Energy Band Gap Behavior as a

Function of Optical Electronegativity

for Semiconducting and Insulating
Binary Oxides
Kristen Dagenais, Chemical Engineering, UMBC
Matthew Chamberlain, Physics and Astronomy, James Madison
Unviersity
Dr. Costel Constantin, Physics and Astronomy, James Madison
University
Topics
Energy Band Gaps
Electronegativity
Current Models
Ionization of Oxygen
Accounting for Band Gap Variation
First Look
Periodic Table
Second Look with Models and Trends
 Energy Band Gaps

Define EF as the level below which all electrons fill up the states (little cups).
METALS - Fermi energy level falls at the middle of the allowed band.
INSULATORS and SEMICONDUCTORS - Fermi energy level falls at
the middle of the forbidden gap.
Semiconducting and Insulating
Binary Oxides
A big part of electronics
Ex. SiO2 used as an insulator in transistors

As devices get smaller, better materials must

be chosen
Band gap is used to justify research
Usually found experimentally

Band gaps models try to replace extra

experiment
Usually relate band gap to electronegativity
Electronegativity
Different Scales
Mulliken, Allred-Rochow, Allen etc.
Most Commonly Used Pauling Scale

Optical Electronegativity
Based on electron transference between atoms

Comparison
Optical Electronegativity is more accurate and
precise
Accepted Models for Eg
Text Book Model [21]

J.A. Duffys Model [2]

*

Di Quarto [20]

Duffy Model
Duffy Model [2]
Developed based on optical electronegativity
Model:

Example: NaBr

But oxides behave differently

Ionization of Oxygen
Optical electronegativity of oxygen varies with
the cation
No fixed value

Duffys Oxide Model [2]

Band Gap Variation
Band gap depends on many other factors
Defects
Growth method
Crystal structure
Temperature
One cation may have different oxide forms
Ex. Ytterbium Oxides two forms

How do we account/handle these changes?

Criteria of Choosing a
Band Gap
At or around room temperature (~300 K)
Most stable form
Most useful form
Ex. Eg of YbO vs Yb2O3

Doesnt solve the problem of

Crystal structure
Defects
Growth method
Substances
MoO3 2.74 3.51
CdO 2.5 3.24
In2O3 3.55 3.31
Compound Eg (eV) * SnO2 3.57 3.41
BaO 5.2 1.9
BeO 10.5 3.15
La2O3 5.5 2.5
B2 O 3 8.45 3.45
CeO2 3.78 2.54
MgO 7.8 2.86
Pr2O3 3.8 2.56
Al2O3 6.96 3.18
Nd2O3 4.6 2.58
Si2O2 9.24 3.38
Sm2O3 5 2.64
CaO 6.26 2.26
Eu2O3 4.3 2.69
TiO2 3.6 3.12
Gd2O3 5.4 2.69
Cr2O3 2.58 3.22
Tb2O3 3.8 2.69
MnO 4 3.13 Dy2O3 4.9 2.72
FeO 3.2 3.33 Ho2O3 5.3 2.74
CoO 3.2 3.37 Er2O3 5.3 2.76
NiO 2.86 3.38 Tm2O3 5.4 2.77
Cu2O 2.04 3.38 Yb2O3 4.9 2.5
ZnO 3.3 3.25 Lu2O3 5.5 2.8
Ga2O3 5.4 3.3 HgO 2.58 3.43
GeO2 5.35 3.44 Tl2O3 2.25 3.19
Se2O3 5 3.64 PbO 2.75 3.57
SrO 6.5 2.11 Bi2O3 2.85 3.44

References [3]-[11]
Band Gap Error
Compoun First Second Average Standar Normalized Average
d Band Band Band d Dev. Standard Error
Gap, Gap, (eV) Gap Dev
(eV)
BeO 10.5 5 7.75 3.889 0.5018 0.215
Cr2O3 2.58 3.25 2.92 0.4737 0.1625
ZnO 3.30 3.7 3.5 0.2828 0.08081
GeO2 5.35 6.1 5.73 0.5303 0.09263
CdO 2.50 1.11 1.81 0.9829 0.5445
La2O3 5.50 5.50 5.50 0 0
CeO2 3.78 3.19 3.49 0.4172 0.1197
HgO 2.58 1.9 2.24 0.4808 0.2146
References [12]-[18]
Final Values
12

10

6
Energy Band Gap (eV)

0
1.5 2 2.5 3 3.5 4

Optical Electronegativity
Using the Periodic Table
With Grouping
12
Rare earth oxides
Row 4 Transition
Metals
10
Poor Metals
Alkali Earth
Metals
8
Rare earth oxides
Linear (Rare
earth oxides)
6
Energy Band Gap (eV) Row 4 Transition
Metals
Linear (Row 4
4
Transition
Metals)

0
1.75 1.95 2.15 2.35 2.55 2.75 2.95 3.15 3.35 3.55 3.75

Optical Electronegativity (arb. units)

Z Number Model for Alkali Earth
Metal Oxides
12

10

6
Band Gap (eV)

0
0 10 20 30 40 50 60

Z number
Z number Model for Poor Metal
Oxides
8

6
Energy Band Gap (eV)
5

0
0 10 20 30 40 50 60 70 80 90

Z number
Viable Models
Alkali Earth Metal Oxides
Electronegativity model:
Z model:

Poor Metal Oxides

Electronegativity model:
Z model:
Transition and Rare Earth
Difficulties
Transition Metal Oxide
Electronegativity model:
Range of values: 1.82 to 3.82 eV

Rare Earth Oxide

Electronegativity model:
Range of values: 3.59 to 5.73 eV
Results
Alkali Earth Metal Oxides

Poor Metal Oxides

Rare Earth Oxides

3.59 to 5.73 eV
Transition Metal Oxides
1.82 to 3.82 eV
Comparison Accepted Models
Conclusion
The behavior of binary oxides band gap can
be related to the chemical groups on the
periodic table

Band gap is affected by the presence of a d

orbital in the valence band

Band gap behavior can be modeled for

individual chemical groups and rows of oxides
Questions?

Acknowledgeme
nts
References
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