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DOE OSTI2021

Atomic Layer Deposition for Improved Biomass Conversion Catalysts

Heterogeneous catalysts are a key enabler of the transition towards a sustainable, bio-based economy for fuels and chemicals. However, the harsh conditions in many biomass conversion processes lead to nanoparticle sintering, support collapse, and metal leaching in conventional PGM catalysts. Next-generation catalysts must be developed to address these stability challenges. This presentation will discuss ongoing work between the Catalytic Carbon Transformation and Scale-Up Center at NREL and various industrial partners to develop scalable and cost-effective atomic layer deposition (ALD) coatings for improving the performance of biomass conversion catalysts. The substantial focus will be devoted to the benefits of TiO2 ALD coatings on supported Pd hydrogenation catalysts. Ten cycles of TiO2 ALD were found to dramatically improve the activity of a conventional Pd/Al2O3 catalyst towards aromatic hydrogenation, despite partial coverage of the Pd sites by the ALD layer. Subsequent advanced characterization and atomic-scale computational modeling revealed that the ALD coating weakened the adsorption strength of hydrogenation surface intermediates, leading to higher reaction rates. Reaction testing after exposure to sulfur impurities, high temperature oxidation, and hydrothermal treatment demonstrated the improved stability of the ALD-coated catalyst. Additionally, the ALD synthesis process was found to be scalable over two orders of magnitude with minimal deviation in synthesized catalyst properties. These results were contextualized with cost models of industrial ALD coating and aromatic hydrogenation processes to further refine the value proposition of ALD coatings. Given the demonstrated improvements in hydrogenation, TiO2 ALD coatings have also been applied to supported Pt catalysts for use in other biomass conversion reactions, such as hydrodeoxygenation for the production of sustainable aviation fuel (SAF) and the oxidation of glucose to bio-derived gluconic acid.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗

DOE OSTI2020

Probing the Atomic-Scale Structure of Amorphous Aluminum Oxide Grown by Atomic Layer Deposition

Atomic layer deposition (ALD) is a well-established technique for depositing nanoscale coatings with pristine control of film thickness and composition. The trimethylaluminum (TMA) and water (H 2 O) ALD chemistry is inarguably the most widely used and yet to date, we have little information about the atomic-scale structure of the amorphous aluminum oxide (AlO x ) formed by this chemistry. This lack of understanding hinders our ability to establish process-structure-property relationships and ultimately limits technological advancements employing AlOx made via ALD. In this work, we employ synchrotron high-energy X-ray diffraction (HE-XRD) coupled with pair distribution function (PDF) analysis to characterize the atomic structure of amorphous AlO x ALD coatings. We combine ex situ and in operando HE-XRD measurements on ALD AlO x and fit these experimental data using stochastic structural modeling to reveal variations in the Al-O bond length, Al and O coordination environment, and extent of Al vacancies as a function of growth conditions. In particular, the local atomic structure of ALD AlO x is found to change with the substrate and number of ALD cycles. The observed trends are consistent with the formation of bulk Al 2 O 3 surrounded by an O-rich surface layer. We deconvolute these data to reveal atomic-scale structural information for both the bulk and surface phases. Overall, this work demonstrates the usefulness of HE-XRD and PDF analysis in improving our understanding of the structure of amorphous ALD thin films and provides a pathway to evaluate how process changes impact the structure and properties of ALD films.

36 MATERIALS SCIENCE↗

DOE OSTI2024

Comprehensive evaluation of commercially scalable atomic-layer-deposited alumina coating impact on full cell battery performance across varied test conditions

