Structure, stability and photoelectronic properties of transition films from amorphous to microcrystalline silicon

A series of hydrogenated silicon films near the threshold of crystallinity was prepared by very high frequency plasma enhanced chemical vapor deposition (VHF-PECVD) from a mixture of SiH4 diluted in H, The effect of hydrogen dilution ratios R-H = [H-2]/[SiH4] on microstructure of the films was investigated. Photoelectronic properties and stability of the films were studied as a function of crystalline fraction. The results show that more the crystalline volume fraction in the silicon films, the higher mobility life-time product (mu tau), better the stability and lower the photosensitivity. Those diphasic films contained 8%-31% crystalline volume fraction can gain both the fine photoelectronic properties and high stability. in the diphasic (contained 12% crystalline volume fraction) solar cell, we obtained a much lower light-induced degradation of similar to 2.9%, with a high initial efficiency of 10.01% and a stabilized efficiency of 9.72% (AM1.5, 100 mW/cm(2)). (c) 2005 Elsevier B.V. All rights reserved.

Transition films from amporphous to microcrystalline silicon and solar cells

A series of hydrogenated silicon films near the threshold of crystallinity was prepared by very high frequency plasmaenhanced chemical vapor deposition (VHF-PECVD)from a mixture of SiH4 diluted in H-2. The effect of hydrogen dilution ratios R = [H-2]/[SiH4] on the microstructure of the films was investigated. The photoelectronic properties and stability of the films were studied as a function of crystalline fraction. The results show that the diphasic films gain both the fine photoelectric properties like a-Si: H and high stability like mu w-Si:H. By using the diphasic silicon films as the intrinsic layer, p-i-n junction solar cells were prepared. Current-voltage (J-V) characteristics and stability of the solar cells were measured under an AM1.5 solar simulator. We observed a light-induced increase of 5.2% in the open-circuit voltage (V-oc) and a light-induced degradation of similar to 2.9% inefficiency.

Numerical simulation of nc-Si : H/c-Si heterojunction solar cells

AMPS simulator, which was developed by Pennsylvania State University, has been used to simulate photovoltaic performances of nc-Si:H/c-Si solar cells. It is shown that interface states are essential factors prominently influencing open circuit voltages (V-OC) and fill factors (FF) of these structured solar cells. Short circuit current density (J(SC)) or spectral response seems more sensitive to the thickness of intrinsic a-Si:H buffer layers inserted into n(+)-nc-Si:H layer and p-c-Si substrates. Impacts of bandgap offset on solar cell performances have also been analyzed. As DeltaE(C) increases, degradation of VOC and FF owing to interface states are dramatically recovered. This implies that the interface state cannot merely be regarded as carrier recombination centres, and impacts of interfacial layer on devices need further investigation. Theoretical maximum efficiency of up to 31.17% (AM1.5,100mW/cm(2), 0.40-1.1mum) has been obtained with BSF structure, idealized light-trapping effect(R-F=0, R-B=1) and no interface states.

Evaluating the effect of dislocation on the photovoltaic performance of metamorphic tandem solar cells

The photovoltaic conversion efficiency for monolithic GaInP/GaInAs/Ge triple-junction cell with various bandgap combination (300 suns, AM1.5d) was theoretically calculated. An impressive improvement on conversion efficiency was observed for a bandgap combination of 1.708, 1.194, and 0.67 eV. A theoretical investigation was carried out on the effect of dislocation on the metamorphic structure's efficiency by regarding dislocation as minority-carrier recombination center. The results showed that only when dislocation density was less than 1.6x10(6) cm(-2), can this metamorphic combination exhibit its efficiency advantage over the fully-matched combination. In addition, we also briefly evaluated the lattice misfit dependence of the dislocation density for a group of metamorphic triple-junction system, and used it as guidance for the choice of the proper cell structure.

