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Tuning the Physical and Chemical Properties of 2D InSe with Interstitial Boron Doping: A First-Principles Study Zhaoming Fu, Bowen Yang, Na Zhang, Zhansheng Lu, Zongxian Yang, and Dongwei Ma J. Phys. Chem. C, Just Accepted Manuscript • DOI: 10.1021/acs.jpcc.7b08588 • Publication Date (Web): 06 Dec 2017 Downloaded from http://pubs.acs.org on December 8, 2017

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The Journal of Physical Chemistry

Tuning the Physical and Chemical Properties of 2D InSe with Interstitial Boron Doping: A First-Principles Study

†

†

†

†

∗, †,‡

Zhaoming Fu, Bowen Yang, Na Zhang, Zhansheng Lu, Zongxian Yang, ,§

Dongwei Ma∗

†

College of Physics and Materials Science, Henan Normal University, Xinxiang, Henan, 453007, China

‡

National Demonstration Center for Experimental Physics Education (Henan Normal University),

Xinxiang, Henan 453007, China §

School of Physics, Anyang Normal University, Anyang, Henan 455000, China.

ABSTRACT: InSe monolayer is a new two-dimensional (2D) material with unique geometric configuration. Its crystal structure has the large atom interval, significantly different from those of graphene and MoS2, two typical 2D materials. This structural characteristic may facilitate interstitial doping, which is obviously impossible in graphene and MoS2. In this work, first-principles calculations are employed to study the effects of interstitial doping of boron atoms on the electronic and magnetic properties of InSe monolayer. For comparison, substitutional doping is also studied with In replaced by boron. It is found that interstitial doping can induce spin-polarized state and nonzero local magnetic moments. In order to investigate the effects of doping contents on electronic structures and magnetism, three dopant concentrations (6.25%, 12.5 %, 25%) are taken into account. For interstitial doping, with increasing the B contents, the local magnetic moments firstly emerge and then disappear, corresponding to the non-monotonic doping-content dependence. For substitutional doping, no local magnetic moments are observed with any doping contents. These results show that B-doping induced magnetism strongly depends on the doping methods and doping contents in InSe monolayer. The reasons leading to the doping behaviors are discussed in detail. This work opens up an alternative way for tuning

∗

Authors to whom correspondence should be addressed: [email protected], Tel./Fax: t86 373 3329346 (ZY) and [email protected] (DM)

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the physical and chemical properties of 2D InSe material, and would be helpful for future InSe-based spintronics devices. 1. INTRODUCTION Two-dimensional materials such as graphene, molybdenum disulfide, and boron nitride (BN) have attracted great attention during the past decade due to their great potentials for the new generation low-dimensional transistors, photo-emitting devices and spintronics devices.1-4 Though many 2D materials exhibit exotic electronic properties,5-7 the further modification is always necessary to improve the functions in electronic applications. As known, the doping is a vital method to modulate the magnetic and electronic properties of 2D materials.8, 9 For example, it was reported that carbon-doped hexagonal BN can induce localized impurity states;10 nitrogen-doped graphene has new transport properties different from pristine graphene.11 Iron-doped graphene has the better catalytic properties compared to undoped graphene

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. However, in these studies only the substitutional doping was

considered. In fact, substitutional doping is applied to almost all of 2D materials. It is worth mentioning that the edge doping, a new and interesting doping method, have been proposed for 2D materials by some authors. 13 On the other hand, the interstitial doping is hardly concerned in the field of 2D materials because it is almost impossible to add atoms to the crystal interval spaces in many 2D materials, such as graphene and molybdenum disulfide. Recently, InSe monolayer as a new class of 2D materials has been prepared from its bulk counterpart by mechanical exfoliation. The crystal structure of InSe monolayer includes two atomic layers and possesses very large interval spaces among the atoms, very different from those of other 2D materials. As a consequence, interstitial doping may be facilitated and should be taken into account as a possible doping method. To our knowledge, no attention has been paid to the effects of interstitial doping on the physical and chemical properties of 2D InSe. As a doping method different from substitution, interstitial dopants might give some new effects tuning electronic structures. Many interesting new behaviors and influences are worth investigating and understanding. The bulk InSe is the layered metal chalcogenide semiconductors with a honeycomb lattice in each layer. 2D InSe can be obtained by abstracting a monolayer from bulk. InSe monolayer exhibits novel physical properties such as high electron

