Chapter 9: Phase Diagrams

ISSUES TO ADDRESS...
• When we combine two elements...
what is the resulting equilibrium state?
• In particular, if we specify...
-- the composition (e.g., wt% Cu - wt% Ni), and
-- the temperature (T)
then...
How many phases form?
What is the composition of each phase?
What is the amount of each phase?

Phase A Phase B

Nickel atom
Copper atom Chapter 9 - 1
 Phase Equilibria: Solubility Limit
• Solution – solid, liquid, or gas solutions, single phase
• Mixture – more than one phase Adapted from Fig. 9.1,
Callister & Rethwisch 8e.

Sugar/Water Phase Diagram

• Solubility Limit: 100
Maximum concentration for Solubility

Temperature (ºC)
which only a single phase 80 Limit L
solution exists. (liquid)
60 +
L
Question: What is the 40 (liquid solution S
solubility limit for sugar in i.e., syrup) (solid
water at 20ºC? 20 sugar)

Answer: 65 wt% sugar.

0 20 40 6065 80 100
At 20ºC, if C < 65 wt% sugar: syrup

Sugar
Water

C = Composition (wt% sugar)

At 20ºC, if C > 65 wt% sugar:
syrup + sugar Chapter 9 - 2
 Components and Phases
• Components:
The elements or compounds which are present in the alloy
(e.g., Al and Cu)
• Phases:
The physically and chemically distinct material regions
that form (e.g., a and b).

Aluminum- b (lighter
Copper
phase)
Alloy

a (darker
Adapted from chapter-
opening photograph,
phase)
Chapter 9, Callister,
Materials Science &
Engineering: An
Introduction, 3e.

Chapter 9 - 3
 Effect of Temperature & Composition
• Altering T can change # of phases: path A to B.
• Altering C can change # of phases: path B to D.
B (100ºC,C = 70) D (100ºC,C = 90)
1 phase 2 phases
100

80 L
Temperature (ºC)

(liquid)
water- 60 +
sugar L S
system (liquid solution (solid
40 i.e., syrup) sugar)
20 A (20ºC,C = 70)
2 phases
Adapted from Fig. 9.1, 0
Callister & Rethwisch 8e. 0 20 40 60 70 80 100
C = Composition (wt% sugar)
Chapter 9 - 4
 Criteria for Solid Solubility

Simple system (e.g., Ni-Cu solution)

Crystal electroneg r (nm)

Structure
Ni FCC 1.9 0.1246
Cu FCC 1.8 0.1278

• Both have the same crystal structure (FCC) and have

similar electronegativities and atomic radii (W. Hume –
Rothery rules) suggesting high mutual solubility.
• Ni and Cu are totally soluble in one another for all proportions.

Chapter 9 - 5
 Phase Diagrams
• Indicate phases as a function of T, C, and P.
• For this course:
- binary systems: just 2 components.
- independent variables: T and C (P = 1 atm is almost always used).
T(ºC)
Phase
1600 • 2 phases:
Diagram L (liquid)
1500
for Cu-Ni L (liquid) a (FCC solid solution)
system 1400 • 3 different phase fields:
L
1300 L+a
a
1200 a Adapted from Fig. 9.3(a), Callister &
Rethwisch 8e. (Fig. 9.3(a) is adapted from
1100
(FCC solid Phase Diagrams of Binary Nickel Alloys,
P. Nash (Ed.), ASM International,
solution) Materials Park, OH (1991).
1000
0 20 40 60 80 100 wt% Ni Chapter 9 - 6
 Isomorphous Binary Phase Diagram
• Phase diagram: T(ºC)
Cu-Ni system. 1600

• System is: 1500 L (liquid) Cu-Ni

-- binary phase
i.e., 2 components: 1400
diagram
Cu and Ni.
1300
-- isomorphous
i.e., complete 1200 a
solubility of one
component in 1100
(FCC solid
another; a phase solution)
field extends from 1000
0 to 100 wt% Ni.
0 20 40 60 80 100 wt% Ni
Adapted from Fig. 9.3(a), Callister &
Rethwisch 8e. (Fig. 9.3(a) is adapted from
Phase Diagrams of Binary Nickel Alloys,
P. Nash (Ed.), ASM International,
Materials Park, OH (1991).
Chapter 9 - 7
 Phase Diagrams:
Determination of phase(s) present
• Rule 1: If we know T and Co, then we know:
-- which phase(s) is (are) present.
T(ºC)
• Examples: 1600
A(1100ºC, 60 wt% Ni): L (liquid)
1 phase: a

