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

Coherent diffractive imaging (CDI) and scanning transmission x-ray microscopy (STXM) are two popular microscopy techniques that have evolved quite independently. CDI promises to reach resolutions below 10 nanometers, but the reconstruction procedures put stringent requirements on data quality and sample preparation. In contrast, STXM features straightforward data analysis, but its resolution is limited by the spot size on the specimen. We demonstrate a ptychographic imaging method that bridges the gap between CDI and STXM by measuring complete diffraction patterns at each point of a STXM scan. The high penetration power of x-rays in combination with the high spatial resolution will allow investigation of a wide range of complex mesoscopic life and material science specimens, such as embedded semiconductor devices or cellular networks.

https://science.sciencemag.org/content/sci/321/5887/379.full.pdf

High-Resolution Scanning X-ray Diffraction Microscopy

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 authors would like to thank M. Chabinyc, H. Ade, B. Collins, R. Noriega, K. Vandewal, and D. Duong for fruitful discussions in the preparation of this review. Stanford Synchrotron Radiation Lightsource (SSRL) is a national user facility operated by Stanford University on behalf of the U.S. Department of Energy, Office of Basic Energy Sciences. This publication was partially supported by the Center for Advanced Molecular Photovoltaics (Award No. KUS-C1-015-21), made by King Abdullah University of Science and Technology (KAUST).

Quantitative determination of organic semiconductor microstructure from the molecular to device scale.

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About these proceedings

A method for the fabrication of ultrahigh-resolution Fresnel zone plate lenses for x-ray microscopy is demonstrated. It is based on the deposition of a zone plate material (Ir) onto the sidewalls of a prepatterned template structure (Si) using an atomic layer deposition technique. This results in a doubling of the effective zone density, thus improving the achievable resolution of x-ray microscopes. Test structures with lines and spaces down to 15 nm were resolved in a scanning transmission x-ray microscope at 1 keV photon energy.

/pdf/zone-doubling-technique-to-produce-ultrahigh-resolution-x-3fmp99s102.pdf

Zone-doubling technique to produce ultrahigh-resolution x-ray optics.

Advanced thin film technology for ultrahigh resolution X-ray microscopy.

Metal fluorides, like CaF2, are interesting dielectric materials which are optically transparent over a wide wavelength range down to the vacuum ultraviolet regime. In addition, CaF2 has a low refractive index and is therefore an attractive material for optical filters. In this study thin films of calcium fluoride were deposited by atomic layer deposition (ALD) at a temperature range of 300−450 °C using TiF4 as a new convenient fluoride precursor. Ca(thd)2 was used as a calcium precursor. Films were analyzed by X-ray diffraction/reflection (XRD/XRR), field emission scanning electron microscopy (FESEM), time-of-flight elastic recoil detection analysis (TOF-ERDA), and UV−vis spectrophotometer. The growth rate of the film was 1.6 A/cycle, which is 4 times higher than that published before for CaF2 ALD. All films were polycrystalline and the impurity levels were low. The refractive index was 1.43 and the permittivity 6.6. This novel ALD process using the new fluoride precursor TiF4 is likely more general and ...

Novel ALD process for depositing CaF2 thin films

Magnesium fluoride is an ultraviolet (UV) transparent material which is widely used in optical applications over a wide wavelength range. We have developed a novel atomic layer deposition (ALD) process for depositing magnesium fluoride thin films for the first time. MgF2 films were grown at 250–400 °C using Mg(thd)2 and TiF4 as precursors. The crystallinity, morphology, composition, thicknesses and refractive indices of the films were analyzed by X-ray diffraction/reflection (XRD/XRR), transmission electron microscopy (TEM), atomic force microscopy (AFM), field emission scanning electron microscopy (FESEM), time-of-flight elastic recoil detection analysis (TOF-ERDA), and UV-vis spectrophotometry. Electrical properties were also measured. The growth rate was temperature dependent decreasing from 1.6 A cycle−1 at 250 °C to 0.7 A cycle−1 at 400 °C. The films were polycrystalline at 250–400 °C. The refractive indices were between 1.34–1.42 and the permittivity 4.9. The impurity levels were below 0.6 at.% in the films deposited at 350–400 °C.

/pdf/study-of-a-novel-ald-process-for-depositing-mgf2-thin-films-1f3m22ks6x.pdf

Tero Pilvi

Papers

Zone-doubling technique to produce ultrahigh-resolution x-ray optics.

Advanced thin film technology for ultrahigh resolution X-ray microscopy.

Novel ALD process for depositing CaF2 thin films

Study of a novel ALD process for depositing MgF2 thin films

Atomic layer deposition of hafnium dioxide thin films from hafnium tetrakis(dimethylamide) and water