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mobility, quantum Hall effect and anomalous optical response, and then has great potential in optoelectronics.14 In the current research, we systemically investigate the influence of the interstitial B atoms on the electronic and magnetic characters of the InSe monolayer using first-principles methods. For comparison, the substitutional doping of B is also simulated. B and In belong to the same main group in the periodic table, and have the similar valence electron configurations (2s22p1 and 5s25p1 respectively). Therefore we consider the substitution with In replaced by B. Additionally, B atom has the relative small radius, which is vital to get a better stability for interstitial doping. Different doping contents are considered to investigate the effects of B dopants on the physical characters of the InSe, and both the substitutional and interstitial doping methods are compared. It is found that two doping methods will lead to completely different influences on the electronic and magnetic characteristics, indicating that the doping method can be used as a control variable. The calculations of electronic structures suggest that the gap states can only be observed in the systems with interstitial doping. Correspondingly, nonzero magnetic moments are induced by interstitial B atoms. Substitutional doping always leads to paramagnetic states. For interstitial doping induced magnetism, the possible long-range magnetic order is also studied. Additionally, the doping contents can also significantly influence the magnitude of magnetic moments. For nanoscale applications, it is very meaningful to seek for and design the two-dimensional materials with magnetism. Very recently, many interesting 2D magnetic materials are theoretically predicted and investigated.

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This study is expected to provide a new

possibility in modifying transport properties and magnetism of InSe monolayer. 2. COMPUTATIONAL METHODS First-principles calculations are performed on the basis of the densityfunctional theory using Vienna ab-initio simulation package (VASP).18 The exchangecorrelation potential is treated with the generalized gradient approximation using the Perdew-Burke-Ernzerhof functional.19 The ion-electron interaction is described by the projector-augmented wave (PAW) method.20 The doped InSe monolayer is modeled with a 4 × 4 supercell containing 64 atoms. In order to hinder interaction between two adjacent slabs, a vacuum space of 15 Å is introduced. The Brillouin zone is sampled by a 4 × 4 × 1 Monkhorst-Pack k-point mesh. The convergence criteria used in the electronic self-consistent and ionic relaxation are set to 10-5 eV for energy and 0.02 3



eV/A for force, respectively. The van der Waals (vdW) interactions are considered using the DFT-D3 method.21 To study the long-range magnetic orders, the more accurate hybrid functional (HSE06)22 are also used to check the predictions of magnetic orders. 3. RESULTS AND DISCUSSION The interstitial- and substitutional-doping models are constructed by inserting B atoms in the interstitials and substituting the lattice In atoms with B atoms, respectively, in the 4 × 4 supercell of pure InSe monolayer. The interstitial- and substitutional-doping systems are optimized with respect to both lattice parameters and atomic positions. As shown in Fig. 1, the first and second row of structures display the interstitial- and substitutional-doping models, respectively. In this work we focus on the effects of interstitial doping, and the calculations on substitutional doping is mainly used for comparison between two doping methods. So we only consider one of dopant arrangements in substitutional-doping models, corresponding to one of substitution modes (see Fig. 1(e) for δ=2 and (f) for δ=4), and leave out other possible dopant distributions. The 4 × 4 supercells with one, two and four B atoms represent the different doping concentrations of 6.25%, 12.5% and 25%, as denoted by In32BδSe32 for interstitial-doping models and In32-δBδSe32 for substitutional-doping models (δ=0, 1, 2 and 4). The calculated lattice constants are given in Table 1. For pristine monolayer InSe, our calculations show that the optimized lattice constants of pristine monolayer InSe are a = b = 4.065 Å and c = 5.365 Å, in agreement with the previous theoretical values in the literature.23 It is found that, for interstitial-doping In32Se32Bδ systems with low B contents (δ=1 and 2), both the in-plane and interlayer lattice constants are slightly increased with enhancing the B concentrations, indicating that the B dopants lead to the lattice expansion. However, for high B contents (δ=4), an obvious anisotropic structural strain is observed with the contraction along a (or b) direction and expansion along c direction. This interesting structural strain is associated with the evolution of magnetism, as discussed below. For substitutional In32-δBδSe32 systems, the changes of lattice constants exhibit monotonic contraction along a, b and c with the increase of B concentration (see Table 1). In order to examine the effects of doping concentrations

