高效无空穴传输层碳基钙钛矿太阳能电池的制备与性能研究

碳基钙钛矿太阳能电池因稳定性高、成本低廉而备受关注,但由于钙钛矿与碳电极之间能级匹配度不高,界面阻力大而导致效率不及金属基钙钛矿太阳能电池.本文制备了碳基无空穴传输层FTO/c-TiO₂/m-TiO₂/CH₃NH₃PbI₃/Carbon电池结构.通过对介孔二氧化钛层、钙钛矿层厚度进行优化,并对钙钛矿的薄膜形貌及钙钛矿激发电子寿命、可见光吸收度、载流子的提取与分离等进行深度分析,讨论了电池效率提升的内在机理.当介孔氧化钛层和钙钛矿层达到最优厚度时,钙钛矿太阳能电池获得了开路电压（V_oc）为0.93 V、电流密度（J_sc）为21.75 mA/cm²、填充因子为55%、光电转化效率达到11.11%.同时对电池进行了稳定性研究,在室温湿度为40%–50%的条件下放置15 d电池性能依旧稳定保持原来的95%,优于金属基钙钛矿太阳能电池,从而为碳电极钙钛矿太阳能电池的商业化发展提供了可能.     

高压下BaF2光学性质的模拟计算

探寻新的冲击窗口材料是高压科学领域中的一个重要课题.为此,在100 GPa范围内,通过第一性原理方法计算了BaF₂晶体的吸收谱以及在532 nm处的折射率.结果表明:1)压力和结构相变因素不会引起BaF₂晶体在可见光区域出现光吸收;氟和钡空位点缺陷的存在将使得BaF₂吸收谱的吸收边红移,但这些红移行为不会导致该材料在可见光区域内出现光吸收的现象,由此可以初步推测,BaF₂晶体有成为冲击窗口材料的可能. 2) BaF₂的折射率在其三个结构相区都随压力的增大而增大,并且BaF₂的高压相变也使得其折射率升高;钡空位点缺陷的存在将导致其折射率减小,而氟空位点缺陷却引起其折射率增加.     

过渡金属(Ni)掺杂ZnV2O4的第一性原理计算

采用基于密度泛函理论下的MS软件模拟了过渡金属Ni掺杂ZnV₂O₄前后的能带结构、态密度以及光学性质.结果表明：ZnV₂O₄具有间接的光学跃迁且能带间隙为0.355 eV,Ni掺杂后能带间隙增加为0.785 eV,且带隙类型不变,引入的Ni-3d轨道电子对ZnV₂O₄的价带和导带组成提供了较大贡献.光学性质结果表明ZnV₂O₄为一种低介电材料,在可见光区的吸收系数和折射率较低,主要表现为紫外吸收.掺杂Ni后,在可见光区的吸收特性和光电导率均增大,有效改善了ZnV₂O₄在可见光区的光电性能.     

甲脒碘化铅单晶基钙钛矿太阳能电池的研究

近年来,CH(NH₂)₂PbI₃(FAPbI₃)由于其带隙接近理想值而受到了广泛关注,成为钙钛矿太阳能电池中最具吸引力的光电功能材料.然而由碘甲脒(FAI)和碘化铅(PbI₂)作为前驱体制备的传统钙钛矿层化学计量比不精准,缺陷密度大,稳定性差且结晶度较低,导致钙钛矿太阳能电池性能很难进一步提高.本文采用FAPbI₃单晶制备的钙钛矿薄膜具有高结晶度,高稳定性,精确的化学计量比和低缺陷密度.单晶钙钛矿薄膜的晶粒尺寸大,晶界少,导致晶界处缺陷较少,提高了钙钛矿太阳能电池的短路电流密度(J_SC)和开路电压(V_OC),使其光电转换效率有了大幅度的提高.本文为制备高稳定性、高结晶度和低缺陷密度的钙钛矿太阳能电池提供了一种有效策略.     

