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At least 379 records · Page 21
All sourcesNASA NTRSDOE OSTI
DOE OSTI2015

Effect of surface pretreatment on interfacial chemical bonding states of atomic layer deposited ZrO{sub 2} on AlGaN

Atomic layer deposition (ALD) of ZrO{sub 2} on native oxide covered (untreated) and buffered oxide etchant (BOE) treated AlGaN surface was analyzed by utilizing x-ray photoelectron spectroscopy (XPS) and high-resolution transmission electron microscopy. Evidenced by Ga–O and Al–O chemical bonds by XPS, parasitic oxidation during deposition is largely enhanced on BOE treated AlGaN surface. Due to the high reactivity of Al atoms, more prominent oxidation of Al atoms is observed, which leads to thicker interfacial layer formed on BOE treated surface. The results suggest that native oxide on AlGaN surface may serve as a protecting layer to inhibit the surface from further parasitic oxidation during ALD. The findings provide important process guidelines for the use of ALD ZrO{sub 2} and its pre-ALD surface treatments for high-k AlGaN/GaN metal–insulator–semiconductor high electron mobility transistors and other related device applications.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Mechanistic study of atomic layer deposition of Al{sub x}Si{sub y}O thin film via in-situ FTIR spectroscopy

A study of surface reaction mechanism on atomic layer deposition (ALD) of aluminum silicate (Al{sub x}Si{sub y}O) was conducted with trimethylaluminum (TMA) and tetraethoxysilane (TEOS) as precursors and H{sub 2}O as the oxidant. In-situ Fourier transform infrared spectroscopy (FTIR) was utilized to elucidate the underlying surface mechanism that enables the deposition of Al{sub x}Si{sub y}O by ALD. In-situ FTIR study revealed that ineffective hydroxylation of the surface ethoxy (–OCH{sub 2}CH{sub 3}) groups prohibits ALD of SiO{sub 2} by TEOS/H{sub 2}O. In contrast, effective desorption of the surface ethoxy group was observed in TEOS/H{sub 2}O/TMA/H{sub 2}O chemistry. The presence of Al-OH* group in vicinity of partially hydroxylated ethoxy (–OCH{sub 2}CH{sub 3}) group was found to propagate disproportionation reaction, which results in ALD of Al{sub x}Si{sub y}O. The maximum thickness from incorporation of SiO{sub x} from alternating exposures of TEOS/H{sub 2}O chemistry in Al{sub x}Si{sub y}O was found to be ∼2 Å, confirmed by high resolution transmission electron microscopy measurements.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Low-temperature SiON films deposited by plasma-enhanced atomic layer deposition method using activated silicon precursor

It has not been an easy task to deposit SiN at low temperature by conventional plasma-enhanced atomic layer deposition (PE-ALD) since Si organic precursors generally have high activation energy for adsorption of the Si atoms on the Si-N networks. In this work, in order to achieve successful deposition of SiN film at low temperature, the plasma processing steps in the PE-ALD have been modified for easier activation of Si precursors. In this modification, the efficiency of chemisorption of Si precursor has been improved by additional plasma steps after purging of the Si precursor. As the result, the SiN films prepared by the modified PE-ALD processes demonstrated higher purity of Si and N atoms with unwanted impurities such as C and O having below 10 at. % and Si-rich films could be formed consequently. Also, a very high step coverage ratio of 97% was obtained. Furthermore, the process-optimized SiN film showed a permissible charge-trapping capability with a wide memory window of 3.1 V when a capacitor structure was fabricated and measured with an insertion of the SiN film as the charge-trap layer. The modified PE-ALD process using the activated Si precursor would be one of the most practical and promising solutions for SiN deposition with lower thermal budget and higher cost-effectiveness.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Atomic layer deposition of NiS and its application as cathode material in dye sensitized solar cell

