The electrons of a single free-standing atom occupy atomic orbitals, which form a discrete set of energy levels. If several atoms are brought together into a molecule, their atomic orbitals split, as in a coupled oscillation. This produces a number of molecular orbitals proportional to the number of atoms. When a large number of atoms (of order or more) are brought together to form a solid, the number of orbitals becomes exceedingly large, and the difference in energy between them becomes very small, so the levels may be considered to form continuous bands of energy rather than the discrete energy levels of the atoms in isolation. However, some intervals of energy contain no orbitals, no matter how many atoms are aggregated, forming band gaps.
Within an energy band, energy levels are so numerous as to be a near continuum. First, the separation between energy levels in a solid is comparable with the energy that electrons constantly exchange with phonons (atomic vibrations). Second, it is comparable with the energy uncertainty due to the Heisenberg uncertainty principle, for reasonably long intervals of time. As a result, the separation between energy levels is of no consequence.
Several approaches to finding band structure are discussed below
Any solid has a large number of bands. In theory, it can be said to have infinitely many bands (just as an atom has infinitely many energy levels). However, all but a few lie at energies so high that any electron that reaches those energies escapes from the solid. These bands are usually disregarded.
Bands have different widths, based upon the properties of the atomic orbitals from which they arise. Also, allowed bands may overlap, producing (for practical purposes) a single large band.
Figure 1 shows a simplified picture of the bands in a solid that allows the three major types of materials to be identified: metals, semiconductors and insulators.
Metals contain a band that is partly empty and partly filled regardless of temperature. Therefore they have very high conductivity.
The lowermost, almost fully occupied band in an insulator or semiconductor is called the valence band by analogy with the valence electrons of individual atoms. The uppermost, almost unoccupied band is called the conduction band because only when electrons are excited to the conduction band can current flow in these materials. The difference between insulators and semiconductors is only that the forbidden band gap between the valence band and conduction band is larger in an insulator, so that fewer electrons are found there and the electrical conductivity is lower. Because one of the main mechanisms for electrons to be excited to the conduction band is due to thermal energy, the conductivity of semiconductors is strongly dependent on the temperature of the material.
This band gap is one of the most useful aspects of the band structure, as it strongly influences the electrical and optical properties of the material. Electrons can transfer from one band to the other by means of carrier generation and recombination processes. The band gap and defect states created in the band gap by doping can be used to create semiconductor devices such as solar cells, diodes, transistors, laser diodes, and others.
where k is called the wavevector, and is related to the direction of motion of the electron in the crystal, and n is the band index, which simply numbers the energy bands. The wavevector k takes on values within the Brillouin zone (BZ) corresponding to the crystal lattice, and particular directions/points in the BZ are assigned conventional names like Γ, Δ, Λ, Σ, etc. These directions are shown for the face-centered cubic lattice geometry in Figure 2.
The available energies for the electron also depend upon k, as shown in Figure 3 for silicon in the more complex energy band diagram at the right. In this diagram the topmost energy of the valence band is labeled and the bottom energy in the conduction band is labeled . The top of the valence band is not directly below the bottom of the conduction band ( is for an electron traveling in direction Γ, in direction X), so silicon is called an indirect gap material. For an electron to be excited from the valence band to the conduction band, it needs something to give it energy and a change in direction/momentum. In other semiconductors (for example GaAs) both are at Γ, and these materials are called direct gap materials (no momentum change required). Direct gap materials benefit the operation of semiconductor laser diodes.
Anderson's rule is used to align band diagrams between two different semiconductors in contact.
While the density of energy states in a band could be very large for some materials, it may not be uniform. It approaches zero at the band boundaries, and is generally highest near the middle of a band. The density of states for the free electron model in three dimensions is given by,
Although the number of states in all of the bands is effectively infinite, in an uncharged material the number of electrons is equal only to the number of protons in the atoms of the material. Therefore not all of the states are occupied by electrons ("filled") at any time. The likelihood of any particular state being filled at any temperature is given by the Fermi-Dirac statistics. The probability is given by the following:
The Fermi level naturally is the level at which the electrons and protons are balanced.
At T=0, the distribution is a simple step function:
At nonzero temperatures, the step "smooths out", so that an appreciable number of states below the Fermi level are empty, and some states above the Fermi level are filled.
Because electron momentum is the reciprocal of space, the dispersion relation between the energy and momentum of electrons can best be described in reciprocal space. It turns out that for crystalline structures, the dispersion relation of the electrons is periodic, and that the Brillouin zone is the smallest repeating space within this periodic structure. For an infinitely large crystal, if the dispersion relation for an electron is defined throughout the Brillouin zone, then it is defined throughout the entire reciprocal space.
