longevity of functional coatings for a multitude of applications. However, molecularly dispersing the inorganic dopants while preserving the cyclosiloxane rings represents a challenge for cross-linked organosiloxane networks. Here, we report a molecular doping strategy using vapor-phase infiltration. On the basis of the proper Lewis acid−base interaction between diethyl zinc (DEZ) and cyclotrisiloxane rings, we achieved a complete infiltration of the organometallic precursors and well-distributed Zn−OH terminal groups formed in the initiated chemical vapor deposited poly(1,3,5-trimethyl-1,3,5-trivinylcyclotrisiloxane) (PV 3 D 3 ) films. X-ray photoelectron spectroscopy and nanoscale infrared spectroscopy together with density functional theory simulation reveal that the formation of a Lewis acid−base adduct rather than a ring-opening process is possibly involved in anchoring DEZ in the cross-linked network of PV 3 D 3 . Because of the incorporation of Zn−OH components, the organic−inorganic hybrid films obtained via our vapor-phase molecular doping exhibit a 10.2% larger elastic modulus and 67.0% higher hardness than the pristine PV 3 D 3 . Unveiling the reaction mechanisms between organometallic precursors and cross-linked organic networks provides new insights for expanding the vapor-phase processing strategies for engineering hybrid materials at the nanoscale.

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Section: Introductionmentioning

confidence: 99%

Vapor-Phase Molecular Doping in Covalent Organosiloxane Network Thin Films Via a Lewis Acid–Base Interaction for Enhanced Mechanical Properties

Qiu

Luo

et al. 2021

ACS Appl. Mater. Interfaces

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“…Radical-initiated cross-linking of the hybrid alumosiloxane thin film in a layer-by-layer manner enhanced the stability and density of the film. 12 As mentioned earlier, functional thin films have a high application potential in biomedicine and tissue engineering, if they are rendered bioactive. Bioactive organic−inorganic hybrid MLD films have been reported in few studies, mostly by the group of Ola Nilsen.…”

Section: ■ Introductionmentioning

confidence: 94%

“…These alumosiloxane films showed an extremely low leakage current density (∼10 –8 A cm –2 at ± 3 MV cm –1 ) and a good thermal stability upon calcination at 1100 °C. Radical-initiated cross-linking of the hybrid alumosiloxane thin film in a layer-by-layer manner enhanced the stability and density of the film …”

Section: Introductionmentioning

confidence: 99%

Biocompatible Silicon-Based Hybrid Nanolayers for Functionalization of Complex Surface Morphologies

Ashurbekova

Alonso-Lerma

Šarić

et al. 2022

ACS Appl. Nano Mater.

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Silicon-based polymers show great promise for various applications in biomedicine, nanotechnology, tissue targeting, and drug delivery. The use of such materials as functional coatings on surfaces requires the development of strongly adhering and flexible conformal films, which is challenging for conventional wet-chemical coating techniques. We have developed a facile, solvent-free molecular layer deposition (MLD) process to grow environmentally stable hybrid alumosilazane thin films. Exceptionally good biocompatibility is testified with significantly higher proliferation of human embryonic kidney (HEK293T) cells than that on glass, which was used as a reference. Such highly biocompatible and conformal films show great promise as functional coatings for scaffolds or implantable devices with complex topologies or high-aspect-ratio structures.

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“…[ 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; [ 17,18,32,40,46,51,57–59,61,63,64,66,81,105–108,114,118,119,121,122,125,129,134–136,139,141,142,156,164,168,189,201–284 ...…”

Section: Organic Precursors In Ald/mldmentioning

confidence: 99%

“…[ 111,231,287–332 ] However, TMA works very well with many other organics as well. [ 40,46,54,108,109,114,125,148,211–213,218,219,221,226,228,230,234,240,244,245,249,252,255,256,258,260,262,264,267–269,273–277,279–284,325,333–369 ] The bulkier dimethyl aluminum isopropoxide precursor has been successfully used with EG as well. [ 323 ] Different TMA + organic processes have been investigated, e.g., to elucidate the effect of the organic backbone length, i.e., long (1,10‐decanediol) or short (1,6‐hexanediol), on the mechanical properties; indeed, as expected, with the increasing chain length, the stretchability was enhanced.…”

Section: Brief Account Of Ald/mld Processes Developedmentioning

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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Radical-triggered cross-linking for molecular layer deposition of SiAlCOH hybrid thin films

Abstract: We developed a thin film growth with a radical-initiated cross-linking of vinyl groups in a layer-by-layer manner via molecular layer deposition (MLD). The cross-linked film exhibited improved properties like 12% higher density and enhanced stability compared to the non-cross-linked film.

Cited by 9 publications

References 25 publications

Vapor-Phase Molecular Doping in Covalent Organosiloxane Network Thin Films Via a Lewis Acid–Base Interaction for Enhanced Mechanical Properties

Vapor-Phase Molecular Doping in Covalent Organosiloxane Network Thin Films Via a Lewis Acid–Base Interaction for Enhanced Mechanical Properties

Biocompatible Silicon-Based Hybrid Nanolayers for Functionalization of Complex Surface Morphologies

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

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