Nickel sulfide (NiS) is grown by atomic layer deposition (ALD) using sequential exposures of bis(2,2,6,6-tetramethylheptane-3,5-dionate)nickel(II) [Ni(thd){sub 2}] and hydrogen sulfide (H{sub 2}S) at 175 °C. Complementary combinations of in situ and ex situ characterization techniques are used to understand the deposition chemistry and the nature of film growth. The saturated growth rate of ca. 0.21 Å per ALD cycle is obtained, which is constant within the ALD temperature window (175–250 °C). As deposited films on glass substrates are found polycrystalline without any preferred orientation. Electrical transport measurement reveals degenerative/semimetallic characteristics with a carrier concentration of ca. 9 × 10{sup 22} cm{sup −3} at room temperature. The ALD grown NiS thin film demonstrates high catalytic activity for the reduction of I{sup −}/I{sub 3}{sup −} electrolyte that opens its usage as cost-effective counter electrode in dye sensitized solar cells, replacing Pt.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Inherent substrate-dependent growth initiation and selective-area atomic layer deposition of TiO{sub 2} using “water-free” metal-halide/metal alkoxide reactants

Titanium dioxide atomic layer deposition (ALD) is shown to proceed selectively on oxidized surfaces with minimal deposition on hydrogen-terminated silicon using titanium tetrachloride (TiCl{sub 4}) and titanium tetra-isopropoxide [Ti(OCH(CH{sub 3}){sub 2}){sub 4}, TTIP] precursors. Ex situ x-ray photoelectron spectroscopy shows a more rapid ALD nucleation rate on both Si–OH and Si–H surfaces when water is the oxygen source. Eliminating water delays the oxidation of the hydrogen-terminated silicon, thereby impeding TiO{sub 2} film growth. For deposition at 170 °C, the authors achieve ∼2 nm of TiO{sub 2} on SiO{sub 2} before substantial growth takes place on Si–H. On both Si–H and Si–OH, the surface reactions proceed during the first few TiCl{sub 4}/TTIP ALD exposure steps where the resulting products act to impede subsequent growth, especially on Si–H surfaces. Insight from this work helps expand understanding of “inherent” substrate selective ALD, where native differences in substrate surface reaction chemistry are used to promote desired selective-area growth.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Plasma-free atomic layer deposition of Ru thin films using H{sub 2} molecules as a nonoxidizing reactant

The ruthenium (Ru) thin films were grown by atomic layer deposition (ALD) using a sequential supply of dicarbonyl-bis(5-methyl-2,4-hexanediketonato) Ru(II) (C{sub 16}H{sub 22}O{sub 6}Ru) and H{sub 2} as a reactant at a substrate temperature of 250 °C. Deposition was possible using H{sub 2} molecules without a plasma by increasing the chamber pressure to above 10 Torr. Specifically, high-quality Ru films with a low resistivity of ∼40 μΩ cm and few amount of oxygen (∼1.2 at. %) were obtained under a chamber pressure of 300 Torr though the oxygen was contained in the precursor. Under the optimized conditions, self-limited film growth with regard to the precursor and reactant pulsing times was confirmed under elevated chamber pressures. The ALD-Ru process proposed in this study showed one of the highest growth rates of 0.12 nm/cycle on a thermally grown SiO{sub 2} substrate, as well as a very low number of incubation cycles (approximately 12 cycles). Cross-sectional view transmission electron microscopy showed that no interfacial oxide had formed during the deposition of the ALD-Ru films on a W surface using H{sub 2} molecules, whereas ∼7 nm thick interfacial oxide was formed when O{sub 2} molecules were used as a reactant. The step coverage of the ALD-Ru film onto very small-sized trenches (aspect ratio: ∼4.5 and the top opening size of 25 nm) and holes (aspect ratio: ∼40 and top opening size of 40 nm) was excellent (∼100%).

