Perovskite Crystallization Control for Large, Oriented Grains with Residual Solvent Restrain via Hydrogen-Bonded Organic Frameworks.

Void-free perovskite films with oriented large grains are considered good performance. However, contradictory requirements on solvent volatilization arise that the growth of large grains requires slow volatilization while the residual solvent problem, which leads to difficult-handled voids at buried interface, requires quick and complete volatilization. Currently, although grain boundary additives help reach large and oriented grains, the occupation of additives in the grain boundary volatilization channel may further deteriorate the residual solvent problem. Herein, porous structures with "switchable pore" nature are constructed based on flexible hydrogen-bonded (HOF-FJU-2) in perovskite grain boundaries to meet both contradictory requirements with achieving crystallization control and residual solvent restrain. The additive molecules prolongs the perovskite crystallization through the Pb-O bond and guides the growth of (100) facet based on its strong ordered accumulation trend. The pre-embedded porous structure opens up the solvent volatilization channel for complete volatilization in annealing stage and then switches to a closed pore state via phase transformation after the solvent completely leaves, preventing the intrusion of the external environment. Combined with theoretical calculations and in situ spectrum tests, the crystallization thermodynamics and dynamics are analyzed. As expected, the target device exhibits enhanced performance (improved from 22.14% to 24.18%) and stability.

Inhibiting Interfacial Nonradiative Recombination in Inverted Perovskite Solar Cells with a Multifunctional Molecule.

Interface-induced nonradiative recombination losses at the perovskite/electron transport layer (ETL) are an impediment to improving the efficiency and stability of inverted (p-i-n) perovskite solar cells (PSCs). Tridecafluorohexane-1-sulfonic acid potassium (TFHSP) is employed as a multifunctional dipole molecule to modify the perovskite surface. The solid coordination and hydrogen bonding efficiently passivate the surface defects, thereby reducing nonradiative recombination. The induced positive dipole layer between the perovskite and ETLs improves the energy band alignment, enhancing interface charge extraction. Additionally, the strong interaction between TFHSP and the perovskite stabilizes the perovskite surface, while the hydrophobic fluorinated moieties prevent the ingress of water and oxygen, enhancing the device stability. The resultant devices achieve a power conversion efficiency (PCE) of 24.6%. The unencapsulated devices retain 91% of their initial efficiency after 1000 h in air with 60% relative humidity, and 95% after 500 h under maximum power point (MPP) tracking at 35 °C. The utilization of multifunctional dipole molecules opens new avenues for high-performance and long-term stable perovskite devices.

Photo-Cross-Linked Fullerene-Based Hole Transport Material for Moisture-Resistant Regular Fullerene Sandwich Perovskite Solar Cells.

Despite the high efficiencies currently achieved with perovskite solar cells (PSCs), the need to develop stable devices, particularly in humid conditions, still remains. This study presents the synthesis of a novel photo-cross-linkable fullerene-based hole transport material named FT12. For the first time, the photo-cross-linking process is applied to PSCs, resulting in the preparation of photo-cross-linked FT12 (PCL FT12). Regular PSCs based on C60-sandwich architectures were fabricated using FT12 and PCL FT12 as dopant-free hole transport layers (HTLs) and compared to the reference spiro-OMeTAD. The photovoltaic results demonstrate that both FT12 and PCL FT12 significantly outperform pristine spiro-OMeTAD regarding device performance and stability. The comparison between devices based on FT12 and PCL FT12 demonstrates that the photo-cross-linking process enhances device efficiency. This improvement is primarily attributed to enhanced charge extraction, partial oxidation of the HTL, increased hole mobility, and improved layer morphology. PCL FT12-based devices exhibit improved stability compared to FT12 devices, primarily due to the superior moisture resistance achieved through photo-cross-linking.

Rational Design of New Small Derivatives of 2,2'-Bithiophene as Hole Transport Material for Perovskite Solar Cells.

