Band Gap Modulation of Graphene with Increasing Concentration of Li/B

Doping
Pooja Rani1, 2, Rajiv Bhandari3 and V. K. Jindal1
Department of Physics, Panjab University Chandigarh, India.
D. A. V. College, Sec-10, Chandigarh, India.
Post Graduate Govt. College, Sec-11, Chandigarh, India.

Abstract

The paper reports the theoretical study of structural and electronic changes in single layer graphene sheet by

replacing the carbon atoms with boron atoms and simultaneously adsorbing with equal amount of Lithium

atoms. Ab-initio density functional theory calculations have been performed to investigate the effects of

Boron-Lithium (Li/B) co-doping in graphene. Spanish Initiative for Electronic Simulation with thousands of

atoms (SIESTA) and VASP codes were used for the calculation and results were compared. The combination

of the hole (B) and electron (Li) doping effects, makes the Dirac point return to the original position. As a

result of p–n co-doping at different concentrations, the electronic structures of graphene are modulated to

open a band gap with width from 0.14 eV to 0.27 eV, depending on the co-doping concentrations. Thus, by

adding equal amount of B and Li we can tune the band gap of graphene in required range which is beneficial

for application of graphene in electronics.

Keywords: graphene, Density functional theory, band gap, co-doping.

*Corresponding author: email: pgoyal0510@gmail.com

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1. Introduction

Carbon nanostructures such as fullerenes and carbon nanotubes have been at the forefront of materials science

for nearly two decades. Graphene, a 2-D constituent of the carbon-allotropes family, has been the topic of

immense research since its discovery. It has taken the scientific world by storm due to its exotic properties and

vast applications. It is basically a one atom thick layer of sp2 hybridized carbon atoms arranged in a

honeycomb lattice. Graphene is strongest material found in nature. Since its successful fabrication in 2004

[1], it has attracted great interest from the researchers due to its unique properties [2, 3] like high charge

carrier mobility due to linear dispersion at the so called Dirac point and ballistic transport over long distances,

finite conductivity at zero carrier concentration. As Si-based semiconductor technology is proceeding towards

its fundamental limits in miniaturizing electronic devices, graphene has the potential to replace silicon as the

next-generation semiconductor material for electronic devices [3, 4]. A pristine graphene layer is however a

zero gap semiconductor which sets limitations in way of its practical applications. The development of

graphene based electronics therefore depends on our ability to open a tunable band gap in otherwise zero gap

graphene sheet. A great amount of effort has been devoted to introduce a band gap in graphene. Different

methods have been proposed to open a band gap in graphene like hetero-atom doping [5-8], functionalization

[9] applying electric fields and depositing graphene on substrates like SiC, SiO2 [10]. Current research on

graphene is more focused on tailoring its properties by doping heteroatoms or forming vacancies in the lattice

of graphene.

Co-doping of electron and hole is an effective method to open the band gap around Fermi level in graphene. A

good number of theoretical and experimental studies have been done on this topic.[11-13] While B/N is the

most popular choice for co-doping in graphene [13], other combinations like B/Li, Al/P [14, 15] have also

been considered. Xiaohui et al report the B/Li combination for co-doping [15], but the study is limited to one

pair only. The complete analysis of engineering the band gap with different concentrations of Li/B has not

been found in literature till date.

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So we, in the present paper, make an attempt to propose a method of band gap modulation in graphene using

different concentrations of electron – hole co-doping. Boron (B) acts as hole doping while Lithium (Li) acts as

electron doping. Two DFT based codes have been employed for all the calculations.

2. Computational Methods

All geometry optimizations and electronic structure calculations have been performed by using the SIESTA

(Spanish Initiative for Electronic Simulations with Thousands of Atoms) [16] and VASP (Vienna ab-initio

Simulation Package) [17, 18] codes based on density functional theory (DFT) [19]. SIESTA uses non

conserving pseudo-potentials in fully non-local form and atomic orbitals as basis set whereas VASP uses

plane wave basis set.

The 4 x 4 supercell (consisting of 32 atoms) is used to simulate the isolated sheet and the sheets are separated

by larger than 15 Å in z direction to avoid spurious interlayer interactions. The Brillouin zone is sampled by

using 9 × 9 × 1 mesh in Monkhorst-Pack scheme. For geometry optimizations, the coordinates were relaxed

until the Hellmann-Feynman forces reduced to less than 0.01eV/Å.

The mesh cutoff was set to 200 Ry in SIESTA. Atomic positions and lattice constants are optimized using the

conjugate gradient method. Core electrons are replaced by norm-conserving, nonlocal Troullier−Martins

pseudopotentials [20].

In VASP code the cut of energy was set to 500 eV. Methfessel-Paxton scheme for smearing has been utilized.

A mix of RMM-DIIS and Davidson algorithim has been used for relaxing the structures.

In our calculations, two approximations local density approximation (LDA) and generalized gradient

approximation (GGA) are used and results for both have been compared. The Perdew-Burke-Ernzerhof (PBE)

[21] exchange-correlation (XC) functional has been used for GGA approximation.

To give an account of the relative stability of the structures, cohesive energy for the optimized structures have

been calculated using the formula

[𝐸𝑡𝑜𝑡 − 𝐸𝑖 𝑛𝑖 ]
𝐸𝑐𝑜ℎ = (𝑖 = 𝐶, 𝐵, 𝐿𝑖)
𝑛

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where Ecoh is the cohesive energy per atom of B/Li doped configuration and Etot and Ei represent total

energies of a structure and of individual elements present within the same supercell, respectively. ni is the

number of respective species present in the configuration, while n is the total number of atoms present in a

supercell (n = 32, in the present case).

