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

Recently, polymer nanocomposites reinforced with lower volume fraction of nanoceramics and carbon nanotubes have attracted steadily growing interest due to their peculiar and fascinating properties as well as their unique applications in commercial sectors. The incorporation of nanoceramics such as layered silicate clays, calcium carbonate or silica nanoparticles arranged on the nanometer scale with a high aspect ratio and/or an extremely large surface area into polymers improves their mechanical performances significantly. The properties of nanocomposites depend greatly on the chemistry of polymer matrices, nature of nanofillers, and the way in which they are prepared. The uniform dispersion of nanofillers in the polymer matrices is a general prerequisite for achieving desired mechanical and physical characteristics. In this review article, current development on the processing, structure, and mechanical properties of polymer nanocomposites reinforced with respective layered silicates, ceramic nanoparticles and carbon nanotubes will be addressed. Particular attention is paid on the structure–property relationship of such novel high-performance polymer nanocomposites.

Structural and mechanical properties of polymer nanocomposites

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

"Bound but not gagged"--immobilizing single-site alpha-olefin polymerization catalysts.

The preparation and rheology characterization of long chain branching polypropylene

Compatibilization of PP/elastomer/microsilica composites with functionalized polyolefins: Effect on microstructure and mechanical properties

Propylene copolymerization with non-conjugated dienes and α-olefins using supported metallocene catalyst

The properties of polypropylene composites can be tailored through the use of nanoclay fillers. The effectiveness of a metallocene-catalyzed hydroxyl-functional polypropylene in the compatibilization of polypropylene layered nanosilicate composites was studied, and the results were compared with those for a commercial maleic anhydride functionalized polypropylene. Polypropylene/organoclay nanocomposites were prepared by melt blending, and two polypropylene/compatibilizer/organoclay ratios, 90/5/5 and 70/20/10, were characterized. The organomodification of the clay was carried out with octadecylamine and N-methylundecenylamine. The structure of the layered silicate was studied by transmission electron microscopy, wide-angle X-ray scattering, and small-angle X-ray scattering. The fracture surfaces of the composites and thus the efficiency of the compatibilizers to penetrate the galleries of the organoclays were characterized by scanning electron microscopy, and the melt viscosity was studied by stress-controlled rotational rheometry. The nanostructure was observed with both alkyl amines used for intercalation. The fillers facilitated the processability of all the composites, consisting of equal amounts of compatibilizer and organoclay filler and, in some of the composites, containing twice as much compatibilizer as organoclay filler.

Polypropylene/organoclay nanocomposites compatibilized with hydroxyl‐functional polypropylenes

Heterogeneous metallocene catalysts were prepared by adsorbing rac -Et(Ind) 2 ZrCl 2 on a modified silica surface in solution. The modification of silica was conducted in gas phase with atomic layer chemical vapor deposition (ALCVD) technique, where the silica, preheated at either 350 or 600°C, was allowed to react with vaporized trimethylaluminum (TMA) at 250°C. Modified carriers and heterogeneous catalysts were characterized with FTIR, 1 H MAS (magic-angle spinning) NMR, 13 C , and 29 Si CP (cross-polarization) MAS NMR spectroscopies and elemental analyses. In the reaction of TMA with silica, a saturated surface was formed consisting of different (O) 4− n Si(CH 3 ) n ( n =1, 2 or 3) and AlCH 3 groups. The ratio of SiMe to AlMe groups was approximately 1.5 in the TMA/SiO 2 carriers. When the metallocene was adsorbed onto the carrier it seemed to react with the surface AlCH 3 groups and possibly ZrCH 3 groups were formed. Heterogeneous catalysts were tested in the polymerization of ethylene and propylene in the presence of methylalumoxane (MAO). And they produced similar polymer as the homogeneous rac -Et(Ind) 2 ZrCl 2 catalyst, but with lower activity. A catalyst with the best activity was achieved from silica that was preheated at 600°C. Moreover, leaching of catalyst was examined whereupon a part of zirconium was observed to desorb from the carrier.

/pdf/heterogenization-of-racemic-ethylenebis-1-indenyl-zirconium-2613bcw8td.pdf

Santeri Paavola

Papers

Compatibilization of PP/elastomer/microsilica composites with functionalized polyolefins: Effect on microstructure and mechanical properties

Propylene copolymerization with non-conjugated dienes and α-olefins using supported metallocene catalyst

Polypropylene/organoclay nanocomposites compatibilized with hydroxyl‐functional polypropylenes

Heterogenization of racemic ethylenebis(1-indenyl)zirconium dichloride on trimethylaluminum vapor modified silica surface

Polymerization of hydroxyl functional polypropylene by metallocene catalysis