笼内金属富勒烯Gd@C_(82)的分离和质谱研究

由于其独特的电子结构，笼内金属富勒烯（碳笼内包容金属原子）的研究一直吸引着人们极大的兴趣，目前已经合成并分离出的笼内金属富勒烯主要包括碳笼内包容铱、钪、镧系原子等。在本论文中我们利用质谱技术对笼内金属富勒烯Gd_2@C_(82)气相离子行为和C_(60)与丙烯酸甲酯气相离子反应进行研究，X光电子能谱对碳笼内轧原子的价态进行研究。笼内金属富勒烯Gd_2@C_(82)是利用电弧放电法合成的。将碳份与三氧化二钆 （C：Gd=1：100, 摩尔比）灌入碳棒，将为棒前处理后，在氦气份保护下进行放电。通过对空心富勒烯在不同沸点的溶解情况进行了研究，发现大碳数的空心富勒烯在高沸点容剂中有较大的溶解度。利用两步高温高压法，既先利用1，2，4－三甲2基苯对大碳数的空心富勒烯进行分离，然后利用吡啶对笼内金属富勒烯进行提取。利用三种不同的质谱电离方式：电喷雾 （ESI），激光解析飞行时间（LDI-TOF），共振电子捕获技术（REC）来研究笼内金属富勒烯的气相离子特征。实验结果表明LDI-TOF和REC电离技术得到的质谱谱图中，笼内金属富勒烯和空心富勒烯均出现分子离子峰，但在电喷雾质谱谱图中只有笼内金属富勒烯出现分子离子峰。结合这一实验结果和理论分析说明碳笼内钆离子偏离碳中心位置。通过对比笼内金属富勒烯Gd@C_(82)和三氧化二钆中钆离子的光电子能谱谱图，Gd@C_(82)的电子结构应表示为Gd~(3+)@C_(82)~(3-)。利用四极杆质谱仪对C_(60)分子[C_(60)H]~+和加成产物为[C_(60)C_4H_3O]~+，后者是丙烯酸甲酯分子经过α短裂后与质子化[C_(60)H]~+ 发生加成反应所得的产物，在限制性Hartree-Fock条件下，采用AM1半经验量子化学计算方法对加成产[C_(60)C_3H_3O]~+八种可能结构的产物进行计算，得出了三种可能的最稳定的环加成同分异构体。

大分子物质的质谱研究

1. 利用解吸化学电离质谱(DCI-MS)，研究了C_(60)与烷基甲醚和伯醇自身化学电离(self-CI)产物之间的气相离子-分子反应，观察到加成离子[C_(60)C_2H_5O]~+和质子化分子[C_(60)H]~+是C_(60)与烷基甲醚等离子体反应的主要产物；相反，没有检测到C_(60)与伯醇离子体系形成的相应加成产物。利用AM1半经验方法对[C_(60)C_2H_5O]~+的十四种可能结构进行了计算。结果表明最稳定的加成产物是[3+2]环加成产物，并提出了该加成产物的形成途径。2. 使用同样方法研究了C_(60)与丙烯酸甲酯离子体系发生的气相离子-分子反应，观察到加成离子[C_(60)C_3H_3O]~+和质子化分子[C_(60)H]~+为主要产物。利用AM1半经验方法对[C_(60)C_3H_3O]~+的八种可能结构进行了计算，结果表明三种环加成产物为最稳定结构。3. 合成了一系列L7和σ因子肽片段，并利用基质辅助激光解吸电离质谱(MALDI-MS)、电喷雾质谱(ESI-MS)和圆二色(CD)对高效液相色谱(HPLC)提纯的合成肽进行了表征。4. 利用ESI-MS研究了L7和σ合成肽与蛋白质G和蛋白质A的复合物，发现了该复合物产生的最佳条件及其稳定性；并结合亲和色谱，证明了L7和σ合成肽与蛋白质G或蛋白质A形成的复合物是具有特异性的非共价复合物。5. 通过竞争酶联免疫吸附实验（ELISA）、亲和色谱和MALDI-MS的联用，发现L7和σ肽与IgG的Fc片断在蛋白质G和蛋白质A的结合位置不同。6. 利用鸡多克隆抗L7抗体通过免疫键合印迹法发现L7和σ肽之间没有交叉反应性。

