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

Quantitative measurement of displacement and strain fields from HREM micrographs

Gallium nitride (GaN) and its allied binaries InN and AIN as well as their ternary compounds have gained an unprecedented attention due to their wide-ranging applications encompassing green, blue, violet, and ultraviolet (UV) emitters and detectors (in photon ranges inaccessible by other semiconductors) and high-power amplifiers. However, even the best of the three binaries, GaN, contains many structural and point defects caused to a large extent by lattice and stacking mismatch with substrates. These defects notably affect the electrical and optical properties of the host material and can seriously degrade the performance and reliability of devices made based on these nitride semiconductors. Even though GaN broke the long-standing paradigm that high density of dislocations precludes acceptable device performance, point defects have taken the center stage as they exacerbate efforts to increase the efficiency of emitters, increase laser operation lifetime, and lead to anomalies in electronic devices. The p...

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Luminescence properties of defects in GaN

This work assesses the Heyd-Scuseria-Ernzerhof (HSE) screened Coulomb hybrid density functional for the prediction of lattice constants and band gaps using a set of 40 simple and binary semiconductors. An extensive analysis of both basis set and relativistic effects is given. Results are compared with established pure density functionals. For lattice constants, HSE outperforms local spin-density approximation (LSDA) with a mean absolute error (MAE) of 0.037 A for HSE vs 0.047 A for LSDA. For this specific test set, all pure functionals tested produce MAEs for band gaps of 1.0–1.3 eV, consistent with the very well-known fact that pure functionals severely underestimate this property. On the other hand, HSE yields a MAE smaller than 0.3 eV. Importantly, HSE correctly predicts semiconducting behavior in systems where pure functionals erroneously predict a metal, such as, for instance, Ge. The short-range nature of the exchange integrals involved in HSE calculations makes their computation notably faster than regular hybrid functionals. The current results, paired with earlier work, suggest that HSE is a fast and accurate alternative to established density functionals, especially for solid state calculations.

Energy band gaps and lattice parameters evaluated with the Heyd-Scuseria-Ernzerhof screened hybrid functional.

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

It is demonstrated by in situ reflection-high-energy-electron-diffraction studies that the growth of hexagonal GaN on AlN occurs either purely in a layer-by-layer mode or in a Stranski-Krastanov mode, depending on the substrate temperature. Nanometric GaN islands embedded in AlN were fabricated by controlling the growth mode. Electron microscopy and atomic-force microscopy revealed that the dimensions of GaN dots could be varied down to values where zero-dimensional quantum effects are expected: the smallest dots were typically 10 nm wide and 2 nm high. These results open the way to the fabrication of quantum dots in materials with optical properties in the uv wavelength range.

Stranski-Krastanov growth mode during the molecular beam epitaxy of highly strained GaN

It is shown that the optical properties of GaN quantum dots with the wurtzite structure result from a balance between confinement and piezoelectric effects. In ``large'' quantum dots with an average height and diameter of 4.1 and 17 nm, respectively, the photoluminescence peak is centered at 2.95 eV, nearly 0.5 eV below the bulk GaN band gap. We attribute this enormous redshift to a giant 5.5 MV/cm piezoelectric field present in the dots, in agreement with theoretical calculations.

Blue-light emission from GaN self-assembled quantum dots due to giant piezoelectric effect

Self-organized GaN islands of nanometric scale were fabricated by controlling the Stranski–Krastanov growth mode of GaN deposited by molecular beam epitaxy on AlN. Evidence for ripening of dots under vacuum has been observed, resulting in changes in dot size distribution. We also show that in superlattice samples, consisting of multiple layers of GaN islands separated by AlN, the GaN islands are vertically correlated provided that the AlN layer thickness remains small enough. The luminescence peak of GaN dots is blueshifted with respect to bulk emission and its intensity does not vary with temperature, both effects demonstrating the strongly zero-dimensional character of these nanostructures.

Growth kinetics and optical properties of self-organized GaN quantum dots

Magneto-optical study of interface mixing in the CdTe-(Cd,Mn)Te system.

Self-assembled InGaN islands were grown by molecular-beam epitaxy on GaN, following a Stranski–Krastanow growth mode. Atomic force microscopy revealed that their dimensions were small enough to expect zero-dimensional quantum effects: the islands were typically 27 nm wide and 2.9 nm high. Strong blue-violet photoluminescence of the dots is observed, persisting up to room temperature. The temperature dependence of the photoluminescence is analyzed and compared to that of InGaN quantum well and bulk samples.

Guy Feuillet

Papers

Stranski-Krastanov growth mode during the molecular beam epitaxy of highly strained GaN

Blue-light emission from GaN self-assembled quantum dots due to giant piezoelectric effect

Growth kinetics and optical properties of self-organized GaN quantum dots

Magneto-optical study of interface mixing in the CdTe-(Cd,Mn)Te system.

Self-assembled InGaN quantum dots grown by molecular-beam epitaxy