MIT 3.

071
Amorphous Materials
10: Electrical and Transport Properties

Juejun (JJ) Hu

1
After-class reading list

 Fundamentals of Inorganic Glasses

 Ch. 14, Ch. 16
 Introduction to Glass Science and Technology
 Ch. 8
 3.024 band gap, band diagram, engineering
conductivity

2
Basics of electrical conduction

 Electrical conductivity  : electrical conductivity

n : charge carrier density
   ni Z i ei
i
Z : charge number
e : elementary charge
v i  i E
 : carrier mobility
 Einstein relation D : diffusion coefficient
v : carrier drift velocity
 i k BT
Di  E : applied electric field
Zi e
1
   Z i e  ni Di
2
   Both ions and electrons
k BT i contribute to electrical
conductivity in glasses

3
Ionic conduction in crystalline materials

Vacancy mechanism Interstitial mechanism

4
Ionic conduction pathway in amorphous solids
 There are low energy
“sites” where ions
preferentially locate
Comparison of Li transport pathways figure removed due to  Ionic conduction results
copyright restrictions. See: Figure 8: Adams, S. and R. Prasada
Rao. "Transport Pathways for Mobile Ions in Disordered Solids from ion transfer
from the Analysis of Energy-scaled Bond-valence Mismatch
Landscapes." Phys. Chem. Chem Phys. 11 (2009): 3210-3216. between these sites
 Ionic conduction is
thermally activated

2-D slices of regions with Li site

energies below a threshold value
in Li2O-SiO2 glasses
Phys. Chem. Chem. Phys. 11, 3210 (2009)

5
A tale of two valleys Electric field E = 0

 Assuming completely random hops,

the average total distance an ion
moves after M hops in 1-D is:
r d  M
+
 Average diffusion distance:

r  2 D (1-D) Average spacing between

adjacent sites: d
r  6 D (3-D)
 For correlated hops:
1 2
 D d (1-D) 1
2 D f d 2 0  f 1
6
1 2
 D d (3-D) Ion hopping frequency: 
6
6
 A tale of two valleys Electric field E = 0

 Attempt (vibration) frequency: 0

 Frequency of successful hops
(ion hopping frequency):

 D Ea  +
v v0 exp   
 k T 
B
Barrier height DEa
1 2  D Ea 
 D fv0 d exp   
6  k B T 
 Equal probability of hopping along all directions: zero net current

7
 A tale of two valleys Electric field E > 0

 Energy difference between

adjacent sites: ZeEd
 Hopping frequency → : DEa

1  D Ea  +
v v0 exp   
2  k T 
B ZeEd
 Hopping frequency ← :

1  D Ea  ZeEd 
v v0 exp   
2  k B T 
 Net ion drift velocity:
v0 ZeEd 2  D Ea 
v  v  v   d  exp   
2k BT  k BT 
8
A tale of two valleys Electric field E > 0

 Ion mobility
v0 Zed 2  D Ea 
  exp    DEa
2 k BT  k B T 
+
 Electrical conductivity (1-D, random
hop) ZeEd
nv0  Zed 
2
 D Ea 
  exp   
2 k BT  k B T 
 Einstein relation (3-D, correlated hops)
fnv0  Zed 
2
1  D Ea   0  D Ea 
 Ze  nD 
2
  exp   
 exp   
k BT 6k BT  k B T  T  k BT 

9
Temperature dependence of ionic conductivity

D Ea Dispersion of activation
Slope: 
kB energy in amorphous
solids leads to slight
non-Arrhenius behavior

D Ea
ln  T   ln  0 
k BT

1/T (× 1,000) (K-1)

Phys. Rev. Lett. 109, 075901 (2012)
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Theoretical ionic conductivity limit in glass
fnv0  Zed 
2
0  D Ea  Note that 0 has a
   exp    0 
T k T 6k B unit of W·cm/K
 B 

 When T → ∞,  → 0 /T
 Extrapolation of the
Arrhenius plot agrees with
infrared spectroscopic
measurements in ionic
liquids (molten salts)

