Complex Oxynitrides

Li [44] have strongly indicated that these materials will prove promising as light-emitting diode (LED) conversion phosphors. 

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In summary, the development of complex oxynitrides during the past thirty years has been slow, but systematic. These are not easy materials to produce, and the cost and associated high temperatures required may act as deterrents against their immediate industrial use. However, an impressive array of these materials is available today, displaying an impressive range of properties. Clearly, as technologies continue to improve, these materials will find appropriate niche applications in the future. 

The three Me nitrides (Me = Al, Si, B) are oxidizable materials, the Me-0 bond being stronger than the Me-N bond (Table 7.5). As a result, the surface of these nitrides is complex and consists of oxides and oxynitrides even in a high vacuum. 

Figure 4.42. Molecular structures of commonly used CVD precursor classes. Shown are (a) metal p-diketonate (acetylacetonate, acac) complex to grow a metal oxide film (H2 as the coreactant gas yields a metal film) (b) a heteroleptic (more than one type of ligand bound to the metal) p-diketonate complex to yield a Cu film the ancillary ligand helps prevent oligomerization, enhancing volatility (c) various types of complexes to deposit metallic, oxide, nitride, or oxynitride films (depending on coreactant gas(es) used - respective ligands are p-ketoiminato, p-diketiminato, amidinato, and guanidinato (d) a metal azolato complex commonly used to deposit lanthanide metal thin films.

But CMCs will be commercially successful only when they are produced cost-effectively. Polymer-derived ceramic (PDC) technology is one of the most promising low cost fabrication methods for ceramic matrix composites, particularly for large, complex shapes. In PDC technology, a silicon-based polymer (siloxane, carbosilane, silazane, etc) with fiber or particle reinforcement is shaped and cured in the polymer condition and then pyrolyzed in a controlled atmosphere to form a stable silicon-based ceramic, such as silicon carbide, sihcon nitride, silicon oxycarbide, or silicon oxynitride. 

The choice of conducting substrate becomes more difficult when postdeposition high-temperature treatments are necessary. This is often the case for complex oxides, such as perovskites or oxynitrides [9], which may require firing at temperatures above 600°C in order to obtain the desired crystalline phase. This prohibits the use of float glass, which softens above 550°C. Certain types of borosilicate glass can be used up to 650 C, while fused silica or sapphire can withstand continuous exposure to temperatures up to 950°C. Unfortunately, the conductivity of ITO films quickly decreases above 350°C. FTO and ITO/FTO coatings are stable up to 600-700 C [2,10], and may still have acceptable conductivities at higher temperatures provided... 

Pt-based catalysts are two necessary approaches at the current technology stage. It is believed that non-noble metal electrocatalysts is probably the sustainable solution for PEM fuel cell commercialization. In the past several decades, various nonnoble metal catalysts for ORR have been explored, including non-pyrolyzed and pyrolyzed transition metal nitrogen-containing complexes, transition metal chalcogenides, conductive polymer-based catalysts, metal oxides/carbides/nitrides/ oxynitrides/carbonitrides, and enzymatic compoimds. The major effort in non-noble metal electrocatalysts for ORR is to increase both the catalytic activity and stability. 

Si-C-N(O) fibers derived from HPZ precursor fibers are nanoporous and heterogeneous with a skin/core structure. The composition changes from SiOxCy in the external porous surface to SiNxC, in the core. The molecuiar formuia of this fiber is close to 4 mol. >4 SiOa, 81 mol.% SiNxCy (x = 1.02, y = 0.23) and 15 mol.% free C [22]. The presence of complex tetrahedral units is supported by the Si NMR spectrum which shows a broad signal covering the chemical shift region expected for silicon oxycarbide, siiicon oxynitride and silicon carbonitride units [21]. The occurrence of free carbon, expected from the nature of the precursor, is supported by the C Is XPS pattern [22]. 

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