Supplemental Information for
Band gaps in the deep ultraviolet borate crystals:
prediction and improvement
Ran He 1,4, a), Hongwei Huang2,a), Lei Kang1,4, Wenjiao Yao1,4,Xingxing Jiang1,4, Zheshuai
Lin1,b) , Jingui Qin3, and Chuangtian Chen1
1
Beijing Center for Crystal R&D, Key Lab of Functional Crystals and Laser Technology of
Chinese Academy of Sciences, Technical Institute of Physics and Chemistry, Chinese
Academy of Sciences, Beijing 100190, P.R. China
2
School of Materials Science and Technology, China University of Geosciences, Beijing,
100083, P.R. China
3
Department of Chemistry, Wuhan University, Wuhan 430072, P.R. China
4
Graduate School of the Chinese Academy of Sciences, Beijing 100049, P.R. China
a)
These author contributed equally to this paper.
to whom correspondence should be addressed: Email address: zslin@mail.ipc.ac.cn
b)Author
Table of Content
1.
Table S1 List of all DUV candidates in the known borates in Inorganic Crystal Structural
Database
2.
Table S2 Comparison of experimental band gaps (Eg) and calculated values from MBVS
method in all DUV borates with measured UV absorption edge.
3.
Figure S1 Electronic structures for the representative UV borates listed in Table 1.
4.
Figure S2 Relationship between the non-bonding states and the energy gaps in the
representative DUV borates.
5.
References in the Supplementary Information.
1. Table S1. List of all DUV candidates in the known borates in Inorganic Crystal
Structural Database (ICSD, 2012-1, Version 1.8.2, by Fachinformatiionszentrum
Karlsruhe).
The chosen candidates satisfy the following two principles: (i) the compounds were
synthesized at ambient environment and the structure with the structural convergence factor R
larger than 0.05 are excluded to make sure the selected structures are reliable, and (ii) in order
to obtain the short absorption edge down to the DUV region, the cations in borates are
confirmed in the alkaline and alkaline-earth metal cations and the lightweight metal cations
without unclosed d or f electronic shells, since the d-d or f-f electronic transitions have
negative influences to the energy band gap. Here the chemical formulae for the compounds
are listed, but most of their phase names are not shown. It should be noted that the borates in
the first row (BPO4, CaAlB3O7, SrB4O7, -LiBO2) are the only four crystals exclusively
containing the BO4 anionic groups.
BPO4
LiB3O5
YAl3B4O12
Sr2B2O5
Mg3B2O6
LiK2BO3
Al4B6O15
Ca2B2O5
LiScSr2B4O10
Ba5B4O10F2
SrBe2B2O6
CsLiB6O10
Rb5B19O31
BaNaB9O15
RbB5O8
Li4CaB2O6
NaK3B8O14
Al2CaB2O7
K3YB2O6
K3Be6B9O21
KB3O5
CsNa2Be6B5O15
NaK2B9O15
CaAlB3O7
K2B4O7
CaMgB2O5
CaAlBO4
Na2KBO3
AlLi2BO4
Na2B8O13
CaB6O10
SrB2O4
CsBO2
KSrB5O9
Na2Cs2B10O17
RbB3O5
SrLiB9O15
CsB9O14
K2Al2B2O7
RbBe4B3O9
Sr2Be2B2O7
Sr3YB3O9
RbBe2B3O7
Ba5B4O11
Rb2Al2B2O7
Na3CaB5O10
SrB4O7
Mg3BO3F3
CaB2O4
BaB2O4
NaCs2Li3B2O6
AlLiB2O5
Rb3B3O6
Na2CsBO3
LiBa2B5O10
Sr3ScB3O9
Mg2B2O5
Al7LiB4O17
SrLiBO3
Sr3B2O6
MgCaB2O5
CsB5O8
Sr2B16O26
Na2Y2B2O7
KBa7Mg2B4O28F5
NaMgBO3
RbBe2BO3F2
Ba3BPO3
Na3MgB5O10
-LiBO2
Na4B2O5
Al5BO9
AlBO3
SrAl2B2O7
AlLi3B2O6
Ca5B3O9F
BaBe2B2O6
CaBeB2O5
Ba2MgB2O6
BaNaBO3
Sr2Sc2B4O11
Al4B2O9
LiKB4O7
Na3B7O12
Ba3Y2B4O12
BaKYB2O6
Na3Sc2B3O9
NaBeB3O6
Na2B4O7
CsBe2BO3F2
NaScB2O5
NaSr3Be3B3O9F4
-LiBO2
Ca3B2O6
Ba2Ca1B6O12
MgScBO4
Y2Sr3B4O12
Li2B4O7
Al6B5O15F3
BaLiBO3
KBe2BO3F2
Ba2CaB2O6
Ba2Sc2B4O11
BaLiB9O15
RbLiB4O7
LiCaBO3
Ba3ScB9O18
Li3Cs2B5O10
LiNaB4O7
KBe2B3O7
NaBa4B3O9
Ba3Y2B6O15
Na2Al2B2O7
BaB4O7
LiB6O9F1
ScBO3
BaAlBO3F2
BaNaScB2O6
BaNaYB2O6
2.