Solid State lonics 18&19, 72 (1986)

Annu. Rev. Phys. Chem. 43, 693 (1992)

11
Fast ion conductors / superionic conductors

Acta Mater. 61, 759 (2013)

12
Band structures in defect-free crystalline solids

 All electronic states are labeled with real Bloch wave vectors k
signaling translational symmetry
 All electronic states are extended states
 No extended states exist in the band gap

13
Band structures in defect-free crystalline solids

Figure removed due to copyright restrictions. See Figure 12, Chapter 7:

Kittel, Charles. Introduction to Solid State Physics. Wiley, 2005.

In the band gap, wave equation solutions have complex wave vectors k

Kittel, Introduction to Solid State Physics, Ch. 7

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Anderson localization in disordered systems

 Localization criterion: V0 / J > 3

P. W. Anderson
Image is in the public domain.
Source: Wikimedia Commons.

Disorder leads to (electron, photon, etc.) wave function localization

15
Anderson localization in disordered systems

Extended states
(Bloch states)

Localized states

16
Density of states (DOS) in crystalline and
amorphous solids
E E
Conduction Conduction band
band

Urbach tail
Defect states
Band gap Mid-gap states

Mobility edge
Valence
band Valence band

DOS DOS
Crystalline solids Amorphous solids

17
Extended state conduction
 Extended state conductivity: Electron drift
mobility in a-Si:H
 ex  neex

ex  1  ftrap  0

0 : free mobility
ftrap : fraction of time in trap states
 Drift mobility ex increases with Electron
temperature (T → ∞, ftrap → 0) mobility in c-Si:
 Extended state conductivity 1400 cm2 V-1 s-1
follows Arrhenius dependence
R. Street, Hydrogenated Amorphous Silicon, Ch. 7

18
Hopping conduction via localized states
 Fixed range hopping: hopping between nearest neighbors
 Hopping between dopant atoms at low temperature
 Variable range hopping (VRH)
 Hopping between localized states near EF
E Mobility edge
  exp   R 

EF R
y
x
g z
DOS
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Variable range hopping
 DE 
 Hopping probability P  exp  2 R     VRH
 k BT 
 Within distance R, the average minimal energy difference DE is:
3
DE 
4 R 3 g
 Optimal hopping distance:
  exp   R 
R   8 g k BT 9 
1 4

1
3
 DE   2  4 R
 2 R    4 
4

 k B T  min  9 gk B T  y
x
  VRH  exp T  1 4
 z
20
DC conductivity in amorphous semiconductors

ln
Extended state conduction
VRH is most
 ex  exp T 1
 pronounced at
low temperature

Measured DC conductivity

Variable range hopping

 VRH  exp T 1 4 

1/T

21
VRH in As-Se-Te-Cu glass

 Near room temperature, mixed ionic and extended state conduction

 At low temperature, variable range hopping dominates

J. Appl. Phys. 101, 063520 (2007)

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Summary
 Basics of electrical transport
 Conductivity: scalar sum of ionic and electronic contributions
   ni Z i ei v i  i E
i

 Einstein relation
 i k BT 1
   Z i e  ni Di
2
Di    
Zi e k BT i
 Ionic conductivity
 Occurs through ion hopping between different preferred “sites”
 Thermally activated process and non-Arrhenius behavior
fnv0  Zed 
2
0  D Ea 
  exp    0 
T  k B T  6k B
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Summary
 Electronic structure of amorphous semiconductors
 Anderson localization: extended vs. localized states
 Density of states
E
 Mobility edge Conduction band
 Band tail and mid-gap states
Urbach tail
 Extended state conduction
 Free vs. drift mobility Mid-gap states
 Thermally activated process
Mobility edge
 Localized state conduction
 Fixed vs. variable range hopping Valence band
 Mott’s T -1/4 law of VRH
DOS
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3.071 Amorphous Materials

Fall 2015

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