Electronic Supplementary Material (ESI) for RSC Advances.
This journal is © The Royal Society of Chemistry 2015
Electronic structure and optical properties of Zn(OH)2:
LDA + U calculations and intense yellow luminescence
Mingsong Wang,*,† Lingxia Jiang,† Eui Jung Kim,*,‡ and Sung Hong Hahn§
†School
of Materials Science and Engineering, Jiangsu University, Zhenjiang 212013, China
‡Department
of Chemical Engineering, University of Ulsan, Ulsan 680-749, South Korea
§Department
of Physics and Energy Harvest-Storage Research Center, University of Ulsan, Ulsan
680-749, South Korea.
*E-mail: [email protected]; [email protected]
Table S1 Optimized lattice constants and difference in volume (ΔV) for ZnO and Zn(OH)2.
a (Å)
b (Å)
c (Å)
ΔV (%)
ZnO
3.247
−
5.252
0.74
Zn(OH)2
4.879
5.099
8.678
0.98
Table S2 Atomic populations (Mulliken) of ZnO and Zn(OH)2.
ZnO
Zn(OH)2
Species
s
p
d
Total
Charge (e)
O
1.83
5.11
0.00
6.94
-0.94
Zn
0.40
0.68
9.98
11.06
0.94
H
0.60
0.00
0.00
0.60
0.40
O
1.82
5.17
0.00
6.99
-0.99
Zn
0.30
0.53
9.99
10.82
1.18
Table S3 Bond populations and lengths of ZnO and Zn(OH)2.
a
Bond
Population
Length (Å)
ZnO
O−Zn (∥c)
0.43
1.978
0.39
1.986
Zn(OH)2
O−Zn (⊥c)
H−O a
0.61
1.004
H−O b
0.09
1.768
O−Zn
0.38
1.982
O−Zn
0.34
1.993
O−Zn
0.36
2.002
O−Zn
0.32
2.005
within OH ion, b between OH ions
3.70
Up = 8.0 eV
3.65
Eg (eV)
3.60
3.55
3.50
3.45
3.40
3.35
5
6
7
8
9
10
Ud (eV)
Figure S1 Variation of the Eg of ZnO as a function of Ud at a fixed Up of 8.0 eV. Nearly linear
increase of the Eg with Ud is observed in the LDA + U calculations.
12
12
a
Up=7.0, Ud=7.32
Up=7.5, Ud=7.32
Up=8.0, Ud=7.32
8
6
4
2
0
Up=7.5, Ud=5.57
Up=7.5, Ud=7.32
Up=7.5, Ud=9.80
10
DOS (electrons/eV)
DOS (electrons/eV)
10
b
8
6
4
2
-15
-10
-5
0
5
0
10
-15
-10
-5
Energy (eV)
0
5
10
Energy (eV)
Figure S2. DOSs for ZnO calculated with LDA + U at fixed Ud (a) and Up (b).
160
Up=6.5, Ud=13.6
Up=7.0, Ud=9.8
Up=7.5, Ud=7.32
Up=8.0, Ud=5.57
Up=8.5, Ud=4.26
DOS (electrons/eV)
140
120
100
80
60
40
5.5
20
0
-15
-10
-5
0
6.0 6.5 7.0
Energy (eV)
5
7.5
10
Energy (eV)
Figure S3. DOSs for Zn(OH)2 calculated with LDA + U using various U parameters. The DOSs in
the CB minimum is magnified as an inset.