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MLD growth evolution depends on the deposition surface and monomer structure of the deposited film.

Area-selective deposition (ASD) of polymers is expected to be useful for self-aligned patterning of nucleation inhibitors, sacrificial layers, and air-gap materials during future bottom-up nanoscal...

Hf0.5Zr0.5O2 (HZO) thin films are promising candidates for non-volatile memory and other related applications due to their demonstrated ferroelectricity at the nanoscale and compatibility with Si processing. However, one reason that HZO has not been fully scaled into industrial applications is due to its deleterious wake-up and fatigue behavior which leads to an inconsistent remanent polarization during cycling. In this study, we explore an interfacial engineering strategy in which we insert 1 nm Al2O3 interlayers at either the top or bottom HZO/TiN interface of sequentially deposited metal-ferroelectric-metal capacitors. By inserting an interfacial layer while limiting exposure to the ambient environment, we successfully introduce a protective passivating layer of Al2O3 that provides excess oxygen to mitigate vacancy formation at the interface. We report that TiN/HZO/TiN capacitors with a 1 nm Al2O3 at the top interface demonstrate a higher remanent polarization (2Pr ∼ 42 μC cm−2) and endurance limit beyond 108 cycles at a cycling field amplitude of 3.5 MV cm−1. We use time-of-flight secondary ion mass spectrometry, energy dispersive spectroscopy, and grazing incidence x-ray diffraction to elucidate the origin of enhanced endurance and leakage properties in capacitors with an inserted 1 nm Al2O3 layer. We demonstrate that the use of Al2O3 as a passivating dielectric, coupled with sequential ALD fabrication, is an effective means of interfacial engineering and enhances the performance of ferroelectric HZO devices.

Current approaches to create zirconium-based metal-organic framework (MOF) fabric composites for catalysis, water purification, wound healing, gas sorption, and other applications often rely on toxic solvents, long reaction/post processing times, and batch methods hindering process scalability. Here, a novel mechanism was reported for rapid UiO-66-NH

Hafnia-zirconia (HfO

Small-molecule inhibitors have recently been introduced for passivation during area-selective deposition (ASD). Small silanes like ( N, N-dimethylamino)trimethylsilane (DMATMS) selectively react with −OH sites on SiO2 to form a less reactive –OSi(CH3)3 terminated surface. The –OSi(CH3)3 surface termination can inhibit many atomic layer deposition (ALD) processes, including TiCl4/H2O ALD. However, the mechanisms by which ALD is inhibited and by which selectivity is eventually lost are not well understood. This study uses in situ Fourier-transform infrared spectroscopy to probe the adsorption of DMATMS on SiO2 and the subsequent reactions when the passivated surface is exposed to TiCl4/H2O ALD. The chemisorption of DMATMS on isolated –OH groups on SiO2 is shown to inhibit the reaction with TiCl4. Further, we find that starting with an inherently inhibiting H-terminated Si surface, DMATMS can also react with residual –OH groups and reduce the extent of nucleation. Finally, using Rutherford backscattering spectrometry, the effectiveness of DMATMS passivation on SiO2 and H-terminated Si is quantified during extended ALD cycle numbers. The insight into the mechanisms of passivation by DMATMS and passivation loss can enable the rational design of highly selective ASD processes by carefully matching compatible surfaces, passivating agents, and ALD precursors.