B (1250ºC,35)
1500
Cu-Ni
B(1250ºC, 35 wt% Ni): 1400 phase
2 phases: L + a diagram
1300 a
(FCC solid
1200
Adapted from Fig. 9.3(a), Callister &
solution)
Rethwisch 8e. (Fig. 9.3(a) is adapted from 1100 A(1100ºC,60)
Phase Diagrams of Binary Nickel Alloys,
P. Nash (Ed.), ASM International,
Materials Park, OH (1991). 1000
0 20 40 60 80 100 wt% Ni
Chapter 9 - 8
 Phase Diagrams:
Determination of phase compositions
• Rule 2: If we know T and C0, then we can determine:
-- the composition of each phase. Cu-Ni
T(ºC) system
• Examples:
TA A
Consider C0 = 35 wt% Ni tie line
At TA = 1320ºC: 1300 L (liquid)
Only Liquid (L) present B
CL = C0 ( = 35 wt% Ni) TB
a
At TD = 1190ºC:
1200 D (solid)
Only Solid (a) present TD
Ca = C0 ( = 35 wt% Ni)
20 3032 35 4043 50
At TB = 1250ºC: CL C 0 Ca wt% Ni
Both a and L present Adapted from Fig. 9.3(a), Callister &
Rethwisch 8e. (Fig. 9.3(a) is adapted from
CL = C liquidus ( = 32 wt% Ni) Phase Diagrams of Binary Nickel Alloys, P.
Nash (Ed.), ASM International, Materials
Ca = C solidus ( = 43 wt% Ni) Park, OH (1991).

Chapter 9 - 9
 Phase Diagrams:
Determination of phase weight fractions
• Rule 3: If we know T and C0, then can determine:
-- the weight fraction of each phase. Cu-Ni
• Examples: T(ºC) system
Consider C0 = 35 wt% Ni TA A
tie line
At TA : Only Liquid (L) present 1300 L (liquid)
WL = 1.00, Wa = 0 B
At TD : Only Solid ( a) present TB R S
a
WL = 0, Wa = 1.00
1200 D (solid)
At TB : Both a and L present TD
S 43  35
WL 
20 3032 35 40 43 50
  0.73 CL C0 Ca wt% Ni
R +S 43  32
Adapted from Fig. 9.3(a), Callister &
Rethwisch 8e. (Fig. 9.3(a) is adapted from
R
Wa 
Phase Diagrams of Binary Nickel Alloys, P.
= 0.27 Nash (Ed.), ASM International, Materials
R +S Park, OH (1991).

Chapter 9 - 10
 The Lever Rule
• Tie line – connects the phases in equilibrium with
each other – also sometimes called an isotherm
T(ºC) What fraction of each phase?
tie line
Think of the tie line as a lever
1300 L (liquid)
(teeter-totter)
B
TB ML Ma
a
1200 (solid)
R S

20 30CL R S
C0 40 Ca 50

wt% Ni Ma x S  ML x R
Adapted from Fig. 9.3(b),
Callister & Rethwisch 8e.

ML S C  C0 R C  CL
WL    a Wa   0
M L  M a R  S C a  CL R  S C a  CL
 Chapter 9 - 11
 Ex: Cooling of a Cu-Ni Alloy
• Phase diagram: T(ºC) L (liquid) L: 35wt%Ni
Cu-Ni system. Cu-Ni
system
• Consider 1300 A
L: 35 wt% Ni
microstuctural a: 46 wt% Ni B
35 46
changes that 32 C 43
accompany the D
24 36 L: 32 wt% Ni
cooling of a a: 43 wt% Ni
C0 = 35 wt% Ni alloy 120 0 E
L: 24 wt% Ni
a: 36 wt% Ni
a
(solid)

110 0
20 30 35 40 50
Adapted from Fig. 9.4, C0 wt% Ni
Callister & Rethwisch 8e.
Chapter 9 - 12
 Cored vs Equilibrium Structures
• Ca changes as we solidify.
• Cu-Ni case: First a to solidify has Ca = 46 wt% Ni.
Last a to solidify has Ca = 35 wt% Ni.
• Slow rate of cooling: • Fast rate of cooling:
Equilibrium structure Cored structure
Uniform Ca:
35 wt% Ni First a to solidify:
46 wt% Ni
Last a to solidify:
< 35 wt% Ni

Chapter 9 - 13
 Mechanical Properties: Cu-Ni System
• Effect of solid solution strengthening on:
-- Tensile strength (TS) -- Ductility (%EL)
Tensile Strength (MPa)

60

Elongation (%EL)
%EL for pure Cu
400 50 %EL for
TS for pure Ni
pure Ni 40
300
TS for pure Cu 30
200 20
0 20 40 60 80 100 0 20 40 60 80 100
Cu Ni Cu Ni
Composition, wt% Ni Composition, wt% Ni
Adapted from Fig. 9.6(a), Adapted from Fig. 9.6(b),
Callister & Rethwisch 8e. Callister & Rethwisch 8e.

