预制层溅射气压对CIGS薄膜结构及器件的影响

研究了金属预制层制备过程中溅射气压对Cu(In_1-xGa_x)Se₂(CIGS)薄膜及电池器件性能的影响.通过调节溅射气压改变预制层的结晶状态及疏松度与粗糙度,在合适的预制层结构下,活性硒化热处理过程中,可使Ga有效地掺入到薄膜中形成优质的CIGS固溶体.高溅射气压会使预制层过于致密,呈现非晶态趋势.经活性硒化热处理后,CIGS薄膜容易产生CIS与CGS"两相分离"现象,从而导致CIGS薄膜太阳电池的开路电压和填充因子降低,电池转换效率由10.03%降低到5.02%.     

铜铟镓硒薄膜的拉曼和可见-近红外光谱表征

采用恒电位电沉积法在ITO上制备了铜铟镓硒(CIGS)前驱体薄膜,该前驱体薄膜在充氩气管式炉中经过高温硒化可得到结晶良好的CIGS薄膜。采用X-射线衍射(XRD)、拉曼光谱(Raman)、扫描电子显微镜(SEM)和紫外-可见光-近红外光谱仪分别表征了CIGS薄膜的结构、形貌、成分以及可见-近红外光谱(Vis-NIR)吸收特性。XRD结果表明前驱体薄膜高温硒化后所得的CIGS薄膜具有(112)择优取向,薄膜中CIGS晶粒的平均尺寸为24.7nm,Raman光谱表明薄膜中的CIGS是具有黄铜矿结构的四元纯相,没有其他二元三元杂相存在。Vis-NIR测量结果表明CIGS的禁带宽度随薄膜中镓含量的增加而增加,当Ga含量达5.41%时,通过吸收光谱测得CIGS的禁带宽度为1.11eV,通过理论计算得到镓铟比为Ga/(In+Ga)=16.3%,小于SEM测量所得的镓铟比Ga/(In+Ga)=21.4%,这表明还需进一步提高CIGS薄膜的结晶度。所有测量表明优化后的ITO/CIGS非常适合用来制作高质量的双面太阳能电池。该研究提出了制备低成本CIGS前驱体薄膜及高温硒化的新方法,通过这些方法在ITO上制备了均匀、致密、附着力好的CIGS薄膜。通过上述表征可知,在新工艺下制备的CIGS薄膜结晶度高,成分合理,无杂相,光吸收性质好。与磁控溅射法类似,电沉积法非常适合大面积工业化生产,该工作对CIGS的规模化生产具有重要的借鉴意义。     

硒化前后电沉积贫铜和富铜的Cu(In1-xGax)Se2薄膜成分及结构的比较

采用电沉积法获得了接近化学计量比的贫铜和富铜的Cu(In1-xGax)Se2(CIGS)预置层,研究比较了两种预置层及其硒化处理后的成分和结构特性.得到了明确的实验证据证明,硒化后富铜薄膜中的CuxSe相会聚集凝结成结晶颗粒分散在表面.研究表明:在固态源硒化处理后,薄膜成分基本不变;当预置层中原子比Cu/(In+Ga)<1.1时,硒化后薄膜表面存在大量的裂纹;而当Cu/(In+Ga) >1.2时,可以消除裂纹的产生,形成等轴状小晶粒;富铜预置层硒化时蒸发沉积少量In,Ga和Se后,电池效率已达到6.8%;而贫铜预置层硒化后直接制备的电池效率大于2%,值得进一步深入研究.     

Ga梯度分布对Cu(In,Ga)Se_2薄膜及太阳电池的影响

传统制备Cu(In,Ga)Se2(CIGS)手段之一是共蒸发三步法,工艺中通过Cu,In,Ga,Se 4种元素相互扩散、作用形成抛物线形的Ga梯度分布.本文通过调整Ga源温度制备了Ga梯度分布不同的CIGS薄膜及电池.利用多种测试方法,研究了Ga梯度分布不同对CIGS薄膜表面及背面结构性质及电性质的影响,计算分析了表面导带失调值及背面电场对电池性能的影响,从而获得了合适的Ga梯度分布,提高了电池光谱相应,获得了较好的电池性能参数.     