Printed component sizes in electronic circuits are approaching 10 nm, but inherent variability in feature alignment during photolithography poses a fundamental barrier for continued device scaling. Deposition-based self-aligned patterning is being introduced, but nuclei defects remain an overarching problem. This work introduces low-temperature chemically self-aligned film growth via simultaneous thin film deposition and etching in adjacent regions on a nanopatterned surface. During deposition, nucleation defects are avoided in nongrowth regions because deposition reactants are locally consumed via sacrificial etching. For a range of materials and process conditions, thermodynamic modeling confirms that deposition and etching are both energetically favorable. We demonstrate nanoscale patterning of tungsten at 220 °C with simultaneous etching of TiO2. Area selective deposition (ASD) of the sacrificial TiO2 layer produces an orthogonal sequence for self-aligned patterning of two materials on one starting pattern, i.e., TiO2 ASD on SiO2 followed by W ASD on Si-H. Experiments also show capacity for self-aligned dielectric patterning via favorable deposition of AlF3 on Al2O3 at 240 °C with simultaneous atomic layer etching of sacrificial ZnO. Simultaneous deposition and etching provides opportunities for low-temperature bottom-up self-aligned patterning for electronic and other nanoscale systems.

Protocols to create metal-organic framework (MOF)/polymer composites for separation, chemical capture, and catalytic applications currently rely on relatively slow solution-based processing to form single MOF composites. Here, we report a rapid, high-yield sorption-vapor method for direct simultaneous growth of single and multiple MOF materials onto untreated flexible and stretchable polymer fibers and films. The synthesis utilizes favorable reactant absorption into polymers coupled with rapid vapor-driven MOF crystallization to form high surface area (>250 m2/gcomposite) composites, including UiO-66-NH2, HKUST-1, and MOF-525 on spandex, nylon, and other fabrics. The resulting composites are robust and maintain their functionality even after stretching. Stretchable MOF fabrics enable rapid solid-state hydrolysis of the highly toxic chemical warfare agent soman and paraoxon-methyl simulant. We show that this approach can readily be scaled by solution spray-coating of MOF precursors and to large area substrates.

The integration of metal–organic frameworks (MOFs) with polymer fibres enables the formation of fibrous composite materials with advantages over traditional single-component polymer films and mixed-matrix membranes. In comparison with mixed-matrix membranes, MOF–polymer fibrous composites offer improved molecular transport through the material and easier access to the active sites of MOFs. These attributes make fibrous composites appealing for clothing, personal protective equipment, air purification and filtration, biomedical equipment and delivery of therapeutics, along with detection and sensing applications. In this Review, we outline approaches for the incorporation of MOFs into, or onto, polymer fibres and present some applications for MOF–polymer fabrics. The integration of MOFs and polymers can either occur prior to fibre formation (namely, MOF-first), via particle deposition (resulting in either covalent or non-covalent attachment) of MOFs to the fibre or by in situ MOF growth after fibre formation (namely, fibre-first). We focus on the structure–processing–activity relationships — for example, MOF loading, MOF crystal size, polymer concentration and processing parameters — that impact the behaviour of fibrous composites. We conclude with a discussion of research avenues that can advance this burgeoning field. Composites made from metal–organic frameworks and polymer fibres are gaining popularity in many applications because of their tailorable morphologies and properties. This Review summarizes various methods for fabricating these composites, explores structure–processing–activity relationships and discusses future research opportunities.

This study investigates the phase-controlled growth of flakes and films of 2D MoTe2 by atmospheric-pressure chemical vapor deposition and presents a thorough understanding on the growth mechanism.

In this study, we present the fabrication of fibers with tunable morphology and porosity from an intrinsically microporous polymer, PIM-1, using a simple one-step electrospinning technique. The met...

Metal–organic framework (MOF) fibrous composites were synthesized in a variety of methods in attempt to incorporate the highly effective reactivity of MOFs into a more facile and applicable format....