Chapter 9 - 14
 Binary-Eutectic Systems
has a special composition
2 components with a min. melting T.
Cu-Ag
T(ºC) system
Ex.: Cu-Ag system 1200
• 3 single phase regions L (liquid)
(L, a, b) 1000
• Limited solubility: a L + a 779ºC L+b b
a: mostly Cu TE 800 8.0 71.9 91.2
b: mostly Ag 600
• TE : No liquid below TE ab
• CE : Composition at 400
temperature TE 200
0 20 40 60 CE 80 100
• Eutectic reaction C, wt% Ag
L(CE) a(CaE) + b(CbE) Adapted from Fig. 9.7,
Callister & Rethwisch 8e.
cooling
L(71.9 wt% Ag) a(8.0 wt% Ag)  b(91.2 wt% Ag)
Chapter 9 - 15
heating
 EX 1: Pb-Sn Eutectic System
• For a 40 wt% Sn-60 wt% Pb alloy at 150ºC, determine:
-- the phases present Pb-Sn
Answer: a + b T(ºC) system
-- the phase compositions
300
Answer: Ca = 11 wt% Sn L (liquid)
Cb = 99 wt% Sn
-- the relative amount a L+ a
200 183ºC L+b b
of each phase 18.3 61.9 97.8
Answer: 150
S Cb - C0 R S
100
W =
a R+S
=
Cb - Ca a+b
99 - 40 59
= = = 0.67
99 - 11 88 0 11 20 40 60 80 99100
C0 - C a Ca C0 Cb
Wb = R = C, wt% Sn
R+S Cb - C a Adapted from Fig. 9.8,
Callister & Rethwisch 8e.
40 - 11 29
= = = 0.33 Chapter 9 - 16
99 - 11 88
 EX 2: Pb-Sn Eutectic System
• For a 40 wt% Sn-60 wt% Pb alloy at 220ºC, determine:
-- the phases present: Pb-Sn
Answer: a + L T(ºC) system
-- the phase compositions
300
Answer: Ca = 17 wt% Sn L (liquid)
CL = 46 wt% Sn L+ a
-- the relative amount 220
200
a R S L+b b
of each phase 183ºC
Answer:
100
Wa =
CL - C0
=
46 - 40 a+b
CL - Ca 46 - 17
6 0 17 20 40 46 60 80 100
= = 0.21 Ca C0 CL
29 C, wt% Sn
Adapted from Fig. 9.8,
C0 - Ca 23 Callister & Rethwisch 8e.
WL = = = 0.79
CL - Ca 29
Chapter 9 - 17
 Microstructural Developments
in Eutectic Systems I

• For alloys for which T(ºC)

400
L: C0 wt% Sn

C0 < 2 wt% Sn L
• Result: at room temperature a
300 L
-- polycrystalline with grains of
a phase having L+ a
a
composition C0 200 (Pb-Sn
TE a: C0 wt% Sn
System)

a+ b
100

0 10 20 30
Adapted from Fig. 9.11, C0 C , wt% Sn
Callister & Rethwisch 8e. 2
(room T solubility limit)

Chapter 9 - 18
 Microstructural Developments
in Eutectic Systems II
L: C0 wt% Sn
• For alloys for which 400
T(ºC)
2 wt% Sn < C0 < 18.3 wt% Sn L
• Result: L
at temperatures in a + b range 300 a
L+a
-- polycrystalline with a grains a: C0 wt% Sn
and small b-phase particles 200 a
TE
a
b
100
a+ b Pb-Sn
system
Adapted from Fig. 9.12, 0 10 20 30
Callister & Rethwisch 8e. 2 C0 C, wt% Sn
(sol. limit at T room ) 18.3
(sol. limit at TE)
Chapter 9 - 19
 Microstructural Developments
in Eutectic Systems III
• For alloy of composition C0 = CE
• Result: Eutectic microstructure (lamellar structure)
-- alternating layers (lamellae) of a and b phases.
Micrograph of Pb-Sn
T(ºC) eutectic
L: C0 wt% Sn microstructure
300 L
Pb-Sn
system
L+a
200
a 183ºC Lb b
TE

100 160 m
ab b: 97.8 wt% Sn
Adapted from Fig. 9.14,
a: 18.3 wt%Sn Callister & Rethwisch 8e.

0 20 40 60 80 100
18.3 CE 97.8
Adapted from Fig. 9.13, 61.9 C, wt% Sn Chapter 9 - 20
Callister & Rethwisch 8e.
 Lamellar Eutectic Structure

Adapted from Figs. 9.14 & 9.15, Callister

& Rethwisch 8e.

Chapter 9 - 21
 Microstructural Developments
in Eutectic Systems IV
• For alloys for which 18.3 wt% Sn < C0 < 61.9 wt% Sn
• Result: a phase particles and a eutectic microconstituent
• Just above TE :
T(ºC) L: C0 wt% Sn L
a Ca = 18.3 wt% Sn
L
300 L CL = 61.9 wt% Sn
Pb-Sn a S
L+ a Wa = = 0.50
system R+S
a
b b
200 R S L+ WL = (1- Wa) = 0.50
TE S
R
• Just below TE :
100 a+b Ca = 18.3 wt% Sn
primary a Cb = 97.8 wt% Sn
eutectic a
eutectic b Wa = S = 0.73
0 20 40 60 80 100 R+S
18.3 61.9 97.8 Wb = 0.27
Adapted from Fig. 9.16,
Callister & Rethwisch 8e. C, wt% Sn Chapter 9 - 22
 Hypoeutectic & Hypereutectic
300
L
T(ºC)
L+ a
Adapted from Fig. 9.8,
Callister & Rethwisch 8e. a L+b b
(Fig. 10.8 adapted from
200
TE
(Pb-Sn
Binary Phase Diagrams,
2nd ed., Vol. 3, T.B. a+b System)
Massalski (Editor-in-Chief), 100
ASM International,
Materials Park, OH, 1990.)