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on the stabilities of InSe monolayers, we define two different doping energies using equation (1) and (2) for interstitial- and substitutional-doping models respectively.

= − − ∙ 1, where EIn32Se32Bδ is the total energy of the InSe monolayer with δ interstitial B atoms; EIn32Se32 is the total energy of a pristine InSe monolayer; while is the chemical potential of B, respectively. Obviously, Eint is just the chemical potential of dopant B in In32Se32Bδ systems. The substitutional doping energy (Esub) is defined as

= − ∙ + ∙ − 2, where E#$ % &% '( is the total energy of the InSe monolayer with δ substitutional B atoms; #$ and & are the chemical potential of In and B, respectively. The two definitions of Eq (1) and (2) have been adopted to study the doping in the previous researches.24, 25 The effects of B contents on the stability of doped system can be investigated based on the Eqs. (1) and (2). To determine the chemical potential, we have used the bulk and gas phases of elementary B (or In) as the references respectively, which correspond to two extreme chemical environments, i.e. the upper (gas under high temperature) and lower (bulk under low temperature) limits of the chemical potential. For the growth and preparation of the materials in experiments, the values of the chemical potential should depend on the temperature, concentration and other environments. Eint and Esub with different doping concentrations are shown in Fig. 2, in which the chemical potentials of B and In are calculated with choosing the bulk and gas phases (see the insets) as references respectively. It can be seen that, from the chemical potentials of gas phases, the calculated doping energies are negative for both the interstitial and replacement doping, corresponding to an exothermic process. For substitutional doping, the doping energy slightly increases with doping contents ranging from 6.25% to 25%. For interstitial doping, the doping energy tends to be a constant at the low doping contents of 6.25% and 12.5%. But a dramatic energy decrease is observed at the doping content of 25%, just corresponding to the structural transition from the in-plane expansion to in-plane contraction.

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Fig. 1 The optimized structure of interstitial and substitutional doping monolayer InSe with dopant B. (a)-(c) represent three structures with one, two, and four interstitial B atoms, respectively. (d)-(f) represent three structures with one, two, and four substitutional B atoms, respectively. Pink, green, blue spheres correspond to indium, selenium and boron atoms, respectively.

Table 1 The lattice parameters of 4×4 supercell of pure and B-doped InSe monolayer, where c* is the average value of the thicknesses. B content 0%

a, b (Å) 16.260

c* (Å) 5.365

Interstitial

6.25% 12.5% 25%

16.267 16.308 16.142

5.379 5.391 5.427

Substitution

6.25% 12.5% 25%

16.148 16.041 15.850

5.315 5.262 5.149

pristine

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4.6

-1.8 Ε (eV/atom)

(a) 4.4

-2.0 -2.2 -2.4 10 15 20 Doping content (%)

25

10 15 20 Doping content (%)

25

4.2 4.0

(b) 0.2 -1.8 Ε (eV/atom)

Ε (eV/atom)

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


0.0

-2.0

-2.2

-0.2

10

15

20

Doping content (%)

25

Fig. 2 The calculated doping energy for B doped InSe monolayer versus doping contents. The red and black lines represent the results of interstitial (the upper row) and substitutional (the lower row) doping. The insets give the calculated doping energies according to the chemical potentials of gas phases.

