Chapter Nine

Semiconductors (Extrinsic)

A note on 𝒏 and 𝒑
In the last lecture, we have shown that product of 𝑛 an 𝑝 is always constant in thermal
equilibrium. What does it mean? We can think of it as a chemical reaction
𝑛 + 𝑝 ⟷ 0
There is a process by which carriers are generated, every time an electron is excited to
conduction band, it leaves a hole behind. This is called generation (G) process. Now electron
in the conduction band will like to come back to ground state via a process called recombination
(R) process.

Fig. 9.1 Schematic of generation and recombination process.

So, 𝑛 and 𝑝 are result of the equilibrium between R and G processes at a given temperature. As
in any other chemical reaction in equilibrium, the rate of forward (recombination) and backward
(generation) reaction would be same; keeping product and reactant (𝑛 and 𝑝) concentration
constant. Using analogy of a chemical reaction, this also leads to 𝑛𝑝 product being constant
at a given temperature.

Extrinsic Semiconductors – bonding picture (Doping)

What will happen if we add a few P (phosphorus) atoms in Si? P atoms goes on substitutional
sites (This is not necessary for all impurities, there can be interstitial impurities as well).

(a)

(b) (c)
Fig. 9.2 Bond picture of Si (a), P (phosphorus) dopant in Si (b) and B (boron) dopant in Si (c).

Lecture Notes for MSE303: Electronic and Magnetic properties of Materials Authors: Deepak Gupta, Monica Katiyar and Anshu Gaur
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If we replace Si by P, four electrons will participate in bonding, but we have fifth electron which
in Fig. 9.2(a) is loosely bound to P, since it is screened by other electrons. By increasing
temperature, it can be easily taken away from the P leaving behind P+ ion. How much energy
we require for the fifth electron to be free? The way we do this is as follows, we show a donor
level in the band diagram for the fifth electron (Fig. 9.3(a)) as ℰ* .
Then if I have sufficient energy ( ℰ+ − ℰ* ) the fifth electron can simple jump and get in the
conduction band. I can, therefore, increase electrons in conduction band – such dopants are
called donors (D). In Si, such donors will be P, As, Sb.

Fig. 10.3 Energy levels for donors, acceptors (shallow levels) and deep levels.

Let us talk about acceptors, for example B (boron) that has three electrons in outer shell. So, to
complete the bonding, it accepts an electron from the valence band. Essentially, a hole is left
behind in the valence band. The amount of energy required to do this is indicated as ℰ- − ℰ. in
Fig. 9.3(b).
Take GaAs example, Si is group IV element and it acts as a donor in GaAs. Si could go on Ga
site or As site. Clearly in first case it will act as a donor and in latter case it will be an acceptor. Si
prefers to go in Ga sites, hence Si is a donor in GaAs. Zn and C act as acceptors. This implies
C is going in As sites.
All the dopants we have discussed so far are shallow dopants, which means ℰ+ − ℰ* or ℰ- − ℰ.
is of the order of 10-100 meV. In other words, at room temperature we have sufficient energy
to promote electron to conduction and holes to valence band. Dopants are not impurities;
impurities are unintentional and dopants are deliberately added to change 𝑛 and 𝑝.
There are also deep levels impurities, where the impurity levels are deep in the band gap (away
from the band edges) as shown in Fig. 9.3(c). Hence, these levels cannot give or take electrons
easily to conduction and from valence band, respectively or in other words, they cannot be
ionized easily. These will not work as dopants. These deep levels can be good and/or bad

Lecture Notes for MSE303: Electronic and Magnetic properties of Materials Authors: Deepak Gupta, Monica Katiyar and Anshu Gaur
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for the semiconductor. For example, Cu, Au or Fe form deep level impurities and they act as
trap of carriers, electrons or holes), so the carriers trapped in these levels will not be available
for conduction. On the other hand, sometimes these levels provide an intermediary state for
recombination of electron and holes, especially in indirect semiconductors in which
recombination is less probable from conduction band to valence band due to momentum
conservation. This can be understood in terms of 𝑘 space as shown in Fig. 9.4, a localized
level at the impurity (in real space) has a large range of possible 𝑘 values at the same energy in
ℰ − 𝑘 diagram (Fig. 9.4), this allows the deep level impurity to capture both electron and
hole and recombination happens at the impurity site.

Fig. 9.4: Schematic of deep level assisted electron-hole recombination in an indirect band semiconductor.

So, deep level impurities can have a bad or good role. Typically, when we are making semiconductor
devices, we make sure that there are no deep level impurities barring few exceptions.

