碱液修饰对硅纳米线阵列电池光谱响应的影响

采用金属催化化学腐蚀法在p型(100)硅基底上制备了硅纳米阵列,然后用碱溶液对纳米线阵列进行修饰。分别研究了碱液修饰对硅纳米线阵列形貌、光电性质的影响。研究表明: 与绒面及纳米线阵列相比,碱修饰30 s硅纳米线阵列的表面分散均匀,反射率降低;光谱响应度显著提高,并且出现最大量子效率对应波长红移现象。最后,详细讨论了碱液修饰硅纳米线阵列电池对光谱响应的影响机制。     

硅纳米线阵列的光学特性

在常温常压条件下,采用改进的金属催化化学腐蚀方法在n型单晶硅片(100)上制备了大面积垂直于硅衬底、直径均匀、排列整齐的硅纳米线阵列。分析了样品的表面形貌和反射谱,纳米线直径为10~50 nm。在腐蚀时间分别为15,30,60 m in时,纳米线长度分别为9,17,34μm。样品的减反射性能优异,在300~1 000nm波段,得到了2.4%的反射率。初步分析了纳米线阵列的减反射机制和不同腐蚀时间样品的反射率差异。     

晶体硅太阳电池表面纳米线阵列减反射特性研究

为增强晶体硅太阳电池的光利用率, 提高光电转换效率, 研究了硅纳米线阵列的光学散射性质. 运用严格耦合波理论对硅纳米线阵列在310—1127 nm波段的反射率进行了模拟计算, 用田口方法对硅纳米线阵列的表面传输效率进行了优化. 结果表明, 当硅纳米线阵列的周期为50 nm, 占空比为0.6, 高度约1000 nm时减反射效果最佳; 该结构在上述波段的平均反射率约为2%, 且在较大入射角度范围保持不变. 采用金属催化化学腐蚀法, 于室温、室压条件下在单晶硅表面制备周期为60 nm,占空比为0.53, 高度为500 nm的硅纳米线阵列结构, 其反射率的实验测试结果与计算模拟值相符, 在上述波段的平均反射率为4%—5%, 相对于单晶硅35%左右的反射率, 减反射效果明显. 这种减反射微结构能够在降低太阳电池成本的同时有效减小单晶硅表面的光反射损失, 提高光电转换效率.     

Pd颗粒表面修饰ZnO纳米线阵列的制备及其气敏特性

采用化学气相沉积(CVD)方法在SiO_2/Si衬底生长了ZnO纳米线阵列,纳米线长约为15μm,直径为100~500 nm。通过改变溅射沉积时间(0~150 s),在ZnO纳米线表面包覆了不同厚度的Pd薄膜。在Ar气氛中,经800℃高温退火后,制备出Pd颗粒表面修饰的ZnO纳米线阵列并对其进行了气敏测试。对于乙醇而言,所有传感器最佳工作温度均为280℃。溅射时间的增加(3~10 s)导致ZnO纳米线表面Pd纳米颗粒数量及尺寸增加,传感器响应值由2.0增至3.6。过长的溅射时间(30~150 s)将导致Pd颗粒尺寸急剧增大甚至形成连续膜,传感器响应度显著降低。所有传感器对H2均表现出相对较好的选择性,传感器具有较好的响应-恢复特性和稳定性。最后,探讨了Pd颗粒表面修饰对ZnO纳米线阵列气敏传感器气敏特性的影响机制。     

硅薄膜太阳电池表面纳米线阵列光学设计

陷光结构的优化是增加硅薄膜太阳电池光吸收进而提高其效率的关键技术之一. 以硅纳米线阵列为代表的光子晶体微纳陷光结构具有突破传统陷光结构Yablonovith极限的巨大潜力. 通常硅纳米线阵列可以用作太阳电池的增透减反层、轴向p-n结、径向p-n结. 针对以上三种应用, 本文运用有限时域差分(FDTD)法系统研究了硅纳米线阵列在 300-1100 nm 波段的光学特性. 结果表明, 当硅纳米线作为太阳电池的减反层时, 周期P=300 nm, 高度H=1.5 μm, 填充率(FR)为0.282条件下时, 反射率最低为7.9%. 当硅纳米线作为轴向p-n结电池时, P=500 nm, H=1.5 μm, FR=0.55条件下纳米线阵列的吸收效率高达22.3%. 硅纳米线作为径向p-n结电池时, 其光吸收主要依靠纳米线, 硅纳米线P=300 nm, H=6 μm, FR= 0.349 条件下其吸收效率高达32.4%, 进一步提高其高度吸收效率变化不再明显. 此外, 本文还分析了非周期性硅纳米线阵列的光学性质, 与周期性硅纳米线阵列相比, 直径随机分布和位置随机分布的硅纳米线阵列都可以使吸收效率进一步提高, 相比于周期性硅纳米线阵列, 优化后直径随机分布的硅纳米线阵列吸收效率提高了39%, 吸收效率为27.8%. 本文运用FDTD法对硅纳米线阵列的光学特性进行设计与优化, 为硅纳米线阵列在太阳电池中的应用提供了理论支持.     