0 20 40 60 80 100 C, wt% Sn
eutectic
hypoeutectic: C0 = 50 wt% Sn 61.9 hypereutectic: (illustration only)
(Figs. 9.14 and 9.17
from Metals
eutectic: C0 = 61.9 wt% Sn
Handbook, 9th ed.,
Vol. 9,
a b
Metallography and a b
Microstructures, a a b b
American Society for a b
Metals, Materials
Park, OH, 1985.) a b
175 m 160 m
Adapted from eutectic micro-constituent Adapted from Fig. 9.17,
Fig. 9.17, Callister & Adapted from Fig. 9.14, Callister & Rethwisch 8e.
Rethwisch 8e. Callister & Rethwisch 8e. (Illustration only)
Chapter 9 - 23
 Intermetallic Compounds

Adapted from
Fig. 9.20, Callister &
Rethwisch 8e.

Mg2Pb

Note: intermetallic compound exists as a line on the diagram - not an

area - because of stoichiometry (i.e. composition of a compound
Chapter 9 - 24
is a fixed value).
 Eutectic, Eutectoid, & Peritectic
• Eutectic - liquid transforms to two solid phases
L cool a + b (For Pb-Sn, 183ºC, 61.9 wt% Sn)
heat

• Eutectoid – one solid phase transforms to two other

solid phases
intermetallic compound
S2 S1+S3 - cementite

 cool a + Fe3C (For Fe-C, 727ºC, 0.76 wt% C)

heat

• Peritectic - liquid and one solid phase transform to a

second solid phase
S1 + L S2
cool
 +L heat  (For Fe-C, 1493ºC, 0.16 wt% C)

Chapter 9 - 25
 Eutectoid & Peritectic
Peritectic transformation  + L 
Cu-Zn Phase diagram

Adapted from Fig. 9.21,

Callister & Rethwisch 8e.
Eutectoid transformation  +
Chapter 9 - 26
 Iron-Carbon (Fe-C) Phase Diagram
• 2 important T(ºC)
1600
points 
- Eutectic (A): 1400 L
L   + Fe3C   +L
1200 1148ºC
A L+Fe3C
- Eutectoid (B): (austenite)

Fe3C (cementite)
  a + Fe3C 1000  
   +Fe3C
727ºC = T eutectoid
a
800
B
600
a+Fe3C
400
0 1 2 3 4 5 6 6.7
(Fe) 0.76 4.30 C, wt% C
120 m
Result: Pearlite = Fe3C (cementite-hard)
alternating layers of
a and Fe3C phases a (ferrite-soft)
(Adapted from Fig. 9.27, Adapted from Fig. 9.24,
Chapter 9 - 27
Callister & Rethwisch 8e.) Callister & Rethwisch 8e.
 Hypoeutectoid Steel
T(ºC)
1600

1400 L
  (Fe-C
  +L
  1200 1148ºC L+Fe3C System)

Fe3C (cementite)
(austenite)
  1000
   + Fe3C Adapted from Figs. 9.24
and 9.29,Callister &
a Rethwisch 8e.
a  800 727ºC (Fig. 9.24 adapted from
 a a Binary Alloy Phase
Diagrams, 2nd ed., Vol.
600
a + Fe3C 1, T.B. Massalski (Ed.-in-
Chief), ASM International,
Materials Park, OH,
400 1990.)
a 0 1 2 3 4 5 6 6.7
(Fe)C0 C, wt% C
0.76

pearlite

Hypoeutectoid
100 m
steel

pearlite proeutectoid ferrite

Adapted from Fig. 9.30, Callister & Rethwisch 8e. Chapter 9 - 28
 Hypoeutectoid Steel
T(ºC)
1600

1400 L
(Fe-C
a   +L
System)
a  1200 1148ºC L+Fe3C

Fe3C (cementite)
(austenite)
 a
1000
 + Fe3C Adapted from Figs. 9.24
Wa = s/(r + s) and 9.29,Callister &
Rethwisch 8e.
800 r s 727ºC
W =(1 - Wa) (Fig. 9.24 adapted from

aRS Binary Alloy Phase

Diagrams, 2nd ed., Vol.
a 600
a + Fe3C 1, T.B. Massalski (Ed.-in-
Chief), ASM International,
pearlite Materials Park, OH,
400 1990.)
0 1 2 3 4 5 6 6.7
(Fe)C0 C, wt% C
0.76

Wpearlite = W
Wa’ = S/(R + S) 100 m
Hypoeutectoid
steel
WFe3C =(1 – Wa’)
pearlite proeutectoid ferrite
Adapted from Fig. 9.30, Callister & Rethwisch 8e. Chapter 9 - 29
 Hypereutectoid Steel
T(ºC)
1600

1400 L (Fe-C
  +L System)
 
 
1200 1148ºC L+Fe3C

Fe3C (cementite)
(austenite)
  1000
   +Fe3C Adapted from Figs. 9.24
and 9.32,Callister &
Fe3C
 
