Dimethylaluminum Isopropoxide Research Articles

Effect of Al precursor’s properties on interactions with self-assembled monolayers for area selective deposition

Area selective deposition (ASD) is a high-precision atomic-level manufacturing technology that enables the development of bottom-up manufacturing methods in the future semiconductor field. The area selective deposition behavior of Al precursors on 1-octadecylthiol (ODT) passivated Cu/SiO2 surfaces was studied through experimental and theoretical analysis. The relationship between precursor steric hindrance, symmetry, penetration depth in ODT, and adsorption energy was elucidated. The loss of selectivity caused by different penetration depths of the precursor in ODT can be post-treated with acids or H2 plasma to remove the physisorption of precursor molecules between ODT chains, thereby improving the selectivity. Reliable ASD technology has been successfully applied to Cu/SiO2 patterns. Dimethylaluminum isopropoxide can selectively deposit about 10 nm of Al2O3 on SiO2 without detectable defects on the Cu area. This provides important insights into the choice of precursors in the ASD process and can extend its application to a wider range of device manufacturing schemes.

Adsorption of dimethylaluminum isopropoxide (DMAI) on the Al2O3 surface: A machine-learning potential study

Dimethylaluminum isopropoxide (DMAI) is attracting attention as an alternative precursor for atomic layer deposition (ALD) of aluminum oxide (Al2O3). However, the surface chemical reaction mechanisms of DMAI during ALD regarding its dimeric structure under vacuum deposition process conditions has yet to be clear. In this work, the adsorption mechanism of dimeric and monomeric DMAI on a fully hydroxylated Al2O3 surface is studied using machine-learning potential (MLP) calculations. The initial adsorption of DMAI appears facile and would result in the coexistence of both methyl and isopropoxy ligands on the surface. The reactivity of DMAI is smaller than that of TMA, owing to the propensity of DMAI to adopt a dimeric form. Especially when the substrate is partially covered by other adsorbate species, the large molecular size and low reactivity of dimeric DMAI considerably hinder its reactivity toward surface adsorption. Current results are in good correspondence with the previous experimental results, where lower growth per cycle (GPC) and higher selectivity in area-selective ALD (AS-ALD) could be observed by using DMAI than compared to those of TMA processes.

Area-Selective Deposition by Cyclic Adsorption and Removal of 1-Nitropropane.

The ever-greater complexity of modern electronic devices requires a larger chemical toolbox to support their fabrication. Here, we explore the use of 1-nitropropane as a small molecule inhibitor (SMI) for selective atomic layer deposition (ALD) on a combination of SiO2, Cu, CuOx, and Ru substrates. Results using water contact angle goniometry, Auger electron spectroscopy, and infrared spectroscopy show that 1-nitropropane selectively chemisorbs to form a high-quality inhibition layer on Cu and CuOx at an optimized temperature of 100 °C, but not on SiO2 and Ru. When tested against Al2O3 ALD, however, a single pulse of 1-nitropropane is insufficient to block deposition on the Cu surface. Thus, a new multistep process is developed for low-temperature Al2O3 ALD that cycles through exposures of 1-nitropropane, an aluminum metalorganic precursor, and coreactants H2O and O3, allowing the SMI to be sequentially reapplied and etched. Four different Al ALD precursors were investigated: trimethylaluminum (TMA), triethylaluminum (TEA), tris(dimethylamido)aluminum (TDMAA), and dimethylaluminum isopropoxide (DMAI). The resulting area-selective ALD process enables up to 50 cycles of Al2O3 ALD on Ru but not Cu, with 98.7% selectivity using TEA, and up to 70 cycles at 97.4% selectivity using DMAI. This work introduces a new class of SMI for selective ALD at lower temperatures, which could expand selective growth schemes to biological or organic substrates where temperature instability may be a concern.

Nucleation dependence of atomic layer deposition on diamond surface termination

Surface termination and interfacial interactions are critical for advanced solid-state quantum applications. In this paper, we demonstrate that atomic layer deposition (ALD) can both provide valuable insight on the chemical environment of the surface, having sufficient sensitivity to distinguish between the common diamond (001) surface termination types and passivate these interfaces as desired. We selected diamond substrates exhibiting both smooth and anomalously rough surfaces to probe the effect of morphology on ALD nucleation. We use high resolution in situ spectroscopic ellipsometry to monitor the surface reaction with sub-angstrom resolution, to evaluate the nucleation of an ALD Al2O3 process as a function of different ex and in situ treatments to the diamond surface. In situ water dosing and high vacuum annealing provided the most favorable environment for nucleation of dimethylaluminum isopropoxide and water ALD. Hydrogen termination passivated both smooth and rough surfaces while triacid cleaning passivated the smooth surface only, with striking effectiveness.

