Side-Chain Functionalized Polymer Hole-Transporting Materials with Defect Passivation Effect for Highly Efficient Inverted Quasi-2D Perovskite Solar Cells

Compared with inverted 3D perovskite solar cell (PSCs), inverted quasi-2D PSCs have advantages in device stability, but the device efficiency is still lagging behind. Constructing polymer hole-transporting materials (HTMs) with passivation functions to improve the buried interface and crystallization properties of perovskite films is one of the effective strategies to improve the performance of inverted quasi-2D PSCs. Herein, two novel side-chain functionalized polymer HTMs containing methylthio-based passivation groups are designed, named PVCz-SMeTPA and PVCz-SMeDAD, for inverted quasi-2D PSCs. Benefited from the non-conjugated flexible backbone bearing functionalized side-chain groups, the polymer HTMs exhibit excellent film-forming properties, well-matched energy levels and improved charge mobility, which facilitates the charge extraction and transport between HTM and quasi-2D perovskite layer. More importantly, by introducing methylthio units, the polymer HTMs can enhance the contact and interactions with quasi-2D perovskite, and further passivating the buried interface defects and assisting the deposition of high-quality perovskite. Due to the suppressed interfacial non-radiative recombination, the inverted quasi-2D PSCs using PVCz-SMeTPA and PVCz-SMeDAD achieve impressive power conversion efficiency (PCE) of 21.41% and 20.63% with open-circuit voltage of 1.23 and 1.22 V, respectively. Furthermore, the PVCz-SMeTPA based inverted quasi-2D PSCs also exhibits negligible hysteresis and considerably improved thermal and long-term stability.     

Pyrite‐Based Bi‐Functional Layer for Long‐Term Stability and High‐Performance of Organo‐Lead Halide Perovskite Solar Cells

Organo‐lead halide perovskite solar cells (PSCs) have received great attention because of their optimized optical and electrical properties for solar cell applications. Recently, a dramatic increase in the photovoltaic performance of PSCs with organic hole transport materials (HTMs) has been reported. However, as of now, future commercialization can be hampered because the stability of PSCs with organic HTM has not been guaranteed for long periods under conventional working conditions, including moist conditions. Furthermore, conventional organic HTMs are normally expensive because material synthesis and purification are complicated. It is herein reported, for the first time, octadecylamine‐capped pyrite nanoparticles (ODA‐FeS₂ NPs) as a bi‐functional layer (charge extraction layer and moisture‐proof layer) for organo‐lead halide PSCs. FeS₂ is a promising candidate for the HTM of PSCs because of its high conductivity and suitable energy levels for hole extraction. A bi‐functional layer based on ODA‐FeS₂ NPs shows excellent hole transport ability and moisture‐proof performance. Through this approach, the best‐performing device with ODA‐FeS₂ NPs‐based bi‐functional layer shows a power conversion efficiency of 12.6% and maintains stable photovoltaic performance in 50% relative humidity for 1000 h. As a result, this study has the potential to break through the barriers for the commercialization of PSCs.     

Efficient and Spectrally Stable Blue Perovskite Light‐Emitting Diodes Based on Potassium Passivated Nanocrystals

Metal halide perovskites have aroused tremendous interest in the past several years for their promising applications in display and lighting. However, the development of blue perovskite light‐emitting diodes (PeLEDs) still lags far behind that of their green and red cousins due to the difficulty in obtaining high‐quality blue perovskite emissive layers. In this study, a simple approach is conceived to improve the emission and electrical properties of blue perovskites. By introducing an alkali metal ion to occupy some sites of peripheral suspended organic ligands, the nonradiative recombination is suppressed, and, consequently, blue CsPb(Br/Cl)₃ nanocrystals with a high photoluminescence quantum efficiency of 38.4% are obtained. The introduced K⁺ acts as a new type of metal ligand, which not only suppresses nonradiative pathways but also improves the charge carrier transport of the perovskite nanocrystals. With further engineering of the device structure to balance the charge injection rate, a spectrally stable and efficient blue PeLED with a maximum external quantum efficiency of 1.96% at the emission peak of 477 nm is fabricated.     

