Quartz crystal microbalance study of precursor diffusion during molecular layer deposition using cyclic azasilane, maleic anhydride, and water

Ju, Ling; Vemuri, Vamseedhara; Strandwitz, Nicholas C.

doi:10.1116/1.5093509

Cited by 6 publications

(6 citation statements)

References 27 publications

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“…17 Recent work shows that these nonreactive surface sites might allow absorption or adsorption of precursor molecules, introducing new reactive surface sites. 91,92 This would eventually lead to typical linear steady state growth as observed in Figure 3. As discussed previously, the EG-based process displays a reservoir effect which is not seen for the GLbased process.…”

Section: ■ Results and Discussionmentioning

confidence: 91%

Molecular Layer Deposition of “Magnesicone”, a Magnesium-based Hybrid Material

et al. 2020

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Molecular layer deposition (MLD) offers the deposition of ultra-thin and conformal organic or hybrid films which have a wide range of applications. However, some critical potential applications require a very specific set of properties. For application as desiccant layers in water barrier films for example, the films need to exhibit water uptake, swelling and be overcoatable. For application as a backbone for a solid composite electrolyte for lithium ions on the other hand, the films need to be stable against lithium, and need to be transformable from a hybrid MLD film to a porous metal oxide film. Magnesium-based MLD films, called "magnesicone", are promising on both these 1 Page 1 of 51 ACS Paragon Plus Environment Chemistry of Materials aspects and thus an MLD process is developed using Mg(MeCp) 2 as metal source and ethylene glycol (EG) or glycerol (GL) as organic reactants. Saturated growth could be achieved at 2Å/cycle to 3Å/cycle in a wide temperature window from 100 • C to 250 • C. The resulting magnesicone films react with ambient air and exhibit water uptake, which is in the case of the GL-based films associated with swelling (up to 10%) and in the case of EG-based magnesicone with Mg(CO) 3 formation, and are overcoatable with ALD of Al 2 O 3 . Furthermore, by carefully tuning the annealing rate, the EG-grown films can be made porous at 350 • C. Hence, these functional tests demonstrate the potential of magnesicone films as reactive barrier layers and as the porous backbone of lithium ion composite solid electrolytes, making it a promising material for future applications.

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Section: ■ Results and Discussionmentioning

confidence: 91%

Molecular Layer Deposition of “Magnesicone”, a Magnesium-based Hybrid Material

et al. 2020

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“…Only at 220 °C was the growth rate on Cu close to zero. It is common for MLD processes that growth rates decrease with increasing temperature 20,24,25,44,45 due to either the desorption of MLD precursors 46 or the consumption of both reactive ends of organic precursor molecules by "double reactions". 24 The unusual increase in the PI MLD rate on Cu at 180−200 °C is assumed to arise from a new MLD reaction which becomes possible at higher temperatures.…”

Section: Resultsmentioning

confidence: 99%

Area-Selective Molecular Layer Deposition of Polyimide on Cu through Cu-Catalyzed Formation of a Crystalline Interchain Polyimide

et al. 2020

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Novel area-selective molecular layer deposition (AS-MLD) of polyimide (PI) on Cu versus native SiO 2 was studied. By use of 1,6-diaminohexane (DAH) and pyromellitic dianhydride (PMDA) as precursors, PI films can be selectively deposited on the Cu surface at 200−210 °C with a rate around 7.8 Å/cycle while negligible growth takes place on SiO 2 . The selectivity was successfully demonstrated also on Cu/SiO 2 patterns at 200 °C; after 180 MLD cycles, around 140 nm thick PI was deposited on Cu regions while <10 nm thick PI was measured on SiO 2 regions. By contrast, at 170 °C, similar growth rates were measured on Cu (4 Å/cycle) and native SiO 2 (5 Å/cycle). To understand the origin of the selectivity, properties of PI film grown on Cu at the selectivity enabling temperature of 200 °C have been thoroughly compared with those grown on both Cu and native SiO 2 at the nonselective temperature of 170 °C. Significant differences in crystallinity, surface morphology, and chemical structure suggest that the PI films grown on Cu at 200 °C have a novel crystalline interchain PI structure. According to this finding, the selectivity mechanism is proposed to derive from a new MLD reaction mechanism catalyzed by copper ions at 200−210 °C that leads to the formation of new crystalline polymer species. Additionally, it is suggested that small amounts of Cu ions can float on the surface of the growing PI film and thereby constantly catalyze the MLD reaction, as evidenced by XRD, XPS, and ToF-ERDA. The high catalytic efficiency has been also proven by using successfully an ultrathin Cu layer, nominally 0.1 nm, as a seed layer to initiate the MLD growth.

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“…New organic components have also been developed for the purely organic MLD processes; the MLD material library already includes, besides the initially introduced polyimides [ 15,17–22,137–143 ] and polyamides, [ 15,23–28,144–149 ] many other polymers: polyurea, [ 29,30,37,38,51,150–164 ] polythiourea, [ 52 ] polyurethane, [ 165,166 ] polyazomethine, [ 167–172 ] poly(3,4‐ethylenedioxy‐thiophene), [ 173–177 ] polyimide–polyamide, [ 141 ] poly(ethylene terephthalate) (PET), [ 50,178–180 ] and others. [ 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; [ …”

Section: Organic Precursors In Ald/mldmentioning

confidence: 99%

“…Along with this recent interest, the MLD material library has been expanded from the polyimides [15,[17][18][19][20][21][22] and polyamides [23][24][25][26][27][28] to many other polymers. [29][30][31][32][33][34][35][36][37][38][39][40][41][42][43][44] Both the parent techniques, ALD and MLD, are based on chemical surface reactions between two different gaseous (or vaporized) precursors sequentially pulsed into a vacuum reactor. The combined ALD/MLD technique for the hybrid metal-organic thin films involves a metal precursor similar to those used in ALD and an organic precursor that matches with the metal precursor (Figure 1).…”

Section: Introduction To Metal-organic Materials and Combined Atomic ...mentioning

confidence: 99%

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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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Quartz crystal microbalance study of precursor diffusion during molecular layer deposition using cyclic azasilane, maleic anhydride, and water

Cited by 6 publications

References 27 publications

Molecular Layer Deposition of “Magnesicone”, a Magnesium-based Hybrid Material

Molecular Layer Deposition of “Magnesicone”, a Magnesium-based Hybrid Material

Area-Selective Molecular Layer Deposition of Polyimide on Cu through Cu-Catalyzed Formation of a Crystalline Interchain Polyimide

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

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