Rethwisch 8e. (Fig. 9.24
800 adapted from Binary Alloy
  a Phase Diagrams, 2nd
ed., Vol. 1, T.B. Massalski
600
a +Fe3C (Ed.-in-Chief), ASM
International, Materials
Park, OH, 1990.)
400
0 1 C0 2 3 4 5 6 6.7
0.76

(Fe) C, wt%C
pearlite

60 mHypereutectoid
steel
pearlite proeutectoid Fe3C
Adapted from Fig. 9.33, Callister & Rethwisch 8e. Chapter 9 - 30
 Hypereutectoid Steel
T(ºC)
1600

1400 L (Fe-C
 +L System)
Fe3C 
  1200 1148ºC L+Fe3C

Fe3C (cementite)
(austenite)
  1000
 +Fe3C Adapted from Figs. 9.24
and 9.32,Callister &
W =x/(v + x) Rethwisch 8e. (Fig. 9.24
800 v x adapted from Binary Alloy
WFe3C =(1-W)
a V X
Phase Diagrams, 2nd
ed., Vol. 1, T.B. Massalski
600
a +Fe3C (Ed.-in-Chief), ASM
pearlite International, Materials
Park, OH, 1990.)
400
0 1 C0 2 3 4 5 6 6.7
0.76

(Fe) C, wt%C
Wpearlite = W
Wa = X/(V + X)
60 mHypereutectoid
WFe =(1 - Wa) steel
3C’
pearlite proeutectoid Fe3C
Adapted from Fig. 9.33, Callister & Rethwisch 8e. Chapter 9 - 31
 Example Problem
For a 99.6 wt% Fe-0.40 wt% C steel at a
temperature just below the eutectoid,
determine the following:
a) The compositions of Fe3C and ferrite (a).
b) The amount of cementite (in grams) that
forms in 100 g of steel.
c) The amounts of pearlite and proeutectoid
ferrite (a) in the 100 g.

Chapter 9 - 32
 Solution to Example Problem
a) Using the RS tie line just below the eutectoid
Ca = 0.022 wt% C
CFe3C = 6.70 wt% C

b) Using the lever rule with 1600

the tie line shown 
1400 L
R C  Ca T(ºC)
WFe 3C   0   +L
R  S CFe 3C  Ca

Fe C (cementite)
1200 1148ºC L+Fe3C
(austenite)
0.40  0.022
  0.057 1000
 + Fe3C
6.70  0.022
800 727ºC
R S
Amount of Fe3C in 100 g 600 a + Fe3C
= (100 g)WFe3C 400
0 1 2 3 4 5 6 6.7
Ca C0 C, wt% C CFe
3C
= (100 g)(0.057) = 5.7 g
Chapter 9 - 33
 Solution to Example Problem (cont.)
c) Using the VX tie line just above the eutectoid and
realizing that
C0 = 0.40 wt% C
Ca = 0.022 wt% C
Cpearlite = C = 0.76 wt% C
1600

1400 L
V C  Ca T(ºC)  +L
Wpearlite   0 

Fe C (cementite)
V  X C  Ca 1200
(austenite)
1148ºC L+Fe3C

0.40  0.022 1000

  0.512  + Fe3C
0.76  0.022
800 727ºC
VX
Amount of pearlite in 100 g 600 a + Fe3C
= (100 g)Wpearlite 400
0 1 2 3 4 5 6 6.7
Ca C0 C C, wt% C
= (100 g)(0.512) = 51.2 g
Chapter 9 - 34
 VMSE: Interactive Phase Diagrams
Microstructure, phase compositions, and phase fractions respond interactively

Change alloy composition Chapter 9 - 35

 Alloying with Other Elements

• Teutectoid changes: • Ceutectoid changes:

Ceutectoid (wt% C)
Ti
T Eutectoid (ºC)

Si
Mo W Ni
Cr
Cr Si
Mn
Mn W
Ti Mo
Ni

wt. % of alloying elements wt. % of alloying elements

Adapted from Fig. 9.34,Callister & Rethwisch 8e. Adapted from Fig. 9.35,Callister & Rethwisch 8e.
(Fig. 9.34 from Edgar C. Bain, Functions of the (Fig. 9.35 from Edgar C. Bain, Functions of the
Alloying Elements in Steel, American Society for Alloying Elements in Steel, American Society for
Metals, 1939, p. 127.) Metals, 1939, p. 127.)

Chapter 9 - 36
 Summary

• Phase diagrams are useful tools to determine:

-- the number and types of phases present,
-- the composition of each phase,
-- and the weight fraction of each phase
given the temperature and composition of the system.
• The microstructure of an alloy depends on
-- its composition, and
-- whether or not cooling rate allows for maintenance of
equilibrium.
• Important phase diagram phase transformations include
eutectic, eutectoid, and peritectic.

