AZO薄膜刻蚀形貌优化及其在硅基薄膜双结太阳能电池中的应用

采用磁控溅射结合酸腐蚀法制备掺铝氧化锌透明导电氧化物薄膜,研究关键溅射工艺参数对AZO薄膜腐蚀后性能的影响.研究发现,在较低沉积温度和较大溅射压强条件下,样品腐蚀后可以形成粗糙度和雾度更大的表面形貌,有利于提高电池性能;而溅射功率增加,虽然能提升样品腐蚀后的粗糙度,但雾度的增加则呈现饱和趋势.将具有优良光电性能、不同雾度的AZO薄膜作为前电极制备非晶/微晶硅薄膜双结太阳能电池,发现雾度越大,电池的短路电流密度越大,特别是底电池电流密度越大,从而电池的光电转换效率也获得提高.这一发现有助于通过优化溅射工艺参数来改进AZO薄膜表面形貌和电池性能.     

溅射气压对直流电源磁控溅射制备掺铝氧化锌薄膜性能的影响

以ZnO∶Al2O3(2wt%)陶瓷为溅射靶材,采用直流磁控溅射的方法,在普通玻璃衬底上制备ZnO∶Al(AZO)薄膜,研究了溅射气压对AZO薄膜的结构特性、表面形貌及其光电性的影响。XRD和SEM测试表明所有样品均为多晶六角纤锌矿结构,薄膜呈(002)晶面择优生长。用体积百分比为0.5%稀盐酸对制备的AZO薄膜进行腐蚀制绒,腐蚀后其表面形貌随溅射气压的不同而改变。在适当溅射气压下(～1.5m Torr)制备的薄膜,通过溅射后腐蚀工艺,可获得表面形貌具有特征陷光结构的AZO薄膜,其表面呈现"弹坑"状,薄膜的绒度随表面形貌的不同而变化。同时通过优化制备工艺,所有溅射气压下制备的AZO薄膜在可见光及近红外范围的平均透过率大于80%,电阻率低于8.5×10-4Ω·cm,可以满足硅基薄膜太阳电池对透明前电极光电性能的要求。     

绒面结构ZnO薄膜及其表面处理

本文制备出(110)峰取向的绒面结构MOCVD-ZnO:B薄膜并提出CH3COOH湿法刻蚀的表面处理技术.研究表明,绒面结构ZnO:B薄膜具有"类金字塔"晶粒形状;处理前后ZnO:B薄膜的微观结构,方块电阻和光学性能变化不大.适当的表面处理有助于使薄膜表面趋于柔和,有望改善ZnO/Si界面特性,从而应用于μc-Si薄膜太阳电池.     

电阻蒸发铝薄膜结构及其对非晶硅太阳电池性能的影响

本文首先采用电阻蒸发法制备了不同厚度的Al薄膜,并选择了两个典型厚度的Al薄膜制备工艺来制备非晶硅太阳电池的Al背电极,研究了Al背电极厚度对电池性能的影响.结果表明,Al背电极的厚度由800nm减薄到70nm时,电池的Voc平均值由0.826V增加到0.829V,电池的Jsc平均值由11.747mA/cm2减小到11.318 mA/cm2,电池的FF平均值由0.701增加到0.728,而电池效率的平均值略有增加,由6.803;增加到6.833;.用扫描电镜(SEM)和X射线衍射(XRD)研究了玻璃衬底上蒸发的Al薄膜和非晶硅电池Al背电极表面形貌和微观结构的变化,分析了电池性能随Al背电极厚度变化的原因.     

衬底温度对MOCVD-ZnO薄膜特性的影响

利用金属有机物化学气相沉积(MOCVD)生长技术,制备本征ZnO薄膜,并研究薄膜的结构、形貌及光电等性能.结果表明:衬底温度对ZnO薄膜的微观结构、电学、光学及表面形貌等有显著影响.在衬底温度为180℃时获得电阻率为2.17×10-2Ω·cm.平均透过率为85;的低电阻、高透过率、结晶质量高、表面呈绒面结构的本征ZnO薄膜.对本征ZnO薄膜进一步掺杂和结构优化有望用于硅薄膜太阳能电池的前电极.     

