Tethered Helical Ladder-Type Aromatic Lactams.

Tethered nonplanar aromatics (TNAs) make up an important class of nonplanar aromatic compounds showing unique features. However, the knowledge on the synthesis, structures, and properties of TNAs remains insufficient. In this work, a new type of TNAs, the tethered aromatic lactams, is synthesized via Pd-catalyzed consecutive intramolecular direct arylations. These molecules possess a helical ladder-type conjugated system of up to 13 fused rings. The overall yields ranged from 3.4 to 4.3%. The largest of the tethered aromatic lactams, 6L-Bu-C14, demonstrates a guest-adaptive hosting capability of TNAs for the first time. When binding fullerene guests, the cavity of 6L-Bu-C14 became more circular to better accommodate spherical fullerene molecules. The host-guest interaction is thoroughly studied by X-ray crystallography, theoretical calculations, fluorescence titration, and nuclear magnetic resonance (NMR) titration experiments. 6L-Bu-C14 shows stronger binding with C70 than with C60 due to the better convex-concave π-π interaction. P and M enantiomers of all tethered aromatic lactams show distinct and persistent chiroptical properties and demonstrate the potential of chiral TNAs as circularly polarized luminescence (CPL) emitters.

Suppressing Ion Migration by Synergistic Engineering of Anion and Cation toward High-Performance Inverted Perovskite Solar Cells and Modules.

Ion migration-induced intrinsic instability and large-area fabrication pose a tough challenge for the commercial deployment of perovskite photovoltaics. Herein, an interface heterojunction and metal electrode stabilization strategy is developed by suppressing ion migration via managing lead-based imperfections. After screening a series of cations and nonhalide anions, the ideal organic salt molecule dimethylammonium trifluoroacetate (DMATFA) consisting of dimethylammonium (DMA+) cation and trifluoroacetate (TFA-) anion is selected to manipulate the surface of perovskite films. DMA+ enables the conversion of active excess and/or unreacted PbI2 into stable new phase DMAPbI3, inhibiting photodecomposition of PbI2 and ion migration. Meanwhile, TFA- can suppress iodide ion migration through passivating undercoordinated Pb2+ and/or iodide vacancies. DMA+ and TFA- synergistically stabilize the heterojunction interface and silver electrode. The DMATFA-treated inverted perovskite solar cells and modules achieve a maximum efficiency of 25.03% (certified 24.65%, 0.1 cm2) and 20.58% (63.74 cm2), respectively, which is the record efficiency ever reported for the devices based on vacuum flash evaporation technology. The DMATFA modification results in outstanding operational stability, as evidenced by maintaining 91% of its original efficiency after 1520 h of maximum power point continuous tracking.

Synchronous Regulation Strategy of Pyrrolidinium Thiocyanate Enables Efficient Perovskite Solar Cells and Self-Powered Photodetectors.

Developing inventive approaches to control crystallization and suppress trap defects in perovskite films is crucial for achieving efficient perovskite photovoltaics. Here, a synchronous regulation strategy is developed that involves the infusion of a zwitterionic ionic liquid additive, pyrrolidinium thiocyanate (PySCN), into the perovskite precursor to optimize the subsequent crystallization and defects. PySCN modification not only orchestrates the crystallization process but also deftly addresses trap defects in perovskite films. Within this, SCN- compensates for positively charged defects, while Py+ plays the role of passivating negatively charged defects. Based on the vacuum flash evaporation without anti-solvent, the air-processed perovskite solar cells (PSCs) with PySCN modification can achieve an extraordinary champion efficiency of 22.46% (0.1 cm2 ) and 21.15% (1.0 cm2 ) with exceptional stability surpassing 1200 h. Further, the self-powered photodetector goes above and beyond, showcasing an ultra-low dark current of 2.13 × 10-10 A·cm-2 , a specific detection rate of 6.12 × 1013  Jones, and an expansive linear dynamic range reaching an astonishing 122.49 dB. PySCN modification not only signifies high efficiency but also ushers in a new era for crystallization regulation, promising a transformative impact on the optoelectronic performance of perovskite-based devices.

Stabilizing Top Interface by Molecular Locking Strategy with Polydentate Chelating Biomaterials toward Efficient and Stable Perovskite Solar Cells in Ambient Air.