Atomic Layer Deposition (ALD) has emerged as a strategic enhancement method for lithium-ion battery (LIB) materials offering potential benefits and durability benefits for industrial battery production. However, the translation from laboratory achievements to commercial-scale applications has been limited. Here, this study aims to bridge this gap by comprehensively evaluating the effects of commercially scalable Al 2 O 3 ALD coatings using full pouch cell performance as a means to assess the ALD impact. We utilized large-scale slot-die coating techniques to ensure consistent electrode quality and tested four configurations of pouch cells to analyze the individual effects of ALD coating on anode and cathode electroactive materials. Our extensive testing matrix included long-term cycling, fast discharge, fast charge, leakage current, and high voltage tests. While at lower C-rates (<~1C), the influence of Al 2 O 3 coatings on cell performance is not significant. Fast charging conditions reveal that the anode ALD coating significantly enhances performance via a passivating effect, while on the cathode, it is detrimental, potentially due to increased resistance of the thin interfacial layer formed during the ALD processing. Leakage current and high-voltage tests show that the application of ALD coatings on either anode or cathode effectively minimizes side reactions at the electrode-electrolyte interface. Additionally, ALD coatings significantly mitigate concentrated and localized lithium plating on the anodes. These insights provide a valuable understanding of the potential of ALD technologies in LIB manufacturing to tailor cell performance, paving the way for safer, more efficient, and cost-effective battery solutions.

25 ENERGY STORAGE↗

DOE OSTI2025

Tuning 3-D Nanomaterial Architectures Using Atomic Layer Deposition to Direct Solution Synthesis

The ability to synthesize nanoarchitected materials with tunable geometries provides a means to control their functional properties, with applications in biological, environmental, and energy fields. To this end, various bottom-up and top-down synthesis processes have been developed. However, many of these processes require prepatterning or etching steps, making them challenging to scale-up to complex, nonplanar substrates. Furthermore, the ability to integrate nanomaterials into hierarchical arrays with precise control of feature spacing and orientation remains a challenge. One approach to overcome these patterning challenges is the use of surface modification layers to guide the resulting geometry of nanomaterial architectures grown from the substrate. A powerful strategy to accomplish this is what we will refer to as “surface-directed assembly,” where the resulting geometric parameters (feature size, shape, orientation) are predetermined by the initial surface layer. In particular, the use of Atomic Layer Deposition (ALD) to form a surface layer, followed by solution-based growth processes, has the ability to synthesize architected structures with tunable geometries on complex, nonplanar surfaces. Over the past decade, we have reported a series of studies where surface-directed assembly is used to synthesize ZnO nanowires (NWs) on top of a variety of substrates. In this case, a thin film of ZnO is deposited onto the substrate using ALD, which can guide the NW diameter, spacing, and angular orientation with respect to the substrate by controlling epitaxial relationships. Furthermore, we have shown that by depositing a submonolayer overcoat of a secondary material (e.g., amorphous TiO 2 ), nucleation sites are partially blocked, which can further tune the spacing between nanowires while minimizing changes to their other geometric properties. This approach can be used to generate multilevel hierarchical structures, such as hyperbranched NW arrays with tunable control of each level of hierarchy using ALD. Finally, we have demonstrated that the tunable control of geometric parameters can be scaled-up to curved, nonplanar substrates. This highlights the power of ALD to conformally and uniformly deposit the seed layers on complex substrates with subnanometer precision. To complement these seeded hydrothermal approaches, we expanded this strategy to include conversion chemistry of the initial ALD seed layers. For example, by replacing ZnO with Al 2 O 3 as the seed layer without changing the hydrothermal growth conditions, Al–Zn layered-double hydroxide nanosheets can be formed instead of nanowires. In another example of conversion chemistry, a solution anion-exchange process was used to incorporate sulfur into ALD metal oxide films. In both of these conversion processes, the properties of the initial ALD film enabled tuning of the resulting nanostructure geometry. In this Account, we describe the use of ALD to guide the growth of diverse nanomaterial systems, with tunable control over their geometry and composition. We further show how these approaches can be used to tune functional properties for a range of applications, including superomniphobic surfaces, antibiofouling coatings, and photocatalysis. In conclusion, we conclude with an outlook on how the combination of ALD and solution synthesis can enable future directions in scalable nanomanufacturing to overcome the limitations of traditional top-down and bottom-up approaches.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2015

Understanding the Structure of Amorphous Thin Film Hafnia (Final Paper)

