First-principles hybrid functional study of the electronic structure and charge carrier mobility in perovskite CH_3NH_3SnI_3

We calculate the electronic properties and carrier mobility of perovskite CH_3NH_3SnI_3 as a solar cell absorber by using the hybrid functional method. The calculated result shows that the electron and hole mobilities have anisotropies with a large magnitude of 1.4 × 10~4cm~2·V~(-1)·s~(-1) along the y direction. In view of the huge difference between hole and electron mobilities, the perovskite CH3NH3 Sn I3can be considered as a p-type semiconductor. We also discover a relationship between the effective mass anisotropy and electronic occupation anisotropy. The above results can provide reliable guidance for its experimental applications in electronics and optoelectronics.     

有机阳离子对卤素钙钛矿太阳能电池性能的影响

采用第一性原理计算了CH_3NH_3PbI_3中有机部分CH_3NH_3~+和CH_3NH_3的静电特性.结果表明:CH_3NH_3~+具有强的亲电特性,CH_3NH_3的CH_3~-端具有弱亲电性,而NH_3~-端具有弱亲核性.发现在CH_3NH_3PbI_3中CH_3NH_3~+之间强静电排斥作用在相变中起着重要的作用,且在室温条件下CH_3NH_3~+在无机笼中具备活性和无序的特性,使得TiO_2/CH_3NH_3PbI_3异质结中n型TiO_2的电子通过界面扩散到CH_3NH_3PbI_3材料,并与CH_3NH_3~+结合形成CH_3NH_3,CH_3NH_3的静电特性导致在内建电场作用下更容易取向,取向的CH_3NH_3周围形成的静电场会变得更弱和更加均匀.这对无机框架上载流子的产生和传输更加有利,这样的异质结比传统的pn结具有更大优势.这是CH_3NH_3PbI_3太阳能电池高的光电转换效率的重要原因.     

CH3NH3I在制备CH3NH3PbI(3-x)Clx钙钛矿太阳能电池中的作用

利用具有钙钛矿结构的有机-无机杂化卤化物制备的太阳能电池, 由于具有溶液可加工性和高光电转换效率, 受到了广泛关注. 在目前报道的最高光电转换效率的器件中, 采用了CH₃NH₃PbI_(3-x)Cl_x碘氯混合钙钛矿作为吸光层, 据报道在这种材料中光电子的扩散长度可以超过1 μm. 本文综述了在CH₃NH₃PbI_(3-x)Cl_x方面现有的研究工作, 指出了薄膜制备条件的重要性, 并研究了CH₃NH₃I在PbCl₂/CH₃NH₃I热解法制备CH₃NH₃PbI_(3-x)Cl_x吸光层中的作用. 扫描电子显微镜研究表明CH₃NH₃I加入量为PbCl₂的2倍到2.75倍时, CH₃NH₃I加入量的增加可以提高CH₃NH₃PbI_(3-x)Cl_x吸光层的覆盖度和结晶度, CH₃NH₃I加入量进一步增加到3倍时, 形貌变化不大. X射线光电子能谱的数据证实了CH₃NH₃I加入量对覆盖度的影响, 并显示在CH₃NH₃I加入量大于PbCl₂的2.5倍以后, CH₃NH₃PbI_(3-x)Cl_x中氯的掺入量急剧下降. 光电测试表明器件性能随CH₃NH₃I加入量增加而增加, 在CH₃NH₃I/PbCl₂为3/1时达到最高, 加入量略小于3/1对性能影响不大.     

In-plane oriented CH_3NH_3PbI_3 nanowire suppression of the interface electron transfer to PCBM

