LI Rui-Feng YU Xin-Jing WEN Cui-Lin② ZHANG Ying-Gn LIN Hui-Ling SA Bi-Sheng②

a (Multiscale Computational Materials Facility, and Key Laboratory of Eco-materials Advanced Technology, College of Materials Science and Engineering, Fuzhou University, Fuzhou 350100, China)

b (College of Materials, Xiamen University, Xiamen 361005, China)

c (College of Mathematics and Informatics, Fujian Normal University, Fuzhou 350100, China)

ABSTRACT Development of the nano-electronics requires materials with both high carrier mobility and a sufficiently large electronic band gap. In this work, by means of ab initio calculations, we have predicted a new 2D Ca2Si monolayer with a quasi-planar hexa-coordinate structure. The geometrical structure, stability and electronic properties of Ca2Si monolayer have been systemically investigated. The Ca2Si monolayer is an indirect semiconductor with band gap of about 0.77 eV, which exhibits stable chemical bonding interactions as well as thermal and dynamic stability. Moreover, the carrier mobility in Ca2Si monolayer is electron dominated with a high electron mobility about 4590.47 cm2·V-1·s-1. It is excited that the 2D Ca2Si monolayer exhibits strong directionally anisotropic carrier mobility, which could effectively facilitate the migration and separation of the generated electron-hole pairs. Our calculations demonstrate that the 2D Ca2Si monolayer is potential for high efficiency solar cells and other nano-electronic applications.

Keywords: two-dimensional materials, Ca2Si, monolayer, first-principles calculations, carrier mobility;

1 INTRODUCTION

The experimentally available graphene has ignited great scientific interest on two-dimensional (2D) materials for use in the next generation high-speed nanoelectronic devices owing to their exotic electronic, optical and catalytic properties[1-3]. The 2D materials with excellent performances like silicene[4-8], germanene[9,10], phosphorene[11,12], transition metal dichalcogenides (TMDs)[13,14]and transition metal carbides/nitrides (MXenes)[15-17]have been synthesized and intensively explored. Among them, silicene has a buckled honeycomb lattice similar to graphene but with a host of exotic electronic properties[7]. Compared with graphene, silicene has several prominent advantages, such as a much stronger spin-orbital coupling, a better tunability of band gap and an easier valley polarization[8]. Furthermore, monolayer silicene was successfully synthesized on various substrates, including Ag (111)[18], Ir (111)[19,20], ZrC (111)[21]and ZrB2[22]surfaces. Tremendous efforts have been devoted to exploring the intrinsic properties as well as potential applications for monolayer silicene and its derivatives, such as chemical sensor[23-25], field effect transisitor (FET)[26-28], thermoelectric device[29,30], hydrogen storage[31-33]and electrode materials for Li battery[34,35].

Inspired by the experimental realization of silicene, 2D silicide monolayers and few-layers materials have attracted increasing research attention for their distinctive pro- perties[36-42]. For instance, unusual chemical bonding in quasi-planar Ni2Si free-standing 2D monolayer has been revealed, which shows higher stability than silicene and germanene[39]. In addition, 2D Fe2Si nanosheet has been theretically predicted as a ferromagnetic half metal with enhanced spin-polarization ratio, and the 2D structure and strong in-plane Fe–Fe interaction endow Fe2Si nanosheet magnetocrystalline anisotropy energy with the magnitude of at least two orders larger than those of Fe, Co and Ni bulks, with great potential for spintronic nanodevices[41]. Moreover, a novel stable planar hexacoordinate 2D Cu2Si monolayer has been designed with strong chemical bonding and high inplane stiffness, which is the global minimum stucture in the 2D space[37]. Excitedly, two-dimensional Dirac nodal line fermions in monolayer Cu2Si have been experimentally realized, which provides opportunities to realize high-speed low-dissipation devices[40]. Therefore, exploring experimen- tally feasible 2D silicide nanosheet and the potential performances in nanoelectronics are of great interest and importance.

