Point defects ionic crystals

¾ Ionic bonding and ionic crystals: Brief review

¾ Defects in ionic crystal and oxides. Kröger-Vink Notation
¾ Site, mass, and charge balance
¾ Frenkel and Schottky defects
¾ Extrinsic point defects in ionic crystals - impurities
¾ Non-stoichiometry in ionic crystals

Electronic defects in semiconductors

optional reading
¾ Electronic defects in intrinsic semiconductors (not tested)
¾ Extrinsic electronic defects in semiconductors - doping

References:
Allen & Thomas, Ch. 5, pp. 263-270
Swalin: Ch. 14, pp. 317-350

University of Virginia, MSE 6020: Defects and Microstructure in Materials, Leonid Zhigilei
 Ionic bonding: Brief review
Ionic bonding - typical between elements from horizontal extremities of the periodic table

give up 1e-
give up 2e-

accept 2e-
accept 1e-

inert
Electronegativity - a measure of how
give up 3e- willing atoms are to accept electrons

Electropositive elements: Readily give up Electronegative elements: Readily acquire

electrons to become positive ions (cations) electrons to become negative ions (anions)

IA: Alkali metals (Li, Na, K…) - one electron in outermost occupied s subshell - eager to give up electron
VIIA: Halogens (F, Br, Cl...) missing one electron in outermost occupied p subshell - want to gain electron
Metals are electropositive – they can give up their few valence electrons to become positively charged ions
University of Virginia, MSE 6020: Defects and Microstructure in Materials, Leonid Zhigilei
 Ionic bonding: Brief review
Example: table salt (NaCl)
Na has 11 electrons, 1 more than needed for a full outer shell (Neon)
11 Protons Na 1S2 2S2 2P6 3S1 donates e- e-
Na Cl
11 Protons Na+ 1S2 2S2 2P6 10 e- left

Cl has 17 electron, 1 less than needed for a full outer shell (Argon)
17 Protons Cl 1S2 2S2 2P6 3S2 3P5 receives e- Na+ Cl-
17 Protons Cl- 1S2 2S2 2P6 3S2 3P6 18 e-

Cohesive energy of NaCl crystal (energy needed to convert NaCl

crystal into individual Na and Cl atoms):
Na (gas) + 5.14 eV (ionization energy) → Na+ + e-
e- + Cl (gas) → Cl- + 3.61 eV (electron affinity)
energy of (long-range) interaction among the ions
Na+ + Cl- → NaCl (crystal) + 7.9 eV
balance: ΔE = 7.9 eV - 5.1 eV + 3.6 eV = 6.4 eV per NaCl formula unit

< 0 → it costs energy to transfer e from Na to Cl

University of Virginia, MSE 6020: Defects and Microstructure in Materials, Leonid Zhigilei
 Ionic crystals: Brief review
• Charge neutrality: the total charge in the base must be zero
• There are no free electrons, ionic crystals are insulators
• Interatomic bonding is mostly defined by long-range inter-ionic Coulomb interactions ±q2/r
and is rather strong (Ec ~ 600-1000 kJ/mol ~ 6-10 eV/atom) and has no directionality

NaCl structure
fcc with 2 atoms in the base: Na+ ions filling octahedral
at (0, 0, 0) and (½, 0, 0) holes in the fcc structure

KCl, AgBr, KBr, PbS,

MgO, FeO

fluorite structure
fcc with 3 atoms in the base: F- ions filling tetrahedral
cations at (0,0,0) and two anions holes in the fcc structure
at (¼, ¼, ¼), and (¼, ¾, ¼)

CaF2 or ZrO2

University of Virginia, MSE 6020: Defects and Microstructure in Materials, Leonid Zhigilei
 Ionic crystals: Brief review
zinc blende structure
fcc with two atoms in the base
at (0,0,0) and (¼, ¼, ¼)
ZnS, CuF, CuCl
GaAs, GaP, InP- semiconductors
CsCl structure
simple cubic with two atoms in
the base at (0,0,0) and (½, ½, ½)
CsCl, TlI, TlCl
AlNi, CuZn - intermetallic comp.