p型透明导电材料BaSnO3的第一性原理研究

基于密度泛函理论,从头计算了N以及N和Sb共掺BaSnO₃的电子结构和光学性质.结果表明N单掺BaSnO₃与N和Sb共掺BaSnO₃均为p型透明导电材料,在可见光区透过率均在80%以上,且N和Sb共掺具有更高的电导率.计算结果为实验上制备p型钙钛矿结构透明导电材料提供了强有力的理论指导. 关键词： p型透明导电材料 电子结构 光学性质     

低温制备SnO2电子传输层用于钙钛矿太阳能电池

SnO₂具有光稳定性优异、可低温溶液制备等优点被视为电子传输层的优异材料之一,广泛应用于高效稳定的平面异质结钙钛矿太阳能电池.本文在低温(150℃)下采用旋涂工艺制备SnO₂电子传输层,探究了SnO₂前驱体溶液不同浓度(SnO₂质量分数为2.5%—10.0%)下制备的SnO₂电子传输层对钙钛矿太阳能电池性能的影响.通过对SnO₂薄膜进行扫描电子显微镜(SEM)、紫外-可见光(UV-Vis)吸收光谱和透射光谱分析,发现基底的覆盖率、透光率和SnO₂薄膜的带隙随SnO₂前驱液浓度的增加而增大;通过对SnO₂/钙钛矿(MAPbI₃)薄膜进行SEM、UV-Vis、X-射线衍射(XRD)、稳态光致发光(PL)光谱分析,发现SnO₂胶体分散液浓度为7.5%制备的SnO₂层上沉积的MAPbI₃的粒径最大,结晶度最好,具...     

醋酸纤维素提高CsPbIBr2无机钙钛矿薄膜质量及其太阳能电池光电性能

由于具有适合的带隙和较高的稳定性,CsPbIBr₂无机钙钛矿被认为是一种较有前景的太阳能电池光吸收材料.但是目前报道的CsPbIBr₂钙钛矿太阳能电池效率还偏低,主要原因是制备的CsPbIBr₂钙钛矿膜质量差、缺陷多.本文通过将醋酸纤维素(CA)加入CsPbIBr₂钙钛矿前驱体溶液中改善CsPbIBr₂钙钛矿结晶过程,从而制备高质量的CsPbIBr₂钙钛矿膜.实验结果表明,CA中的C=O基团与前驱体溶液中的Pb²⁺间存在明显的相互作用,这种相互作用结合CA加入引起的前驱体溶液粘度增加,使CsPbIBr₂钙钛矿的结晶速率明显降低,从而制备了致密、结晶度高、晶粒尺寸大、晶界和缺陷少的高质量CsPbIBr₂钙钛矿膜.同时,CA的保护作用显著提高了CsPbIBr₂钙钛矿膜的稳定性.用碳材料层作为空穴传输层和背电极,制备结构为FTO/TiO₂/CsPbIBr...     

采用PEABr添加剂获得高效且稳定的碳基CsPbBr3太阳能电池

全无机CsPbBr₃钙钛矿材料因其本征稳定性好、成本低廉从而在光伏领域展现出巨大的应用潜力,但目前CsPbBr₃太阳能电池的光电转换效率仍远低于其他体系的钙钛矿太阳能电池.本文以无空穴传输层结构的碳基CsPbBr₃全无机钙钛矿电池作为研究对象,以多步旋涂法为基础,通过在PbBr₂(DMF)溶液中添加2-苯乙胺溴盐(PEABr)来调控CsPbBr₃薄膜的结晶质量,降低薄膜缺陷态密度,钝化晶粒间界,并对其中的关键工艺参数包括CsBr的用量(旋涂次数)、旋涂PbBr₂薄膜时的衬底预热温度以及退火温度进行了优化.最终在大气环境下获得了兼具稳定和高效的无空穴传输层结构的碳基CsPbBr₃太阳能电池,器件的光电转换效率达到8.25%,并在无封装条件下保存1500 h仍可保持90%以上的效率,对于进一步拓展CsPbBr₃钙钛矿电池的优化设计思路具有重要意义.     