Moreover, 2D materials with planar hyper-coordinate motifs are extremely rare due to the difficulty in stabilizing the planar hyper-coordinate configurations in extended systems[37,43]. It is challenging to create 2D planar hyper- coordinate materials, which needs to match the constituent elements both geometrically and electronically. It is interesting to note that the transition metal related silicides prefer being in close-packed atomic configuration with hexa-coordination in 2D space, such as 2D Cu2Si, Ni2Si and Fe2Si monolayers just mentioned, which is contrary to the honeycomb structure of prototypical graphene with tri- coordination. Then it is natural to wonder if there is any other stable 2D silicide featuring this planar hyper-coordinate structure with novel electronic properties besides these 2D transition metal related silicides.

Interestingly, recently an infinite CaSi monolayer[42]with quasi-planar pentacoordinate silicon has been explored theoretically on the condition that the bonding pattern of planar penta-coordinate silicon species of Ca4Si22-is discovered. It shows that CaSi monolayer is a natural semiconductor with an indirect band gap of 0.5 eV, which has rather strong optical absorption in the visible region of solar spectrum. On the other hand, Ca2Si as one of the typical alkaline earth metal (AEM) silicide with semiconductor character has gained attentions for its potential applications in thermoelectrics and optoelectronics[44,45]. However, to the best of our knowledge, there is no report on the stability of 2D Ca2Si nanosheet and its electronic properties until now.

In this work, by means of ab initio evolutionary algorithm calculations, we predict a novel 2D Ca2Si monolayer with quasi-planar hexa-coordinate structure. Our calculations demonstrate that the Ca2Si monolayer is an indirect semiconductor with the band gap of about 0.77 eV, which is thermally and dynamically stable for experimental synthesis. It is interesting that the Ca2Si monolayer exhibits high electron carrier mobility with strong directionally anisotropic character, which could effectively facilitate the migration and separation of the electron-hole pairs for nano-electronic devices.

2 COMPUTATIONAL METHODS

The calculations were based on density functional theory (DFT) implemented in the Vienna ab initio simulation package (VASP)[46–49]in conjunction with the projector augmented wave (PAW) pseudopotentials[49,50]. The gene- ralized gradient approximation (GGA)[51]of Perdew-Burke- Ernzerhof (PBE)[52]was used for the exchange correlation interactions between electrons[52,53]. The cutoff energy was set to 500 eV, which was sufficient to accurately describe the outer valence electrons of Ca: 3s23p64s2and Si: 3s23p2. The convergence criteria for energy and force were set to 10-5eV·atom-1and 0.02 eV·?-1, respectively, and the lattice constant was optimized using the same method. We maintained a sufficiently large vacuum space (20 ? vacuum layer) in a direction perpendicular to the plane of the plate to ensure that there was no significant interaction between the two adjacent layers. In geometric optimization and static self-consistent calculations, k-sampling was performed using 13 × 13 × 1 points by the Monkhorst-Pack[54]k meshes for structural optimization and electronic structure calculation. Compared with the band gap with underestimated PBE functional, the HSE06 hybrid density functional[55]was used to precisely evaluate the electronic band structure of Ca2Si monolayer.

The electron localization function (ELF)[56,57]was calculated from the VASP electronic densities:

For 2D intrinsic inorganic semiconductor, the carrier mobility is mainly dominated by the phonon scattering, which can be described by the deformation potential theory. Therefore, the carrier mobility of Ca2Si monolayer was studied based on the deformation potential theory with the following analytical expression[60–62]:

3 RESULTS AND DISCUSSION

By means of the ab initio evolutionary algorithm calculations, we have obtained the novel 2D Ca2Si monolayer with a = 4.694 ?. The optimized structure of the symmetric Ca2Si monolayer exhibits a quasi-planar 2D hexa-coordinated structure with each Si atom coordinated by six Ca atoms (hexa-coordinate silicon) and each Ca coordinated by three Si and three Ca atoms (hexa-coordinate calcium), as illustrasted in Fig. 1a. The structure is the first example in hexa-coor- dinated AEM silicide, which is similar to the quasi-planar 2D Ni2Si[39]and Fe2Si[41]monolayers.

