热丝辅助MW ECR CVD技术高速沉积高质量氢化非晶硅薄膜

氢化非晶硅薄膜具有优异的光电特性,在制备薄膜太阳能电池中有重要的应用.本文采用热丝辅助MWECR CVD技术,通过调整各种工艺参数,制备了高沉积速率(DR＞2.5nm/s)及高光敏性(σph/σD＞105)的氢化非晶硅薄膜.实验表明,在衬底表面温度的分布中,热丝辐射和离子轰击引起的温度对薄膜的光敏性影响较大;在薄膜沉积的最后几分钟适当加大H2稀释率,有利于薄膜光电特性的改善.     

PECVD生长掺磷纳晶硅薄膜的电导特性研究

采用等离子体增强化学气相沉积(PECVD)技术,在玻璃衬底上低温沉积了优质本征纳晶硅(nc-Si:H)薄膜和掺磷纳晶硅(nc-Si(P):H)薄膜.通过拉曼散射谱和XRD衍射谱分别研究了PH3浓度对nc-Si(P):H薄膜的晶化率(Xc)和晶格微观畸变(Ls)的影响,结果显示随着PH3浓度的增加,Xc和Ls.均呈现了先增加后减小的相似趋势,暗示二者之间存在紧密的关联;利用四探针法测量了nc-Si(P):H薄膜的电导率(σ),结果表明,nc-Si(P):H薄膜的σ比nc-Si:H薄膜提高了约5个数量级,且随着PH,浓度的增大而单调增大.该变化可以从Xc、Ls的角度得到合理解释.     

PECVD沉积参数对非晶硅向微晶硅薄膜转化的影响

采用等离子体增强化学气相沉积(PECVD)系统,以硅烷和氢气为反应气源,通过改变射频功率、硅烷浓度来制备氢化硅基薄膜材料.研究了沉积参数的变化对硅基薄膜材料微结构的影响.通过红外吸收谱、紫外可见光谱以及X射线衍射谱对样品材料进行表征.实验结果表明,随着射频功率的增加,薄膜中氢含量也相应地增大,而光学带隙表现出先增大后减小的规律.当硅烷浓度逐渐降低时,薄膜材料的光学带隙相应地降低,并从非晶硅薄膜逐渐向微晶硅薄膜材料转变,且薄膜材料在(111)方向的晶粒尺度达到了10.92 nm.实现了在高沉积压强、大射频功率、低硅烷浓度条件下可以有效优化改善硅基薄膜质量.     

热丝化学气相沉积微晶硅薄膜结构及性质研究

采用热丝化学气相沉积(HWCVD)技术,以钨丝作为热丝,在不同热丝温度和氢稀释度下,分别在玻璃和单晶硅片衬底上沉积微晶硅(μc-Si∶H)薄膜材料.对所制备的微晶硅薄膜材料使用XRD、傅里叶变换红外吸收光谱、透射谱等进行结构与性能的表征分析.结果表明,随着热丝温度升高,氢稀释度变大,薄膜呈现明显的(220)择优生长取向,晶粒尺寸逐渐增大,光学吸收边出现红移,光学带隙逐渐变小.通过优化沉积参数,在热丝温度为1577℃、氢稀释浓度为95.2;、衬底温度为350℃,沉积速率为0.6 nm/s和沉积气压8 Pa条件下,制备的微晶硅薄膜呈现出了(220)方向的高度择优生长取向,平均晶粒尺寸为146 nm,光学带隙约为1.5 eV,光电导率σ.为3.2×10-6Ω-1·cm-1,暗电导率σrd为8.6×10-7 Ω-1·cm-1,表明制备的材料是优质微晶硅薄膜材料.     