利用PNA添加剂来调控钙钛矿薄膜结晶和覆盖率实现高效太阳能电池

钙钛矿薄膜形貌的控制是一个提高太阳能电池能量转换效率的关键问题,而引入添加剂是解决这一问题的一种有效而简便的方法。利用聚丙烯腈（PNA）作为CH₃NH₃PbI₃前驱体溶液溶剂添加剂,通过其浓度可以调控钙钛矿薄膜结晶和表面的覆盖率。本文通过SEM、XRD以及UV-Vis研究了PNA掺杂CH₃NH₃PbI₃钙钛矿薄膜后的表面形貌、结晶度和光学性能的变化。结果表明,通过添加少量的PNA可以优化钙钛矿薄膜的性能,其强烈影响薄膜的结晶过程,有助于形成均匀连续的薄膜,减少针孔,从而增强了钙钛矿层的覆盖率和光吸收。当PNA 的含量为1%（质量分数）时,钙钛矿太阳能电池的各项性能最佳,能量转换效率达到了8.38%。与未加PNA 的电池效率（1.31%） 相比,提高了540%。这些结果表明,PNA可以有效调控钙钛矿薄膜的晶体生长和薄膜形貌,在钙钛矿太阳能电池的大规模生产过程中是一种可以改善钙钛矿薄膜质量的有效添加剂。     

Cs掺杂FAPbBr3薄膜变温光学特性及光伏器件设计

甲脒(FA)基钙钛矿比甲胺(MA)基钙钛矿具有更高的内在稳定性，而无机Cs离子掺杂可以进一步提高钙钛矿的湿度、热和结构稳定性。通过一步反溶剂法制备了Cs掺杂的FA_1-x Cs_xPb Br₃ (x=0,0.05,0.10,0.15)钙钛矿薄膜，采用椭圆偏振光谱研究了材料的复介电函数并以此进行外量子效率(EQE)模拟。EQE模拟结果显示掺杂比例为0.05时，钙钛矿薄膜具有最高的功率转换效率(PCE)，可达23.47%。进一步对FA_0.95Cs_0.05Pb Br₃进行变温椭偏分析，发现：随着温度升高，材料带隙增大，在393 K左右，从变温复介电函数的二阶导谱中可观察到相变现象，钙钛矿材料由正交相转变为四方相。对基于FA_0.95Cs_0.05Pb Br₃的太阳能电池进行变温EQE模拟，结果表明：温度对器件的最高PCE影响不大，其效率可以稳定在23.47%左右，但是高温会导致器件近红外区的外量子效率降低...     

Ferroelectricity of perovskites under pressure

Ab initio simulations and experimental techniques are combined to reveal that, unlike what was commonly accepted for more than 30 years, perovskites and related materials enhance their ferroelectricity as hydrostatic pressure increases above a critical value. This unexpected high-pressure ferroelectricity is different in nature from conventional ferroelectricity because it is driven by an original electronic effect rather by long-range interactions.     

First-principles study of defect control in thin-film solar cell materials

A solar cell is a photovoltaic device that converts solar radiation energy to electrical energy, which plays a leading role in alleviating global energy shortages and decreasing air pollution levels typical of conventional fossil fuels. To render solar cells more efficient, high visible-light absorption rates and excellent carrier transport properties are required to generate high carrier levels and high output voltage. Hence, the core material, i.e., the absorption layer, should have an appropriate direct band gap and be effectively doped by both p-and n-types with minimal carrier traps and recombination centers. Consequently, defect properties of absorbers are critical in determining solar cell efficiency. In this work, we review recent first-principles studies of defect properties and engineering in four representative thin-film solar cells, namely CdTe, Cu(In,Ga)Se_2, Cu_2ZnSnS_4, and halide perovskites. The focal points include basic electronic and defect properties, existing problems, and possible solutions in engineering defect properties of those materials to optimize solar cell efficiency.     