磁控溅射技术室温生长氢化ZnO∶Ga薄膜及其特性研究

采用直流脉冲磁控溅射方法,在室温下生长氢化Ga掺杂ZnO薄膜(GZO/H),并通过湿法后腐蚀技术获得绒面结构.研究了室温下H2流量对薄膜结构、光电性能及表面形貌的影响.实验表明,氢化GZO(GZO/H)薄膜具有良好的(002)晶面择优取向生长,引入适当流量的H2可以有效提高薄膜的电学特性,GZO/H薄膜具有更低的电阻率以及较高的迁移率和载流子浓度.当通入H2流量为6 sccm时,薄膜电阻率为6.8 ×10-4 Ω·cm,Hall迁移率达34.2 cm2/Ⅴ·s,制备的GZO/H薄膜可见光区域平均透过率优于85;.此外,研究了H2流量对湿法腐蚀后绒面GZO/H薄膜表面形貌的影响,提出了一种薄膜绒面结构形成过程模型.     

铝诱导表面织构玻璃及其对硅薄膜陷光作用的影响

采用铝诱导表面织构方法在玻璃衬底上制备了蜂窝状的凹坑结构;使用热丝化学气相沉积技术在该类衬底上制备了硅薄膜.扫描探针显微镜(SPM)图像表明,通过改变刻蚀时间、刻蚀溶液比例、Al膜厚度和退火时间等制备条件,可以有效控制玻璃表面凹坑结构的尺寸,使其在直径上从0.5μm到6μm,深度上从60 nm到700 nm可调.光吸收谱测试表明此类衬底对硅薄膜的光吸收有着明显的增强效果,以凹坑平均直径为2.3 μm,深度为358nm的铝诱导表面织构玻璃为衬底所制备的厚度为150 nm的硅薄膜,在350～1200 nm波长范围内的光吸收与使用平面玻璃为衬底的样品相比可提高28.5;.凹坑的尺寸大小对光吸收增强效果有重要影响.     

LPCVD法在制绒单晶硅片衬底上制备ZnO∶B透明导电薄膜及其性能的研究

采用低压化学气相沉积法(LPCVD)在制绒的单晶硅片衬底上制备了B掺杂ZnO(BZO)的透明导电薄膜,研究了B2H6掺杂量、沉积时间对BZO薄膜的微观形貌、导电性能及光学减反性能的影响.结果表明,在制绒单晶硅片衬底上制备的BZO薄膜均呈现“类金字塔”的绒面结构,其平均晶粒尺寸在200 ～ 500 nm之间,并随B2H6掺杂量增加而减小;BZO薄膜的方阻随沉积时间的增加而呈线性迅速减小的趋势,当沉积时间为420 s时,BZO薄膜的方块电阻低至28 Ω/□;在制绒单晶硅片上制备BZO薄膜后,表面平均反射率由15;明显降低至5;左右,表现出优异的光学减反性能.     

薄膜厚度对MOCVD法沉积ZnO透明导电薄膜的影响

本文研究了薄膜厚度对MOCVD技术制备未掺杂ZnO薄膜的微观结构和电学特性影响.XRD和SEM的研究结果表明,随着薄膜厚度的增加,ZnO薄膜(110)峰趋于择优取向,且晶粒逐渐长大,薄膜从球状和细长棒状演变为具有类金字塔绒面结构特征的ZnO薄膜;Hall测量表明,较厚的ZnO薄膜有助于提高薄膜电学特性,可归于晶粒长大和晶体质量提高.40min沉积时间(膜厚为1250nm)制备出的ZnO薄膜具有明显绒面结构,其晶粒尺寸为300～500nm,电阻率为7.9×10-3Ω·cm,迁移率为26.8cm2/Vs.     

薄膜厚度对 Mn-W 共掺杂 ZnO 透明导电薄膜性能的影响

利用直流磁控溅射法在低温玻璃衬底上制备了高导电透明的 Mn-W 共掺杂 ZnO(ZMWO)薄膜,并研究了厚度对薄膜结构、光学及电学性能的影响.X 射线衍射结果表明 ZMWO 均为六方纤锌矿结构的多晶薄膜,具有垂直于衬底方向的 c 轴择优取向.薄膜厚度对 ZMWO 薄膜的晶化程度、电阻率和方块电阻有很大影响.当薄膜厚度从97 nm 增大到456 nm 时,ZMWO 薄膜的晶化程度提高,而电阻率和方块电阻减小.当厚度为 456 nm 时,所制备ZMWO 薄膜的电阻率达到最小,其值仅为8.8×10-5 Ω·cm,方块电阻为1.9 Ω/□.所有薄膜样品在可见光区的平均透过率都较高,其值约为89;.当薄膜厚度从97 nm 增大到 456 nm时,光学带隙从3.41 eV增大到3.52 eV.     

