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

During the past decade, enormous progress has been made in growing ultrathin organic films and multilayer structures with a wide range of exciting optoelectronic properties. This progress has been made possible by several important advances in our understanding of organic films and their modes of growth. Perhaps the single most important advance has been the use of ultrahigh vacuum (UHV) as a means to achieve, for the first time, monolayer control over the growth of organic thin films with extremely high chemical purity and structural precision.1-3 Such monolayer control has been possible for many years using well-known techniques such as Langmuir-Blodgett film deposition,4 and more recently, self-assembled monolayers from solution have also been achieved.5 However, ultrahighvacuum growth, sometimes referred to as organic molecular beam deposition (OMBD) or organic molecular beam epitaxy (OMBE), has the advantage of providing both layer thickness control and an atomically clean environment and substrate. When combined with the ability to perform in situ highresolution structural diagnostics of the films as they are being deposited, techniques such as OMBD have provided an entirely new prospect for understanding many of the fundamental structural and optoelectronic properties of ultrathin organic film systems. Since such systems are both of intrinsic as well as practical interest, substantial effort worldwide has been invested in attempting to grow and investigate the properties of such thin-film systems. This paper is a review of recent progress made in organic thin films grown in ultrahigh vacuum or using other vapor-phase deposition methods. We will describe the most important work which has been published in this field since the emergence of OMBD in the mid-1980s. Both the nature of thin-film growth and structural ordering will be discussed, as well as some of the more interesting consequences to the physical properties of such organic thin-film systems will be considered both from a theoretical as well as an experimental viewpoint. Indeed, it will 1793 Chem. Rev. 1997, 97, 1793−1896

Ultrathin Organic Films Grown by Organic Molecular Beam Deposition and Related Techniques.

Chemical vapour deposition of coatings

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

Nanoscale GaN quantum dots were fabricated on AlxGa1−xN layer surfaces via metalorganic chemical vapor deposition. In order to achieve a self‐assembling dot structure, a two‐dimensional growth mode (step flow) of GaN films on AlxGa1−xN (x=0–0.2) surfaces that is energetically commenced under the conventional growth conditions was intentionally modified into a three‐dimensional mode by using a ‘‘surfactant.’’ The surfactant is believed to inhibit the GaN film from wetting the AlGaN surface due to the change in surface free energy. The resulting morphological structures of GaN dots were found to be sensitive to the doping rate of tetraethyl silane used as a surfactant, the Al content (x) of the AlxGa1−xN layer, and the growth temperature. A very intense photoluminescence emission was observed from the GaN dots embedded in the AlGaN layers.

Self‐assembling GaN quantum dots on AlxGa1−xN surfaces using a surfactant

Nanoscale GaN dots were successfully formed on AlxGa1−xN/6H-SiC(0001) surfaces by gas-source molecular beam epitaxy. It was found that the growth mode can be changed by introducing Si before GaN growth, where the Si is believed to play an important role in the change of the AlxGa1−xN surface free energy. Without introducing Si, the GaN growth mode was two dimensional and (1×3) reconstruction was observed. The growth mode of GaN was changed from two-dimensional to three-dimensional by introducing Si on the AlxGa1−xN surface. In situ reflection high-energy electron diffraction and atomic force microscopy observations were used to monitor and characterize the growth processes and surface morphology.

The formation of GaN dots on AlxGa1−xN surfaces using Si in gas-source molecular beam epitaxy

Growth characteristics of a laser metalorganic vapor‐phase epitaxy (laser MOVPE) and the electrical and optical properties of the epitaxial layer grown by the technique are examined. The growth rate under laser MOVPE decreases with increasing substrate temperature in contrast with conventional MOVPE. The growth rate also depends on the type of the substrate, total gas flow rate and the incident laser power. The mechanism of laser MOVPE seems not to be a photothermal effect but a surface photochemical effect. The intensity of the photoluminescence at room temperature for the epitaxial layer grown by the laser MOVPE is found to be stroger than that of the epitaxial layer grown without the laser irradiation under the same growth condition. The carrier concentration is also found to be modified by the laser irradiation. It is emphasized that the laser MOVPE is very useful as a new crystal growth technology.

Characteristics of laser metalorganic vapor‐phase epitaxy in GaAs

Atomic layer epitaxy of AlP and its application to X-ray multilayer mirror

Metalorganic vapor phase epitaxy (MOVPE) of GaAs is analyzed using a new growth model. Surface reactions for trimethylgallium or triethylgallium adsorbed on the substrate surfaces are assumed to be the growth-rate-limiting steps. A catalytic effect is taken into account by assuming different decomposition rates for adsorbed alkyls on Ga- and As-terminated surfaces. The surface reactions are expressed in terms of reaction times and analyzed using a rate equation approach. Parameters in a rate equation are determined by fitting to the experimental results obtained by various methods: conventional MOVPE with and without laser irradiation, pulsed MOVPE, and laser atomic layer epitaxy. Good agreement between experiments and calculations in all growth methods shows the usefulness of the model.

https://iopscience.iop.org/article/10.1143/JJAP.27.795/pdf

Sohachi Iwai

Papers

Self‐assembling GaN quantum dots on AlxGa1−xN surfaces using a surfactant

The formation of GaN dots on AlxGa1−xN surfaces using Si in gas-source molecular beam epitaxy

Characteristics of laser metalorganic vapor‐phase epitaxy in GaAs

Atomic layer epitaxy of AlP and its application to X-ray multilayer mirror

A Growth Analysis for Metalorganic Vapor Phase Epitaxy of GaAs