36 MATERIALS SCIENCE↗
DOE OSTI2016

Defect analysis in low temperature atomic layer deposited Al{sub 2}O{sub 3} and physical vapor deposited SiO barrier films and combination of both to achieve high quality moisture barriers

Al{sub 2}O{sub 3} [20 nm, atomic layer deposition (ALD)] and SiO films' [25 nm, physical vacuum deposition (PVD)] single barriers as well as hybrid barriers of the Al{sub 2}O{sub 3}/SiO or SiO/Al{sub 2}O{sub 3} have been deposited onto single 100 nm thick tris-(8-hydroxyquinoline) aluminum (AlQ{sub 3}) organic films made onto silicon wafers. The defects in the different barrier layers could be easily observed as nonfluorescent AlQ{sub 3} black spots, under ultraviolet light on the different systems stored into accelerated aging conditions (85 °C/85% RH, ∼2000 h). It has been observed that all devices containing an Al{sub 2}O{sub 3} layer present a lag time τ from which defect densities of the different systems start to increase significantly. This is coherent with the supposed pinhole-free nature of fresh, ALD-deposited, Al{sub 2}O{sub 3} films. For t > τ, the number of defect grows linearly with storage time. For devices with the single Al{sub 2}O{sub 3} barrier layer, τ has been estimated to be 64 h. For t > τ, the defect occurrence rate has been calculated to be 0.268/cm{sup 2}/h. Then, a total failure of fluorescence of the AlQ{sub 3} film appears between 520 and 670 h, indicating that the Al{sub 2}O{sub 3} barrier has been totally degraded by the hot moisture. Interestingly, the device with the hybrid barrier SiO/Al{sub 2}O{sub 3} shows the same characteristics as the device with the single Al{sub 2}O{sub 3} barrier (τ = 59 h; 0.246/cm{sup 2}/h for t > τ), indicating that Al{sub 2}O{sub 3} ALD is the factor that limits the performance of the barrier system when it is directly exposed to moisture condensation. At the end of the storage period (1410 h), the defect density for the system with the hybrid SiO/Al{sub 2}O{sub 3} barrier is 120/cm{sup 2}. The best sequence has been obtained when Al{sub 2}O{sub 3} is passivated by the SiO layer (Al{sub 2}O{sub 3}/SiO). In that case, a large lag time of 795 h and a very low defect growth rate of 0.032/cm{sup 2}/h (t > τ) have been measured. At the end of the storage test (2003 h), the defect density remains very low, i.e., only 50/cm{sup 2}. On the other hand, the device with the single PVD-deposited SiO barrier layer shows no significant lag time (τ ∼ 0), and the number of defects grows linearly from initial time with a high occurrence rate of 0.517/cm{sup 2}/h. This is coherent with the pinhole-full nature of fresh, PVD-deposited, SiO films. At intermediate times, a second regime shows a lower defect occurrence rate of 0.062/cm{sup 2}/h. At a longer time span (t > 1200 h), the SiO barrier begins to degrade, and a localized crystallization onto the oxide surface, giving rise to new defects (occurrence rate 0.461/cm{sup 2}/h), could be observed. At the end of the test (2003 h), single SiO films show a very high defect density of 600/cm{sup 2}. Interestingly, the SiO surface in the Al{sub 2}O{sub 3}/SiO device does not appeared crystallized at a high time span, suggesting that the crystallization observed on the SiO surface in the AlQ{sub 3}/SiO device rather originates into the AlQ{sub 3} layer, due to high humidity ingress on the organic layer through SiO pinholes. This has been confirmed by atomic force microscopy surface imaging of the AlQ{sub 3}/SiO surface showing a central hole in the crystallization zone with a 60 nm depth, deeper than SiO thickness (25 nm). Using the organic AlQ{sub 3} sensor, the different observations made in this work give a quantitative comparison of defects' occurrence and growth in ALD-deposited versus PVD-deposited oxide films, as well as in their combination PVD/ALD and ALD/PVD.

