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Based on first-principles calculations within the framework of density functional theory, the structural features, electronic and optical properties of sulfur-doped ZnO nanowires are systematically investigated in this work, revealing the regulation mechanism of doping on material performance. The results show that sulfur incorporation induces local lattice distortions in ZnO, resulting in a substitutional doping structure. These structural modifications significantly affect the electronic properties, causing the Fermi level to shift toward the bottom of the conduction band and a redshift in the band gap. Importantly, the orbital-projected band structures reveal that the 3p orbitals of sulfur generate impurity states near the top of the valence band, thereby enhancing both carrier concentration and mobility. Furthermore, sulfur doping leads to a notable change in the optical properties, including the emergence of new characteristic peaks in both the real and imaginary parts of the dielectric function, as well as considerable increases in optical parameters such as the absorption coefficient, extinction coefficient, and reflectivity. Moreover, as the doping concentration increases, the changes in optical properties become more pronounced. Overall, this investigation offers valuable theoretical insights into optimizing the performance of sulfur-doped ZnO nanowires in optoelectronic applications, such as photodetectors and light-emitting diodes, revealing the intrinsic correlation mechanism between the microscopic electronic structure and the macroscopic optical response.
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Keywords:
- sulfur-doped zinc oxide /
- electronic properties /
- optical properties /
- first-principles calculations
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图 1 4种纳米线结构 (a) 六边形氧化锌纳米线结构; (b) 六角星形氧化锌纳米线结构; (c) 12个硫掺杂的六角星形纳米线结构(ZnSO); (d) 24个硫掺杂的六角星形纳米线结构(ZnSSO); 其中红球代表O原子, 灰球代表Zn原子, 黄球代表S原子
Figure 1. Four nanowire configurations: (a) Hexagonal ZnO; (b) star-shaped ZnO; (c) 12 S-doped star ZnO (ZnSO); (d) 24 S-doped star ZnO (ZnSSO). Atomic colors: O (red); Zn (gray); S (yellow).
图 2 各高对称点Γ, Z, R对应的布里渊区位置, 轴向方向为(0001)
Figure 2. Locations within the Brillouin zone corresponding to the high-symmetry points Γ, Z, and R, with the axial direction along (0001).
图 3 能带结构 (a) 六角星形氧化锌纳米线能带结构; (b) 12个硫掺杂的六角星形氧化锌纳米线结构(ZnSO); (c) 24个硫掺杂的六角星形氧化锌纳米线结构(ZnSSO); 高对称点Γ, Z, R对应的布里渊区位置分别为Γ(0, 0, 0), Z(0, 0, 0.5), R(0.5, 0.5, 0.5); s纳米线的轴向方向为(0001)
Figure 3. Band structures: (a) Star-shaped ZnO nanowire; (b) 12 S-doped star-shaped nanowire (ZnSO); (c) 24 S-doped star-shaped nanowire (ZnSSO). The high-symmetry points Γ, Z, and R correspond to the following positions in the Brillouin zone: Γ (0, 0, 0), Z (0, 0, 0.5), and R (0.5, 0.5, 0.5). The axial direction of the nanowire is (0001).
图 4 GGA+U计算的能带结构 (a) 六角星形氧化锌纳米线能带结构; (b) 12个硫掺杂的六角星形氧化锌纳米线结构(ZnSO); (c) 24个硫掺杂的六角星形氧化锌纳米线结构(ZnSSO); 高对称点Γ, Z, R对应的布里渊区位置分别为Γ(0, 0, 0), Z(0, 0, 0.5), R(0.5, 0.5, 0.5); 纳米线的轴向方向为(0001)
Figure 4. Band structure of GGA+U calculations: (a) Star-shaped ZnO nanowire; (b) 12 S-doped star-shaped nanowire (ZnSO); (c) 24 S-doped star-shaped nanowire (ZnSSO). The high-symmetry points Γ, Z, and R correspond to the following positions in the Brillouin zone: Γ (0, 0, 0), Z (0, 0, 0.5), and R (0.5, 0.5, 0.5). The axial direction of the nanowire is (0001).
