We have investigated the adsorption and thermal reaction processes of NO with silicene spontaneously formed on the ZrB2/Si(111) substrate using synchrotron radiation x-ray photoelectron spectroscopy (XPS) and density-functional theory calculations. NO is dissociatively adsorbed on the silicene surface at 300 K. An atomic nitrogen is bonded to three Si atoms most probably by a substitutional adsorption with a Si atom of silicene (N≡Si3). An atomic oxygen is inserted between two Si atoms of the silicene (Si—O—Si). With increasing NO exposure, the two-dimensional honeycomb silicene structure gets destroyed, judging from the decay of typical Si 2p spectra for silicene. After a large amount of NO exposure, the oxidation state of Si becomes Si4+ predominantly, and the intensity of the XPS peaks of the ZrB2 substrate decreases, indicating that complicated silicon oxinitride species have developed three-dimensionally. By heating above 900 K, the oxide species start to desorb from the surface, but nitrogen-bonded species still exist. After flashing at 1053 K, no oxygen species is observed on the surface; SiN species are temporally formed as a metastable species and BN species also start to develop. In addition, the silicene structure is restored on the ZrB2/Si(111) substrate. After prolonged heating at 1053 K, most of nitrogen atoms are bonded to B atoms to form a BN layer at the topmost surface. Thus, BN-covered silicene is formed on the ZrB2/Si(111) substrate by the adsorption of NO at 300 K and prolonged heating at 1053 K.

1.
P.
Ajayan
,
P.
Kim
, and
K.
Banerjee
,
Phys. Today
69
(
9
),
38
(
2016
).
2.
A. H.
Castro Neto
,
F.
Guinea
,
N. M. R.
Peres
,
K. S.
Novoselov
, and
A. K.
Geim
,
Rev. Mod. Phys.
81
,
109
(
2009
).
3.
K.
Takeda
and
K.
Shiraishi
,
Phys. Rev. B
50
,
14916
(
1994
).
4.
S.
Cahangirov
,
M.
Topsakal
,
E.
Aktürk
,
H.
Şahin
, and
S.
Ciraci
,
Phys. Rev. Lett.
102
,
236804
(
2009
).
5.
A.
Kara
,
H.
Enriquez
,
A. P.
Seitsonen
,
L. C.
Lew Yan Voon
,
S.
Vizzini
,
B.
Aufray
, and
H.
Oughaddou
,
Surf. Sci. Rep.
67
,
1
(
2012
).
6.
N.
Takagi
,
C.-L.
Lin
,
K.
Kawahara
,
E.
Minamitani
,
N.
Tsukahara
,
M.
Kawai
, and
R.
Arafune
,
Prog. Surf. Sci.
90
,
1
(
2015
).
7.
M.
Ezawa
,
J. Phys. Soc. Jpn.
84
,
121003
(
2015
).
8.
Silicene: Structure, Properties, and Applications
, edited by
M. J. S.
Spencer
and
T.
Morishita
(
Springer
,
Switzerland
,
2016
).
9.
B.
Lalmi
,
H.
Oughaddou
,
H.
Enriquez
,
A.
Kara
,
S.
Vizzini
,
B.
Ealet
, and
B.
Aufray
,
Appl. Phys. Lett.
97
,
223109
(
2010
).
10.
B.
Aufray
,
A.
Kara
,
S.
Vizzini
,
H.
Oughaddou
,
C.
Léandri
,
B.
Ealet
, and
G.
Le Lay
,
Appl. Phys. Lett.
96
,
183102
(
2010
).
11.
C.-L.
Lin
,
R.
Arafune
,
K.
Kawahara
,
N.
Tsukahara
,
E.
Minamitani
,
Y.
Kim
,
N.
Takagi
, and
M.
Kawai
,
Appl. Phys. Express
5
,
045802
(
2012
).
12.
R.
Arafune
,
C.-L.
Lin
,
K.
Kawahara
,
N.
Tsukahara
,
E.
Minamitani
,
Y.
Kim
,
N.
Takagi
, and
M.
Kawai
,
Surf. Sci.
608
,
297
(
2013
).
13.
P.
Vogt
,
P.
De Padova
,
C.
Quaresima
,
J.
Avila
,
E.
Frantzeskakis
,
M. C.
Asensio
,
A.
Resta
,
B.
Ealet
, and
G.
Le Lay
,
Phys. Rev. Lett.
108
,
155501
(
2012
).
14.
B.
Feng
,
Z.
Ding
,
S.
Meng
,
Y.
Yao
,
X.
He
,
P.
Cheng
,
L.
Chen
, and
K.
Wu
,
Nano Lett.
12
,
3507
(
2012
).
15.
L.
Chen
,
H.
Li
,
B.
Feng
,
Z.
Ding
,
J.
Qiu
,
P.
Cheng
,
K.
Wu
, and
S.
Meng
,
Phys. Rev. Lett.
110
,
085504
(
2013
).
