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

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

Damascene copper electroplating for on-chip interconnections, a process that we conceived and developed in the early 1990s, makes it possible to fill submicron trenches and vias with copper without creating a void or a seam and has thus proven superior to other technologies of copper deposition. We discuss here the relationship of additives in the plating bath to superfilling, the phenomenon that results in superconformal coverage, and we present a numerical model which accounts for the experimentally observed profile evolution of the plated metal.

Damascene copper electroplating for chip interconnections

▪ Abstract Polycrystalline films have wide variety of applications in which their grain structures affect their performance and reliability. Thin film growth techniques and growth conditions affect grain shapes, the distribution of grain sizes, and the distribution of the crystallographic orientations of grains. Variations in these structural properties are affected by the conditions under which grain nucleation, growth, coarsening, coalescence, and thickening occur. General trends in structural evolution in polycystalline films, as a function of processing conditions and materials class, are discussed in terms of these fundamental kinetic processes.

Structure Evolution During Processing of Polycrystalline Films

We present a model which accounts for the dramatic evolution in the microstructure of electroplated copper thin films near room temperature. Microstructure evolution occurs during a transient period of hours following deposition, and includes an increase in grain size, changes in preferred crystallographic texture, and decreases in resistivity, hardness, and compressive stress. The model is based on grain boundary energy in the fine-grained as-deposited films providing the underlying energy density which drives abnormal grain growth. As the grain size increases from the as-deposited value of 0.05–0.1 μm up to several microns, the model predicts a decreasing grain boundary contribution to electron scattering which allows the resistivity to decrease by tens of a percent to near-bulk values, as is observed. Concurrently, as the volume of the dilute grain boundary regions decreases, the stress is shown to change in the tensile direction by tens of a mega pascal, consistent with the measured values. The small ...

Mechanisms for microstructure evolution in electroplated copper thin films near room temperature

Metal-gate FinFET and FDSOI devices were fabricated using total gate silicidation. Devices satisfy the following metal-gate technology requirements: ideal mobility, low gate leakage, high transconductance, competitive I/sub on//I/sub off/, and adjustable V/sub t/. Six silicide gate materials are presented, as well as two silicide workfunction engineering methods.

Metal-gate FinFET and fully-depleted SOI devices using total gate silicidation

We report that the ion implantation of a small dose of Mo into a silicon substrate before the deposition of a thin film of Ti lowers the temperature required to form the commercially important low resistivity C54–TiSi2 phase by 100–150 °C. A lesser improvement is obtained with W implantation. In addition, a sharp reduction in the dependence of C54 formation on the geometrical size of the silicided structure is observed. The enhancement in C54 formation observed with the ion implantation of Mo is not explained by ion mixing of the Ti/Si interface or implant‐induced damage. Rather, it is attributed to an enhanced nucleation of C54–TiSi2 out of the precursor high resistance C49–TiSi2 phase.

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Reduction of the C54–TiSi2 phase transformation temperature using refractory metal ion implantation

Ta thin films were grown on Si(001) and polycrystalline Si substrates by plasma-enhanced atomic-layer deposition (PE-ALD) using TaCl5 and atomic hydrogen as precursors. The grown films have resistivity of 150–180 μm cm with a small Cl concentration between 0.5 and 2 at. %. The diffusion barrier properties were investigated using bilayer structures consisting of 200 nm Cu deposited by sputtering on ALD Ta films with various thicknesses. Three in situ analysis techniques consisting of x-ray diffraction, elastic light scattering, and resistance analysis were used to determine the diffusion barrier failure temperature of Ta films. The barriers were annealed at a temperature ramp rate of 3 °C/s from 100 to 1000 °C in forming gas. For this method using x-ray diffraction, the barrier failure temperatures were determined by monitoring the disappearance of the Cu(111) x-ray diffraction peak and appearance of Cu silicide diffraction peaks. At the diffusion barrier failure temperature, elastic light scattering indic...

Diffusion barrier properties of transition metal thin films grown by plasma-enhanced atomic-layer deposition

To address the future use of alloying elements for Cu interconnect applications in integrated circuits, first, available bulk experimental data such as residual resistivity per at. % solute and binary phase diagrams are used to arrive at a set of 24 potential elements. Next, experimental results in thin films and lines allow the authors to arrive at a smaller set that includes ten elements, namely, Pd, Au, Al, Ag, Nb, Cr, B, Ti, In, and Mn, with higher priority and six, namely, Zn, V, C, Mg, P, and Sn with lower priority for further studies. These additional studies are needed before a strong case for or against alloying additions to Cu can be made. The available thin film and line data are summarized in a series of tables that should prove useful for the readers. In particular, the thin film data allow the authors to obtain an effective average residual resistivity (EARR) per at. % solute that combines the effects of impurity scattering, second phase precipitates, and grain size refinement resulting from...

C. Cabral

Papers

Mechanisms for microstructure evolution in electroplated copper thin films near room temperature

Metal-gate FinFET and fully-depleted SOI devices using total gate silicidation

Reduction of the C54–TiSi2 phase transformation temperature using refractory metal ion implantation

Diffusion barrier properties of transition metal thin films grown by plasma-enhanced atomic-layer deposition

On the use of alloying elements for Cu interconnect applications