Improving Charge Transport via Intermediate‐Controlled Crystal Growth in 2D Perovskite Solar Cells

Reduced‐dimensional hybrid perovskite semiconductors have recently attracted significant attention due to their promising stability and optoelectronic properties. However, the issue of poor charge transport in 2D perovskites limits its application. Here, studies on intermediate‐controlled crystal growth are reported to improve charge carrier transport in 2D perovskite thin films. It is shown that the coordination strength of solvents with perovskite precursor affects the initial state of intermediate phase formation as well as the subsequent perovskite layer growth. Tuning the solvent composition with a mixture (5:5) of dimethyl formamide (DMF) and dimethyl sulfoxide (DMSO) leads to the growth of highly orientated 2D perovskite films with much‐improved optoelectronic properties (faster transport by ≈50x, longer carrier lifetime by ≈4x, and lower defect density by ≈30x) than the film prepared with pure DMF. Consequently, perovskite solar cells based on DMF/DMSO (5:5) show >80% efficiency improvement than the devices based on pure DMF.     

Recent progress of dopant-free organic hole-transporting materials in perovskite solar cells

Organic-inorganic hybrid perovskite solar cells have undergone especially intense research and transformation over the past seven years due to their enormous progress in conversion efficiencies. In this perspective, we review the latest developments of conventional perovskite solar cells with a main focus on dopant-free organic hole transporting materials (HTMs). Regarding the rapid progress of perovskite solar cells, stability of devices using dopant-free HTMs are also discussed to help readers understand the challenges and opportunities in high performance and stable perovskite solar cells.     

Hybrid Perovskite Quantum Dot/Non-Fullerene Molecule Solar Cells with Efficiency Over 15%

Organic-inorganic hybrid film using conjugated materials and quantum dots (QDs) are of great interest for solution-processed optoelectronic devices, including photovoltaics (PVs). However, it is still challenging to fabricate conductive hybrid films to maximize their PV performance. Herein, for the first time, superior PV performance of hybrid solar cells consisting of CsPbI₃ perovskite QDs and Y6 series non-fullerene molecules is demonstrated and further highlights their importance on hybrid device design. In specific, a hybrid active layer is developed using CsPbI₃ QDs and non-fullerene molecules, enabling a type-II energy alignment for efficient charge transfer and extraction. Additionally, the non-fullerene molecules can well passivate the QDs, reducing surface defects and energetic disorder. The champion CsPbI₃ QD/Y6-F hybrid device has a record-high efficiency of 15.05% for QD/organic hybrid PV devices, paving a new way to construct solution-processable hybrid film for efficient optoelectronic devices.     

Constructing High-Performance Solar Cells and Photodetectors with a Doping-Free Polythiophene Hole Transport Material

The emerging solution-based solar cells and photodetectors have gained worldwide research interest over the past decades. Hole transport materials (HTMs) have greatly advanced the progress of these solution-based electronics. Nevertheless, developing low-cost and efficient HTMs is far from satisfactory. In this contribution, poly(3-pentylthiophene) (P3PT) is introduced as a facile, low-cost, and versatile dopant-free polymer HTM for both quantum dot (QD) and perovskite electronic devices. Compared to the broadly used poly(3-hexylthiophene), P3PT presents the reduced molecular aggregation and preferential face-on orientation, which can markedly enhance the hole-carrier transport in optoelectronic devices. Accordingly, P3PT can deliver the substantial improvement of photovoltaic performance from ∼8.6% to ∼9.5% for QD/polythiophene solar cells and from ∼16% to ∼18.8% for perovskite/polythiophene solar cells, which are both among the topmost values in the corresponding fields. Furthermore, P3PT HTMs can also significantly enhance the photodetection performance of QD and perovskite photodetectors by a factor of ∼3, indicating its great application potential in a variety of emerging optoelectronics.     

Double‐Sided Surface Passivation of 3D Perovskite Film for High‐Efficiency Mixed‐Dimensional Perovskite Solar Cells

Defect‐mediated carrier recombination at the interfaces between perovskite and neighboring charge transport layers limits the efficiency of most state‐of‐the‐art perovskite solar cells. Passivation of interfacial defects is thus essential for attaining cell efficiencies close to the theoretical limit. In this work, a novel double‐sided passivation of 3D perovskite films is demonstrated with thin surface layers of bulky organic cation–based halide compound forming 2D layered perovskite. Highly efficient (22.77%) mixed‐dimensional perovskite devices with a remarkable open‐circuit voltage of 1.2 V are reported for a perovskite film having an optical bandgap of ≈1.6 eV. Using a combination of experimental and numerical analyses, it is shown that the double‐sided surface layers provide effective defect passivation at both the electron and hole transport layer interfaces, suppressing surface recombination on both sides of the active layer. Despite the semi‐insulating nature of the passivation layers, an increase in the fill factor of optimized cells is observed. The efficient carrier extraction is explained by incomplete surface coverage of the 2D perovskite layer, allowing charge transport through localized unpassivated regions, similar to tunnel‐oxide passivation layers used in silicon photovoltaics. Optimization of the defect passivation properties of these films has the potential to further increase cell efficiencies.     

