The main objective of paper Feature-rich electronic properties of germanene nanoribbons under fluorine doping effect: A DFT study is to understand the most stable adsorption configurations, binding energies, densities of states, specific densities of states, and region structures of the system.
Feature-Rich Electronic Properties of Germanene Nanoribbons Under Fluorine Doping Effect: A DFT Study Vo Van On1 and Duy Khanh Nguyen1 Institute of Applied Technology, Thu Dau Mot University, Binh Duong, Vietnam, Corresponding author: onvv@tdmu.edu.vn ABSTRACTS The first-principles calculations are carried out to study the structural and electronic properties of fluorine-adsorbed germanene nanoribbons (GeNRs) Specifically, the feature-rich properties are determined through the complete theoretical framework developed under the DFT calculations, including the binding energies, optimal lattice parameters, atom-projected band structures, orbital- and atom-projected density of states (DOSs), and charge density distributions Fluorine (F) adatom favorably adsorbs at the top site of GeNRs, regardless of concentrations, edge structures, and distributions The F adatom absorbs electron from GeNRs to leave free hole in the system due to its very strong electron affinity that can be regarded as the p-type doping The F-doped systems belong to chemical adsorptions due to their large binding energies, resulting in very strong chemical bonding in F-Ge Whether the π bonding is seriously distorted or terminated that directly determines the p-type metallic or semiconducting behaviors Under the single F adatom adsorption, the pristine GeNRs become the p-type metal with high free hole density After the adsorption configuration with the concentration of 16.6%, the bandgap of the adsorbent systems opened up as the concentration increased, these systems became semiconductors However, the configuration with 66.7% concentration is again semimetallic with a bandgap of 0.08eV The feature-rich electronic properties of GeNRs induced by F adatom doping effect are suitable for various applications in electronic devices Keyword: germanene, germanene nanoribbons, halogen, adsorption, band structure, and electronic applications 66 Các tính chất giàu đặc tính dải nano germanene hấp phụ nguyên tử flo: Nghiên cứu DFT Vo Van On1, Duy Khanh Nguyen1 Institute of Applied Technology, Thu Dau Mot University TĨM TẮT Các tính tốn ngun lý thực để nghiên cứu đặc tính cấu trúc điện tử dải nano germanene 1D (GeNRs) hấp phụ nguyên tử flo Cụ thể, tính chất vật lý thiết yếu xác định thông qua khung lý thuyết hồn chỉnh phát triển thơng qua tính tốn DFT, bao gồm lượng liên kết, thông số mạng tối ưu, cấu trúc vùng điện tử, mật độ trạng thái (DOS) mật độ điện tích khơng gian F hấp phụ ưu tiên vị trí top GeNRs, nồng độ, cấu trúc cạnh phân bố nguyên tử F F hấp thụ điện tử từ GeNRs để sinh lỗ trống tự do lực điện tử mạnh nó, q trình xem pha tạp loại p Hấp phụ F lên GeNRs tạo lượng hấp phụ lớn, xem xét hấp phụ hóa học Liệu liên kết π bị biến dạng nghiêm trọng kết thúc trực tiếp xác định tính chất kim loại chất bán dẫn loại p Dưới hấp phụ đơn nguyên tử F, GeNR nguyên sinh trở thành kim loại loại p với mật độ lỗ trống cao Khi hấp phụ với nồng độ 16,6%, độ rộng vùng cấm mở hệ thống trở thành chất bán dẫn Tuy nhiên, cấu hình có nồng độ 66,7% lại bán kim loại với độ rộng vùng cấm 0,08 eV Các đặc tính điện tử phong phú GeNRs hấp phụ F dẫn đến tính chất điện tử phong phú phù hợp cho nhiều ứng dụng điện tử Từ khóa: germanene, dải nano germanene, flo, hấp phụ, cấu trúc vùng điện tử tính tốn DFT Introduction Recently, two-dimensional hexagonal lattice such as silicene and germanene have attracted special attention They have a warped honeycomb structure of sp3 and sp2 hybridization in reverse to the planar honeycomb lattice of graphene Despite this difference, they exhibit some similarities to graphene in electronic and physical properties and also exhibit semi-metallic nature with no band gap [1-3] Fabrication of germanene sheets on Pt(111)[4], Ag(111)[5], Al(111)[6], Au[7] and Ge2Pt [8] crystals was performed It has been suggested that silicene and 67 germanene are expected to enhance the performance and scalability of current Si-based nanotechnology [9] Notably, the special mechanical properties of silicene and germanene make them candidates for the design of sensing applications [1, 10] Unlike the two-dimensional structure, nanobands can create an electron band gap and thus they may be promising candidates for next-generation integrated circuit (IC) device components such as transistor