We propose previously unrecognized allotropes of monolayer boron phosphorus (BP) based on ab initio density functional calculations. In addition to the hexagonal structure of h-BP, four types of boron phosphide compounds were predicted to be stable as monolayers. They can form sp2 hybridized planar structures composed of 6-membered rings, and buckled geometries including 4–8 or 3–9 membered rings with sp3 like bonding for P atoms. The calculated Bader charges illustrate their ionic characters with the charge transfers from B to P atoms. The competing between the electrostatic energy and the bonding energy of sp2 and sp3 hybridizations reflected in P atoms results in multiple structures of BP. These 2D BP structures can be semiconducting or metallic depending on their geometric structures. Our findings significantly broaden the diversity of monolayer BP allotropes and provide valuable guidance to other 2D group-III-V allotropes.

1.
B.
Feng
,
Z.
Ding
,
S.
Meng
,
Y.
Yao
,
X.
He
,
P.
Cheng
,
L.
Chen
, and
K.
Wu
,
Nano Lett.
12
,
3507
(
2012
).
2.
M.
Dávila
,
L.
Xian
,
S.
Cahangirov
,
A.
Rubio
, and
G.
Le Lay
,
New J. Phys.
16
,
095002
(
2014
).
3.
F.-F.
Zhu
,
W.-J.
Chen
,
Y.
Xu
,
C.-L.
Gao
,
D.-D.
Guan
,
C.-H.
Liu
,
D.
Qian
,
S.-C.
Zhang
, and
J.-F.
Jia
,
Nat. Mater.
14
,
1020
(
2015
).
4.
H. L.
Zhuang
,
A. K.
Singh
, and
R. G.
Hennig
,
Phys. Rev. B
87
,
165415
(
2013
).
5.
H.
Şahin
,
S.
Cahangirov
,
M.
Topsakal
,
E.
Bekaroglu
,
E.
Akturk
,
R. T.
Senger
, and
S.
Ciraci
,
Phys. Rev. B
80
,
155453
(
2009
).
6.
Y.
Kubota
,
K.
Watanabe
,
O.
Tsuda
, and
T.
Taniguchi
,
Science
317
,
932
(
2007
).
7.
A. J.
Mannix
,
X.-F.
Zhou
,
B.
Kiraly
,
J. D.
Wood
,
D.
Alducin
,
B. D.
Myers
,
X.
Liu
,
B. L.
Fisher
,
U.
Santiago
,
J. R.
Guest
 et al,
Science
350
,
1513
(
2015
).
8.
B.
Feng
,
J.
Zhang
,
Q.
Zhong
,
W.
Li
,
S.
Li
,
H.
Li
,
P.
Cheng
,
S.
Meng
,
L.
Chen
, and
K.
Wu
,
Nat. Chem.
8
,
563
(
2016
).
9.
L.
Li
,
Y.
Yu
,
G. J.
Ye
,
Q.
Ge
,
X.
Ou
,
H.
Wu
,
D.
Feng
,
X. H.
Chen
, and
Y.
Zhang
,
Nat. Nanotechnol.
9
,
372
(
2014
).
10.
F.
Xia
,
H.
Wang
, and
Y.
Jia
,
Nat. Commun.
5
,
4458
(
2014
).
11.
Z.
Zhu
,
C.
Li
,
W.
Yu
,
D.
Chang
,
Q.
Sun
, and
Y.
Jia
,
Appl. Phys. Lett.
105
,
113105
(
2014
).
12.
M.
Wu
,
H.
Fu
,
L.
Zhou
,
K.
Yao
, and
X. C.
Zeng
,
Nano Lett.
15
,
3557
(
2015
).
13.
Y.
Wang
,
J.
Lv
,
L.
Zhu
, and
Y.
Ma
,
Phys. Rev. B
82
,
094116
(
2010
).
14.
P. E.
Blöchl
,
Phys. Rev. B
50
,
17953
(
1994
).
15.
G.
Kresse
and
D.
Joubert
,
Phys. Rev. B
59
,
1758
(
1999
).
16.
J. P.
Perdew
,
K.
Burke
, and
M.
Ernzerhof
,
Phys. Rev. Lett.
77
,
3865
(
1996
).
17.
H. J.
Monkhorst
and
J. D.
Pack
,
Phys. Rev. B
13
,
5188
(
1976
).
18.
A.
Togo
,
F.
Oba
, and
I.
Tanaka
,
Phys. Rev. B
78
,
134106
(
2008
).
19.
J.
Heyd
,
G. E.
Scuseria
, and
M.
Ernzerhof
,
J. Chem. Phys.
118
,
8207
(
2003
).
20.
E. V.
Anslyn
and
D. A.
Dougherty
,
Modern Physical Organic Chemistry
(
University Science Books
,
Sausalito, CA
,
2006
).
21.
A. S.
Rodin
,
A.
Carvalho
, and
A. H.
Castro Neto
,
Phys. Rev. Lett.
112
,
176801
(
2014
).
22.
J.
Dong
,
H.
Li
, and
L.
Li
,
NPG Asia Mater.
5
,
e56
(
2013
).
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