Area-Selective Deposition of AlOx and Al-Silicate for Fully Self-Aligned Via Integration

The rush for better-performing electronics, and manufacturing processes that heavily rely on "top-down" patterning techniques, is making the integration of "self-aligned" fabrication methods, such as area-selective deposition (ASD), a critical objective for continued device scaling. The fully self-aligned via (FSAV) scheme is broadly proposed as a "killer application" to determine whether ASD can shift from an R&D process to high-volume manufacturing. Nevertheless, the lack of a suitable low-κ deposition process has prevented the realization of FSAV by dielectric-on-dielectric ASD. This is primarily due to the high temperature and/or strong oxidizers employed during low-κ dielectric deposition and their unsuitability in the presence of organic masks, such as self-assembled monolayers (SAMs), used to prevent material nucleation during ASD. In this work, AlOx and Al-silicate atomic layer deposition (ALD) processes are studied to provide suitable materials for ASD-enabled FSAV. Dimethylaluminum isopropoxide and H2O are utilized to deposit the metal oxide, whereas Al-silicate is grown by adding 2,2-dimethoxy-1,6-diaza-2-silacyclooctane (DMDAcO) pulses to the AlOx ALD cycle. The selectivity of such processes is demonstrated on 50 nm Cu/SiO2 structures, using octadecanethiol-derived SAMs to inhibit material nucleation on the metal lines. Scanning and transmission electron microscopies are employed to assess the quality of the ASD processes and investigate the mechanisms behind defect generation on a nongrowth surface. X-ray photoelectron spectroscopy measurements show the high purity of the AlOx film, whereas DMDAcO-ligand incorporation into the Al-silicate matrix is observed. Planar capacitor structures are used to assess the electrical properties of both ASD films, revealing that the silicate film exhibits a relatively low κ-value (5.3 ± 0.2), with a high acceleration field factor (32.4 ± 1.4) and a dielectric breakdown voltage of 6.0 ± 0.3 V at 100 °C.

Molecular layer deposition of alucone in high aspect ratio trenches: The effect of TMA outgassing on step-coverage

Infiltration of trimethylaluminum (TMA) in molecular layer deposition-enabled alucone thin films on planar substrates is a common observation reported in the literature. An insufficient TMA purge time in such cases is often found to lead to a CVD component in the overall film growth due to the reactions between the outgassing TMA and the co-reactant. In this work, the effect of the CVD component on the step coverage of alucone films when grown in high-aspect ratio trenches is studied. The thickness was initially found to increase with increasing distance from the trench aperture before starting to decrease up to the film’s maximum penetration depth. With the support of modeling, the reason behind the observed thickness profile was investigated and attributed to the combination of an increasing outgassing rate of TMA and a decreasing ethylene glycol (EG) concentration along the trench depth. Furthermore, the maximum thickness and the position where it is obtained in the trench are found to depend on TMA and EG doses, TMA purge time, the trench height, and the trench depth. Finally, the possibility of adopting the additional CVD component in film growth for void-less gap fill of 3D trenches is discussed, as well as the suppression of the same CVD component, without compromising the growth rate, by using dimethylaluminum isopropoxide as a substitute for TMA is evaluated.

Relation between Reactive Surface Sites and Precursor Choice for Area-Selective Atomic Layer Deposition Using Small Molecule Inhibitors.

