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PECVD Fabrication, Electrical Characterization and Laser Dopant Activation of Silicon Nanocrystals

机译:硅纳米晶的PECVD制备,电学表征和激光掺杂活化

摘要

This thesis presents insights into the electrical properties of doped silicon nanocrystals (ncSi) for 3rd generation photovoltaic solar cells. While investigating doping of PECVD ncSi-based PV devices (Chapter 3), it has become clear that commonly used techniques to dope and characterise these ncSi films are not effective. In view of this, specially designed structures for Capacitance-Voltage (CV) measurementsand pulsed laser annealing techniques have been developed to characterise the doping effects and improve doping efficiency, respectively.Two first-author journal papers have been published based on the work presented in Chapter 4 and Chapter 5 of this thesis. Chapter 4 presents the research about CV measurements and evaluations of electrically active boron doping concentrations in ncSi. The work about improved dopants (Boron and Phosphorus) activation in ncSi by pulsed KrF laser is mainly included in Chapter 5. The characterization and fabrication techniques also presented in this thesis have assisted other journal publications on the research of doped ncSi material, ncSi-based photovoltaic devices and renewable energy applications.The two most important contributions of this thesis are:1. The demonstration of an inverted MOS structure to measure doping using CV measurements and2. The improvement of the conductivity of ncSi films using a pulsed KrF excimer laser after the crystal growth.This thesis starts with the investigation of plasma-enhanced chemical vapour deposition (PECVD) for fabricating silicon nanocrystals along with boron (B) and phosphorus (P) doping. The material properties of non-stoichiometric silicon oxide before and after annealing and the B/P doped ncSi are investigated. After the demonstration of ncSi preparation and doping by PECVD, ncSi-based photovoltaic devices were eventually fabricated and analysed. The devices showed diode I-V characteristics and an open-circuit voltage of 230 mV was achieved. However, the parameters extracted from electrical measurements indicated severe limitations due to low carrier transport and strong nonradiative recombination. These limiting factors can be attributed to the ineffective doping in ncSi, which is a general problem for nanostructured semiconductor materials.To investigate the doping in ncSi with high resistivity, we proposed an inverted MOS structure for CV measurements. Numerical CV modelling is developed to quantify the electrical properties such as doping concentration, doping type and interface trap density distribution. We investigated highly resistive boron doped ncSi films, which unexpectedly show a high doping concentration. The saturation of doping and the low doping efficiency, less than 5%, are observed and discussed. The corresponding low effective mobility is attributed to a strong scattering of excess impurities and defects.Lastly, as a means to improve the electrical quality of these films, we demonstrated that a pulsed KrF excimer laser (λ=248 nm, τ=22 ns) can be used as a post-furnace annealing method to greatly increase the electrically active doping concentration in ncSi, which potentially can reduce the extremely high impurity density currently used for doping ncSi. We propose that the increase in free carrier concentration after the laser treatment is the result of interstitial P/B dopants activation, which is initially inside the ncSi. Evidence of mobility-limited carrier transport and degenerate doping in the ncSi are measured with temperature-dependent conductivity, which further reveal the carrier-conduction mechanism in doped ncSi.
机译:本文提出了对第三代光伏太阳能电池的掺杂硅纳米晶体(ncSi)的电性能的见解。在研究基于PECVD ncSi的PV器件的掺杂时(第3章),很明显,掺杂和表征这些ncSi膜的常用技术并不有效。有鉴于此,已开发出专门设计的电容电压(CV)测量结构和脉冲激光退火技术,以表征掺杂效应并提高掺杂效率。在此基础上,发表了两篇第一作者的期刊论文。本文的第四章和第五章。第四章介绍了有关ncSi中CV测量和电活性硼掺杂浓度评估的研究。第5章主要介绍了通过脉冲KrF激光改善ncSi中的掺杂剂(硼和磷)活化的工作。本论文中介绍的表征和制造技术还协助其他期刊发表关于基于ncSi的ncSi掺杂材料的研究。光伏设备和可再生能源的应用。本文的两个最重要的贡献是:1。演示了使用CV测量和2来测量掺杂的倒置MOS结构。晶体生长后使用脉冲KrF准分子激光提高ncSi薄膜的电导率。本文从研究等离子体增强化学气相沉积(PECVD)以及硼(B)和磷(P)制备硅纳米晶体的研究开始。掺杂。研究了退火前后非化学计量氧化硅的材料性能以及B / P掺杂的ncSi。在通过PECVD对ncSi制备和掺杂进行演示后,最终制造并分析了基于ncSi的光伏器件。该器件显示了二极管的I-V特性,并实现了230 mV的开路电压。然而,由于低载流子传输和强非辐射复合,从电学测量中提取的参数显示出严重的局限性。这些限制因素可归因于ncSi的无效掺杂,这是纳米结构半导体材料的一个普遍问题。为了研究高电阻率ncSi的掺杂,我们提出了一种倒置MOS结构用于CV测量。开发了数值CV建模来量化电学特性,例如掺杂浓度,掺杂类型和界面陷阱密度分布。我们研究了高电阻硼掺杂ncSi薄膜,该薄膜出乎意料地显示出高掺杂浓度。观察并讨论了掺杂的饱和度和低于5%的低掺杂效率。相应的低有效迁移率归因于过量杂质和缺陷的强烈散射。最后,作为改善这些薄膜电性能的一种手段,我们证明了脉冲KrF准分子激光器(λ= 248 nm,τ= 22 ns)可以将其用作炉后退火方法,以大大提高ncSi中的电活性掺杂浓度,这有可能降低目前用于ncSi掺杂的极高杂质浓度。我们提出,激光处理后自由载流子浓度的增加是间隙P / B掺杂物激活的结果,该激活最初在ncSi内部。用与温度有关的电导率来测量ncSi中迁移率受限的载流子传输和简并掺杂的证据,这进一步揭示了掺杂的ncSi中的载流子传导机理。

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