One-dimensional nanowire is an important candidate for lead-halide perovskite-based photonic detectors and solar cells. Its surface population, diameter, and growth direction, etc., are critical for device performance. In this research,we carried out a detailed study on electron transfer process at the interface of nanowire CH_3 NH_3 PbI_3(N-MAPbI_3)/Phenyl C61 butyric acid methyl-ester synonym(PCBM), as well as the interface of compact CH_3 NH_3 PbI_3(C-MAPbI_3)/PCBM by transient absorption spectroscopy. By comparing the carrier recombination dynamics of N-MAPbI_3, N-MAPbI_3/PCBM,C-MAPbI_3, and C-MAPbI_3/PCBM from picosecond(ps) to hundred nanosecond(ns) time scale, it is demonstrated that electron transfer at N-MAPbI_3/PCBM interface is less efficient than that at C-MAPbI_3/PCBM interface. In addition, electron transfer efficiency at C-MAPbI_3/PCBM interface was found to be excitation density-dependent, and it reduces with photo-generation carrier concentration increasing in a range from 1.0 × 1018 cm~(-3)–4.0 × 1018 cm~(-3). Hot electron transfer,which leads to acceleration of electron transfer between the interfaces, was also visualized as carrier concentration increases from 1.0 × 10~(18) cm~(-3)–2.2 × 10~(18) cm~(-3).     

Electronegativity explanation on the efficiency-enhancing mechanism of the hybrid inorganic–organic perovskite ABX_3 from first-principles study

Organic–inorganic hybrid perovskites play an important role in improving the efficiency of solid-state dye-sensitized solar cells. In this paper, we systematically explore the efficiency-enhancing mechanism of ABX_3(A = CH_3NH_3; B = Sn,Pb; X = Cl, Br, I) and provide the best absorber among ABX_3 when the organic framework A is CH_3NH_3 by first-principles calculations. The results reveal that the valence band maximum(VBM) of the ABX_3 is mainly composed of anion X p states and that conduction band minimum(CBM) of the ABX_3 is primarily composed of cation B p states. The bandgap of the ABX_3 decreases and the absorptive capacities of different wavelengths of light expand when reducing the size of the organic framework A, changing the B atom from Pb to Sn, and changing the X atom from Cl to Br to I. Finally, based on our calculations, it is discovered that CH_3NH_3 Sn I_3has the best optical properties and its light-adsorption range is the widest among all the ABX_3 compounds when A is CH_3NH_3. All these results indicate that the electronegativity difference between X and B plays a fundamental role in changing the energy gap and optical properties among ABX_3 compounds when A remains the same and that CH_3NH_3 Sn I_3 is a promising perovskite absorber in the high efficiency solar batteries among all the CH_3NH_3BX_3 compounds.     

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.     

High efficiency ETM-free perovskite cell composed of CuSCN and increasing gradient CH3NH3PbI3

To enhance device performance and reduce fabrication cost,a series of electron transporting material(ETM)-free perovskite solar cells(PSCs)is developed by TCAD Atlas.The accuracy of the physical mode of PSCs is verified,due to the simulations of PEDOT:PSS-CH₃NH₃PbI₃-PCBM and CuSCN-CH₃NH₃PbI₃-PCBM p-i-n PSCs showing a good agreement with experimental results.Different hole transporting materials(HTMs)are selected and directly combined with n-CH₃NH₃PbI₃,and the CuSCN-CH₃NH₃PbI₃ is the best in these ETM-free PSCs.To further study the CuSCN-CH₃NH₃PbI₃ PSC,the influences of back electrode material,gradient band gap,thickness,doping concentration,and bulk defect density on the performance are investigated.Energy band and distribution of electric field are utilized to optimize the design.As a result,the efficiency of CuSCN-CH₃NH₃PbI₃ PSC is achieved to be 26.64%.This study provides the guideline for designing and improving the performances of ETM-free PSCs.     

十二烷二酸修饰TiO_2电子传输层改善钙钛矿太阳电池的电流特性

在经典的平面异质结钙钛矿太阳电池中,TiO_2致密层的电子传输性能一直是获得优异光伏性能的决定性因素之一.相较于spriro-OMe TAD等常见的空穴传输材料优异的空穴传输能力,作为电子传输材料的TiO_2的导电性较弱,无法形成良好的电荷匹配.为了解决这个问题,我们使用自组装的十二烷二酸(DDDA)单分子层来修饰TiO_2致密层的表面,TiO_2致密层的导电性能得到大幅提升,并且其能带结构得到优化,促进了电子传输,降低了电子积聚和载流子复合,使得电池的短路电流密度(JSC)从修饰前的20.34 mA·cm~(-2)提升至修饰后的23.28 mA·cm~(-2),进而使得电池在标准测量条件下的光电能量转换效率从14.17%提升至15.92%.同时还发现,通过DDDA修饰TiO_2致密层,所制备的器件的光稳定性显著提升,器件未封装暴露在AM 1.5光强100 mW·cm~(-2)的模拟太阳光下超过720 min,保持初始效率的71%以上且趋于稳定.     

