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Photovoltaics: Carrier Concentrations (Part 1)



In the previous post, we have introduced band diagrams and you learned about the conduction and valence energy band. Now we will start taking a deeper look at the charge carriers that can occupy energy states in those bands. The occupation of energy states in the valence and conduction bands of semiconductors determines the concentrations of charge carriers.
Concentration of charge carriers is a very important property for understanding performance of solar cells. Let’s start with the equilibrium condition. We define equilibrium of a system as a state in which the system is unperturbed. Therefore, no external forces are applied on this system. These forces could be: external voltage, magnetic field, illumination or mechanical stress. We can define the thermal equilibrium of as ystem as a condition in which its parameters do not change with time.

We use the word thermal because the equilibrium conditions will change depending on the temperature. Several steps are necessary to take into account to determine the concentration of carriers in a semiconductor. The first one is to determine the available energy states for electrons in the conduction and valence band. In the previous posts, we have described the concept of energy levels and energy bands. We saw that only few of the levels are effectively occupied by charge carriers. The density of energy states, which we denote as ‘g’, is an important parameter that tell us the number of allowed energy states per unit volume as a function of energy.

The further we move from the edges of the bands, the more energy states are available. ‘g_C’ represents the density of states in the conduction band. If you remember from the previous post, the conduction band represents energy states of mobile electrons. ‘g_V’ on the other hand, represents the density of states of holes in the valence band. Holes essentially occupy the states in the valence band of missing electrons.

The electrons that have been excited to the conduction band. You will learn much more about holes in future posts. Let’s look into the equations that represent these densities. We can express the equation for the density of states in the conduction band as follows. The equation is based on a few constants like the Plank’s constant and the effective mass of an electron. However, please note, that the dependence on energy is a square root relationship. As the energy gets further away from the conduction band edge denoted by E_C, the amount of allowed energy states increases. Now let’s continue with the valence band. The equations are very similar to that of ‘g_C’ but now we have to use the effective mass of holes instead of electrons. So now we know the density of allowed energy states of mobile electrons and holes.

In order to calculate the total charge-carrier concentrations we also need to know how many of energy states are really occupied. For this purpose, we introduce what is called the occupation function. This function is known as the Fermi-Dirac distribution function. The Fermi-Dirac distribution function expresses the probability that an available energy state will be occupied at a certain temperature. This function depends on the difference between the energy level of interest and the so called Fermi level E_F. I will explain the definition of the Fermi level in a couple of slides, but let’s first take a look at the temperature dependence of this distribution function. At zero Kelvin, the Fermi-Dirac distribution function is a step function. It means, only the energy levels below the Fermi level are occupied.

Energy states of the conduction band that are above the Fermi level are empty, so no electrons occupy these states. However, if the temperature goes up, the probability of occupation of higher energy levels increases. The more the temperature rises, the probability of occupation gets higher and more electrons can fill these states. This is the result of thermal excitation. The excited electrons are getting energy from the ambient heat. If the temperature is higher than zero Kelvin, electrons can occupy energy levels above the conduction band edge. Before we go any further, let me explain a very important concept: the Fermi Level.

So, what is exactly the Fermi level? In general it represents the total averaged energy of valence electrons of a material. This energy takes into account the electro-chemical energy of all the electrons in the conduction and valence band. From the Fermi-Dirac distribution function we can easily calculate that the probability that the energy level corresponding to the Fermi level is occupied is zero point five. The position of the Fermi level in an intrinsic semiconductor is close to the middle of the band gap. Depending on the position of the Fermi level in the band gap we can simplify the Fermi-Dirac distribution function.

If the Fermi level is within 3 times k_b times T from both the conduction band edge and the valence band edge, so in the pink area of the band diagram we can use this simplified equation. This equation is known as the Boltzmann Approximation. We have now discussed the density of states function and the Fermi Dirac distribution function. In the next post we will use these parameters to determine the charge carrier concentration in thermal equilibrium. Now let’s continue with the valence band. The equations are very similar to that of ‘g_C’ but now we have to use the effective mass of holes instead of electrons. So now we know the density of allowed energy states of mobile electrons and holes. In order to calculate the total charge-carrier concentrations we also need to know how many of energy states are really occupied.

For this purpose, we introduce what is called the occupation function. This function is known as the Fermi-Dirac distribution function. The Fermi-Dirac distribution function expresses the probability that an available energy state will be occupied at a certain temperature. This function depends on the difference between the energy level of interest and the so called Fermi level E_F.

I will explain the definition of the Fermi level in a couple of slides, but let’s first take a look at the temperature dependence of this distribution function. At zero Kelvin, the Fermi-Dirac distribution function is a step function. It means, only the energy levels below the Fermi level are occupied. Energy states of the conduction band that are above the Fermi level are empty, so no electrons occupy these states. However, if the temperature goes up, the probability of occupation of higher energy levels increases.

The more the temperature rises, the probability of occupation gets higher and more electrons can fill these states. This is the result of thermal excitation. The excited electrons are getting energy from the ambient heat. If the temperature is higher than zero Kelvin, electrons can occupy energy levels above the conduction band edge. Before we go any further, let me explain a very important concept: the Fermi Level. So, what is exactly the Fermi level? In general it represents the total averaged energy of valence electrons of a material. This energy takes into account the electro-chemical energy of all the electrons in the conduction and valence band. From the Fermi-Dirac distribution function we can easily calculate tha tthe probability that the energy level corresponding to the Fermi level is occupied is zero point five.

The position of the Fermi level in an intrinsic semiconductor is close to the middle of the band gap. Depending on the position of the Fermi level in the band gap we can simplify the Fermi-Dirac distribution function. If the Fermi level is within 3 times k_b times T from both the conduction band edge and the valence band edge, so in the pink area of the band diagram we can use this simplified equation. This equation is known as the Boltzmann Approximation. We have now discussed the density of states function and the Fermi Dirac distribution function. In the next post we will use these parameters to determine the charge carrier concentration in thermal equilibrium.

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