Atomic layer deposition: an overview.

Solid-state electrolytes are attracting increasing interest for electrochemical energy storage technologies. In this Review, we provide a background overview and discuss the state of the art, ion-transport mechanisms and fundamental properties of solid-state electrolyte materials of interest for energy storage applications. We focus on recent advances in various classes of battery chemistries and systems that are enabled by solid electrolytes, including all-solid-state lithium-ion batteries and emerging solid-electrolyte lithium batteries that feature cathodes with liquid or gaseous active materials (for example, lithium–air, lithium–sulfur and lithium–bromine systems). A low-cost, safe, aqueous electrochemical energy storage concept with a ‘mediator-ion’ solid electrolyte is also discussed. Advanced battery systems based on solid electrolytes would revitalize the rechargeable battery field because of their safety, excellent stability, long cycle lives and low cost. However, great effort will be needed to implement solid-electrolyte batteries as viable energy storage systems. In this context, we discuss the main issues that must be addressed, such as achieving acceptable ionic conductivity, electrochemical stability and mechanical properties of the solid electrolytes, as well as a compatible electrolyte/electrode interface. This Review details recent advances in battery chemistries and systems enabled by solid electrolytes, including all-solid-state lithium-ion, lithium–air, lithium–sulfur and lithium–bromine batteries, as well as an aqueous battery concept with a mediator-ion solid electrolyte.

Lithium battery chemistries enabled by solid-state electrolytes

Atomic layer deposition(ALD), a chemical vapor deposition technique based on sequential self-terminating gas–solid reactions, has for about four decades been applied for manufacturing conformal inorganic material layers with thickness down to the nanometer range. Despite the numerous successful applications of material growth by ALD, many physicochemical processes that control ALD growth are not yet sufficiently understood. To increase understanding of ALD processes, overviews are needed not only of the existing ALD processes and their applications, but also of the knowledge of the surface chemistry of specific ALD processes. This work aims to start the overviews on specific ALD processes by reviewing the experimental information available on the surface chemistry of the trimethylaluminum/water process. This process is generally known as a rather ideal ALD process, and plenty of information is available on its surface chemistry. This in-depth summary of the surface chemistry of one representative ALD process aims also to provide a view on the current status of understanding the surface chemistry of ALD, in general. The review starts by describing the basic characteristics of ALD, discussing the history of ALD—including the question who made the first ALD experiments—and giving an overview of the two-reactant ALD processes investigated to date. Second, the basic concepts related to the surface chemistry of ALD are described from a generic viewpoint applicable to all ALD processes based on compound reactants. This description includes physicochemical requirements for self-terminating reactions,reaction kinetics, typical chemisorption mechanisms, factors causing saturation, reasons for growth of less than a monolayer per cycle, effect of the temperature and number of cycles on the growth per cycle (GPC), and the growth mode. A comparison is made of three models available for estimating the sterically allowed value of GPC in ALD. Third, the experimental information on the surface chemistry in the trimethylaluminum/water ALD process are reviewed using the concepts developed in the second part of this review. The results are reviewed critically, with an aim to combine the information obtained in different types of investigations, such as growth experiments on flat substrates and reaction chemistry investigation on high-surface-area materials. Although the surface chemistry of the trimethylaluminum/water ALD process is rather well understood, systematic investigations of the reaction kinetics and the growth mode on different substrates are still missing. The last part of the review is devoted to discussing issues which may hamper surface chemistry investigations of ALD, such as problematic historical assumptions, nonstandard terminology, and the effect of experimental conditions on the surface chemistry of ALD. I hope that this review can help the newcomer get acquainted with the exciting and challenging field of surface chemistry of ALD and can serve as a useful guide for the specialist towards the fifth decade of ALD research.

Surface chemistry of atomic layer deposition: A case study for the trimethylaluminum/water process

Atomic layer deposition (ALD) is gaining attention as a thin film deposition method, uniquely suitable for depositing uniform and conformal films on complex three-dimensional topographies. The deposition of a film of a given material by ALD relies on the successive, separated, and self-terminating gas–solid reactions of typically two gaseous reactants. Hundreds of ALD chemistries have been found for depositing a variety of materials during the past decades, mostly for inorganic materials but lately also for organic and inorganic–organic hybrid compounds. One factor that often dictates the properties of ALD films in actual applications is the crystallinity of the grown film: Is the material amorphous or, if it is crystalline, which phase(s) is (are) present. In this thematic review, we first describe the basics of ALD, summarize the two-reactant ALD processes to grow inorganic materials developed to-date, updating the information of an earlier review on ALD [R. L. Puurunen, J. Appl. Phys. 97, 121301 (2005)], and give an overview of the status of processing ternary compounds by ALD. We then proceed to analyze the published experimental data for information on the crystallinity and phase of inorganic materials deposited by ALD from different reactants at different temperatures. The data are collected for films in their as-deposited state and tabulated for easy reference. Case studies are presented to illustrate the effect of different process parameters on crystallinity for representative materials: aluminium oxide, zirconium oxide, zinc oxide, titanium nitride, zinc zulfide, and ruthenium. Finally, we discuss the general trends in the development of film crystallinity as function of ALD process parameters. The authors hope that this review will help newcomers to ALD to familiarize themselves with the complex world of crystalline ALD films and, at the same time, serve for the expert as a handbook-type reference source on ALD processes and film crystallinity.

