Vapor phase processing: a novel approach for fabricating functional hybrid materials

Ashurbekova, Ka. N.; Ashurbekova, Kr. N.; Botta, Gabriele A.; Yurkevich, Oksana; Knez, Mato

doi:10.1088/1361-6528/ab8edb

Cited by 31 publications

(33 citation statements)

References 136 publications

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“…Molecular layer deposition (MLD) is a gas-phase thin-film deposition technique for organic and hybrid organic–inorganic thin films that enables precise thickness and composition control. − The efficiency of the method has been demonstrated with the conformal deposition of ultrathin (<10 nm) and ultrasmooth (<1 nm RMS roughness) MLD coatings onto high aspect ratio and geometrically complex substrates . By high-temperature pyrolysis of hybrid MLD films, one can synthesize a wide spectrum of conductive metal oxide-carbon composites or graphitic thin films …”

Section: Introductionmentioning

confidence: 99%

Ultrathin Hybrid SiAlCOH Dielectric Films through Ring-Opening Molecular Layer Deposition of Cyclic Tetrasiloxane

Ashurbekova

Šarić

et al. 2021

Chem. Mater.

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Molecular layer deposition (MLD) is a powerful vapor phase approach for growing thin polymer films with molecular-level thickness control. We applied the ring-opening MLD process to deposit a siloxane-alumina hybrid organic–inorganic thin film using tetramethyl-tetravinylcyclotetrasiloxane (V4D4) and trimethylaluminum (TMA) as precursors. In situ studies of this process with a quartz crystal microbalance (QCM) showed a linear mass increase with the number of MLD cycles within a processing temperature window between 120 and 200 °C. The QCM study also revealed self-limiting surface chemistry. A growth per cycle of 1.4 and 1.6 Å and a density of 1.9 and 2.2 g cm–3 were determined by X-ray reflectivity (XRR) for the V4D4/TMA film deposited at 150 and 200 °C, respectively. X-ray photoelectron spectroscopy (XPS), attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR), and in situ QCM were employed to analyze the structural changes and composition of the film. High-resolution transmission electron microscopy (HRTEM) was used to confirm the conformality of the obtained coatings. The grown siloxane-alumina film, even as thin as 12 nm, showed an extremely low leakage current density (lower than 5.1 × 10–8 A cm– 2 at ± 2.5 MV cm–1), a dielectric constant (k) of 4.7, and a good thermal stability after one-hour annealing in air at 1100 °C. The obtained highly conformal and thermally stable siloxane-alumina insulating film can be used as a component of field-effect transistors, flash memories, and capacitors in modern electronic systems.

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Section: Introductionmentioning

confidence: 99%

Ultrathin Hybrid SiAlCOH Dielectric Films through Ring-Opening Molecular Layer Deposition of Cyclic Tetrasiloxane

Ashurbekova

Šarić

et al. 2021

Chem. Mater.

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“…[10][11][12][13][14][15][16] Fully aromatic poly[2,2-(m-phenylene)-5,5-bibenzimidazole] or meta-PBI (m-PBI) (Scheme 1) is the most common commercially available PBI polymer. In addition to m-PBI, different types of PBIs are prepared by using various Molecular layer deposition (MLD) [27][28][29][30][31][32][33][34][35] is a vapor phase thin film deposition method with similar characteristics as atomic layer deposition (ALD). [28][29][30][31] These techniques provide uniform and conformal deposition of thin films with accurately controlled thickness.…”

Section: Introductionmentioning

confidence: 99%

“…Molecular layer deposition (MLD) [ 27–35 ] is a vapor phase thin film deposition method with similar characteristics as atomic layer deposition (ALD). [ 28–31 ] These techniques provide uniform and conformal deposition of thin films with accurately controlled thickness.…”

Section: Introductionmentioning

confidence: 99%

Molecular Layer Deposition of Thermally Stable Polybenzimidazole‐Like Thin Films and Nanostructures