The magnetic properties of B-doped InSe monolayer are investigated. In the interstitial In32BδSe32 systems with the B concentrations of 6.25% and 12.5%, magnetism can be induced by interstitial B dopants due to the unpaired electrons. To check the stabilities of these two magnetic systems, the phonon analysis is performed. No imaginary frequencies are observed for all vibrational modes, indicating the local minimum of the energy. At the doping content of 6.25% and 12.5%, the induced local magnetic moment by each B retains about 1 µB, shown in Fig. 3. For 12.5% concentration, the local magnetic moments tend to antiferromagnetic arrangement. The possible long-range orders will be discussed below. Interestingly, the induced magnetic moments by B atom will vanish when B content reaches 25% (see Fig. 3), i.e. high concentration doping cannot induce net magnetic moments, suggesting that

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doping contents have significant influence on magnetic moments. In addition, the vanishing of the induced magnetism corresponds to the lattice contraction along a (and b) with 25% B. Therefore, the transition of magnetism is associated with the structural strains mentioned above. For substitutional doping, no magnetic moments are observed with any concentration of B, i.e. the substituted B dopants cannot induce magnetism. The results suggest that not only the doping contents but also the doping methods play important roles for inducing magnetism, which provides an idea for manipulating the magnetic and electrical properties. In previous studies on α-SnO26 and GaSe27 monolayer, some authors have revealed the possibility of doping-induced tunable magnetism in quasi-2D semiconductors due to the special band structures. Our present work helps to get a deeper understanding of the doping-induced magnetism in 2D materials.

1

M (µΒ)

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0 0

5

10

15

20

25

Doping content (%) Fig. 3 The local magnetic moment of each B versus the doping contents in interstitial doping monolayer InSe.

Based on the total and partial density of states (TDOS and PDOS), we investigate the tunable electronic properties of the InSe monolayer with B impurities, as shown in Fig. 4. For In32Se32Bδ systems with interstitial doping, we give the DOS of the ferromagnetic orders in order to observe the spin splitting. An obvious asymmetry of the spin up and down can be found near the Fermi level with the doping contents of 6.25% and 12.5% in Fig. 4, generating the local spin polarized state. These polarized impurity states appear in the band gap of the pristine InSe monolayer, 8


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which is responsible for the induced magnetic moments. Importantly, with enhancing the B contents to 25%, though the gap states is increased obviously, the spin splitting vanish from DOS results, corresponding to nonmagnetic state. On the other hand, Fig. 4(a) also shows that, the interstitial B atoms can induce deep-level defect states including both acceptor level and donor level in band gap at the low-concentration (6.25%, 12.5%), but the band gap will be closed completely as the doping content reaches 25%, indicating that a phase transition from semiconductor to metal occurs with enhancing the B contents. For metallic In32B4Se32 with 25% doping, we analyze the spatial distribution of the electronic states across Fermi level. These states mainly come from the dopant B atoms, indicating that the high doping concentration lead to the emergence of B-B hoping. The electrons of B dopants enter the itinerant states from localized states with enhancing the doping concentration. This delocalization of doping electrons is beneficial for the B-B and B-In (or Se) hybridization, and then is responsible for the crystal contraction at 25% doping. These results suggest that the electronic structures can be controlled by doping content of interstitial B, and the optical and transport properties would be significantly affected correspondingly. For comparison, the TDOS of substitutional doping is calculated and shown in Fig. 4(b). The symmetry of the spin up and spin down bands confirms the nonmagnetic nature of InSe monolayer. No local impurity states are observed in the band gap with In replaced by B, which is the reason that the substitution always yield nonmagnetic states. Therefore, the impurity states may be necessary to induce nozero magnetic moments.

70

(a) δ=0

0

Density of states (1/eV)

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


-70 70

δ=1

-70 70

δ=0

δ=2

-70 70

0

0 -70 70

δ=4

0

δ=1

δ=2

-70 3 -3

(c) B_s B_p

0 Energy (eV)

5

Se_p

0

(d) B_s B_p

3

Se_p

0 In_s

0 -3 3 -5

0.5 0.0

3 δ=4

0 0 Energy (eV)

3 0

0

-70 70

-70 -3

(b)

0

0

-70 70

70

1

In_s In_p

0 In_p

0 Energy (eV)

-1 5 -5

0 Energy (eV)

Fig. 4 Total DOS of interstitial (a) and substitutional (b) doping monolayer InSe; (c) The PDOS of B and the nearest neighbored Se and In in In32Se32B system; 9


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(d) The PDOS of B and the nearest neighbored Se and In in In31Se32B system.