Table S2 Comparison of experimental band gaps (Eg) and calculated values from
MBVS method in all DUV borates with measured UV absorption edge. The VM(min)
factors are listed as well.
Experimental
Compound
-BaB2O4
BaAlBO3F2
KBe2BO3F2
RbBe2BO3F2
CsBe2BO3F2
LiB3O5
CsB3O5
CsLiB6O10
Li2B4O7
K2Al2B2O7
BaCaBO3F
Ba3Sr4(BO3)3F5
SrB2O4
Ca5B3O9F
Li6Rb5B11O22
BaMgBO3F
CsBaB3O6
Li4Cs3B7O14
Ba2Mg(B3O6)2
Li3Cs2B5O10
La2CaB10O19
NaSr3B3O6F4
YAl3(BO3)4
KB5O8.4H2O
NaBe2BO3F2
Calculated
cutoff(nm)
Eg (eV)
Ref.
Eg (eV)
VM(min)
185
165
150
155
151
155
167
175
160
180
210
210
200
196
190
190
190
190
178
175
170
170
165
160
150
6.71
7.52
8.27
8.01
8.22
8.01
7.43
7.09
7.76
6.89
5.91
5.91
6.21
6.33
6.53
6.54
6.53
6.53
6.97
7.09
7.30
7.30
7.52
7.76
8.27
[1]
[1]
[1]
[1]
[1]
[1]
[1]
[1]
[1]
[1]
[2]
[3]
[4]
[5]
[6]
[7]
[8]
[9]
[10]
[11]
[1]
[12]
[1]
[1]
[13]
6.35
7.34
8.08
8.08
8.05
7.67
7.69
7.67
7.34
7.27
6.12
5.96
6.16
6.19
6.40
6.43
6.55
6.49
7.01
6.51
7.36
7.20
7.78
7.47
7.90
1.060
1.602
2.007
2.006
1.988
1.788
1.790
1.780
1.599
1.565
0.937
0.846
0.957
0.974
1.088
1.103
1.167
1.135
1.425
1.149
1.610
1.526
1.839
1.670
1.905
3. Figure S1. Electronic structures for the representative UV borates listed in Table I.
Partial densities of states (PDOS) are shown on the left panels and the shadow regions
indicate the non-bonding states, while the project of the non-bonding orbitals on the structural
spaces are shown on the right panels. The charge densities are shown in the same scale. The
black numbers are the VM values calculated by the MBVS method, while the red numbers are
those by mulliken bond population analysis.
1) BBO
100
BBO
Ba
B
O
80
60
40
20
density of states (1/eV)
0
3
-10
-5
0
5
10
Oa
Oa
2
VM=1.16
0.98
1
0
3
Ob
2
VM=1.93
1.39
1
0
-10
-5
0
5
Energy(eV)
10
2) BABF
40
B
O
Al
F
Ba
30
20
BABF
10
0
-10
-5
0
5
3
10
O
2
VM=1.60
1.21
1
0
-10
-5
0
Energy(eV)
5
10
Ob
3) KBBF
60
KBBF
O
B
Be
F
K
30
0
3
O
2
1.66 VM=2.007
1
0
-10
-5
0
5
Energy(eV)
10
4) RBBF
O
B
Rb
Be
F
16
8
RBBF
0
O
3
2
1.66
VM=2.006
1
0
-10
-5
0
5
Energy(eV)
10
5) CBBF
12
Cs
Be
B
O
F
6
CBBF
6)
0
-10
-5
0
5
3
10
O
2
1.64
VM=1.988
1
0
-10
-5
0
Energy(eV)
5
10
6) LBO
40
Li
B
O
30
20
LBO
10
0
3
O1
O1
2
VM=1.79
1.54
1
O2
0
3
O2
2
1.47 VM=1.87
1
0
-10
-5
0
5
Energy (eV)
10
7) CBO
40
Cs
B
O
20
CBO
O2
0
3
O1
2
1.5
1
VM=1.861
O1
0
3
O2
2
VM=1.812
1.5
1
0
-10
-5
0
Energy (eV)
5
10
8) CLBO
40
30
Li
Cs
B
O
20
10
CLBO
0
3
O1
O1
O2
2
1.50
1
1.905
0
3
O2
2
1.806
1.47
1
0
-10
-5
0
Energy(eV)
5
10
9) LB4
40
o
B
Li
30
20
Li2B4O7
10
0
3
O1
2
1.40
1.73
O2
1
O1
0
3
O2
2
1.65
1.44
1
0
-10
-5
0
Energy(ev)
5
10
10) KABO
K
Al
B
O
60
30
KABO
0
5
Oa
1.701
4
1.36
3
Ob
2
1
0
5
Ob
1.593
4
1.23
3
2
1
0
-10
-5
0
Energy(eV)
5
10
Oa
4. Figure S2. Relationship between the non-bonding states and the energy gaps in the
representative DUV borates listed in Table 1. The straight line is fitted from the least
squares method.
BBO
6
KABO
LB4
BABF
CLBO
7
CBO
8
LBO
KBBF
CBBF
9
RBBF
Experimental band gap (eV)
10
5
0.5
1.0
1.5
2.0
2.5
3.0
Amount of the non-bonding electrons (e)
3.5
5.
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