铜铟镓硒(CIGS)光伏薄膜的磁控溅射及组成调控研究进展

铜铟镓硒(Cu(In_xGa_(1–x))Se_2,CIGS)薄膜是目前备受关注的一种太阳能电池材料,磁控溅射是其重要的制备方法。本文从溅射工艺(衬底温度、溅射功率、工作气压)和组成调控(硒含量、Ga梯度)两个方面简述了关于磁控溅射CIGS薄膜的研究进展(尤其是对其光伏性能的调控),提出了提高CIGS薄膜电池光电转换效率的建议及研究方向。     

不同溅射功率制备的Zn0.97Co0.03O薄膜的结构和光学性质研究

采用磁控溅射法在不同射频功率下制备了Zn_(0. 97)Co_(0. 03)O薄膜。利用X射线衍射(XRD)、拉曼光谱(Raman)、紫外-可见光谱和室温光致发光谱对薄膜进行了表征。XRD和Raman结果表明,Zn_(0. 97)Co_(0. 03)O薄膜为六方纤锌矿结构,沿(002)晶面择优取向。随着溅射功率的增大,薄膜的(002)晶面择优取向增强,晶化程度提高,晶粒尺寸增大。不同溅射功率制备的Zn_(0. 97)Co_(0. 03)O薄膜均具有较高的可见光透过率。随溅射功率增加,光学带隙减小,光吸收边红移。光致发光谱表明不同溅射功率制备的Zn_(0. 97)Co_(0. 03)O薄膜均具有较强的带边紫外发光峰。随着溅射功率的增加,该发光峰的峰位发生红移,且峰强度增强。以上研究结果表明,溅射功率对Zn_(0. 97)Co_(0. 03)O薄膜的生长速率、结晶质量及光学性能有明显影响,但不会影响薄膜的成分。     

低温制备Mn-W共掺ZnO透明导电薄膜

利用直流磁控溅射法成功地在室温玻璃衬底上制备出了电阻率低、透光率高的Mn-W共掺ZnO（ZMWO）透明导电薄膜。溅射功率在65-150 W之间变化。实验结果表明,溅射功率对ZMWO薄膜的晶化程度和电阻率有很大影响,而对其透光率和光学带隙影响不大。实验制备的ZMWO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。考虑到薄膜的电学、光学性能及结晶质量,我们认为本实验中的最佳值溅射功率为90 W,在此功率下制备的ZMWO薄膜的电阻率具有最小值9.8×10-4Ωcm,其可见光透过率为89%。     

磁控溅射氧化钛薄膜在不同溅射温度下的光电性能研究

通过磁控反应溅射,在玻璃基底上制备了不同溅射温度下的氧化钛薄膜.通过对其光电性能的分析测试,探讨了溅射温度对氧化钛薄膜性能的影响.实验表明:低温溅射下,薄膜表面颗粒较小,结构较为疏松,高温溅射下,薄膜颗粒较大,薄膜表面颗粒出现团聚现象;随着溅射温度的升高,溅射速率减小;薄膜方阻减小,载流子浓度增大;溅射温度越高,薄膜在紫外可见光波段内透射越弱,光学带隙越小.     

溅射气压对氧化镓薄膜光学特性的影响

采用射频磁控溅射法在石英衬底上制备了氧化镓(Ga2O3)薄膜.利用X射线衍射仪和紫外-可见-红外分光光度计分别对Ga2O3薄膜的晶体结构和光学带隙进行了表征,并在室温下测量了 Ga2O3薄膜的光致发光(PL)谱.结果表明:制备的Ga2O3薄膜呈非晶态.吸收边随着溅射气压的增加先蓝移后红移,光学带隙值范围为5.06～5.37 eV,溅射气压为1 Pa时,制备的Ga2O3薄膜具有最大的光学带隙.在325 nm激光激发下,400 nm附近和525 nm附近处出现与缺陷能级相关的发光峰.     

