Graphene, with its unique band structure, mechanical stability, and high charge mobility, holds great promise for next-generation electronics. Nevertheless, its zero bandgap challenges the control of current flow through electrical gating, consequently limiting its practical applications. Recent research indicates that atomic oxygen can oxidize epitaxial graphene in a vacuum without causing unwanted damage. In this study, we have investigated the effects of chemisorbed atomic oxygen on the electronic properties of epitaxial graphene using scanning tunneling microscopy (STM). Our findings reveal that oxygen atoms effectively modify the electronic states of graphene, resulting in a bandgap at its Dirac point. Furthermore, we demonstrate that it is possible to selectively induce desorption or hopping of oxygen atoms with atomic precision by applying appropriate bias sweeps with an STM tip. These results suggest the potential for atomic-scale tailoring of graphene oxide, enabling the development of graphene-based atomic-scale electronic devices.

1.
K. S.
Novoselov
,
A. K.
Geim
,
S. V.
Morozov
,
D.
Jiang
,
Y.
Zhang
,
S. V.
Dubonos
,
I. V.
Grigorieva
, and
A. A.
Firsov
,
Science
306
,
666
(
2004
).
2.
K. I.
Bolotin
,
K. J.
Sikes
,
Z.
Jiang
,
M.
Klima
,
G.
Fudenberg
,
J.
Hone
,
P.
Kim
, and
H. L.
Stormer
,
Solid State Commun.
146
,
351
(
2008
).
3.
S. V.
Morozov
,
K. S.
Novoselov
,
M. I.
Katsnelson
,
F.
Schedin
,
D. C.
Elias
,
J. A.
Jaszczak
, and
A. K.
Geim
,
Phys. Rev. Lett.
100
,
016602
(
2008
).
4.
C.
Lee
,
X.
Wei
,
J. W.
Kysar
, and
J.
Hone
,
Science
321
,
385
(
2008
).
5.
G.
Eda
,
C.
Mattevi
,
H.
Yamaguchi
,
H.
Kim
, and
M.
Chhowalla
,
J. Phys. Chem. C
113
,
15768
(
2009
).
6.
V.
López
,
R. S.
Sundaram
,
C.
Gómez-Navarro
,
D.
Olea
,
M.
Burghard
,
J.
Gómez-Herrero
,
F.
Zamora
, and
K.
Kern
,
Adv. Mater.
21
,
4683
(
2009
).
8.
A.
Lipatov
,
M. J.-F.
Guinel
,
D. S.
Muratov
,
V. O.
Vanyushin
,
P. M.
Wilson
,
A.
Kolmakov
, and
A.
Sinitskii
,
Appl. Phys. Lett.
112
,
053103
(
2018
).
9.
Z.
Luo
,
P. M.
Vora
,
E. J.
Mele
,
A. T. C.
Johnson
, and
J. M.
Kikkawa
,
Appl. Phys. Lett.
94
,
111909
(
2009
).
10.
A.
Mathkar
,
D.
Tozier
,
P.
Cox
,
P.
Ong
,
C.
Galande
,
K.
Balakrishnan
,
A.
Leela Mohana Reddy
, and
P. M.
Ajayan
,
J. Phys. Chem. Lett.
3
,
986
(
2012
).
11.
W. S.
Hummers
and
R. E.
Offeman
,
J. Am. Chem. Soc.
80
,
1339
(
1958
).
12.
H. R.
Byon
,
S. W.
Lee
,
S.
Chen
,
P. T.
Hammond
, and
Y.
Shao-Horn
,
Carbon
49
,
457
(
2011
).
13.
S.
Pei
and
H.-M.
Cheng
,
Carbon
50
,
3210
(
2012
).
14.
G. M.
Rutter
,
J. N.
Crain
,
N. P.
Guisinger
,
T.
Li
,
P. N.
First
, and
J. A.
Stroscio
,
Science
317
,
219
(
2007
).
15.
E.
Stolyarova
,
K. T.
Rim
,
S.
Ryu
,
J.
Maultzsch
,
P.
Kim
,
L. E.
Brus
,
T. F.
Heinz
,
M. S.
Hybertsen
, and
G. W.
Flynn
,
Proc. Natl. Acad. Sci. U. S. A.
104
,
9209
(
2007
).
16.
Y.
Zhang
,
V. W.
Brar
,
C.
Girit
,
A.
Zettl
, and
M. F.
Crommie
,
Nat. Phys.
5
,
722
(
2009
).
17.
K. S.
Kim
,
T.-H.
Kim
,
A. L.
Walter
,
T.
Seyller
,
H. W.
Yeom
,
E.
Rotenberg
, and
A.
Bostwick
,
Phys. Rev. Lett.
110
,
036804
(
2013
).
18.
D.
Pandey
,
R.
Reifenberger
, and
R.
Piner
,
Surf. Sci.
602
,
1607
(
2008
).
19.
N. A.
Vinogradov
,
K.
Schulte
,
M. L.
Ng
,
A.
Mikkelsen
,
E.
Lundgren
,
N.
Mårtensson
, and
A. B.
Preobrajenski
,
J. Phys. Chem. C
115
,
9568
(
2011
).
20.
M. Z.
Hossain
,
J. E.
Johns
,
K. H.
Bevan
,
H. J.
Karmel
,
Y. T.
Liang
,
S.
Yoshimoto
,
K.
Mukai
,
T.
Koitaya
,
J.
Yoshinobu
,
M.
Kawai
,
A. M.
Lear
,
L. L.
Kesmodel
,
S. L.
Tait
, and
M. C.
Hersam
,
Nat. Chem.
4
,
305
(
2012
).
21.
C.
Harthcock
,
A.
