Question #1. How carrier density varies with temperature?
What is the effect of temperature on donor/acceptor concentration?
Donor atoms/acceptor atoms need energy for its activation/ionization. This energy is
the thermal energy (kBT). If there are sufficient donor/acceptor atoms, and sufficient
thermal energy is not available for ionization/activation, what will happen?
Question #2. What is freeze-out effect?
Can an N-type semiconductor be converted into a P-type one?
Question #3. What is Dopant Compensation?
We need both type of carriers, viz. N- and P-type for device applications, say, for
fabrication of p-n junction.
Question #4. Can all the semiconductors be doped with both p- and n-type?
Donor activation, providing one additional negative carrier to the lattice:
D D e N D N D e
Acceptor activation provides one additional positive charge carrier (hole) to the lattice:
A A h N A N A h
Energy levels for an isolated hydrogen atom are given by the Bohr model:
m0 q 4
E H 2 2 2
8 0 h n
We can estimate the ionization energy for the donor ED by replacing m0 with the electron effective mass
me* and taking into account the semiconductor permittivity εs in the hydrogen atom model.
2
0 me*
E D E H
s m0
Measured ionization energies (in eV) for various impurities in Si and GaAs. The levels below the gap center are
measured from the top of the valence band and are acceptor levels unless indicated by D for donor level. The
levels above the gap center are measured from the bottom of the conduction band and are donor levels unless
indicated by A for acceptor level.
Semiconductor Devices, 2/E by S. M. Sze
Copyright © 2002 John Wiley & Sons. Inc. All
rights reserved.
There are four types of charged species in a semiconductor:
(i) Electrons (n), (ii) Holes (p), (iii) Positive donor ions (Nd), and (iv) Negative acceptors ions (Na).
Charge neutrality requires that the densities of the negative particles and positive particles are equal:
n Na p Nd
2
Also we have np ni
Combining the above two expressions, we can solve for n and p:
1 1
Nd Na Nd Na
2
Na Nd Na Nd
2 2 2
2
n ni p 2
ni
2 2 2 2
Simplification:
1 1
Na Nd Na Nd
2
Nd Na Nd Na
2 2 2
2
n 2
ni p ni
2 2 2 2
1. Nd – Na >>ni (i.e., N-type), 2. Na – Nd >>ni (i.e., P-type),
n N d N a p N a N d
ni2 ni2
p n
n p
If, furthermore, Nd>>Na, then If, furthermore, Na>>Nd, then
n N d p N a
ni2 ni2
p n
Nd Na
n N d N a p N a N d
ni2 ni2
p n
n p
So, we find an acceptor can effectively negate the effect of a donor or vice versa.
This fact is known as Dopant Compensation.
One can start with p-type Si and convert a portion of it into N-type simply by adding enough
donors. This is one of the techniques employed to make p-n junction.
What are values of n and p in a Si sample with Nd = 6 x 1016 cm-3 and Na = 2 x 1016 cm-3? What
would be their values if 6 x 1016 cm-3 acceptors are added to the sample?
Eg
ni N C NV exp
2kT
At very high temperature, ni is large and it is possible to have ni N d N a
1 1
Nd Na Nd Na
2
Na Nd Na Nd
2 2 2
2 2
n ni p ni
2 2 2 2
Then from the above two expressions: n = p = ni
The semiconductor becomes intrinsic at very high temperature.
At very low temperature, most of the donor (or acceptor, in case of P-type) atoms can remain
nonionized. [The fifth electrons stay with the donors].
This phenomenon is called carrier freeze-out effect.
The carrier concentration may be significantly less than the dopant concentration.
Intrinsic carrier densities in Si and GaAs as
a function of the reciprocal of temperature.
Semiconductor Devices, 2/E by S. M. Sze
Copyright © 2002 John Wiley & Sons. Inc. All rights
reserved.
Carrier freeze-out
1
N N 2 E Ed
n c d exp c
2 2kT
Freeze-out is a concern when semiconductor devices are operated at the liquid nitrogen temperature
(77 K) or liquid helium temperature (4.2 K) in order to achieve low noise and high speed.
Electron density as a function of
temperature for a Si sample with a
donor concentration of 1015 cm-3.
Semiconductor Devices, 2/E by S. M. Sze
Copyright © 2002 John Wiley & Sons. Inc. All rights
reserved.
Stoichiometric Compounds: Compounds those have an integer ratio of atoms.
CaF2: two F atoms bond with one Ca atom.
ZnO: if there is one O atom for every Zn atom, the compound is stoichiometric
Since there are equal numbers of O2- anions and Zn2+ cations, the crystal is overall neutral.
It is also possible to have non-stoichiometric ZnO in which there is excess zinc (insufficient oxygen during
the preparation of ZnO).
Baodan Liu
Northeastern University
(a) S toichiom etric Z nO crystal w ith equal num ber of
anions and cations and no free electrons.
O2
Z n2 +
" F ree" (or m obile)
electron w ithin the
cry sta l.
(b) N on-S toichiom etric Z nO crystal w ith excess Z n in
interstitial sites as Z n 2 + cations.
Fig. 1.54: Stoichiometry and nonstoichiometry and the
resulting defect structure.
From Principles of Electronic Materials and Devices, Second Edition, S.O. Kasap (© McGraw-Hill, 2002)
[Link]
Zn2+ ion has a radius of 0.074 nm, which is about 1.9 times smaller than the O 2- anion (radius =
0.14 nm), so it is much easier for a Zn2+ ion to enter an interstitial site than the O2- ion or the
Zn atom itself which has a radius of 0.133 nm.
Excess Zn atoms therefore occupy interstitial sites as Zn2+ cations. Even though the excess Zn
atoms are still ionized within the crystal, their lost electrons cannot be taken by oxygen atoms
which are all O2- anions.
Thus the non-stoichiometric ZnO with excess Zn has Zn2+ cations in interstitial sites and mobile
electrons within the crystal, which can contribute to the conduction of electricity (n-type).
ZnO cannot be doped p-type because of self-compensation caused by native defects:
for instance, in an attempt to dope the material p type, certain native defects which acts as
donors may spontaneously form and compensate the deliberately introduced acceptors.
When EF moves close to the valence band maximum (VBM), spontaneously, the formation
energy of the charge donor defects decreases because they will donate the electrons into
Fermi reservoir.
Solubility of dopants and concentration of intrinsic defects are depended on the growth
conditions