CHAPTER 5 BOUND ELECTRONS AND THE PERIODIC POTENTIAL 5.3 THE ORIGIN OF ENERGY BANDS IN SOLIDS: THE TIGHT-BINDING APPROXIMATION How can we view the electron energy levels in a material as if they had evolved from the energy levels in single atoms? We have already seen in the previous discussion that there is a qualitative differ- ence in the properties of the high-energy, quasi-free electrons which are responsible for electrical and thermal conduction; and the low-énergy bound electrons which are trapped in the atomic potential wells located on the lattice sites. Now we shall take another approach originated by Bloch [7] which also contri- butes to our understanding of the properties of electrons in solids. It is well known that the energy levels of electrons within a single isolated atom are highly discrete. This was shown, for example, in the Bohr model of the atom, in which these energies were given by me) 4 eS (ay le Ca where 7 is an integer, m is the mass of the electron, e is the charge of the electron, 4 is Planck’s constant and co is the permittivity of free space. Energy (eV) o O58 1.0 16 Interatomic spacing (nm) Figure 5.5. Broadening of the allowed electron energy states into electron ‘bands’ as the interatome spacing ais reduced. Reproduced with permission of R. H. Bube, Electronics in Solids ‘An Introductory Survey, published by Academic Press, 1971,THE ORIGIN OF ENERGY BANDS IN SOLIDS: THE TIGHT-BINDING APPROXIMATION 9 Ri 4s MMOS 3p oe 3s 2p 0.37 nm 1.0 nm oo @) ©) © Figure 5.6 Energy ‘spectrum’ of allowed siates for (@) free electrons outside a solid, (b) band slecirons within a solid and (c) bound electrons in isolated atoms, Reproduced with permission of RH. Bube, Electronics in Sols: An introductory Survey, published by Academic Press, 1971 if we consider what happens to these sharply defined electronic energy levels as atoms of a solid are brought together we find that they become broadened, S occurs because the Pauli exclusion principle does not allow two electrons to save completely identical states. Therefore, the energies which were identical in < isolated atoms must shift relative to one another, and the closer the atoms are ecther the more marked is the shift in available energy states. Furthermore, the vember of different energy states is dependent on the number of atoms, This means that a discrete energy level in a particular type of atom broadens sso an allowed band of energies when a large number of identical such atoms are cought together in a solid. The higher-energy states broaden first as the atoms we brought closer together. The broadening of the lower-energy states, which are ser to the atomic cores, is less marked, we look more at the three cases consisting of the two extreme cases of bound rons and free electrons and the intermediate case of electrons in a solid, we the following types of energy spectrum, 53.1 The tight-binding approximation versus the free electron approximation Sow do the extreme viewpoints of single atom versus collective electron compare? © approach which we have just taken, considering the energy levels in the fated atom and then bringing the atoms together and modifying the énergy svels, is known as the ‘tight-binding approximation’ because we start from tightlyCHAPTER 5 BOUND ELECTRONS AND THE PERIODIC POTENTIAL bound electrons in the atoms. The previous approach, beginning with the free electron model and progressing through to a periodic potential model is known as the free electron approximation. Both should lead to the same result if their conditions are relaxed sufficiently. Both are valid methods of looking at the electronic properties of materials but approach the problem from different directions. In fact, an intermediate model by Herring [8] has also been used to calculate the energy states of electrons in solids by combining the best aspects of both models. This is known as the orthogonalized _ plane wave method. In metals, of course, as we have already noted, the higher-energy electrons behave as if almost free. Therefore, the free electron approximation is more relevant in these cases. In semiconductors and insulators, the electrons do not become free in the same serise because the highest-occupied energy states in the ground state are localized at the atomic lattice sites, and so in this case the tight- binding approximation is more relevant. However, in either model we are led te the conclusion that when large numbers of atoms ate brought together, energy bands arise and these bands are separated by forbidden energy regions or band gaps. 5.3.2 Transition from insulator to metal under pressure What happens to the electronic properties of an insulator if it is subjected te extremely high pressure? Since in their ground states electrons will always occupy the lowest available energy state, it is possible to convert an insulator to a metal under very intense pressure as a result of the broadening of the energy bands which occurs when the atomic cores are moved closer together. Insulator Semiconductor Metal Energy E Fermilevel Pressure 5.7 Effects of pressure on the allowed electron energy levels of atoms. At low. pressure the "By atoms are isolated. At intermediate pressure they form an insulator and at very hig pressures they form a metal, Compare with Figs, 5.5 and 5.6,