硒化前后电沉积贫铜和富铜的Cu(In1-xGax)Se2薄膜成分及结构的比较

采用电沉积法获得了接近化学计量比的贫铜和富铜的Cu（In_1-xGa_x）Se₂（CIGS）预置层,研究比较了两种预置层及其硒化处理后的成分和结构特性.得到了明确的实验证据证明,硒化后富铜薄膜中的Cu_xSe相会聚集凝结成结晶颗粒分散在表面.研究表明：在固态源硒化处理后,薄膜成分基本不变;当预置层中原子比Cu/（In+Ga）<11时,硒化后薄膜表面存在大量的裂纹;而当Cu/（In+Ga） >12时,可以消除裂纹的产生,形成等轴状小晶粒;富铜预置层硒化时蒸发沉积少量In,Ga和Se后,电池效率已达到68%;而贫铜预置层硒化后直接制备的电池效率大于2%,值得进一步深入研究. 关键词： 1-xGa_x）Se₂薄膜')" href="#">Cu（In_1-xGa_x）Se₂薄膜 电沉积 硒化处理 贫铜或富铜薄膜     

铜铟镓硒太阳能电池多层膜的结构分析

对于溅射后硒化和共蒸发等方法制备的铜铟镓硒（CIGS）太阳能电池薄膜,利用多种分析方法研究了CIGS多层膜的复杂结构等．研究表明：卢瑟福背散射（RBS）在分析CIGS多层膜方面具有其独特优势和可靠的结果;溅射后硒化方法制备的CIGS薄膜中,Ga和In在CIGS薄膜中呈梯度分布,这种Ga表层少而内层多的不均匀分布与Mo层没有必然关系;RBS和俄歇电子能谱分析（AES）均显示CIGS太阳能电池器件多层膜界面处存在扩散,尤其是CdS与CIGS,Mo与CIGS的界面处;X射线荧光（XRF）结果表明,电池效率最高的CIGS层中In,Ga比例为In：Ga=0．7：0.3;X射线衍射（XRD）结果显示：退火后的CIGS／Mo薄膜结晶品质得到了优化．     

Cu(In,Ga)Se2 薄膜在共蒸发"三步法"中的相变过程

CIGS薄膜的结晶相是制备高质量薄膜的关键问题. 本文采用共蒸发"三步法"工艺沉积Gu(In, Ga)Se₂ (CIGS) 薄膜, 通过X射线衍射仪 (XRD) 和X射线荧光光谱仪 (XRF)、扫描电镜 (SEM) 结合的方法详细研究了"三步法"工艺的相变过程, 并制备出转换效率超过15% 的 CIGS 薄膜太阳电池. 关键词： CIGS薄膜 共蒸发三步法 相变过程     

利用Raman散射光谱研究铜铟镓硒薄膜表面的掺杂调节作用

主要研究了采用溅射后硒化方法制备CIGS(铜铟镓硒)薄膜太阳电池的吸收体材料中的表面层掺杂调节问题。并利用Raman散射谱分析研究了样品表面层特征峰的移用,研究结果表明: CIGS薄膜表面层由富In表面层调节为富CuGa表面层后,Raman特征峰位向高波数移动,表明薄膜表面的Ga含量随之变化,并导致表面能带的相应改变,经计算证实了富CuGa表面层样品较之富In表面层样品具有更高的表面能带,从而改善了以此材料为吸收层的太阳电池器件性能, V_oc提高了74 mV,填充因子上升8％,最终使器件转换效率η相应提高了约2％。提高了V_oc与FF。同时表明Raman散射谱作为一种灵敏的表面表征手段,在研究太阳电池吸收层表面状态时十分有力。     

不同成分比例CIGS薄膜及太阳电池的快速退火

研究了110~180 ℃(2 min)下的快速热退火对Cu(In,Ga)Se2(CIGS)薄膜特性及CIGS太阳电池性能的影响.结果表明:对于不同成分比例的CIGS(正常、富Cu、高Ga)电池来说,150 ℃,2 min的快速退火最利于电池性能及二极管特性的增加.其中,退火对富Cu电池的开路电压Voc改善最大,这是因为快速热退火对消除部分CIGS薄膜中的CuSex有积极作用,从薄膜的电阻率有少量提高,器件的短路电流Jsc有少量下降可以得到验证;而对于高Ga电池来说,填充因子FF的改善最大,这是因为高Ga样品的缺陷较多,退火会消除薄膜内部的部分缺陷,从而薄膜的迁移率及Jsc都有所提高,使得FF有较大的增加.     

不同成分比例CIGS薄膜及太阳电池的快速退火

研究了110~180 ℃（2 min）下的快速热退火对Cu(In,Ga)Se2(CIGS)薄膜特性及CIGS太阳电池性能的影响.结果表明：对于不同成分比例的CIGS（正常、富Cu、高Ga）电池来说,150 ℃,2 min的快速退火最利于电池性能及二极管特性的增加.其中,退火对富Cu电池的开路电压Voc改善最大,这是因为快速热退火对消除部分CIGS薄膜中的CuSex有积极作用,从薄膜的电阻率有少量提高,器件的短路电流Jsc有少量下降可以得到验证|而对于高Ga电池来说,填充因子FF的改善最大,这是因为高Ga样品的缺陷较多,退火会消除薄膜内部的部分缺陷,从而薄膜的迁移率及Jsc都有所提高,使得FF有较大的增加.     