3. Results and Discussion

Xiaohui et al [15] have discussed this possibility by doping graphene with a single atom of boron, followed by

adsorption of Li atom. In the present paper we are studying different concentrations of Li adsorbed on BG,

while the amount of B and Li is kept same. Different structures doped with increasing amount of B/Li

concentrations are shown in fig. 1.

We started our simulations by first minimizing a pure graphene lattice structure. Its lattice constant is found

out to be 2.45 Å which is slightly less than the experimental value of 2.46 Å. The calculated C−C bond length

is 1.41 Å, which agrees with previous research [22].

Then we replaced a single carbon atom of the pristine graphene sheet by a boron atom and subsequently

adsorbing a Li atom on the graphene sheet. Then we optimized the structures for by minimizing the energy

and forces. The minimum energy structure was then used to study the band dispersion.

It is observed that the cohesive energy value is positive and significant for the resulting structure that means

the structure is stable. However value of is lower than that of the pure graphene sheet thereby indicating the

lesser stability as compared to pristine graphene.

The electronic structure analysis shows that in case of boron doped graphene (BG), the Fermi level EF is

shifted below the Dirac point, indicating that Boron doping can be termed as hole doping. In case of Li, the

Fermi level EF is shifted above the Dirac point indicating Lithium doping as electron doping. Boron atom has

three electrons in its valence orbital. The lack of one electron makes the BG p-type conductor. Due to one

unpaired electron in 2s orbital of Li, LiG will behave as n-type conductor.

As discussed above, Boron doping and Lithium adsorption can shift the EF below and above the Dirac point,

respectively. Therefore, if we co-dope graphene with Li/B, then the combined effect of Li/B can make the

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Fermi level reach the original position and lead to band gap opening at the Fermi level which can be beneficial

in use of graphene in electronic devices. After Lithium is adsorbed on BG, the Dirac point, which was shifted

above the Fermi level EF due to Boron doping, is pushed to EF and a band gap of width 0.14 eV is opened as

shown in fig 1 (a).

We have compared the results for minimum energy of the structure and band gap introduced in graphene

calculated by both the codes (SIESTA and VASP) under both the approximations (LDA and GGA). The

results for both the codes are fairly in agreement. GGA approximation underestimates the band gap as

expected. From the cohesive energy curve for different structures containing increasing number of boron and

lithium atoms as shown in fig. 2, It can be observed the in general VASP code gives the more optimized

structures than the SIESTA code.

Now it is expected that if we go on adding the number of adsorbed Li atoms, the gap is closed and the Fermi

level is again shifted from the Dirac point. So we keep the number of Boron and Lithium atoms same. This

not only retains the band gap but the increased doping concentration leads to widening of band gap. The

cohesive energies for relaxed geometries for the different concentrations of B/Li doped graphene are shown in

Fig. 2, and the corresponding values of band gap are shown in Table 1. So we can generate a series of band

gaps, if we dope graphene with different concentrations of boron followed by adsorption of same no. of Li

atoms. We have a band gap of about 0.27 eV with 18.75 % doping. But we see that at high doping

concentration (25 %) the band gap is again closed and at even higher concentration the band structure is

completely destroyed. This problem can be overcome by taking large amount of host atoms (graphene sheet)

so that we can have a wide range of band gaps.

4. Conclusions

We have performed the density functional calculations to investigate the band gap opening in graphene by

electron-hole co-doping. Boron and Lithium are used for co-doping into graphene. Boron doping elevates the

Dirac point above the Fermi energy, and Lithium down-shifts the Dirac point below the Fermi energy. The

combination of the two effects, makes the Dirac point return to the original position. The results show that by

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adding equal amount of B and Li we can tune the band gap of graphene in required range. The idea can be

utilized in nano-electronics industry for band gap engineering for device application.

5. Acknowledgments

We express our gratitude to SIESTA team for providing such an efficient code and Panjab University for

computational support. We are grateful to IUAC New Delhi for the HPCC facilities for running the VAPS

code. PR wishes to acknowledge UGC for financial support. VKJ acknowledges support from CSIR as

Emeritus Scientist

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Fig. 1.

(a) (b) (c)

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Fig. 1. Relaxed structures and band structures of graphene sheet doped with increasing concentrations of B
followed by adsorption of same amount of Li. The blue, green and red balls denote the carbon, boron and
lithium atoms respectively. The upper panel represents the optimized structures while the lower panel
a) dispersion curves.
represents the band b)

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 Fig. 2.

Fig. 2. Cohesive energy of the relaxed structures doped with increasing concentrations of B followed by Li
adsorption.

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Tables

Table. 1 Minimum Energy and Band Gaps of graphene sheet doped with different concentrations of Li/B

Band gap (eV) Energy (eV)

Configuration SIESTA VASP SIESTA VASP
LDA GGA LDA GGA LDA GGA LDA GGA
(a) 9.52 8.09 9.13 7.95 0.16 0.14 0.16 0.14
(b) 9.51 8.07 9.09 7.86 0.23 0.26 0.27
(c) 9.43 7.85 8.99 7.71 0.21 0.24 0.22 0.22
(d) 9.39 7.73 8.92 7.50 0.10 0.13 0.12 0.10
(e) 9.34 7.53 8.85 7.32 0.12 0.12 0.12 0.14
(f) 9.29 7.32 8.78 7.22 - - - -

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