Multifunctional Molecular Design of a New Fulleropyrrolidine Electron Transport Material Family Engenders High Performance of Perovskite Solar Cells

[6,6]-phenyl-C₆₁-butyric acid methyl ester remains indispensable as the electron transport material (ETM) for perovskite solar cells (PSCs), but its synthesis involves complicated multisteps with low productivity. In contrast, the potential of synthesizing simpler fulleropyrrolidine derivatives has long been overlooked, and little has been understood regarding their structure-dependent effects on photovoltaic (PV) performance. Herein, seven novel fulleropyrrolidine derivatives (F1–F7) are deliberately designed, synthesized, and comprehensively characterized in both solution and thin-film states and subsequently investigated as ETMs for PSCs. Notably, the F4 delivers the highest power conversion efficiencies over 20% of devices, which surpass all reported fulleropyrrolidine ETMs due to its optimal photoelectric property. Moreover, the structure-dependent effects of the fullerenes on PV parameters are uncovered, including solubility, intermolecular interaction, packing structure, and charge-transfer ability, which can guide the future design of high-performance and stable fullerene ETMs for PSCs.     

Plasmonic Electrically Functionalized TiO2 for High‐Performance Organic Solar Cells

Optical effects of the plasmonic structures and the materials effects of the metal nanomaterials have recently been individually studied for enhancing performance of organic solar cells (OSCs). Here, the effects of plasmonically induced carrier generation and enhanced carrier extraction of the carrier transport layer (i.e., plasmonic‐electrical effects) in OSCs are investigated. Enhanced charge extraction in TiO₂ as a highly efficient electron transport layer by the incorporation of metal nanoparticles (NPs) is proposed and demonstrated. Efficient device performance is demonstrated by using Au NPs incorporated TiO₂ at a plasmonic wavelength (560–600 nm), which is far longer than the originally necessary UV light. By optimizing the concentration ratio of the Au NPs in the NP‐TiO₂ composite, the performances of OSCs with various polymer active layers are enhanced and efficiency of 8.74% is reached. An integrated optical and electrical model, which takes into account plasmonic‐induced hot carrier tunneling probability and extraction barrier between TiO₂ and the active layer, is introduced. The enhanced charge extraction under plasmonic illumination is attributed to the strong charge injection of plasmonically excited electrons from NPs into TiO₂. The mechanism favors trap filling in TiO₂, which can lower the effective energy barrier and facilitate carrier transport in OSCs.     

Molecular Configuration Engineering in Hole-Transporting Materials toward Efficient and Stable Perovskite Solar Cells

The development of hole-transporting materials (HTMs) that can passivate defects in perovskite is of great significance in improving the efficiency and long-term stability of perovskite solar cells. To date, the investigation on HTMs mainly focus on exploring new structures, while molecular configuration is seldomly concerned. In this work, two small molecules are developed as HTMs with benzil and phenanthrene quinone as the core structure, respectively. With similar structure and the same defect passivation groups, whereas, the two molecules exhibit different configurations, thus distinct properties. Compared to 3,6-bis(3,6-bis(bis(4-methoxyphenyl)amino)-9H-carbazol-9-yl)phenanthrene-9,10-dione (PQ) with a rigid core structure, the benzil group in 1,2-bis(4-(3,6-bis(bis(4-methoxyphenyl)amino)-9H-carbazol-9-yl)phenyl)ethane-1,2-dione (DB) is flexible and can adjust molecular configuration to efficiently interact with the underlying perovskite material, which is confirmed from both experimental results and theoretical simulations. The DB-based device exhibits a high power conversion efficiency of 22.21% with excellent long-term stability, superior to the PQ-based device (20.22%). This study demonstrates that molecular configuration engineering will directly affect the properties of hole transport materials, as well as their interactions with perovskite, which should also be taken into consideration when devising HTMs.     

