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

Atomic layer etching (ALE) is a technique for removing thin layers of material using sequential reaction steps that are self-limiting. ALE has been studied in the laboratory for more than 25 years. Today, it is being driven by the semiconductor industry as an alternative to continuous etching and is viewed as an essential counterpart to atomic layer deposition. As we enter the era of atomic-scale dimensions, there is need to unify the ALE field through increased effectiveness of collaboration between academia and industry, and to help enable the transition from lab to fab. With this in mind, this article provides defining criteria for ALE, along with clarification of some of the terminology and assumptions of this field. To increase understanding of the process, the mechanistic understanding is described for the silicon ALE case study, including the advantages of plasma-assisted processing. A historical overview spanning more than 25 years is provided for silicon, as well as ALE studies on oxides, III–V compounds, and other materials. Together, these processes encompass a variety of implementations, all following the same ALE principles. While the focus is on directional etching, isotropic ALE is also included. As part of this review, the authors also address the role of power pulsing as a predecessor to ALE and examine the outlook of ALE in the manufacturing of advanced semiconductor devices.

https://avs.scitation.org/doi/pdf/10.1116/1.4913379

Overview of atomic layer etching in the semiconductor industry

Successful ex situ and in situ cleaning procedures for AlN and GaN surfaces have been investigated and achieved. Exposure to HF and HCl solutions produced the lowest coverages of oxygen on AlN and GaN surfaces, respectively. However, significant amounts of residual F and Cl were detected. These halogens tie up dangling bonds at the nitride surfaces hindering reoxidation. The desorption of F required temperatures >850 °C. Remote H plasma exposure was effective for removing halogens and hydrocarbons from the surfaces of both nitrides at 450 °C, but was not efficient for oxide removal. Annealing GaN in NH3 at 700–800 °C produced atomically clean as well as stoichiometric GaN surfaces.

Cleaning of AlN and GaN surfaces

The emergence of new ultrafast optical modulation techniques has opened the way towards a new femtosecond laser technology based on solid-state gain media. The authors address the requirements for stable ultrashort pulse generation in these novel femtosecond sources. The theoretical considerations are backed up by experimental results obtained with a number of different laser systems. The conclusions drawn from the presented theoretical and experimental investigations provide general guidelines for the design and optimization of a wide range of femtosecond solid-state laser oscillators. >

Femtosecond solid-state lasers

Surface chemical kinetics during the growth of GaAs by chemical beam epitaxy

We report the operation of strained‐layer InAsyP1−y/InP multiple quantum well optical modulators at wavelengths compatible with solid‐state lasers such as neodymium‐doped yttrium aluminum garnet. A structure having 50 periods of 100 A InAsyP1−y quantum wells with 100 A InP barriers is described that has an exciton peak at 1.05 μm and a single pass transmission contrast ratio of 1.4. Favorable comparison is made to similar InxGa1−xAs/GaAs structures.

InAsyP1−y/InP multiple quantum well optical modulators for solid‐state lasers

We compare InP‐based materials systems for multiple quantum well modulator application in the 1.06 μm wavelength range. Quantum well/barrier systems studied are the lattice‐matched system InxGa1−xAsyP1−y/InP, the strained system InAsyP1−y/InP, and the strain‐balanced system InAsyP1−y/InxGa1−xP. 50 period samples were grown on InP substrates by chemical beam epitaxy. We find the ternary systems to be better than the quaternary in terms of exciton peak sharpness. The InAsyP1−y/InxGa1−xP system was best overall, with our results suggesting that it is coherently strained to the InP substrate.

Multiple quantum well light modulators for the 1.06 μm range on InP substrates: InxGa1−xAsyP1−y/InP, InAsyP1−y/InP, and coherently strained InAsyP1−y/InxGa1−xP

Using a strain‐balanced growth approach, we show that the pseudomorphic InAsP/InGaP multiple quantum well structures, grown by chemical beam epitaxy, have superior material properties for 1.06 μm modulator application when compared to the strained InAsP/InP or the lattice‐matched InGaAsP/InP systems. The broadening in absorption edge due to dislocations in the strained system, or composition fluctuations in the lattice‐matched system as a consequence of growth temperature instability, can be greatly minimized. A strong reduction in the nonradiative recombination centers in the strain‐balanced InAsP/InGaP system has been observed.

T. H. Chiu

Papers

Surface chemical kinetics during the growth of GaAs by chemical beam epitaxy

InAsyP1−y/InP multiple quantum well optical modulators for solid‐state lasers

Multiple quantum well light modulators for the 1.06 μm range on InP substrates: InxGa1−xAsyP1−y/InP, InAsyP1−y/InP, and coherently strained InAsyP1−y/InxGa1−xP

Growth of strain‐balanced InAsP/InGaP superlattices for 1.06 μm optical modulators

Characterization of the GaAs:C and AlGaAs:C doping superlattice grown by chemical beam epitaxy