The instability of top interface induced by interfacial defects and residual tensile strain hinders the realization of long-term stable n-i-p regular perovskite solar cells (PSCs). Herein, one molecular locking strategy is reported to stabilize top interface by adopting polydentate ligand green biomaterial 2-deoxy-2,2-difluoro-d-erythro-pentafuranous-1-ulose-3,5-dibenzoate (DDPUD) to manipulate the surface and grain boundaries of perovskite films. Both experimental and theoretical evidence collectively uncover that the uncoordinated Pb2+ ions, halide vacancy, and/or I─Pb antisite defects can be effectively healed and locked by firm chemical anchoring on the surface of perovskite films. The ingenious polydentate ligand chelating is translated into reduced interfacial defects, increased carrier lifetimes, released interfacial stress, and enhanced moisture resistance, which should be liable for strengthened top interface stability and inhibited interfacial nonradiative recombination. The universality of the molecular locking strategy is certified by employing different perovskite compositions. The DDPUD modification achieves an enhanced power conversion efficiency (PCE) of 23.17-24.47%, which is one of the highest PCEs ever reported for the devices prepared in ambient air. The unsealed DDPUD-modified devices maintain 98.18% and 88.10% of their initial PCEs after more than 3000 h under a relative humidity of 10-20% and after 1728 h at 65 °C, respectively.

Polydentate Ligand Reinforced Chelating to Stabilize Buried Interface toward High-Performance Perovskite Solar Cells.

The instability of the buried interface poses a serious challenge for commercializing perovskite photovoltaic technology. Herein, we report a polydentate ligand reinforced chelating strategy to strengthen the stability of buried interface by managing interfacial defects and stress. The bis(2,2,2-trifluoroethyl) (methoxycarbonylmethyl)phosphonate (BTP) is employed to manipulate the buried interface. The C=O, P=O and two -CF3 functional groups in BTP synergistically passivate the defects from the surface of SnO2 and the bottom surface of the perovskite layer. Moreover, The BTP modification contributes to mitigated interfacial residual tensile stress, promoted perovskite crystallization, and reduced interfacial energy barrier. The multidentate ligand modulation strategy is appropriate for different perovskite compositions. Due to much reduced nonradiative recombination and heightened interface contact, the device with BTP yields a promising power conversion efficiency (PCE) of 24.63 %, which is one of the highest efficiencies ever reported for devices fabricated in the air environment. The unencapsulated BTP-modified devices degrade to 98.6 % and 84.2 % of their initial PCE values after over 3000 h of aging in the ambient environment and after 1728 h of thermal stress, respectively. This work provides insights into strengthening the stability of the buried interface by engineering multidentate chelating ligand molecules.

Functional-Group-Induced Single Quantum Well Dion-Jacobson 2D Perovskite for Efficient and Stable Inverted Perovskite Solar Cells.

In two-dimensional/three-dimensional (2D/3D) perovskite heterostructure, randomly distributed multiple quantum wells (QW) 2D perovskites are frequently generated, which are detrimental to carrier transport and structural stability. Here, the high quality 2D/3D perovskite heterostructure is constructed by fabricating functional-group-induced single QW Dion-Jacobson (DJ) 2D perovskites. The utilization of ─OCH3 in the precursor solution facilitates the formation of colloidal particles with uniform size, resulting in the production of a pure 2D DJ perovskite with an n value of 3. This strategy facilitates the improvement of 3D structural stability and expedites carrier transport. The resultant devices accomplish a power conversion efficiency of 25.26% (certified 25.04%) and 23.56% at a larger area (1 cm2 ) with negligible hysteresis. The devices maintain >96% and >89% of their initial efficiency after continuous maximum power point tracking under simulated AM1.5 illumination for 1300 h and under damp-heat conditions (85 °C and 85% RH) for 1010 h, respectively.

Rationally Tailoring Chiral Molecules to Minimize Interfacial Energy Loss Enables Efficient and Stable Perovskite Solar Cells Using Vacuum Flash Technology.

Facing the defects and energy barrier at the interface of perovskite solar cells, we propose a chiral molecule engineering strategy to simultaneously heal interfacial defects and regulate interfacial energy band alignment. S-ibuprofen (S-IBU), R-ibuprofen (R-IBU), and racemic ibuprofen (rac-IBU) are used to post-treat perovskite films. rac-IBU molecules possess the strongest anchoring on the surface of perovskites among all chiral molecules, translating into the best defect passivation effect. The hydrophobic isobutyl group and benzene ring could increase the film moisture resistance ability. Due to reduced interfacial defects and interfacial energy barrier, rac-IBU enables efficient devices with a maximum efficiency exceeding 24% based on vacuum flash technology without antisolvents. The encapsulated rac-IBU-modified device could maintain 90% of its initial performance after 1040 h of continuous maximum power point tracking. This work provides a feasible route to minimize interfacial nonradiative recombination losses by controlling spatial conformation via rational chiral molecule engineering.