Fig. 1. (a) Side and top views of the optimized structure of 2D Ca2Si monolayer. (b) ELF profile on the (110) plane of Ca2Si monolayer. The interval between the contour lines is 0.16. (c) The calculated COHP of Ca-Si and Ca-Ca bonds in Ca2Si monolayer. The inset of Fig. 1c is the 3D ELF profile of Ca2Si monolayer

To understand the chemical bonding interaction, we introduced electron localization function (ELF) analyses for Ca2Si monolayer. The ELF contour plots on the (110) plane of Ca2Si monolayer using PBE are displayed in Fig. 1b. It shows that the ELF value at Ca and Si atom sites is very small, while there is strong electron localization around the Ca–Si bonds with the ELF value of about 0.86, illustrating strong covalent bonding states with localized electron character in the Ca2Si monolayer. On the other hand, the weak localized electrons between two Ca atoms indicate the two neighbored Ca atoms are weakly bonded. To further explore the Ca–Si and Ca–Ca bonding interactions in Ca2Si monolayer, we performed the crystal orbital Hamilton population (COHP) to describe the energy resolved chemical bonding character by presenting the delocalized electronic structure in real space[63]. Fig. 1c displays the calculated COHP of Ca–Si and Ca–Ca bonds in Ca2Si monolayer, where the bonding interaction exhibits a negative Hamiltonian off- site element and the antibonding interaction is characterized by a positive one[64]. It should be noted that no antibonding states occupied the Fermi level, suggesting chemical bonding interactions are stable for Ca2Si monolayer. Additionally, Ca2Si monolayer exhibits a typical semiconductor with the band gap of about 0.37 eV from the interactions of Ca–Si and Ca–Ca bonds in Fig. 1c. The three-dimensional (3D) ELF profile of Ca2Si monolayer also exhibits strong electron localization around the Ca–Si bond, as shown in the inset of Fig. 1c.

To verify the stability of Ca2Si monolayer at ambient condition, we employed ab initio molecular dynamics (AIMD) simulations and phonon dispersion curves to evaluate the thermal and lattice dynamical stabilities. The evolution of the total energy and structure snapshots performed by AIMD simulations is illustrated in Fig. 2a～2e. After annealing from 300 to 1200 K for 10 ps, the evolution of the total energy oscillates only over a very narrow range and the atoms well maintain with slight vibration around their equilibrium positions in the network structure, keeping quasi- planar hexa-coordinate motifs. However, after annealing up to 1500 K for 10 ps, the crystal structure of Ca2Si monolayer is seriously disrupted with atoms deviating significantly from their equilibrium positions and the chemical bonds broken. The results reveal that the Ca2Si monolayer has very good thermal stability and can maintain its structural integrity up to 1200 K. Furthermore, we calculated the phonon dispersion curves to explore the lattice stability of Ca2Si monolayer under ambient condition, as displayed in Fig. 2f. Ca2Si monolayer exhibits good lattice dynamical stability without any negative or imaginary frequency, indicating that the Ca2Si monolayer could be lattice dynamically stable. Considering the rapid development of experimental techniques for low-dimensional materials in recent years, we are optimistic that the Ca2Si monolayer can be synthesized in future.

Fig. 2. Evolution of total energy and snapshots from AIMD simulations at 0 and 10 ps at (a) 300 K, (b) 600 K, (c) 900 K, (d) 1200 K and (e) 1500 K of Ca2Si monolayer. (f) Phonon dispersion curve of Ca2Si monolayer under ambient condition using PBE functional

To get insight into electronic properties, the projected energy band structure of Ca2Si monolayer was respectively calculated by GGA-PBE and HSE06 hybrid functional methods, as plotted in Figs. 3a and 3b. It shows that Ca2Si monolayer exhibits indirect semiconductor behavior with band gap about 0.36 eV by GGA-PBE method, but with relatively larger band gap about 0.77 eV using the HSE06 method. It can be understood easily that the PBE calculation often appropriately underestimates the value of band gap. Note that both PBE and HSE06 results exhibit similar band dispersion curves for Ca2Si monolayer, with the conduction band minimum (CBM) located at G point and the valence band maximum (VBM) occupied at the M point. Moreover, the conductive band of Ca2Si monolayer is contributed by Si electrons, while the valence band near Fermi level is mainly occupied by Ca electrons.