Summary Metal-organic frameworks (MOFs) can catalyze toxic chemical decontamination, but new MOF materials and synthesis strategies are needed to improve performance, particularly in field-usable MOF-textile formats. This article reports for the first time the exceptional photocatalytic reactivity of Al-PMOF (Al-porphyrin-based MOF), composed of an earth-abundant metal-containing Al(OH)O4 cluster bridged by H2TCPP (5,10,15,20-tetrakis(4-carboxyphenyl)porphyrin) chromophores, against the toxic sulfur mustard simulant 2-chloroethyl ethyl sulfide (CEES) under visible-light irradiation. Furthermore, Al-PMOF is strongly immobilized into polymeric fibers via well-controlled Al2O3 solid film conversion using dimethylformamide/water cosolvent. The approach enables a secure integration of conformal Al-PMOF films onto polymer fibers at a relatively low synthesis temperature (120°C). In addition, on a per-unit mass of MOF basis, the surface-bound Al-PMOF films enable extremely rapid CEES detoxification turnover frequency, up to 170 mol CEES mol chromophore − 1 min − 1 , more than 10-fold faster than the best MOF powders and 2-fold better than MOF films reported to date.

Molecular layer deposition (MLD) is an increasingly important thin film synthesis technique in areas such as sensors, microelectronics, protective coatings, and catalysis. However, new analytical a...

Recently, metal–organic framework (MOF)-based polymeric substrates show promising performance in many engineering and technology fields. However, a commonly known drawback of MOF/polymer composites is MOF crystal encapsulation and reduced surface area. This work reports a facile and gentle strategy to produce self-supported MOF predominant hollow fiber mats. A wide range of hollow MOFs including MIL-53(Al)–NH2, Al-PMOF, and ZIF-8 are successfully fabricated by our synthetic method. The synthetic strategy combines atomic layer deposition (ALD) of metal oxides onto polymer fibers and subsequent selective removal of polymer components followed by conversion of remaining hollow metal oxides into freestanding MOF predominant hollow fiber structures. The hollow MOFs show boosted surface area, superb porosity, and excellent pore accessibility, and exhibit a significantly improved performance in CO2 adsorption (3.30 mmol g−1), CO2/N2 separation selectivity (24.9 and 21.2 for 15/85 and 50/50 CO2/N2 mixtures), and catalytic removal of HCHO (complete oxidation of 150 ppm within 60 min).

Two-dimensional (2D) molybdenum ditelluride (MoTe

Ferroelectric (Hf,Zr)O2 thin films have attracted increased interest from the ferroelectrics community and the semiconductor industry due to their ability to exhibit ferroelectricity at nanoscale dimensions. The properties and performance of the ferroelectric (Hf,Zr)O2 films generally depend on various factors such as surface energy (e.g., through grain size or thickness), defects (e.g., through dopants, oxygen vacancies, or impurities), electrodes, interface quality, and preferred crystallographic orientation (also known as crystallographic texture or simply texture) of grains and/or domains. Although some factors affecting properties and performance have been studied extensively, the effects of texture on the material properties are still not understood. Here, the influence of texture of the bottom electrode and Hf0.5Zr0.5O2 (HZO) films on properties and performance is reported. The uniqueness of this work is the use of a consistent deposition process known as Sequential, No-Atmosphere Processing (SNAP) that produces films with different preferred orientations yet minimal other differences. The results shown in this study provide both new insight on the importance of the bottom electrode texture and new fundamental processing-structure–property relationships for the HZO films.

Bottom-up self-aligned area-selective deposition (ASD) plays an important role in patterning of advanced electronic devices. Specifically, ASD of organic materials can be utilized for nucleation inhibitors, sacrificial layers, and air-gap materials for next-generation nanoscale processing. This work introduces fundamental growth behavior of various conjugated polymers including polypyrrole, polythiophene, and polyaniline via oxidative molecular layer deposition and chemical vapor deposition. Effects of process parameters on film properties are described, and ASD behavior of different polymers are quantitatively characterized. These findings expand fundamental understanding of conjugated polymer deposition and provide new perspectives for ASD of organic thin films.