FA1-xCsxPbI3-yBry钙钛矿材料优化及太阳电池性能计算

甲脒铅碘钙钛矿(FAPbI3)因其优异的光电性能而成为新兴太阳电池最具潜力的候选材料,但是稳定性较差成为制约其发展的主要瓶颈.通过离子掺杂可以有效地改善FAPbI3的稳定性,如通过共掺杂Cs^+和Br^-形成FA1-xCsxbI3-yBry钙钛矿材料,其耐热及耐水稳定性得到显著改善.本文利用第一性原理计算了FA1-xCsxPbI3-yBry(x=0.125,y=0-0.6)体系的几何结构、电子结构和光学性质.通过分析发现Cs^+和Br^-的掺入使得体系能量降低,FA0.875Cs0.125PbI2.96 Br0.04最稳定.利用等效光学导纳法模拟计算了平面结构钙钛矿太阳电池的吸收率、载流子收集效率、外量子效率、短路电流密度、开路电压和伏安特性.对于FA1-xCsxPb I3-yBry钙钛矿太阳电池,当x=0.125,y=0.04,厚度为0.5—1.0μm时,电池的短路电流密度均为24.7mA·cm^-2,开路电压为1.06 V.结果表明Cs^+和Br^-的共掺杂在没有降低电池短路电流的同时提高了体系的稳定性,可为实验上制备高效稳定的钙钛矿太阳电池提供理论参考.     

Efficient design of perovskite solar cell using mixed halide and copper oxide

Solar cells based on perovskites have emerged as a transpiring technology in the field of photovoltaic. These cells exhibit high power conversion efficiency. The perovskite material is observed to have good absorption in the entire visible spectrum which can be well illustrated by the quantum efficiency curve. In this paper, theoretical analysis has been done through device simulation for designing solar cell based on mixed halide perovskite. Various parameters have efficacy on the solar cell efficiency such as defect density, layer thickness, doping concentration, band offsets, etc. The use of copper oxide as the hole transport material has been analyzed. The analysis divulges that due to its mobility of charge carriers, it can be used as an alternative to spiro-OMeTAD. With the help of simulations, reasonable materials have been employed for the optimal design of solar cell based on perovskite material. With the integration of copper oxide into the solar cell structure, the results obtained are competent enough. The simulations have shown that with the use of copper oxide as hole transport material with mixed halide perovskite as absorber, the power conversion efficiency has improved by 6%.The open circuit voltage has shown an increase of 0.09 V, short circuit current density has increased by 2.32 m A/cm~2, and improvement in fill factor is 8.75%.     

The influence of localized states on the optical absorption and carrier transport properties of acylamino hybrid perovskites with tunable electronic structures

Organic-inorganic hybrid perovskite solar cells have excellent optoelectronic properties, but their low thermal and chemical stabilities limit their commercial applications. In this paper, a new type of organic-inorganic hybrid perovskite is proposed. Malondiamide (MA,CH₂(CONH₂)₂) and propionamide (PA, CH₃CH₂CONH₂) were used as organic layers, with Pb-I octahedral inorganic layers to form quasi three-dimensional (3D) perovskites. The crystal structure, stability, electronic structure, and optical properties of MAPbI₄ and PAPbI₄ perovskites were investigated, and the results showed that there were localized states that corresponded to the number of acyl groups in the two perovskites. Energy band calculations showed that the localized states of the two perovskites rose above the bottom of the conduction band. This can be used to regulate the band gap of the two perovskites, which affects the electronic properties and optical absorption characteristics of the two perovskites. Compared with PAPbI₄, MAPbI₄ has a lower formation energy, lower band gap, lower effective mass of electrons and holes, wider energy range, and larger absorption coefficient, which indicates that MAPbI₄ is more suitable for use in solar cells. This study provides guidance for obtaining efficient and stable photovoltaic materials.     

