铜锌锡硫系薄膜太阳电池的专利分析

铜锌锡硫(CZTS)系薄膜太阳电池因其高吸收系数、适宜的带隙宽度而成为太阳电池领域非常有前途的光吸收层材料。本文针对CZTS系薄膜太阳电池进行专利技术综述的分析,对国内外专利申请情况进行梳理,为国内薄膜太阳电池研究发展提供参考。     

基于CuInS2量子点的介孔太阳电池

采用预合成法合成铜铟硫(Cu In S2)量子点并将其应用于介孔太阳电池中。利用紫外可见吸收光谱、XRD和TEM等表征手段深入研究氧化物、硫化物、硒化物等不同包覆层对Cu In S2量子点敏化太阳电池性能的影响。结果表明,硫化物包覆层对Cu In S2量子点敏化太阳电池具有较优的性能,尤其是Cd S包覆,电池短路电流密度为13.6 m A/cm2,光电转换效率达到2.67%。最后探索Cu In S2量子点在有机-无机杂化钙钛矿太阳电池中的应用,其作为空穴传输材料,电池效率可达6.57%。     

H2Se气体硒化中温度对CIGS吸收层特性的影响

采用H_2Se气体对铜-铟-镓金属预制层进行硒化制备铜铟镓硒(CIGS)光吸收层,研究硒化过程中温度对CIGS结晶质量及光学特性的影响。400~500℃单一温度硒化制作的CIGS薄膜的表面平整性较差,存在颗粒状聚集物。在硒化前引入200℃低温预处理过程,可提高CIGS薄膜表面的平整性和致密性。在400℃硒化后导入500℃高温热处理过程可提高CIGS的结晶质量并改善Ga元素掺入的均匀性。光学特性测量显示,优化硒化温度可降低CIGS薄膜的缺陷态,从而提高Ga元素在薄膜中的掺入效果,CIGS薄膜的光学带隙可达1.14 e V。利用CIGS薄膜制备的太阳电池光电转换效率达13.1%,开压为519 m V,有效面积为0.38 cm~2。     

三维石墨烯包覆的硫掺杂碳负载二硫化硒复合材料的制备及其储锂性能研究

二硫化硒（SeS₂）作为储锂的正极材料,具有硒和硫以外的独特优势。采用硫掺杂介孔碳（sulfur-doped mesoporous carbon, SMC）负载SeS₂,然后用三维石墨烯（three-dimensional grapheme, 3DG）对其进行包覆,制备了双重限定的SeS₂基正极结构。通过透射电子显微镜（transmission electron microscope, TEM）,扫描电子显微镜（scanning electron microscopy, SEM）以及X射线衍射（X-ray diffraction, XRD）对所制备的3DG-SMC-SeS₂纳米复合材料的形态和结构进行表征。结果显示,SeS₂均匀地分布在SMC基体的介孔通道中,3DG良好地包裹SMC-SeS₂复合材料。受益于SeS₂不可或缺的优势和独特设计的主体构架,3DG-SMC-SeS₂正极表现出极好的循环性能和优异的高倍率性能。这种新型SeS₂基正极材料为克服目前锂硫电池的主要瓶颈提供了一种可行的策略。     

喷涂法制备混合阳离子钙钛矿太阳电池

采用热基底喷涂法分别制备了FA_0.85MA_0.15PbI₃和(FAPbI₃)_0.85(MAPbBr₃)_0.15两种混合阳离子钙钛矿薄膜,对两种薄膜进行了扫描电镜（SEM）、X-射线衍射（XRD）、紫外-可见光吸收光谱（UV-Vis）测试表征。结果表明,该方法制备的混合阳离子钙钛矿薄膜平整致密,FA_0.85MA_0.15PbI₃结晶性更好,并且吸收带边和吸收强度更大。将两种薄膜组装成平板太阳能电池,对电池的光电性能和稳定性进行了分析。结果表明,FA_0.85MA_0.15PbI₃ PSCs光电转换效率为13.21%,(FAPbI₃)_0.85(MAPbBr₃)_0.15 PSCs光电转换效率为12.08%,并且(FAPbI₃)_0.85(MAPbBr₃)_0.15 PSCs在放置80 d后,性能基本无变化,表明喷涂法制备(FAPbI₃)_0.85(MAPbBr₃)_0.15 PSCs具有较好的稳定性。     

多元化合物太阳电池

多元化合物太阳电池指不是用单一元素半导体材料制成的太阳电池。现在各国研究的品种繁多,大多数尚未工业化生产,主要有以下几种：a）硫化镉太阳能电池b）砷化镓太阳能电池c）铜铟硒太阳能电池（新型多元带隙梯度cu（In,Ga）Se2薄膜太阳能电池）Cu（In,Ga）Se2是一种性能优良太阳光吸收材料.     