Hafnium Oxide (HfO 2 ) amorphous thin films are being used as gate oxides in transistors because of their high dielectric constant (κ) over Silicon Dioxide. The present study looks to find the atomic structure of HfO 2 thin films which hasn’t been done with the technique of this study. In this study, two HfO 2 samples were studied. One sample was made with thermal atomic layer deposition (ALD) on top of a Chromium and Gold layer on a silicon wafer. The second sample was made with plasma ALD on top of a Chromium and Gold layer on a Silicon wafer. Both films were deposited at a thickness of 50nm. To obtain atomic structure information, Grazing Incidence X-ray diffraction (GIXRD) was carried out on the HfO 2 samples. Because of this, absorption, footprint, polarization, and dead time corrections were applied to the scattering intensity data collected. The scattering curves displayed a difference in structure between the ALD processes. The plasma ALD sample showed the broad peak characteristic of an amorphous structure whereas the thermal ALD sample showed an amorphous structure with characteristics of crystalline materials. This appears to suggest that the thermal process results in a mostly amorphous material with crystallites within. Further, the scattering intensity data was used to calculate a pair distribution function (PDF) to show more atomic structure. The PDF showed atom distances in the plasma ALD sample had structure up to 10 Å, while the thermal ALD sample showed the same structure below 10 Å. This structure that shows up below 10 Å matches the bond distances of HfO 2 published in literature. The PDF for the thermal ALD sample also showed peaks up to 20 Å, suggesting repeating atomic spacing outside the HfO 2 molecule in the sample. This appears to suggest that there is some crystalline structure within the thermal ALD sample.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

DOE OSTI2015

Understanding the Structure of High-K Gate Oxides - Oral Presentation [Slides]

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

DOE OSTI2022

Tailoring Corrosion Resistance of Additively Manufactured Metals with Atomic Layer Deposition

The goal of this work is to develop a scalable post-manufacturing capability at LANL that utilizes atomic layer deposition (ALD) for corrosion-resistant coatings onto additively manufactured (AM) metals. This will provide fundamentally new and essential capabilities towards the interchangeability of AM metals with traditionally wrought or machined material. This will be accomplished by (1) formulating novel ALD precursor doses and film thicknesses onto as-printed coupons of AM metals and (2) providing electrochemical characterization of corrosion susceptibility as a function of deposited film thickness. While ALD is well-established, the unique aspect (risk) of this work is application to rough AM surfaces. This risk is mitigated by repeating ALD deposition cycles, where thicker coatings laterally branch, resulting in a uniform coating. This risk will be assessed in the phase 1 feasibility study, wherein the application of ALD coatings to small AM coupon surfaces will be demonstrated using existing hardware and characterization tools at Sigma. This study alone will provide ground-breaking insight on the compatibility of ALD coating techniques with AM metals. Going beyond the phase 1 study, a standalone deposition chamber will be built, so full AM components can be coated and tested. While this MFR investment is focused on corrosion mitigation, it is critical to highlight external benefits of this technique outside the scope of this proposed study. ALD has extraordinary universality, whereby almost any material can be given almost any coating or graded density coating with atomic precision; and, the only limiting factors to scalability is the size of the dosing chamber. The self-limiting reactions intrinsic to ALD offers high conformity to part geometry and tolerance, even for internal surfaces where electroplating or conventional chemical vapor deposition falls short due to differential diffusion. This uniquely positions ALD at the forefront of post-manufacturing strategies for AM components, especially for those with complex geometry and internal surfaces.

