Atomic layer deposition: an overview.

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) are used widely in today's consumer electronics and offer great potential for hybrid electric vehicles (HEVs), plug-in HEVs, pure EVs, and also in smart grids as future energy-storage devices. However, many challenges must be addressed before these future applications of LIBs are realized, such as the energy and power density of LIBs, their cycle and calendar life, safety characteristics, and costs. Recently, a technique called atomic layer deposition (ALD) attracted great interest as a novel tool and approach for resolving these issues. In this article, recent advances in using ALD for LIB studies are thoroughly reviewed, covering two technical routes: 1) ALD for designing and synthesizing new LIB components, i.e., anodes, cathodes, and solid electrolytes, and; 2) ALD used in modifying electrode properties via surface coating. This review will hopefully stimulate more extensive and insightful studies on using ALD for developing high-performance LIBs.

Emerging applications of atomic layer deposition for lithium-ion battery studies.

Publisher Summary This chapter deals with atomic layer deposition (ALD), which is a chemical gas phase thin film deposition method based on alternate saturative surface reactions. As distinct from the other chemical-vapor-deposition techniques, in ALD the source vapors are pulsed into the reactor alternately—one at a time—separated by purging or evacuation periods. Each precursor exposure step saturates the surface with a monomolecular layer of that precursor. This results in a unique self-limiting film-growth mechanism with a number of advantageous features—such as excellent conformality and uniformity and simple and accurate film-thickness control. As the current interest in ALD is largely centered on non-epitaxial films, the chapter focuses on these materials and the related chemistry. ALD is a unique process based on alternate surface reactions, which are accomplished by dosing the gaseous precursors on the substrate alternately. Under ideal conditions, these reactions are saturative, ensuring many advantageous features, such as excellent conformity, large-area uniformity, accurate and simple film-thickness control, repeatability, and large-batch processing capability.

Atomic layer deposition

A 150-200°C atomic layer deposition (ALD) process has been developed for advanced gap and tunnel junction applications for thin films heads. The primary advantage of the ALD process is the near 100% step coverage with properties that are uniform along the sidewall. This process provides smooth (R a ≃ 2 A), pure (impurities <2 atom %), AlO x films with excellent breakdown strength (9-10 MV/cm). The process uses trimethylaluminum (TMA) as the aluminum source and water as the oxidant. The optimal precursor/oxidant delivery methods for high breakdown strengths were found to be vapor draw for the TMA and a bubbler for the water. For both reagents, a sweep gas is used to reduce the transit time to the wafer. The ALD AlO x films are continuous and exhibit excellent insulating characteristics even down to 5-10 A making them a potential candidate for tunnel barriers for magnetic tunnel junctions. By plasma annealing the films in situ every 25-50 A, the as-deposited tensile stress becomes slightly compressive and the breakdown field exceeds 10 MV/cm. ALD provides a relatively low deposition rate of 0.8 A/cycle. A small chamber volume that allows the cycle time of 5 s is the key to meeting production throughput requirements of 4-6 w h -1 for a 100 A film.

Atomic Layer Deposition of AlO x for Thin Film Head Gap Applications

The use of copper interconnects enables higher speed, enhanced electromigration lifetime reliability, reduced power consumption, and ultimately reduced manufacturing cost for silicon integrated circuits. The formation of planarized inlaid copper interconnects requires sequential deposition of a continuous diffusion barrier layer followed by copper seed/fill deposition and chemical-mechanical polishing (CMP). In this article we present a vacuum-integrated cluster tool technology for deposition of a TaN barrier and copper seed/fill layers using metalorganic chemical vapor deposition (MOCVD). The MOCVD-based TaN layers deposited at substrate temperatures below 430 °C are highly conformal, have 800–1000 μΩ cm resistivity, have satisfactory adhesion to silicon dioxide, and provide superior diffusion barrier properties compared to Ta and TaN layers deposited by physical vapor deposition. The cluster MOCVD-Cu process is capable of depositing conformal and low-resistivity copper seed layers with satisfactory adhe...

Ultralarge scale integrated metallization and interconnects

A Universal Thermal Module™ (UTM™) has been developed for vacuum-integrated cluster RTP and MOCVD as well as stand-alone atmospheric RTP applications. The UTM™ architecture provides highly modular RTP and MOCVD tool configurations for various single-wafer thermal processes. The UTM™ design comprises a temperature-controlled UHV-grade process chamber as well as an ultraclean gearless wafer rotation assembly for improved temperature uniformity and enhanced built-in reliability. The UTM™ RTP employs bottom/backside wafer heating using a multi-zone axisymmetric illuminator and a reflective multi-zone gas showerhead located above the wafer. Precision RTP control is achieved using a multi-zone controller in conjunction with a multipoint sensor system with real-time multi-zone compensations for wafer emissivity and illuminator light interference effects. The RTP temperature measurement and control techniques fully compensate for any axisymmetric or non-axisymmetric wafer emissivity patterns, eliminating the need for pre-RTP wafer backside conditioning. The UTM™ showerhead provides capabilities for ultraclean multi-zone gas injection and in-situ RF plasma for MOCVD and RTCVD processes. The UTM™ MOCVD module meets the most stringent specifications and tool parameters for various metallization and high-K dielectric deposition applications. This module has been used for deposition of low-resistivity copper films with excellent void-free sub-half-micron gap fill for high-performance multilevel interconnects. The UTM™ RTP and MOCVD modules have been implemented based on design optimizations in a virtual reactor environment.

A Universal Thermal Module™ for Clusterable RTP and MOCVD Applications

The insertion of single-wafer thermal and CVD technologies into the front- and back-end of the line processing starts with study of the integrated circuits manufacturing and device performance requirements. Relying upon the lessons learned and using the concurrent engineering approach, next generation processing equipment design architecture is then defined. In order to meet the process performance, throughput, and cost of ownership requirements of semiconductor IC manufacturing as defined in the SIA road map, heavy emphasis must be put on sensor fusion and model-based process control. In the existing semiconductor IC manufacturing equipment, process control is usually accomplished by control of equipment settings, qualification wafer runs and ex-situ measurements of the various wafer properties, as well as design architecture for stable equipment performance. The conventional approach, however, suffers from slow drifts of various equipment state parameters such as infrared absorbing quartz media causing thermal memory effects, or deposition of films on the reactor walls causing variation in the optical characteristics of the reactor as well as chemical and particle memory effects. Using model-based real-time control in conjunction with implementation of various in-situ and ex-situ sensors, these effects can be well monitored and controlled. This paper is to discuss various production related issues with single-wafer thermal and CVD technologies.

The Insertion of Single-Wafer Integrated Thermal/CVD Technology in Front-End and Back-End of the Line Processing; Lessons Learned

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Papers

Atomic Layer Deposition of AlO x for Thin Film Head Gap Applications

Ultralarge scale integrated metallization and interconnects

A Universal Thermal Module™ for Clusterable RTP and MOCVD Applications

The Insertion of Single-Wafer Integrated Thermal/CVD Technology in Front-End and Back-End of the Line Processing; Lessons Learned