The ansatz is the special case of electron waves in a periodic crystal lattice using Bloch waves as treated generally in the dynamical theory of diffraction. Every crystal is a periodic structure which can be characterized by a Bravais lattice, and for each Bravais lattice we can determine the reciprocal lattice, which encapsulates the periodicity in a set of three reciprocal lattice vectors (, , ). Now, any periodic potential which shares the same periodicity as the direct lattice can be expanded out as a Fourier series whose only non-vanishing components are those associated with the reciprocal lattice vectors. So the expansion can be written as:
where for any set of integers .
From this theory, an attempt can be made to predict the band structure of a particular material, however most ab initio methods for electronic structure calculations fail to predict the observed band gap.
In the nearly-free electron approximation in solid state physics interactions between electrons are completely ignored. This approximation allows use of Bloch's Theorem which states that electrons in a periodic potential have wavefunctions and energies which are periodic in wavevector up to a constant phase shift between neighboring reciprocal lattice vectors. The consequences of periodicity are described mathematically by the Bloch wavefunction:
where the function is periodic over the crystal lattice, that is,
Here index n refers to the n-th energy band, wavevector k is related to the direction of motion of the electron, r is position in the crystal, and R is location of an atomic site..
where the coefficients are selected to give the best approximate solution of this form. Index n refers to an atomic energy level and R refers to an atomic site. A more accurate approach using this idea employs Wannier functions, defined by .
In present days physics literature, the large majority of the electronic structures and band plots is calculated using the density-functional theory (DFT) which is not a model but rather a theory, i.e. a microscopic first-principle theory of condensed matter physics that tries to cope with the electron-electron many-body problem via the introduction of an exchange-correlation term in the functional of the electronic density. DFT calculated bands are found in many cases in agreement with experimental measured bands, for example by angle-resolved photoemission spectroscopy (ARPES). In particular, the band shape seems well reproduced by DFT. But also there are systematic errors of DFT bands with respect to the experiment. In particular, DFT seems to underestimate systematically by a 30-40% the band gap in insulators and semiconductors.
It must be said that DFT is in principle an exact theory to reproduce and predict ground state properties (e.g. the total energy, the atomic structure, etc.). However DFT is not a theory to address excited state properties, such as the band plot of a solid that represents the excitation energies of electrons injected or removed from the system. What in literature is quoted as a DFT band plot is a representation of the DFT Kohn-Sham energies, that is the energies of a fictive non-interacting system, the Kohn-Sham system, which has no physical interpretation at all. The Kohn-Sham electronic structure must not be confused with the real, quasiparticle electronic structure of a system, and there is no Koopman's theorem holding for Kohn-Sham energies, like on the other hand for Hartree-Fock energies that can be truly considered as an approximation for quasiparticle energies. Hence in principle DFT is not a band theory, not a theory suitable to calculate bands and band-plots.
To calculate the bands including electron-electron interaction many-body effects, one can resort to so called Green's function methods. Indeed, the knowledge of the Green's function of a system provides both ground (the total energy) and also excited state observables of the system. The poles of the Green's function are the quasiparticle energies, the bands of a solid. The Green's function can be calculated by solving the Dyson equation once the self-energy of the system is known. For real systems like solids, the self-energy is a very complex quantity and usually approximations are needed to solve the problem. One of such approximations is the GW approximation, so called from the mathematical form the self-energy takes as product of the Green's function and the dynamically screened interaction . This approach is more pertinent to address the calculation of band plots (and also quantities beyond, such as the spectral function) and can be also formulated in a completely ab initio way. The GW approximation seems to provide band gaps of insulators and semiconductors in agreement with the experiment and hence to correct the systematic DFT underestimation.
Although the nearly-free electron approximation is able to describe many properties of electron band structures, one consequence of this theory is that it predicts the same number of electrons in each unit cell. If the number of electrons is odd, we would then expect that there is an unpaired electron in each unit cell, and thus that the valence band is not fully occupied, making the material a conductor. However, materials such as CoO that have an odd number of electrons per unit cell are insulators, in direct conflict with this result. This kind of material is known as a Mott insulator, and requires inclusion of detailed electron-electron interactions (treated only as an averaged effect on the crystal potential in band theory) to explain the discrepancy. The Hubbard model is an approximate theory that can include these interactions.
Calculating band structures is an important topic in theoretical solid state physics. In addition to the models mentioned above, other models include the following:
Each model describes some types of solids very well, and others poorly. The nearly-free electron model works well for metals, but poorly for non-metals. The tight binding model is extremely accurate for ionic insulators, such as metal halide salts (e.g. NaCl).