tetrahedral sites are preferred because of the

relative sizes of the positive and negative ions, but
not all of them are filled to maintain stoichiometry

spinel structure
named after the mineral spinel (MgAl2O4)
Fe3+( Fe2+ Fe3+)O4, Mg2+( Al23+)O4, Fe3+(Cr23+)O4
can contain vacancies as an integral part of the
structure to satisfy the charge balance,
Fe21,67Vac2,33O32 if all Fe converted to Fe+3

University of Virginia, MSE 6020: Defects and Microstructure in Materials, Leonid Zhigilei
 Defects in ionic crystal and oxides. Kröger-Vink Notation
Introduction of a concentration α of vacancies to Na+ sites (or the same
concentration of Cl- interstitials) creates net charge of -eαN charge in a
crystal with N lattice sites → very high energy → Na1-αCl cannot exist
pure ionic crystals must be perfectly stoichiometric (?)
introduction of impurities with different valence and electronegativity
than the host ions can require additional point defects to charge balance

The concentration of vacancies can be much higher than required by thermal equilibrium -
electrochemical equilibrium must be maintained. How to incorporate point defects into chemical
reaction equations?
Kröger-Vink Notation: X YZ
X – nature of species located on a site: element symbol for an atom, V for vacancy
Y – type of the site occupied by X: (i for an interstitial, element symbol for site normally
occupied by this element)
Z – charge relative to the normal ion charge on the site
′ negative relative charge
• positive relative charge
x zero relative charge (x is often omitted)

University of Virginia, MSE 6020: Defects and Microstructure in Materials, Leonid Zhigilei
 Kröger-Vink Notation X YZ

Examples:
interstitial Ag ion in AgCl: Ag•i In a generic discussion of defect
vacancy on a Ag site in AgCl:
'
VAg reactions, M and X are often used:
M - atom of electropositive element
Ca2+ ion on a Na site in NaCl: Ca•Na
X - atom of electronegative element
vacancy on an O site in Al2O3: VO••
Cu+ on a Cu2+ site CuO: Cu'Cu

Intrinsic point defects and Pu

X U4+ ion O2- ion Vacancy Pu4+ ion
Y
impurity in UO2 crystal U site UxU O'U''''' VU'''' Pu xU
O site U•O••••• OOx VO•• Pu•O•••••
i site U•i ••• Oi'' Vix Pu•i •••

University of Virginia, MSE 6020: Defects and Microstructure in Materials, Leonid Zhigilei
 Site, mass, and charge balance
Formation and annihilation of point defects in ionic crystals must satisfy the following 3 rules:

1. Site balance
– Ratios of regular lattice sites must be conserved, i.e., fixed proportion of M
and X sites must be created regardless of whether they are occupied or not.
Total number of sites may change, but the ratio must remain constant.
Example: Al2O3: by oxidation of aluminum create 3OO then 2AlAl must
also be created, although they may be vacant.
2. Mass balance
– Total number of atoms of each species on right and left side of defect formation reaction
must be equal
– Vacancies and electronic defects do not affect mass balance

3. Charge balance (electroneutrality)

– Compounds are assumed to remain neutral

Any charge inbalance, global or local, leads to high electrostatic energy that exceed any
other contributions to the Gibbs free energy, making the charged state to be strongly
nonequilibrium one.