CIGSe吸收层与Mo背电极接触界面层研究

预制膜+硒化两步法可以实现大面积、均匀制备CIGSe太阳电池吸收层。在背电极Mo和吸收层CIGSe接触界面上往往会形成由比较疏松包含一些孔洞的细小颗粒组成的界面层。该文通过对不同结构的预制膜进行硒化,分析了这一界面层的产生原因,认为Ga元素在背电极处的富集导致形成了细小的晶粒;在硒化过程开始阶段由于界面处Se含量较少形成了具有挥发性的In_2Se,进而导致了界面层中孔洞的形成。     

石墨烯包封Na3V2(PO4)3用作钠离子电池负极材料的电化学性能探究

具有三维网络结构的NASICON型Na₃V₂(PO₄)₃材料,由于其稳定的电压平台,较高的理论容量(117 mA·h/g),被视为一种具有良好应用前景的钠离子电池负极材料。采用溶剂热和进一步热处理的方式,获得石墨烯包封Na₃V₂(PO₄)₃的复合材料[Na₃V₂(PO₄)₃/G],有效提高了Na₃V₂(PO₄)₃的电子导电性。在0.01～3.00 V电压区间,0.2 C倍率进行测试时,Na₃V₂(PO₄)₃/G复合材料在230圈循环后,其放电比容量保持在100.9 mA·h/g,容量保持率高达68.4%,即使在5 C倍率,其放电比容量仍可达65.2 mA...     

一步法制备高效TiO2/PbS异质结量子点太阳电池

采用一步涂层法制备TiO₂/PbS异质结且带有不同浓度PbS量子点光吸收层的太阳电池器件。测试结果表明,用浓度为200 mg/mL的PbS量子点制备的太阳电池在AM1.5模拟光照下获得的能量转换效率（PCE）为9.08%,其开路电压（V_OC）为0.570 V、短路电流（J_SC）为29.6 mA/cm²、填充因子（FF）为0.539。研究证实了一步法的可行性与可靠性。与传统的层层旋涂法相比,一步涂层法具有操作过程简单、材料消耗少、制备薄膜质量好等优点,可用于大批量制备高效率量子点太阳电池。     

金属预置层后硒化法制备的CuInSe2薄膜结构特性研究

CulnSe2(简称CIS)薄膜是太阳电池吸收层的重要材料。利用连续溅射金属层后硒化法制备CulnSe2薄膜。薄膜的XRD图样显示：CulnSe2薄膜的形成与制备条件密切相关；在较大Cu、In原子比的范围内，在一定的硒化条件下，都可以形成以CulnSe2为基体的薄膜。SEM图样显示，不同Cu／In比值的表面形貌有较大的不同。Cu／In接近1时，薄膜的表面形貌均质且颗粒致密。Raman谱图显示，Cu、In配比不当会使薄膜中出现少量的杂相组织，在632．8nm激发波波长下。还有210cmll和229cmll两处的特征峰。通过光吸收测量得到CulnSe2的带隙是1．05eV，通过电导率测量得到其激活能为0．486eV。     

Novel device structure for Cu(In,Ga)Se2 thin film solar cells using transparent conducting oxide back and front contacts