Using Density Functional Theory (DFT) and Time Dependent DFT (TD-DFT) methods, this inquiry theoretically examines seven novel hole-transport materials (HTMs) namely DFBT1, DFBT2, DFBT3, DFBT4, DFBT5, DFBT6, and DFBT7 based on the 2,2'bithiophene core for future use as HTMs for perovskite solar cells (PSCs). The model molecule has been modified through substituting the end groups situated on the diphenylamine moieties with a tow acceptor bridged by thiophene, this modification was performed to test the impact of the π-bridge and acceptor on the electronic, photophysical, and photovoltaic properties of the newly created molecules. DFBT1 - DFBT7 displayed a lower band gap (1.49 eV to 2.69 eV) than the model molecule (3.63 eV). Additionally, the newly engineered molecules presented a greater λmax ranging from 393.07 nm to 541.02 nm in dimethylformamide solvent, as compared to the model molecule (380.61 nm). The PCEs of all newly designed molecules (22.42% to 29.21%) were high compared with the reference molecule (19.62%). Thus, this study showed that all seven newly small molecules were excellent candidates for a novel PSC.

Zinc Aluminum Oxide Encapsulation Layers for Perovskite Solar Cells Deposited Using Spatial Atomic Layer Deposition.

An atmospheric-pressure spatial atomic layer deposition system is used to rapidly deposit 60 nm zinc-aluminum oxide (Zn-AlOx ) thin-film-encapsulation layers directly on perovskite solar cells at 130 °C without damaging the temperature-sensitive perovskite and organic materials. Varying the Zn/Al ratio has a significant impact on the structural properties of the films and their moisture barrier performance. The Zn-AlOx films have higher refractive indexes, lower concentrations of OH─ groups, and lower water-vapor transmission rates (WVTR) than AlOx films without zinc. However, as the Zn/Al ratio increases beyond 0.21, excess Zn atoms segregate, leading to an increase in the number of available hydroxyl groups on the surface of the deposited film and a slight increase in the WVTR. The stability of the p-i-n formamidinium methylammonium lead iodide solar cells under standard ISOS-D-3 testing conditions (65 °C and 85% relative humidity) is significantly enhanced by the thin encapsulation layers. The layers with a Zn/Al ratio of 0.21 result in a seven-fold increase the time required for the cells to degrade to 80% of their original efficiency.

Modulation of Charge Transport from Two-Dimensional Perovskites to Industrial Charge Transport Layers by the Organic Spacer-Dependent Exciton-Phonon Interactions.

In the past decade, two-dimensional (2D) perovskite surface treatment has emerged as a promising strategy to improve the performance of three-dimensional (3D) perovskite solar cells (PSCs). However, systematic studies on the impact of organic spacers of 2D perovskites on charge transport in 2D/3D PSCs are still lacking. Here, using 2D perovskite film/C60 heterostructures with different organic spacers [butylamine (BA), phenylethylamine (PEA), and 3-fluorophenethylamine (m-F-PEA)], we systematically investigated the carrier diffusion and interfacial transfer process. Using a 2D perovskite film with a thickness of ∼7 nm, we observed subtle differences in electron transfer time between 2D perovskites and C60 layers, which can be attributed to limited thickness and similar electron coupling strength. However, with the thickness of 2D perovskite increasing, electron transfer efficiency in the (BA)2PbI4/C60 heterostructure exhibits the most rapid decrease due to poor carrier diffusion of (BA)2PbI4 caused by stronger exciton-phonon interactions compared to (PEA)2PbI4 and (m-F-PEA)2PbI4 in thickness-dependent charge transfer research. Meanwhile, the fill factor of 2D/3D PSC treated with BAI exhibits the most rapid decrease compared to PEAI- and m-F-PEAI-treated 2D/3D PSCs with the concentration increase of passivators. This study indicates that it is easier to enhance open-circuit voltages and minimize the decrease of fill factor by increasing the concentration of passivators in 2D/3D PSCs when using passivators with a rigid molecular structure.

Effect of different oxygen precursors on alumina deposited using a spatial atomic layer deposition system for thin-film encapsulation of perovskite solar cells.

