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

The present invention provides for sequential chemical vapor deposition by employing a reactor operated at low pressure, a pump to remove excess reactants, and a line to introduce gas into the reactor through a valve. A first reactant forms a monolayer on the part to be coated, while the second reactant passes through a radical generator which partially decomposes or activates the second reactant into a gaseous radical before it impinges on the monolayer. This second reactant does not necessarily form a monolayer but is available to react with the monolayer. A pump removes the excess second reactant and reaction products completing the process cycle. The process cycle can be repeated to grow the desired thickness of film.

Sequential chemical vapor deposition

Solution combustion is an exciting phenomenon, which involves propagation of self-sustained exothermic reactions along an aqueous or sol–gel media. This process allows for the synthesis of a variety of nanoscale materials, including oxides, metals, alloys, and sulfides. This Review focuses on the analysis of new approaches and results in the field of solution combustion synthesis (SCS) obtained during recent years. Thermodynamics and kinetics of reactive solutions used in different chemical routes are considered, and the role of process parameters is discussed, emphasizing the chemical mechanisms that are responsible for rapid self-sustained combustion reactions. The basic principles for controlling the composition, structure, and nanostructure of SCS products, and routes to regulate the size and morphology of the nanoscale materials are also reviewed. Recently developed systems that lead to the formation of novel materials and unique structures (e.g., thin films and two-dimensional crystals) with unusual...

Solution Combustion Synthesis of Nanoscale Materials

The quantum-confined Stark effect in single cadmium selenide (CdSe) nanocrystallite quantum dots was studied. The electric field dependence of the single-dot spectrum is characterized by a highly polarizable excited state (∼10 5 cubic angstroms, compared to typical molecular values of order 10 to 100 cubic angstroms), in the presence of randomly oriented local electric fields that change over time. These local fields result in spontaneous spectral diffusion and contribute to ensemble inhomogeneous broadening. Stark shifts of the lowest excited state more than two orders of magnitude larger than the linewidth were observed, suggesting the potential use of these dots in electro-optic modulation devices.

Quantum Confined Stark Effect in Single CdSe Nanocrystallite Quantum Dots

Emission color variation of M2SiO4:Eu2+ (M=Ba, Sr, Ca) phosphors for light-emitting diode

The origin of emission color of reduced and oxidized ZnGa2O4 phosphors

Emission color tuning from blue to green through cross-relaxation in heavily Tb3+-doped YAlO3

Optical and electrical properties of ZnGa2O4/Mn2+ powder electroluminescent device

Optical properties of SrBi2Ta2O9 (SBT) ferroelectric thin films were investigated by spectroscopic ellipsometry at room temperature in the 15–55 eV spectral range The films were grown on platinized silicon (Pt/Ti/SiO2/Si) with a Bi/Sr ratio (x) range from 12 to 28 by pulsed-laser deposition The measured pseudodielectric functions of the samples indicate the band-gap energy of SBT shifts to lower energies as x increases The optical constants and band-gap energies of the SBT films were determined through multilayer analyses on their pseudodielectric functions The band-gap energy of SBT is found to shift to lower energies quite linearly with x The band-gap energy at stoichiometric composition (x=2) is estimated to be 41 eV

H. L. Park

Papers

Emission color variation of M2SiO4:Eu2+ (M=Ba, Sr, Ca) phosphors for light-emitting diode

The origin of emission color of reduced and oxidized ZnGa2O4 phosphors

Emission color tuning from blue to green through cross-relaxation in heavily Tb3+-doped YAlO3

Optical and electrical properties of ZnGa2O4/Mn2+ powder electroluminescent device

Spectroscopic ellipsometry study of SrBi2Ta2O9 ferroelectric thin films