The electronic properties of 2D materials are mainly determined by the carrier mobility (μ), which is greatly influenced by their effective masses[65]. Herein, we studied the carrier mobility of Ca2Si monolayer to explore the mechanism of migration and separation of the generated electron-hole pairs along zigzag (x) and armchair (y) directions. Here we used an orthorhombic lattice to calculate the intrinsic responses of Ca2Si monolayer under uniaxial strain. The orthorhombic structure, transformed Brillouin zone as well as band structure of Ca2Si monolayer are displayed in Fig. 4a–b. The band nature of CBM or VBM occupying the Г point implies the effective mass (m*) of carriers, and usually a stronger dispersion of the band indicates a smaller m*for carriers. To obtain the elastic modulus C2Dand deformation potential constant Ei, we respectively calculated the total energy shift E – E0and band edge positions as a function of the uniaxial strain ε along x and y directions by PBE, as shown in Fig. 4c–d. The calculated m*·m0–1, C2D, Eiand μ for Ca2Si monolayer are summarized in Table 1. The effective masses of Ca2Si monolayer are 1.064 m0(0.986 m0) for electrons and 1.105 m0(28.902 m0) for holes along x (y) direction, respectively. The predicted carrier mobility of electrons is 4590.47 cm2·V–1·s–1along the y direction, which is larger than that along the x direction (1894.92 cm2·V–1·s–1). On the contrary, the carrier mobility of holes along the x direction is larger than that along y (22.13 vs. 0.24 cm2·V–1·s–1). The results illustrate that Ca2Si monolayer exhibits a very high directionally anisotro- pic transport character for electrons and holes.

Table 1. Calculated Effective Mass (m*), Elastic Modulus C2D, Deformation Potential Constant Ei, and Carrier Mobilityμ for Electrons and Holes along Both the Zigzag (x) and Armchair (y) Directions at 300 K in Ca2Si Monolayer

Fig. 3. Projected energy band structure of Ca2Si monolayer by (a) GGA-PBE and (b) HSE06 hybrid functional methods. The red and blue solid lines represent the projected specific gravity of Si electrons and Ca electrons, respectively. The fermi level is set to E = 0.0 eV

To visualize the anisotropy of carrier mobility for Ca2Si monolayer, the carrier mobility of electrons and holes as a function of directions is plotted in Fig. 5. It is obvious that the electron mobility along y direction is twice larger than that along x, while the hole mobility along the x direction is nearly 91 times larger than that along y. The results indicate that the carrier mobility of Ca2Si monolayer is directionally anisotropic, where the electrons mainly migrate along y direction and the holes tend to absolutely migrate along x direction, leading to the effective separation of electron-hole pairs. Moreover, it is worth noting that the electrons mobility is significantly larger than that of the holes both along the x and y directions (more than 85 times larger), indicating that carrier mobility for Ca2Si monolayer is electron-dominated, which is attributed by the relatively small effective mass and the deformation potential constant. The migration of electrons in Ca2Si monolayer is competitive compared with the black phosphorous monolayer (from hundreds to thousands)[65]and higher than that of single-layer MoS2(～200 cm2·V–1·s–1)[66]. Therefore, the carrier mobility with strong directional anisotropy in Ca2Si monolayer facilitates fast migration and efficient separation of the generated electron-hole pairs, indicating that Ca2Si monolayer has great potential for high efficiency solar cells and other electronic applications. Moreover, this mechanism for the separation of electron-hole pairs can provide design principles to other low-dimensional semiconductors.

4 CONCLUSION

In summary, we have predicted a new 2D Ca2Si monolayer with quasi-planar hexa-coordinate structure based on irst-principles calculations. The calculated COHP of Ca–Si nd Ca–Ca bonds shows that the chemical bonding nteractions are stable in Ca2Si monolayer. Additionally, AIMD calculations and phonon dispersion curves exhibit that he Ca2Si monolayer is thermally and dynamically stable. The HSE06 band structure analyses show that Ca2Si monolayer is a semiconductor with indirect band gap about 0.77 eV. It is interesting that the calculated electron mobility along the y direction is larger than that along x (4590.47 vs. 1894.92 cm2·V–1·s–1), while the hole mobility along the x direction is larger than that along y (22.13 vs. 0.24 cm2·V–1·s–1). The results indicate strong directionally anisotropic carrier mobility in Ca2Si monolayer, which could effectively facilitate the migration and separation of the generated electron-hole pairs. Our calculations demonstrate that the Ca2Si monolayer could be a potential candidate for nano- electronic devices in future.

Fig. 5. Carrier mobility of electrons and holes as a function of directions for Ca2Si monolayer