表面钝化对多晶硅绒面形貌的影响

多晶硅表面制绒技术是太阳能光伏产业亟待突破的一个关键技术.本文根据多晶硅强酸制绒的基本原理,提出了表面活性剂钝化多晶硅表面以降低硅原子与酸反应速度从而改善多晶硅绒面形貌的方法.实验研究了不同含量的添加剂对酸液刻蚀多晶硅绒面形貌的影响,用扫描电镜观察对应的绒面结构,用积分反射仪测量其绒面的表面反射率.实验结果表明:加入活性剂后酸液能使多晶硅表面陷阱坑分布更加均匀,并且能有效消除产生漏电流的缺陷性深沟槽,样品表面反射率比较低,其表面反射率降低到21.5%.与传统酸液腐蚀的多晶硅绒面结构相比,陷阱坑密度明显增加,这种方法在多晶硅太阳电池的生产中是有价值的.     

硅纳米线阵列光电探测器研究进展

硅(Si)作为最重要的半导体材料之一,被广泛应用于太阳电池、光电探测器等光电器件中.由于硅和空气之间的折射率差异,大量的入射光在硅基表面即被反射.为了抑制这种反射带来的损失,多种具有强陷光效应的硅纳米结构被研发出来.采用干法蚀刻方案多数存在成本高昂、制备复杂的问题,而湿法蚀刻方案所制备的硅纳米线阵列则存在间距等参数可控性较低、异质结有效面积较小等问题.聚苯乙烯微球掩膜法可结合干法及湿法蚀刻各自的优点,容易得到周期性硅纳米线(柱)阵列.本文首先概述了硅纳米线结构的性质和制备方法,总结了有效提升硅纳米线(柱)阵列光电探测器性能的策略,并分析了其中存在的问题.进而,讨论了基于硅纳米线(柱)阵列光电探测器的最新进展,重点关注其结构、光敏层的形貌以及提高光电探测器性能参数的方法.最后,简要介绍了其存在的主要问题及可能的解决方案.     

金催化的硅纳米线的可控制备及光学特性研究

硅纳米线是新型一维半导体纳米材料的典型代表。利用阳极氧化铝薄膜为模版复制出具有有序纳米结构的金膜,在金的催化辅助下对单晶硅进行湿法刻蚀,得到尺寸、形状、分布可控的硅纳米线阵列,并对其光学特性进行了研究。研究结果表明,金代替银作为催化剂,可以有效地抑制二次刻蚀,金的化学性质相对于银更加稳定,克服了银膜在较高的温度或较长刻蚀时间下产生的结构性破坏,得到形貌规整、尺寸可控的硅纳米线阵列。对该阵列在400 nm~1 200 nm波段的反射率、透过率进行了测试,并对比分析了金模板催化与传统方法机理的异同。测试结果表明,相较于传统金属辅助化学刻蚀法,文中提出的金模板催化法制备的硅纳米线阵列尺寸及分布更加均匀可控,在宽光谱范围内的抗反射性得到了显著提高。     

正方形纳米线及纳米孔阵列辐射特性研究

晶体硅纳米线及纳米孔阵列结构不仅有着优异的增吸收特性,而且与传统的硅膜电池相比能大幅降低原料成本,因而在光伏市场中有着巨大发展前景。本文采用严格耦合波分析(RCWA)研究了晶体硅正方形纳米线和纳米孔阵列结构的辐射特性,证明了两种结构的应用潜力。在AM1.5太阳能光谱辐射强度下,纳米线和纳米孔阵列结构最终效率都大于24%,高出同等厚度晶体硅薄膜70%P以上。两种纳米结构在周期600 nm附近达到最高,其中纳米线阵列结构有着更低的最优填充率。不同角度混合极化入射下,两种结构的最终效率能够维持在大的角度范围内(0~60°),表现了良好的角度特性。     