University of Virginia, MSE 6020: Defects and Microstructure in Materials, Leonid Zhigilei
 Frenkel defects
Frenkel defect (Frenkel pair) = vacancy + interstitial in close proximity
first discussed in 1926 by Frenkel for AgCl
+
two types of Frenkel defects:
• cation Frenkel pair: cation vacancy + cation interstitial
• anion Frenkel pair: anion vacancy + anion interstitial
Typically, the enthalpies of formation are very different for the two types and, in
a given crystal, one type of Frenkel defect is prevalent.

formation reaction for a cation Frenkel pair in AgCl: AgxAg ↔ Ag•i + VAg
'

this reaction satisfies the mass, charge, and site balance

Analysis of the equilibrium concentration of Frenkel defects can be done similarly to our
derivation for vacancies. We just have to keep in mind that both vacancy and self-interstitial are
generated and ni = nv = nFP

University of Virginia, MSE 6020: Defects and Microstructure in Materials, Leonid Zhigilei
 Frenkel defects
Equilibrium concentration of Frenkel defects: ΔG = n FP ( Δh FP
f − T Δs f ) − T Δ S c
FP n

N! N i! where Ni is the number of interstitial sites (may

S = k B ln v
n
+ k B ln i
c
n ! N −n !
v
( )
n ! N i − ni ! ( ) depend on configuration, e.g., dumbbell vs. octahedral)

n i = n v = n FP
1/ 2
∂Δ G ⎛ neq neq ⎞ neqFP ⎛ Ni ⎞ ⎛ ΔsvFP ⎞ ⎛ Δh FP ⎞
= Δh FP
− TΔs FP
+ k BT ln ⎜⎜ ⎟=0
i ⎟ = ⎜⎜ ⎟⎟ exp ⎜⎜ ⎟⎟ exp ⎜ − f
⎟
∂n FP
f v
⎝ N N ⎠ ⎜ 2k T ⎟
n FP = neq
FP N ⎝ N ⎠ ⎝ 2k B ⎠ ⎝ B ⎠

compound reaction Δh FP
f , eV
to measure the concentration of intrinsic
AgBr x
AgAg ↔ Ag•i + VAg'
1.1
point defects, ionic crystals of high purity
FFx ↔ VF• + Fi' 2.3-2.8 have to be made, e.g., by zone refining
CaF2 x
CaCa ↔ Ca•i • + VCa
''
7
Li2O x
LiLi ↔ Lii• + VLi' 2.3
Δh FP
f includes energy of electrostatic interactions
OOx ↔ VO•• + Oi'' 8.7
TiO2 x
TiTi ↔ Tii•••• + VTi'''' 12
OOx ↔ VO•• + Oi'' 3.0
UO2 many more anion Frenkel defects than cation ones
UxU ↔ U•i ••• + VU'''' 9.5
ZnO OOx ↔ VO•• + Oi'' 2.5 from Allen & Thomas
University of Virginia, MSE 6020: Defects and Microstructure in Materials, Leonid Zhigilei
 Schottky defects
Schottky defect = cation vacancy + anion vacancy in close proximity

formation reaction for a Schottky defect in BeO:

x
BeBe + OOx ↔ VBe
''
+ VO•• + BeBe
x
+ OOx
this reaction satisfies the mass, charge, and side balance

electrostatic attraction between cation and

anion vacancies → binding energy of the
compound Schottky defect Δh SD
f , eV Schottky defect and temperature dependent
α-Al2O3 2VAl''' + 3Vo•• 26 degree of association

CaF2 ''
VCa + 2VF• 5.5 equilibrium concentration:
BeO ''
VBe + VO•• 6
neqSD ⎛ ΔsvSD ⎞ ⎛ Δh SD ⎞
TiO2 V + 2V
'''' ••
5.2 = exp ⎜⎜ ⎟⎟ exp ⎜ − f
⎟
⎜ 2k T ⎟
⎝ 2k B
Ti O
••
N ⎠ ⎝ B ⎠
UO2 V + 2V
''''
U O 6.4
•
NaCl V +V
'
Na Cl 2.2-2.4
• relative low Δhf → Schottky defects dominate
KCl VK' + V Cl 2.6
from Allen & Thomas
University of Virginia, MSE 6020: Defects and Microstructure in Materials, Leonid Zhigilei
 Extrinsic point defects in ionic crystals - impurities
Introduction of impurities may require simultaneous introduction of additional defects, e.g., in
addition to the thermally-induced (intrinsic) vacancies, some additional extrinsic vacancies may
be induced by impurity ions with valence different from the one of the ions in the host crystal.
Let’s consider incorporation of CaCl2 to KCl crystal as a substitutional impurity:
CaCl2 (s) + 2K Kx + 2ClCl
x
↔ Ca •K + VK' + 2ClCl
x
+ 2KCl(g)
or CaCl2 ↔ Ca •K + VK' + 2ClCl
x