During TiO2 atomic layer deposition (ALD) using TiCl4 and H2O at ∼150 °C, nucleation proceeds rapidly on hydroxylated SiO2 but is inherently delayed on passivated surfaces such as H-terminated silicon (Si-H) and trimethylsilyl-passivated SiO2 (SiO2-TMS) formed using dimethylamino-trimethylsilane (DMA-TMS) as a small molecule inhibitor. In this work, we explore details of TiO2 nucleation on both Si-H and SiO2-TMS and show that the mechanisms leading to unwanted nuclei depend strongly on the passivation mechanism. Initial growth is observed as a function of ALD cycles using scanning electron microscopy to obtain average particle size, density, and overall surface coverage fraction. Also, average film thickness vs cycle is estimated using ellipsometry or Rutherford backscattering spectrometry. Data are compared to an analytical model that considers that either nucleation sites are present on the starting non-growth surface or sites are generated during the ALD process. On the Si-H surface, data and modeling indicate that nucleation occurs predominantly from a fixed number of nucleation sites present on the starting growth surface that start to immediately grow. However, on TMS-passivated SiO2, nucleation sites are predominantly generated during the growth process so that the density of nucleation sites increases as growth proceeds. Results indicate that nucleation sites are created when adsorbed ALD reactants become kinetically trapped on the SiO2-TMS surface. This demonstrates that mechanisms associated with unwanted nucleation during area-selective deposition (ASD) can depend on details of the surface passivation scheme, thereby providing insight to help to improve ASD strategies for advanced applications.

The sequential vapor infiltration (SVI) method, based on atomic layer deposition chemistry, allows the creation of a polymer–inorganic hybrid material through the diffusion of metal–organic vapor reagents into a polymer substrate. This study investigates the reactivity of the ester, amide, and carboxylic acid functional groups of poly(methyl methacrylate) (PMMA), poly(vinylpyrrolidone) (PVP), and poly(acrylic acid) (PAA), respectively, in the presence of trimethylaluminum (TMA) vapor. This work explores the possible reaction mechanisms of these functional groups through in situ Fourier transform infrared spectroscopy and ab initio quantum chemical analysis. At temperatures of ≤100 °C, TMA physisorbs to the carbonyl groups of PMMA. As the temperature is increased, TMA forms a covalent bond with PMMA. TMA physisorbs to PVP and then partially desorbs in the presence of water for all studied temperatures of ≤150 °C. PAA readily reacts with TMA to form a covalent bond with the carbonyl group at 60 °C. This inc...

New approaches for area-selective deposition (ASD) are becoming critical for advanced semiconductor patterning. Atomic layer deposition (ALD) and atomic layer etching (ALE), that is, “inverse ALD”, are considered important for ASD, but to date, direct integration of ALD and ALE for ASD has not been reported. This work demonstrates that self-limiting thermally driven ALE, using WF6 and BCl3, can be directly coupled with self-limiting thermal ALD, using TiCl4 and H2O, in a single isothermal reactor at temperature 0.9, nearly a 10× improvement over previous reports of inherent TiO2 ASD. After ALD/ALE (=30/5) 14 supercycles at 170 °C, X-ray photoelectron spectroscopy da...

Currently, air permeable chemical/biological (CB) protective garments are based on activated carbon technology, which reduces moisture vapor transport needed for evaporative cooling and has potential to absorb and concentrate toxic materials. Researchers are exploring classes of sorbent materials that can selectively accumulate and decompose target compounds for potential to enhance protective suits and allow for novel filtration devices. Here, the metal-organic frameworks (MOFs) UiO-66-NH2 and HKUST-1 have been identified as such materials. To better understand how MOFs can perform in future CB protective systems, atomic layer deposition (ALD) and solution deposition were used to modify nonwoven polypropylene and flame-resistant fabrics with HKUST-1 and UiO-66-NH2. Air permeation, water vapor transport, filtration efficiency, and chemical reactivity against chemical agent simulants were assessed in relation to ALD thickness and MOF crystal size. MOF deposition on substrates decreased both air and chemical permeation while increasing filtration efficiency and chemical sorption. Moisture vapor transport was not affected by MOF growth on substrates, which is promising when considering thermal properties of protective garments. Future work should continue to explore how MOF deposition onto fiber and textile substrates impacts transport properties and chemical absorbance.