三元多晶硫属化物CuInX_2 (X= Se，S)的光电化学研究

CuInS_2、CuInSe_2等三元半导体化合物具有光电转化效率较高，稳定性好等优点，近来在光电转化方面很受重视。本文总结了CuInSe_2、CuInS_2等化合物在光电化学转化方面的大部分工作。以及概要地介绍了半导体光电化学原理。采用电流沉积和喷涂热解的方法成功地制备了CuInSe_2和CuInS_2多晶薄膜，并对它们的光电化学性能进行了较详细的研究。我们所用的电沉积溶液是1.4mM CuCl_2 + 10mM InCl_3 + 4.2mM SeO_2 + 10mM KCl (pH = 1.6～1.7)，控制电位-0.8 V (v.s.SCE)，在荃底钛上得到了结构为黄铜矿的CuInSe_2藻膜。将薄膜退火后与多硫溶液构成PEC，在AM1的光照条件下，得到开路光电压220mV。短路光电流～5mA cm~(-2)，光电转化效率为0.23%。薄膜中Cu和In的比例由电沉积溶液的组成控制；薄膜中Cu/In < 1，则薄膜是n型光电响应，Cu/In > 1，则呈弱的P型响应。退火对薄膜的结构和光电活性影响很大，最佳的退火温度是350 ℃，用光谱响应的方法测出了CuInSe_2薄膜的禁带宽度为0.98 eV，与太阳光谱相匹配。用MoH-SchoHky方法和开路光电压与光强的关系求出了薄膜电极在多硫溶液中的平带电位，从而确定了CuInSe_2半导体的能带结构。CuInSe_2薄膜电极在多硫溶液中稳定性较好，CuInSe-多硫溶液PEC在短路状态、AM1光照强度下连续放电三小时，光电流没有变化。荃底物质和电沉积溶液对薄膜的光电活性的影响表明，CuInSe_2薄膜与荃底的接触好坏极大地影响了PEC的光电流及光电转化效率。另外，CuInSe_2薄膜电极在铁氯溶液中的光活性得到了改善，然而其稳定性却不理想。喷涂热解法制备CuInS_2新用的溶液为CuCl_2、InCl_3和硫脲的水溶液。制备的薄膜由X射线衍射分析确定其结构为闪锌矿型。在AM1光照条件下，CuInS_2-多硫溶液PEC给出开路光电压为170mV，短路光电流为3.8mA cm~(-2)。由光谱响应法测得CuInS_2薄膜的禁带宽度为1.25eV，比单晶CuInS_2的标准值1.55eV小得多。CuInS_2-多硫溶液PEC在短路状态、AM1光照强度下放电一小时，光电流下降近一半，可见，CuInS_2薄膜电极稳定性较差。

Microcrystalline silicon films and tandem solar cells prepared by triode PECVD

This paper investigates the effects of the diphasic structure on the optoelectronic properties of hydrogenated microcrystalline silicon (mu c-Si:H) films prepared in a triode three-chamber plasma-enhanced chemical vapor deposition (PECVD) system. The influences of boron-compensation doping on the dark-and photo-conductivity of mu c-Si:H films are also described. A tandem solar cell with an entirely mu c-Si:H p-i-n bottom cell and an a-Si:H top cell has been prepared with an initial conversion efficiency of 8.91% (0.126 cm(2), AM1.5, 100 mW/cm(2)).

纳米硅薄膜制备及HIT太阳能电池

在较高工作气压(332.5～399Pa)下,采用等离子增强化学气相沉积(PECVD)工艺制备了优质的本征纳米硅薄膜及掺磷的纳米硅薄膜,并采用X射线衍射(XRD)、拉曼散射(Raman) 测试技术对其进行了测试和分析.结果表明纳米硅薄膜的XRD谱中存在(111)、(220)和(331)峰位;Raman谱中显示出其薄膜中的晶粒的大小(2～5nm)符合纳米晶的要求.将制备的纳米硅薄膜初步用于栅极/ITO/n-nc-Si∶H/i-nc-Si∶H/p-c-Si/Al/Ag结构的异质结(HIT)太阳能电池,开路电压(Voc)达404mV,短路电流密度(Jsc)可达到34.2mA/cm2(AM1.5,100mW/cm~2,25℃).