Stage2沉积速率对低温生长CIGS薄膜特性及器件的影响

研究了三步法第二步沉积速率对低温生长Cu(In,Ga)Se₂薄膜结构、 电学特性和器件特性的影响. 通过改变第二步沉积速率发现, 提高沉积速率可以显著促进薄膜晶粒生长, 提高晶粒紧凑程度降低晶界复合, 同时有效改善两相分离现象, 提高电池的开路电压和短路电流, 有助于Cu(In,Ga)Se₂电池光电转换效率的提高. 但同时研究表明, 随着第二步沉积速率的增加, 会促进暂态Cu_2-xSe晶粒的生长, 引起Cu(In,Ga)Se₂薄膜表面粗糙度增大, 并阻碍Na向Cu(In,Ga)Se₂薄膜表面的扩散, 造成施主缺陷钝化效应降低, 薄膜载流子浓度下降和电阻率升高, 且过高的沉积速率会引起电池内部复合增加并产生分流路径, 造成开路电压下降进而引起电池效率恶化. 最终, 通过最佳化第二步沉积速率, 在衬底温度为420℃时, 得到最高转换效率为11.24%的Cu(In,Ga)Se₂薄膜太阳电池.     

Cu元素对Cu(In,Ga)Se_2薄膜及太阳电池的影响

Cu元素成分对Cu(In,Ga)Se2(简称CIGS)薄膜材料的电学性质及其电池器件性能有很重要的影响.本文利用蒸发法制备了贫Cu和富Cu的CIGS吸收层(0.7Cu/(Ga+In)1.15)及相应的电池器件.扫描电镜和Hall测试发现,富Cu材料的结构特性(晶粒大、结晶状态好)和电学特性(电阻率低、迁移率高等)优于贫Cu材料,而性能测试表明贫Cu器件的效率优于富Cu器件.变温性能测试分析表明,贫Cu器件的主要复合路径是体复合,激活能与CIGS禁带宽度相当;富Cu器件的主要复合路径是界面复合,其激活能远小于CIGS禁带宽度,这大大降低了开路电压Voc,从而降低了电池效率.最后利用蒸发三步法制备了体材料稍富Cu表面贫Cu的CIGS吸收层,降低了短路电流和开路电压的损失,获得了超过15%的电池效率.     

Inkjet printed Cu(In,Ga)S<Subscript>2</Subscript> nanoparticles for low-cost solar cells

Cu(In,Ga)Se₂ (CIGSe) thin film solar cells were fabricated by direct inkjet printing of Cu(In,Ga)S₂ (CIGS) nanoparticles followed by rapid thermal annealing under selenium vapor. Inkjet printing is a low-cost, low-waste, and flexible patterning method which can be used for deposition of solution-based or nanoparticle-based CIGS films with high throughput. XRD and Raman spectra indicate that no secondary phase is formed in the as-deposited CIGS film since quaternary chalcopyrite nanoparticles are used as the base solution for printing. Besides, CIGSe films with various Cu/(In + Ga) ratios could be obtained by finely tuning the composition of CIGS nanoparticles contained in the ink, which was found to strongly influence the devices performance and film morphology. To date, this is the first successful fabrication of a solar device by inkjet printing of CIGS nanoparticles.     

Surface modification of CIGS film by annealing and its effect on the band structure and photovoltaic properties of CIGS solar cells

The composition of Cu(In,Ga)Se₂ (CIGS) films employed in CIGS solar cells is Cu deficient. There can be point defects, including Cu vacancies, Se vacancies, and metal anti-site defects. The surface composition and defects are not well controlled right after CIGS film fabrication with a three-stage co-evaporation process. This fabrication technique can result in a large variation in cell efficiency. In order to control the CIGS film in a reproducible way, we annealed the CIGS film in air, S, or Se. With this annealing procedure, the Cu content of the CIGS surface was significantly reduced and Ga content was strongly increased. An intrinsic CIGS layer with a lower valence-band maximum and a wider ban gap was formed at the surface. By annealing the CIGS film, the open-circuit voltage and fill factor were significantly improved, which indicates that the surface intrinsic layer acts as a hole-blocking layer so that the surface recombination rate is suppressed. In addition to CIGS film annealing, with subsequent annealing of the completed devices using rapid thermal annealing, the efficiency and reproducibility of CIGS solar cells were markedly improved.     

