Tetrabutylammonium Bromide Functionalized Ti3C2Tx MXene as Versatile Cathode Buffer Layer for Efficient and Stable Inverted Perovskite Solar Cells

2D Ti₃C₂T_x MXene, possessing facile preparation, high electrical conductivity, flexibility, and solution processability, shows good application potential for enhancing device performance of perovskite solar cells (PVSCs). In this study, tetrabutylammonium bromide functionalized Ti₃C₂T_x (TBAB-Ti₃C₂T_x) is developed as cathode buffer layer (CBL) to regulate the PCBM/Ag cathode interfacial property for the first time. By virtue of the charge transfer from TBAB to Ti₃C₂T_x demonstrated by electron paramagnetic resonance and density functional theory, the TBAB-Ti₃C₂T_x CBL with high electrical conductivity exhibits significantly reduced work function of 3.9 eV, which enables optimization of energy level alignment and enhancement of charge extraction. Moreover, the TBAB-Ti₃C₂T_x CBL can effectively inhibit the migration of iodine ions from perovskite layer to Ag cathode, which synergistically suppresses defect states and reduce charge recombination. Consequently, utilizing MAPbI₃ perovskite without post-treatment, the TBAB-Ti₃C₂T_x based device exhibits a dramatically improved power conversion efficiency of 21.65% with significantly improved operational stability, which is one of the best efficiencies reported for the devices based on MAPbI₃/PCBM with different CBLs. These results indicate that TBAB-Ti₃C₂T_x shall be a promising CBL for high-performance inverted PVSCs and inspire the further applications of quaternary ammonium functionalized MXenes in PVSCs.     

Mitigating Detrimental Effect of Self-Doping Near the Anode in Highly Efficient Organic Solar Cells

Poly(3,4-ethylenedioxythiophene):polystyrene sulfonate (PEDOT:PSS) has been one of the most established hole transport layers (HTL) in organic solar cells (OSCs) for several decades. However, the presence of PSS⁻ ions is known to deteriorate device performance via a number of mechanisms including diffusion to the HTL-active layer interface and unwanted local chemical reactions. In this study, it is shown that PSS⁻ ions can also result in local p-doping in the high efficiency donor:non-fullerene acceptor blends – resulting in photocurrent loss. To address these issues, a facile and effective approach is reported to improve the OSC performance through a two-component hole transport layer (HTL) consisting of a self-assembled monolayer of 2PACz ([2-(9H-Carbazol-9-yl)ethyl]phosphonic acid) and PEDOT:PSS. The power conversion efficiency (PCE) of 17.1% using devices with PEDOT:PSS HTL improved to 17.7% when the PEDOT:PSS/2PACz two-component HTL is used. The improved performance is attributed to the overlaid 2PACz layer preventing the formation of an intermixed p-doped PSS⁻ ion rich region (≈5–10 nm) at the bulk heterojunction-HTL contact interface, resulting in decreased recombination losses and improved stability. Moreover, the 2PACz monolayer is also found to reduce electrical shunts that ultimately yield improved performance in large area devices with PCE enhanced from 12.3% to 13.3% in 1 cm² cells.     

Spidermen Strategy for Stable 24% Efficiency Perovskite Solar Cells

The interface energetics-modification plays an important role in improving the power conversion efficiency (PCE) among the perovskite solar cells (PSCs). Considering the low carrier mobility caused by defects in PSCs, a double-layer modification engineering strategy is adopted to introduce the “spiderman” NOBF₄ (nitrosonium tetrafluoroborate) between tin dioxide (SnO₂ and perovskite layers. NO⁺, as the interfacial bonding layer, can passivate the oxygen vacancy in SnO₂, while BF₄⁻ can optimize the defects in the bulk of perovskite. This conclusion is confirmed by theoretical calculation and transmission electron microscopy (TEM). The synergistic effect of NO⁺ and BF₄⁻ distinctly heightens the carrier extraction efficiency, and the PCE of PSCs is 24.04% with a fill factor (FF) of 82.98% and long-term stability. This study underlines the effectiveness of multifunctional additives in improving interface contact and enhancing PCE of PSCs.     

