Nitrides block metal

Hydrides of variable composition are not only formed with pure metals as solvents. A large number of the binary metal hydrides are non-stoichiometric compounds. Non-stoichiometric compounds are in general common for d,f and some p block metals in combination with soft anions such as sulfur, selenium and hydrogen, and also for somewhat harder anions like oxygen. Hard anions such as the halides, sulfates and nitrides form few non-stoichiometric compounds. Two factors are important the crystal structures must allow changes in composition, and the transition metal must have accessible oxidation states. These factors are partly related. FeO,... 

Nitrides of the J-block metals are hard, inert solids which resemble metals in appearance, and have high melting points and electrical conductivities (see Box 14.5). They can be prepared from the metal or metal hydride with N2 or NH3 at high temperatures. Most possess structures in which the nitrogen atoms occupy octahedral holes in a close-packed metal lattice. Full occupancy of these holes leads to the stoichiometry MN (e.g. TiN, ZrN, HfN, VN, NbN) cubic close-packing of the metal atoms and an NaCl lattice for the nitride MN is favoured for metals in the earhest groups of the J-block. 

By referring to relevant sections earlier in the book, write a brief account of the formation of hydrides, borides, carbides and nitrides of the [Pg.553]

Main-group elements X such as monovalent F, divalent O, and trivalent N are expected to form families of transition-metal compounds MX (M—F fluorides, M=0 oxides, M=N nitrides) that are analogous to the corresponding p-block compounds. In this section we wish to compare the geometries and NBO descriptors of transition-metal halides, oxides, and nitrides briefly with the isovalent hydrocarbon species (that is, we compare fluorides with hydrides or alkyls, oxides with alkylidenes, and nitrides with alkylidynes). However, these substitutions also bring in other important electronic variations whose effects will now be considered. 

Solid-state metathesis reactions. For a number of compounds, solid-state metathesis (exchange) reactions have the advantages of a rapid high-yield method that starts from room-temperature solids and needs little equipment. The principle behind these reactions is to use the exothermicity of formation of a salt to rapidly produce a compound. We may say that for instance a metal halide is combined with an alkali (or alkaline earth) compound of a /7-block element to produce the wanted product together with a salt which is then washed away with water or alcohol. Metathesis reactions have been used successfully in the preparation of several crystalline refractory materials such as borides, chalcogenides, nitrides. 

In [55] a large-area fabrication of hexagonally ordered metal dot arrays with an area density of 10u/cm2 was demonstrated. The metal dots were produced by an electron beam evaporation followed by a lift-off process. The dots size was 20 nm dots with a 40 nm period by combining block copolymer nanolithography and a trilayer resist technique. A self-assembled spherical-phase block copolymer top layer spontaneously generated the pattern, acting as a template. The pattern was first transferred to a silicon nitride middle layer by reactive ion etch, producing holes. The nitride layer was then used as a mask to further etch into a polyamide bottom layer. 

Reactivity Nitrogen is present as N2 (N0 N) and is very inert at ordinary temperatures and does not react with many metals directly. However at higher temperatures it reacts with s block elements. For example it forms magnesium and lithium nitrides when they are heated in it. 

In Chapters 20 and 21 we shall look at individual elements of the c -block in detail. However, a few general points are given here as an overview. In general, the metals are moderately reactive and combine to give binary compounds when heated with dioxygen, sulfur or the halogens (e.g. reactions 19.1-19.3), product stoichiometry depending, in part, on the available oxidation states (see below). Combination with H2, B, C or N2 may lead to interstitial hydrides Section 9.7), borides Section 12.10), carbides Section 13.7) or nitrides Section 14.6). 

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