Comparison of optical properties of periodic photonic–plasmonic and randomly textured back reflectors for nc-Si solar cells

Light trapping is essential to harvest long-wavelength red and near-infrared photons in thin film silicon solar cells. Light trapping in p-i-n thin film cells is commonly achieved with back-reflectors, and in n-i-p cells with textured front transparent conductors. We systematically compare the optical properties and performance of randomly roughened back reflectors with periodic plasmonic-photonic back-reflectors in p-i-n solar cells. The randomly textured back reflectors were prepared to have very high diffuse reflectance comparable to the state of the art. The periodic back reflectors of tapered nano-pillars/bumps show enhanced quantum efficiency and optical absorption over randomly structured back reflectors using the same solar cell architecture in nc-Si solar cells. The strong diffraction and light concentration in periodic back reflectors may be more beneficial than the light scattering offered by randomly textured back reflectors.     

Inline deposited thin-film silicon solar cells on imprinted foil using linear PECVD sources

The standard way to improve the light management of thin film solar cells is to introduce a light scattering structure, either on the front window or at the back reflector. Usually, growth conditions of TCO layers are adjusted to get random surface roughness on the front window. In this paper we present an alternative method, which can be applied both on the front window and at the back reflector. It involves imprinting a UV curable coating layer allowing full control on the texture (random or periodic) to fully optimise the light trapping. Light trapping is even more important for microcrystalline Si solar cells. We have fabricated thin film nip Si solar cells with sputtered Ag/ZnO back contacts on embossed barrier layers on steel foil. We show that the UV curable coating is well-suited as imprintable barrier layer between the steel foil and the active layers. For nip a-Si cells we can obtain light trapping, as measured by the short-circuit current, that is almost as good as that of nip a-Si cells made on Asahi U-type glass, covered with a Ag/ZnO back reflector. Furthermore, we show that dynamically processed a-Si nip cells on foil realised efficiencies of over 7%, which are only slightly less than for cells made in a UHV lab-scale cluster tool in static processing. Finally, a-Si/a-Si tandems and μc-Si/a-Si tandems have been fabricated. Initial efficiencies of around 8% on textured barrier layer on steel foil have been achieved.     

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.     

Influence of textured c-Si surface morphology on the interfacial properties of heterojunction silicon solar cells

For the HIT solar cells, the properties of interface between intrinsic thin film and c-Si are critical for the resulting device. The interfacial properties mainly depend on the surface passivation quality of c-Si, which is found to be affected by the morphology of textured surfaces. In this study, four kinds of textured c-Si substrates are fabricated: large pyramids without chemical polished (CP), large pyramids with CP, small pyramids without CP and small pyramids with CP. We investigated the effects of textured-surface morphology on the passivation of c-Si, the thin layer coverage and the interfacial properties of heterojunction prepared by HWCVD. Minority carrier lifetime measurements show that the wafer with small pyramids leads to better surface passivation than the one with large pyramids. The good coverage and contact between the thin film and the substrate can be achieved and no epitaxial growth occurs on the wafer with small pyramids through the study of TEM. Dark I-V measurements reveal that the heterojunction on wafer with small pyramids and CP has low recombination at the a-Si:H/c-Si interface. Our results indicate that the surface with small pyramids and low surface roughness is beneficial to the performance of HIT solar cells.     

以溶液法PEDOT∶PSS作为空穴传输层的免光刻背接触硅太阳电池

对PEDOT∶PSS(聚(3,4亚乙二氧基噻吩)-聚(苯乙烯磺酸))薄膜与Mg、Al和Ag三种金属接触后的I-V特性曲线进行了测试分析,发现Mg和Al与PEDOT∶PSS薄膜接触后呈现高电阻特性,可以起到绝缘隔离层的作用。在此基础上,以PEDOT∶PSS作为空穴传输层,以LiF作为电子传输层,以PEDOT∶PSS与Mg/Al的接触作为隔离层,不采用光刻工艺,设计制备了只需一次掩膜工艺的背接触太阳电池。通过在PEDOT∶PSS上采用热丝氧化升华技术制备MoO_x层,通过优化LiF薄膜的厚度,在抛光硅片上初步实现了开路电压最高为592 mV和效率最高为10.13%的背接触太阳电池。采用金属辅助腐蚀制备硅纳米线陷光结构改善前表面陷光效果,得到了开路电压为587 mV,短路电流密度为35.57 mA/cm²,填充因子为69.97%,效率为14.61%的背接触太阳电池。     