Cu(In_1−xGa_x)Se₂ (CIGS)-based thin film solar cells fabricated using transparent conducting oxide (TCO) front and back contacts were investigated. The cell performance of substrate-type CIGS devices using TCO back contacts was almost the same as that of conventional CIGS solar cells with metallic Mo back contacts when the CIGS deposition temperatures were below 500 °C for SnO₂:F and 520 °C for ITO. CIGS thin film solar cells fabricated with ITO back contacts had an efficiency of 15.2% without anti-reflection coatings. However, the cell performance deteriorated at deposition temperatures above 520 °C. This is attributed to the increased resistivity of the TCO’s due to the removal of fluorine from SnO₂ or undesirable formation of a Ga₂O₃ thin layer at the CIGS/ITO interface. The formation of Ga₂O₃ was eliminated by inserting an intermediate layer such as Mo between ITO and CIGS. Furthermore, bifacial CIGS thin film solar cells were demonstrated as being one of the applications of semi-transparent CIGS devices. The cell performance of bifacial devices was improved by controlling the thickness of the CIGS absorber layer. Superstrate-type CIGS thin film solar cells with an efficiency of 12.8% were fabricated using a ZnO:Al front contact. Key techniques include the use of a graded band gap Cu(In,Ga)₃Se₅ phase absorber layer and a ZnO buffer layer along with the inclusion of Na₂S during CIGS deposition.     

基于不同类型全无机钙钛矿材料的太阳能电池研究

随着新型光伏电池的发展,卤族钙钛矿太阳能电池备受关注,其中全无机钙钛矿材料因其良好的热稳定性、高吸光系数、带隙可调、制备工艺简单等优点,在光电和光伏器件领域具有良好的应用前景,基于全无机钙钛矿太阳能电池的最高效率达到了20.4％.本文总结了基于ABX3、A2BX6、A2B1+B3+X6以及类钙钛矿材料等全无机钙钛矿太阳...     

Cu(In,Ga)Se2 thin film solar cells with buffer layer alternative to CdS

Progress in fabricating Cu(In,Ga)Se₂ (CIGS) solar cells with ZnS(O,OH) buffer layers prepared by chemical bath deposition (CBD) is discussed in this paper. Such buffer layers could potentially replace CdS in the CIGS solar cell. Total-area conversion efficiency of up to 18.6% has been reported previously using ZnS(O,OH) prepared by CBD. The reported 100 nm CBD ZnS(O,OH) layer was prepared by at least three consecutive depositions, which would make it a relatively expensive replacement for CdS. The recent development of a ZnS(O,OH) layer that enabled to obtain high-efficiency devices using a single-layer CBD is reported in this paper. A 14.4%-efficient device is obtained by using one-layer CBD ZnS(O,OH) on commercial-grade Shell Solar Cu(In,Ga)(S,Se)₂ (CIGSS) absorber and an up to 17.4% device is obtained by using two-layer CBD ZnS(O,OH) on an NREL CIGS absorber.     

A new approach to high-efficiency solar cells by band gap grading in Cu(In,Ga)Se2 chalcopyrite semiconductors

High efficiencies in Cu(In,Ga)(S,Se)₂ solar cells result from alloying CuInSe₂ base material with the corresponding Ga- or S-containing compound. Compositional grading is one important issue in these devices. To obtain high efficiencies a reconstructed Cu-depleted absorber surface is essential. We consider this Cu/In grading non-intentional, process related and present a model which explains its importance. Another approach to improve performance is controlled intentional band gap grading via Ga/In and S/Se grading during the deposition. We show that appropriate grading can improve current and voltage of the device simultaneously. The key objective is to design a larger band gap for recombination and a lower band gap for absorption to energetically separate the mechanisms of carrier recombination and current generation.     

Quantum efficiency and admittance spectroscopy on Cu(In,Ga)Se2 solar cells

We investigate the electronic transport properties of Cu(In,Ga)Se₂ solar cells by means of quantum efficiency and temperature dependent admittance spectroscopy. A simple evaluation scheme of quantum efficiency data is introduced which accounts for recombinatoric losses in the Us buffer layer and in the Cu(In,Ga)Se₂ absorber. By admittance spectroscopy, we find that the controlled incorporation of Na into the absorber material leads to a shallow acceptor state at about 75 meV above the valence band.     