The Fermi level has been set to zero and indicated by the vertical dashed line.

In addition, we also calculate the partial DOS (PDOS) of B, In and Se for lowconcentration doping of B (6.25%), shown in Fig. 4(c) and (d), which can reveal the details of orbital hybridization between the dopants and atoms of InSe. Obviously, the partial-wave states of interstitial and substitutional B have completely different band structures at low doping contents. The former displays the sharp peaks, corresponding to localized orbitals, the latter is expanded, corresponding to the strong dispersion. In the In32Se32B system, the hybridization between the B 2p orbitals with the In 5p and Se 4p only occur near the Fermi level (see Fig. 4(c)). Both the In and Se close to dopants have localized gap states induced by hybridization, but only the Se 4p orbital dominantly contributes to the net magnetic moments because of the splitting of spinup and spin-down states. Fig. 4(d) suggests that, in the substitutional doping system, the B 2p electrons strongly hybridize in a large energy interval with the electrons of lattice Se and In. These electrons occupying the hybrid orbitals have no spin-splitting, just yielding the nonmagnetic states of In31Se32B. Therefore, the induced magnetism dramatically depends on the localized gap states and spin splitting. Finally, we investigate the possible long-range spin ordering in the interstitial doping InSe (In32BδSe32). In order to simplify the discussion, we only focus on the In32B2Se32 system with a dopant concentration of 12.5%. Firstly, we detailedly investigated stabilities of different doping patterns (see Supporting Information). It is found that the clustering state of B dopants in InSe is more energetically preferred, which could quench the magnetic moment. However, the phonon analysis and molecular dynamics simulations suggest that the separating state of B in InSe also has good structure stability (see Supporting Information). Therefore, we postulate the possible long-range magnetic orders can be obtained by ingenious chemosynthesis technique. Figure 5(a) and (b) display the ferromagnetic (FM) and antiferromagnetic (AFM) orders at the doping concentration of 12.5% respectively, where the cell vectors and atomic positions have been relaxed for each magnetic configuration. It is found that the antiferromagnetic ordering has a better stability than that of ferromagnetic state with an energy difference of 14 meV (EAFM － EFM ＝ -14 meV), suggesting that the AFM order is formed. The energies of the anti- and ferromagnetic

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supercells are also calculated by hybrid functional (HSE06). The energy difference is 8 meV, smaller than the value of conventional DFT with a self-interaction error. However, the predictions remain qualitatively consistent compared to the results of DFT. In addition, for the same doping pattern shown in Fig. 5(a), we replace the B by H or C dopants and get the paramagnetic states for the both cases, instead of AFM order, which indicate that the magnetic structures can be tuned by changing the substitutional dopant elements. As known, the two-dimensional magnetic lattice models exhibit the extremely abundant physics, such as frustration phenomenon, spin liquid and spin ice.28-30 However, it is difficult to design an actual 2D magnetic material to match these theoretical lattice models. Our research could provide an idea to prepare 2D magnetic systems in experiments based on the theoretical models.

Fig. 5 The spin density distribution of ferromagnetic (a) and antiferromagnetic (b) order of B-interstitial In monolayer. The blue and red colors represent the net spin-up and spin-down electron density, respectively.

