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Efficient doping of functionalized graphene and h-BN by molecular adsorption

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Shiyang Fu
Shiyang Fu
Shiyang Fu
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Yuhan Yang
Yuhan Yang
Yuhan Yang
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Mai Zhang
Mai Zhang
Mai Zhang
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Nan Gao
Nan Gao
Nan Gao
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Abstract and Figures

In this work, we investigate the structural and electronic properties of molecular acceptors and donors adsorbed on H/F-functionalized graphene and h-BN by using first principles calculation. Graphane adsorbed with acceptors show p-type doping features, and fluorographene with donors are n-type doping. On the other hand, both H- and F-functionalized BN adsorbed systems exhibit n-type doping. The different doping characteristics depend on the relative energy level alignment of the molecules and substrates, which determines the electron transfer direction. In addition, the bands of adatoms are close to the band edges of substrates near Fermi level (0.0004–0.113 eV), denoting the efficient doping for H/F-functionalized graphene and h-BN. These results provide important indications for designing novel two-dimensional materials with suitable doped characteristics for opto-electronics applications.
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Phys. Scr. 99 (2024)065920 https://doi.org/10.1088/1402-4896/ad406d
PAPER
Efficient doping of functionalized graphene and h-BN by molecular
adsorption
Shiyang Fu
1
, Yuhan Yang
1
, Mai Zhang
1
, Nan Gao
1,∗
, Qiliang Wang
1,2,∗
and Hongdong Li
1,2,∗
1
State Key Lab of Superhard Materials, College of Physics, Jilin University, Changchun 130012, People’s Republic of China
2
Shenzhen Research Institute, Jilin University, Shenzhen 518057, People’s Republic of China
∗
Authors to whom any correspondence should be addressed.
E-mail: gaon@jlu.edu.cn,wangqiliang@jlu.edu.cn and hdli@jlu.edu.cn
Keywords: functionalized graphene and BN, surface transfer doping, molecular adsorption, first principles calculation
Supplementary material for this article is available online
Abstract
In this work, we investigate the structural and electronic properties of molecular acceptors and donors
adsorbed on H/F-functionalized graphene and h-BN by using first principles calculation. Graphane
adsorbed with acceptors show p-type doping features, and fluorographene with donors are n-type
doping. On the other hand, both H- and F-functionalized BN adsorbed systems exhibit n-type doping.
The different doping characteristics depend on the relative energy level alignment of the molecules
and substrates, which determines the electron transfer direction. In addition, the bands of adatoms are
close to the band edges of substrates near Fermi level (0.0004–0.113 eV), denoting the efficient doping
for H/F-functionalized graphene and h-BN. These results provide important indications for
designing novel two-dimensional materials with suitable doped characteristics for opto-electronics
applications.
1. Introduction
After the experimental preparation, graphene has emerged as a rising star for two-dimensional electronics,
owing to its exceptional electronic and mechanical properties [1,2]. While graphene is a zero-gap
semiconductor, and the band gap should be open for its practical application in electronic devices. A natural and
effective approach for this purpose is to convert the sp
2
bonds in graphene to sp
3
bonds via surface
functionalization. Graphane (hydrogenated graphene)was first theoretically predicted by Sofo et al [3], and it
was subsequently synthesized by graphene with hydrogen plasma [4]. A similar graphene derivative is
fluorinated graphene (fluorographene), which is realized by exposing graphene to atomic fluorine formed by
decomposition of XeF
2
[5]. Graphane and fluorographene possess wide band gaps [5,6], which is advantageous
for electronic applications.
Hexagonal boron nitride (h-BN), an analogous two-dimensional structure to graphene, also exhibits diverse
electronic properties and great potential for high-quality nanodevices [7,8]. h-BN is a typical insulator with a
band gap of 5.8 eV [9], due to the strong ionicity of B-N bonds. Unlike the case of graphene, hydrogenation and
fluorination of h-BN lead to the reduced band gaps [10]. Although the hydrogenated BN (BNH
2
)monolayer has
not yet been experimentally prepared, its structural stability has been demonstrated [11], and its dynamic and
thermal stabilities have been proved [12].
Numerous studies have been conducted to unveil the intriguing properties and applications of
functionalized graphene and BN with dopants [13–15]. The doping of transition metal atoms in graphane forms
a robust structure and induces magnetism [16]. In addition, metals [17], metal oxides [18]and organic
molecules [19]are also successfully doped onto graphene experimentally to invoke the p-type or n-type
semiconducting behavior. Li-doped graphene [20], transition metal doped graphene [21]and Li decorated
BNH
2
[22]have been suggested as potential candidates for gas storage, and defected BNH
2
is proposed to trap
formaldehyde [23]. Additionally, based on the surface transfer doping mechanism, molecular adsorption could
RECEIVED
23 October 2023
REVISED
8 April 2024
ACCEPTED FOR PUBLICATION
18 April 2024
PUBLISHED
3 May 2024
© 2024 IOP Publishing Ltd
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