Chapter 9 - 37
 Nanostructured materials

• 0D: quantum dots

• 1D: Nanowires
• 2D: superlattices and heterostructures
• Nano-Photonics
• Magnetic nanostructures
• Nanofluidic devices and surfaces

Copyright Stuart Lindsay 2009 Chapter 9 -

Nanostructured materials derive their special properties from
having one or more dimensions made small compared to a
length scale critical to the physics of the process.

Copyright Stuart Lindsay 2009 Chapter 9 -

 Development of electronic
properties as a function of cluster
size

Each band has a width that reflects the interaction between atoms,
with a bandgap between the conduction and the valence bands that
reflects the original separation of the bonding ad antibonding states.
Chapter 9 -
Electronic DOS and dimensionality

Size effects are most

evident at band edges
(semiconductor NPs).

DOS (dn/dE) as
a function of
dimensionality.
3D case is for
free particles.
Copyright Stuart
ChapterLindsay
9- 2009
 k-space is filled with an
uniform grid of points each
separated in units of 2π/L
along any axis.
The volume of k-space
occupied by each point is:
 2 
3

 
 L 

r-space: k-space:
4 r 2 dr 4 k 2 dk 4 L3 k 2 dk

V Vk 8 3 Chapter 9 -
 3D DOS
Density of states in a volume V dn Vk 2

per unit wave vector: dk 2 2

2k 2 dE  2 k
For a free electron gas: E 
2m dk m
1
dn dn dk Vk 2 m Vm 2mE
  2 2  2 2  E 2
dE dk dE 2  k  2 2

Copyright Stuart
ChapterLindsay
9- 2009
 2D DOS

dn A2k dE  2 k
 
dk 2 2 dk m

dn dn dk Am
  Constant for each
dE dk dE 2 2 electronic band

Copyright Stuart
ChapterLindsay
9- 2009
 1D DOS

dn L dE  2 k
 
dk 2 dk m
1
dn Lm 
 E 2
dE 2 k
2

At each atomic level, the DOS

in the 1D solid decreases as
the reciprocal of the square
root of energy.

Copyright Stuart Lindsay 2009 Chapter 9 - 45

 0 D DOS

In zero dimensions the energy states are sharp levels corresponding

to the eigenstates of the system.

Copyright Stuart Lindsay 2009 Chapter 9 -

 0D Electronic Structures:
Quantum Dots

Light incident on a semiconductor at an energy greater than the

bandgap forms an exciton, i.e. an electron-hole quasiparticle,
representing a bound state.

Chapter 9 -
Excitons can be treated as “Bohr atoms”

mV 2
1 e 2
40  2
 r
r 40 r 2 2 *
e m

When the size of the nanoparticle approaches that of an exciton,

size quantization occurs.

Electronic  
2 2
 1 1  e 2
E  E 0   *  *   1.8
2 
energy gap 2 R  me mh  R

Intrinsic NP radius electrostatic

band gap correction
Chapter 9 -
 1-D Electronic Structures: Carbon Nanotubes

  
Wrapping vector: n  n1a1  n2 a2

Diameter: d  n12  n22  n1n2 0.0783nm

The folding of the sheet controls the electronic properties of the

Chapter 9 -
nanotubes.
 Conduction in CNTs
pz electrons hybridize to form π e π* valence and conduction bands
that are separated by an energy gap of about 1V (semiconductor).

For certain high simmetry directions (the K points in the reciprocal

lattice) the material behaves like a metal.

k  wave vector perpendicular to the

CNT long axis

Apex: at this point CB

meets VB for graphene
sheets (metal-like
behavior)

Allowed K  states
Chapter 9 -
The component of the wave vector perpendicular to the CNT long
axis is quantized

2n
k 
D

D = diameter of the nanotube

Metallic behavior: the allowed values of k  intersect the k points

at which the conduction and valence bands meet.

CNTs can be either metals or semiconductors depending on their

chirality.

Chapter 9 -
Field effect transistor made from
a single semiconducting CNT
connecting source and drain
connectors.

Chapter 9 -
 Semiconductor Nanowires
• Ga-P/Ga-As p/n nanojunctions

TEM images

Line profiles of
(IOP)
the composition
through the
Copyright Stuart Lindsay 2009
junctionChapter
region9-
 2D Electronic Structures:
superlattices and heterostructures
Variation of electron energy in an
MBE grown superlattice
Superlattice:
alternating layers of small
bandgap semiconductors
(GaAs) interdispersed with
layers of wide bandgap
semiconductors (GaAlAs).
The thickness of each layer
is considerably smaller
than the electron mean free
path.
Chapter 9 - 54
 Modulation of the structure on
the length scale d (thickness of
the layer in the superlattice)
gives rise to the formation of
new bands inside the original
Brillouin zone .

Electrons can pass freely from

one small bandgap region to
another without scattering.

Band splitting into sub-bands

Chapter 9 -
 Low scattering in 2-D means reaching zone boundaries at
reasonable fields, accelerating electrons at the band edges.

