An electron hole is the conceptual and mathematical opposite of an electron, useful in the study of physics, chemistry, and electronic engineering. The concept describes the lack of an electron at a position where one could exist in an atom or atomic lattice. It is different from the positron, which is an actual particle of antimatter.
The electron hole was introduced into calculations for the following situations:
- If an electron is excited into a higher state it leaves a hole in its old state. This meaning is used in Auger electron spectroscopy (and other x-ray techniques), in computational chemistry, and to explain the low electron-electron scattering-rate in crystals (metals, semiconductors).
- In crystals, electronic band structure calculations lead to an effective mass for the electrons, which typically is negative at the top of a band. The negative mass is an unintuitive concept, and in these situations a more familiar picture is found by considering a positive charge with a positive mass.
Solid state physics
In solid-state physics, an electron hole (usually referred to simply as a hole) is the absence of an electron from an otherwise full valence band. A hole is essentially a way to conceptualize the interactions of the electrons within a nearly full system, which is missing just a few electrons. In some ways, the behavior of a hole within a semiconductor crystal lattice is comparable to that of the bubble in an otherwise full bottle of water.
Simplified analogy: Empty seat in an auditorium
Hole conduction in a valence band can be explained by the following analogy. Imagine a row of people seated in an auditorium, where there are no spare chairs. Someone in the middle of the row wants to leave, so he jumps over the back of the seat into an empty row, and walks out. The empty row is analogous to the conduction band, and the person walking out is analogous to a free electron.
Now imagine someone else comes along and wants to sit down. The empty row has a poor view; so he does not want to sit there. Instead, a person in the crowded row moves into the empty seat the first person left behind. The empty seat moves one spot closer to the edge and the person waiting to sit down. The next person follows, and the next, et cetera. One could say that the empty seat moves towards the edge of the row. Once the empty seat reaches the edge, the new person can sit down.
In the process everyone in the row has moved along. If those people were negatively charged (like electrons), this movement would constitute conduction. If the seats themselves were positively charged, then only the vacant seat would be positive. This is a very simple model of how hole conduction works.
In reality, due to the crystal structure properties, the hole is not localized to a single position as described in the previous example. Rather, the hole spans an area in the crystal lattice covering many hundreds of unit cells. This is equivalent to being unable to tell which broken bond corresponds to the "missing" electron.
Instead of analyzing the movement of an empty state in the valence band as the movement of many separate electrons, a single equivalent imaginary particle called a "hole" is considered. In an applied electric field, the electrons move in one direction, corresponding to the hole moving in the other. If a hole associates itself with a neutral atom, that atom loses an electron and becomes positive. Therefore the hole is taken to have positive charge of +e, precisely the opposite of the electron charge.
Detailed picture: A hole is the absence of a negative-mass electron
- The dispersion relation determines how electrons respond to forces (via the concept of effective mass).
A dispersion relation is the relationship between wavevector (k-vector) and energy in a band, part of the electronic band structure. In quantum mechanics, the electrons are waves, and energy is the wave frequency. A localized electron is a wavepacket, and the motion of an electron is given by the formula for the group velocity of a wave. An electric field affects an electron by gradually shifting all the wavevectors in the wavepacket, and the electron moves because its wave group velocity changes. Therefore, again, the way an electron responds to forces is entirely determined by its dispersion relation. An electron floating in space has the dispersion relation E=ℏ2k2/(2m), where m is the (real) electron mass and ℏ is reduced Planck's constant. In the conduction band of a semiconductor, the dispersion relation is instead E=ℏ2k2/(2m*) (m* is the effective mass), so a conduction-band electron responds to forces as if it had the mass m*.
The dispersion relation near the top of the valence band is E=ℏ2k2/(2m*) with negative effective mass. So electrons near the top of the valence band behave like they have negative mass. When a force pulls the electrons to the right, these electrons actually move left! This is solely due to the shape of the valence band, and unrelated to whether the band is full or empty. If you could somehow empty out the valence band and just put one electron near the valence band maximum (an unstable situation of course), this electron would move the "wrong way" in response to forces.
- Positively-charged holes as a shortcut for calculating the total current of an almost-full band.
A perfectly-full band always has zero current. One way to think about this fact is that the electron states near the top of the band have negative effective mass, and those near the bottom of the band have positive effective mass, so the net motion is exactly zero. If an otherwise-almost-full valence band has a state without an electron in it, we say that this state is occupied by a hole. There is a mathematical shortcut for calculating the current due to every electron in the whole valence band: Start with zero current (the total if the band were full), and subtract the current due to the electrons that would be in each hole state if it wasn't a hole. Since subtracting the current caused by a negative charge in motion is the same as adding the current caused by a positive charge moving on the same path, the mathematical shortcut is to pretend that each hole state is carrying a positive charge, while ignoring every other electron state in the valence band.
- A hole near the top of the valence band moves the same way as an electron near the top of the valence band would move.
This fact follows from the discussion and definition above. This is an example where the auditorium analogy above is misleading. When a person moves left in a full auditorium, an empty seat moves right. But in this section we are imagining how electrons move through k-space, not real space, and the effect of a force is to move all the electrons through k-space in the same direction at the same time. So a better analogy is a bubble underwater in a river: The bubble moves the same direction as the water, not opposite.
- Conclusion: Hole as a positive-charge, positive-mass quasiparticle.
From the above, a hole (A) carries a positive charge, and (B) responds to electric and magnetic fields as if it had a positive charge and positive mass. (The latter is because a particle with positive charge and positive mass responds to electric and magnetic fields in the same way as a particle with negative charge and negative mass.) That explains why holes can be treated in all situations as ordinary positively-charged quasiparticles.
Role in semiconductor technology
In some semiconductors, such as silicon, the hole's effective mass is dependent on direction (anisotropic), however a value averaged over all directions can be used for some macroscopic calculations.
In most semiconductors, the effective mass of a hole is much larger than that of an electron. This results in lower mobility for holes under the influence of an electric field and this may slow down the speed of the electronic device made of that semiconductor. This is one major reason for adopting electrons as the primary charge carriers, whenever possible in semiconductor devices, rather than holes.
Holes in quantum chemistry
An alternate meaning for the term electron hole is used in computational chemistry. In coupled cluster methods, the ground (or lowest energy) state of a molecule is interpreted as the "vacuum state"—conceptually, in this state there are no electrons. In this scheme, the absence of an electron from a normally-filled state is called a "hole" and is treated as a particle, and the presence of an electron in a normally-empty state is simply called an "electron". This terminology is almost identical to that used in solid-state physics.
- Band gap
- Carrier generation and recombination
- Effective mass
- Electrical resistivity and conductivity
- For these negative mass electrons, momentum is opposite to velocity, so forces on acting these electrons cause their velocity to change in the 'wrong' direction. As these electrons gain energy (moving towards the top of the band), they slow down.
- Weller, Paul F. (1967). "An analogy for elementary band theory concepts in solids". J. Chem. Educ 44 (7): 391. Bibcode:1967JChEd..44..391W. doi:10.1021/ed044p391.
- Kittel, Introduction to Solid State Physics 8th edition, page 194-196