An atmospheric-pressure spatial atomic layer deposition system operated in atmospheric-pressure spatial chemical vapor deposition conditions is employed to deposit alumina (AlOx) thin films using trimethylaluminum and different oxidants, including water (H2O), hydrogen peroxide (H2O2), and ozone (O3). The impact of the oxygen precursor on the structural properties of the films and their moisture-barrier performance is investigated. The O3-AlOxfilms, followed by H2O2-AlOx, exhibit higher refractive indexes, lower concentrations of OH- groups, and lower water-vapor-transmission rates compared to the films deposited using water (H2O-AlOx). The AlOxfilms are then rapidly deposited as thin-film-encapsulation layers on perovskite solar cells at 130 °C without damaging the temperature-sensitive perovskite and organic materials. The stability of thep-i-nformamidinium methylammonium lead iodide solar cells under standard ISOS-D-3 testing conditions (65 °C and 85% relative humidity) is significantly enhanced by the encapsulation layers. Specifically, the O3-AlOxand H2O2-AlOxlayers result in a six-fold increase in the time required for the cells to degrade to 80% of their original efficiency compared to un-encapsulated cells.

p-Type Functionalized Carbon Nanohorns and Nanotubes in Perovskite Solar Cells.

The incorporation of p-type functionalized carbon nanohorns (CNHs) in perovskite solar cells (PSCs) and their comparison with p-type functionalized single- and double-walled carbon nanotubes (SWCNTs and DWCNTs) are reported in this study for the first time. These p-type functionalized carbon nanomaterial (CNM) derivatives were successfully synthesized by [2 + 1] cycloaddition reaction with nitrenes formed from triphenylamine (TPA) and 9-phenyl carbazole (Cz)-based azides, yielding CNHs-TPA, CNHs-Cz, SWCNTs-Cz, SWCNTs-TPA, DWCNTs-TPA, and DWCNTs-Cz. These six novel CNMs were incorporated into the spiro-OMeTAD-based hole transport layer (HTL) to evaluate their impact on regular mesoporous PSCs. The photovoltaic results indicate that all p-type functionalized CNMs significantly improve the power conversion efficiency (PCE), mainly by enhancing the short-circuit current density (Jsc) and fill factor (FF). TPA-functionalized derivatives increased the PCE by 12-17% compared to the control device without CNMs, while Cz-functionalized derivatives resulted in a PCE increase of 4-8%. Devices prepared with p-type functionalized CNHs exhibited a slightly better PCE compared with those based on SWCNTs and DWCNTs derivatives. The increase in hole mobility of spiro-OMeTAD, additional p-type doping, better energy alignment with the perovskite layer, and enhanced morphology and contact interface play important roles in enhancing the performance of the device. Furthermore, the incorporation of p-type functionalized CNMs into the spiro-OMeTAD layer increased device stability by improving the hydrophobicity of the layer and enhancing the hole transport across the MAPI/spiro-OMeTAD interface. After 28 days under ambient conditions and darkness, TPA-functionalized CNMs maintained the performance of the device by over 90%, while Cz-functionalized CNMs preserved it between 75 and 85%.

Magnetic Field-Assisted Interface Embedding Strategy to Construct 2D/3D Composite Structure for Stable Perovskite Solar Cells with Efficiency Over 24.

Perovskite solar cells (PSCs) based on 2D/3D composite structure have shown enormous potential to combine high efficiency of 3D perovskite with high stability of 2D perovskite. However, there are still substantial non-radiative losses produced from trap states at grain boundaries or on the surface of conventional 2D/3D composite structure perovskite film, which limits device performance and stability. In this work, a multifunctional magnetic field-assisted interfacial embedding strategy is developed to construct 2D/3D composite structure. The composite structure not only improves crystallinity and passivates defects of perovskite layer, but also can efficiently promote vertical hole transport and provide lateral barrier effect. Meanwhile, the composite structure also forms a good surface and internal encapsulation of 3D perovskite to inhibit water diffusion. As a result, the multifunctional effect effectively improves open-circuit voltage and fill factor, reaching maximum values of 1.246 V and 81.36%, respectively, and finally achieves power conversion efficiency (PCE) of 24.21%. The unencapsulated devices also demonstrate highly improved long-term stability and humidity stability. Furthermore, an augmented performance of 21.23% is achieved, which is the highest PCE of flexible device based on 2D/3D composite perovskite films coupled with the best mechanical stability due to the 2D/3D alternating structure.