Jahanbekam
,
Y.
Zhang
, and
D. Y.
Lee
,
J. Phys. Chem. C
121
,
20051
(
2017
).
22.
T.-C.
Shen
,
C.
Wang
,
G. C.
Abeln
,
J. R.
Tucker
,
J. W.
Lyding
,
P.
Avouris
, and
R. E.
Walkup
,
Science
268
,
1590
(
1995
).
23.
M.
Fuechsle
,
J. A.
Miwa
,
S.
Mahapatra
,
H.
Ryu
,
S.
Lee
,
O.
Warschkow
,
L. C. L.
Hollenberg
,
G.
Klimeck
, and
M. Y.
Simmons
,
Nat. Nanotechnol.
7
,
242
(
2012
).
24.
F.
Bianco
,
D. R.
Bowler
,
J. H. G.
Owen
,
S. A.
Köster
,
M.
Longobardi
, and
C.
Renner
,
ACS Nano
7
,
4422
(
2013
).
25.
R.
Achal
,
M.
Rashidi
,
J.
Croshaw
,
D.
Churchill
,
M.
Taucer
,
T.
Huff
,
M.
Cloutier
,
J.
Pitters
, and
R. A.
Wolkow
,
Nat. Commun.
9
,
2778
(
2018
).
26.
L.
Tapasztó
,
G.
Dobrik
,
P.
Lambin
, and
L. P.
Biró
,
Nat. Nanotechnol.
3
,
397
(
2008
).
27.
M. Z.
Hossain
,
M. A.
Walsh
, and
M. C.
Hersam
,
J. Am. Chem. Soc.
132
,
15399
(
2010
).
28.
A. J.
Martínez-Galera
,
I.
Brihuega
,
A.
Gutiérrez-Rubio
,
T.
Stauber
, and
J. M.
Gómez-Rodríguez
,
Sci. Rep.
4
,
7314
(
2014
).
29.
J.
Díez-Albar
,
M. D.
Jiménez-Sánchez
, and
J. M.
Gómez-Rodríguez
,
J. Phys. Chem. C
123
,
5525
(
2019
).
30.
A. J.
Heinrich
,
C. P.
Lutz
,
J. A.
Gupta
, and
D. M.
Eigler
,
Science
298
,
1381
(
2002
).
31.
M.
Ostler
,
F.
Speck
,
M.
Gick
, and
T.
Seyller
,
Phys. Status Solidi B
247
,
2924
(
2010
).
32.
G.
Yazdi
,
T.
Iakimov
, and
R.
Yakimova
,
Crystals
6
,
53
(
2016
).
33.
T.
Ohta
,
A.
Bostwick
,
T.
Seyller
,
K.
Horn
, and
E.
Rotenberg
,
Science
313
,
951
(
2006
).
34.
C.
Virojanadara
,
M.
Syväjarvi
,
R.
Yakimova
,
L. I.
Johansson
,
A. A.
Zakharov
, and
T.
Balasubramanian
,
Phys. Rev. B
78
,
245403
(
2008
).
35.
T.
Ahn
,
S.
Song
,
U.
Ham
, and
T.-H.
Kim
,
Rev. Sci. Instrum.
94
,
063702
(
2023
).
36.
During the acquisition of the dI/dV spectra, the tunneling condition was established with parameters V s and I t. After the STM feedback was turned off, the tip's position was automatically adjusted by Z offset. Subsequently, the dI/dV signal was recorded as a function of the applied bias voltage.
37.
P.
Lauffer
,
K. V.
Emtsev
,
R.
Graupner
,
T.
Seyller
,
L.
Ley
,
S. A.
Reshanov
, and
H. B.
Weber
,
Phys. Rev. B
77
,
155426
(
2008
).
38.
B.
Premlal
,
M.
Cranney
,
F.
Vonau
,
D.
Aubel
,
D.
Casterman
,
M. M.
De Souza
, and
L.
Simon
,
Appl. Phys. Lett.
94
,
263115
(
2009
).
39.
J.
Choi
,
H.
Lee
, and
S.
Kim
,
J. Phys. Chem. C
114
,
13344
(
2010
).
40.
Y.
Dai
,
S.
Ni
,
Z.
Li
, and
J.
Yang
,
J. Phys.: Condens. Matter
25
,
405301
(
2013
).
41.
Q.
Li
,
S.
Zheng
,
J.
Pu
,
J.
Sun
,
L.-F.
Huang
,
L.
Wang
, and
Q.
Xue
,
Phys. Chem. Chem. Phys.
21
,
12121
(
2019
).
42.
A. M.
Suarez
,
L. R.
Radovic
,
E.
Bar-Ziv
, and
J. O.
Sofo
,
Phys. Rev. Lett.
106
,
146802
(
2011
).
43.
S.
Yi
,
J.-H.
Choi
,
H.-J.
Kim
,
C. H.
Park
, and
J.-H.
Cho
,
Phys. Chem. Chem. Phys.
19
,
9107
(
2017
).
44.
B. C.
Stipe
,
M. A.
Rezaei
,
W.
Ho
,
S.
Gao
,
M.
Persson
, and
B. I.
Lundqvist
,
Phys. Rev. Lett.
78
,
4410
(
1997
).
45.
L. J.
Lauhon
and
W.
Ho
,
J. Phys. Chem. A
104
,
2463
(
2000
).
46.
S.-W.
Hla
,
G.
Meyer
, and
K.-H.
Rieder
,
ChemPhysChem
2
,
361
(
2001
).
47.
S.-W.
Hla
,
G.
Meyer
, and
K.-H.
Rieder
,
Chem. Phys. Lett.
370
,
431
(
2003
).
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