Crystallinity of inorganic films grown by atomic layer deposition: Overview and general trends

Lithium-ion batteries (LIBs) continue to draw vast attention as a promising energy storage technology due to their high energy density, low self-discharge property, nearly zero-memory effect, high open circuit voltage, and long lifespan. In particular, high-energy density lithium-ion batteries are considered as the ideal power source for electric vehicles (EVs) and hybrid electric vehicles (HEVs) in the automotive industry, in recent years. This review discusses key aspects of the present and the future battery technologies on the basis of the working electrode. We then discuss how lithium-ion batteries evolve to meet the growing demand on high charge capacity and electrode stability. An account of a stand-alone energy device (off-grid system) that combines an energy harvesting technology with a lithium-ion battery is also provided. The main discussion is categorized into three perspectives such as the evolution from the conventional to the advanced LIBs (e.g., Li-rich transition metal oxide and Ni-rich transition metal oxide batteries), to the state-of-the-art LIBs (e.g., Li–air, Li–sulfur batteries, organic electrode batteries, solid-state batteries, and Li–CO2 batteries), and to the hybridized LIBs (e.g., metal halide perovskite batteries).

Lithium-ion batteries: outlook on present, future, and hybridized technologies

Platinum thin films were grown at 300 °C by atomic layer deposition (ALD) using (methylcyclopentadienyl)trimethylplatinum (MeCpPtMe3) and oxygen as precursors. The films had excellent uniformity, low resistivity, and low-impurity contents. Structural studies by X-ray diffraction showed that the films were strongly (111) oriented. Growth rates of 0.45 A cycle-1 were obtained with 4 s total cycle times. The film thickness was found to linearly depend on the number of the reaction cycles. Also, the possible reaction mechanism is discussed.

Atomic Layer Deposition of Platinum Thin Films

Thin films of metallic ruthenium were grown by atomic layer deposition (ALD) in the temperature range 275–400 °C using bis(cyclopentadienyl)ruthenium (RuCp2) and oxygen as precursors. The ruthenium films were grown on thin Al2O3 and TiO2 films on glass. X-ray diffraction (XRD) analysis indicated that the films were polycrystalline metallic ruthenium and scanning electron microscopy (SEM) studies showed that the films had excellent conformality. The impurity content of the films, as measured by time-of-flight elastic recoil detection analysis (TOF-ERDA), were very low. All the films had resistivities below 20 μΩ cm.

Ruthenium Thin Films Grown by Atomic Layer Deposition

Reaction mechanisms in atomic layer deposition (ALD) of ruthenium from bis(cyclopentadienyl)ruthenium (RuCp 2 ) and oxygen were studied in situ with a quadruple mass spectrometer (QMS) and a quartz crystal microbalance (QCM). In addition, QMS was used to study ALD of platinum from (methylcyclopentadienyl)trimethylplatinum (MeCpPtMe 3 ) and oxygen. The QMS studies showed that the reaction by-products H 2 O and CO 2 were released during both the oxygen and the metal precursor pulses. Adsorbed oxygen layer on the metal surface thus oxidizes part of the ligands during the metal precursor pulse. The remaining ligand species become oxidized and a new layer of adsorbed oxygen forms on the surface during the following oxygen pulse. The QCM analysis of the ruthenium process showed a mass decrease during the RuCp 2 pulse and a mass increase during the oxygen pulse, which further supports the proposed mechanism.

https://iopscience.iop.org/article/10.1149/1.1595312/pdf

Reaction Mechanism Studies on Atomic Layer Deposition of Ruthenium and Platinum

The invention relates generally to processes for producing electrically conductive noble metal thin films on a substrate by atomic layer deposition. According to one embodiment of the invention a substrate with a surface is provided in a reaction chamber and a vaporised precursor of a noble metal is pulsed into the reaction chamber. By contacting the vaporised precursor with the surface of the substrate, no more than about a molecular layer of the metal precursor is formed on the substrate. In a next step, a pulse of molecular oxygen-containing gas is provided in the reaction chamber, where the oxygen reacts with the precursor on the substrate. Thus, high-quality metal thin films can be deposited by utilising reactions between the metal precursor and oxygen. In one embodiment, electrically conductive layers are deposited in structures that have high aspect ratio vias and trenches, local high elevation areas or other similar surface structures that make the surface rough.

Process for producing metal thin films by ALD

The low limit of the deposition temperature for atomic layer deposition (ALD) of noble metals has been studied. Two approaches were taken; using pure oxygen instead of air and using a noble metal starting surface instead of Al2O3. Platinum thin films were obtained by ALD from MeCpPtMe3 and pure oxygen at deposition temperature as low as 200 °C, which is significantly lower than the low-temperature limit of 300 °C previously reported for the platinum ALD process in which air was use da s the oxygen source. The platinum films grown in this study had smooth surfaces, adhered well to the substrate, and had low impurity contents. ALD of ruthenium, on the other hand, took place at lower deposition temperatures on an iridium seed layer than on an Al2O3 layer. On iridium surface, ruthenium films were obtained from RuCp2 and oxygen at 225 °C and from Ru(thd)3 and oxygen at 250 °C, whereas no films were obtained on Al2O3 at temperatures lower than 275 and 325 °C, respectively. The crystal orientation of the ruthenium films was found to depend on the precursor. ALD of palladium from a palladium -ketoiminate precursor and oxygen at 250 and 275 °C was also studied. However, the film-growth rate did not saturate to a constant level when the precursor pulse times were increased.

Titta Aaltonen

Papers

Atomic Layer Deposition of Platinum Thin Films

Ruthenium Thin Films Grown by Atomic Layer Deposition

Reaction Mechanism Studies on Atomic Layer Deposition of Ruthenium and Platinum

Process for producing metal thin films by ALD

Atomic layer deposition of noble metals: Exploration of the low limit of the deposition temperature