高RF功率制备的ZnO:Li薄膜性能研究

实验采用射频(RF)磁控溅射法在高射频功率(550 W)下制备了Zn0.9Li0.1O薄膜,探讨了薄膜的光学性能,并与低溅射功率制备的薄膜性能进行了比较。结果表明,高功率下溅射的薄膜晶粒均匀细小,表面平整致密,在可见光波长范围内,透过率达80%。该薄膜的光学带隙约3.29 eV,明显低于低功率溅射的薄膜(3.44 eV)。其室温光致发光(PL)谱结果显示,最强峰是由Li杂质能级引起的399 nm峰,热处理后,370 nm的带间发光峰增强,而低功率制备的薄膜其PL谱与纯ZnO材料的特征谱相似。     

CdS薄膜的真空热蒸发制备及在CIGS薄膜太阳电池中的应用

采用真空热蒸发(VTE)的方法制备了CdS多晶薄膜,研究了不同衬底温度对其微观结构与光电性能的影响。结果显示,不同衬底温度下制备的CdS薄膜均属于六方相多晶结构且具有(002)择优取向;随着衬底温度的升高,(002)特征衍射峰强度增加,半高宽变小,相应薄膜结晶度增大;由CdS薄膜的透射光谱可知,在500~1 000nm波段平均透过率均超过80%,光学带隙随着衬底温度的升高而增大(2.44~2.56eV),表明真空热蒸发方法制备的CdS薄膜可以作为CIGS薄膜太阳电池的缓冲层。将真空热蒸发法制备CdS薄膜与磁控溅射法制备CIGS薄膜太阳电池相结合,在同一真空室内得到了CIGS薄膜太阳电池器件,为CIGS薄膜太阳电池的工业化推广提供了新途径。     

铜薄膜的直流磁控溅射制备与表征

根据薄膜的形成机理,用直流磁控溅射方法制备出了表面结构平滑、致密的Cu薄膜.实验中,采用纯度＞99.9%的铜靶,工作气压保持在2.7 Pa不变,玻璃衬底温度随环境温度变化.用X射线衍射仪(XRD)、扫描电镜(SEM)研究了薄膜的织构、晶粒尺寸和表面形貌.结果表明,随着溅射功率增大,薄膜织构减弱;溅射功率增大和溅射时间增加均可使薄膜的晶粒尺寸增大,在溅射功率≤100 W时获得的薄膜晶粒细小,有裂纹缺陷;溅射功率为150 W,溅射时间为30 min时,薄膜表面结构平滑、致密,晶粒尺寸相对较大.须进一步改进工艺参数,如衬底温度等,从而制备出表面结构平滑、致密、晶粒细小的薄膜.     

溅射压力对制备a-GaAs1-xNx 薄膜光学常数的影响

采用反应磁控溅射法在室温条件下制备了a-GaAs_1-xN_x 薄膜。实验测定了薄膜厚度、氮含量、载流子浓度和光学透过率及并研究了其随溅射压的变化。系统研究了溅射压对所制备薄膜的光学带隙、折射率和色散参数的影响。所制备的薄膜为直接带隙材料,利用Cauchy和Wemple模型能够很好地拟合所制备薄膜的折射率色散曲线。     

一种双靶磁控溅射制备的Mg掺杂的NiO薄膜

采用磁控溅射“共溅射”方法,将Ar气作为溅射气体,高纯NiO和MgO双陶瓷靶作为溅射靶材。当控制NiO和MgO靶的溅射功率分别为190 W和580 W,溅射真空度为2 Pa,衬底温度为300℃时,得到了Mg掺杂的NiO(Ni_0.61Mg_0.39O)薄膜。该薄膜是一种具有(200)择优取向的晶态薄膜。薄膜表面比较平整,晶粒分布致密,晶粒尺寸约46.9 nm。(200)衍射峰位置相对未掺杂的NiO薄膜向小角度偏移约0.2°。合金薄膜在可见光波段具有较大的透过率,而在300 nm附近透过率陡然下降,其光学带隙向高能方向移动到了3.95 eV。该研究为采用磁控溅射制备高质量的Mg掺杂的NiO薄膜提供了技术支撑。     

Effect of processing parameter on structural,optical and electrical properties of photovoltaic chalcogenide nanostructured RF magnetron sputtered thin absorbing films