Temperature-dependent photoluminescence on organic-inorganic metal halide perovskite CH_3NH_3PbI_(3-x)Cl_x prepared on ZnO/FTO substrates using a two-step method

Temperature-dependent photoluminescence characteristics of organic-inorganic halide perovskite CH_3NH_3Pb I_(3-x)Cl_x films prepared using a two-step method on ZnO/FTO substrates were investigated. Surface morphology and absorption characteristics of the films were also studied. Scanning electron microscopy revealed large crystals and substrate coverage. The orthorhombic-to-tetragonal phase transition temperature was~140 K. The films' exciton binding energy was 77.6 ± 10.9 meV and the energy of optical phonons was 38.8 ± 2.5 meV. These results suggest that perovskite CH_3NH_3Pb I_(3-x)Cl_x films have excellent optoelectronic characteristics which further suggests their potential usage in perovskitebased optoelectronic devices.     

高效钙钛矿-有机本体异质结杂化串联太阳能电池

制备了一种有机铅卤钙钛矿-有机本体异质结杂化串联太阳能电池。采用紫外可见吸收光谱、原子力显微镜对薄膜形貌进行了表征。结果表明:有机本体异质结层可以有效改善钙钛矿的表面形貌, 增强了可见光的吸收。优化后的串联结构电池的短路电流可达19.14mA/cm², 开路电压为0.76V, 光电转换效率达到了6.54%。钙钛矿电池和有机本体异质结电池串联结构可以同时提高短路电流及填充因子, 二者具有较好的相容性和协同作用。     

退火温度对电子束蒸发沉积Cu_2O薄膜性能的影响

近年来,钙钛矿太阳电池(PSCs)得到了迅猛发展,而无机空穴传输材料(IHTMs)的使用可进一步降低电池的成本,提高电池的稳定性.本文通过电子束蒸发制备了Cu_2O薄膜,研究了空气中退火温度及时间对薄膜组成、结构及光电性能的影响,并构筑了p-i-n反型平面异质结钙钛矿太阳电池.研究发现:由于热解作用,直接通过电子束蒸发制备的薄膜为Cu_2O和Cu的混合物;而在空气中经过退火后,由于氧化作用,随着退火温度的升高,薄膜的组分由混合物转变为纯的Cu_2O,再转变成纯的CuO.通过控制退火温度制备的Cu_2O薄膜的光学带隙约为2.5 eV,载流子迁移率约为30 cm~2·V~(-1)·s~(-1).应用于PSCs,薄膜的最佳厚度为40 nm,但电池性能低于PEDOT:PSS基的PSCs.这主要是由于钙钛矿前驱液在Cu_2O薄膜的润湿性较差,吸收层中有大量微孔洞存在,致使漏电流增强,电池的性能降低.然而,当采用Cu_2O/PEDOT:PSS双HTMs设计时,由于PEDOT:PSS对Cu_2O具有较强的腐蚀作用,使电池性能恶化.     

有机无机杂化固态太阳能电池的研究进展

近年来, 由于钙钛矿材料优良的光学吸收和电荷传导特性, 有机无机杂化固态太阳能电池取得了突破性的进展. 自2009年首次报道了光电转换效率为3.8%的钙钛矿太阳能电池以来, 该类电池的效率不断突破. 基于介孔薄膜的电池已取得了超过16.7%的认证光电转换效率, 基于平板异质结结构电池光电转换效率达到19.3%, 已接近传统硅基太阳能电池的光电转换效率. 本文将介绍有机无机杂化钙钛矿作为光电材料的光学物理结构特性, 以及在固态太阳能电池中的应用. 基于固态钙钛矿太阳能电池结构上的差异, 分别介绍其在多孔结构、平板异质结结构、柔性结构以及无空穴传导材料结构电池工作特性和各自优势, 以及影响电池特性的主要影响因素, 特别是钙钛矿成膜控制等. 并阐述对钙钛矿电池的理解和进一步提高固态钙钛矿电池光电转换效率需要关注的重点以及展望.     