静水压力对Al14Mn2P16磁光性质影响的密度泛函理论研究

采用第一性原理，研究不同静水压力（0~20 GPa）下Al₁₄Mn₂P₁₆的弹性与磁光性质.计算得到基态是铁磁态.弹性稳定性判据表明该体系是稳定的.研究发现磁矩随静水压力的增加而减小.静水压力低于5 GPa时，居里温度达到184 K，随着静水压力的增加略有下降；有趣的是，当静水压力高于5 GPa时，随着静水压力的增加，居里温度急剧下降，在18 GPa时消失.同时还发现随静水压力的增加可见光范围的吸收峰有明显的蓝移，当静水压力达到20 GPa时，可见光范围的吸收峰消失.     

Stability,electronic structure,and optical properties of lead-free perovskite monolayer Cs3B2X9(B=Sb,Bi;X=Cl,Br,I)and bilayer vertical heterostructure Cs3B2X9/Cs3B’2X9(B,B’=Sb,Bi;X=Cl,Br,I)

The lead-free perovskites Cs₃B₂X₉(B=Sb,Bi;X=Cl,Br,I)as the popular photoelectric materials have excellent optical properties with lower toxicity.In this study,we systematically investigate the stable monolayer Cs₃B₂X₉and bilayer vertical heterostructure Cs₃B₂X₉/Cs3B02X9(B,B0=Sb,Bi;X=Cl,Br,I)via first-principles simulations.By exploring the electrical structures and band edge positions,we find the band gap reduction and the band type transition in the heterostructure Cs₃B₂X₉/Cs3B02X9 due to the charge transfer between layers.Furthermore,the results of optical properties reveal light absorption from the visible light to UV region,especially monolayer Cs3Sb2I9 and heterostructure Cs3Sb2I9/Cs3Bi2I9,which have absorption peaks in the visible light region,leading to the possibility of photocatalytic water splitting.These results provide insights for more two-dimensional semiconductors applied in the optoelectronic and photocatalytic fields.     

Role of surface metal nanoparticles on the absorption in solar cells

The effect of absorption enhancement with metallic nanoparticles on solar cell surfaces is often confused with various optical processes. In this work, the effective absorption rates in the active materials of solar cells are explicitly calculated including all possible factors. The results show that, although the total absorption is highly enhanced in general, the effective absorption in the active region is not much enhanced and even strongly reduced in the blue-violet regime. As the solar spectrum is considered, the integrated absorbed power in the solar cell materials is shown to be similar for structures with or without metallic nanoparticles.     

First-principles investigations on the mechanical,thermal,electronic,and optical properties of the defect perovskites Cs_2SnX_6(X= Cl,Br, I)

The mechanical properties, thermal properties, electronic structures, and optical properties of the defect perovskites Cs_2SnX_6(X = Cl, Br, I) were investigated by first-principles calculation using PBE and HSE06 hybrid functional. The optic band gaps based on HSE06 are 3.83 eV for Cs_2SnCl_6, 2.36 eV for Cs_2SnBr_6, and 0.92 eV for Cs_2SnI_6, which agree with the experimental results. The Cs_2SnCl_6, Cs_2SnBr_6, and Cs_2SnI_6 are mechanically stable and they are all anisotropic and ductile in nature. Electronic structures calculations show that the conduction band consists mainly of hybridization between the halogen p orbitals and Sn 5s orbitals, whereas the valence band is composed of the halogen p orbitals. Optic properties indicate that these three compounds exhibit good optical absorption in the ultraviolet region, and the absorption spectra red shift with the increase in the number of halogen atoms. The defect perovskites are good candidates for probing the lead-free and high power conversion efficiency of solar cells.     

新型碳材料在钙钛矿太阳电池中的应用研究进展

新型碳材料如石墨烯及其氧化物、碳纳米管、富勒烯及石墨炔等因其优异的热学、力学、电学、光学性能成为了钙钛矿太阳电池研究的又一亮点. 本文总结了新型碳材料在钙钛矿太阳电池对电极、电子传输材料及空穴传输材料中的研究进展, 新型碳材料的引入有效地提高了钙钛矿电池的性能, 为下一步新型碳材料的应用开发以及钙钛矿电池器件的研究提供了新的思路.