Solid Solvation Assisted Electrical Doping Conserves High-Performance in 500 nm Active Layer Organic Solar Cells

Organic solar cells (OSCs) process fascinating solution-printing capability to achieve low-cost and large-scale manufacture. However, the rapid power conversion efficiency (PCE) decay with active layer thickness enlargement inhibits the implement of OSCs’ potential advantages. To overcome the bottlenecks of PCE decay in thick active layer OSCs, the electrical doping with componential selectivity in bulk heterojunction (BHJ) film is achieved by introducing a solid solvation additive. Benefiting from the higher exciton splitting efficiency together with the longer drift (L_dr) and diffusion (L_diff) lengths, an OSC with 100 nm BHJ film demonstrates a PCE increment from 16.44% to 18.24% with prolonged dark and illuminated storage stabilities. Applying the solid solvation assisted (SSA) doping method in the OSCs with 500 nm active layer, the PCE significantly increases by 31.9%, from the original value of 11.79% to 15.55%. It further improves to 15.84% in a ternary blend thick-film device, which is the record value to the best of our knowledge. Besides, the SSA doping narrows the PCE gap between the 0.04 and 1 cm² devices. All improvements demonstrate the great potential of SSA doping for OSC commercial manufacture, since it optimizes the photovoltaic performance under all practical conditions of long-term, thick-film, and large-area.     

Energy Transfer Induced by TADF Polymer Enables the Recycling of Excitons in Perovskite Solar Cells

Formamidinium lead triiodide (FAPbI₃) has been demonstrated as the most efficient perovskite system to date, due to its excellent thermal stability and an ideal bandgap approaching the Shockley-Queisser limit. Whereas, there are intrinsic quantum confinement effects in FAPbI₃, which lead to unwanted non-radiative recombination. Additionally, the black α-phase of FAPbI₃ is unstable under room temperature due to the significant residual tensile stress in the film. To simultaneously address the above issues, a thermally-activated delayed fluorescence polymer P1 is designed in the study to modify the FAPbI₃ film. Owing to the spectral overlap between the photoluminescence of P1 and absorption of the above-bandgap quantum wells of FAPbI₃, the Förster energy transfer occurs at the P1/FAPbI₃ interface, which further triggers the Dexter energy transfer within FAPbI₃. The exciton “recycling” can thus be realized, which reduces the non-radiative recombination losses in perovskite solar cells (PSCs). Moreover, P1 is found to introduce compressive stress into FAPbI₃, which relieves the tensile stress in perovskite. Consequently, the PSCs with P1 treatment achieve an outstanding power conversion efficiency (PCE) of 23.51%. Moreover, with the alleviation of stress in the perovskite film, flexible PSCs (f-PSCs) also deliver a high PCE of 21.40%.     

Mitigating Surface Deficiencies of Perovskite Single Crystals Enables Efficient Solar Cells with Enhanced Moisture and Reverse-Bias Stability

Metal halide perovskite single crystals are promising for diverse optoelectronic applications due to their outstanding properties. In comparison to the bulk, the crystal surface suffers from high defect density and is moisture sensitive; however, surface modification strategies of perovskite single crystals are relatively deficient. Herein, solar cells based on methylammonium lead triiodide (MAPbI₃) thin single crystals are selected as a prototype to improve single-crystal perovskite devices by surface modification. The surface trap passivation and protection against moisture of MAPbI₃ thin single crystals are achieved by one bifunctional molecule 3-mercaptopropyl(dimethoxy)methylsilane (MDMS). The sulfur atom of MDMS can coordinate with bare Pb²⁺ of MAPbI₃ single crystals to reduce surface defect density and nonradiative recombination. As a result, the modified devices show a remarkable efficiency of 22.2%, which is the highest value for single-crystal MAPbI₃ solar cells. Moreover, MDMS modification mitigates surface ion migration, leading to enhanced reverse-bias stability. Finally, the cross-link of silane molecules forms a protective layer on the crystal surface, which results in enhanced moisture stability of both materials and devices. This work provides an effective way for surface modification of perovskite single crystals, which is important for improving the performance of single-crystal perovskite solar cells, photodetectors, X-ray detectors, etc.     