用于GaAs太阳能电池的NaYF4中Tb3+-Er3+耦合对的光谱转换

观测到一种以Tb³⁺-Er³⁺进行光谱转换的量子剪裁现象。一个高能紫外光子(Tb³⁺的⁷F₆→⁵L₁)被量子剪裁成两个低能光子:一个是近红外光子(Er³⁺的⁴I_9/2→⁴I_15/2),另一个是蓝色光子(Tb³⁺的⁵D₄→⁷F₆),它们两个 都可以被GaAs太阳能电池有效地吸收。量子剪裁效率高达188%,接近理论极限的200%。从Tb³⁺(⁵L₁→ ⁵D₄) 到Er³⁺(⁴I_15/2→⁴I_9/2)的能量传递的能量失配是237 cm^-1,比NaYF₄中的声子能400 cm^-1小,能量传递是近共振的。Tb³⁺施主间的能量迁移可以近似地用扩散模型处理, 从Tb³⁺-Er³⁺对之间能量传递的初始过程发现,偶极-偶极相互作用占主导地位。     

胆甾液晶掺杂活性层对有机太阳能电池性能的影响

以poly(3-hexylthiophene)(P3HT)为电子给体,indene-C60bisadduct(ICBA)为电子受体,通过掺杂不同浓度胆甾液晶氯化胆甾醇制备了有机体异质结太阳能电池.结果表明,适当浓度掺杂使器件的开路电压提高到了0.78 V,但短路电流密度却有所降低,填充因子几乎不变,能量转换效率提高了10%.利用X射线、光致发光、原子力显微镜及紫外-可见吸收光谱进行表征,发现液晶掺杂对活性层的结晶度、分子内部排列情况、薄膜表面形貌和光吸收特性等都有明显影响.     

First-principles analysis of the structural,electronic, and elastic properties of cubic organic-inorganic perovskite HC(NH_2)_2PbI_3

The structural, electronic, and elastic properties of cubic HC(NH_2)_2PbI_3 perovskite are investigated by density functional theory using the Tkatchenko–Scheffler pairwise dispersion scheme. Our relaxed lattice parameters are in agreement with experimental data. The hydrogen bonding between NH_2 and I ions is found to have a crucial role in FAPbI_3 stability. The first calculated band structure shows that HC(NH_2)_2PbI_3 has a direct bandgap(1.02 eV) at R-point, lower than the bandgap(1.53 eV) of CH_3NH_3PbI_3. The calculated density of states reveals that the strong hybridization of s(Pb)–p(I) orbital in valence band maximum plays an important role in the structural stability. The photo-generated effective electron mass and hole mass at R-point along the R–Γ and R–M directions are estimated to be smaller: m_e~*= 0.06 m0 and m_h~*= 0.08 m0 respectively, which are consistent with the values experimentally observed from long range photocarrier transport. The elastic properties are also investigated for the first time, which shows that HC(NH_2)_2PbI_3 is mechanically stable and ductile and has weaker strength of the average chemical bond. This work sheds light on the understanding of applications of HC(NH_2)_2PbI_3 as the perovskite in a planar-heterojunction solar cell light absorber fabricated on flexible polymer substrates.     