图 5 六角星形ZnO纳米线的原子轨道投影能带结构, 其中(a)为总的, (b)为O原子, (c)为Zn原子; 六角星形ZnSO纳米线的原子轨道投影能带结构, 其中(d)为总的, (e)为O原子, (f)为Zn原子, (g)为S原子; 六角星形ZnSSO纳米线的原子轨道投影能带结构, 其中(h)为总的, (i)为O原子, (j)为Zn原子, (k)为S原子. 高对称点Γ, Z, R对应的布里渊区位置分别为 Γ(0, 0, 0), Z(0, 0, 0.5), R(0.5, 0.5, 0.5); 纳米线的轴向方向为(0001)
Figure 5. Orbital-projected band structures of hexagonal star-shaped: (a)–(c) ZnO nanowire (total, O, Zn); (d)–(g) ZnSO nanowire (total, O, Zn, S); (h)–(k) ZnSSO nanowire (total, O, Zn, S). The high-symmetry points Γ, Z, and R correspond to the following positions in the Brillouin zone: Γ (0, 0, 0), Z (0, 0, 0.5), and R (0.5, 0.5, 0.5). The axial direction of the nanowire is (0001).
图 6 介电函数 (a) 六边形氧化锌纳米线介电函数实部和虚部; (b) 六角星形氧化锌纳米线介电函数实部和虚部; (c) 12个硫掺杂的六角星形纳米线(ZnSO)介电函数实部和虚部; (d) 24个硫掺杂的六角星形纳米线(ZnSSO)介电函数实部和虚部
Figure 6. Dielectric functions (real and imaginary parts): (a) Hexagonal ZnO nanowire; (b) hexagonal star-shaped ZnO nanowire; (c) 12 S-doped star-shaped nanowire (ZnSO); (d) 24 S-doped star-shaped nanowire (ZnSSO).
图 7 六边形ZnO与六角星形ZnO, ZnSO, ZnSSO纳米线的折射率随入射光能量的变化
Figure 7. Refractive indices of hexagonal ZnO nanowire, hexagonal star-shaped ZnO nanowire, 12 S-doped star-shaped nanowire (ZnSO), 24 S-doped star-shaped nanowire (ZnSSO) as a function of incident photon energy.
图 8 六边形ZnO与六角星形ZnO, ZnSO, ZnSSO纳米线的消光系数随入射光能量的变化
Figure 8. Extinction coefficients of hexagonal ZnO nanowire, star-shaped ZnO nanowire, 12 S-doped star-shaped nanowire (ZnSO), 24 S-doped star-shaped nanowire (ZnSSO) as a function of incident photon energy.
图 9 六边形ZnO与六角星形ZnO, ZnSO, ZnSSO纳米线的吸收系数
Figure 9. Absorption coefficients of hexagonal ZnO nanowire, star-shaped ZnO nanowire, 12 S-doped star-shaped nanowire (ZnSO), 24 S-doped star-shaped nanowire (ZnSSO).
图 10 六边形ZnO与六角星形ZnO, ZnSO, ZnSSO纳米线的反射率
Figure 10. Reflectance spectra of hexagonal ZnO nanowire, star-shaped ZnO nanowire, 12 S-doped star-shaped nanowire (ZnSO), 24 S-doped star-shaped nanowire (ZnSSO).
表 1 星形氧化锌纳米线(ZnO Star)、12个硫掺杂的六角星形纳米线(ZnSO)以及24个硫掺杂的六角星形纳米线结构(ZnSSO)的结构参数
Table 1. Structural parameters for hexagonal star-shaped ZnO, 12 S-doped star ZnO(ZnSO) and 24 S-doped star ZnO(ZnSSO).
Structural parameters ZnO Star ZnSO ZnSSO Lateral dimensions
a, b/Å33.0×33.0 33.0×33.0 30.0×30.0 Axial dimension c/Å 5.2065 5.2065 5.2065 Unit cell volume/ų 5673.5 5673.5 4685.9 Number of O atoms 102 90 78 Number of S atoms 0 12 24 Number of Zn atoms 102 102 102 
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