Ionization of dopants
Suppose we have ionization reactions for a monovalent donor and acceptor as follows (keeping
our discussion to monovalent dopants here, in the lecture we had given a general expression
with the possibility of multivalency of the impurities.)
𝐷1 → 𝐷3 + 𝑒 5
𝐴1 → 𝐴5 + ℎ3
It can be shown using chemical reaction kinetics that the ratio of ionized to non-ionized
donors/acceptors is given by
𝑁*3 ℰ* − ℰ=
1 = exp 𝑘> 𝑇
[9.1]
𝑁*
𝑁-5 ℰ= − ℰ-
1 = exp 𝑘> 𝑇
[9.2]
𝑁-
Where, 𝑁*3 , 𝑁*1 and 𝑁-5 , 𝑁-1 are numbers (per unit volume) of ionized and non-ionized donors and
acceptors respectively.
What does it mean? I have fixed number of donors and acceptors, some are in zero charge states
and some have ionized by exchanging electrons and holes with the conduction and valence
bands, respectively.

Lecture Notes for MSE303: Electronic and Magnetic properties of Materials Authors: Deepak Gupta, Monica Katiyar and Anshu Gaur
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or 𝑁*3 + 𝑁*1 = 𝑁* and 𝑁-5 + 𝑁-1 = 𝑁-
In the band diagram, this means some dopant levels are occupied by electrons or holes and
some are not occupied, and the ratio of ionized to non-ionized donors is given by Eq. 9.1 and 9.2,
we can change this to fraction of ionized donors
𝑁*3 1
= [9.3]
𝑁* 1 + 𝑔 exp ℰ= − ℰ*
* 𝑘> 𝑇
5
𝑁- 1
= [9.4]
𝑁- 1 + 𝑔 exp ℰ- − ℰ=
- 𝑘> 𝑇
Now, we will use this information to get 𝑛 and 𝑝 in an extrinsic semiconductor as a function
of temperature. Remember, our earlier equations for 𝑛 and 𝑝 are still valid provided we
know ℰ= in an extrinsic semiconductor.

Qualitative effect of Fermi level on ionization fraction

Let us first start with a qualitative understanding of effect of the Fermi level on ionization
fraction, if we add some donor to the semiconductor. If (suppose) Fermi energy is
somewhere near the intrinsic level (we have yet to find out where it will be), then the fraction
of donor ionized will be almost 1 according to 9.3 (ℰ𝐹 − ℰ𝐷 is large negative value). If
Fermi energy moves to ℰ𝐷 level itself then fraction ionized is ½ according to equation 9.3. So,
if ℰ𝐹 is at donor level then only half of the donors would have given up their electron. So one
can see that moving the Fermi level can change the ionization fraction. Same argument can be
made for acceptors also.

Compensation and charge neutrality

Suppose we have added 𝑁* donors and 𝑁- acceptors (𝑁* ≫ 𝑁- ), what is the picture at 0K?
Electron from donors can go to acceptors and thereby reduce their overall energy. Now, if we
raise the temperature, then only available electrons (𝑁𝐷 − 𝑁𝐴) can go to conduction band. The
same argument will hold for 𝑁- ≫ 𝑁* .
Further, a material in equilibrium has no charge build up, hence charge neutrality in the material
must be maintained:
𝑁-5 + 𝑛 = 𝑁*3 + 𝑝 [9.5]
Quantitative estimation of 𝒏 and 𝒑
We know from chapter 8, for non-degenerate semiconductor
ℰ= − ℰ+
𝑛 = 𝑁+∗ exp
𝑘> 𝑇
ℰ. − ℰ=
𝑝 = 𝑁.∗ exp
𝑘> 𝑇
Since we do not know ℰ𝐹 apriori, let us find value of 𝑛 and 𝑝 for different conditions of
ionization.

Lecture Notes for MSE303: Electronic and Magnetic properties of Materials Authors: Deepak Gupta, Monica Katiyar and Anshu Gaur
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 Determine 𝒏 and 𝒑 when there is complete ionization
𝑁* ≫ 𝑁- for the following discussion and 𝑁*3 = 𝑁* and 𝑁-5 = 𝑁-
Inserting this into neutrality condition and using the 𝑛𝑝 = 𝑛EF property of semiconductor
(see lecture notes for details), we find the solution for 𝑛 as

𝑁* − 𝑁- + 𝑁* − 𝑁- F + 4𝑛EF [9.6]
𝑛=
2
As you can see, we know all parameters on the right side and hence it is possible to calculate
𝑛 and 𝑝 (using 𝑝 = 𝑛EF 𝑛). For a given dopant level, if 𝑁𝐷 − 𝑁𝐴 ≫ 2𝑛E , we find that 𝑛 = 𝑁* −
𝑁- , which corroborates with our qualitative picture of compensation discussed earlier. Similarly
if 𝑁𝐴 − 𝑁𝐷 ≫ 2𝑛E , we have 𝑝 = 𝑁- − 𝑁* .
Once we know 𝑛 and 𝑝, we can calculate the Fermi level for the extrinsic semiconductor for
this case using equations from chapter 8.