碳电极钙钛矿太阳能电池光吸收层厚度对光伏性能的影响研究

本文使用两步法,通过控制PbI₂(DMSO)溶液的浓度制备了不同厚度的有机-无机杂化钙钛矿(MAPbI₃)光吸收层薄膜,并组装了大面积基于碳电极且无空穴传输层的钙钛矿太阳能电池。对不同厚度MAPbI₃光吸收层薄膜的晶相、光吸收性质、表面形貌、元素组成进行分析,并进一步测试了基于MAPbI₃薄膜制备的钙钛矿太阳能电池的光伏性能。结果表明,MAPbI₃光吸收层薄膜厚度与PbI₂(DMSO)浓度呈正相关关系,浓度为1.3 mol/L的PbI₂溶液制备的MAPbI₃薄膜厚度约为350 nm,具有较好的结晶度和光吸收强度,且薄膜表面致密平整,无明显缺陷,基于350 nm MAPbI₃光吸收层的钙钛矿太阳能电池获得了8.48%的光电转换效率。     

自支撑氮化硅膜结构制备工艺优化

自支撑氮化硅膜结构一般是基于微纳加工技术来制备的。为了提高膜结构的品质,本文分别对自支撑氮化硅膜结构制备中的干法刻蚀参数和各向异性湿法腐蚀参数进行了研究和优化,其中干法刻蚀参数主要包括反应气体配比和刻蚀时间,各向异性湿法腐蚀参数主要包括腐蚀剂浓度和腐蚀温度。在不同的参数组合下进行实验,使用光学显微镜观察并比较不同样品的表面形貌,得到了较理想的参数组合。在干法刻蚀的反应气体中加入少量O₂可改善刻蚀效果,反应气体配比V(SF₆)∶V(CHF₃)∶V(O₂)=6∶37∶3,刻蚀时间2 min。湿法腐蚀中腐蚀剂在质量分数25%处达到最大的硅腐蚀速率,同时氮化硅表面形貌也较理想。     

Characteristics of p-type nanocrystalline silicon thin films developed for window layer of solar cells

Different rf-power and chamber pressures have been used to deposit boron doped hydrogenated silicon films by the PECVD method. The optoelectronic and structural properties of the silicon films have been investigated. With the increase of power and pressure the crystallinity of the films increases while the absorption decreases. As a very thin p-layer is needed in p–i–n thin film solar cells the variation of properties with film thickness has been studied. The fraction of crystallinity and thus dark conductivity vary also with the thickness of the film. Conductivity as high as 2.46 S cm⁻¹ has been achieved for 400 Å thin film while for 3000 Å thick film it is 21 S cm⁻¹. Characterization of these films by XRD, Raman Spectroscopy, TEM and SEM indicate that the grain size, crystalline volume fraction as well as the surface morphology of p-layers depend on the deposition conditions as well as on the thickness of the film. Optical band gap varies from 2.19 eV to 2.63 eV. The thin p-type crystalline silicon film with high conductivity and wide band gap prepared under high power and pressure is suitable for application as window layer for Silicon thin film solar cells.     

绒面ZnO/Si异质结太阳能电池的初步研究

以p型单晶硅<100>作为衬底材料,通过化学腐蚀法得到硅绒面表面结构,采用喷雾热解法沉积掺Al的ZnO薄膜于绒面硅上,结合微电子光刻、磁控溅射和真空蒸镀等工艺制作上、下表面电极,于400 ℃氮气氛围下快速退火合金,得到Ag/Ti/n-ZnO/p-Si/Al异质结太阳能电池.对电池样品进行了原子力显微镜、霍尔效应测试、X射线衍射谱、电流电压特性等分析.得到电池最佳性能为:开路电压V_(oc)=355 mV,短路电流I_(sc)=36 mA,填充因子FF=0.41,电池效率达到5.2;.绒面异质结构有效降低了电池表面的光反射,相对增加了p-n结的有效面积,电池效率得到一定程度的提高.ZnO与Si界面之间SiO_2层的存在是目前影响电池效率的主要因素.     

Preparation and characterization of Si sheets by renewed SSP technique

Silicon sheets from powder (SSP) ribbons have been prepared by modified SSP technique using electronic-grade (9N purity) silicon powder. The surface morphology, crystallographic quality, composition and electric properties of the SSP ribbons were investigated by surface profiler, X-ray diffraction (XRD), scanning electron microscopy (SEM), metallurgical microscope, Auger electron spectroscopy (AES) and four-point probe apparatus, respectively. The results show that the SSP ribbon made from electronic-grade silicon powder is a suitable candidate for the substrates of crystalline silicon thin film (CSiTF) solar cells, which could meet the primary requirements of CSiTF solar cell process on the substrates, including surface smoothness, crystallographic quality, purity and electric conductivity, etc.