Opportunities and challenges of hole transport materials for high-performance inverted hybrid-perovskite solar cells.

Inverted perovskite solar cells (inverted-PSCs) have exhibited advantages of longer stability, less hysteresis, and lower fabrication temperature when compared to their regular counterparts, which are important for industry commercialization. Because of the great efforts that have been conducted in the past several years, the obtained efficiency of inverted-PSCs has almost caught up with that of the regular ones, 25.0% versus 25.7%. In this perspective, the recent studies on the design of high-performance inverted-PSCs based on diverse hole transport materials, as well as device fabrication and characterization are first reviewed. After that, the authors moved on to the interface and additive engineering that were exploited to suppress the nonradiative recombination. Finally, the challenges and possible research pathways for facilitating the industrialization of inverted-PSCs were envisaged.

Advances in chloride additives for high-efficiency perovskite solar cells: multiple points of view.

Chloride (Cl) additives are rather effective in improving the performance of perovskite solar cells (PSCs) through the modulation of crystallization process and surface morphology. After incorporating Cl-containing additives, the optoelectrical properties of perovskite films, such as the electron/hole diffusion length and carrier lifetime, are greatly enhanced. However, only a trace amount of Cl has been identified in the resultant perovskite film, and the mechanism of efficiency improvement induced by Cl remains unclear. In this review, we discuss organic and inorganic Cl additives systematically from the perspective of their solubility, volatility, cation size and chemical groups. In addition, the roles of residual Cl anions and cations are analyzed in detail. Finally, some valuable future perspectives of Cl additives are proposed.

Multidentate Chelation Achieves Bilateral Passivation toward Efficient and Stable Perovskite Solar Cells with Minimized Energy Losses.

Defects in the electron transport layer (ETL), perovskite, and buried interface will result in considerable nonradiative recombination. Here, a bottom-up bilateral modification strategy is proposed by incorporating arsenazo III (AA), a chromogenic agent for metal ions, to regulate SnO2 nanoparticles. AA can complex with uncoordinated Sn4+/Pb2+ in the form of multidentate chelation. Furthermore, by forming a hydrogen bond with formamidinium (FA), AA can suppress FA+ defects and regulate crystallization. Multiple chemical bonds between AA and functional layers are established, synergistically preventing the agglomeration of SnO2 nanoparticles, enhancing carrier transport dynamics, passivating bilateral defects, releasing tensile stress, and promoting the crystallization of perovskite. Ultimately, the AA-optimized power conversion efficiency (PCE) of the methylammonium-free (MA-free) devices (Rb0.02(FA0.95Cs0.05)0.98PbI2.91Br0.03Cl0.06) is boosted from 20.88% to 23.17% with a high open-circuit voltage (VOC) exceeding 1.18 V and ultralow energy losses down to 0.37 eV. In addition, the optimized devices also exhibit superior stability.

Dual Improvement in Sensitivity and Humidity Tolerance of a NO2 Sensor Based on 3-Aminopropyltriethoxysilane Self-Assembled Monolayer-Functionalized SnSe2 for Explosive Photolysis Gas Detection.

Explosives can be analyzed for their content by detecting the photolytic gaseous byproducts. However, to prevent electrostatic sparking, explosives are frequently preserved in conditions with low temperatures and high humidity, impeding the performance of gas detection. Thus, it has become a research priority to develop gas sensors that operate at ambient temperature and high humidity levels in the realm of explosive breakdown gas-phase detection. In this work, 3-aminopropyltriethoxysilane (APTES) self-assembled monolayer-functionalized tin diselenide (APTES-SnSe2) nanosheets were synthesized via a facile solution stirring strategy, resulting in a room-temperature NO2 sensor with improved sensitivity and humidity tolerance. The APTES-SnSe2 sensor with moderate functionalization time outperforms the pure SnSe2 sensor in terms of the response value (317.51 vs 110.98%) and response deviation (3.11 vs 24.13%) under humidity interference to 500 ppb NO2. According to density functional theory simulations, the stronger adsorption of terminal amino groups of the APTES molecules to NO2 molecules and stable adsorption energy in the presence of H2O are the causes of the improved sensing capabilities. Practically, the APTES-SnSe2 sensor achieves accurate detection of photolysis gases from trace nitro explosives octogen, pentaerythritol tetranitrate, and trinitrotoluene at room temperature and various humidity levels. This study provides a potential strategy for the construction of gas sensors with high responsiveness and antihumidity capabilities to identify explosive content in harsh environments.

