Studies on atomic layer deposition of MOF-5 thin films

Salmi, Leo D.; Heikkilä, Mikko; Puukilainen, Esa; Sajavaara, Timo; Grosso, David; Ritala, Mikko

doi:10.1016/j.micromeso.2013.08.024

Cited by 83 publications

(93 citation statements)

References 29 publications

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“…22 Hybrid thin films were first deposited using ZnAc 2 and 2,6-NDC as the precursors. The asdeposited amorphous films were crystallized in moist air resulting in an unknown structure.…”

Section: Discussionmentioning

confidence: 99%

“…22 The samples were placed in a humidity-controlled chamber for 24 h at room temperature. It was found out that these films needed a slightly higher humidity of 70% for crystallization compared to the MOF-5 films.…”

Section: A121-mentioning

confidence: 99%

“…A similar shift was also seen in the MOF-5 studies. 22 The shift was permanent in N 2 [ Fig. 6(a)] and reversible in moist air [ Fig.…”

Section: A121-mentioning

confidence: 99%

“…In our earlier study, we have demonstrated the deposition of MOF-5 thin films by combining ALD and a two-step postdeposition crystallization process. 22 The as-deposited amorphous films were first crystallized in moist air. This unknown phase was then recrystallized into the desired MOF-5 phase in an autoclave using dimethylformamide (DMF) as the solvent.…”

Section: Introductionmentioning

confidence: 99%

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Studies on atomic layer deposition of IRMOF-8 thin films

Salmi

Heikkilä

Vehkamäki

et al. 2014

Journal of Vacuum Science &Amp; Technology A: Vacuum, Surfaces, and Films

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Deposition of IRMOF-8 thin films by atomic layer deposition was studied at 260–320 °C. Zinc acetate and 2,6-naphthalenedicarboxylic acid were used as the precursors. The as-deposited amorphous films were crystallized in 70% relative humidity at room temperature resulting in an unknown phase with a large unit cell. An autoclave with dimethylformamide as the solvent was used to recrystallize the films into IRMOF-8 as confirmed by grazing incidence x-ray diffraction. The films were further characterized by high temperature x-ray diffraction (HTXRD), field emission scanning electron microscopy, Fourier transform infrared spectroscopy (FTIR), time-of-flight elastic recoil detection analysis (TOF-ERDA), nanoindentation, and energy-dispersive x-ray spectroscopy. HTXRD measurements revealed similar behavior to bulk IRMOF-8. According to TOF-ERDA and FTIR, composition of the films was similar to IRMOF-8. Through-porosity was confirmed by loading the films with palladium using Pd(thd)2 (thd = 2,2,6,6-tetramethyl-3,5-heptanedionato) as the precursor.

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“…22 Hybrid thin films were first deposited using ZnAc 2 and 2,6-NDC as the precursors. The asdeposited amorphous films were crystallized in moist air resulting in an unknown structure.…”

Section: Discussionmentioning

confidence: 99%

Section: A121-mentioning

confidence: 99%

“…A similar shift was also seen in the MOF-5 studies. 22 The shift was permanent in N 2 [ Fig. 6(a)] and reversible in moist air [ Fig.…”

Section: A121-mentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Studies on atomic layer deposition of IRMOF-8 thin films

Salmi

Heikkilä

Vehkamäki

et al. 2014

Journal of Vacuum Science &Amp; Technology A: Vacuum, Surfaces, and Films

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“…However, sequential deposition makes it difficult to form the complex metal clusters found in MOF structures; instead giving amorphous structures without the required clusters. Even approaches using metal precursors providing suitable clusters in the gas phase16 have required sequential wet-based hydrothermal treatment to crystallize in the desired structure.…”

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confidence: 99%

All-gas-phase synthesis of UiO-66 through modulated atomic layer deposition

2016

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Thin films of stable metal-organic frameworks (MOFs) such as UiO-66 have enormous application potential, for instance in microelectronics. However, all-gas-phase deposition techniques are currently not available for such MOFs. We here report on thin-film deposition of the thermally and chemically stable UiO-66 in an all-gas-phase process by the aid of atomic layer deposition (ALD). Sequential reactions of ZrCl4 and 1,4-benzenedicarboxylic acid produce amorphous organic–inorganic hybrid films that are subsequently crystallized to the UiO-66 structure by treatment in acetic acid vapour. We also introduce a new approach to control the stoichiometry between metal clusters and organic linkers by modulation of the ALD growth with additional acetic acid pulses. An all-gas-phase synthesis technique for UiO-66 could enable implementations in microelectronics that are not compatible with solvothermal synthesis. Since this technique is ALD-based, it could also give enhanced thickness control and the possibility to coat irregular substrates with high aspect ratios.

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Zinc‐Imidazolate Films as an All‐Dry Resist Technology

Corkery,

Waltz,

Eckhert

et al. 2023

Adv Funct Materials

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Motivated by the drawbacks of solution phase processing, an all‐dry resist formation process is presented that utilizes amorphous zinc‐imidazolate (aZnMIm) films deposited by atomic/molecular layer deposition (ALD/MLD), patterned with electron beam lithography (EBL), and developed by novel low temperature (120 °C) gas phase etching using 1,1,1,5,5,5‐hexafluoroacetylacetone (hfacH) to achieve well‐resolved 22 nm lines with a pitch of 30 nm. The effects of electron beam irradiation on the chemical structure and hfacH etch resistance of aZnMIm films are investigated, and it is found that electron irradiation degrades the 2‐methylimidazolate ligands and transforms aZnMIm into a more dense material that is resistant to etching by hfacH and has a C:N:Zn ratio effectively identical to that of unmodified aZnMIm. These findings showcase the potential for aZnMIm films to function in a dry resist technology. Sensitivity, contrast, and critical dimensions of the patterns are determined to be 37 mC cm−2, 0.87, and 29 nm, respectively, for aZnMIm deposited on silicon substrates and patterned at 30 keV. This work introduces a new direction for solvent‐free resist processing, offering the prospect of scalable, high‐resolution patterning techniques for advanced semiconductor fabrication processes.

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Studies on atomic layer deposition of MOF-5 thin films

Cited by 83 publications

References 29 publications

Studies on atomic layer deposition of IRMOF-8 thin films

Studies on atomic layer deposition of IRMOF-8 thin films

All-gas-phase synthesis of UiO-66 through modulated atomic layer deposition

Zinc‐Imidazolate Films as an All‐Dry Resist Technology

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