36 MATERIALS SCIENCE↗

DOE OSTI2019

Tin Nitride Atomic Layer Deposition Using N2H4

There is substantial lag in the development of atomic layer deposition (ALD) processes for nitrides compared to the high-quality, conformal oxides for which ALD has become the standard. A major factor in this disparity is the ready availability of highly reactive oxygen sources (mainly H2O, O2, and H2O2). High-energy nitrogen precursors are similarly required for the efficient incorporation of nitrogen in a film. Ammonia has often been used in conjunction with metal chlorides but requires relatively high temperatures for thermal ALD. Plasma-enhanced ALD can utilize molecular nitrogen as a precursor but can reduce film conformality on complex supports and damage the underlying substrate. Hydrazine (N2H4) is an alternative precursor which has been rarely explored for the fabrication of nitrides in ALD, but which is experiencing a surge in popularity due to its high reactivity, which enables the deposition of nitrides as-yet undemonstrated by ALD.(1) The added reactivity and volatility of liquid hydrazine may enable new reaction mechanisms, lower deposition temperatures, and conformality for high aspect ratio applications. Sn3N4 is a metastable semiconductor which shares a crystal structure with its analog, Si3N4; unlike Si3N4, Sn3N4 has only recently been grown by ALD,(2) being synthesized much more often through reactive sputtering.(3) As a binary, Sn3N4 has applications as a battery anode material, for photoelectrochemistry, and optoelectronic devices. We will report progress on the deposition of SnxNy films from tetrakis(dimethylamido) tin (TDMASn) and N2H4. Growth per cycle of this material (determined by x-ray reflectivity) is 0.4 A at 200 C, similar to the sole report of Sn3N4 from PE-ALD,(2) despite films being substantially Sn-rich. Identification of ALD growth window and self-limiting deposition characteristics are underway; initial testing indicates a competing chemical vapor deposition process which can be eliminated with adequate tuning of pulse/purge characteristics. A comparison of film conductivity and optical absorption at different growth temperatures will be presented. General issues of N2H4 purity and routes to prevent or control oxynitride formation will be discussed. (1) Du, L., et al. The First Atomic Layer Deposition Process for FexN Films. Chem. Comm., 2019, ASAP. DOI: 10.1039/C8CC10175B. (2) Stewart, D. M., et al. Tin Oxynitride Anodes by Atomic Layer Deposition for Solid-State Batteries. Chem. Mater. 2018, 30, 2526-34. (3) Caskey, C. M., et al. Semiconducting Properties of Spinel Tin Nitride and Other IV3N4 Polymorphs. J. Mater. Chem. C 2015, 3, 1389-96.

14 SOLAR ENERGY↗

DOE OSTI2019

Nanocrystalline ZrN thin film development via atomic layer deposition for U-Mo powder

Zirconium nitride (ZrN) thin film deposited via thermal atomic layer deposition (ALD) has been recently chosen as a candidate technology for application of a diffusion barrier coating on the low enriched uranium alloy powder considered in the NNSA research reactor conversion program. Reported here is the first instance of using ALD for coating actinide materials. For this study, a modified ALD system was constructed to produce one micron thick zirconium nitride (ZrN) coating over spherical particulate of natural uranium-molybdenum (U-Mo) based fuel. The ALD system was designed to have a rotating drum system, with provisions for facilitating sequential exposures of chemicals such as tetrakis dimethyl amido zirconium (TDMAZr) and ammonia (NH 3 ) in order to deposit ZrN. The ALD system was successful in developing a highly conformal ZrN coating covering every individual U-7Mo particle. This article describes the ZrN film synthesis details and reports the produced microstructure and composition of the ALD ZrN as deposited on fuel particulates. The as-fabricated coating was determined to have a nanocrystalline structure in the cubic-ZrN (cF8) phase. It exhibited a dense microstructure with adequate interfacial bonding. TEM-EELS characterization demonstrated that the coating contains a very low amount of oxygen impurity. To understand the potential microstructural evolution for ALD ZrN during reactor operation, an in-situ heavy ion (Kr) irradiation experiment was performed at the IVEM-Tandem facility. A total fluence of 7.5 x 10 15 ions/cm 2 (similar to 10 dpa) was achieved, and apart from minor grain coarsening in the ALD ZrN coating, no significant radiation effects were observed.

36 MATERIALS SCIENCE↗

DOE OSTI2022

Selective Hydroxylation of In 2 O 3 as A Route to Site-Selective Atomic Layer Deposition

We report that several atomic layer deposition (ALD) processes are now known that leverage the distinct surface chemistry of two disparate substrates (e.g., metal vs oxide) to realize markedly different ALD nucleation rates in an approach referred to as area-selective ALD. In contrast, few ALD processes have been identified that allow selective reaction at distinct surface sites of a single material surface, in a process that might be called site-selective ALD (SS-ALD). We describe one potential strategy to discriminate among several distinct surface sites on bixbyite In 2 O 3 to achieve site selectivity. Using density functional theory, we predict the discriminant hydration and hydroxylation of In 2 O 3 terrace and step-edge sites that depend strongly on the substrate temperature at low water coverage. Infrared measurement of surface hydroxyls on In 2 O 3 nanoparticles supports the predicted temperature dependence. The in situ examination of MgO ALD nucleation also shows results consistent with the predicted temperature dependence of In 2 O 3 hydroxylation. Together, these findings suggest that a selective hydroxylation approach may be a viable route to SS-ALD on In 2 O 3 .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2025