Synergistic Modification of 2D Perovskite with Alternating Cations in the Interlayer Space and Multisite Ligand toward High-Performance Inverted Solar Cells.

The preparation of high-quality perovskite films is key to realize efficient and stable inverted perovskite solar cells. The trap-assisted nonradiative recombination at grain boundary (GB) and surface poses a serious challenge for fabricating high-quality perovskite films. Here, a synergistic modulation strategy of two-dimensional (2D) perovskite with alternating cations in the interlayer space (ACI) and multisite ligand 2-mercapto-1,3,4-thiadiazole (MTD) for fabricating high-quality methylammonium-free perovskite films is reported. The formation of ACI 2D perovskite promotes the nucleation of three-dimensional (3D) perovskites, suppresses the generation of yellow phase, and promotes the formation of black phase, leading to increased grain size and crystallinity. Due to the synergistic effect of ACI 2D perovskite and MTD, the defects at GBs and surface are healed simultaneously. The significantly inhibited nonradiative recombination enables realization of high-efficiency inverted devices with a fascinating power conversion efficiency (PCE) of 24.58%, which is one of the highest PCEs reported for inverted devices. The synergistically modified unsealed device demonstrates an excellent long-term ambient stability, retaining 90.5% of its initial PCE after 3000 h under a relative humidity of 30-40%. This work provides deep insights into minimizing nonradiative recombination losses through the rational synergistic engineering of GB and surface toward efficient and stable inverted devices.

Molecular Synergistic Passivation for Efficient Perovskite Solar Cells and Self-Powered Photodetectors.

The interface between the perovskite and electron-transporting material is often treated for defect passivation to improve the photovoltaic performance of devices. A facile 4-Acetamidobenzoic acid (containing an acetamido, a carboxyl, and a benzene ring)-based molecular synergistic passivation (MSP) strategy is developed here to engineer the SnOx /perovskite interface, in which dense SnOx are prepared using an E-beam evaporation technology while the perovskite is deposited with vacuum flash evaporation deposition method. MSP engineering can synergistically passivate defects at the SnOx /perovskite interface by coordinating with Sn4+ and Pb2+ with functional group CO in the acetamido and carboxyl. The optimized solar cell devices can achieve the highest efficiency of 22.51% based on E-Beam deposited SnOx and 23.29% based on solution-processed SnO2 , respectively, accompanied by excellent stability exceeding 3000 h. Further, the self-powered photodetectors exhibit a remarkably low dark current of 5.22 × 10-9  A cm-2 , a response of 0.53 A W-1 at zero bias, a detection limit of 1.3 × 1013  Jones, and a linear dynamic range up to 80.4 dB. This work proposes a molecular synergistic passivation strategy to enhance the efficiency and responsivity of solar cells and self-powered photodetectors.

Managing Interfacial Defects and Carriers by Synergistic Modulation of Functional Groups and Spatial Conformation for High-Performance Perovskite Photovoltaics Based on Vacuum Flash Method.

Interfacial nonradiative recombination loss is a huge barrier to advance the photovoltaic performance. Here, one effective interfacial defect and carrier dynamics management strategy by synergistic modulation of functional groups and spatial conformation of ammonium salt molecules is proposed. The surface treatment with 3-ammonium propionic acid iodide (3-APAI) does not form 2D perovskite passivation layer while the propylammonium ions and 5-aminopentanoic acid hydroiodide post-treatment lead to the formation of 2D perovskite passivation layers. Due to appropriate alkyl chain length, theoretical and experimental results manifest that COOH and NH3 + groups in 3-APAI molecules can form coordination bonding with undercoordinated Pb2+ and ionic bonding and hydrogen bonding with octahedron PbI6 4- , respectively, which makes both groups be simultaneously firmly anchored on the surface of perovskite films. This will strengthen defect passivation effect and improve interfacial carrier transport and transfer. The synergistic effect of functional groups and spatial conformation confers 3-APAI better defect passivation effect than 2D perovskite layers. The 3-APAI-modified device based on vacuum flash technology achieves an alluring peak efficiency of 24.72% (certified 23.68%), which is among highly efficient devices fabricated without antisolvents. Furthermore, the encapsulated 3-APAI-modified device degrades by less than 4% after 1400 h of continuous one sun illumination.

1-Adamantanamine Hydrochloride Resists Environmental Corrosion to Obtain Highly Efficient and Stable Perovskite Solar Cells.