Resonant tunneling through different sub-bands

Negative differential resistance: electrons slow down with increasing

bias when approaching the first sub-band boundary (≈20mV).
Chapter 9 -
 Quantum Hall resistance of 2D electron gas
Electrons in a layer are accelerated by an applied magnetic
field at a frequency:
eB
C 
m
Magnetic quantization in
2D electron gas
A series of steps in the Hall
resistance corresponding
exactly at twice the
Landauer frequency were
observed.
h
RH  2 von Klitzing resistance
ne Nobel in Physics 1985
Copyright Stuart Lindsay 2009 Chapter 9 -
 Confinement on optical length scales
Plasmonics
Small (d<<λ) metal particles exhibit a phenomenon called plasma
resonance, i.e. plasma-polariton resonance of the free electrons in
the metal surface.

A resonant metal particle can capture light over a region of many

wavelengths in dimension even if the particle itself is only a fraction
of a wavelength in diameter (resonant antennas).

Free electrons in metals polarize excluding electric fields from the

interior of the metal showing a negative dielectric constant.
The polarizability of a sphere of volume V and dielectric constant εr
is:
 r 1
a   0 3V
r  2 Chapter 9 -
 When εr →-2 a→∞
For d<<λ the resonant frequency is independent on the particle
size, but depends on particle shape.
2
b
For a prolate spheroid of eccentricity e: e  1  
2

a
 0V
1 r
a
L (1 L  1)   r
where:
1.6
1  e2  1 1 e   a 
L  2   1  ln   1  
e  2e 1  e   b 

For Ag =-2 at 400 nm, but resonance moves to 700 nm for a/b=6.
The resonance is tunable throughout the visible by engineering the
particle shape.
Chapter 9 -
 Plasmon enhanced optical absorption
Placing a chromophore near a resonant metal nanoparticle:

dye layer

Electric field surrounding

a resonant nanoparticle Enhanced fluorescence
(E=Ez) Reduced decay times Chapter 9 -
The plasmon resonance results in local enhancement of the electric
field: doubling the electric field quadruples the light absorption.

Enhanced fluorescence

A single dye
molecule is
only visible in
fluorescence
when the gold
NP passes over
it.

The increased absorption cross section is accompanied by a

decrease in fluorescence lifetime.
Chapter 9 -
 Photonic engineering
3D Modern semiconductor lasers are
made from semiconductors
heterostructures designed to trap
excited electrons and holes in the
2D optically active part of the laser.
Performance of a solid-state laser
material in various geometries.
Lasing effect: the gain of the laser
1D
medium must exceed the cavity
losses.
Dashed lines: density of states
0D In quantum dots all of available
gain is squeezed into a narrow
Chapter 9 - 62
bandwidth.
Optical cavity
Quantum dot laser
Quantum dots of the right size can
place all of the exciton energies at
the right value for lasing.

The QDs are chosen to have a

bandgap that is smaller than that of
the medium.

Excitons are stabilized in the

optical cavity, because the
electrons are confined to the low-
energy part of the conduction band
and the holes are confined to the
top of the valence band.Chapter 9 -
 Photonic crystals:
concentrating photon energy into bands

Opalescent materials from colloidal crystal (polystyrene latex beads)

The concentration of modes into bands results in an increase in the

density of states in the allowed bands, particularly near bands edges.
Optical wavelengths require that materials should be structured on
the half-micron scale.
Opalescence comes from sharp (Bragg) reflection in only certain
directions. Copyright Stuart Lindsay
Chapter 9 - 2009
For a given spacing in some direction in the colloidal crystal lattice ,
the wavelength of the reflected beam is given by the Bragg law.

Bragg’s law
  2ndhkl cos  int 
 2d hkl n  sin  ext
2 2

Colloidal particles spaced sin ext  n sin int

with polymer spacers

hkl = Miller indices of the colloidal crystal lattice

n = refraction index
dhkl = spacing between Bragg planes in the hkl direction
Chapter 9 -
 3D Photonic crystals
Require “non spherical” atoms to give zero “structure factor” in
directions where propagation must be suppressed

Optical dispersion in a crystal made by non spherical atoms. A 3D

bandgap appear when structures are designed to have zero intensity
in directions of allowed Bragg reflections.
Repeat period is on the order of 30μm (3D optical bandgap in the far
IR, limit of today technology).
Photonic crystals convert heat into light! See Optics Letters 28
Chapter 9 -
1909, 2003.
 Magnetic properties
• Diamagnetism:
Zero-spin systems give rise to circulating currents that oppose the
applied field (negative magnetic susceptibility, Larmor
diamagnetism).

• Paramagnetism:
Free-electrons are magnetically polarized by an external magnetic
field (positive magnetic susceptibility, Pauli paramagnetism).

• Ferromagnetism:
Spontaneous magnetic ordering due to electron-electron interactions.

Antiferromagnetism: polarization alternates from atom to atom. No

net macroscopic magnetic moment arises.
Chapter 9 -
 Magnetic Interactions
• Exchange (electron-electron) interaction (many-particle
wavefunction antisymmetry)
- atomic scales
• Dipole-dipole interactions between locally ordered magnetic
regions
Dipole interaction energy grows with the volume of the
ordered region. The size of the individual domains is set by
a competition between volume and surface energy effects.
- hundreds of atoms to micron scales
• Magnetic Anisotropy energy
Magnetization interacts with angular momentum of the
atoms in the crystal.
– many microns
Chapter 9 -
 Super-paramagnetic particles
• Ferromagnetic domains, created by d-electrons exchange
interactions, develop only when a cluster of iron atoms reaches a
critical size (ca. microns).