The aim of this work was to develop high quality of CuIn_1−xGa_xSe₂ thin absorbing films with x (Ga/In+Ga)<0.3 by sputtering without selenization process. CuIn_0.8Ga_0.2Se₂ (CIGS) thin absorbing films were deposited on soda lime glass substrate by RF magnetron sputtering using single quaternary chalcogenide (CIGS) target. The effect of substrate temperature, sputtering power & working pressure on structural, morphological, optical and electrical properties of deposited films were studied. CIGS thin films were characterised by X-ray diffraction (XRD), Field emission scanning electron microscope (FE-SEM), Energy dispersive X-ray spectroscopy (EDAX), Atomic force microscopy (AFM), UV–vis–NIR spectroscopy and four probe methods. It was observed that microstructure, surface morphology, elemental composition, transmittance as well as conductivity of thin films were strongly dependent on deposition parameters. The optimum parameters for CIGS thin films were obtained at a power 100 W, pressure 5 mT and substrate temperature 500 °C. XRD revealed that thin film deposited at above said parameters was polycrystalline in nature with larger crystallite size (32 nm) and low dislocation density (0.97×10¹⁵ lines m⁻²). The deposited film also showed preferred orientation along (112) plane. The morphology of the film depicted by FE-SEM was compact and uniform without any micro cracks and pits. The deposited film exhibited good stoichiometry (Ga/In+Ga=0.19 and In/In+Ga=0.8) with desired Cu/In+Ga ratio (0.92), which is essential for high efficiency solar cells. Transmittance of deposited film was found to be very low (1.09%). The absorption coefficient of film was ~10⁵ cm⁻¹ for high energy photon. The band gap of CIGS thin film evaluated from transmission data was found to be 1.13 eV which is optimum for solar cell application. The electrical conductivity (7.87 Ω⁻¹ cm⁻¹) of deposited CIGS thin film at optimum parameters was also high enough for practical purpose.     

CIGS Thin Films for Cd-Free Solar Cells by One-Step Sputtering Process

Cu(In_1?x Ga _x )Se₂ (CIGS) thin films were deposited by a one-step radio frequency (RF) magnetron sputtering process using a quaternary CIGS target. The influence of substrate temperature on the composition, structure, and optical properties of the CIGS films was investigated. All the CIGS films exhibited the chalcopyrite structure with a preferential orientation along the (112) direction. The CIGS film deposited at 623 K showed significant improvement in film crystallinity and surface morphology compared to films deposited at 523 and 573 K. To simplify the manufacturing procedure of solar cells and avoid the use of the toxic element Cd, the properties of ZnS films prepared by RF sputtering were also investigated. The results revealed that the sputtered ZnS film exhibits good lattice matching with the sputtered CIGS film with significantly lower optical absorption loss. Finally, all-sputtered Cd-free CIGS-based heterojunction solar cells with the structure SLG/Mo/CIGS/ZnS/AZO/Al grids were fabricated without post-selenization. Furthermore, the results demonstrated the feasibility of using a full sputtering process for the fabrication of Cd-free CIGS-based solar cell.     

不同温度硫化生长ZnS薄膜的性能

采用磁控溅射方法在玻璃衬底上室温下沉积了Zn薄膜,接着将薄膜在硫蒸气和氩气氛中于200℃预热1 h,然后升温至250~500℃退火1 h。以XRD、SEM、EDS和紫外可见分光光度计对薄膜进行表征,并结合热力学计算结果研究了Zn薄膜硫化生长机理。Zn转变为ZnS的过程包括硫化反应以及S原子和Zn原子的扩散。研究还表明:第一步的200℃预热可在Zn薄膜表面形成ZnS,随后第二步退火的硫化温度对硫化薄膜光透过率、S/Zn摩尔比和结晶性都有明显影响;在大于或等于300℃的硫化温度下制备的ZnS薄膜在400~1100 nm范围光透过率高达约80%,带隙为3.54~3.60 eV,晶体结构为六方。     

溅射功率对NiO薄膜性质的影响

在室温条件下,采用射频磁控溅射的方法在石英衬底上制备了NiO薄膜,深入研究了不同溅射功率对NiO的结构、光学和电学特性的影响。随着溅射功率的升高,NiO薄膜逐渐由非晶态薄膜转变成具有(111)择优取向的晶态薄膜,同时发现NiO薄膜在可见光区透过率较大,而在紫外光区透过率减小;随着溅射功率的升高,薄膜在可见光区域和紫外区域的光学透过率均明显减小,同时禁带宽度也减小,但导电性增强。     

无镉的铜铟镓硒太阳电池关键膜层XPS及AFM分析

应用溅射后硒化法和原子层沉积法分别制备了无镉的铜铟镓硒电池关键膜层CIGS光吸收薄膜和ZnO缓冲层,着重对该两膜层进行XPS和AFM表面分析,得到比较理想的制备工艺条件,并结合其它检测方法:SEM、XRD及吸收光谱等,证明采用操作简便、成本低廉的该工艺能制备出无镉的铜铟镓硒电池。通过I-V测试结果,该电池有一定的光电转换效率。     

Fabrication and characterization of thin-film Cu (In,Ga) Se2 solar cells on a PET plastic substrate using screen printing

