Can you tell at a glance how the electrons in a material behave? Amazingly, the answer is “yes”, and in this post I’ll explain how.
I want to introduce the concept of something called ‘band structure’ because it is an idea that underpins a lot of the quantum mechanics of electrons in real materials. In particular, the band structure of material can make it really easy to know if a material is a good conductor of electricity or not. So, here goes.
To describe how electrons behave in a particular material, a good place to start is by working out what quantum states they are allowed to be in. In essence, the band structure is simply a map of these allowed quantum states. One place where things can be a bit confusing is the coordinates that are used to draw this map. Band structure uses the momentum of the quantum state as its coordinate, and gives the energy of that state at each point.
The reason for this is that the momentum and energy of the quantum states are linked to each other so it just makes sense to draw things this way. But why not use the position of the quantum state? This is because position and momentum cannot both be known at the same time due to Heisenberg’s Uncertainty Principle. If the momentum is known very accurately then the position must be completely unknown.
In fact, there’s even more to it than that. Most solids have a periodic lattice structure and this periodicity means that only certain momentum values are important. Roughly speaking, if the size of the repeating pattern in the lattice has length a, then there is a repeating pattern of allowed energy states in momentum with length 1/a. This means that we can draw the map of the allowed quantum states in only the first of these zones. This zone has a finite size, which is very helpful when trying to draw it!
The band structure of silicon. (Picture credit: Dissertation by Wilfried Wessner, TU Wien.)
Let’s take silicon as an example because it’s a really important material since a lot of electronics are made from it. The picture above shows the band structure (left) and the shape of the first repeating zone of allowed momenta (right) of silicon. The zone of allowed momenta has quite a complicated shape which is related to the crystal structure of the silicon. Some of the important points in that zone are labeled, for example, the center of the zone is called the Γ point (pronounced “gamma point”), while the center of the square face at the edge of the zone is the X point. It’s impossible to draw all the allowed states at every momentum point in a 3D zone, so what is usually done is to draw the allowed quantum states along certain lines between these important points, and that is what is on the left of the picture. You can probably see that these allowed states form bands, which is where the name ‘band structure’ comes from.
There’s one more concept that is really important, called the “Fermi surface”. Electrons are fermions, and so they are allowed to occupy these quantum states so that there is at most one electron in each state. In nature, the overwhelming tendency is for the total energy of a system to be minimized as this is the most efficient arrangement. This is done by filling up all the quantum states, starting from the bottom, until all the electrons are in their own state. There are never enough electrons to fill all the allowed quantum states, and so the energy of the last filled (or first empty) states is called the Fermi surface. In a three dimensional material, the cutoff between filled and empty states is a two-dimensional surface.
So, how does knowing the band structure help us to understand the electronic properties of a material? As an example, let’s think about whether the material conducts electricity well or not. It turns out that for electrical conduction, most of the quantum states of the electrons play no role at all. The important ones are those near the Fermi surface.
To conduct electricity, an electron has to jump from its state below the Fermi surface to one above it, where it is free to move around the material. To do this, it has to absorb some energy from somewhere. This usually either comes from an electric field that is driving the electrical current (like a battery or a plug socket), or from the thermal energy of the material itself.
Take a look at the sketches below. They are cartoons of band structures near the Fermi surface (which is shown by the green dotted line). The filled bands are shown by thick blue lines while the empty bands are shown by thin blue lines. In the left-hand cartoon there is a big gap between the filled and empty bands so it’s very difficult for an electron to gain enough energy to make the jump from the filled band to the empty band. That means that a material with a large band gap at the Fermi surface is an insulator – it can’t conduct electricity easily. The middle cartoon shows a material with only a small band gap. That means it’s possible, but kinda difficult for an electron to make the jump and become conducting. Materials with narrow gaps are semiconductors.
The right-hand cartoon shows a material where the Fermi surface goes through one of the bands, so there are both empty states and filled states right at the Fermi surface. This means it’s really easy for an electron to jump above the Fermi surface and become conducting because it takes only a tiny amount of energy to do this. These materials are conductors.
Going back to silicon, we can look at the band structure above and see that there is a gap of about 1 electron volt at the Fermi energy. (The Fermi energy is zero on the y axis). One electron volt is too large an energy for an electron to become conducting by absorbing thermal energy, but small enough that it can be done by an electric field. This means that silicon is a semiconductor – it has a narrow gap.
One final question: How do you find the band structure of your favorite material? There is an experimental technique called ARPES where you shine high energy light at a material, and the photons hitting it cause electrons to be ejected from the surface. These electrons can be caught and the energy and momentum that they have reflect the energy and momentum of the quantum states they were filling in the material. So by careful measurement you can reconstruct the map of these states.
Another way is to use mathematics to theoretically predict the band structure. There has been a huge amount of work done to come up with accurate ways to go from the spatial definition of a crystal to its band structure with no extra information. In some cases, these work very well, but the calculations which do this are often very complicated and require supercomputers to run!
So, that is band structure. An easy way to make a link between complicated quantum mechanics and everyday properties like conduction of electricity.