Fujishima and Honda (1972) demonstrated the potential of titanium dioxide (TiO2) semiconductor materials to split water into hydrogen and oxygen in a photo-electrochemical cell. Their work triggered the development of semiconductor photocatalysis for a wide range of environmental and energy applications. One of the most significant scientific and commercial advances to date has been the development of visible light active (VLA) TiO2 photocatalytic materials. In this review, a background on TiO2 structure, properties and electronic properties in photocatalysis is presented. The development of different strategies to modify TiO2 for the utilization of visible light, including non metal and/or metal doping, dye sensitization and coupling semiconductors are discussed. Emphasis is given to the origin of visible light absorption and the reactive oxygen species generated, deduced by physicochemical and photoelectrochemical methods. Various applications of VLA TiO2, in terms of environmental remediation and in particular water treatment, disinfection and air purification, are illustrated. Comprehensive studies on the photocatalytic degradation of contaminants of emerging concern, including endocrine disrupting compounds, pharmaceuticals, pesticides, cyanotoxins and volatile organic compounds, with VLA TiO2 are discussed and compared to conventional UV-activated TiO2 nanomaterials. Recent advances in bacterial disinfection using VLA TiO2 are also reviewed. Issues concerning test protocols for real visible light activity and photocatalytic efficiencies with different light sources have been highlighted.

/pdf/a-review-on-the-visible-light-active-titanium-dioxide-2qg81s4yao.pdf

A review on the visible light active titanium dioxide photocatalysts for environmental applications

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

https://cyberleninka.org/article/n/247805.pdf

A brief review of atomic layer deposition: from fundamentals to applications

Chemical vapor deposition of a thin titanium dioxide (TiO2) film on lightweight native nanocellulose aerogels offers a novel type of functional material that shows photoswitching between water-superabsorbent and water-repellent states. Cellulose nanofibrils (diameters in the range of 5–20 nm) with native crystalline internal structures are topical due to their attractive mechanical properties, and they have become relevant for applications due to the recent progress in the methods of their preparation. Highly porous, nanocellulose aerogels are here first formed by freeze-drying from the corresponding aqueous gels. Well-defined, nearly conformal TiO2 coatings with thicknesses of about 7 nm are prepared by chemical vapor deposition on the aerogel skeleton. Weighing shows that such TiO2-coated aerogel specimens essentially do not absorb water upon immersion, which is also evidenced by a high contact angle for water of 140° on the surface. Upon UV illumination, they absorb water 16 times their own weight and show a vanishing contact angle on the surface, allowing them to be denoted as superabsorbents. Recovery of the original absorption and wetting properties occurs upon storage in the dark. That the cellulose nanofibrils spontaneously aggregate into porous sheets of different length scales during freeze-drying is relevant: in the water-repellent state they may stabilize air pockets, as evidenced by a high contact angle, in the superabsorbent state they facilitate rapid water-spreading into the aerogel cavities by capillary effects. The TiO2-coated nanocellulose aerogels also show photo-oxidative decomposition, i.e., photocatalytic activity, which, in combination with the porous structure, is interesting for applications such as water purification. It is expected that the present dynamic, externally controlled, organic/inorganic aerogels will open technically relevant approaches for various applications.

Photoswitchable Superabsorbency Based on Nanocellulose Aerogels

Titanium dioxide thin films were grown by atomic layer deposition (ALD) at 200–400 °C from a new titanium precursor, titanium tetramethoxide, and water. As compared with other titanium alkoxides studied earlier, titanium methoxide shows the highest stability with respect to thermal decomposition, and can thus be used over the widest range of temperatures. The films deposited at 250 °C and above were polycrystalline with the anatase structure, whereas those deposited at 200 °C were amorphous. Except for the film deposited at 200 °C, the films contained only minor amounts of carbon and hydrogen residues. The crystalline films were shown to have photocatalytic activity in decomposing both methylene blue in aqueous solution, and solid stearic acid coated on the film surface.

Atomic Layer Deposition of Photocatalytic TiO2 Thin Films from Titanium Tetramethoxide and Water

Methods and precursors for depositing silicon nitride films by atomic layer deposition (ALD) are provided. In some embodiments the silicon precursors comprise an iodine ligand. The silicon nitride films may have a relatively uniform etch rate for both vertical and the horizontal portions when deposited onto three-dimensional structures such as FinFETS or other types of multiple gate FETs. In some embodiments, various silicon nitride films of the present disclosure have an etch rate of less than half the thermal oxide removal rate with diluted HF (0.5%).

Si PRECURSORS FOR DEPOSITION OF SiN AT LOW TEMPERATURES

In one aspect, methods of silicidation and germanidation are provided. In some embodiments, methods for forming metal silicide can include forming a non-oxide interface, such as germanium or solid antimony, over exposed silicon regions of a substrate. Metal oxide is formed over the interface layer. Annealing and reducing causes metal from the metal oxide to react with the underlying silicon and form metal silicide. Additionally, metal germanide can be formed by reduction of metal oxide over germanium, whether or not any underlying silicon is also silicided. In other embodiments, nickel is deposited directly and an interface layer is not used. In another aspect, methods of depositing nickel thin films by vapor phase deposition processes are provided. In some embodiments, nickel thin films are deposited by ALD.

Metal silicide, metal germanide, methods for making the same

TiO2 replicas of filter paper with nanometer-level accuracy were prepared by atomic layer deposition of thin conformal TiO2 coating, followed by a removal of the paper by air-anneal at 450 °C. Photocatalytic anatase TiO2/cellulose composites were also made by leaving the paper intact. The TiO2 films were deposited from Ti(OMe)4 and H2O at 150−250 °C. The photocatalytic activity of the TiO2/cellulose composite was verified by photocatalytic reduction of Ag(I) from an aqueous solution to Ag nanoparticles on the TiO2 surface. The TiO2/cellulose composites are mechanically more stable than the free-standing TiO2 replicas and are therefore potentially suitable as lightweight, high surface area photocatalysts.

Viljami Pore

Papers

Photoswitchable Superabsorbency Based on Nanocellulose Aerogels

Atomic Layer Deposition of Photocatalytic TiO2 Thin Films from Titanium Tetramethoxide and Water

Si PRECURSORS FOR DEPOSITION OF SiN AT LOW TEMPERATURES

Metal silicide, metal germanide, methods for making the same

Atomic layer deposition in nanometer-level replication of cellulosic substances and preparation of photocatalytic TiO2/cellulose composites.