掺磷nc-Si:H薄膜的微结构与光电特性

采用常规射频等离子体增强化学气相沉积方法,以高氢稀释的SiH4为源气体和以PH3为掺杂剂,制备了磷掺杂的氢化纳米晶硅薄膜.结果表明,薄膜的生长速率随PH3/SiH4流量比(Cp)增加而显著减小.Raman谱的研究证实,随CP增加,薄膜的晶化率经历了先增大后减小的过程,当C,=1.0;,晶化率达到最大值45.9;.傅里叶变换红外吸收谱测量结果显示,薄膜中的H含量在CP=2.0;时达到最低值9.5;.光学测量结果表明,本征和掺P的氢化纳米晶硅薄膜在可见光谱范围呈现出良好的光吸收特性,在0.8 ～3.0 eV范围内,nc-Si (P):H薄膜的吸收系数显著大于c-Si.和α-Si:H薄膜相比,虽然短波范围的吸收系数较低,但是在hv＜1.7 eV区域,nc-Si(P):H薄膜的吸收系数要高两到三个量级,显示出优良的红光响应.电学测量表明,适当掺P会显著提高氢化纳米晶硅薄膜的暗电导率,当CP=0.5;时,薄膜的暗电导率可达5.4S·cm-1.     

衬底温度对nc-Si∶H薄膜微结构和氢键合特征的影响

采用射频等离子体增强型化学气相沉积(RF-PECVD)技术,以H2和SiH4作为反应气体源,在不同的衬底温度下沉积了nc-Si∶H薄膜.采用Raman散射、X射线衍射、红外吸收等技术分析了薄膜的微结构和氢键合特征.结果表明,随衬底温度的升高,nc-Si∶H薄膜的沉积速率不断增大,晶化率和晶粒尺寸增加,纳米硅颗粒呈现出Si(111)晶面的择优生长趋势.键合特性显示,薄膜中的氢含量随衬底温度升高而逐渐减小,薄膜均匀性先增大后减小.     

氧化硅中纳米晶硅薄膜的低温沉积及其键合特性研究

以Ar和H2为溅射气体,采用Si和SiO2双靶活性溅射技术实现了镶嵌纳米晶硅(nc-Si)的富硅氧化硅(SiOx)薄膜的300℃低温生长,并分析了氢气掺入对薄膜微观结构及键合特性的影响.结果表明,氢气流量比的增加导致纳米硅粒子尺寸增加,而生长速率逐渐减小.薄膜中Si-O键合结构以Si(O4)键为主,随H2流量比的增加,Si-O4-nSin(n=0,1)键密度减小,Si-O4-nSin(n=2,3)和SiH2键密度持续增加,而所对应Si-H键密度呈现先减小后增加趋势,该结果可解释为等离子体内氢原子对反应前驱物中氧的去除效应增强和氢原子与表面氧的解吸附反应几率的增加.     

P型微晶硅氧薄膜光电性能研究

本工作采用甚高频等离子体化学气相沉积(VHF-PECVD)技术制备了P型微晶硅氧窗口层薄膜,讨论了P型微晶硅氧的光电特性随硼烷掺杂率的变化.采用紫外-可见透射光谱,拉曼光谱,傅立叶变换红外吸收光谱(FTIR),暗电导测量对薄膜的光电特性进行了表征.结果表明,P型微晶硅氧材料均表现为微晶态,随着硼烷掺杂率增加,晶化程度逐步降低,暗电导率快速减小,光学带隙持续降低.该结果可归因于硼烷掺杂的增加抑制晶化使得非晶成分增多,有效掺杂率降低导致薄膜电导率下降,另一方面,对硅氧物相分离的阻碍作用导致薄膜带隙下降.硼烷掺杂率为0.4;样品的电导率高达0.158 S/cm且光学带隙为2.2 eV,兼具高透射性和良好电导率,可作为高效硅基太阳电池的窗口层.     