非晶／微晶相变域硅薄膜及其太阳能电池

采用甚高频等离子体增强化学气相沉积(VHF—PECVD)法，成功制备出从非晶到微晶过渡区域的硅薄膜．样品的微结构、光电特性及光致变化的测量结果表明这些处于相变域的硅薄膜兼具非晶硅优良的光电性质和微晶硅的稳定性．用这种两相结构的材料作为本征层制备了p-i-n太阳能电池，并测量了其稳定性．结果在AM1．5(100mW／c^m2)的光强下曝光800-5000min后，开路电压略有升高，转换效率仅衰退了2．9％．

纳米非晶硅(na-Si:H)P-i-n太阳电池

该文报道了通过适当氢稀释(RH=15)和合适的衬底温度(Ts=170℃)下,用PECVD制备得到的宽带隙氢化纳米非晶硅(na-Si:H)薄膜,并将其用作pin太阳电池的本征层.经过电池结构和工艺条件的优化设计,在p/i,i/n界面插入渐变带隙缓冲层,制备出了glass/ITO/p-a-SiC:H/i-na-Si:H/n-nc-Si:H/Al结构的pin太阳电池.电池初始开路电压(Voc)高达0.94V,同时还能保证0.72的填充因子(FF).光电转换效率(Eff)达到8.35%(AM1.5,100mW/cm2).

纳米硅(nc-Si:H )/晶体硅(c-Si)异质结太阳电池的数值模拟分析

运用美国宾州大学发展的AMPS程序模拟分析了n-型纳米硅(n+-nc-Si:H)/p-型晶体硅(p-c-Si)异质结太阳电池的光伏特性.分析表明,界面缺陷态是决定电池性能的关键因素,显著影响电池的开路电压(VOC)和填充因子(FF),而电池的光谱响应或短路电流密度(JSC)对缓冲层的厚度较为敏感.对不同能带补偿(bandgap offset)的情况所进行的模拟分析表明,随着ΔEc的增大,由于界面态所带来的开路电压和填充因子的减小逐渐被消除,当ΔEc达到0.5eV左右时界面态的影响几乎完全被掩盖.界面层的其他能带结构特征对器件性能的影响还有待进一步研究.最后计算得到了这种电池理想情况下(无界面态、有背面场、正背面反射率分别为0和1)的理论极限效率ηmax=31.17% (AM1.5,100mW/cm2,0.40-1.10μm波段).

RTCVD工艺制备poly-Si薄膜太阳电池的研究

报道了快速热化学气相沉积(RTCVD)工艺制备多晶硅(poly -Si)薄膜及电池的实验和结果。采用SiH_2Co_2作为原料气体，衬底温度为1030℃时，薄膜的生长速率为10nm/s。发现薄膜的平均晶粒度及载流子迁移率与衬底温度和材料有关。用该薄膜在未抛光重掺杂磷的硅衬底上制备1cm~2的p~+n结样品电池，无减反射涂层，其转换效率为4.54%(AM1.5,100mW/cm~2,25℃)。

H原子吸附对Si（113）表面的影响

采用半经验分子轨道理论方法AM1研究用Si_(16)H_(21)模拟的Si(113)高指数表面及其吸附H原子的体系,得到生成热和表面原子上受力随吸附的变化。从生成热分析得知,Si(113)表面上形成Si─H_2吸附比Si─H容易,且为放热吸附;受力分析指出了表面原子再构发生的趋向,而吸附则引起趋向改变。

Characterization of polymorphous silicon thin film and solar cells

Polymorphous silicon (pm-Si:H) films have been prepared by a new regime of plasma enhanced chemical vapour deposition in the region adjacent of phase transition from amorphous to microcrystalline state. Comparing to the conventional amorphous silicon (a-Si:H), the pm-Si:H has higher photoconductivity (sigma(ph)), better stability, and a broader light spectral response range in the longer wavelength range. It can be found from Raman spectra that there is a notable improvement in the medium range order. There are a blue shift for the stretching mode of IR spectra and a red shift for the wagging mode. The shifts are attributed to the variation of the microstructure. By using pm-Si:H film as intrinsic layer, a p-i-n junction solar cell was prepared with the initial efficiency of 8.51% and a stabilized efficiency of 8.01% (AM1.5, 100mw/cm(2)) at room temperature (T-R).