基于FTO/VO2/FTO结构的VO2薄膜电压诱导相变光调制特性

采用直流磁控溅射和后退火工艺在掺氟的SnO₂(FTO)导电玻璃衬底上制备VO₂薄膜, 研究了不同退火时间和不同比例的氮氧气氛对VO₂薄膜性能的影响, 对VO₂薄膜的结晶取向、表面形貌、表面元素的相对含量和透过率随波长变化进行了测试分析, 结果表明在最佳工艺条件下制备得到了组分相对单一的VO₂薄膜. 基于FTO/VO₂/FTO结构在VO₂薄膜两侧的透明导电膜上施加电压并达到阈值电压时, 观察到了明显的电流突变. 当接触面积为3 mm×3 mm时, 阈值电压为1.7 V, 阈值电压随接触面积的增大而增大. 与不加电压的情况相比, FTO/VO₂/FTO结构在电压作用下高低温的红外透过率差值可达28%, 经反复施加电压, 该结构仍保持性能稳定, 具有较强的电致调控能力.     

银纳米颗粒对聚合物太阳能电池性能的提高

采用水溶性银纳米颗粒附着在反型太阳能电池的电子传输层上,用以提高有机太阳能电池的短路电流。所制备的器件结构为ITO/ZnO/Ag NPs/P3HT(Poly 3-hexylthiophene):PC_[60]BM/MoO₃/Ag。其金属银纳米颗粒的表面等离激元在410 nm处出现了共振吸收峰,半峰全宽约为60 nm。器件的光电流在可见光范围内均有所增加,短路电流相对于标准器件提高了20.2%,光电转化效率相对提高了17.2%。     

Optimization of the CIGS based thin film solar cells: Numerical simulation and analysis

Chalcopyrite Cu(In,Ga)Se (CIGS) is a very promising material for thin film photovoltaics and offers a number of interesting advantages compared to the bulk silicon devices. CIGS absorbers today have a typical thickness of about 1–2 μm. However, on the way toward mass production, it will be necessary to reduce the thickness even further. This paper indicates a numerical study to optimization of CIGS based thin film solar cells. An optimum value of the thickness of this structure has been calculated and it is shown that by optimizing the thickness of the cell efficiency has been increases and cost of production can be reduces. Numerical optimizations have been done by adjusting parameters such as the combination of band gap and mismatch as well as the specific structure of the cell. It is shown that by optimization of the considered structure, open circuit voltage increases and an improvement of conversion efficiency has been observed in comparison to the conventional CIGS system. Capacitance–voltage characteristics and depletion region width versus applied voltage for optimized cell and typical cell has been calculated which simulation results predict that by reducing cell layers in the optimized cell structure, there is no drastically changes in depletion layer profile versus applied voltage. From the simulation results it was found that by optimization of the considered structure, optimized value of CIGS and transparent conductive oxide thickness are 0.3 μm and 20 nm and also an improvement of conversion efficiency has been observed in comparison to the conventional CIGS which cell efficiency increases from 17.65 % to 20.34%, respectively.     

Cu(In,Ga)Se2 thin film solar cells from nanoparticle precursors

A non-vacuum process for Cu(In,Ga)Se₂ (CIGS) thin film solar cells from nanoparticle precursors was described in this work. CIGS nanoparticle precursors was prepared by a low temperature colloidal route by reacting the starting materials (CuI, InI₃, GaI₃ and Na₂Se) in organic solvents, by which fine CIGS nanoparticles of about 15 nm in diameter were obtained. The nanoparticle precursors were then deposited onto Mo/glass substrate by the doctor blade technique. After heat treating the CIGS/Mo/glass layers in Se gas atmosphere, a complete solar cell structure was fabricated by depositing the other layers including CdS buffer layer, ZnO window layer and Al electrodes by conventional methods. The resultant solar cell showed a conversion efficiency of 0.5%.     

Chemical elaboration of well defined Cu(In,Ga)Se2 surfaces after aqueous oxidation etching

The present work is an attempt to prepare well defined surfaces of Cu(In,Ga)Se₂ (CIGS) thin films in order to answer to basic questions about the relationship between bulk and surface composition. The approach is to use an oxidative etch with an aqueous bromine solution, known to lead to specular surfaces. The CIGS surface is then analyzed by mechanical profilometry, SEM and XPS, allowing for determination of the surface roughness and the nature of surface species. After short time bromine etch, a Se⁰ film is formed on the CIGS surface which can be completely removed by KCN treatment, leaving a CIGS specular surface. An highlight result is that under specific conditions, the surface composition is close to the stoichiometry of the Cu(In,Ga)₃Se₅ copper deficient phase. This is the first time that such a study is conducted on technology relevant thin polycrystalline CIGS film. It is expected that the method described will help conducting experiments (e.g. Angle resolved XPS, SIMS, etc.) with an improved resolution.