P-type semiconductivity

At the other end of the conduction spectrum, many oxides have conductivities dominated by electron and positive hole contributions to the extent that some, such as Re03, SnOa and tire perovskite LaCrOs have conductivities at the level of metallic conduction. High levels of p-type semiconduction are found in some transition metal perovskites especially those containing alio-valent ions. Thus the lanthairum-based perovskites containing transition metal ions, e.g. LaMOs (M-Cr, Mn, Fe, Co, Ni) have eirlranced p-type semiconduction due to the dependence of the transition metal ion valencies on the ambient... 

Bocarsly AB, Bookbinder DS, Dominey RN, Lewis NS, Wrighton MS (1980) Photoreduction at illuminated p-type semiconducting silicon photoelectrodes. Evidence for Fermi level pinning. J Am Chem Soc 102 3683-3688... 

A comparative study of oxides which were closely related, but had different electrical properties, showed that both n- and p-type semiconduction promoted the oxidation reaction, forming CO as the major carbon-containing product. In a gas mixture which was 30% methane, 5% oxygen, and 65% helium, reacted at 1168 K the coupling reactions were best achieved with the electrolyte Lao.9Sro.1YO 1.5 and the /i-lype semiconductor Lao.sSro MntL A and the lily pe semiconductor LaFeo.sNbo.2O1 a produced CO as the major oxidation product (Alcock et al., 1993). The two semiconductors are non-stoichiometric, and the subscript 3 — x varies in value with the oxygen pressure and temperature. Again, it is quite probable that the surface reactions involve the formation of methyl radicals and O- ions. 

Figure 6.40 Proposed band structure for an oxidized p-type semiconducting polymer. Reprinted, by permission, from J. M. G. Cowie, Polymers Chemistry Physics of Modern Materials, 2nd ed., p. 419. Copyright 1991 by J. M. G. Cowie.

If we place n- and p-type semiconducting crystals in contact (a p-n junction), we create a device that conducts electricity preferentially in one direction this is the basis of action of the semiconductor diodes used in the electronics industry, although specially refined silicon (Section 17.8.2) is usually employed rather than Ge. Transistors and electronic chips are designed using similar basic principles—typically with n-p-n or p-n-p junctions. We consider chemical aspects of electronic devices in more detail in Chapter 19. 

In this context, Pcs appear as perfect candidates for incorporation in such photovoltaic systems, as they present intense absorption in the UV/blue and the red/near IR region of the solar spectrum while still maintaining a rich redox chemistry and p-type semiconducting properties. 

LaCrC>3 is one of the family of lanthanide perovskites RTO3, where R is a lanthanide and T is a period 4 transition element. In the cubic unit cell R occupies the cube corners, T the cube centre and O the face-centre positions. The coordination numbers of T and R are 6 and 8 respectively. LaCrC>3 loses chromium at high temperatures, leaving an excess of O2- ions. The excess charge is neutralized by the formation of Cr4+ which results in p-type semiconductivity with hole hopping via the localized 3d states of the Cr3+ and Cr4+ ions. The concentration of Cr4+ can be enhanced by the substitution of strontium for lanthanum. A 1 mol.% addition of SrO causes the conductivity to increase by a factor of approximately 10 (see Section 2.6.2). 

RE2CUO4 perovskites exhibit important and varying magnetic and electrical characteristics, and they are broadly studied as potential high-Tc superconductive materials. At room temperature, they show p-type semiconducting behaviors, and are used as electrode materials in fuel batteries. The catalytic properties of the perovskite oxides also make them effective in various oxidation and reduction reaction, hence they are considered as promising substitutes to the classical Pt/Rh-based catalysts applied to automotive pollution control. 

The procedure is best illustrated by an example. Suppose that a nonstoichiometric phase of composition MA can have an existence range, which spans both sides of the stoichiometric composition, MX, oo. Assume that in this phase only vacancies are of importance, so that the stoichiometric composition will occur when the number of vacancies on the cation sublattice is exactly equal to the number of vacancies on the anion sublattice, which is, therefore, due to a population of Schottky defects. At other compositions, electrical neutrality is adjusted via mobile electrons or holes, leading to n-type or p-type semiconductivity. Thus there are four defects to consider, electrons, e, holes, h, vacancies on metal sites, Vm, and vacancies on anion sites, Vx. Finally, assume that the most important gaseous component is X2 as is the case in most oxides, halides, and sulphides. 

Fermi level is a kind of measiue of equilibrium electronic energy of a solid material. It is thought that Fermi level is located just below the CB bottom and above the VB top for n-type and p-type semiconducting materials 13), respectively. Most metal oxides are categorized as n-type semiconductors with Fermi levels more cathodic (higher) than the standard electrode potential of electrolyte in contact with the metal oxide and thereby electrons in donor levels a little below the CB are injected into the electrol5rte to form a space charge (depletion) layer with an electric field, that is, Schottky barrier. In the... 

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