42 ENGINEERING↗
DOE OSTI2016

Unusual stoichiometry control in the atomic layer deposition of manganese borate films from manganese bis(tris(pyrazolyl)borate) and ozone

The atomic layer deposition (ALD) of films with the approximate compositions Mn{sub 3}(BO{sub 3}){sub 2} and CoB{sub 2}O{sub 4} is described using MnTp{sub 2} or CoTp{sub 2} [Tp = tris(pyrazolyl)borate] with ozone. The solid state decomposition temperatures of MnTp{sub 2} and CoTp{sub 2} are ∼370 and ∼340 °C, respectively. Preparative-scale sublimations of MnTp{sub 2} and CoTp{sub 2} at 210 °C/0.05 Torr afforded >99% recoveries with <0.1% nonvolatile residues. Self-limited ALD growth was demonstrated at 325 °C for MnTp{sub 2} or CoTp{sub 2} with ozone as the coreactant. The growth rate for the manganese borate process was 0.19 Å/cycle within the ALD window of 300–350 °C. The growth rate for the cobalt borate process was 0.39–0.42 Å/cycle at 325 °C. X-ray diffraction of the as-deposited films indicated that they were amorphous. Atomic force microscopy of 35–36 nm thick manganese borate films grown within the 300–350 °C ALD window showed root mean square surface roughnesses of 0.4–0.6 nm. Film stoichiometries were assessed by x-ray photoelectron spectroscopy and time of flight-elastic recoil detection analysis. The differing film stoichiometries obtained from the very similar precursors MnTp{sub 2} and CoTp{sub 2} are proposed to arise from the oxidizing ability of the intermediate high valent manganese oxide layers and lack thereof for cobalt.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Atomic layer deposition of 2D and 3D standards for synchrotron-based quantitative composition and structure analysis methods

Atomic layer deposition (ALD) is a scalable deposition technique known for producing uniform, conformal films of a wide range of compounds on nearly any substrate material. These traits make it an ideal deposition method for producing films to replace the National Institute of Standards and Technology (NIST) standards and create Standard Reference Materials (SRMs) on a wide range of relevant two-dimensional and three-dimensional substrates. The use of SRM from NIST for quantitative analysis of chemical composition using synchrotron based x-ray fluorescence (SR-XRF) and scanning transmission x-ray microscopy (STXM) is common. Such standards, however, can suffer from inhomogeneity in chemical composition and thickness and often require further calculations, based on sample mounting and detector geometry, to obtain quantitative results. These inhomogeneities negatively impact the reproducibility of the measurements and the quantitative measure itself. Utilizing Rutherford backscattering, x-ray reflectivity, quartz crystal microbalance, STXM, and SR-XRF, the authors show that ALD is capable of producing high quality standards that are homogenous over scales ranging from nanometers to 100s of micrometers.

Becker, Nicholas G.↗
DOE OSTI2020

Continuous polymer films deposited on top of porous substrates using plasma-enhanced atomic layer deposition and molecular layer deposition

Molecular layer deposition (MLD) is able to produce ultrathin polymer films with control over thickness, cross-linking, and chemical composition. With these capabilities, MLD should be useful in the fabrication of novel polymer membranes on porous supports. However, confining a continuous MLD film to the surface of porous substrates is difficult because of MLD film growth in the pores. The deposition in the pores lowers the conductance of the porous support. This paper presents a method to deposit continuous polymer films on top of porous substrates. In this method, Al2O3 plasma-enhanced atomic layer deposition (PE-ALD) using trimethylaluminum and oxygen plasma as the reactants was first used to cap the pores of the substrate. Subsequently, a polyamide MLD film was deposited on the Al2O3 PE-ALD capping layer using m-phenylenediamine and trimesoyl chloride as the reactants. The Al2O3 pore caps were then removed from the porous substrate by etching from the backside using a timed exposure to a dilute sodium hydroxide solution. This method was demonstrated using anodic aluminum oxide (AAO) and polyethersulfone (PES) porous substrates. Al2O3 PE-ALD film growth was limited to the top of the porous substrate, resulting in rapid surface recombination or high sticking coefficients for the reactive plasma species within the pores. Gas permeance measurements confirmed the pore capping of the AAO substrates. The reopening of the pores by dissolving the Al2O3 pore caps with a sodium hydroxide solution was monitored using gas permeance versus etch time. The removal of the Al2O3 pore caps from the PES substrates could also dissolve the Al2O3 layer underneath the MLD film. The loss of this Al2O3 layer led to the detachment of the MLD film from the PES substrate. However, the MLD film could be anchored to the PES support at fractures located in the Al2O3 film prior to the MLD. The Al2O3 film fracture allowed the MLD film to anchor firmly to the PES substrate by MLD in the pores of the PES porous substrate. The distance between the anchor points was a function of fracture density. This distance could be controlled by applying a tensile stress to the Al2O3 PE-ALD film to fracture the film through sample bending. This method produced firmly anchored polymer MLD films on top of the PES porous substrates.