Chalcopyrite copper indium gallium diselenide (CIGS) ink was prepared by dissolving copper, indium, gallium acetylacetonate and Se powder in oleylamine using the hot injection methods. CIGS films were deposited on a PET plastic substrate by a screen-printing technique using CIGS ink with a Ga content ranging from 0.3 to 0.6. X-ray diffraction patterns reveal that the films exhibit a chalcopyrite-type structure. The crystalline grain sizes of the films decrease with increasing Ga content. AFM data shows that the root mean square (RMS) surface roughness of the CIGS film decreases with increasing Ga content. The effects of the Ga content in the CIGS absorber layer on the optical properties of the corresponding thin films and solar cells were studied. The band-gap energies of the CIGS thin films increased with an increasing Ga/(In+Ga) ratio. The short-circuit current (I_SC) of the solar cell decreased linearly with the Ga/(In+Ga) ratio, while the open-circuit voltage (V_OC) increased with this ratio. The solar cell exhibited its highest efficiency of 4.122% at a Ga/(In+Ga) ratio of 0.3.     

PMNT薄膜可见-红外光学性质的研究

通过对不同组分的铌镁钛酸铅(PMNT)薄膜的紫外-可见透射光谱以及红外椭圆偏振光谱的分析,利用Tauc-Lorentz(T-L) Cauchy色散关系和经典中红外色散关系,得到了该材料在可见和中红外区的光学常数,发现在可见和中红外区,薄膜的折射率随着PT(PbTiO3)含量的增加而增大,但是薄膜的光学禁带宽度随之而减小.     

基于皮秒激光诱导击穿光谱技术的镓酸锌薄膜的快速定量分析研究

采用射频磁控溅射方法在不同的溅射功率下制备了掺杂Ga元素的ZnO透明导电薄膜材料(ZnGa₂O₄, GZO),在GZO薄膜的制备过程中,溅射功率会对样品的组分配比产生影响,从而导致GZO薄膜的性能产生差异。文中利用皮秒激光诱导击穿光谱技术(PS-LIBS)对GZO薄膜进行了微烧蚀分析,对GZO薄膜的关键元素浓度比进行了快速定量分析研究。结果表明GZO薄膜的光学性能与元素谱线强度比之间存在一定的联系,随着溅射功率的增加,Zn/Ga的谱线强度比值与浓度比呈现出一致的变化,Ga元素的含量与样品的禁带宽度变化一致。同时,使用玻耳兹曼斜线法与斯塔克展宽法对等离子体温度与电子密度进行了计算。所有结果表明,PS-LIBS技术可以实现GZO薄膜关键组分配比的快速分析,为磁控溅射法制备GZO薄膜的工艺现场的快速性能分析、制备参数的实时优化提供了技术参考。     

Effect of MoSe2 on the performance of CIGS solar cells

A CuIn1-xGaxSe2 (CIGS) thin film solar cell model with MoSe2 transition layer was established, using SCAPS-1D software. The influence of MoSe2 interface layer formed between absorption layer CIGS and the back contact Mo on the solar cell performance was investigated.By changing the doping concentration,thickness and bandgap of MoSe2 layer, it is found that the MoSe2 and the variation of parameters have a significant effect on the electrical characteristics and photovoltaic parameters of CIGS thin film solar cells. Based on the energy band, the interfaces of Mo/MoSe2 and MoSe2/CIGS are analyzed. It is considered that Mo/MoSe2 is a Schottky contact, MoSe2/CIGS is an ohmic contact. When suitable parameters of MoSe2 layer are formed into the interface, it will provide a new path for designing CIGS solar cells with thinner absorption layer.     

Effect of bath temperature on the properties of CuInxGa1-x Se2 thin films grown by the electrodeposition technique

Electrodeposition is a promising and low cost method to synthesize CulnxGa1-xSe2 (CIGS)thin films as an absorber layer for solar cells. The effect of bath temperature on the properties of CIGS thin films was investigated in this paper. CIGS films of 1 μm thickness were electrodeposited potentiostatically from aqueous solution, containing trisodium citrate as a complexing agent, on Mo/glass substrate under a voltage of-0.75 V, and bath temperatures were varied from 20 to 60 ℃. The effects of bath temperature on the properties of CIGS thin films were characterized by X-ray diffraction (XRD) and scanning electron microscopy. XRD revealed the presence of the CuIn0.7Ga0.3Se2 phase, the optimal phase for application in solar cells. The grain dimensions and crystallizability increase along with the increase of the bath temperature, and the films become stacked and homogeneous. There were few changes in surface morphology and the composition of the films.