Determine 𝒏 and 𝒑 when there is incomplete ionization

If there is incomplete ionization, then equation 10.6 reduces to

𝑁*3 − 𝑁-5 + 𝑁*3 − 𝑁-5 F + 4𝑛EF [9.7]

𝑛=
2
Now, equation 9.7 for a given semiconductor has to be solved numerically as we know all the
expressions, but solution has to be obtained numerically. We can still look at some special
cases.
First case is when all acceptors are ionized (i.e. 𝑁-5 = 𝑁- ), but all donors are not ionized (i.e. 𝑁*3 ≠
𝑁* ). Since, 𝑁* ≫ 𝑁- , all acceptors will be ionized by accepting electrons from donors (higher
energy level) and some donors will be ionized.
Since all the donors are not ionized, it is also known as freeze out zone (carriers freeze out from
respective band edges, Fig 9.5), as all electrons cannot be excited to the conduction band, this
determines the lower limit of temperature where the exhaustion zone ends. Starting from the
neutrality condition again we can write 𝑁-5 + 𝑛 = 𝑁*3 + 𝑝
Using the ionization fraction expression and assumption that 𝑝 ≪ 𝑛, since 𝑁* ≫ 𝑁-
𝑁*
𝑛 + 𝑁- =
ℰ − ℰ*
1 + exp =
𝑘> 𝑇
Rewriting it as
𝑁*
𝑛 + 𝑁- =
ℰ= − ℰ+ ℰ − ℰ*
1 + exp exp +
𝑘> 𝑇 𝑘> 𝑇
and rearranging terms using equation 8.16
𝑁*
𝑛 + 𝑁- =
𝑛 ℰ − ℰ*
1+ exp +
𝑁+∗ 𝑘> 𝑇

Lecture Notes for MSE303: Electronic and Magnetic properties of Materials Authors: Deepak Gupta, Monica Katiyar and Anshu Gaur
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Observe that there is no Fermi level in this equation and can be rewritten in the following form:

𝑛 𝑛 + 𝑁- ℰ* − ℰ+
= 𝑁+∗ exp [9.8]
𝑁* − 𝑁- − 𝑛 𝑘> 𝑇
Since we are looking at freeze-out region, we know 𝑁𝐷 − 𝑁𝐴 > 𝑛 (𝑁𝐷 > 𝑛, as 𝑁* ≫ 𝑁- ), now
there can be two cases, when 𝑛 > 𝑁- and 𝑛 < 𝑁- .
(i) when 𝑛 > 𝑁- , equation 9.8 reduces to
ℰ* − ℰ+
𝑛F = 𝑁+∗ 𝑁* exp [9.9]
𝑘> 𝑇
ℰ𝐷 − ℰ𝑐
or 𝑛 ∝ exp
2𝑘𝐵 𝑇
and this is shown in Fig. 9.5 as the first slope in the “freeze out zone”. I suggest that you workout
the second case, (ii) 𝑛 < 𝑁- to show that
ℰ𝐷 − ℰ𝑐
𝑛 ∝ exp
𝑘𝐵 𝑇
shown as the second slope in the “freeze out zone” (Fig. 9.5).

Fig. 9.5 Schematic of temperature dependence of carrier concentration in an extrinsic semiconductor

The discussion above for complete and in-complete ionization and compensation can be easily
visualized from Fig. 9.5 where temperature dependence of carrier concentration (𝑛 for example)
is plotted. You can clearly see three different regions in the plot namely “intrinsic region”,
“exhaustion region” and “freeze out zone”.
Yes, even doped semiconductors start to behave like intrinsic semiconductor above a certain
temperature. (Doping is limited and limits extrinsic carrier concentration; however, intrinsic
carrier concentration increases exponentially with temperature and at some temperature starts to

Lecture Notes for MSE303: Electronic and Magnetic properties of Materials Authors: Deepak Gupta, Monica Katiyar and Anshu Gaur
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exceed the doping.) Beyond this temperature, we have equal concentration of 𝑛 and 𝑝, which is
the hallmark of intrinsic semiconductor. For this reason, semiconductors can only be used upto a
certain maximum temperature (and that is why we have cooling fans in our computers).
In the “exhaustion region” the carrier concentration remains constant with respect to temperature
and is defined by doping concentrations (𝑁* and 𝑁- , since all the dopants are ionized) which can
be reproducibly controlled. Most of the semiconductor devices work within the temperature zone
defined by the exhaustion region.
If we decrease the temperature further, the dopants start to “freeze out” or in other words, they are
no longer ionized (incomplete ionization). The start of “freeze out zone” represents the minimum
temperature at which semiconductor devices can be used reliably.

Lecture Notes for MSE303: Electronic and Magnetic properties of Materials Authors: Deepak Gupta, Monica Katiyar and Anshu Gaur
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