Welch, Brian C. (ORCID:000000029747045X)↗
DOE OSTI2020

Plasma enhanced atomic layer deposition of thin film Li 1+x Mn 2-x O 4 for realization of all solid-state 3D lithium-ion microbatteries

Here, the plasma enhanced atomic layer deposition (PEALD) process for MnO 2 was demonstrated, exhibiting self-limiting growth as well as stable composition and stable growth rate over a temperature window of 205–265 °C. The PEALD process for MnO 2 was combined with the thermal ALD process for LiOH to synthesize Li 1+x Mn 2-x O 4 thin film cathodes, where the stoichiometry was effectively controlled to allow for crystallization in the electrochemically active spinel phase. A 3D nanostructure consisting of an Li 1+x Mn 2-x O 4 cathode layer, ALD Li x Al y Si z O solid electrolyte, and SiGe nanowire anode was fabricated and characterized via TEM. The Li 1+x Mn 2-x O 4 thin films maintained 66% of the areal capacity upon a 100× increase in the rate (4–360 μ A cm -2 ) as well as 97% capacity retention over 100 cycles at ~5C. The ALD Li 1+x Mn 2-x O 4 thin films exhibited a volumetric capacity of 52 μ Ah cm -2 μ m -1 at a C-rate of ~0.5C and, coupled with the high operating voltage (4.0 V), offer some of best areal energy densities for ALD thin film cathodes, making it a viable material for integration with 3D lithium-ion microbatteries.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Modeling scale-up of particle coating by atomic layer deposition

Atomic layer deposition (ALD) is a promising technique to functionalize particle surfaces for energy applications including energy storage, catalysis, and decarbonization. In this work, we present a set of models of ALD particle coating to explore the transition from lab scale to manufacturing. Our models encompass the main particle coating manufacturing approaches including rotary bed, fluidized bed, and continuously vibrating reactors. These models provide key metrics, such as throughput and precursor utilization, required to evaluate the scalability of ALD manufacturing approaches and their feasibility in the context of energy applications. Our results show that designs that force the precursor to flow through fluidized particles transition faster to a transport-limited regime where throughput is maximized. They also exhibit higher precursor utilization. In the context of continuous processes, our models indicate that it is possible to achieve self-extinguishing processes with almost 100% precursor utilization. A comparison with past experimental results of ALD in fluidized bed reactors shows excellent qualitative and quantitative agreement.

25 ENERGY STORAGE↗
DOE OSTI2025

Nonpyrophoric alternative to trimethylaluminum for the atomic layer deposition of Al 2 O 3