Site balance: the 1:1 ratio of K and Cl sites must be maintained. Two Cl anions occupy the
existing Cl sites → two cation sites must be created. One of the cation sites is occupied by Ca2+
and one is left vacant.
Mass balance: the numbers of atoms of each species on both sides of the equation are equal.

Charge balance: placing Ca2+ on a K+ gives a net charge of +1 that has to be compensated by a
vacancy.

If Ca2+ occupies an interstitial site, the equation has to be modified:

CaCl2 (s) + 2K Kx + 2ClCl
x
↔ Ca i•• + 2VK' + 2ClCl
x
+ 2KCl(g)

or CaCl2 ↔ Ca i•• + 2VK' + 2ClCl

x

University of Virginia, MSE 6020: Defects and Microstructure in Materials, Leonid Zhigilei
 Extrinsic point defects in ionic crystals - impurities
Different schemes of impurity incorporation can be sometimes distinguished from experimental
measurements of the effect of impurity concentration on material density.

Let’s consider incorporation of ZrO2 to Y2O3 crystal

Two simplest options:

(1) Zr4+ fully occupy Y sites and anion defects take care of the charge balance
2ZrO2 ↔ 2ZrY• + 3O Ox + Oi''

(2) O2- fully occupy O sites and cation defects take care of the charge balance
3ZrO2 ↔ 6O Ox + 3ZrY• + VY'''
Experimental observation that density of Y2O3 increases with addition of ZrO2 is in favor of
option (1), since appearance of vacancies would decrease density and Zr has slightly higher
atomic mass and smaller ionic radius than Y.

University of Virginia, MSE 6020: Defects and Microstructure in Materials, Leonid Zhigilei
 Extrinsic point defects in ionic crystals - impurities
Let’s consider incorporation of CaO to ZrO2 Ca2+ cation, Zr4+ cation, O2- anion
We have two possible scenarios:
(1) charge compensation by anion vacancy CaO ↔ Ca 'Zr' + O Ox + VO••

(2) charge compensation by Zr interstitials 2CaO + ZrZrx ↔ 2Ca 'Zr' + 2O Ox + Zri••••

site balance: 1Zr = 2Zr + 2O need an extra Zr site

null = ZrO2 2CaO + ZrZrx + 2O Ox + ZrZrx ↔ 2Ca 'Zr' + 2O Ox + Zri•••• + ZrO2
Solid solutions produced by these different reactions will have different densities.
For reaction (1), the defective formula unit is made up of one Ca, one O, and one vacancy.
For reaction (2), the defective formula unit is made up of one Ca, two O, and one half of a Zr (in
an interstitial site). Thus, the formulas for weight and density of each solid solution are:
1
(1) x(M CaO ) + (1 − x)M ZrO2 (2) x(M CaO2 + M Zr ) + (1 − x)M ZrO2
2
Z × [ x(M CaO ) + (1 − x)M ZrO2 ] Z × [ x(M CaO2 + 0.5M Zr ) + (1 − x)M ZrO2 ]
ρ= ρ=
N aVcell N aVcell

where M is the molecular weights of the corresponding species, Vcell is the volume of the unit
cell, and ZofisVirginia,
University the number of6020:
MSE formula unitsand
Defects perMicrostructure
unit cell. in Materials, Leonid Zhigilei
 Extrinsic point defects in ionic crystals - impurities
CaO ↔ Ca 'Zr' + O Ox + VO•• 2CaO + ZrZrx ↔ 2Ca 'Zr' + 2O Ox + Zri••••