4. CONCLUSIONS The structural, electronic, and magnetic characters of the B-doped InSe monolayer via interstitial and substitutional doping method have been studied using first-principles calculations. In interstitial-doping structures, increasing doping content can lead to the non-monotonic changes of in-plane lattice constant and local magnetic moments consistently. The interstitial doping of B can induce the magnetic moments of about 1 µB on each B atom at the low doping concentration (6.25% and 12.5%). With increasing the B contents, the magnetism eventually disappears. Instead, in substitutional structures the in-plane lattice constants monotonously

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decrease with increasing the doping contents. However, the substitutional doping cannot induce magnetism in the whole range of doping concentration considered. These results indicate that both the doping contents and doping methods have decisive effects on the induced magnetism. In addition, the interstitial doping can sensitively tune the band gap of the InSe monolayer and even cause the transition from semiconductor to conductor. ACKNOWLEDGMENTS This work was supported by National Natural Science Foundation of China (Grant Nos. 11247021, U1504108, 11474086 and 111504093). The computational resources were provided by the Supercomputing Center of Henan Normal University. REFERENCES (1) Lin, Y.-M.; Jenkins, K. A.; Valdes-Garcia, A.; Small, J. P.; Farmer, D. B.; Avouris, P. Operation of Graphene Transistors at Gigahertz Frequencies. Nano Lett.

2009, 9, 422-426. (2) Radisavljevic, B.; Radenovic, A.; Brivio, J.; Giacometti, V.; Kis, A. Single-layer MoS2 Transistors. Nat. Nanotech. 2011, 6, 147-150. (3) Eda, G.; Yamaguchi, H.; Voiry, D.; Fujita, T.; Chen, M.; Chhowalla, M. Photoluminescence from Chemically Exfoliated MoS2. Nano Lett. 2011, 11, 51115116. (4) Huang, B.; Xiang, H.; Yu, J.; Wei, S.-H. Effective Control of the Charge and Magnetic States of Transition-Metal Atoms on Single-Layer Boron Nitride. Phys. Rev.

Lett. 2012, 108, 206802. (5) Novoselov, K. S.; Geim, A. K.; Morozov, S. V.; Jiang, D.; Zhang, Y.; Dubonos, S. V.; Grigorieva, I. V.; Firsov, A. A. Electric Field Effect in Atomically Thin Carbon Films. Science 2004, 306, 666-669. (6) Castro Neto, A. H.; Guinea, F.; Peres, N. M. R.; Novoselov, K. S.; Geim, A. K. The Electronic Properties of Graphene. Rev. Mod. Phys. 2009, 81, 109-162. (7) Mak, K. F.; Lee, C.; Hone, J.; Shan, J.; Heinz, T. F. Atomically Thin MoS2: A New Direct-Gap Semiconductor. Phys. Rev. Lett. 2010, 105, 136805. (8) Dai, J.; Yuan, J. Modulating the Electronic and Magnetic Structures of P-doped Graphene by Molecule Doping. J. Phys.: Condens. Matter 2010, 22, 225501.

12


Page 12 of 16

Page 13 of 16 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


(9) Ramasubramaniam, A.; Naveh, D. Mn-doped Monolayer MoS2: An Atomically Thin Dilute Magnetic Semiconductor. Phys. Rev. B 2013, 87, 195201. (10) Park, H.; Wadehra, A.; Wilkins, J. W.; Castro Neto, A. H. Magnetic States and Optical Properties of Single-layer Carbon-doped Hexagonal Boron Nitride. Appl.