We have examined the atomic layer deposition (ALD) of Al 2 O 3 using a nonpyrophoric precursor, which possesses only Al–N bonds and no Al–C bonds: Al(N(CH 3 ) 2 ) 2 (–N(C 2 H 5 )–C 2 H 4 –N(C 2 H 5 ) 2 ), which we refer to as bis-dimethylamino-diamino-aluminum (BDMADA-Al). We employed a quartz crystal microbalance (QCM) to monitor ALD in situ and in real time, and the deposited thin films have been characterized using x-ray photoelectron spectroscopy, spectroscopic ellipsometry, x-ray reflectivity, and atomic force microscopy. Films deposited with BDMADA-Al result in near-stoichiometric Al2O3 at temperatures ranging from T = 120 to 285 °C using H 2 O as the coreactant and at T = 285 °C using t-BuOH as the coreactant. The properties of the films (density, C incorporation, stoichiometry, growth rates) are comparable using either BDMADA-Al or trimethylaluminum (TMA) as the precursor under similar reaction conditions. The N content in the films deposited with BDMADA-Al as the precursor is <1% at both T = 120 and 285 °C. Additionally, both BDMADA-Al|t-BuOH and TMA|t-BuOH processes deposit near-stoichiometric Al 2 O 3 at T = 285 °C, while neither process chemistry produces a constant growth rate per cycle at T = 120 °C. Close examination of single cycle QCM data from BDMADA-Al ALD indicates unique ligand exchange reaction mechanisms during each of the half-reactions. Experimentally, we have evidence supporting the mechanism in which upon the chemisorption of BDMADA-Al, the species on the surface retains the –N(CH 3 ) 2 ligands, while the diamine ligand is mostly lost on dissociative adsorption, except possibly at the higher temperature (285 °C). As a result, our work demonstrates that BDMADA-Al can be used as an effective alternative precursor to TMA for the ALD of Al 2 O 3 .

36 MATERIALS SCIENCE↗
DOE OSTI2025

Modeling diffusion and depletion in high-aspect-ratio atomic layer deposition processes: Process parameters and manufacturing impacts

Atomic layer deposition (ALD) is a powerful technique for modifying the surface chemistry and properties of substrates with complex and nonplanar topologies. However, achieving uniform and conformal deposition on ultrahigh-aspect-ratio substrates remains challenging, typically requiring large quantities of precursors and long exposure times. Furthermore, process optimization is often performed empirically and involves substantial trial and error. In this work, we perform a combined experimental and computational study of ALD Al 2 O 3 infiltration into silica aerogel monoliths (aspect ratio >10 5 ). A reaction-diffusion model is used to explore the effects of key processing parameters, namely, exposure time per dose, precursor source temperature, number of aerogels in the reactor, and reactor volume. The model is based on quasi-static mode ALD, where the dosed precursor is held in the chamber for a fixed period of time before purging. We analyze the trade-offs between process throughput and precursor utilization for each of these parameters. Furthermore, we investigate the co-optimization and interactions between multiple process parameters, demonstrating the potential for further improvements. Furthermore, this physics-based model can be used to identify a set of process parameters for high-aspect-ratio ALD that meet specific manufacturing objective functions, including throughput, cost, and sustainability.

Aerogel↗
DOE OSTI2025

Controlled phosphate doping into nanoscopic SiO 2 proton conducting membranes

This article describes a method to introduce phosphate (PO 4 ) into SiO 2 atomic layer deposition (ALD) films in a self-limiting fashion. The method involves the use of a less common phosphate precursor, trimethyl phosphite [P(OMe) 3 ], to introduce PO 4 as a low-level dopant, <1 at. %, into a SiO 2 ALD process using bis(ethylmethylamino)silane and a modified O 3 conversion. P(OMe) 3 does not deposit a film with typical oxygen sources but incorporates as PO 4 in an ABC-type ALD scheme at deposition temperatures ranging from 100 to 300 °C. Addition of up to ∼1 at. % of PO 4 does not significantly impact the film density or concentrations of carbon and nitrogen impurities, which are both <0.4 at. %. Despite the relatively low dopant concentrations, PO 4 incorporation is shown to have a large impact on transport properties of the film. When explored as proton (H + )-conducting membranes, undoped SiO 2 ALD films showed H + conductivities (3 × 10 −6 –8 × 10 −5 S cm −1 ) and low H 2 permeabilities (<10 −9 cm 2 s −1 ) when measured at room temperature. The addition of PO 4 is shown to increase H + conductivity to 2 × 10 −4 S cm −1 , while maintaining low H 2 permeability of <10 −9 cm 2 s −1 . The ratio of H + conductivity to H 2 permeability, a key performance metric for H + -conducting membranes used in water electrolyzers, exceeds that of commercial Nafion-117 membranes. Here, the moderate H + conductivity and very low H 2 permeability of PO 4 -doped SiO 2 films make them promising candidates as fluorine-free replacements for Nafion in applications such as water electrolysis, hydrogen fuel cells, and redox flow batteries.