上转换材料TiO2∶Er3+/Yb3+/Li+的制备及其在玻璃盖板中的应用

采用溶胶凝胶法和旋转镀膜法制备Er³⁺/Yb³⁺/Li⁺掺杂TiO₂胶体和薄膜,确定上转换材料最优制备方案为n(乙酰丙酮)∶n(C₁₆H₃₆O₄Ti∶H₂O)∶n(异丙醇)∶n(Er(NO₃)₃·5H₂O)∶n(Yb(NO₃)₃·5H₂O)∶n(LiNO₃)=1∶3∶9∶70∶0.12∶0.60∶0.15(物质的量之比),水的滴加速率为10 s/滴,溶液pH值为2～3,溶胶呈透明均匀淡黄色。吸收光谱在近红外区峰值明显。可见光透光率最高可达94.42%,较普通玻璃提高1%～2%。光伏组件通过光电转换效率测量系统进行检测,玻璃盖板镀膜后光伏组件的光电转换效率从16.5%升至17.2%,增加约0.7%。研究结果表明,该薄膜可提高玻璃盖板透光率,扩大光伏组件光谱吸收范围...     

Second generation CIS solar modules

Multinary Cu(In,Ga)(Se,S)₂ absorbers (abrev. CIGSSe) are promising candidates for reducing the cost of photovoltaics well below the cost of crystalline silicon. Shell Solar has pioneered production of this new thin film technology and is now with the first generation at a volume of well over 1 MW/year. In a separate pilot line for second generation products we have further improved the performance of CIGSSE based solar modules. We developed a novel CIGSSE formation technique called stacked elemental layer rapid thermal processing (SEL-RTP). This process has recently been scaled up from initial laboratory sized mini-modules (10 × 10 cm²) to full sized power modules of 60 × 90 cm². The present paper concentrates on in situ and ex situ characterization techniques that were developed to control and further improve large area CIGSSE processing. The crystalline thin film formation process has been analyzed with in situ thin film calorimetry and in situ X-ray diffraction (XRD). That work has added fundamental insights and accelerates the optimization process. The depth distribution of gallium and sulfur has been determined by secondary ion mass spectroscopy (SIMS) for different selenization and sulfurization processes. Appropriate profiles of these elements allow for a deliberate bandgap profiling within the Cu(In,Ga)(S,Se)₂ absorber. In addition further quality control tools like X-ray fluorescence analysis and Raman spectroscopy for stoichiometry monitoring, photoluminescence lifetime mapping and thermographic imaging have been developed in order to improve large area uniformity and reproducibility.

Some first full sized modules from the new pilot line look very promising: Aperture area efficiencies of up to 13.1% for monolithic thin film circuits on 0.54 m² and a module power of 65 W represent an international champion value for large are thin film solar modules.     

Band-gap engineering in CuIn(Se,S)2 absorbers for solar cells

Thin films based on CuInSe₂ have become very successful as absorber layers for solar cells. It is only in the recent past that gallium (Ga) and sulfur (S) were incorporated into CuInSe₂ in order to increase the energy band gap of the film to an optimum value with the ultimate aim of producing more efficient devices. This paper focuses on the incorporation of S into partly selenized CuInSe₂ films in order to produce CuIn(Se,S)₂ films with varying S/Se+S ratios, resulting in different band-gap energies. This was achieved by varying the conditions when selenizing Cu/In alloys in H₂Se/Ar, and then exposing these various partly selenized films to H₂S/Ar under identical conditions.     

High efficiency solar energy water splitting to generate hydrogen fuel: Probing RuS2 enhancement of multiple band electrolysis

The conditions under which an oxygen photocatalyst can improve multiple band gap (semiconductor) solar energy water splitting are probed. Recently, we provided evidence that previous models significantly underestimated the magnitude of H₂ fuel which may be generated by solar energy, and demonstrated a bipolar band gap solar system electrolyzing water at V_H2O

H₂O→H₂+1/2O₂; V_H2O>E°_H2O=E°_O2−E°_H2;E°_H2O(25°C)=1.229 V

at an unprecedented 18.3% solar energy conversion efficiency. Three conditions are shown in which oxygen photocatalyst addition can further improve this process; (i) a reduction in V_H2O; (ii) at V_H2O, capability to sustain electrolysis currentsgenerated photocurrents, and (iii) catalyst activation at hν_photo-O2>hν_{photo-bipolar}. We show that RuS₂ with 1% Fe is capable of meeting these conditions.