Valence insulators

Figure 9.8(a) shows how the conduction band C and the empty valence band V are not separated in a conductor whereas Figure 9.8(c) shows that they are well separated in an insulator. The situation in a semiconductor, shown in Figure 9.8(b), is that the band gap, between the conduction and valence bands, is sufficiently small that promotion of electrons into the conduction band is possible by heating the material. For a semiconductor the Fermi energy E, such that at T= 0 K all levels with E < are filled, lies between the bands as shown. 

Semiconductors may also be made from a maferial which is normally an insulator by infroducing an impurify, a process known as doping. Figure 9.9 shows fwo ways in which an impurify may promote semiconducting properties. In Figure 9.9(a) fhe dopanf has one more valence election per atom fhan fhe hosf and confribufes a band of filled impurify levels 1 close to fhe conduction band of fhe hosf. This characterizes an n-fype semiconductor. An example is silicon (KL3s 3p ) doped wifh phosphoms (KL3s 3p ), which reduces fhe band gap to abouf 0.05 eY Since kT af room femperafure is abouf 0.025 eY the phosphoms... 

Figure 9.8 Conduction band, C, and valence band, V, in (a) a conductor, (b) a semiconductor and (c) an insulator...

Heterogeneous Photocatalysis. Heterogeneous photocatalysis is a technology based on the irradiation of a semiconductor (SC) photocatalyst, for example, titanium dioxide [13463-67-7] Ti02, zinc oxide [1314-13-2] ZnO, or cadmium sulfide [1306-23-6] CdS. Semiconductor materials have electrical conductivity properties between those of metals and insulators, and have narrow energy gaps (band gap) between the filled valence band and the conduction band (see Electronic materials Semiconductors). 

In insulating oxides, ionic defects arise from the presence of impurities of different valence from the host cation. An aluminum ion impurity substituting in a magnesium oxide [1309-48-4] MgO, hostlattice creates Mg vacancies. 

It is to be expected that tire conduction data for ceramic oxides would follow the same trends as those found in semiconductors, i.e. the more ionic the metal-oxygen bond, the more the oxides behave like insulators or solid elee-trolytes having a large band gap between the valence electrons and holes, and... 

Valence electrons also can be excited by interacting with the electron beam to produce a collective, longitudinal charge density oscillation called a plasmon. Plas-mons can exist only in solids and liquids, and not in gases because they require electronic states with a strong overlap between atoms. Even insulators can exhibit... 

Materials in which there is a substantial difference in energy between occupied and vacant MOs are poor electron conductors. Diamond, where the gap between the filled valence band and the empty conduction band is 500 kj/mol, is an insulator. Silicon and germanium, where the gaps are 100 kj/mol and 60 kj/mol respectively, are semiconductors. 

In the case of negative bias, the Fermi level moves closer to the valence band edge. Consequently, the concentration of the majority of carriers (holes) at die insulator-semiconductor interface becomes laiger than in the bulk. This corresponds to the accumulation regime. When a positive bias is applied to die metal, the... 

Aluminum, silicon, and sulfur are close together in the same row of the periodic table, yet their electrical conductivities are widely different. Aluminum is a metal silicon has much lower conductivity and is called a semiconductor sulfur has such low conductivity it is called an insulator. Explain these differences in terms of valence orbital occupancy. 

Bonding in solids may be described in terms of bands of molecular orbitals. In metals, the conduction bands are incompletely filled orbitals that allow electrons to flow. In insulators, the valence bands are full and the large band gap prevents the promotion of electrons to empty orbitals. 

FIGURE 3.44 In a typical insulating solid, a full valence band is separated by a substantial energy gap from the empty conduction band. Note the break in the vertical scale. 

Pauling, L. Herman, Z.S. Expanded and Contracted d Orbitals and Change in Valence Explain the Conductor-Insulator Transition in V203 . To be submitted. 

In the spectrum from classical intermetaUics to valence compounds to insulators, a smooth transition in their chemical bonding (metallic to ionic) is observed. At the border between Zind phases and metaUic phases, the typical properties of Zind phases diminish and metallic conductivity appears. However, it is inaccurate to impose and define a sharp boundary between classical Zind phases and the metallic phases (e.g.. Laves and Hume-Rothery phases), and it is in the overlapping regimes where much chemistry stiU remains to be discovered and understood. 

Metallic lead is dark in color and is an electrical conductor. Diamond, the most valuable form of carbon, is transparent and is an electrical insulator. These properties are very different yet both lead and carbon are in Group 14 of the periodic table and have the same valence configuration, s p Why, then, are diamonds transparent insulators, whereas lead is a dark-colored conductor ... 

However, in oxides, e.g. that of aluminium, AI2O3, the sp band of the aluminium hybridizes with the p orbitals of the oxygen to form a new band below the Fermi level, which leaves a gap of 7 eV to the antibonding part of the band. The lower part is the valence band, the upper part the conduction band, and the separation between them is the band gap. This material is an insulator, as it will be hard for an electron to become excited to the conduction band so that it can move through the oxides. 

In the solid, electrons reside in the valence band but can be excited into the conduction band by absorption of energy. The energy gap of various solids depends upon the nature of the atoms comprising the solid. Semiconductors have a rather narrow energy gap (forbidden zone) whereas that of insulators is wide (metals have little or no gap). Note that energy levels of the atoms "A" are shown in the valence band. These will vary depending upon the nature atoms present. We will not delve further into this aspect here since it is the subject of more advanced studies of electronic and optical materieds. 

In class I compounds (or complexes) the two sites are very different from each other and the valences are strongly localized. The properties of the complex are the sum of the properties of the constituting ions. The optical MMCT transitions are at high energy. The compounds are insulators. Here are some examples [60, 97]. In GaCl2, or Ga(I)[Ga(III)Cl4] there are dodecahedrally coordinated Ga(I) ions with Ga-Cl distances of 3.2-3.3 A and tetrahedrally coordinated Ga(III) ions with Ga-Cl distance 2.2 A. In [Co(III)(NH3)6]2- Co(II)Cl4)3 there are low-spin, octahedrally coordinated Co(III) ions and high-spin, tetrahedrally coordinated Co(II) ions. For our purpose this class is not the most interesting one. 

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