Atomic layer deposition↗
DOE OSTI2018

Zeolitic imidazolate framework membranes made by ligand-induced permselectivation

Zeolitic imidazolate framework (ZIF) membranes are emerging as a promising energy-efficient separation technology. However, their reliable and scalable manufacturing remains a challenge. We demonstrate the fabrication of ZIF nanocomposite membranes by means of an all-vapor-phase processing method based on atomic layer deposition (ALD) of ZnO in a porous support followed by ligand-vapor treatment. After ALD, the obtained nanocomposite exhibits low flux and is not selective, whereas after ligand-vapor (2-methylimidazole) treatment, it is partially transformed to ZIF and shows stable performance with high mixture separation factor for propylene over propane (an energy-intensive high-volume separation) and high propylene flux. Membrane synthesis through ligand-induced permselectivation of a nonselective and impermeable deposit is shown to be simple and highly reproducible and holds promise for scalability.

Science & Technology - Other Topics↗
DOE OSTI2016

In Situ Ramp Anneal X-ray Diffraction Study of Atomic Layer Deposited Ultrathin TaN and Ta 1-x Al x N y Films for Cu Diffusion Barrier Applications

Ultrathin TaN and Ta 1-x Al x N y films with x = 0.21 to 0.88 were deposited by atomic layer deposition (ALD) and evaluated for Cu diffusion barrier effectiveness compared to physical vapor deposition (PVD) grown TaN. Cu diffusion barrier effectiveness was investigated using in-situ ramp anneal synchrotron X-ray diffraction (XRD) on Cu/1.8 nm barrier/Si stacks. A Kissinger-like analysis was used to assess the kinetics of Cu 3 Si formation and determine the effective activation energy (E a ) for Cu silicidation. Compared to the stack with a PVD TaN barrier, the stacks with the ALD films exhibited a higher crystallization temperature (T c ) for Cu silicidation. The Ea values of Cu 3 Si formation for stacks with the ALD films were close to the reported value for grain boundary diffusion of Cu whereas the Ea of Cu 3 Si formation for the stack with PVD TaN is closer to the reported value for lattice diffusion. For 3 nm films, grazing incidence in-plane XRD showed evidence of nanocrystallites in an amorphous matrix with broad peaks corresponding to high density cubic phase for the ALD grown films and lower density hexagonal phase for the PVD grown film further elucidating the difference in initial failure mechanisms due to differences in barrier crystallinity and associated phase.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Coating Strategies to Improve Lithium-ion Battery Safety

This work investigated the effects of Al 2 O 3 ALD coatings on the performance and thermal abuse tolerance of graphite based anodes and Li(NixMnyCoz)O 2 (NMC) based cathodes. It was found that 5 cycles of Al 2 O 3 ALD on the graphite anode increased the onset temperature of thermal runaway by approximately 20 °C and drastically reduced the anode’s contribution to the overall amount of heat released during thermal runaway. Although Al 2 O 3 ALD improves the cycling stability of NMC based cathodes, the thermal abuse tolerance was not greatly improved. A series of conductive aluminum oxide/carbon composites were created and characterized as potential thicker protective coatings for use on NMC based cathode materials. A series of electrodes were coated with manganese monoxide ALD to test the efficacy of an oxygen scavenging coating on NMC based cathodes.

25 ENERGY STORAGE↗