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

The reduction and removal of surface oxides from GaAs substrates by atomic layer deposition (ALD) of Al2O3 and HfO2 are studied using in situ monochromatic x-ray photoelectron spectroscopy. Using the combination of in situ deposition and analysis techniques, the interfacial “self-cleaning” is shown to be oxidation state dependent as well as metal organic precursor dependent. Thermodynamics, charge balance, and oxygen coordination drive the removal of certain species of surface oxides while allowing others to remain. These factors suggest proper selection of surface treatments and ALD precursors can result in selective interfacial bonding arrangements.

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GaAs interfacial self-cleaning by atomic layer deposition

Interface engineering and chemistry of Hf-based high-k dielectrics on III–V substrates

Lacking a suitable gate insulator, practical GaAs metal-oxide-semiconductor field-effect transistors (MOSFETs) have remained all but a dream for more than four decades. The physics and chemistry of III–V compound semiconductor surfaces or interfaces are problems so complex that our understanding is still limited even after enormous research efforts. Most research is focused on surface pretreatments, oxide formation, and dielectric materials; less attention is paid to the III–V substrate itself. The purpose of this article is to show that device physics more related to III–V substrates is as important as surface chemistry for realizing high-performance III–V MOSFETs. The history and present status of III–V MOSFET research are briefly reviewed. A model based on the charge neutrality level is proposed to explain all experimental work he performed on III–V MOSFETs using ex situ atomic-layer-deposited high-k dielectrics. This model can also explain all reported experimental observations on III–V MOSFETs using ...

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Main determinants for III–V metal-oxide-semiconductor field-effect transistors (invited)

The reduction in III–V interfacial oxides by atomic layer deposition of Al2O3 on InGaAs is studied by interrupting the deposition following individual trimethyl aluminum (TMA) and water steps (half cycles) and interrogation of the resultant surface reactions using in situ monochromatic x-ray photoelectron spectroscopy (XPS) TMA is found to reduce the interfacial oxides during the initial exposure Concentrations of Ga oxide on the surface processed at 300 °C are reduced to a concentration on the order of a monolayer, while AsOx species are below the level of detection of XPS

Half-cycle atomic layer deposition reaction studies of Al2O3 on In0.2Ga0.8As (100) surfaces

An interfacial self-cleaning phenomenon was found in the atomic layer deposition of HfO2 on In0.15Ga0.85As∕GaAs substrate using Hf(NCH3C2H5)4, i.e., TEMAH, and H2O as the precursors. The native oxides of InGaAs were all satisfactorily removed from the interface through ligand exchange (substitution) reactions with the TEMAH precursor. It relieves the Fermi-level pinning in the HfO2∕InGaAs heterostructure, as verified by the clear transition from accumulation to depletion in high-frequency capacitance-voltage relations and inversion in quasistatic measurement. A very low leakage current was also found from the metal-oxide-semiconductor capacitors of Au∕Ti∕HfO2∕InGaAs.

T.-D. Lin

Papers

Interfacial self-cleaning in atomic layer deposition of HfO2 gate dielectric on In0.15Ga0.85As