Probing the Effects of Dimethyl Aluminum Isopropoxide Surface Reaction Byproducts on Atomic Layer Deposition Nucleation

Atomic layer deposition (ALD) processes that leverage a myriad of metal–organic and complementary reactant combinations have been identified to realize precise and conformal thin film growth. However, the effects of the ALD reaction byproducts on nucleation and growth mechanisms are rarely considered. Site-selective ALD processes provide an opportunity for the detailed investigation of uniform surface sites with atomistic accuracy. Intentional pretreatment with a known ALD reaction byproduct – isopropanol – enables a significant improvement in the nucleation rate reproducibility of dimethylaluminum isopropoxide and water ALD on rutile TiO 2 (110). In situ spectroscopic ellipsometry reveals a partially reversible byproduct binding that is site-selective for TiO 2 (110) surface oxygen vacancies. First-principles calculations reveal surface site-specific thermodynamics for adsorption of isopropanol and water that may influence ALD nucleation. In conclusion, the sensitivity of site-selective ALD motivates consideration of secondary surface reactions when designing precision deposition processes, including area- or site-selective ALD reactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2020

Synthesis of a Hybrid Nanostructure of ZnO-Decorated MoS 2 by Atomic Layer Deposition

We introduce here the synthesis of hybrid nanostructures comprised of ZnO nanocrystals (NCs) decorating nanosheets and nanowires (NWs) of MoS 2 prepared by atomic layer deposition (ALD). The concentration, size, and surface-to-volume ratio of the ZnO NCs can be systematically engineered by controlling both the number of ZnO ALD cycles and the properties of the MoS 2 substrates, which are prepared by sulfurizing ALD MoO 3 . Analysis of the chemical composition combined with electron microscopy and synchrotron X-ray techniques as a function of the number of ZnO ALD cycles, together with the results of quantum chemical calculations, help elucidate the ZnO growth mechanism and its dependence on the properties of the MoS 2 substrate. The defect density and grain size of MoS 2 nanosheets are controlled by the sulfurization temperature of ALD MoO 3 , and the ZnO NCs in turn nucleate selectively at defect sites on MoS 2 surface and enlarge with increasing ALD cycle numbers. At higher ALD cycle numbers, the coalescence of ZnO NCs contributes to an increase in areal coverage and NC size. Furthermore, the geometry of the hybrid structures can be tuned by changing the dimensionality of the MoS 2 , by employing vertical NWs of MoS 2 as the substrate for ALD ZnO NCs, which in turn leads to improvement of the relevant surface-to-volume ratio. Such materials are expected to find use in newly expanded applications, especially those such as sensors or photo-devices based on a p-n heterojunction which relies on coupling transition metal dichalcogenides (TMDCs) with NCs.

36 MATERIALS SCIENCE↗

DOE OSTI2017

Lithium metal protected by atomic layer deposition metal oxide for high performance anodes

We present that lithium metal is a highly desirable anode material for lithium batteries due to its extremely high theoretical capacity (3860 mA h g -1 ), low potential (-3.04 V versus standard hydrogen electrode), and low density (0.534 g cm -3 ). However, dendrite growth during cycling and low coulombic efficiency, resulting in safety hazards and fast battery fading, are huge barriers to commercialization. Herein, we used atomic layer deposition (ALD) to prepare conformal, ultrathin aluminum oxide coatings on lithium. We investigated the growth mechanism during Al 2 O 3 ALD on lithium by in situ quartz crystal microbalance and found larger growth than expected during the initial cycles. We also discovered that the ALD Al 2 O 3 enhances the wettability of the Li surface towards both carbonate and ether electrolytes, leading to uniform and dense SEI formation and reduced electrolyte consumption during battery operation. Scanning electron microscopy verified that the bare Li surfaces become rough and dendritic after electrochemical cycling, whereas the ALD Al 2 O 3 coated Li surfaces remain smooth and uniform. Analysis of the Li surfaces after cycling using X-ray photoelectron spectroscopy and in situ transmission electron microscopy revealed that the ALD Al 2 O 3 coating remains intact during electrochemical cycling, and that Li ions diffuse through the coating and deposit on the underlying Li. Coin cell testing demonstrated more than two times longer cycling life for the ALD Al 2 O 3 protected Li, and a coulombic efficiency as high as ~98% at a practical current rate of 1 mA cm -2 . More significantly, when the electrolyte volume was reduced from 20 to 5 μL, the stabilizing effect of the ALD coating became even more pronounced and the cycling life was around four times longer. Finally, these results indicate that ALD Al 2 O 3 coatings are a promising strategy to stabilize Li anodes for high performance energy storage devices such as Li–S batteries.