The magnetic moment per

atom decreases toward the
bulk value as cluster size is
increased.

Stable domains cannot be

established in crystals that
are smaller than the intrinsic
domain size.
Chapter 9 -
• Small particles can have very high magnetic susceptibility with
permanent magnetic dipole.
Small clusters consisting of a single ferromagnetic domain
follow the applied field freely (super-paramagnetism).
The magnetic susceptibility of superparamagnetic particles is
orders of magnitude larger than bulk paramagnetic materials.

Ferromagnetic limit

Magnetic response for

particles of increasing
size (Gd clusters)

Chapter 9 -
 Superparamagnetic separations
Induced magnetic moment:
M  H

Magnetic force:

B
Fz  M z
z
B   0 (H  M)
MFS: microfabricated
Magnetic sorting of cells labeled
ferromagnetic strips
with superparamagnetic beads

Particle were pulled to point of highest field gradient

Chapter 9 -
Copyright Stuart Lindsay 2009
 Giant Magnetoresistance
Magnetic hard drives are based on a nanostructured device, called
giant magnetoresistance sensor.
Albert Fert, Peter Grünbers Nobel Prize in Physics 2007
Hitachi hard drive reading head

The magnetization on the surface

of the disk can be read out as
fluctuations in the resistance of
the conducting layer.

Co, magnetic layer

Layers have a width that Cu, electrically conducting layer

is smaller than electron NiFe alloy, magnetic layer
scattering length. An easily re-alignable magnetization
Chapter 9 -
Giant magnetoresistance occurs when the magnetic layers above
and below the conductor are magnetized in opposite direction.

Electron scattering in magnetic

media is strongly dependent on
spin polarization.
When magnetic layers are
parallely magnetized, only one
I II III spin polarization is scattered
(I,III).
For antiparallel magnetic layers both spin polarizations are
scattered, giving rise to super-resistance (II). Chapter 9 -
 Nanofluidics
Fluid flow in small structures is entirely laminar and dominated
by the chemical boundaries of the channel.
Reynolds number (Re), a dimensionless number quantifying the
ratio of inertial to viscous forces that act on the volume of a
liquid:
channel narrowest
density
dimension
uL
Re 

viscosity

Re >> 1: turbulence regime

Re << 1: viscous regime
Chapter 9 -
 
Kinematic viscosity 
u

For water: ν =1·10-6 m2s-1 (25°C)

Re in a L=100nm channel with <u> = 1mm/s not exceeds 10-4

Flow in nanoscale channels is dominated by viscosity!

Fluids do not mix in a nanofluidic device.
The chemistry of the interface becomes critical and aqueous
fluids will not generally enter a channel with hydrophobic
surfaces.

Chapter 9 -
 1-D Nanochannel devices
A significant stretching of large molecules can occur in a large ion
gradient or electric field in a channel that is comparable to the
radius of giration of the molecule.

Ex. A 17μm DNA (fully stretched length) is equivalent to 340

freely jointed segments each of 5 nm length.
The relative giration radius is:

r  340  5  92nm
It can be significantly extended in a channel of 100 nm diameter,
owing to the strong interaction between the fluid and the wall.

Chapter 9 -
DNA is introduced through the microchannel and then transported
through the nanochannels by an applied voltage.

DNA cutting starts

Mg ions introduced

Time
Fluorescently labeled
DNA at various times distance
Continous time course
Microchannels of the cutting process
DNA + cutting
enzymes introduced Chapter 9 -
 Nanopores: 0D fluidic nanostructure
2-nm diameter holes: only a single DNA molecule can pass
through it at a given time.

electrophoresis

Polystyrene
bead
Optical tweezer

The passage of DNA molecules can be measured by the drops in

currents that occur when a single DNA molecule occludes the hole.
Chapter 9 -
 Flow in Carbon Nanotubes

A. Fabrication of a layer of
CNTs penetrating a silicon
nitride membrane;

B. and C. SEM images before

and after filling with silicon
nitride;

D. Individual finished device:

E. An array of devices

The measured rate of water flow through 2nm-diameter CNTs was found
to be 1000 times higher than predicted by classical hydrodynamics.
Chapter 9 - 79
 2D Nanostructures:
Superhydrophobic surfaces
The angle formed by a tangent to a flat surface of a drop of water at
the point of contact (contact angle) is given in terms of the interfacial
energies of the system by the Young equation:
 AB   AC
cos c 
 BC

γAB= air/surface interfacial tension

γAC= water/surface interfacial tension

γBC= air/water interfacial tension

Chapter 9 -
cos c  1 Water/surface repulsion (large interfacial tension)

Water drop

Si Nanowires Coated Si surface Coated nanostructured

(planar) surface (rough)

Roughening on the nanoscale can greatly increase hydrophobicity.

Chapter 9 -