The Energy Bands

Accurate energy bands obtained from first principles by computer calculation are available for most covalent solids. A display of the bands obtained by the Empirical Pseudopotential Method for Si, Ge, and Sn and for the compounds of groups 3-5 and 2-6 that are isoclec-tronic with Ge and Sn shows the principal trends with mctallicity and polarity. The interpretation of trends is refined and extended on the basis of the LCAO fitting of the bands, which provides bands of almost equal accuracy in the form of analytic formulae. This fitting is the basis of the parameters of the Solid State Table, and a plot of the values provides the test of the d dependence of interatomic matrix elements. 

The conduction-band minima and valence-band maxima are studied in terms of the k p method, which relates the effective masses to the oscillator strengths discussed in Chapter 4. Wannier excitons and impurity states are also understandable in this context. 

In Chapter 3 we gave a preliminary discussion of the energy bands in terms of the simple LCAO theory, and illustrated, in Fig. 3-7, the form of more accurately determined energy bands. For most of the studies made in this text, that description will be sufficient. However, the bands are of some interest in their own right and are important to the understanding of the electronic properties of semiconductors, and a consideration of them increases one s understanding of the electronic structure of covalent solids. In this chapter, therefore, we shall look at a more extensive set of accurate bands and at their interpretation in terms of the con- 

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Figure Al.3.7. Evolution of energy bands in the Kronig-Penney model as the separation between wells, b (figure A 1,3.61 is deereased from (a) to (d). In (a) the wells are separated by a large distanee (large value of b) and the energy bands resemble diserete levels of an isolated well. In (d) the wells are quite elose together (small value of b) and the energy bands are free-eleetron-like.

In fignre A1.3.9 the Brillouin zone for a FCC and a BCC crystal are illustrated. It is a connnon practice to label high-synnnetry point and directions by letters or symbols. For example, the k = 0 point is called the F point. For cubic crystals, there exist 48 symmetry operations and this synnnetry is maintained in the energy bands e.g., E k, k, k is mvariant under sign pennutations of (x,y, z). As such, one need only have knowledge of (k) in Tof the zone to detennine the energy band tlnoughout the zone. The part of the zone which caimot be reduced by synnnetry is called the irreducible Brillouin zone. 

Other methods for detennining the energy band structure include cellular methods. Green fiinction approaches and augmented plane waves [2, 3]. The choice of which method to use is often dictated by die particular system of interest. Details in applying these methods to condensed matter phases can be found elsewhere (see section B3.2). 

Several factors detennine how efficient impurity atoms will be in altering the electronic properties of a semiconductor. For example, the size of the band gap, the shape of the energy bands near the gap and the ability of the valence electrons to screen the impurity atom are all important. The process of adding controlled impurity atoms to semiconductors is called doping. The ability to produce well defined doping levels in semiconductors is one reason for the revolutionary developments in the construction of solid-state electronic devices. 

It is possible to identify particular spectral features in the modulated reflectivity spectra to band structure features. For example, in a direct band gap the joint density of states must resemble that of critical point. One of the first applications of the empirical pseudopotential method was to calculate reflectivity spectra for a given energy band. Differences between the calculated and measured reflectivity spectra could be assigned to errors in the energy band... 

Is 2s 2p 3s 3p 3d 4s. If the 3d states were truly core states, then one might expect copper to resemble potassium as its atomic configuration is ls 2s 2p 3s 3p 4s The strong differences between copper and potassium in temis of their chemical properties suggest that the 3d states interact strongly with the valence electrons. This is reflected in the energy band structure of copper (figure Al.3.27). 

MetaUic behavior is observed for those soHds that have partially filled bands (Fig. lb), that is, for materials that have their Fermi level within a band. Since the energy bands are delocalized throughout the crystal, electrons in partially filled bands are free to move in the presence of an electric field, and large conductivity results. Conduction in metals shows a decrease in conductivity at higher temperatures, since scattering mechanisms (lattice phonons, etc) are frozen out at lower temperatures, but become more important as the temperature is raised. 

The most extensive calculations of the electronic structure of fullerenes so far have been done for Ceo- Representative results for the energy levels of the free Ceo molecule are shown in Fig. 5(a) [60]. Because of the molecular nature of solid C o, the electronic structure for the solid phase is expected to be closely related to that of the free molecule [61]. An LDA calculation for the crystalline phase is shown in Fig. 5(b) for the energy bands derived from the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) for Cgo, and the band gap between the LUMO and HOMO-derived energy bands is shown on the figure. The LDA calculations are one-electron treatments which tend to underestimate the actual bandgap. Nevertheless, such calculations are widely used in the fullerene literature to provide physical insights about many of the physical properties. 

Fig. 18. One-dimensional energy dispersion relations for (a) armchair (5,5) nanotubes, (b) zigzag (9,0) nanotubes, and (c) zigzag (10,0) nano tubes. The energy bands with a symmetry arc non-degenerate, while the e-bands are doubly degenerate at a general wave vector k [169,175,176].

The existence of carbon nanotubes with diameters small compared to the de Broglie wavelength has been described by Iijima[l,2,3] and others[4,5]. The energy band structures for carbon nanotubes have been calculated by a number of authors and the results are summarized in this issue by M.S. Dresselhaus, G. Dres-selhaus, and R. Saito. In short, the tubules can be either metallic or semiconducting, depending on the tubule diameter and chirality[6,7,8]. The calculated density of states[8] shows singularities... 

Fig. 4.10. The conductivity of uniaxially compressed (111) and (100) high purity germanium crystals leads to a determination of the shear deformation potential for the designated valley minima in the energy band (after Davison and Graham [79D01]).

In the optical absorption, two different polarisations of light should be considered the electric field is along (parallel or y polarisation) and perpendicular (perpendicular or x) to the axis. Figure 5 shows the energy band of a metallic CNT for flux < )/< )o =0, 1/4 and 1/2 and the process of optical transitions for the parallel and perpendicular polarisations. Some examples of calculated absorption... 

Since it is the d- electrons that are responsible for the formation of mtiferromagnetic order in Cr, it would be reasonable to take into account in expression (10) only the energy bands with addition of 3d—electrons. In view of double degeneracy, the number of such bmds amounts to 12J r. This magnitude will determine the minimum number of basis functions to be allowed for in expansion (10). 

The scope of the early papers was to use the SK approach to accurately interpolate the results of first principles calculations of the energy bands and densities of states. An important characteristic of these calculations is that the first, second, and third nearest neighbor interactions are treated as independent parameters, which is advantageous for minimizing the rms deviation from the first principles bands. 

Recent papers [4-6] of the NRL group have concentrated on a tight-binding methodology that simultaneously fits the energy bands and the total ener — of the fee and bcc structures as a function of volume, and correctly predicts the ground state for those metals that crystallize in the hep or even the Of-Mn structure. 

A unique feature of our method is that we fit the above Hamiltonian simultaneously to the energy bands and the total energy of a given matei.u.1. We write the total energy as follows ... 

The energy of the state is a continuous function of k within the appropriate BriUouin zone. The energy bands for these potentials are given by... 

The interaction energy of the valence electron with the two atomic 3d electrons, with parallel spins, is accordingly —0.67 ev, and the width of the energy band that would be occupied by uncoupled valence electrons is 1.34 ev. The number of orbitals in this band can be calculated from the equation for the distribution of energy levels for an electron in a box. The number of levels per atom is... 

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