Implementation of vapor/phase dosing of small molecule inhibitors (SMIs) in advanced atomic layer deposition (ALD) cycles is currently being considered for bottom-up fabrication by area-selective ALD. When SMIs are used, it can be challenging to completely block precursor adsorption due to the inhibitor size and the relatively short vapor/phase exposures. Two strategies for precursor blocking are explored: (i) physically covering precursor adsorption sites, i.e., steric shielding, and (ii) eliminating precursor adsorption sites from the surface, i.e., chemical passivation. In this work, it is determined whether steric shielding is enough for effective precursor blocking during area-selective ALD or whether chemical passivation is required as well. At the same time, we address why some ALD precursors are more difficult to block than others. To this end, the blocking of the Al precursor molecules trimethylaluminum (TMA), dimethylaluminum isopropoxide (DMAI), and tris(dimethylamino)aluminum (TDMAA) was studied by using acetylacetone (Hacac) as inhibitor. It was found that DMAI and TDMAA are more easily blocked than TMA because they adsorb on the same surface sites as Hacac, while TMA is also reactive with other surface sites. This work shows that chemical passivation plays a crucial role for precursor blocking in concert with steric shielding. Moreover, the reactivity of the precursor with the surface groups on the non-growth area dictates the effectiveness of blocking precursor adsorption.

Functionalization of the SiO2 Surface with Aminosilanes to Enable Area-Selective Atomic Layer Deposition of Al2O3.

Small-molecule inhibitors are promising for achieving area-selective atomic layer deposition (ALD) due to their excellent compatibility with industrial processes. In this work, we report on growth inhibition during ALD of Al2O3 on a SiO2 surface functionalized with small-molecule aminosilane inhibitors. The SiO2 surface was prefunctionalized with bis(dimethylamino)dimethylsilane (BDMADMS) and (N,N-dimethylamino)trimethylsilane (DMATMS) through solution and the vapor phase. ALD of Al2O3 using dimethylaluminum isopropoxide (DMAI) and H2O was performed on these functionalized SiO2 surfaces. Our in situ four-wavelength ellipsometry measurements show superior growth inhibition when using BDMADMS and DMATMS in sequence over just using BDMADMS or DMATMS. Vapor phase functionalization provided a growth delay of ∼30 ALD cycles, which was similar to solution-based functionalization. Using in situ attenuated total reflection Fourier transform infrared spectroscopy, we show that the interaction of DMAI with SiO2 surfaces leads to pronounced changes in absorbance for the Si-O-Si phonon mode without any detectable DMAI absorbed on the SiO2 surface. Detailed analysis of the infrared spectra revealed that the decrease in absorbance was likely caused by the coordination of Al in DMAI to O atoms in surface Si-O-Si bonds without the breaking the Si-O-Si bonds. Finally, we postulate that a minimal amount of DMAI remains adsorbed on surface Si-O-Si bonds even after purging, which can initiate ALD of Al2O3 on functionalized SiO2: this highlights the need for higher surface coverage for enhanced steric blocking.

Spatial atmospheric pressure molecular layer deposition of alucone films using dimethylaluminum isopropoxide as the precursor.

Trimethylaluminum is the most used aluminum precursor in atomic and molecular layer deposition (ALD/MLD). It provides high growth-per-cycle (GPC), is highly reactive and is relatively low cost. However, in the deposition of hybrid alucone films, TMA tends to infiltrate into the films requiring very long purge steps and thereby limiting the deposition rate (nm s-1) of the process. From our previous studies, we know that dimethylaluminum isopropoxide (DMAI) could be a potential candidate to substitute TMA in alucone depositions as it does not seem to infiltrate into the films. In this study, we perform a more detailed investigation of MLD of alucone on an atmospheric pressure spatial MLD system using DMAI as the aluminum precursor. The effect of deposition temperature and reactant purge times on the overall GPC has been investigated and a decreasing GPC with increasing deposition temperature and increasing EG purge time has been observed. Furthermore, the DMAI alucone films have been compared for their chemical environment and degradation with the films prepared using TMA and EG, showing striking similarities between the two. The results demonstrate that DMAI can be used as an alternative precursor to TMA for MLD of alucone films and this work can be used as a guide for designing efficient MLD processes in the future.

Effects of Al Precursors on the Characteristics of Indium-Aluminum Oxide Semiconductor Grown by Plasma-Enhanced Atomic Layer Deposition.