channels [11] and sensors [12] Germanene carbon nanotubes were experimentally synthesized by Han et al [13] They exhibit interesting properties similar to those of graphene nanoribbons [14-16] Theoretical studies of electronic properties have established that armchair germanene nanobands are non-magnetic semiconductors with a direct band gap at the point Γ [17] Like graphene, the adsorption of organic and conventional gas molecules on germanene nanostructures has also been reported and its application as a gas sensor has been examined [1820] The atomic binding for germanene is much stronger than for graphene, and the calculated adsorption energy for germanene is higher than that of the molecules adsorbed on graphene and silicene [21] In fact, germanene could be a promising candidate in the field of bioelectronics [22] While the adsorption of common gases on 2D germanene sheets and germanene nanostructures has been studied extensively, the adsorption of atoms, especially highly electronegative atoms such as F, on germanene nano bands has not been thoroughly studied Therefore, our objective is to study the adsorption properties of the F atoms on germanene nanoribbon in this paper The main objective of this paper is to understand the most stable adsorption configurations, binding energies, densities of states, specific densities of states, and region structures of the system Furthermore, the charge density redistribution was also studied The paper is planned as follows: in section 2, the computational method is presents; section presents the adsorption configuration; the adsorption energy in section 4; band structure and density of state in section 5; the charge distribution in section 6; The conclusion of the paper in section Computational Method To perform the current density functional theoretical (DFT) calculations, Vienna ab initio Simulation package (VASP) was employed [23] Using the Perdew–Burke–Ernzerhof (PBE) potential under the frame of generalized gradient approximation (GGA) as the electronic exchange and correlation potential was investigated [24, 25] The convergence criteria of energy 68 and force were × 10−6 eV and 0.01 eV/Å, respectively The electronic structure calculations were evaluated at the level of GGA-PBE For plane wave expansion, an energy cutoff of 450 eV was preferred To sample the k-points in the Brillouin zone, a × × 13 Monkhorst-Pack kpoint mesh size was used [26] To avoid the coupling effects between the layers, the vacuum spacing of 18 Å perpendicular to GeNRGe plane was assumed The adsorption configuration Nanoribbons germanene pristine consist of 12 atoms of Ge in zigzag form It has closed strings and a half of open string, the top and the bottom of the nanoribbon are passivated by two hydrogen atoms as shown in fig.1 The average bond length between Ge-Ge atoms increases as the adsorbent concentration increases, while the bond distance between F atoms and Ge atoms decreases as the adsorbent concentration increases We also see that the maximum buckling of the adsorbent systems is not much different as the concentration of F atoms increases; however, the binding energy of the adsorption systems decreases markedly with the increase of the adsorption concentration as shown in Table a Pristine b c 1:6 1:12 d 1:2 69 e 2:3 f 1:1 Figure The pristine germanene nanoribbons and the adsorption configurations of F atoms on Germanene nanoribbons with different concentrations Table The parameters of adsorption configurations The system The average bond length(Å) Mininum distance (Ge-K)( Å) Maximum Bukcling Binding energy (eV) Pristine GeNR 2.41 No 0.06 -60.11 1F.GeNR 2.44 1.83 0.10 -64.55 2F.GeNR 2.45 1.82 0.07 -69.63 6F.GeNR 2.51 1.79 0.06 -90.27 8F.GeNR 2.50, 2.51 1.79 0.09 -100.18 12F.GeNR 2.50, 2.51 1.79 0.15 -121.09 The adsorption Energy To compare the most stable configuration, we first calculated adsorption energy (Ead) of considered configurations Following relation has been used for calculating the Ead, Ead = Etotal - Esubstrate - Eatoms (1) Where Etotal , Esubstrate and Eatoms are the total energy of the the adsorption system, pristine germanene nanoribbons, and F atoms adsorbed on germanene nanoribbons, respectively As per the definition adopted here, negative adsorption energy exhibits that the process is exothermic while the magnitude signifies thermodynamic stability The calculation results showed that the adsorbed samples with the most stable adsorbed energy both are in top positions Both adsorptions of the configurations are chemisorption as are shown in table 70 Table