36 MATERIALS SCIENCE↗

DOE OSTI2014

Integrating atomic layer deposition and ultra-high vacuum physical vapor deposition for in situ fabrication of tunnel junctions

Atomic Layer Deposition (ALD) is a promising technique for growing ultrathin, pristine dielectrics on metal substrates, which is essential to many electronic devices. Tunnel junctions are an excellent example which require a leak-free, ultrathin dielectric tunnel barrier of typical thickness around 1 nm between two metal electrodes. A challenge in the development of ultrathin dielectric tunnel barriers using ALD is controlling the nucleation of dielectrics on metals with minimal formation of native oxides at the metal surface for high-quality interfaces between the tunnel barrier and metal electrodes. This poses a critical need for integrating ALD with ultra-high vacuum (UHV) physical vapor deposition. In order to address these challenges, a viscous-flow ALD chamber was designed and interfaced to an UHV magnetron sputtering chamber via a load lock. A sample transportation system was implemented for in situ sample transfer between the ALD, load lock, and sputtering chambers. Using this integrated ALD-UHV sputtering system, superconductor-insulator-superconductor (SIS) Nb-Al/Al{sub 2}O{sub 2}/Nb Josephson tunnel junctions were fabricated with tunnel barriers of thickness varied from sub-nm to ∼1 nm. The suitability of using an Al wetting layer for initiation of the ALD Al{sub 2}O{sub 3} tunnel barrier was investigated with ellipsometry, atomic force microscopy, and electrical transport measurements. With optimized processing conditions, leak-free SIS tunnel junctions were obtained, demonstrating the viability of this integrated ALD-UHV sputtering system for the fabrication of tunnel junctions and devices comprised of metal-dielectric-metal multilayers.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

DOE OSTI2016

Near room-temperature direct encapsulation of organic photovoltaics by plasma-based deposition techniques

Plasma-assisted atomic layer deposition (ALD) is used for the deposition of environmental barriers directly onto organic photovoltaic devices (OPVs) at near room temperature (30 °C). To study the effect of the ALD process on the organic materials forming the device, the precursor diffusion and intermixing at the interface during the growth of different plasma-assisted ALD inorganic barriers (i.e. Al 2 O 3 and TiO 2 ) onto the organic photoactive layer (P3HT:ICBA) was investigated in this paper. Depth profile x-ray photoelectron spectroscopy was used to analyze the composition of the organic/inorganic interface to investigate the infiltration of the plasma-assisted ALD precursors into the photoactive layer as a function of the precursor dimension, the process temperature, and organic layer morphology. The free volume in the photoactive layer accessible to the ALD precursor was characterized by means of ellipsometric porosimetry (EP) and spectroscopic ellipsometry as a function of temperature. The organic layer is shown to exhibit free volume broadening at high temperatures, increasing the infiltration depth of the ALD precursor into the photoactive layer. Furthermore, based on previous investigations, the intrinsic permeation properties of the inorganic layers deposited by plasma-assisted ALD were predicted from the nano-porosity content as measured by EP and found to be in the 10 -6 gm -2 d -1 range. Insight from our studies was used to design and fabricate multilayer barriers synthesized at near-room temperature by plasma-assisted ALD in combination with plasma-enhanced CVD onto organic photovoltaic (OPVs) devices. Finally, encapsulated OPVs displayed shelf-lifetimes up to 1400 h at ambient conditions.