Atomic layer deposition (ALD) has attracted much attention, particularly for applications in nanoelectronics because of its atomic-level controllability and high-quality products. In this study, we developed a plasma-enhanced atomic layer deposition (PEALD) process to fabricate a homogeneous indium aluminum oxide (IAO) semiconductor film. Trimethylaluminum (TMA) and dimethylaluminum isopropoxide (DMAI) were used as Al precursors, which yielded different compositions. Density functional theory (DFT) calculations on the surface reactions between indium and aluminum precursors showed that while highly reactive TMA would etch In, DMAI with lower reactivity would allow indium to persist in the films, resulting in a more controlled doping of Al. The In/Al composition ratio could be further precisely controlled by adjusting the indium precursor dose time to sub-saturation. IAO based on DMAI was applied to fabricate thin-film transistors (TFTs), showing that Al can be a carrier suppressor of indium oxide. TFTs with PEALD IAO containing 3.8 atomic % Al showed a turn-on voltage of -0.4 ± 0.3 V, a subthreshold slope of 0.09 V/decade, and a field effect mobility of 18.9 cm2/(V s).

Unravelling the selective growth mechanism of AlOx with dimethylaluminum isopropoxide as a precursor in atomic layer deposition: a combined theoretical and experimental study

The selective encapsulation of Pt nano catalysts is achieved to maintain the durability and reactivity.

Efficient, durable protection of the Ti6242S titanium alloy against high-temperature oxidation through MOCVD processed amorphous alumina coatings

With their exceptional strength-to-weight ratio, titanium alloys find applications in numerous key enabling technologies. However, their implementation in harsh environments comes up against their limited resistance to high-temperature oxidation. To face this problem, in this work dense, amorphous alumina, Al2O3 coatings are applied on the surface of Ti6242S alloy by metalorganic chemical vapor deposition, MOCVD, from aluminum triisopropoxide, ATI and from dimethylaluminum isopropoxide, DMAI. Isothermal oxidation tests show that the parabolic rate constants of the mass gain of the coated Ti6242S coupons are reduced up to two orders of magnitude compared with the bare material. 5000 h long oxidation of DMAI Al2O3 coated alloy at 600 °C results in 0.180 mg cm−2 weight gain to be compared with 1.143 mg cm−2 for the bare alloy. In these conditions, an interfacial layer is formed, containing the complex Ti3(Al0.5Sn0.5) (or (Ti,Sn)2N) phase. Cyclic oxidation consisting of eighty, 1 h cycles between 50 and 600 °C show null mass gain of the coated sample. Finally, the hardness profiles determined on cross sections of oxidized coupons reveal a very limited oxygen dissolution for the coated alloy. MOCVD coatings of amorphous Al2O3 have great potential for efficient, durable protection against oxidation of Ti6242S alloys.

The Effect of Al2O3 ALD Precursors on the Electrochemical Performance of Cathode Materials for Lithium-Based Battery Applications

Al2O3 coatings prepared by atomic layer deposition (ALD) using trimethyl aluminum (TMA) and H2O on various cathode materials have been shown to enhance the battery cycle stability of lithium ion batteries. Interestingly, not all cathode materials are enhanced by Al2O3 ALD coating. For example, while Al2O3 coating on lithium cobalt oxide (LCO) using 1-2 TMA/H2O ALD cycles dramatically improves cycle performance [1], much less positive effect on lithium manganese oxide (LMO) was observed [2]. We revealed the TMA surface reactions on LMO are unusual in that they do not involve hydroxyls, ethane is released, and the manganese undergoes redox chemistry from our previous study [2]. Furthermore, density functional theory (DFT) calculations reveal that this unique mechanism is driven by the large free energy changes upon methyl loss from TMA [2]. This information leads us to speculate that the surface reactions and subsequent electrochemistry might also depend on different Al precursors. To evaluate our hypothesis, we are exploring a range of aluminum precursors including trimethyl aluminum (TMA), tris(dimethylamido) aluminum (Al-TDMA), aluminum trichloride (AlCl3), dimethyl aluminum isopropoxide (DMAI), and aluminum triisopropoxide (ATIP) on LCO and LMO cathode materials. Our preliminary results showed that very different ALD chemistries on between LCO and LMO cathode materials. It suggests a correlation between cation reduction on the cathode surface and the relative Lewis acidity of the Al precursor ligands. We will elaborate on these findings using results from XPS measurements, DFT calculations, electrochemical characterizations, and battery cycling studies. [1] Y. S. Jung et. al., J. Electrochem. Soc. 157 (1) A75-A81, (2010). [2] L. Chen et. al., Chem 4 2418-2435 (2018).