16.
Y.
Du
,
J.
Zhuang
,
J.
Wang
,
Z.
Li
,
H.
Liu
,
J.
Zhao
,
X.
Xu
,
H.
Feng
,
L.
Chen
,
K.
Wu
,
X.
Wang
, and
S. X.
Dou
,
Sci. Adv.
2
,
e1600067
(
2016
).
17.
A.
Fleurence
,
R.
Friedlein
,
T.
Ozaki
,
H.
Kawai
,
Y.
Wang
, and
Y.
Yamada-Takamura
,
Phys. Rev. Lett.
108
,
245501
(
2012
).
18.
C.-C.
Lee
,
A.
Fleurence
,
R.
Friedlein
,
Y.
Yamada-Takamura
, and
T.
Ozaki
,
Phys. Rev. B
88
,
165404
(
2013
).
19.
C.-C.
Lee
,
A.
Fleurence
,
R.
Friedlein
,
Y.
Yamada-Takamura
, and
T.
Ozaki
,
Phys. Rev. B
90
,
241402(R)
(
2014
).
20.
A.
Fleurence
,
Y.
Yoshida
,
C.-C.
Lee
,
T.
Ozaki
,
Y.
Yamada-Takamura
, and
Y.
Hasegawa
,
Appl. Phys. Lett.
104
,
021605
(
2014
).
21.
C.-C.
Lee
,
A.
Fleurence
,
Y.
Yamada-Takamura
,
T.
Ozaki
, and
R.
Friedlein
,
Phys. Rev. B
90
,
075422
(
2014
).
22.
Y.
Yamada-Takamura
and
R.
Friedlein
,
Sci. Technol. Adv. Mater.
15
,
064404
(
2014
).
23.
R.
Friedlein
,
A.
Fleurence
,
K.
Aoyagi
,
M. P.
de Jong
,
H.
Van Bui
,
F. B.
Wiggers
,
S.
Yoshimoto
,
T.
Koitaya
,
S.
Shimizu
,
H.
Noritake
,
K.
Mukai
,
J.
Yoshinobu
, and
Y.
Yamada-Takamura
,
J. Chem. Phys.
140
,
184704
(
2014
).
24.
L.
Meng
,
Y.
Wang
,
L.
Zhang
,
S.
Du
,
R.
Wu
,
L.
Li
,
Y.
Zhang
,
G.
Li
,
H.
Zhou
,
W. A.
Hofer
, and
H.-J.
Gao
,
Nano Lett.
13
,
685
(
2013
).
25.
T.
Aizawa
,
S.
Suehara
, and
S.
Otani
,
J. Phys. Chem. C
118
,
23049
(
2014
).
26.
T.
Aizawa
,
S.
Suehara
, and
S.
Otani
,
J. Phys.: Condens. Matter
27
,
305002
(
2015
).
27.
C.-C.
Lee
,
J.
Yoshinobu
,
K.
Mukai
,
S.
Yoshimoto
,
H.
Ueda
,
R.
Friedlein
,
A.
Fleurence
,
Y.
Yamada-Takamura
, and
T.
Ozaki
,
Phys. Rev. B
95
,
115437
(
2017
).
28.
T. H.
Osborn
,
A. A.
Farajian
,
O. V.
Pupysheva
,
R. S.
Aga
, and
L. C.
Lew Yan Voon
,
Chem. Phys. Lett.
511
,
101
(
2011
).
29.
N.
Gao
,
W. T.
Zheng
, and
Q.
Jiang
,
Phys. Chem. Chem. Phys.
14
,
257
(
2012
).
30.
J.
Sivek
,
H.
Sahin
,
B.
Partoens
, and
F. M.
Peeters
,
Phys. Rev. B
87
,
085444
(
2013
).
31.
R.
Friedlein
,
A.
Fleurence
,
J. T.
Sadowski
, and
Y.
Yamada-Takamura
,
Appl. Phys. Lett.
102
,
221603
(
2013
).
32.
L.
Ma
,
J.-M.
Zhang
,
K.-W.
Xu
, and
V.
Ji
,
Physica B
425
,
66
(
2013
).
33.
R.
Friedlein
,
H.
Van Bui
,
F. B.
Wiggers
,
Y.
Yamada-Takamura
,
A. Y.
Kovalgin
, and
M. P.
De Jong
,
J. Chem. Phys.
140
,
204705
(
2014
).
34.
L.
Ma
,
J.-M.
Zhang
,
K.-W.
Xu
, and
V.
Ji
,
Physica E
60
,
112
(
2014
).
35.
W.
Hu
,
N.
Xia
,
X.
Wu
,
Z.
Li
, and
J.
Yang
,
Phys. Chem. Chem. Phys.
16
,
6957
(
2014
).
36.
F. B.
Wiggers
,
H.
Van Bui
,
R.
Friedlein
,
Y.
Yamada-Takamura
,
J.