Advanced Characterization and Optimization of NiOx:Cu-SAM Hole-Transporting Bi-Layer for 23.4% Efficient Monolithic Cu(In,Ga)Se2-Perovskite Tandem Solar Cells

The performance of five hole-transporting layers (HTLs) is investigated in both single-junction perovskite and Cu(In, Ga)Se₂ (CIGSe)-perovskite tandem solar cells: nickel oxide (NiO_x,), copper-doped nickel oxide (NiO_x:Cu), NiO_x+SAM, NiO_x:Cu+SAM, and SAM, where SAM is the [2-(3,-6Dimethoxy-9H-carbazol-9yl)ethyl]phosphonic acid (MeO-2PACz) self-assembled monolayer. The performance of the devices is correlated to the charge-carrier dynamics at the HTL/perovskite interface and the limiting factors of these HTLs are analyzed by performing time-resolved and absolute photoluminescence ((Tr)PL), transient surface photovoltage (tr-SPV), and X-ray/UV photoemission spectroscopy (XPS/UPS) measurements on indium tin oxide (ITO)/HTL/perovskite and CIGSe/HTL/perovskite stacks. A high quasi-Fermi level splitting to open-circuit (QFLS-V_oc) deficit is detected for the NiO_x-based devices, attributed to electron trapping and poor hole extraction at the NiO_x-perovskite interface and a low carrier effective lifetime in the bulk of the perovskite. Simultaneously, doping the NiO_x with 2% Cu and passivating its surface with MeO-2PACz suppresses the electron trapping, enhances the holes extraction, reduces the non-radiative interfacial recombination, and improves the band alignment. Due to this superior interfacial charge-carrier dynamics, NiO_x:Cu+SAM is found to be the most suitable HTL for the monolithic CIGSe-perovskite tandem devices, enabling a power-conversion efficiency (PCE) of 23.4%, V_oc of 1.72V, and a fill factor (FF) of 71%, while the remaining four HTLs suffer from prominent V_oc and FF losses.     

Passivating Defects of Perovskite Solar Cells with Functional Donor-Acceptor–Donor Type Hole Transporting Materials

In this study, a series of donor–acceptor–donor (D-A-D) type small molecules based on the fluorene and diphenylethenyl enamine units, which are distinguished by different acceptors, as holetransporting materials (HTMs) for perovskite solar cells is presented. The incorporation of the malononitrile acceptor units is found to be beneficial for not only carrier transportation but also defects passivation via Pb–N interactions. The highest power conversion efficiency of over 22% is achieved on cells based on V1359, which is higher than that of spiro-OMeTAD under identical conditions. This st shows that HTMs prepared via simplified synthetic routes are not only a low-cost alternative to spiro-OMeTAD but also outperform in efficiency and stability state-of-art materials obtained via expensive cross-coupling methods.     

基于改进样板机法的风光互补新能源电站容量配比优化

风光等新能源电站出力具有间歇性和波动性,合理的风光容量配比可以充分实现二者的互补。不准确的电站理论功率计算会影响风光真实特征的提取,进而导致较大的容量配比误差。本文在新能源电站理论功率计算所通常采用的样板机法基础上进行改进,首先对异常数据进行识别及重构,然后识别新能源电站中的异常样板机并更新样板机集合,进一步根据非样板机的实际运行情况选取动态信息窗,利用动态信息窗内样板机和非样板机的实测功率,对非样板机分组并动态识别每组非样板机的比例系数,从而计算新能源电站的理论功率。基于多年历史理论功率对新能源电站进行特征分析,模拟随机出力场景,并进行场景筛选,建立了基于源荷不匹配风险的风光配比优化方法。通过算例验证了改进样板机法的准确性,利用该方法得到西北某地区电网风、光伏电站多年的改进理论功率数据,并优化得到该地区的风光最优配比。     

计及置信容量的光热电站储热容量优化配置

为探索光热电站的容量价值,文中基于光热电站的容量置信度和度电成本,提出一种光热电站集热面积和储热容量优化方法。文中建立光热电站发电效率模型和经济性模型,基于序贯蒙特卡洛方法计算发电系统可靠性,使用粒子群算法计算光热电站置信容量,研究太阳倍数和储热时长分别对光热电站容量置信度和度电成本的影响;并以容量置信度和度电成本作为优化目标,使用加权理想点法建立目标优化函数、熵权法确定指标权重值,对太阳倍数和储热时长进行优化。以西北某地区光热规划为例,使用该地区实际太阳辐照资源数据建立模型,发现随着太阳倍数和储热时长的增加,容量置信度单调递增,而度电成本呈先降后升的趋势,可优化得到约束条件下最佳太阳倍数和储热时长。