Enhancing the photo-luminescence stability of CH3NH3PbI3 film with ionic liquids

The methylammonium lead triiodide (CH₃NH₃PbI₃)-based perovskite shows a great alluring prospect in areas of solar cells, lasers, photodetectors, and light emitting diodes owing to their excellent optical and electrical advantages. However, it is very sensitive to the surrounding oxygen and moisture, which limits its development seriously. It is urgent to spare no effort to enhance its optical and electrical stability for further application. In this paper, we synthesize the MAPbI₃ perovskite film on the glass substrate with/without the ionic liquid (IL) of 1-Butyl-3-methylimidazolium tetrafluoroborate (BMIMBF₄) by a simple two-step sequential solution method. The additive of BMIMBF₄ can improve the quality of crystal structure. Moreover, the photo-luminescence (PL) intensity of MAPbI₃ film with BMIMBF₄ is much stronger than the pure MAPbI₃ film after a week in the air, which is almost ten-fold of the pure one. Meanwhile, under the illumination of 405-nm continuous wave (CW) laser, the fluorescent duration of the MAPbI₃ film with BMIMBF₄ is approximately 2.75 min, while the pure MAPbI₃ film is only about 6 s. In fact, ionic liquid of BMIMBF₄ in the perovskite film plays a role of passivation, which prevents the dissolution of MAPbI₃ into CH₃NH₃ and PbI₂ and thus enhances the stability of environment. In addition, the ionic liquid of BMIMBF₄ possesses high ionic conductivity, which accelerates the electron transport, so it is beneficial for the perovskite film in the areas of solar cells, photodetectors, and lasers. This interesting experiment provides a promising way to develop the perovskite's further application.     

A simulation study on p-doping level of polymer host material in P3HT:PCBM bulk heterojunction solar cells

In this study,we investigate the influence of doping on the charge transfer and device characteristics parameters in the bulk heterojunction solar cells based on poly(3-hexylthiophene)(P3HT) and a methanofuUerene derivative(PCBM).Organic semiconductors are also known to be not pure and they have defects and impurities,some of them are being charged and act as p-type or n-type dopants.Calculations of the solar cell characteristics parameters versus the p-doping level have been done at three different n-dopings(N_d) that consist of 5 × 10~(17) cm~(-3),10~(18) cm~(-3),and 5 × 10~(18) cm~(-3).We perform the analysis of the doping concentration through the drift-diffusion model,and calculate the current and voltage doping dependency.We find that at three different n-dopant levels,optimum p-type doping is about N_p = 6 × 10~(18) cm~(-3).Simulation results have shown that by increasing doping level,V_(oc) monotonically increases by doping.Cell efficiency reaches its maximum at somewhat higher doping as FF has its peak at N_p = 3 × 10~(18) cm~(-3).Moreover,this paper demonstrates that the optimum value for the p-doping is about N_p = 6 × 10~(18) cm~(-3) and optimum value for n-dopant is N_d = 10~(18) cm~(-3),respectively.The simulated results confirm that doping considerably affects the performance of organic solar cells.     

无铅和少铅的有机-无机杂化钙钛矿太阳电池研究进展

基于有机-无机杂化卤化铅材料的钙钛矿太阳电池的转换效率在短短几年内已迅速突破22%,为未来能源问题的解决带来了曙光,同时也引起了高度重视.但紧随其后的商品化、产业化发展需求极大地增加了对绿色、无毒的高效无铅钙钛矿太阳电池进行研究和开发的重要性和紧迫性.为进一步加快环境友好型钙钛矿太阳电池的研发进度,对目前无铅和少铅钙钛矿太阳电池的发展现状进行了综述.着重讨论了替代元素种类及其浓度、制备工艺等对薄膜和电池性能的影响,以期对电池的工作机理、替代元素的作用机理有更加深刻的认识,为新型环保、高效的钙钛矿太阳电池的制备提供指导.     

溶剂对钙钛矿薄膜形貌和结晶性的影响研究

溶剂对钙钛矿太阳能电池器件有着至关重要的影响. 基于目前常用的N, N-二甲基甲酰胺(DMF)和丁内酯(GBL)溶剂, 一步溶液旋涂技术和介孔电池结构, 制备的钙钛矿薄膜的形貌、结晶性, 以及最终的器件光电转化效率存在较大的差异, 利用DMF作为溶剂, 效率仅为2.8%, 而基于GBL的电池效率可以达到10.1%. 结合SEM, HRTEM, XRD和UV等表征手段, 分析了钙钛矿从DMF溶液和GBL溶液中结晶析出的不同机理, 明确了溶剂跟PbI₂的配位作用对钙钛矿的溶解、析出过程的制约作用, 揭示了造成器件效率差异的本质原因.     

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.