衬底温度对微晶硅薄膜微结构的影响

采用等离子体化学气相沉积(RF-PECVD)技术,在不同衬底温度Ts下沉积了氢化微晶硅(μc-Si:H)薄膜,并深入研究了衬底温度对微晶硅薄膜微结构的影响.研究结果表明随着衬底温度的升高,表征μc-Si:H 薄膜微结构的晶化率和平均晶粒尺寸均呈现了相似的变化规律,其临界温度点随着硅烷浓度的增加向高温方向移动.该实验结果可通过"表面扩散模型"得到合理解释.     

P／I界面处理对a-Si：H柔性太阳能电池性能的影响

采用等离子体辅助化学汽相沉积(PECVD)技术制备本征非晶硅薄膜,对p/i界面进行处理.在此基础上,制备P型微晶硅(μc-Si:H)薄膜与柔性太阳能电池.对P型硅薄膜及太阳能电池的性能进行研究.结果表明:对p/i界面采用H等离子体处理,再引入一定厚度的成核层,可以成功得到高电导率的P型微晶硅窗口层,提高柔性太阳能电池的光伏特性.其中的成核层,不仅促进微晶相P层的生长,还可以起到界面缓冲层的作用.     

Thirty years trajectory of amorphous and nanocrystalline silicon materials and their optoelectronic devices

A review is given on research trajectory of hydrogenated amorphous and nanocrystalline silicon (a-Si:H and nc-Si) materials with their device applications ongoing since the period of 1970. A brief explanation on the motivation to start amorphous semiconductors research is given to produce a new kind of synthetic semiconductor having continuous energy gap controllability with valency electron controllability. Due to the result of some basic research on the film quality improvement of a-Si:H and nc-Si, some innovative devices had been developed since middle of 1980s in R&D phase such as a-SiC/a-Si heterojunction solar cells, a-Si/a-SiGe and also a-Si/nc-Si tandem type solar cells. Finally, the state of the art on the industrialization of the new devices is introduced and discussed.     

Improvement of amorphous silicon n-i-p solar cells by incorporating double-layer hydrogenated nanocrystalline silicon structure

We develop a double-layer p-type hydrogenated nanocrystalline silicon (p-nc-Si:H) structure consisting of a low hydrogen diluted i/p buffer layer and a high hydrogen diluted p-layer to improve the hydrogenated amorphous silicon (a-Si:H) n-i-p solar cells. The electrical, optical and structural properties of p-nc-Si:H films with different hydrogen dilution ratio (R_H) are investigated. High conductivity, low activation energy and wide band gap are achieved for the thin films. Raman spectroscopy and high-resolution transmission electron microscopy (HRTEM) analyses indicate that the thin films contain nanocrystallites with grain size around 3-5 nm embedded in the amorphous silicon matrix. By inserting a p-nc-Si:H buffer layer at the i/p interface, the overall performance of the solar cell is improved significantly compared to the bufferless cell. The improvement is correlated with the reduction of the density of defect states at the i/p interface.     

ESR study of the hydrogenated nanocrystalline silicon thin films

We studied the stability and light-induced paramagnetic centers in hydrogenated nanocrystalline silicon thin films (nc-Si:H) by electron-spin-resonance (ESR) and photothermal-deflection-spectroscopy (PDS). There is no measurable change in defect density upon illumination with white light with a light intensity of 300 mW cm^?2 for 300 h. At low temperatures, upon illumination with sub-bandgap light, a light-induced ESR signal appears. This signal is similar to that in hydrogenated micro-crystalline silicon (μc-Si:H).     

灯丝温度对热丝CVD法制备p型氢化纳米晶硅薄膜微结构与光电性能的影响

本文采用热丝化学气相沉积法在不同灯丝温度(1650 - 1850℃)下沉积了p型氢化纳米晶硅薄膜,研究了灯丝温度对薄膜微结构、光学性能及电学性能的影响.结果表明,随着灯丝温度的升高,薄膜的晶化率先增大后略微减小,最大值是55.5;.载流子浓度和霍尔迁移率先分别从5×1017 cm-3和0.27 cm2/V·s增加到1.32×1020 cm-3和0.43 cm2/V·s后略微减小,同时电导率从0.02 S/cm显著增加到8.95 S/cm,而电导激活能则从271.5 meV急剧减小至25 meV.     