Understanding the Effects of Ultra-Thin Al2O3 Coatings Prepared By Atomic Layer Deposition on Lithium Ion Battery Cathode Materials

Although various cathode materials possessing high capacity have been developed to date, most of them are still suffering from early capacity fading. Several strategies such as doping, surface treatment and coating have been adopted to minimize this problem. Among a variety of coating strategies, atomic layer deposition (ALD) is regarded as the best technique for coating of cathode materials. ALD is a thin-film growth technique that offers the unique capability to coat complex, three-dimensional objects with precise, conformal layers by atomic-level control over thickness and composition. Over the last decade, ALD has emerged as an effective strategy for coating cathode materials to enhance the overall performance Li-ion batteries. ALD Al2O3 coatings prepared using trimethyl aluminum (TMA) and H2O have been evaluated previously on cathodes including LiCoO2 (LCO), LiMn2O4 (LMO), and Li(NixMnyCoz)O2 (NMC), and the effect of the coating on cycling stability was found to vary between these different materials. Moreover, our recent study of TMA/H2O chemistry on LMO revealed a unique nucleation mechanism leading to unexpected products and altered electrochemical behavior. In an effort to better understand these observations, we are exploring Al2O3 ALD using a range of aluminum precursors (TMA, tris(dimethylamido) aluminum, aluminum trichloride, dimethyl aluminum isopropoxide, and aluminum triisopropoxide) and a variety of cathode materials (LCO, LMO, and several NMCs). We discovered that the ALD aluminum precursor reduces cations on the cathode surface, and the degree of reduction depends on the relative Lewis acidity of the precursor ligands, and on the composition of the cathode surface. In this presentation we will elaborate on these findings and describe the correlations between the chemistry of the ALD-modified cathode surface and the resulting electrochemical behavior and cycling performance.

Amorphous Alumina Films Efficiently Protect Ti6242S against Oxidation and Allow Operation above 600 °C

The protection of the titanium based Ti6242S alloy against oxidation at moderate temperature is investigated, through the application on its surface of a 300 nm thick, amorphous alumina film. The latter is processed by metalorganic chemical vapor deposition at 500 °C from dimethyl aluminum isopropoxide. Upon oxidation at 600 °C for 5000 h, an interfacial zone is created between the alloy and the external protective layer, composed of unaffected alumina. In these conditions, the mass gain per unit area is eight times lower than that of the bare alloy, while the hardness of the alloy remains unaffected, revealing negligible oxygen ingress attributed to the efficiency of the protective coating. Finally, alumina coated samples show negligible mass change after 80 one-hour thermal cycles between 50 °C and 600 °C, showing excellent coating adherence on the Ti alloy.

Improving the Silicon Surface Passivation by Aluminum Oxide Grown Using a Non‐Pyrophoric Aluminum Precursor

In this work, an alternative nonpyrophoric Al‐precursor [dimethylaluminum isopropoxide (DMAI)] is used to deposit Al2O3 on p‐type c‐Si by plasma‐enhanced and thermal atomic layer deposition (ALD). Al2O3 films grown by thermal ALD provide a relatively modest level of crystalline silicon surface passivation compared to their plasma‐assisted ALD grown counterparts. This difference is attributed to a significant difference in the interfacial SiOx film as identified by Brewster's angle Fourier transform infrared spectroscopy. The energy barrier for DMAI to react with Si‐H groups on the surface is significantly lower compared to TMA, which impedes the formation of the interfacial SiOx layer. As thermal ALD is the strongly preferred method in the photovoltaic industry, there is a strong incentive to improve the performance of the thermal ALD process to allow for the application of this intrinsically safer Al2O3 deposition process. A chemically grown thin oxide is shown to significantly improve the level of surface passivation provided by the thermal ALD Al2O3 film resulting in an increase in implied open circuit voltage from 653 to 723 mV. This surface pretreatment thus solves a major barrier for the application of this intrinsically safer process in the photovoltaic industry.