Enhanced Activation Energy Released by Coordination of Bifunctional Lewis Base d-Tryptophan for Highly Efficient and Stable Perovskite Solar Cells.

Perovskite defect passivation with molecule doping shows great potential in boosting the efficiency and stability of perovskite solar cells (PSCs). Herein, an efficient and low-cost bifunctional Lewis base additive d-tryptophan is introduced to control the crystallization and growth of perovskite grains and passivation defects. It is found that the additive doped in the solution precursors could retard crystal growth by increasing activation energy, resulting in improved crystallization of large grains with reduced grain boundaries, as well as inhibiting ion migration and PbI2 aggregation. As a result, the PSCs incorporated with d-tryptophan additives achieve an improved power conversion efficiency from 18.18 to 21.55%. Moreover, the d-tryptophan passivation agent improves the device stability, which retains 86.85% of its initial efficiency under ambient conditions at room temperature after 500 h. This work provides Lewis base small-molecule d-tryptophan for efficient defect passivation of the grain boundaries toward efficient and stable PSCs.

Progress in Perovskite Solar Cells towards Commercialization-A Review.

In recent years, perovskite solar cells (PSCs) have experienced rapid development and have presented an excellent commercial prospect as the PSCs are made from raw materials that are readily and cheaply available depending on simple manufacturing techniques. However, the commercial production and utilization of PSCs remain immature, leading to substantial efforts needed to boost the development of scalable fabrication of PSCs, pilot scale tests, and the establishment of industrial production lines. In this way, the PSCs are expected to be successfully popularized from the laboratory to the photovoltaic market. In this review, the history of power conversion efficiency (PCE) for laboratory-scale PSCs is firstly introduced, and then some methods for maintaining high PCE in the upscaling process is displayed. The achievements in the stability and environmental friendliness of PSCs are also summarized because they are also of significance for commercialization. Finally, this review evaluates the commercialization prospects of PSCs from the economic view and provides a short outlook.

Strategies for Improving the Stability of Tin-Based Perovskite (ASnX3) Solar Cells.

Although lead-based perovskite solar cells (PSCs) are highly efficient, the toxicity of lead (Pb) limits its large-scale commercialization. As such, there is an urgent need to find alternatives. Many studies have examined tin-based PSCs. However, pure tin-based perovskites are easily oxidized in the air or just in glovebox with an ultrasmall amount of oxygen. Such a characteristic makes their performance and stability less ideal compared with those of lead-based perovskites. Herein, how to address the instability of tin-based perovskites is introduced in detail. First, the crystalline structure, optical properties, and sources of instability of tin-based perovskites are summarized. Next, the preparation methods of tin-based perovskite are discussed. Then, various measures for solving the instability problem are explained using four strategies: additive engineering, deoxidizer, partial substitution, and reduced dimensions. Finally, the challenges and prospects are laid out to help researchers develop highly efficient and stable tin-based perovskites in the future.

Recent progress in perovskite solar cells: the perovskite layer.

Perovskite solar cells (PSCs) are set to be game changing components in next-generation photovoltaic technology due to their high efficiency and low cost. In this article, recent progress in the development of perovskite layers, which are the basis of PSCs, is reviewed. Achievements in the fabrication of high-quality perovskite films by various methods and techniques are introduced. The reported works demonstrate that the power conversion efficiency of the perovskite layers depends largely on their morphology and the crystalline quality. Furthermore, recent achievements concerning the scalability of perovskite films are presented. These developments aim at manufacturing large-scale perovskite solar modules at high speed. Moreover, it is shown that the development of low-dimensional perovskites plays an important role in improving the long-term ambient stability of PSCs. Finally, these latest advancements can enhance the competitiveness of PSCs in photovoltaics, paving the way for their commercialization. In the closing section of this review, some future critical challenges are outlined, and the prospect of commercialization of PSCs is presented.

