Lanthanide-based luminescent hybrid materials.

The surface and materials science of tin oxide

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

A surface science perspective on TiO2 photocatalysis

This Review focuses on recent developments in the use of ZnO nanostructures for dye-sensitized solar cell (DSC) applications. It is shown that carefully designed and fabricated nanostructured ZnO films are advantageous for use as a DSC photoelectrode as they offer larger surface areas than bulk film material, direct electron pathways, or effective light-scattering centers, and, when combined with TiO2, produce a core–shell structure that reduces the combination rate. The limitations of ZnO-based DSCs are also discussed and several possible methods are proposed so as to expand the knowledge of ZnO to TiO2, motivating further improvement in the power-conversion efficiency of DSCs.

https://depts.washington.edu/solgel/documents/pub_docs/journal_docs/2009/advanced_material2009.pdf

ZnO Nanostructures for Dye-Sensitized Solar Cells

Influence of process parameters on atomic layer deposition of ZrO2 thin films from CpZr(NMe2)(3) and H2O

TiO2–Cr2O3 nanolaminates were atomic layer deposited on (0 1 2)-oriented sapphire and (1 0 0)-oriented silicon. The thickness of the alternating layers in the eight-layer laminates grown was close to 10 nm. The laminates were characterized by cross-sectional high-resolution transmission electron microscopy, high-resolution scanning electron microscopy, atomic force microscopy, reflection high-energy electron diffraction, and micro-Raman spectroscopy. A highly oriented growth of the laminate on sapphire and its growth with a very little preferred orientation on silicon were revealed. The laminate grown on sapphire had, along with better crystallinity, more exactly defined and more planar interphase boundaries. The amount of indefiniteness of the boundaries increased with the layer distance from the substrate. The crystalline phase of titania was rutile in the laminate grown on sapphire and anatase in the laminate grown on silicon, while the crystalline phase of chromia had eskolaite structure. In the laminate grown on sapphire, titania contained numerous twins; compressively strained chromia had in this case more perfect structure.

Structural characterization of TiO2–Cr2O3 nanolaminates grown by atomic layer deposition

Graphene that is a single hexagonal layer of carbon atoms with very high intrinsic charge carrier mobility (more than 200 000 cm2/Vs at 4.2 K for suspended samples; Bolotin, et al., 2008) attracts attention as a promising material for future nanoelectronics. During last few years, significant advancement has been made in preparation of large-area graphene. The lateral sizes of substrates for graphene layers have been increased up to 3⁄4 m (Bae et al., 2010) and continuous roll-to-roll deposition of graphene has been published (Hesjedal, 2011). This kind of progress might allow one to apply similar planar technologies for fabricating graphene-based devices in future as currently used for processing of siliconbased structures. After very first experiments (Novoselov et al., 2004), in which the electrical properties of isolated graphene sheets were characterized, a lot of attention has been paid to the similar studies, i.e. investigation of uncovered graphene flakes deposited on oxidized silicon wafers that served as back gates. However, in order to realize graphene-based devices, a highquality dielectric on top of graphene is required for electrostatic gates as well as for tunnel barriers for spin injection. For efficient control of charge carrier movement dielectric layers deposited on graphene should be very thin, a few nanometers thick, and of very uniform thickness without any pinholes. At the same time, the dielectric should possess high dielectric constant, high breakdown voltage and low leakage current even at a small thickness. And, of course, it is expected that the high mobility of charge carriers in graphene should not be markedly affected by the dielectric layer. In order to make top-gated graphene-based Field Effect Transistor (FET), Lemme et al. (2007) applied evaporation techniques for preparation of a gate stack with ~20 nm thick SiO2 dielectric layer on graphene. They used p-type Si(100) wafers with a boron doping concentration of 1015 cm-3, which were oxydized to a SiO2 thickness of 300 nm. On these wafers, micromechanically exfoliated graphene flakes were sticked. The Ti/Au source and drain electrodes were prepared using optical lift-off lithography. Next, electron beam lift-off lithography was applied to define a top gate electrode on top of the graphene flake covered with the dielectric (Fig. 1a). Lemme et al. were first to demonstrate that the combined effect of back and top gates can be applied to graphene devices. However, measurements of the back-gate characteristics before

/pdf/atomic-layer-deposition-of-high-k-oxides-on-graphene-3ummkp60jc.pdf

Atomic Layer Deposition of High-k Oxides on Graphene

Precursor-dependent structural and electrical characteristics of atomic layer deposited films: Case study on titanium oxide

The proper choice of coating materials and methods in core–shell nanowire (NW) engineering is crucial to assuring improved characteristics or even new functionalities of the resulting composite structures. In this paper, we have reported electron-beam-induced reversible elastic-to-plastic transition in Ag/Al2O3 and Au/Al2O3 NWs prepared by the coating of Ag and Au NWs with Al2O3 by low-temperature atomic layer deposition. The observed phenomenon enabled freezing the bent core–shell NW at any arbitrary curvature below the yield strength of the materials and later restoring its initially straight profile by irradiating the NW with electrons. In addition, we demonstrated that the coating efficiently protects the core material from fracture and plastic yield, allowing it to withstand significantly higher deformations and stresses in comparison to uncoated NW.

https://iopscience.iop.org/article/10.1088/1361-6528/aa973c/pdf

Jaan Aarik

Papers

Influence of process parameters on atomic layer deposition of ZrO2 thin films from CpZr(NMe2)(3) and H2O

Structural characterization of TiO2–Cr2O3 nanolaminates grown by atomic layer deposition

Atomic Layer Deposition of High-k Oxides on Graphene

Precursor-dependent structural and electrical characteristics of atomic layer deposited films: Case study on titanium oxide

Enhanced flexibility and electron-beam-controlled shape recovery in alumina-coated Au and Ag core-shell nanowires.