X射线光电子能谱法研究硅纳米线的能带结构

制备了氧辅助热分解法,以一氧化硅为原料,以氩气为载气,维持管内压强为1000Pa,在高温炉中于1250℃下反应5 h后得到硅纳米线。硅纳米线经5%氢氟酸水溶液处理5 min后,与1×10-3 mol·L-1的氯化金溶液中反应5 min,在硅纳米线的表面上修饰了金纳米粒子,用X射线粉末衍射表征了产物的结构,同时观察到单质硅和金的XRD图谱;用电子扫描和透射显微镜观察了产物的形貌,表明氧辅助方法可制得大量均匀的硅纳米线,修饰在硅纳米线上的金纳米点形状整齐,尺寸均匀,平均直径约8 nm;并用X射线光电子能谱分析了修饰过程中能带结构的变化。结果表明,金纳米粒子表面带负电,它在施主能级和受主能级上都有电子存在;由于氧杂质的存在,硅纳米线的费米能级移向价带顶。     

Fabrication of silver-coated silicon nanowire arrays for surface-enhanced Raman scattering by galvanic displacement processes

Silver-coated silicon nanowire (SiNW) arrays were prepared utilizing galvanic displacement processes consisting of three steps: galvanic displacement deposition of silver particles using a HF-AgNO₃ or NH₄F-AgNO₃ aqueous solution; formation of SiNW arrays by a silver-assisted chemical etching process conducted in the HF-H₂O₂ aqueous solution; deposition of silver particles on the SiNW arrays from the NH₄F-AgNO₃ aqueous solution. The effects of the morphology of pre-deposited silver particles and deposition solution on the formation of silver-coated SiNW arrays were discussed. Surface-enhanced Raman scattering (SERS) performances have been studied using Rhodamine 6G (R6G) probe molecules on the silver-coated SiNW substrates.     

Formation of aligned silicon nanowire on silicon by electroless etching in HF solution

It was demonstrated that the etching in HF-based aqueous solution containing AgNO₃ and Na₂S₂O₈ as oxidizing agents or by Au-assisted electroless etching in HF/H₂O₂ solution at 50 °C yields films composed of aligned Si nanowire (SiNW). SiNW of diameters ∼10 nm were formed. The morphology and the photoluminescence (PL) of the etched layer as a function of etching solution composition were studied. The SiNW layers formed on silicon were investigated by scanning electron microscopy (SEM), energy-dispersive X-ray (EDX) and photoluminescence. It was demonstrated that the morphology and the photoluminescence of the etched layers strongly depends on the type of etching solution. Finally, a discussion on the formation process of the silicon nanowires is presented.     

Raman spectroscopy and field electron emission properties of aligned silicon nanowire arrays

Arrays of aligned silicon nanowire (SiNW) were synthesized on a silicon (1 0 0) substrate by self-assembling electroless nanoelectrochemistry. Compared with that of bulk crystal silicon, the first-order Raman peak of the silver cap-removed SiNW arrays shows a downshift and asymmetric broadening due to the phonon quantum confinement effects, and intensity enhancement. Field electron emission from the SiNWs was also investigated. The turn-on field was found to be about 12 V/μm at a current density of 0.01 mA/cm². These highly densified and ordered SiNW arrays can be expected to have favorable applications in vacuum electronic or optoelectronic devices.     

Fabrication and characterization of polycrystalline silicon nanowires with silver-assistance by electroless deposition

Single crystal silicon wafers are widely used as the precursors to prepare silicon nanowires by employing a silver-assisted chemical etching process. In this work, we prepared polycrystalline silicon nanowire arrays by using solar-grade multicrystalline silicon wafers. The chemical composition and bonding on the surface of silicon nanowire arrays were characterized by Fourier Transform Infrared spectroscope, and X-ray photoelectron spectroscope. The photoluminescence spectra of silicon nanowires show red light emissions centered around 700 nm. Due to the passivation effect of Si dangling bonds by concentrated HNO₃ aqueous solution, the photoluminescence intensities are improved by 2 times. The influences of surface chemical states on the wettability of silicon nanowire arrays were also studied. We obtained a superhydrophobic surface on the as-etched silicon nanowire arrays without surface modification with any organic low-surface-energy materials, and realized the evolution from superhydrophobicity to superhydrophilicity via surface modifications with HNO₃ solutions.     