Schmitz
,
A. Y.
Kovalgin
, and
M. P.
de Jong
,
J. Chem. Phys.
144
,
134703
(
2016
).
37.
M.
Nishijima
,
H.
Kobayashi
,
K.
Edamoto
, and
M.
Onchi
,
Surf. Sci.
137
,
473
(
1984
).
38.
Y.
Taguchi
,
M.
Fujisawa
,
Y.
Kuwahara
,
M.
Onchi
, and
M.
Nishijima
,
Surf. Sci.
217
,
L413
(
1989
).
39.
Z.
Ying
and
W.
Ho
,
J. Vac. Sci. Technol., A
7
,
2099
(
1989
).
40.
B.
Rottger
,
R.
Kliese
, and
H.
Neddermeyer
,
J. Vac. Sci. Technol., B
14
,
1051
(
1996
).
41.
Y. D.
Chung
,
J. W.
Kim
,
C. N.
Whang
, and
H. W.
Yeom
,
Phys. Rev. B
65
,
155310
(
2002
).
42.
A.
Kamath
,
D. L.
Kwong
,
Y. M.
Sun
,
P. M.
Blass
,
S.
Whaley
, and
J. M.
White
,
Appl. Phys. Lett.
70
,
63
(
1997
).
43.
M.
Riehl-Chudoba
,
L.
Surnev
, and
P.
Soukiassian
,
Surf. Sci.
306
,
313
(
1994
).
44.
J. P.
Perdew
,
K.
Burke
, and
M.
Ernzerhof
,
Phys. Rev. Lett.
77
,
3865
(
1996
).
45.
See http://www.openmx-square.org/ for the code, OpenMX, pseudo-atomic basis functions, and pseudopotentials.
46.
G.
Theurich
and
N. A.
Hill
,
Phys. Rev. B
64
,
073106
(
2001
).
47.
I.
Morrison
,
D. M.
Bylander
, and
L.
Kleinman
,
Phys. Rev. B
47
,
6728
(
1993
).
48.
49.
T.
Ozaki
and
H.
Kino
,
Phys. Rev. B
69
,
195113
(
2004
).
50.
T.
Ozaki
and
H.
Kino
,
Phys. Rev. B
72
,
045121
(
2005
).
51.
F.
Eckert
,
P.
Pulay
, and
H.-J.
Werner
,
J. Comput. Chem.
18
,
1473
(
1997
).
52.
T.
Ozaki
and
C.-C.
Lee
,
Phys. Rev. Lett.
118
,
026401
(
2017
).
53.
Z.
Shuxian
,
W. K.
Hall
,
G.
Ertl
, and
H.
Knözinger
,
J. Catal.
100
,
167
(
1986
).
54.
A.
Baraldi
,
V. R.
Dhanak
,
M.
Kiskinova
, and
R.
Rosei
,
Appl. Surf. Sci.
78
,
445
(
1994
).
55.
J. A.
Taylor
,
G. M.
Lancaster
,
A.
Ignatiev
, and
J. W.
Rabalais
,
J. Chem. Phys.
68
,
1776
(
1978
).
56.
M.
Delfino
,
J. A.
Fair
, and
S.
Salimian
,
Appl. Phys. Lett.
60
,
341
(
1992
).
57.
G. M.
Ingo
,
N.
Zacchetti
,
D.
Della Sala
, and
C.
Coluzza
,
J. Vac. Sci. Technol., A
7
,
3048
(
1989
).
58.
See https://srdata.nist.gov/xps/Default.aspx for NIST X-ray Photoelectron Spectroscopy Database.
59.
T.
Aizawa
,
S.
Suehara
,
S.
Hishita
,
S.
Otani
, and
M.
Arai
,
Phys. Rev. B
71
,
165405
(
2005
).
60.
J.
Tang
,
K.
Nishimoto
,
S.
Ogawa
,
A.
Yoshigoe
,
S.
Ishidzuka
,
D.
Watanabe
,
Y.
Teraoka
, and
Y.
Takakuwa
,
e-J. Surf. Sci. Nanotechnol.
11
,
116
(
2013
).
61.
P.
Widmayer
,
H.-G.
Boyen
,
P.
Ziemann
,
P.
Reinke
, and
P.
Oelhafen
,
Phys. Rev. B
59
,
5233
(
1999
).
62.
K.
Aoyagi
,
F. B.
Wiggers
,
R.
Friedlein
,
F.
Gimbert
,
A.
Fleurence
,
T.
Ozaki
, and
Y.
Yamada-Takamura
,
J. Appl. Phys.
126
,
135305
(
2019
).
63.
F. B.
Wiggers
,
A.
Fleurence
,
K.
Aoyagi
,
T.
Yonezawa
,
Y.
Yamada-Takamura
,
H.
Feng
,
J.
Zhuang
,
Y.
Du
,
A. Y.
Kovalgin
, and
M. P.
de Jong
,
2D Mater.
6
,
035001
(
2019
).
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