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摘要: 为在新型纳米结构太阳能电池中应用ZnO纳米柱阵列材料，则要求能够对纳米柱的几何形貌与光电物理性质进行裁剪与操控。本文使用电沉积方法制备了ZnO纳米柱阵列，通过在电解液中使用Al（NO3）3 和NH4NO3，实现了对纳米柱晶体质量、直径、阵列密度、柱间距、Al掺杂浓度、光学带隙、近带边发射、斯托克斯位移等物理性质的调控。其可在28~102 nm范围内操控ZnO纳米柱的直径。NH4NO3的使用可将纳米柱的阵列密度降低至2.7×109 /cm2及将纳米柱间距增大至164 nm。电解液中NH4NO3的使用可将ZnO纳米柱中的Al/Zn重量比提升至2.92%，结果表明NH4NO3可以有效地促进ZnO纳米柱的Al掺杂。通过Al（NO3）3与NH4NO3可以对ZnO纳米柱的光学带隙在3.36~3.55 eV范围内进行裁剪，并对ZnO纳米柱的近带边发射性质进行操控。Al（NO3）3的引入使ZnO纳米柱的斯托克斯位移增大至200 meV。NH4NO3能够有效地将样品的斯托克斯位移降低至26 meV。通过使用Al（NO3）3 和NH4NO3实现了对ZnO纳米柱阵列几何形貌与光电物理性质的有效裁剪，获得了高质量的纳米柱阵列材料。Abstract: In order to achieve the implantation of the ZnO nanorod arrays in the nanostructured solar cells, it is necessary to tailor and control the nanorods’ morphology, optical and electrical properties. ZnO nanorods arrays were fabricated by electrodeposition. The physical properties such as the crystalline quality, diameter, density, distance, Al doping concentration, optical band gap energy, near band emission and stokes shift can be adjusted by using Al(NO3)3 and NH4NO3. The ZnO nanorods’ diameter can be adjusted from 28 nm to 102 nm. The nanorod arrays’ density can be reduced to 2.7×109 /cm2 by using NH4NO3, resulting in an increase in the distance between nanorods to 164 nm. The Al/Zn weight ratio was increased to 2.92% by using NH4NO3, indicating that NH4NO3 can boost Al doping in ZnO nanorods. The ZnO nanorods’ optical band gap energy can be tailored from 3.36 eV to 3.55 eV by using Al(NO3)3 and NH4NO3 and the near band edge emission can also be adjusted. The use of Al(NO3)3 led to the increase of the Stokes shift to 200 meV, but it can be greatly reduced to 26 meV as a result of the NH4NO3. The use of Al(NO3)3 and NH4NO3 resulted in the fabrication of high-quality ZnO nanorod arrays with effectively tailored morphology and optical properties.
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Key words:
- ZnO /
- ammonium nitrate /
- aluminum nitrate /
- electrodeposition /
- optical band gap energy /
- stokes shift
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图 5 样品1~5的光学带隙拟合图谱（线性拟合线为红色直线）
Figure 5. Fitting plots of the band gap energies of samples 1~5 (The linear fitting curve is shown in red)
图 6 样品1~5的室温光致发光图谱
Figure 6. Photoluminescence spectra of samples 1~5 at room temperature
图 7 样品1~5的室温光致发光图谱在300~470 nm范围的高斯拟合结果
Figure 7. Gauss fitting results of photoluminescence spectra of samples 1~5 (300~470 nm) at room temperature
表 1 ZnO纳米柱的直径、密度、间距
Table 1. ZnO nanorods’ diameter, density and distance
Samples Diameter/nm Density/109 cm−2 Distance/nm 1 54±15 13.0 − 2 57±20 11.0 − 3 65±24 6.8 56 4 102±44 1.9 127 5 28±16 2.7 164 
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表 2 样品1~5中ZnO纳米柱的NBE 1、NBE 2峰位、斯托克斯位移。（样品1~5的近带边发射峰位为拟合峰）
Table 2. NBE 1, NBE 2 peak positions, and stokes shift of the ZnO nanorods in samples 1~5. The NBE peaks in samples 1~5 were from the fitting peaks.
Samples NBE 1(eV) NBE 2(eV) Stokes shift (meV) 1 3.347 3.252 183 2 3.350 3.263 200 3 3.336 3.227 94 4 3.334 3.221 26 5 3.353 3.236 67
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