MITOCW | Tutorial: Doping

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PROFESSOR: Hello, everyone. Today we'll talk about doping, which is the process of intentionally
adding impurities to a semiconductor in order to change its electrical properties.

Doping is a critical process in the tech world.

It's used in manufacturing almost all semiconductor technologies today. Without

doping, the solar industry would not exist, but even though doping is common today,

the effects of impurities confused semiconductor physicists in the 1950s, who had
trouble reproducing results. Eventually, they realized that contamination levels, as

low as 1 in a billion, were vastly changing the electrical properties of their samples.

Today, we'll show you how this works with a very simple experiment. We'll be

measuring the electrical conductivity of two silicon slabs using an ohmmeter. One is
doped with impurities, phosphorus in our case, and the other is ultra-pure, or what
we call intrinsic.

Let's go over our experiment. We'll start with a slab of silicon, which we attach metal
contacts to. We'll use an ohmmeter, that we connect to our sample with metal wires

to measure the conductivity. The conductivity describes how well electricity can flow
through the material.

The measured resistance from our ohmmeter is related to the inverse of the
conductivity. The resistance also varies according to the physical size and shape of
our sample, which adds a length over area term to our equation, like so.
Rearranging this equation, gives is what we're looking for, the conductivity. Let's
measure our samples, and estimate the conductivity.

Here are two samples, notice that the doped sample looks identical to the intrinsic

one, or undoped sample. Because we've only added trace impurities, the optical
properties are nearly identical between the two samples. Let's hook up the
ohmmeter to the intrinsic sample. We can see that the resistance is 130,000 ohms,
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which roughly corresponds to a conductivity of 0.0002 inverse ohm centimeters.

Let's compare this to the doped sample. We read a resistance of 34 ohms, which
corresponds to roughly 0.6 inverse ohm centimeters. So we can see that the dope
sample is around 3,000 times more conductive. But why would adding small amount
of our doping, about one phosphorus atom for every million silicon atoms, make our
sample 3,000 times more conductive?

On the periodic table, we see that silicon is in the fourth column, which means it has
four valence electrons. Phosphorus, which is just to the right in column five, has five
valence electrons, one extra compared to silicon. I'd also like to point out boron in
column three, with one fewer valence electron than silicon. Later, I'll explain what
happens when you add boron as a dopant.

We'll start with a 2D representation of a single silicon atom, with the nucleus in the
center, and its four valence electrons in a silicon crystal, each silicon atom bonds to
four other silicon atoms around it. These rigid covalent bonds, shown here, keep all

of the electrons effectively immobile, and are therefore, unable to aid in the full
electricity. Our intrinsic silicon, or undoped example, has this material structure,

which is why it has a very low conductivity.

Let's quantify this relationship between conductivity and mobile electrons.

Conductivity is defined as n times mu times e. n is a number of free or mobile

electrons. Again, in this drawing of intrinsic silicon, all electrons are covalently
bonded so there are no mobile electrons, and n is 0.

The symbol mu represents the mobility, a material parameter which you can look up
in a textbook, or online, and it basically describes how well the charge can move

around in the material. e is simply the amount of charge that each mobile particle

possesses, which in all of our cases, is simply the charge of an electron. So let's
ask, what happens when we add dopants like phosphorus and boron to the silicon

lattice?

Now, let's dope our material by replacing one of the silicon atoms with a phosphorus

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atom. First, we'll remove a silicon atom, and for contrast, we'll dim the background

silicon lattice so we can emphasize the dopant atom. Notice that the inserted
phosphorus atom has five valence electrons, four of which form four covalent bonds

with their neighboring silicon atoms and are immobile.

The fifth electron is not bonded, and as a result, is free to move around the lattice.
When the negatively charged electron leaves, the phosphorus dopant is now

positively charged. So we see that each phosphorus atom that is added will
contribute a single mobile electron. So basically, in our case, the number of mobile

electrons is roughly equal to the number of phosphorus atoms in our system.

Now, let's remove our phosphorus atom and put in an element with three valence
electrons, such as boron. We see here that boron lacks the necessary valence

electrons to form covalent bonds to its four neighboring silicon atoms. This missing
electron is actually referred to as a hole, and is represented by an H+ symbol.

This hole acts as a mobile positive charge because it can swap places with

neighboring covalently bonded electrons and move around the crystal. When the
positively charged hole leaves its nucleus, the boron atom becomes negatively

charged. So we've demonstrated that introducing atoms that have one more, or one
less, valence electron than silicon, can add mobile charges and make the material

more conductive.

In our examples, the conductivity of silicon is proportional with the density of either
phosphorus or boron atoms. While phosphorus and boron both affect the

conductivity in a very similar manner, they introduce mobile and static charges of
the opposite sign. Phosphorus introduces mobile negative charges and immobile

positive charges, while boron creates mobile positive charges and immobile

negative charges.

This subtle difference between phosphorus and boron dopants will be crucial in our

final video when we discuss solar cell operation. Today we learned that we can use
doping to control the conductivity of semiconductors by changing the number of

mobile charges in the material. When we look at the range of conductivities that
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silicon possess, it is truly amazing.

Through doping, we have a very powerful way of varying the conductivity of

like metals. Next time, we'll be discussing how light can be used to generate mobile
charges in silicon, so watch our next video. I'm Joe Sullivan, and thanks for
watching.

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