On the development of single and multijunction solar cells with hot-wire CVD deposited active layers

We present an overview of the scientific challenges and achievements during the development of thin film silicon based single and multijunction solar cells with hot-wire chemical vapor deposition (HWCVD) of the active silicon layers. The highlights discussed include the development of Ag/ZnO coatings with a proper roughness and morphology for optimal light trapping in single and multijunction thin film silicon solar cells, studies of the structural defects created by a rough substrate surface and their influence on the performance of nc-Si:H n–i–p single junction solar cells, and studies of the phase change during the growth of nc-Si:H by HWCVD and the use of a ‘reverse’ H₂ profiling technique to achieve nc-Si:H single junction n–i–p cells with high performance. Thus far, the best AM1.5 efficiency reached for n–i–p cells on stainless-steel with HWCVD i-layers is 8.6% for single junction nc-Si:H solar cells and 10.9% for triple junction solar cells. The opportunities for further improvement of cell efficiency are also discussed. We conclude that the uniqueness of HWCVD and of the i-layers deposited with this technique require some adjustments in the strategy for optimization of single or multijunction solar cells, such as using a reverse H₂ profiling technique for the deposition of nc-Si:H i-layers. However, the output performance of solar cells with HWCVD deposited i-layers is close to those with i-layers deposited by other techniques. The difference between the best nc-Si:H n–i–p cells obtained so far in our lab and the reported best n–i–p cells with PECVD i-layers can be mainly attributed to the differences in the rough substrates and to the use of rather thin i-layers.     

纯化器对VHF-PECVD制备的不同结构硅薄膜特性的影响

本文采用VHF-PECVD技术制备了不同结构的硅薄膜,分析研究了有、无纯化器对制备薄膜特性的影响.电学特性和结构特性测试结果表明:在10W的功率条件下,使用纯化器时制备的薄膜是光敏性满足非晶硅电池要求的材料,而在不使用纯化器时制备的材料是适用于太阳能电池有源层的纳米硅材料;在30W时,不使用纯化器制备薄膜的晶化明显增大,光敏性也相应的降低,50W的条件表现出相类似的结果,初步分析是氧引起的差别;激活能的测试结果也表明,使用纯化器会降低材料中的氧含量,即表现激活能相对大;另外,沉积速率的测试结果也给出:耗尽区所在位置与是否使用纯化器有很大关系.     

GaN-MOVPE气相自由基反应的量子化学研究

利用量子化学的密度泛函理论(DFT),对TMG/NH₃/H₂体系中自由基参与的金属有机气相外延(MOVPE)反应进行计算分析,特别针对H、NH₂自由基对Ga(CH₃)₃(简称TMG)热解路径、氢解路径以及加合路径的影响进行研究。通过计算不同反应路径的吉布斯自由能差ΔG和能垒ΔG^*/RT,确定了自由基参与的气相反应在不同温度下不同的反应路径。研究发现:当T<683 K时,TMG与NH₃反应生成加合物TMG:NH₃。当T>683 K时,TMG:NH₃重新分解为TMG和NH₃。TMG在MOVPE温度下很难直接热解,在H自由基作用下则易热解产生Ga(CH₃)₂(简称DMG)、GaCH₃(简称MMG)和Ga原子。当T<800 K时,TMG与NH₃的氨基反应速率大于自由基参与的热解反应,故氨基反应占主导;当T>800 K时,自由基参与的TMG热解反应速率大于氨基反应,故热解反应占主导。氢解反应由于能垒很高,因此可忽略。TMG及其热解产物与NH₂自由基反应很容易产生氨基物。氨基物DMGNH₂可以与H自由基继续反应,最终生成表面反应前体GaNH₂。     