Although 10 years have passed since the initial report of ferroelectricity in hafnia (HfO2), researchers are still intensely fascinated by this material system and the promise it holds for future applications. A wide variety of deposition methods have been deployed to create ferroelectric HfO2 thin films such as atomic layer deposition, chemical solution deposition, and physical vapor deposition methods such as sputtering and pulsed laser deposition. Process and design parameters such as deposition temperature, precursor choice, target source, vacuum level, reactive gases, substrate strain, and many others are often integral in stabilizing the polar orthorhombic phase and ferroelectricity. We examine processing parameters across four main different deposition methods and their effect on film microstructure, phase evolution, defect concentration, and resultant electrical properties. The goal of this review is to integrate the process knowledge collected over the past 10 years in the field of ferroelectric HfO2 into a single comprehensive guide for the design of future HfO2-based ferroelectric materials and devices.

New materials and chemical knowledge for improved personal protection are among the most pressing needs in the international community. Reported attacks using chemical warfare agents (CWAs,) including organophosphate soman (GD) and thioether mustard gas (HD) are driving research in field-deployable catalytic composites for rapid toxin degradation. In this work, we report simple template-free low temperature synthesis that enables for the first time, a deployable-structured catalytic metal-organic framework/polymer textile composite "MOF-fabric" showing rapid hydrolysis and oxidation of multiple active chemical warfare agents, GD and HD, respectively, and their simulants. Our method yields new zirconium-porphyrin based nano-crystalline PCN-222 MOF-fabrics with adjustable MOF loading and robust mechanical adhesion on low-cost nonwoven polypropylene fibers. Importantly, we describe quantitative kinetic analysis confirming that our MOF-fabrics are as effective as or better than analogous MOF powders for agent degradation, especially for oxidation. Faster oxidation using the MOF-fabrics is ascribed to the composite geometry, where active MOF catalysts are uniformly displayed on the MOF-textile enabling better reactant transport and reactive oxidant generation. Furthermore, we note the discovery of visible photo-activation of GD hydrolysis by a MOF-fabric, which is ascribed to oxidation at the active metal node site, significantly increasing the rate over that observed without illumination. These results provide important new insights into the design of future materials and chemical systems to protect military, first-responders, and civilians upon exposure to complex chemical toxins.

Deposition-based patterning is becoming an important need in advanced manufacturing. Several new approaches are emerging where chemical etching is being coupled with atomic layer deposition to achieve area-selective deposition of dielectrics and metals. During ALD, selectivity is generally lost when undesired nuclei form on the targeted non-growth surface. These undesired nuclei can sometimes be removed by periodic etching, improving the overall selectivity. However, it is not known to what extent these coupled deposition/etching sequences can proceed while maintaining good selectivity. As desirable deposition and etching reactions proceed, other changes in the process can occur to enhance unwanted nucleation and/or impede desired etching, thereby limiting the net selectivity. Recent experiments in our lab have used in-situ probes to explore coupled thermal ALD and ALE super-cycles, performed sequentially under isothermal conditions in a single reaction chamber, to achieve area selective deposition of TiO2 on SiO2 with hydrogen-terminated silicon (100) as the desired non-growth surface. We find that as ALD/ALE super-cycles proceed, small changes occur in the ALD and ALE reactions, particularly during the transition from ALD to ALE, or from ALE to ALD. Likewise, a new thermally-driven ALE process for tungsten has been applied in ALD/ALE super-cycles to improve W ASD. In this case, the ALE process alters the ALD surface leading to significant changes in the ALD. Modeling studies allow us to quantitatively analyze the ASD results and compare our findings to other known approaches. These insights will be helpful to understand opportunities and challenges in advanced deposition-based patterning.