Fluorinated Pentafulvalene-Fused Hole-Transporting Material Enhances the Performance of Perovskite Solar Cells with Efficiency Exceeding 23%

Organic small molecular materials with coplanar π-conjugated system as HTMs in perovskite solar cells (PSCs) have attracted considerable attention due to their high charge transport capability and thermal stability. Herein, three novel pentafulvalene-fused derivatives with or without fluorine atoms incorporated ( YSH-oF and YSH-mF and YSH-H , respectively) are designed, synthesized, and applied as hole-transporting materials (HTMs) in PSCs fabrication. The fluorinated HTMs, YSH-oF and YSH-mF , exhibited higher hole mobility and better charge extraction at the perovskite/HTM interface than non-fluorinated one do, presumably due to the closer intermolecular π–π packing interactions. As a result, small-area (0.09 cm²) PSCs made with YSH-oF and YSH-mF achieved an impressive power conversion efficiency (PCE) of 23.59% and 22.76% respectively, with negligible hysteresis, in contrast with the 20.57% for the YSH-H -based devices. Furthermore, for large-area (1.00 cm²) devices, the PSCs employing YSH-oF exhibited a PCE of 21.92%. Moreover, excellent long-term device stability is demonstrated for PSCs with F-substituted HTMs ( YSH-oF and YSH-mF ), presumably due to the higher hydrophobicity. This study shows the great potential of fluorinated pentafulvalene-fused materials as low-cost HTM for efficient and stable PSCs.     

Porous Organic Cage Induced Spontaneous Restructuring of Buried Interface Toward High-Performance Perovskite Photovoltaic

In perovskite solar cells (PSCs), the buried interface containing high concentrations of defects is critical for efficient charge extraction toward high-performance device. Herein, porous organic cage (POC) is introduced between tin dioxide and perovskite to spontaneously reconstitute the buried interface. Through the chemical linkage formed by polydentate chelation of POC with SnO₂ and perovskite, the buried interface achieves greatly reduced defect density and enhanced carrier extraction. More importantly, it is found that iodide ions in aged devices to migrate down to the electron transport layer and even invade the ITO electrode, changing the work function of ITO. This detrimental effect can be well resolved by POC since the host-guest interaction of POC can effectively suppress the iodide ions trying to migrate downward. As a result, the PSC fabricated by POC-restructured strategy yields a superior PCE of 24.13%. Moreover, the unencapsulated PSCs exhibit conspicuous improved long-term stability and retain 93% of its initial efficiency after 5000 h in ambient condition.     

Orientation-Engineered Small-Molecule Semiconductors as Dopant-Free Hole Transporting Materials for Efficient and Stable Perovskite Solar Cells

Crystallized p-type small-molecule semiconductors have great potential as an efficient and stable hole transporting materials (HTMs) for perovskite solar cells (PSCs) due to their relatively high hole mobility, good stability, and tunable highest occupied molecular orbitals. Here, a thienoacene-based organic semiconductor, 2,9-diphenyldinaphtho[2,3-b:2′,3′-f]thieno[3,2-b]thiophene (DPh-DNTT), is thermally evaporated and employed as the dopant-free HTM that can be scaled up for large-area fabrication. By controlling the deposition temperature, the molecular orientation is modulated into a dominant face-on orientation with π–π stacking direction perpendicular to the substrate surface, maximizing the out-of-plane carrier mobility. With an engineered face-on orientation, the DPh-DNTT film shows an improved out-of-plane mobility of 3.3 × 10⁻² cm² V⁻¹ s⁻¹, outperforming the HTMs reported so far. Such orientation-reinforced mobility contributes to a remarkable efficiency of 20.2% for CH₃NH₃PbI₃ inverted PSCs with enhanced stability. The results reported here provide insights into engineering the orientation of molecules for the dopant-free organic HTMs for PSCs.     

Strategies Toward Efficient Blue Perovskite Light-Emitting Diodes

Substantial progress has been made in blue perovskite light-emitting diodes (PeLEDs). In this review, the strategies for high-performance blue PeLEDs are described, and the main focus is on the optimization of the optical and electrical properties of perovskites. In detail, the fundamental device working principles are first elucidated, followed by a systematical discussion of the key issues for achieving high-quality perovskite nanocrystals (NCs) and quasi-2D perovskites. These involve ligand optimization and metal doping in enhancing the carrier transport and reducing the traps of perovskite NCs, as well as the perovskite phase modulation and defect passivation in improving energy transfer and emission efficiency of quasi-2D perovskites. The strategies for efficient 3D mixed-halide perovskite and lead-free perovskite blue LEDs are then briefly introduced. After that, other strategies, including effective charge transport layer, efficient perovskite emission system, and effective device architecture for high light outcoupling efficiency, are further discussed to boost the blue PeLED performances. Meanwhile, the testing standard of blue PeLED lifetime is suggested to enable the direct comparisons of the device operational stability. Finally, challenges and future directions for blue PeLEDs are addressed.     