Phys. Lett. 2012, 100, 253115. (11) Lherbier, A.; Blase, X.; Niquet, Y.-M.; Triozon, F.; Roche, S. Charge Transport in Chemically Doped 2D Graphene. Phys. Rev. Lett. 2008, 101, 036808. (12) Zitolo, A.; Goellner, V.; Armel, V.; Sougrati, M.-T.; Mineva, T.; Stievano, L.; Fonda, E.; Jaouen, F. Identification of Catalytic Sites for Oxygen Reduction in Ironand Nitrogen-doped Graphene Materials. Nat. Mater. 2015, 14, 937-942. (13) Saab, M.; Raybaud, P. Tuning the Magnetic Properties of MoS2 Single Nanolayers by 3d Metals Edge Doping. J. Phys. Chem. C 2016, 120, 10691-10697. (14) Bandurin, D. A.; Tyurnina, A. V.; Yu, G. L.; Mishchenko, A.; Zolyomi, V.; Morozov, S. V.; Kumar, R. K.; Gorbachev, R. V.; Kudrynskyi, Z. R.; Pezzini, S. et al. High Electron Mobility, Quantum Hall Effect and Anomalous Optical Response in Atomically Thin InSe. Nat. Nanotech. 2017, 12, 223-227. (15) Dong, L.; Kumar, H.; Anasori, B.; Gogotsi, Y.; Shenoy, V. B. Rational Design of Two-Dimensional Metallic and Semiconducting Spintronic Materials Based on Ordered Double-Transition-Metal MXenes. J. Phys. Chem. Lett. 2017, 8, 422-428. (16) Anasori, B.; Xie, Y.; Beidaghi, M.; Lu, J.; Hosler, B. C.; Hultman, L.; Kent, P. R. C.; Gogotsi, Y.; Barsoum, M. W. Two-Dimensional, Ordered, Double Transition Metals Carbides (MXenes). ACS Nano 2015, 9, 9507-9516. (17) Anasori, B.; Shi, C.; Moon, E. J.; Xie, Y.; Voigt, C. A.; Kent, P. R.; May, S. J.; Billinge, S. J.; Barsoum, M. W.; Gogotsi, Y. Control of Electronic Properties of 2D Carbides (MXenes) by Manipulating Their Transition Metal Layers. Nanoscale Horiz.

2016, 1, 227-234. (18) Kresse, G.; Furthmüller, J. Efficient Iterative Schemes for Ab Initio Totalenergy Calculations Using a Plane-wave Basis Set. Phys. Rev. B 1996, 54, 1116911186. (19) Perdew, J. P.; Burke, K.; Ernzerhof, M. Generalized Gradient Approximation Made Simple. Phys. Rev. Lett. 1996, 77, 3865-3868. (20) Blöchl, P. E. Projector Augmented-wave Method. Phys. Rev. B 1994, 50, 1795317979.

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Page 14 of 16

(21) Grimme, S.; Antony, J.; Ehrlich, S.; Krieg, H. A Consistent and Accurate Ab Initio Parametrization of Density Functional Dispersion Correction (DFT-D) for the 94 Elements H-Pu. J. Chem. Phys. 2010, 132, 154104. (22) Heyd, J.; Scuseria, G. E.; Ernzerhof, M. Erratum:“Hybrid Functionals Based on a Screened Coulomb Potential”[J. Chem. Phys. 118, 8207 (2003)]. J. Chem. Phys.

2006, 124, 219906. (23) Huang, W.; Gan, L.; Li, H.; Ma, Y.; Zhai, T. 2D Layered Group IIIA Metal Chalcogenides: Synthesis,

Properties and

Applications

in

Electronics

and

Optoelectronics. CrystEngComm 2016, 18, 3968-3984. (24) Dolui, K.; Rungger, I.; Das Pemmaraju, C.; Sanvito, S. Possible Doping Strategies for MoS2 Monolayers: An Ab Initio Study. Phys. Rev. B 2013, 88, 075420. (25) Wu, H.-C.; Peng, Y.-C.; Shen, T.-P. Electronic and Optical Properties of Substitutional and Interstitial Si-Doped ZnO. Materials 2012, 5, 2088-2100. (26) Seixas, L.; Rodin, A.; Carvalho, A.; Neto, A. C. Multiferroic Two-dimensional Materials. Phys. Rev. Lett. 2016, 116, 206803. (27) Cao, T.; Li, Z.; Louie, S. G. Tunable Magnetism and Half-metallicity in Holedoped Monolayer GaSe. Phys. Rev. Lett. 2015, 114, 236602. (28) Venderbos, J. W. F.; Daghofer, M.; van den Brink, J.; Kumar, S. Macroscopic Degeneracy and Emergent Frustration in a Honeycomb Lattice Magnet. Phys. Rev.

Lett. 2011, 107, 076405. (29) Balents, L. Spin Liquids in Frustrated Magnets. Nature 2010, 464, 199-208. (30) Bramwell, S. T.; Gingras, M. J. Spin Ice State in Frustrated Magnetic Pyrochlore Materials. Science 2001, 294, 1495-1501.

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Tuning the Physical and Chemical Properties of 2D ... - ACS Publications

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