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

Spatial atomic layer deposition (ALD) is a new version of ALD based on the separation of reactant gases in space instead of time. In this paper, the authors present results for spatial ALD on flexible substrates using a modular rotating cylinder reactor. The design for this reactor is based on two concentric cylinders. The outer cylinder remains fixed and contains a series of slits. These slits can accept a wide range of modules that attach from the outside. The modules can easily move between the various slit positions and perform precursor dosing, purging, or pumping. The inner cylinder rotates with the flexible substrate and passes underneath the various spatially separated slits in the outer cylinder. Trimethyl aluminum and ozone were used to grow Al2O3 ALD films at 40 °C on metallized polyethylene terephthalate (PET) substrates to characterize this spatial ALD reactor. Spectroscopic ellipsometry measurements revealed a constant Al2O3 ALD growth rate of 1.03 A/cycle with rotation speeds from 40 to 100...

Spatial atomic layer deposition on flexible substrates using a modular rotating cylinder reactor

Time-dependent dielectric breakdown of atomic-layer-deposited Al 2 O 3 films on GaN

Photoluminescence (PL) spectra induced in LaAlO3 by ultraviolet (UV) photons were measured for two types of samples, i.e., single-crystal plates and thin films. The films, which were amorphous when deposited, became polycrystalline after being annealed at 800 °C or higher. When the excitation photon energy exceeded the band-gap energy of LaAlO3, three PL peaks appeared at approximately 1.60 eV in the single crystals and polycrystalline films deposited and annealed on a Si single-crystal substrate. When the films were deposited and annealed on a CaF2 single-crystal substrate, the in-plane lattice parameters became smaller and the energies of the three PL peaks shifted to higher values. This indicates that the three PL peaks are susceptible to a crystal field. Furthermore, the intensities of the three PL peaks did not depend on the measurement temperature. Taking these results together with their spectral shapes into consideration, the three PL peaks are due to the R-line luminescence resulting from Cr3+ impurities in LaAlO3. The detection of Cr3+ ions by inductively coupled plasma optical emission spectrometry failed, indicating that the Cr3+ content of the present samples is below 1 ppm. The fact that the PL peaks appeared in both the single-crystal plates and thin films obtained from different raw chemicals with different processes indicates that there is a strong possibility that the Cr3+ ions are present in Al ore. Another PL peak appearing at 2.8 eV in the single crystals was assumed to originate from oxygen vacancies.

https://iopscience.iop.org/article/10.1143/JJAP.49.091102/pdf

Cr3+ impurities and photoluminescence in LaAlO3

An interpoly dielectric stack consisting of silicon dioxide, aluminum oxide, and silicon dioxide (OAO stack) has been proposed to replace the oxide-nitride-oxide (ONO) stack in flash memory. Atomic layer deposition and annealing conditions of Al2O3 films were studied to achieve low equivalent oxide thickness (EOT) and leakage current. Aluminum oxide films were deposited from alternating pulses of trimethylaluminum and ozone. The within-wafer nonuniformity and wafer-to-wafer thickness repeatability were both typically below 1.0% (1σ). The OAO interpoly dielectric exhibited leakage current density below 0.1μA∕cm2 at an electric field of 5MV∕cm while an 11% reduction in EOT to 12.5nm was achieved as compared with an ONO stack. The OAO stack has higher breakdown field and greater charge to breakdown than the ONO stack.

Equivalent oxide thickness reduction of interpoly dielectric using ALD-Al2O3 for flash device application

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Equivalent oxide thickness reduction of interpoly dielectric using ALD-Al2O3 for flash device application