Benefits of the Hydrophobic Surface for CH3NH3PbI3 Crystalline Growth Towards Highly Efficient Inverted Perovskite Solar Cells.

In inverted perovskite solar cells (PSCs), high-quality perovskite film grown on hole-transporting material (HTM) with pinhole-free coverage and a large grain size is crucial for high efficiency. Here, we report on the growth of pinhole-free and large grain CH3NH3PbI3 crystals favored by a hydrophobic small molecular HTM, namely, 4,4'-Bis(4-(di-p-toyl)aminostyryl)biphenyl (TPASBP). The hydrophobic surface induced by TPASBP suppressed the density of the perovskite nuclei and heterogeneous nucleation, thus promoting the perovskite to grow into a dense and homogeneous film with a large grain size. The CH3NH3PbI3 deposited on the TPASBP exhibited better crystallization and a lower trap density than that on the hydrophilic surface of indium tin oxide (ITO), resulting in a significant reduction in carrier recombination. Combined with the efficient hole extraction ability of TPASBP, a high efficiency of 18.72% in the inverted PSCs fabricated on TPASBP was achieved.

Efficient Carbon-Based CsPbBr3 Inorganic Perovskite Solar Cells by Using Cu-Phthalocyanine as Hole Transport Material.

Metal halide perovskite solar cells (PSCs) have attracted extensive research interest for next-generation solution-processed photovoltaic devices because of their high solar-to-electric power conversion efficiency (PCE) and low fabrication cost. Although the world's best PSC successfully achieves a considerable PCE of over 20% within a very limited timeframe after intensive efforts, the stability, high cost, and up-scaling of PSCs still remain issues. Recently, inorganic perovskite material, CsPbBr3, is emerging as a promising photo-sensitizer with excellent durability and thermal stability, but the efficiency is still embarrassing. In this work, we intend to address these issues by exploiting CsPbBr3 as light absorber, accompanied by using Cu-phthalocyanine (CuPc) as hole transport material (HTM) and carbon as counter electrode. The optimal device acquires a decent PCE of 6.21%, over 60% higher than those of the HTM-free devices. The systematic characterization and analysis reveal a more effective charge transfer process and a suppressed charge recombination in PSCs after introducing CuPc as hole transfer layer. More importantly, our devices exhibit an outstanding durability and a promising thermal stability, making it rather meaningful in future fabrication and application of PSCs.

Small Molecule-Polymer Composite Hole-Transporting Layer for Highly Efficient and Stable Perovskite Solar Cells.

Effective and stable hole-transporting materials (HTMs) are necessary for obtaining excellent planar perovskite solar cells (PSCs). Herein, we reported a solution-processed composite HTM consisting of a polymer poly(3,4-ethylenedioxythiophene):polystyrenesulfonate (PEDOT:PSS) and a small-molecule copper phthalocyanine-3,4',4″,4‴-tetrasulfonated acid tetrasodium salt (TS-CuPc) with optimized doping ratios. The composite HTM is crucial for not only enhancing the hole transport and extraction but also improving the perovskite crystallization. In addition, the composite HTM can weaken the indium tin oxide erosion by reducing the acidity and increasing the dispersibility of the PEDOT:PSS aqueous dispersion via incorporating suitable TS-CuPc. Consequently, a highly efficient device was fabricated with a power conversion efficiency (PCE) of 17.29%. Its short-circuit current (JSC) is 22.23 mA/cm2, and its open-circuit voltage (VOC) is 1.01 V. Meanwhile, it exhibited a higher fill factor (FF) of 77% and improved cell stability. The developed composite HTM provides a good potential anode interfacial layer for fabricating outstanding PSCs.