The Photo-Hall Effect in High-Mobility Organic Semiconductors

High-mobility crystalline organic semiconductors are important for applications in advanced organic electronics and photonics. Photogeneration and transport of mobile photocarriers in these materials, although very important, remain underexplored. The photo-Hall effect can be used to address the fundamental charge transport properties of these functional molecular materials, without the need for fabricating complex transistor devices or chemical doping. Here, a photo-Hall effect is demonstrated in organic semiconductors, using a benchmark molecular system rubrene as an experimental platform. It is shown that this technique can be used to directly measure the charge carrier mobility and photocarrier density, decouple the surface and bulk transport phenomena, and thus significantly deepen the understanding of the mechanism of photoconductivity in these high-performance molecular materials.     

Mixed Dimensional 2D/3D Hybrid Perovskite Absorbers: The Future of Perovskite Solar Cells?

The cost‐effective processability and high efficiency of the organic–inorganic metal halide perovskite solar cells (PSCs) have shown tremendous potential to intervene positively in the generation of clean energy. However, prior to an industrial scale‐up process, there are certain critical issues such as the lack of stability against over moisture, light, and heat, which have to be resolved. One of the several proposed strategies to improve the stability that has lately emerged is the development of lower‐dimensional (2D) perovskite structures derived from the Ruddlesden–Popper (RP) phases. The excellent stability under ambient conditions shown by 2D RP phase perovskites has made the scalability expectations burgeon since it is one of the most credible paths toward stable PSCs. In this review, the 2D/3D mixed system for photovoltaics (PVs) is elaborately discussed with the focus on the crystal structure, optoelectronic properties, charge carrier dynamics, and their impact on the photovoltaic performances. Finally, some of the further challenges are highlighted while outlining the perspectives of 2D/3D perovskites for high‐efficiency stable solar cells.     

Self-Powered Red/UV Narrowband Photodetector by Unbalanced Charge Carrier Transport Strategy

Narrowband photodetector (NB-PD) with selective light detection is critical for artificial vision and imaging. Intrinsic (optical-filter-free) NB-PDs using conjugated organics or halide perovskite materials have been developed for eliminating the current complex filtering systems in NB-PDs. However, the poor performance and external driving circuit of organic NB-PDs as well as complex doping and uncontrollable recombination reactions in typical perovskite NB-PDs have limited their applicational diversification. A p-type self-doped perovskite for intrinsic NB detection is reported which exhibits unique unbalanced electron–hole transfer kinetics. In conjunction with the optical field distribution, an unbalanced charge transport within the self-doped perovskite triggers a wavelength-dependent photo-carrier collection, resulting in a novel spontaneous internal quantum efficiency narrowing mechanism. As a result, by reverting the device architectural polarity, an NB detection at a monochromic light of either red or UV is observed. Using such a revertible asymmetric device design, self-powered NB-PDs are successfully achieved. Briefly, the corresponding NB-PDs exhibit excellent narrow response with a response window of ≈100 nm, high detectivity ≈10¹¹ Jones, and fast response speed (f_−3dB ≈ 60 kHz) at zero bias. These results demonstrate a new strategy of manipulating internal charge transport to realize power-free and filter-free intrinsic NB-PDs.     

有机光电材料载流子迁移率测量方法

有机光电材料大致可分为小分子或低聚物和聚合物两类.载流子迁移率是衡量有机光电材料导电性能的重要参数,直接关系到材料对电荷的传输能力.因此,测量材料的载流子迁移率是研究有机光电材料的基本工作之一.通过对几种不同测试方法的总结与分析,报道了几种载流子迁移率测试技术,并指出各种测试方法的应用原理及适用的测试范围,对采用合理的...     

Double Charge Transfer Dominates in Carrier Localization in Low Bandgap Sites of Heterogeneous Lead Halide Perovskites

Heterogeneous organic-inorganic halide perovskites possess inherent non-uniformities in bandgap that are sometimes engineered and exploited on purpose, like in quasi-2D perovskites. In these systems, charge carrier and excitation energy migration to lower-bandgap sites are key processes governing luminescence. The question, which of them dominates in particular materials and under specific experimental conditions, still remains unanswered, especially when charge carriers comprise excitons. In this study transient absorption (TA) and transient photoluminescence (PL) techniques are combined to address the excited state dynamics in quasi-2D and other heterogeneous perovskite structures in broad temperature range, from room temperature down to 15 K. The data provide clear evidence that charge carrier transfer rather than energy migration dominates in heterogeneous quasi-2D perovskite films.