Ghafourisaleh

Hatanpää

Vihervaara

et al. 2022

Adv Materials Inter

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aliphatic or aromatic derivatives as monomers for optimizing application specific properties for bioactive materials and fuel cell membranes, for example. [17,18] In recent years, with the developments of using insulating polymer materials in electronic devices, needs for high-thermalresistance polymer dielectrics have been increasingly emphasized in order to ensure high reliability of devices operating at high temperatures. [19] While conventional polyethylene and polypropylene possess intrinsically excellent insulating properties, [20] they are facing great challenges in advanced electrical devices due to their limited service temperatures below 105 °C and increased leakage currents at elevated temperatures. [2,20,21] Another prevalent area for PBI lies in membrane applications such as H 2 separation membranes, fuel cells, and redox battery membranes. High intrinsic H 2 selectivity over larger gas molecules, such as CO 2 , N 2 , and CH 4 , was demonstrated with PBI film membranes prepared using flat and hollow polyamide P84 fibers as a support material. [8] PBI has gained great interest also as a membrane material in vanadium redox flow batteries where ion-selectivity for vanadium was obtained with a thin layer of PBI polymer. [22] Polybenzimidazoles and their more complex derivatives are often classified as expensive specialty plastics due to their outstanding properties but also difficulties in manufacturing. PBI plastics are known as the thermally most stable thermoplastics with a glass transition temperature (T g ) higher than 400 °C. [11] In a previous study by Iqbal et al. [19] PBI exhibited excellent thermal stability up to a temperature of 500 °C with a total weight loss of only 15%. The stability of PBI polymers drives from the high number of aromatic rings incorporated in the polymer chain. Aromatic rings are efficiently absorbing both thermal and radiation energy and aid in redistributing the excitation energy throughout the material. [18,19] Conventional PBI polymers are usually prepared via hightemperature polycondensation reactions in either solution or melt to achieve high degree of cyclization. [23][24][25] PBIs are typically synthesized from aromatic tetraamines (bis-o-diamines) and dicarboxylates (acids, esters, or amides) [26] (Scheme 2).PBI thin films are scarcely reported. Previous depositions were carried out either by a casting solution method from formic acid and dimethylsulfoxide (DMSO) solutions or dip-coating and blade-casting methods. [23] The deposition of polybenzimidazole (PBI)-like thin films by molecular layer deposition is reported here for the first time using isophthalic acid (IPA) and 3,3′-diaminobenzidine (DAB) as monomers and trimethylaluminum (TMA) as a linker precursor. Two precursor pulsing sequences are tested, the ABCB (TMA + IPA + DAB + IPA) and ABC (TMA + IPA + DAB) type MLD processes result in different types of PBI-like films. With the ABCB sequence thin film growth per cycle (GPC) of 6.0 Å is obtained at 225-280 °C, whereas GPC of 7.0 Å is obtained with the ABC s...

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“…However, ALD precursor molecules can dissolve and/or diffuse into the polymer leading to subsurface growth of the ALD material. This type of growth, when promoted by the conditions of the deposition process and favored by the type of polymer, produces organic/inorganic hybrid subsurface layers and falls into the category of so-called sequential infiltration synthesis (SIS), sequential vapor infiltration (SVI), vapor phase infiltration (VPI), or multiple pulsed vapor phase infiltration (MPI) [49][50][51]. On the other hand, for polymers with functional groups inherently present in their chemical structure and available at the surface, the ALD nucleation and growth mostly occurs at the surface, obtaining an ALD film on top of the polymer and a distinct interface between both materials.…”

Section: Introductionmentioning

confidence: 99%

Investigating the Nucleation of AlOx and HfOx ALD on Polyimide: Influence of Plasma Activation

et al. 2021

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There is an increasing interest in atomic layer deposition (ALD) on polymers for the development of membranes, electronics, (3D) nanostructures and specially for the development of hermetic packaging of the new generation of flexible implantable micro-devices. This evolution demands a better understanding of the ALD nucleation process on polymers, which has not been reported in a visual way. Herein, a visual study of ALD nucleation on polymers is presented, based on the different dry etching speeds between polymers (fast) and metal oxides (slow). An etching process removes the polyimide with the nucleating ALD acting as a mask, making the nucleation features visible through secondary electron microscopy analyses. The nucleation of both Al2O3 and HfO2 on polyimide was investigated. Both materials followed an island-coalescence nucleation. First, local islands formed, progressively coalescing into filaments, which connected and formed meshes. These meshes evolved into porous layers that eventually grew to a full layer, marking the end of the nucleation. Cross-sections were analyzed, observing no sub-surface growth. This approach was used to evaluate the influence of plasma-activating polyimide on the nucleation. Plasma-induced oxygen functionalities provided additional surface reactive sites for the ALD precursors to adsorb and start the nucleation. The presented nucleation study proved to be a straightforward and simple way to evaluate ALD nucleation on polymers.

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Vapor phase processing: a novel approach for fabricating functional hybrid materials

Cited by 31 publications

References 136 publications

Ultrathin Hybrid SiAlCOH Dielectric Films through Ring-Opening Molecular Layer Deposition of Cyclic Tetrasiloxane

Ultrathin Hybrid SiAlCOH Dielectric Films through Ring-Opening Molecular Layer Deposition of Cyclic Tetrasiloxane

Molecular Layer Deposition of Thermally Stable Polybenzimidazole‐Like Thin Films and Nanostructures

Investigating the Nucleation of AlOx and HfOx ALD on Polyimide: Influence of Plasma Activation

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