Metal-organic framework (MOF) fibrous composites were synthesized in a variety of methods in attempt to incorporate the highly effective reactivity of MOFs into a more facile and applicable format. Recent advances have demonstrated incorporating a metal oxide nucleation surface or reactive layer promotes conformal, well-adhered MOF growth on substrates. These materials have demonstrated promising reactivity in capturing or degrading chemical warfare agents and simulants. Here, we examine the mechanisms for MOF nucleation from metal oxide thin films to explore why some metal oxide sources are better suited for one synthesis mechanism over another. We isolate metal oxide extent of hydroxylation as an indicative factor as to whether the film serves as a nucleation promoter or may be converted directly to the MOF thin films. MOF-525 growth on Al

The production of heat by reactive nanomaterials occurs at a fuel/oxidizer interface. In order to understand how such materials can be initiated by shock, we studied a model system consisting of a reactive nanolaminate (RNL) with a well-defined planar interface. In addition, an organic thin layer could be intercalated between the fuel and oxidizer to modulate the reaction. We studied a stoichiometric mixture of Zr fuel and CuO oxidizer and the modulator layer was polyurea produced by molecular layer deposition. The RNL was shocked using 0.5 mm diameter Al flyer plates launched by a pulsed laser at 1.5 km/s. We found that little or no reaction was produced immediately under the flyer plate where the interface experiences compression only. Instead the reaction was efficiently initiated by shear waves propagating out from the edges of the flyer plate. The RNL reaction temperature during shock was 4000K, and after the shock dissipated, the RNL reacted at 3000K. Modulator layers caused the reaction to slow down with the effect increasing with increasing modulator thickness up to 500 nm.

Metal organic frameworks (MOFs), the UiO series in particular, have attracted much attention because of the high surface area and ability to capture and decontaminate chemical warfare agents. Much work has been done on incorporating these MOFs into or onto textile materials while retaining the desirable properties of the MOF. Many different techniques have been explored to achieve this. Atomic layer deposition (ALD) of TiO2 followed by solvothermal synthesis of MOF has become one of the most adaptable techniques for growing MOFs on the surface of many different polymer fabric materials. However, little work has been done with using this technique on polymer composite materials. In this work, UiO-66-NH2 was grown onto the surface of poly(methyl methacrylate) (PMMA)/Ti(OH)4 and poly(vinylidene fluoride) (PVDF)/Ti(OH)4 composite fibers by first modifying the surface with ALD of TiO2 (@TiO2) followed by solvothermal synthesis of MOF (@MOF). The catalytic activity of these materials was then evaluated using the simulant paraoxon-methyl (DMNP). These new MOF-functionalized composite fabrics were compared to polyamide-6 (PA-6)@TiO2@MOF- and polypropylene (PP)@TiO2@MOF-functionalized fabrics. PMMA/Ti(OH)4@TiO2@MOF fibers resulted in unique hollowed fibers with high surface area of 264 m2/g and fast catalytic activity. The catalytic activity of these samples was found to be related to the active MOF mass fraction on the MOF-functionalized composite fabric, with the hollowed PMMA/Ti(OH)4@TiO2@MOF having the highest weight percent of active MOF and a DMNP t1/2 of 26 min followed by PA-6@TiO2@MOF with 45 min, PVDF/Ti(OH)4@TiO2@MOF with 61 min, and PP@TiO2@MOF with 83 min.

RF sources are used in many applications, including high-power radar, communications, cancer therapy and diagnosis, electronic countermeasures, and high-energy accelerators. Many of these sources are located in well controlled environments where high-quality coolant fluids are readily available. Others, however, are located on platforms where harsh environmental conditions exist, and high-quality coolants are not easily provided. This includes ships at sea and remote transmitters in the second-world and third-world countries. Corrosive ethylene glycol mixtures may be required where extreme temperatures are encountered. Essentially, all high-power RF sources are fabricated from brazed copper structures, which are particularly susceptible to corrosion from corrosive coolants. This paper demonstrates using atomic layer deposition (ALD) to deposit nanometer-scale ceramic coatings inside coolant passages to separate the coolant from the underlying metal surface. This effectively reduces or eliminates corrosion and erosion, thereby increasing lifetime and reliability of RF sources. We describe ALD equipment and process specifically focused on RF sources and related components. The results of numerous experiments are reported, confirming the efficacy of the technology.

