Mesoporous ZnO thin films obtained from molecular layer deposited “zincones”

Perrotta, Alberto; Berger, Richard; Muralter, Fabian; Coclite, Anna Maria

doi:10.1039/c9dt02824b

Cited by 10 publications

(17 citation statements)

References 65 publications

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“…The MLD process included the following four steps, repeated for each cycle: (1) DEZ dose, (2) Ar purging, (3) EG dose, and (4) Ar purging. To ensure the saturation behavior of the four steps as previously investigated [ 36 ], the deposition recipe was fixed to 0.15 s for the DEZ dose, 60 s for the first Ar purge, 0.2 s for the EG exposure, and 170 s for the second Ar purge. The 16 sccm set for the Ar flow resulted in working pressure of 0.15 torr, and relative precursor pressures of Δp = (0.2 ± 0.02) torr for DEZ and of Δp = (0.1 ± 0.02) torr for EG.…”

Section: Methodsmentioning

confidence: 99%

“…Previous work from our group [ 35 ] showed that zincone-like thin films can be deposited via sub-saturated plasma-enhanced atomic layer deposition and that porous ZnO can be obtained from them via calcination, albeit the porosity achieved was quite low (1–5%). More promising porosity values were reached in the following publication [ 36 ], in which the zincone thin films were deposited via MLD using diethyl zinc (DEZ) and ethylene glycol (EG) as the metal and organic precursor, respectively. Subsequent calcination at 400 °C led to an open porosity of approximately 19% in the obtained ZnO thin film.…”

Section: Introductionmentioning

confidence: 99%

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Tuning the Porosity of Piezoelectric Zinc Oxide Thin Films Obtained from Molecular Layer-Deposited “Zincones”

Kräuter

Ali²,

Stadlober³

et al. 2022

Materials

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Porous zinc oxide (ZnO) thin films were synthesized via the calcination of molecular layer-deposited (MLD) “zincone” layers. The effect of the MLD process temperature (110 °C, 125 °C) and of the calcination temperature (340 °C, 400 °C, 500 °C) on the chemical, morphological, and crystallographic properties of the resulting ZnO was thoroughly investigated. Spectroscopic ellipsometry reveals that the thickness of the calcinated layers depends on the MLD temperature, resulting in 38–43% and 52–56% of remaining thickness for the 110 °C and 125 °C samples, respectively. Ellipsometric porosimetry shows that the open porosity of the ZnO thin films depends on the calcination temperature as well as on the MLD process temperature. The maximum open porosity of ZnO derived from zincone deposited at 110 °C ranges from 14.5% to 24%, rising with increasing calcination temperature. Compared with the 110 °C samples, the ZnO obtained from 125 °C zincone yields a higher porosity for low calcination temperatures, namely 18% for calcination at 340 °C; and up to 24% for calcination at 500 °C. Additionally, the porous ZnO thin films were subjected to piezoelectric measurements. The piezoelectric coefficient, d33, was determined to be 2.8 pC/N, demonstrating the potential of the porous ZnO as an, e.g., piezoelectric sensor or energy harvester.

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Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Tuning the Porosity of Piezoelectric Zinc Oxide Thin Films Obtained from Molecular Layer-Deposited “Zincones”

Kräuter

Ali²,

Stadlober³

et al. 2022

Materials

Self Cite

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“…Diethylzinc is the most common precursor for zinc in the ALD/MLD processes; it is often combined with HQ, [54,55,66,107,133,230,[244][245][246][247]250,361,366,[370][371][372][373][374][375][376][377][378] but also with many other organic components. [46,48,115,134,211,212,226,228,233,238,239,241,265,272,278,324,345,349,[379][380][381][382][383][384][385][386][387][388]…”

Section: Aluminum- Zinc- and Titanium-based Processesmentioning

confidence: 99%

“…Diethylzinc is the most common precursor for zinc in the ALD/MLD processes; it is often combined with HQ, [ 54,55,66,107,133,230,244–247,250,361,366,370–378 ] but also with many other organic components. [ 46,48,115,134,211,212,226,228,233,238, 239,241,265,272,278,324,345,349,379–390 ] The DEZ + HQ process has been widely utilized for the growth of different superlattice structures in which the Zn–HQ layers are combined with thicker ZnO layers grown with ALD cycles from DEZ plus H 2 O. Another zinc precursor employed in ALD/MLD is zinc acetate.…”

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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“…Once the alucone film was irreversibly saturated with Li atoms, it became electronically conductive. Thirdly, MLD hybrid films (e.g., zincone, magnesicone) have been converted to corresponding highly porous metal oxide materials (e.g., ZnO, MgO) by removing the organic backbones via post-annealing (Perrotta et al, 2019a;Perrotta et al, 2019b;Kint et al, 2020). These porous metal oxide structures might be used reactive barrier layers or porous substrates for Li-ion composite solid electrolytes.…”

Section: Other New Mld Thin Films Promising For Rechargeable Batteriesmentioning

confidence: 99%

New Hybrid Organic-Inorganic Thin Films by Molecular Layer Deposition for Rechargeable Batteries

Liu

Wang

2021

Front. Energy Res.

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The design of multifunctional thin films holds the key to manipulate the surface and interface structure of the electrode and electrolyte in rechargeable batteries and achieve desirable performance for various applications. Molecular layer deposition (MLD) is an emerging thin-film technique with exclusive advantages of depositing hybrid organic-inorganic materials at a nanoscale level and with well tunable and unique properties that conventional thin films might not have. Herein, we provide a timely mini-review on the most recent progress in the surface chemistry and MLD process of novel hybrid organic-inorganic thin films and their applications as the anode, cathode, and solid electrolytes in lithium-ion batteries. Perspectives for future research in designing new MLD process and precursors, enriching MLD material library, and expanding their potential applications in other energy storage systems, are discussed at the end.

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Mesoporous ZnO thin films obtained from molecular layer deposited “zincones”

Abstract: The synthesis of MLD-derived mesoporous ZnO with 20% of porosity is demonstrated and studied by advanced in situ characterization techniques.

Cited by 10 publications

References 65 publications

Tuning the Porosity of Piezoelectric Zinc Oxide Thin Films Obtained from Molecular Layer-Deposited “Zincones”

Tuning the Porosity of Piezoelectric Zinc Oxide Thin Films Obtained from Molecular Layer-Deposited “Zincones”

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

New Hybrid Organic-Inorganic Thin Films by Molecular Layer Deposition for Rechargeable Batteries

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