Z × [ x(M CaO ) + (1 − x)M ZrO2 ] Z × [ x(M CaO2 + 0.5M Zr ) + (1 − x)M ZrO2 ]

ρ= ρ=
N aVcell N aVcell

small amount of CaO stabilizes cubic fluorite structure a

(we are neglecting changes in the size of the unit cell with composition) 4×(ZnO2) per unit cell

For x = 0.15, Z = 4, MCaO = 56.2 g/mole, MZrO2 = 123.2 g/mole,

MCaO2 = 72.1 g/mole, MZr = 91.2 g/mole, and the cubic lattice
constant a = 5.15 Å, we calculate densities of ρ = 5.5 g/cm3 and
ρ = 5.95 g/cm3 for the vacancy and interstitial models, respectively.

Thus, the two hypothetical models predict ~8% difference in

ρ, g/cm3
the density. When mass and volume measurements can be
done with sufficient accuracy, it is possible to distinguish the
models.

Experiments by Diness and Roy [Solid State Commun. 3, 123, 1965]

University of Virginia, MSE 6020: Defects and Microstructure in Materials, Leonid Zhigilei
 Extrinsic point defects in ionic crystals - impurities
concentration of point defects in
KCl with 0.1 ppm CaCl2

intrinsic (Schottky) defects:

K Kx + ClCl
x
↔ VK' + VCl• + K Kx + ClCl
x

neqSD ⎛ ΔsvSD ⎞ ⎛ Δh SD ⎞
= exp ⎜⎜ ⎟⎟ exp ⎜ − f
⎟
⎜ 2k T ⎟
N ⎝ 2k B ⎠ ⎝ B ⎠

ln(10-7) = 16.12 Δh SD
f = 2.6 eV

extrinsic defects
CaCl2 ↔ Ca •K + VK' + 2ClCl
x

extrinsic defects dominate at low T

from Allen & Thomas

University of Virginia, MSE 6020: Defects and Microstructure in Materials, Leonid Zhigilei
 Non-stoichiometry
While some of the compounds become unstable at small deviations from stoichiometric
composition (e.g. NaCl), other compounds can exhibit large deviations from stoichiometric
composition or even be unstable at the stoichiometric composition (e.g. FeO - wüstite
phase).
MO M1−δO
1
For a transfer of oxygen to a metal oxide MO: O2 ( g ) ↔ OOx + VM (transfer of neutral O)
2
But if the crystal is ionic, O will accept 2 e- that should 1
O2 ( g ) ↔ OOx + 2h• + VNi''
come from metal that is already ionized, e.g., for NiO: 2

O2- Ni2+ O2- Ni2+ O2- Ni2+ O2- Ni2+ O2-

1
2+ 2+ O2 ( g )
Ni O 2-
Ni O 2-
2 Ni2+ • O2- VNi'' O2- Ni2+
h 2+
O2- Ni2+ O2- Ni2+ O Ni • O2- Ni2+
2-

h
Ni2+ O2- Ni2+ O2- Ni2+ O2- Ni2+ O2-
cation vacancy + 2 holes
Ni2+ can then transform into Ni3+ (2 Ni ions have to be transformed for each vacancy)
(equivalent to solution of Ni2O3 in NiO)
This scenario works for transition metals (e.g., Fe, Ti, Cu, Ni), where the ionization energy is
low, but not for metals with high ionization energy (e.g. Na or K)
University of Virginia, MSE 6020: Defects and Microstructure in Materials, Leonid Zhigilei
 Non-stoichiometry

University of Virginia, MSE 6020: Defects and Microstructure in Materials, Leonid Zhigilei
 Electronic defects in semiconductors

¾ Electronic defects in intrinsic semiconductors

¾ Extrinsic electronic defects in semiconductors - doping

optional reading
(not tested)

University of Virginia, MSE 6020: Defects and Microstructure in Materials, Leonid Zhigilei
 insulators - semiconductors - metals