The demand for transistors and memory devices with smaller feature sizes and increasingly complex architectures furthers the need for advanced thin film patterning techniques. A prepatterned, sacrificial layer can be used as a template for bottom-up fill of new materials which would otherwise be difficult to pattern using traditional top-down lithographic methods. This work investigates initial growth of TiN, TiO2, and HfO2 thin films during thermal atomic layer deposition (ALD) onto a high density, amorphous carbon (aC) sacrificial layer. ALD of TiN by TiCl4/NH3 at 390 °C, TiO2 by Ti(OCH3)4/H2O at 250 °C, and HfO2 by HfCl4/H2O at 300 °C on as-deposited aC films resulted in uninhibited, continuous thin film growth. We find that carbon surface reduction and passivation using a H2 plasma resulted in delayed film coalescence for TiN, TiO2, and HfO2 on the aC. After 200 TiN cycles on H2 plasma-treated aC, Rutherford backscattering spectrometry shows Ti levels below the detection limit (8 × 1013 at/cm2), where...

The semiconductor industry faces a tremendous challenge in the development of a transistor device with sub-10 nm complex features. Self-limiting atomic layer etching (ALE) is essential for enabling the manufacturing of complex transistor structures. In this study, we demonstrated a thermally driven ALE process for tungsten (W) using sequential exposures of O2 and WF6. Based on the insight gained from the previous study on TiO2 thermal ALE, we proposed that etching of W could proceed in two sequential reaction steps at 300 °C: (1) oxidation of metallic tungsten using O2 or O3 to form WO3(s) and (2) formation and removal of volatile WO2F2(g) during the reaction between WO3(s) and WF6(g). The O2/WF6 etch process was experimentally studied using a quartz crystal microbalance (QCM). We find that both the O2 and WF6 ALE half reactions are self-limiting, with an estimated steady-state etch rate of ∼6.3 A/cycle at 300 °C. We also find that etching of W proceeds readily at 300 °C, but not at temperatures lower tha...

Metal–organic frameworks (MOFs) chemically bound to polymeric microfibrous textiles show promising performance for many future applications. In particular, Zr-based UiO-66-family MOF-textiles have been shown to catalytically degrade highly toxic chemical warfare agents (CWAs), where favorable MOF/polymer bonding and adhesion are attained by placing a nanoscale metal-oxide layer on the polymer fiber preceding MOF growth. To date, however, the nucleation mechanism of Zr-based MOFs on different metal oxides and how product performance is affected are not well understood. Herein, we provide new insight into how different inorganic nucleation films (i.e., Al2O3, ZnO, or TiO2) conformally coated on polypropylene (PP) nonwoven textiles via atomic layer deposition (ALD) influence the quality, overall surface area, and the fractional yield of UiO-66-NH2 MOF crystals solvothermally grown on fiber substrates. Of the materials explored, we find that TiO2 ALD layers lead to the most effective overall MOF/fiber adhesio...

Molecular layer deposition and chemical vapor deposition are emerging and promising techniques for the incorporation of high-performance conductive polymers into high surface area devices, such as sintered tantalum anodes for electrolytic capacitors. Until recently, vapor-phase synthesis of poly(3,4-ethylenedioxythiophene) (PEDOT) has relied on solid reactants which require relatively high temperatures and complex dosing schemes for sequential layer-by-layer processes. This work introduces a facile and high-performing layer-by-layer oxidative molecular layer deposition (oMLD) scheme using the volatile liquid oxidant antimony(V) chloride (SbCl5) to deposit PEDOT thin films. Effects of reactor parameters on PEDOT film characteristics are described, and the necessary foundation for future studies aiming to understand the nucleation and growth of layer-by-layer oMLD PEDOT is detailed.