14 SOLAR ENERGY↗

DOE OSTI2015

Atomic layer deposition of ultrathin platinum films on tungsten atomic layer deposition adhesion layers: Application to high surface area substrates

Platinum (Pt) atomic layer deposition (ALD) usually yields Pt nanoparticles during initial film growth. In contrast, deposition of continuous and ultrathin Pt films is needed for many important applications, such as the oxygen reduction reaction in polymer electrolyte membrane (PEM) fuel cells. A continuous and high radius of curvature Pt film is more stable and has a higher area-specific activity than the Pt nanoparticles commonly used in PEM fuel cells. However, the Pt film must be ultrathin and have a large surface area to be cost effective. In this paper, a review of earlier Pt ALD studies on flat substrates is presented that demonstrates that tungsten, with a higher surface energy than platinum, can serve as an adhesion layer to achieve Pt ALD films that are continuous at ultrathin thicknesses of ∼1.5 nm. This work utilized MeCpPtMe{sub 3} and H{sub 2} plasma as the Pt ALD reactants. The deposition of continuous and ultrathin Pt ALD films using MeCpPtMe{sub 3} and H{sub 2} plasma as the reactants is then studied on two high surface area substrate materials: TiO{sub 2} nanoparticles and 3M nanostructured thin film (NSTF). Transmission electron microscopy (TEM) showed uniform and continuous Pt films with thicknesses of ∼4 nm on the TiO{sub 2} nanoparticles. TEM with electron energy loss spectroscopy analysis revealed W ALD and Pt ALD films with thicknesses of ∼3 nm that were continuous and conformal on the high aspect ratio NSTF substrates. These results demonstrate that cost effective use of Pt ALD on high surface area substrates is possible for PEM fuel cells.

36 MATERIALS SCIENCE↗

DOE OSTI2015

Influence of atomic layer deposition valve temperature on ZrN plasma enhanced atomic layer deposition growth

Atomic layer deposition (ALD) relies on a sequence of self-limiting surface reactions for thin film growth. The effect of non-ALD side reactions, from insufficient purging between pulses and from precursor self-decomposition, on film growth is well known. In this article, precursor condensation within an ALD valve is described, and the effect of the continuous precursor source from condensate evaporation on ALD growth is discussed. The influence of the ALD valve temperature on growth and electrical resistivity of ZrN plasma enhanced ALD (PEALD) films is reported. Increasing ALD valve temperature from 75 to 95 °C, with other process parameters being identical, decreased both the growth per cycle and electrical resistivity (ρ) of ZrN PEALD films from 0.10 to 0.07 nm/cycle and from 560 to 350 μΩ cm, respectively. Our results show that the non-ALD growth resulting from condensate accumulation is eliminated at valve temperatures close to the pressure corrected boiling point of precursor.

36 MATERIALS SCIENCE↗

DOE OSTI2016

Plasma enhanced atomic layer deposition of ZnO with diethyl zinc and oxygen plasma: Effect of precursor decomposition

Although atomic layer deposition (ALD) of ZnO using diethyl zinc (DEZ) precursor has been extensively reported, variation in growth-per-cycle (GPC) values and the range of substrate temperature (T{sub sub}) for ALD growth between related studies remain unexplained. For identical processes, GPC for the characteristic self-limiting ALD growth is expected to be comparable. Hence, a significant variation in GPC among published ZnO ALD studies strongly suggests a concealed non-ALD growth component. To investigate this, the authors report plasma-enhanced ALD growth of ZnO using DEZ precursor and O{sub 2} inductively coupled plasma. The effect of T{sub sub} on ZnO GPC was studied with deposition cycles (1) 0.02 s–15 s–6 s–15 s, (2) 0.10 s–15 s–15 s–15 s, and (3) 0.20 s–15 s–30 s–15 s, where the cycle parameters t{sub 1}–t{sub 2}–t{sub 3}–t{sub 4} denote duration of DEZ pulse, post-DEZ purge, plasma exposure, and postplasma purge, respectively. The non-ALD growth characteristics observed at T{sub sub} ≥ 60 °C are discussed and attributed to DEZ precursor decomposition. The authors demonstrate ZnO growth at T{sub sub} = 50 °C to be self-limiting with respect to both t{sub 1} and t{sub 3} giving GPC of 0.101 ± 0.001 nm/cycle. The effect of precursor decomposition related (non-ALD) growth at T{sub sub} ≥ 60 °C is illustrated from comparison of optical dielectric function, electrical resistivity, and surface roughness of ZnO films deposited at T{sub sub} = 50, 125, and 200 °C.

42 ENGINEERING↗