Al2O3 thin films prepared by plasma-enhanced chemical vapor deposition of dimethylaluminum isopropoxide

Al2O3 thin films were deposited by plasma-enhanced chemical vapor deposition using a dimethylaluminum isopropoxide precursor in the absence of additional oxygen sources. The deposition rate ranged from 0.77 to 1.07Å/s and increased with increasing deposition temperature between 300 and 500°C. The O/Al ratios in the films deposited at 300–500°C were ~1.5, consistent with the formula Al2O3 and the carbon contents were 8.3–9.7at.%. The film deposited at 30°C had relatively higher values of O/Al ratio (2.04) and carbon content (47.1at.%). Al2p, O1s, and C1s peaks observed from X-ray photoelectron spectroscopy analysis were mainly attributed to Al2O3. Fourier transform infrared analyses indicated that the functional groups such as Al2O3 bending and stretching vibrations were primarily from Al2O3 species with some carbon contents. From the dry etching test, the Al2O3 film deposited at 400°C had the high etch selectivity of 9.13 over SiO2, which showed the potential for application to the dry etch hard mask material.

Atomic Layer Deposition in a Metal–Organic Framework: Synthesis, Characterization, and Performance of a Solid Acid

NU-1000, a zirconium-based metal–organic framework (MOF) featuring mesoporous channels, has been postsynthetically metalated via atomic layer deposition in a MOF (AIM) employing dimethylaluminum iso-propoxide ([AlMe2OiPr]2, DMAI), a milder precursor than widely used trimethylaluminum (AlMe3, TMA). The aluminum-modified NU-1000 (Al-NU-1000) has been characterized with a comprehensive suite of techniques that points to the formation of aluminum oxide clusters well dispersed through the framework and stabilized by confinement within small pores intrinsic to the NU-1000 structure. Experimental evidence allows for identification of spectroscopic similarities between Al-NU-1000 and γ-Al2O3. Density functional theory modeling provides structures and simulated spectra, the relevance of which can be assessed via comparison to experimental IR and EXAFS data. The catalytic performance of Al-NU-1000 has been benchmarked against γ-Al2O3, with promising results in terms of selectivity.

Engendering Long-Term Air and Light Stability of a TiO2-Supported Porphyrinic Dye via Atomic Layer Deposition.

Organic and porphyrin-based chromophores are prevalent in liquid-junction photovoltaic and photocatalytic solar-cell chemistry; however, their long-term air and light instability may limit their practicality in real world technologies. Here, we describe the protection of a zinc porphyrin dye, adsorbed on nanoparticulate TiO2, from air and light degradation by a protective coating of alumina grown with a previously developed post-treatment atomic layer deposition (ALD) technique. The protective Al2O3 ALD layer is deposited using dimethylaluminum isopropoxide as an Al source; in contrast to the ubiquitous ALD precursor trimethylaluminum, dimethylaluminum isopropoxide does not degrade the zinc porphyrin dye, as confirmed by UV-vis measurements. The growth of this protective ALD layer around the dye can be monitored by an in-reactor quartz crystal microbalance (QCM). Furthermore, greater than 80% of porphyrin light absorption is retained over ∼1 month of exposure to air and light when the protective coating is present, whereas almost complete loss of porphyrin absorption is observed in less than 2 days in the absence of the ALD protective layer. Applying the Al2O3 post-treatment technique to the TiO2-adsorbed dye allows the dye to remain in electronic contact with both the semiconductor surface and a surrounding electrolyte solution, the combination of which makes this technique promising for numerous other electrochemical photovoltaic and photocatalytic applications, especially those involving the dye-sensitized evolution of oxygen.

Amorphous alumina thin films deposited on titanium: Interfacial chemistry and thermal oxidation barrier properties

Ti/Al2O3 bilayer stacks are used as model systems to investigate the role of atomic layer deposition (ALD) and chemical vapor deposition (CVD) to prepare 30–180 nm thick amorphous alumina films as protective barriers for the medium temperature oxidation (500–600 °C) of titanium, which is employed in aeronautic applications. X‐ray diffraction (XRD), transmission electron microscopy (TEM) with selected area electron diffraction (SAED), and X‐ray photoelectron spectroscopy (XPS) results show that the films produced from the direct liquid injection (DLI) CVD of aluminum tri‐isopropoxide (ATI) are poor oxygen barriers. The films processed using the ALD of trimethylaluminum (TMA) show good barrier properties but an extensive intermixing with Ti which subsequently oxidizes. In contrast, the films prepared from dimethyl aluminum isopropoxide (DMAI) by CVD are excellent oxygen barriers and show little intermixing with Ti. Overall, these measurements correlate the effect of the alumina coating thickness, morphology, and stoichiometry resulting from the preparation method to the oxidation barrier properties, and show that compact and stoichiometric amorphous alumina films offer superior barrier properties.