Controlled thin film etching is essential for further development of sub-10 nm semiconductor devices. Vapor-phase thermal etching of oxides is appealing for achieving highly conformal etching of high aspect ratio features. We show that tungsten hexafluoride (WF6) can be used to selectively etch amorphous TiO2 films versus other oxides including Al2O3. Chemical vapor etching (CVE) of TiO2 by WF6 was studied with quartz crystal microbalance (QCM), spectroscopic ellipsometry, X-ray photoelectron spectroscopy (XPS), and thermodynamic modeling. The XPS results show evidence for a WOxFy layer that forms on of the TiO2 films during the etch process, which may act as a surfactant layer to help enable fluorination of the TiO2. Direct CVE of TiO2 by WF6 is strongly temperature dependent, where etching proceeds readily at 220 °C, but not at T ≤ 170 °C. This is consistent with thermodynamic modeling showing that the etching rate is determined by the volatilization of metal fluoride and WF2O2 product species. We also ...

Metal–organic frameworks (MOFs) are chemically functionalized micro- and mesoporous materials with high surface areas and are attractive for multiple applications including filtration, gas storage, and catalysis. Postsynthetic modification (PSM), via solution or vapor-based techniques, is a way to impart additional complexity and functionality into these materials. There is a desire to shift toward vapor-phase methods in order to ensure more controlled modification and more efficient reagent and solvent removal from the modified MOF material. In this work we explore how the metal precursors titanium tetrachloride (TiCl4) and trimethylaluminum (TMA), commonly used in atomic layer deposition, react with UiO-66-NH2 MOF. Using in situ quartz crystal microbalance (QCM) and Fourier transform infrared spectroscopy (FTIR) at 150 and 250 °C, we find that the ALD precursors react with μ3-OH hydroxyl and μ3-O bridging oxygen groups on Zr6 nodes, as well as oxygen from carboxylate linker groups. The reactions occur p...

Highly tunable metal–organic framework (MOF) materials, including, for example, UiO-66-NH2, are known to be effective catalysts to degrade chemical warfare agents (CWAs) with half-lives near 1 min. Therefore, many researchers have been actively working on producing supported MOF materials to improve application effectiveness by using relatively slow solvothermal synthesis or repetitious stepwise layer-by-layer methods. Herein, we demonstrate a facile route to rapidly assemble presynthesized UiO-66-NH2 crystals onto nonwoven polypropylene (PP) fibrous mats at ambient temperature. Crystal assembly is chemically directed using β-cyclodextrin (β-CD) and cetyltrimethylammonium bromide (CTAB) as surfactant assembly agents, where the agents quickly (within 5 min) self-assemble on the crystal surface and promote physically robust chemical surface attachment while simultaneously impeding solution-phase crystal agglomeration. Furthermore, we find that when the PP is preconditioned using conformal metal oxide thin f...

Atomic layer deposition (ALD) is a viable means to add corrosion protection to copper metal. Ultrathin films of Al2O3, TiO2, ZnO, HfO2, and ZrO2 were deposited on copper metal using ALD, and their corrosion protection properties were measured using electrochemical impedance spectroscopy (EIS) and linear sweep voltammetry (LSV). Analysis of ∼50 nm thick films of each metal oxide demonstrated low electrochemical porosity and provided enhanced corrosion protection from aqueous NaCl solution. The surface pretreatment and roughness was found to affect the extent of the corrosion protection. Films of Al2O3 or HfO2 provided the highest level of initial corrosion protection, but films of HfO2 exhibited the best coating quality after extended exposure. This is the first reported instance of using ultrathin films of HfO2 or ZrO2 produced with ALD for corrosion protection, and both are promising materials for corrosion protection.