Facile synthesis of an organic/inorganic hybrid 2D structure tincone film by molecular layer deposition

Beak, GeonHo; Lee, Seung Hwan; Kim, Hye‐Mi; Choi, Suhwan; Park, Jin‐Seong

doi:10.1039/d1dt02984c

Cited by 5 publications

(5 citation statements)

References 53 publications

(51 reference statements)

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“…However, the GPC observed in this study for the PA-MLD process is lower than expected, considering the approximate height of 6 Å of the benzene ring. This occurs because, during the MLD reaction, aromatic ring-type precursors such as Phl do not adsorb vertically onto the growing film but are thermodynamically preferred to adsorb at a certain angle, tilting [23]. Therefore, the actual GPC in MLD processes using aromatic ring-type precursors is typically lower than the height of the benzene ring.…”

Section: Resultsmentioning

confidence: 99%

Synthesis of low-k SiONC thin films by plasma-assisted molecular layer deposition with tetraisocyanatesilane and phloroglucinol

Park,

Yang,

Kim

et al. 2024

Nanotechnology

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Low-k SiONC thin films with excellent thermal stabilities were deposited using plasma-assisted molecular layer deposition (PA-MLD) with a tetraisocyanatesilane (Si(NCO)4) precursor, N2 plasma, and phloroglucinol (C6H3(OH)3). By adjusting the order of the N2 plasma exposure steps within the PA-MLD process, we successfully developed a deposition technique that allows accurate control of thickness at the Ångström level via self-limiting reactions. The thicknesses of the thin films were measured through spectroscopic ellipsometry (SE). By tuning the N2 plasma power, we facilitated the formation of -NH2 sites for phloroglucinol adsorption, achieving a growth per cycle of 0.18 Å/cycle with 300 W of N2 plasma power. Consequently, the thickness of the films increased linearly with each additional cycle. Moreover, the organic linkers within the film formed stable bonds through surface reactions, resulting in a negligible decrease in thickness of approximately −11% even upon exposure to a high annealing temperature of 600 ℃. This observation was confirmed by SE, distinguishing the as-prepared film from previously reported low-k films that fail to maintain their thickness under similar conditions. X-ray photoelectron spectroscopy (XPS) and current–voltage (I–V) and capacitance–voltage (C–V) measurement were conducted to evaluate the composition, insulating properties, and dielectric constant according to the deposition and annealing conditions. XPS results revealed that as the plasma power increased from 200 to 300 W, the C/Si ratio increased from 0.37 to 0.67, decreasing the dielectric constant from 3.46 to 3.12. Furthermore, there was no significant difference in the composition before and after annealing, and the hysteresis decreased from 0.58 to 0.19 V owing to defect healing, while maintaining the leakage current density, breakdown field, and dielectric constant. The low dielectric constant, accurate thickness control, and excellent thermal stability of this MLD SiONC thin film enable its application as an interlayer dielectric in back-end-of-line process.

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Section: Resultsmentioning

confidence: 99%

Synthesis of low-k SiONC thin films by plasma-assisted molecular layer deposition with tetraisocyanatesilane and phloroglucinol

Park,

Yang,

Kim

et al. 2024

Nanotechnology

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“…[ 424 ] Tin‐based hybrid films have been deposited from Sn–TDMA together with GL, [ 220,425 ] and EG, [ 220 ] and also from HS–Sn with HQ. [ 426 ] Also, Ta 2 O 5 /polyimide nanolaminate structures have been deposited using Ta(OEt) 5 and water as precursors for Ta 2 O 5 and pyromellitic dianhydride (PMDA) and 1,6‐diaminohexane (DAH) as precursors for polyimide. [ 209 ]…”

Section: Brief Account Of Ald/mld Processes Developedmentioning

confidence: 99%

“…[ 432 ] Interestingly, the postdeposition treatment can be based on annealing only, as was recently demonstrated for Sn–HQ films which were initially weakly nanocrystalline but could be better crystallized through a postdeposition annealing. [ 426 ]…”

Section: Crystallinity Of Ald/mld Filmsmentioning

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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“…To date, three MLD processes have been reported for tincones: TDMASn (tetrakisdimethyl aminotin)-GL, 59,60) and HS-Sn [N,N′-tert-butyl-1,1-dimethyl-ethylene-diamine stannylene(II)]-HQ. 61) Kerckhove et al 59) first achieved hybrid Sn-organic thin films called "tincones" using TDMASn as the metal precursor and GL as the organic reactant. The GL-based process displayed linear growth and self-limiting surface reactions in a broad temperature window ranging from 75 °C to 200 °C.…”

Section: Introductionmentioning

confidence: 99%

“…Beak et al 61) fabricated tincone films using the MLD process; a SnO structure combined with a benzene ring was deposited using a divalent Sn precursor and HQ as an organic precursor. From their previous studies, SnO could be fabricated through a reaction with H 2 O, which has low a oxidizing power.…”

Section: Introductionmentioning

confidence: 99%

Review of molecular layer deposition process and application to area selective deposition via graphitization

Baek

Yang

Park

et al. 2023

Jpn. J. Appl. Phys.

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As patterning technology for manufacturing highly integrated devices develops in the current semiconductor market, sophisticated technology nodes of 5 nm or smaller are required. Area selective deposition (ASD) is a promising technology alternative to traditional top-down methods by reducing-edge placement error (EPE) and creating self-alignment. A new strategy for applying the qualified molecular layer deposition (MLD) process of highly conformal deposition to ASD as an inhibition material is being studied. In the case of metalcones manufactured using an aromatic ring as an organic precursor, graphitic carbonization proceeds through high-temperature annealing, and the inhibition property can be activated by removing surface functional groups. The characteristics of feasible patterning can be noted as metal elements in the thin film are removed during the annealing process, especially in the case of graphitic carbon. In this review, we introduce the potential application of MLD materials in the development of inhibitors for advanced ASD

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Facile synthesis of an organic/inorganic hybrid 2D structure tincone film by molecular layer deposition

Abstract: Organic/inorganic hybrid tincone films were deposited by molecular layer deposition (MLD) using N,N′-tert-butyl-1,1-dimethylethylenediamine stannylene(II) as a precursor and hydroquinone (HQ) as organic reactants. As a result of previous studies it...

Cited by 5 publications

References 53 publications

Synthesis of low-k SiONC thin films by plasma-assisted molecular layer deposition with tetraisocyanatesilane and phloroglucinol

Synthesis of low-k SiONC thin films by plasma-assisted molecular layer deposition with tetraisocyanatesilane and phloroglucinol

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

Review of molecular layer deposition process and application to area selective deposition via graphitization

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