Influence of the deposition parameters on the microstructure and opto-electrical properties of hydrogenated nanocrystalline silicon films by HW-CVD

Hydrogenated nanocrystalline silicon (nc-Si:H) films were prepared at high deposition rates (> 13 Å/s) from pure silane without hydrogen dilution by hot wire deposition method by varying filament-to-substrate distance (d_s-f). In this study we have systematically and carefully investigated the effect of filament-to-substrate distance on structural, optical and electrical properties of the Si:H films. A variety of characterization techniques, including Raman spectroscopy, low angle X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, Atomic Force Microscopy (AFM), Field Emission Scanning Electron Microscopy (FE-SEM), UV-Visible-NIR spectroscopy and electrical dark and photoconductivity measurement were used to characterize these films. Films deposited at d_s-f > 5 cm are amorphous while those deposited at d_s-f < 5 cm are biphasic; a crystalline phase and an amorphous phase with nano-sized crystallites embedded in it. Low angle X-ray diffraction analysis showed that the crystallites in the films have preferential orientation along (111) directions. Decrease in d_s-f, the crystallinity and crystalline size increases whereas hydrogen bonding shifts from mono-hydride (SiH) to di-hydride (SiH₂) and poly-hydride (SiH₂)_n complexes. The band gaps of nc-Si:H films (~ 1.9-2.0 eV) are high compared to the a-Si:H films, while hydrogen content remains < 10 at.%. We attribute the high band gap to the quantum size effect. A correlation between electrical and structural properties has been established. Finally, from the present study it has been concluded that the filament-to-substrate distance is a key process parameter to induce the crystallinity in the films by hot wire method. The ease of depositing films with variable crystallite size and its volume fraction, and tunable band gap is useful for fabrication of tandem/micro-morph solar cells.     

Hydrogenated amorphous silicon with substrate-dependent structure

Hydrogenated amorphous silicon (a-Si:H) thin films grown at 250°C on (1 0 0) crystalline substrate using plasma-enhanced chemical vapor deposition (PECVD) with SiH₄/H₂ gas flow ratio equal to 5/1 (sccm) are investigated by transmission electron microscopy. It is found that the thin film is totally amorphous when grown on a glass substrate. But when the substrate is changed to crystalline silicon, some crystalline grains are found embedded in the amorphous structure in certain regions even if the thickness of the film reaches 600 nm. It is suggested that the amorphous silicon film grown on a crystalline silicon substrate at a temperature of 250°C without heavy H₂ dilution is a mixed network of a small amount of crystalline silicon and the major portion of amorphous silicon.     

Properties of light-induced degradation and the electronic properties of nanocrystalline silicon solar cells grown under functionally graded hydrogen dilutions

The electronic properties of hydrogenated nanocrystalline silicon (nc-Si:H) were studied using drive-level capacitance profiling (DLCP) to obtain defect density profiles as well as transient photocapacitance (TPC) and transient photocurrent (TPI) spectroscopies to study the spectra of defect related optical transitions. These measurements were performed on a series of n–i–p solar cell devices with intrinsic layer thickness of roughly 1 μm. The nc-Si:H intrinsic layers were deposited using RF or MVHF glow discharge with various hydrogen dilution profiles predominantly on specular stainless steel substrates (SS/n⁺/i nc-Si:H/p⁺/ITO), but also on textured back reflectors (SS/Ag/ZnO/n⁺/i nc-Si:H/p⁺/ITO) in some cases. Crystallite fractions were estimated using Raman spectroscopy. The electronic properties determined by our measurements could be correlated with variations in structural device parameters and with the degree of hydrogen dilution profiling during growth. We also found, depending on the growth conditions, that the devices exhibited markedly different behaviors after prolonged light exposure (100 h using light at 610 nm and 500 mW/cm² intensity). We discuss one specific microscopic mechanism that may be responsible for the light-induced changes that we have observed.