σ = n|e|μe + p|e|μh
σ (Ωcm)-1

n ~ 1 cm-3 n ≈ 1.4×1010 cm-3 (Si at 300 K) n ≈ 1.8×1023 cm-3 (Al)

n - number of “free” or conduction electrons per unit volume
partially filled band overlapping bands

Energy
Energy Energy
Energy empty empty
empty
conduction conduction
band band band
? GAP empty
Eg > 2 eV Eg < 2 eV band
filled partly
filled filled filled
filled states

filled states
filled states

valence valence band

filled states
band
band band

filled filled filled filled

band band band band

Cu: 1s22s22p63s23p63d104s1 Mg: 1s22s22p63s2

University of Virginia, MSE 6020: Defects and Microstructure in Materials, Leonid Zhigilei
 Electronic defects in intrinsic semiconductors
ε ε
conduction band T=0K electrons, e T>0K
EC
Eg
Fermi level, EF
EV

valence band holes, h

0 1 f(ε) 0 1 f(ε)
EF represents probability of ½ that an available Thermal generation of electron-hole pairs.
energy state is occupied by an electron Electrons excited to the conduction band leave holes
EF = electrochemical potential of electrons in the valance band

The concentration of electrons, n, in the conduction band

material Eg, eV
−1 3/ 2
∞ ∞
⎡ ⎛ ε − EF ⎞⎤ ⎛ 2πme*kBT ⎞ ⎛ E − EF ⎞
Si 1.1 n = ∫ g (ε) f (ε, T )dε = ∫ g (ε)⎢1 + exp⎜⎜ ⎟⎟⎥ dε ≈ 2⎜⎜ 2
⎟⎟ exp⎜⎜ − C ⎟⎟
EC EC ⎣ ⎝ kBT ⎠⎦ ⎝ h ⎠ ⎝ kBT ⎠
SiC 2.9
3/ 2
ZnO 3.3 ⎛ 2me* ⎞
We used the free electron gas model approximations: g (ε) = 4π⎜⎜ 2 ⎟⎟ (ε − EC )1/ 2
Al2O3 9.5 ∞
⎝ h ⎠
⎛ ⎞ ⎛ ⎞
as well as 1 + exp⎜⎜ ε − EF ⎟⎟ ≈ exp⎜⎜ ε − EF ⎟⎟ and ∫ x exp(− x) = π / 2
⎝ kBT ⎠ ⎝ kBT ⎠ 0
University of Virginia, MSE 6020: Defects and Microstructure in Materials, Leonid Zhigilei
 Electronic defects in intrinsic semiconductors
ε 3/ 2
⎛ 2πme*kBT ⎞ ⎛ E − EF ⎞ ⎛ E − EF ⎞
n = 2⎜⎜ 2
⎟⎟ exp⎜⎜ − C ⎟⎟ = Neff
C
exp⎜⎜ − C ⎟⎟
⎝ h ⎠ ⎝ kBT ⎠ ⎝ kBT ⎠
EC
Similarly, the concentration of holes, p, in the valence band
3/ 2
EV ⎛ 2πmh*kBT ⎞ ⎛ E − EV ⎞ ⎛ E − EV ⎞
p = 2⎜⎜ ⎟⎟ exp⎜⎜ − F ⎟⎟ = Neff
V
exp⎜⎜ − F ⎟⎟
g(ε) ⎝ h
2
⎠ ⎝ kBT ⎠ ⎝ kBT ⎠
C V
Neff and Neff - effective densities of state at the conduction and valence band edges

for an intrinsic semiconductor:

Eg
3 mh* Eg
ni = n = p EF = + kBT ln * ≈
2 4 me 2

intrinsic concentration of charge carriers:

⎛ Eg ⎞
ni = np = Neff
C V
Neff exp⎜⎜ − ⎟⎟ n = C T3/2 exp(-Eg/2kT)
⎝ 2kBT ⎠

depends only on T and Eg = EC -EV

University of Virginia, MSE 6020: Defects and Microstructure in Materials, Leonid Zhigilei
 Electronic defects in intrinsic semiconductors
3/ 2
⎛ 2πme*kBT ⎞ ⎛ Eg ⎞ ⎛ Eg ⎞
n = 2⎜⎜ 2
⎟⎟ exp⎜⎜ − ⎟⎟ = Neff
C
exp⎜⎜ − ⎟⎟
⎝ h ⎠ ⎝ B ⎠
k T ⎝ 2k B ⎠
T
3/ 2
⎛ 2πme*kBT ⎞
for T = 1500 K
C
Neff = 2⎜⎜ 2
⎟⎟ = 2.8 ×1026 m-3
⎝ h ⎠
⎛ Eg ⎞
h = 6.626×10−34 Js exp⎜⎜ − ⎟⎟ = 0.014
⎝ 2k B ⎠
T
kB = 1.381×10−23 J/K
me* ≈ 9.11×10−31 kg surprisingly good semi-
quantitative agreement,
given that very rough
approximations are used, e.g.
g(ε) for free electron model,
Eg = 0.67 eV for Ge
decrease of Eg with
increasing T is neglected… Eg = 1.11 eV for Si

- can find Eg from the temperature dependence of

intrinsic carrier concentration

University of Virginia, MSE 6020: Defects and Microstructure in Materials, Leonid Zhigilei
 Electronic defects in extrinsic semiconductors
Extrinsic semiconductors - electrical conductivity is defined by impurity atoms.
Si is considered to be extrinsic at room T if impurity concentration is one impurity per 1012 lattice sites
Unlike intrinsic semiconductors, an extrinsic intrinsic: n ≈ 1.4×1016 m-3 (Si at 300 K)
semiconductor may have different molar volume of Si ≈12 cm3/mol
concentrations of holes and electrons. NA ≈ 6×1023 atoms/mol
6×1023 / 12×10-6 = 5×1028 atoms/m3
p-type if p > n and n-type if n > p fraction of excited intrinsic electrons per atom ~10-13

One can engineer conductivity of extrinsic semiconductors by controlled addition of impurity

atoms – doping (addition of a very small concentration of impurity atoms). Two common
methods of doping are diffusion and ion implantation.

n-type: excess electron carriers are produced by substitutional impurities that have more valence electron per
atom than the semiconductor matrix (elements in columns V and VI of the periodic table are donors for
semiconductors in the IV column, Si and Ge)
Example: P (or As, Sb..) with 5 valence electrons, is an electron donor in Si since only 4 electrons are used to
bond to the Si lattice when it substitutes for a Si atom. Fifth outer electron of P atom is weakly bound in a
donor state (~ 0.01 eV) and can be easily promoted to the conduction band.

p-type: excess holes are produced by substitutional impurities that have fewer valence electrons per atom
than the matrix (elements in columns III of the periodic table (B, Al, Ga) are donors for semiconductors in
the IV column, Si and Ge)

University of Virginia, MSE 6020: Defects and Microstructure in Materials, Leonid Zhigilei
 Electronic defects in extrinsic semiconductors
Ec Ec Ec Ec
EF Ed EF Ed
EF EF Ea
EV Ea EV
EV EV

T = 0K T > 0K T = 0K T > 0K

donor dopant creates energy level near conduction
band
easy to promote electron from donor level to
conduction band
Fermi level moves toward conduction band
acceptor dopant creates energy level near valence
band
easy to promote electrons from valence levels to
acceptor band (create holes are in valence band)
Fermi level moves toward valence band.

Out of the total number of dopants (substitutional extrinsic point defects), some will be neutral
and some ionized. For example, for P in Si, the total concentration [P] = [P]0 + [P]+

⎛ E − Ed ⎞
[P+ ] = [P]{1 − f (Ed , EF , T)} ≈ [P] exp⎜⎜ F ⎟⎟
⎝ kBT ⎠

vacancies can also introduce energy levels within the band gap and can be ionized
University of Virginia, MSE 6020: Defects and Microstructure in Materials, Leonid Zhigilei