Sulfur-doped black silicon formed by metal-assist chemical etching and ion implanting

We fabricated sulfur-doped black silicon by metal-assist chemical etching (MCE) and ion implanting. The morphologies of silicon nanowire (SiNW) arrays and the concentration of sulfur in black silicon were analyzed by scanning electron microscope (SEM). Sulfur-doped black silicon shows higher absorption in entire 0.3–2.5 μm wavelength range as compared to undoped SiNW arrays and flat silicon. The changes in the absorption spectra of black silicon with different etching durations and annealing temperature are also shown. Upon annealing, the absorption decreases significantly in 2–2.5 μm wavelength region. The novel results clearly indicate that sulfur implanting could produce below band gap absorption in the silicon substrate.     

Effects of silver and gold catalytic activities on the structural and optical properties of silicon nanowires

The metal-assisted chemical etching of silicon in an aqueous solution of hydrofluoric acid and hydrogen peroxide is established for the fabrication of large area, uniform silicon nanowire (SiNW) arrays. In this study, silver (Ag) and gold (Au) are considered as catalysts and the effect of different catalysts with various thicknesses on the structural and optical properties of the fabricated SiNWs is investigated. The morphology of deposited catalysts on the silicon wafer is characterized by atomic force microscopy (AFM) and field emission scanning electron microscopy (FESEM). It is shown that the morphology of the fabricated silicon nanostructures remarkably depends upon the catalyst layer thickness, and the catalyst etching time directly affects the structural and optical properties of the synthesized SiNWs. FESEM images show a linear increment of the nanowire length versus time, whereas the etching rate for the Au-etched SiNWs was lower than the Ag-etched ones. Strong light scattering in SiNWs caused the total reflection to decrease in the range of visible light, and this decrement was higher for the Ag-etched SiNW sample, with a longer length than the Au-etched one. A broadband visible photoluminescence (PL) with different peak positions is observed for the Au- and Ag-etched samples. The synthesized optically active SiNWs can be considered as a promising candidate for a new generation of nano-scale opto-electronic devices.     

Effect of temperature and silicon resistivity on the elaboration of silicon nanowires by electroless etching

The morphology of silicon nanowire (SiNW) layers formed by Ag-assisted electroless etching in HF/H₂O₂ solution was studied. Prior to the etching, the Ag nanoparticles were deposited on p-type Si(1 0 0) wafers by electroless metal deposition (EMD) in HF/AgNO₃ solution at room temperature. The effect of etching temperature and silicon resistivity on the formation process of nanowires was studied. The secondary ion mass spectra (SIMS) technique is used to study the penetration of silver in the etched layers. The morphology of etched layers was investigated by scanning electron microscope (SEM).     

Fabrication and field emission properties of multi-walled carbon nanotube/silicon nanowire array

Silicon nanowire (SiNW) arrays were fabricated on silicon wafers by the metal-assisted chemical etching method. Varied average diameters of SiNW arrays were realized through further treatment in a mixed agent of HF and HNO₃ of certain concentrations. After the treatment, there were more than 93% SiNWs with diameters smaller than 100 nm. The tip of each SiNW was subsequently wrapped with multi-walled carbon nanotubes (MWCNTs) with chemical vapor deposition method. The as-fabricated MWCNT/SiNW arrays were fabricated into electric field emitters, with turn-on field of 2.0 V/μm (current density: 10 μA/cm²), much lower than that of SiNW array (5.0 V/μm). The turn-on electric field of MWCNT/SiNW array decreased with the decreasing of the average diameter of SiNWs, indicating the performance of the field emission is relative to the morphology of SiNWs. As the SiNW array is uniform in height and easy to fabricate, the MWCNT/SiNW array shows potential applications in flat electric display.     

High-resolution analytical electron microscopy of catalytically etched silicon nanowires

We report on the characterization of hexagonally ordered, vertically aligned silicon nanowires (SiNW) by means of analytical transmission electron microscopy. Combining colloidal lithography, plasma etching, and catalytic wet etching arrays of SiNW of a sub-50 nm diameter with an aspect ratio of up to 10 could be fabricated. Scanning transmission electron microscopy has been applied in order to investigate the morphology, the internal structure, and the composition of the catalytically etched SiNW. The analysis yielded a single-crystalline porous structure composed of crystalline silicon, amorphous silicon, and SiO _x with x≤2.