The adsorption energy of systems Configuration Adsorption energy per atom K (eV) Band gap(eV) Pristine GeNR No 0.50 1F.GeNR.bridge -2.96 No 2F.GeNR.bridge -2.07 0.175 6F.GeNR -3.50 0.72 8F.GeNR -3.76 0.08 12F.GeNR -3.71 1.33 From table 2, the adsorption energy per one F atom in the configurations 8F.NRGe is the smallest, while that of the configuration 2F.GeNr is the biggest Band structure and Density of State Figure shows the band structure and the density of state of the pristine nanoribbon germanene and the adsorption configurations of 1F.GeNR, 2F.GeNR, 6F.GeNR, 8F.GeNr , and 12F.GeNR We can see from table that the direct band gap of the pristine nanoribbon germanene is 0.5 eV, it behaves the metallic property with the electrons predominating The electrons mainly concentrate in the valence region with low energy and the conduction region with high energy The adsorption configuration of 1F.GeNR is a metallic, while that of 2F.GeNR and 8F.GeNR is semi metallic but the electron concentration is low in the region near Fermi level This is a consequence of more electrons shifting towards the F atom, reducing the charge density on the substrate Two adsorption configurations of 6F.GeNR and 12F.GeNR are metallic with band gap is 0.72 eV and 1.33 eV, respectively 71 pristine 1F.GeNR 2F.GeNR 6F.GeNR 8F.GeNR 12F.GeNR Figure Band structures and the density of state of adsorption configurations From the graphs of the density of state of the pristine germanene nanoribbons and the adsorption configurations in figure 2, we can see that they are completely symmetric, which indicates that these configurations are not magnetized Obtained calculation results also confirm that their magnetizations all are zero The figure (a, b, c, d, e) show the part density of state of each elements in the adsorption configurations 72 1F.GeNR 2F.GeNR 6F.GeNR 8F.GeNR 73 12F.GeNR Figure PDOS of each element in the adsorption configuration of 1F.GeNR, 2F.GeNR, 6F.GeNR, 8F.GeNR, and 12F.NRGe From the graphs of the part density of states (PDOS) in fig 3, we can see that the distribution of PDOS of Ge_S(orange solid line) is mainly in low energy region (valence region), while that of PDOS of Ge_P(green solid line) is mainly in the region near the Fermi level and high energy conduction region The state density of F_S has a negligible contribution over the entire energy range, it is significant in the valence region with very low energy, while the state density of F_P is only significant in the low energy region below the Fermi level The charge distribution Figure shows the charge distribution in the adsorption configurations of 1F.GeNR, 2F.GeNR, 6F.GeNR, 8F.GeNR and 12F.GeNR a b 74 , c d e f Figure The charge distribution of the adsorption configurations of 1F.NRGe, 2F.GeNR, 6F.GeNR, 8F.GeNR and 12F.NRGe It is clear that the charge is pulled toward F atoms by the larger electronegativity of F atoms comparable to Ge atoms, this decreases the charge concentration of the substrates The charge distribution of two strings of Ge atoms in the substrates are slightly different, the distribution of the adsorption system of 2F.NRGe is symmetrically larger than another by two F atoms on two sides of the substrate The volume of the blue space region is due to the charge reduction in the middle of the rings of Ge atoms of the 2F.NRGe configuration is larger and more circular The lower buckling in the 2F.NRGe configuration also affects the symmetry of this charge-reducing blue region 75 Conclusion In conclusion, we studied the structural and electronic properties of adsorption systems of adsorption configurations of 1F.NRGe, 2F.NRGe, 6F.GeNR, 8F.GeNR, and 12F.GeNR Results show that the bond lengths of Ge-Ge increase as the concentration of F atoms increase, while the binding energy decrease; the adsorption property of all systems are chemical adsorptions; the adsorption configuration of 8F.NRGe is the best stable with the adsorption energy of -3.76 eV, while the configuration of 2F.GeNR is not the best stable with adsorption of -2.07eV There is the shift of charges 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nanobands can create an electron band gap... armchair germanene nanobands are non-magnetic semiconductors with a direct band gap at the point Γ [17] Like graphene, the adsorption of organic and conventional gas molecules on germanene nanostructures... calculations, Vienna ab initio Simulation package (VASP) was employed [23] Using the Perdew–Burke–Ernzerhof (PBE) potential under the frame of generalized gradient approximation (GGA) as the electronic