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

For 50 years the exponential rise in the power of electronics has been fuelled by an increase in the density of silicon complementary metal-oxide-semiconductor (CMOS) transistors and improvements to their logic performance. But silicon transistor scaling is now reaching its limits, threatening to end the microelectronics revolution. Attention is turning to a family of materials that is well placed to address this problem: group III-V compound semiconductors. The outstanding electron transport properties of these materials might be central to the development of the first nanometre-scale logic transistors.

Nanometre-scale electronics with III–V compound semiconductors

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

III-V semiconductors have high mobility and will be used in field effect transistors with the appropriate gate dielectric. The dielectrics must have band offsets over 1eV to inhibit leakage. The band offsets of various gate dielectrics including HfO2, Al2O3, Gd2O3, Si3N4, and SiO2 on III-V semiconductors such as GaAs, InAs, GaSb, and GaN have been calculated using the method of charge neutrality levels. Generally, the conduction band offsets are found to be over 1eV, so they should inhibit leakage for these dielectrics. On the other hand, SrTiO3 has minimal conduction band offset. The valence band offsets are also reasonably large, except for Si nitride on GaN and Sc2O3 on GaN which are 0.6–0.8eV. There is reasonable agreement with experiment where it exists, although the GaAs:SrTiO3 case is even worse in experiment.

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Band offsets of high K gate oxides on III-V semiconductors

We report on a GaN metal-oxide-semiconductor high-electron-mobility-transistor (MOS-HEMT) using atomic-layer-deposited (ALD) Al2O3 as the gate dielectric. Compared to a conventional GaN high-electron-mobility-transistor (HEMT) of similar design, the MOS-HEMT exhibits several orders of magnitude lower gate leakage and several times higher breakdown voltage and channel current. This implies that the ALD Al2O3∕AlGaN interface is of high quality and the ALD Al2O3∕AlGaN∕GaN MOS-HEMT is of high potential for high-power rf applications. In addition, the high-quality ALD Al2O3 gate dielectric allows the effective two-dimensional (2D) electron mobility at the AlGaN∕GaN heterojunction to be measured under a high transverse field. The resulting effective 2D electron mobility is much higher than that typical of Si, GaAs or InGaAs metal-oxide-semiconductor field-effect-transistors (MOSFETs).

GaN metal-oxide-semiconductor high-electron-mobility-transistor with atomic layer deposited Al2O3 as gate dielectric

A GaAs metal–oxide–semiconductor field-effect transistor (MOSFET) with thin Al2O3 gate dielectric in nanometer (nm) range grown by atomic layer deposition is demonstrated. The nm-thin oxide layer with significant gate leakage current suppression is one of the key factors in downsizing field-effect transistors. A 1 μm gate-length depletion-mode n-channel GaAs MOSFET with an Al2O3 gate oxide thickness of 8 nm, an equivalent SiO2 thickness of ∼3 nm, shows a broad maximum transconductance of 120 mS/mm and a drain current of more than 400 mA/mm. The device shows a good linearity, low gate leakage current, and negligible hysteresis in drain current in a wide range of bias voltage.

GaAs metal–oxide–semiconductor field-effect transistor with nanometer-thin dielectric grown by atomic layer deposition

For the first time, a III-V compound semiconductor MOSFET with the gate dielectric grown by atomic layer deposition (ALD) is demonstrated. The novel application of the ALD process on III-V compound semiconductors affords tremendous functionality and opportunity by enabling the formation of high-quality gate oxides and passivation layers on III-V compound semiconductor devices. A 0.65-/spl mu/m gate-length depletion-mode n-channel GaAs MOSFET with an Al/sub 2/O/sub 3/ gate oxide thickness of 160 /spl Aring/ shows a gate leakage current density less than 10/sup -4/ A/cm/sup 2/ and a maximum transconductance of 130 mS/mm, with negligible drain current drift and hysteresis. A short-circuit current-gain cut-off frequency f/sub T/ of 14.0 GHz and a maximum oscillation frequency f/sub max/ of 25.2 GHz have been achieved from a 0.65-/spl mu/m gate-length device.

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GaAs MOSFET with oxide gate dielectric grown by atomic layer deposition

Recently, significant progress has been made on GaAs metal-oxide-semiconductor field-effect transistors (MOSFETs) using atomic-layer deposition (ALD)-grown Al2O3 as gate dielectric. We show here that further improvement can be achieved by inserting a thin In0.2Ga0.8As layer as part of the channel between Al2O3 and GaAs channel. A 1-μm-gate-length, depletion-mode, n-channel In0.2Ga0.8As/GaAs MOSFET with an Al2O3 gate oxide of 160 A shows a gate leakage current density less than 10−4 A/cm2, a maximum transconductance ∼105 mS/mm, and a strong accumulation current at Vgs>0 in addition to buried-channel conduction. Together with longer gate-length devices, we deduce electron accumulation surface mobility for In0.2Ga0.8As as high as 660 cm2/V s at Al2O3/In0.2Ga0.8As interface.

Depletion-mode InGaAs metal-oxide-semiconductor field-effect transistor with oxide gate dielectric grown by atomic-layer deposition

Oxide surface passivation grown by atomic layer deposition (ALD) has been applied to GaAs metal–semiconductor field-effect transistors (MESFETs). The breakdown characteristic of a MESFET is greatly improved by both Al2O3 and HfO2 passivation. Three-terminal transistor breakdown voltage is improved to a maximum level of 20 V with Al2O3 passivation from 11 V without any surface passivation. With the removal of native oxide and passivation on GaAs surface at drain–gate (D–G) and source–gate (S–G) spacings, the device breakdown characteristics are significantly improved. � 2005 Elsevier Ltd. All rights reserved.

Improvement of GaAs metal–semiconductor field-effect transistor drain–source breakdown voltage by oxide surface passivation grown by atomic layer deposition

J. Bude

Papers

GaN metal-oxide-semiconductor high-electron-mobility-transistor with atomic layer deposited Al2O3 as gate dielectric

GaAs metal–oxide–semiconductor field-effect transistor with nanometer-thin dielectric grown by atomic layer deposition

GaAs MOSFET with oxide gate dielectric grown by atomic layer deposition

Depletion-mode InGaAs metal-oxide-semiconductor field-effect transistor with oxide gate dielectric grown by atomic-layer deposition

Improvement of GaAs metal–semiconductor field-effect transistor drain–source breakdown voltage by oxide surface passivation grown by atomic layer deposition