Passivating the defective surface of perovskite film is a promising strategy to improve the stability and efficiency of perovskite solar cells (PSCs). Herein, 1-adamantanamine hydrochloride (ATH) is introduced to the upper surface of the perovskite film to heal the defects of the perovskite surface. The best-performance ATH-modified device has a higher efficiency (23.45%) than the champion control device (21.53%). The defects are passivated, interfacial nonradiative recombination is suppressed, and interface stress is released by the ATH deposited on the perovskite film, leading to longer carrier lifetimes and enhancement in open-circuit voltage (VOC) and fill factor (FF) of the PSCs. With obvious improvement, VOC and FF of 1.159 V and 0.796 for the control device are raised to 1.178 V and 0.826 for the ATH-modified device, respectively. Finally, during an operational stability measurement of more than 1000 h, the ATH-treated PSC exhibited better moisture resistance, thermal persistence, and light stability.

Precise Control of Crystallization and Phase-Transition with Green Anti-Solvent in Wide-Bandgap Perovskite Solar Cells with Open-Circuit Voltage Exceeding 1.25 V.

Wide-bandgap perovskite solar cells (PSCs) have attracted a lot of attention due to their application in tandem solar cells. However, the open-circuit voltage (VOC ) of wide-bandgap PSCs is dramatically limited by high defect density existing at the interface and bulk of the perovskite film. Here, an anti-solvent optimized adduct to control perovskite crystallization strategy that reduces nonradiative recombination and minimizes VOC deficit is proposed. Specifically, an organic solvent with similar dipole moment, isopropanol (IPA) is added into ethyl acetate (EA) anti-solvent, which is beneficial to form PbI2 adducts with better crystalline orientation and direct formation of α-phase perovskite. As a result, EA-IPA (7-1) based 1.67 eV PSCs deliver a power conversion efficiency of 20.06% and a VOC of 1.255 V, which is one of the remarkable values for wide-bandgap around 1.67 eV. The findings provide an effective strategy for controlling crystallization to reduce defect density in PSCs.

Application of Natural Molecules in Efficient and Stable Perovskite Solar Cells.

Perovskite solar cells (PSCs), one of the most promising photovoltaic technologies, have been widely studied due to their high power conversion efficiency (PCE), low cost, and solution processability. The architecture of PSCs determines that high PCE and stability are highly dependent on each layer and the related interface, where nonradiative recombination occurs. Conventional synthetic chemical materials as modifiers have disadvantages of being toxic and costly. Natural molecules with advantages of low cost, biocompatibility, and being eco-friendly, and have improved PCE and stability by modifying both functional layers and interface. In this review, we discuss the roles of natural molecules on PSCs devices in terms of the perovskite active layer, interface, carrier transport layers (CTLs), and substrate. Finally, the summary and outlook for the future development of natural molecule-modified PSCs are also addressed.

Precise modulation strategies of 2D/3D perovskite heterojunctions in efficient and stable solar cells.

2D/3D perovskite heterojunctions exhibit promising prospects in the improvement of efficiency and stability of perovskite solar cells (PSCs). However, many challenges remain in the development of high-quality 2D/3D heterojunctions, such as a reliable pathway to control the perovskite phase and generally poor performance in inverted (p-i-n) devices, which limit their commercialization. Fortunately, many excellent works have proposed lots of strategies to solve these challenges, which have triggered a new wave of research on 2D/3D perovskite heterojunctions in recent years. In this paper, the latest research progress and the critical factors involved in the modulating mechanisms of PSCs with 2D/3D heterojunctions have been summarized and laid out systematically. The advantages of constructing 2D/3D perovskite heterojunctions in PSCs are highlighted, and the problems and related solutions of low-dimensional perovskites as passivation layers towards high-performance PSCs are also discussed in depth. Finally, the prospects of 2D/3D perovskite heterojunctions utilized in the passivation strategies to further improve the photovoltaic performance of PSCs in the future have been presented.

Stabilizing Buried Interface via Synergistic Effect of Fluorine and Sulfonyl Functional Groups Toward Efficient and Stable Perovskite Solar Cells.

The interfacial defects and energy barrier are main reasons for interfacial nonradiative recombination. In addition, poor perovskite crystallization and incomplete conversion of PbI2 to perovskite restrict further enhancement of the photovoltaic performance of the devices using sequential deposition. Herein, a buried interface stabilization strategy that relies on the synergy of fluorine (F) and sulfonyl (S=O) functional groups is proposed. A series of potassium salts containing halide and non-halogen anions are employed to modify SnO2/perovskite buried interface. Multiple chemical bonds including hydrogen bond, coordination bond and ionic bond are realized, which strengthens interfacial contact and defect passivation effect. The chemical interaction between modification molecules and perovskite along with SnO2 heightens incessantly as the number of S=O and F augments. The chemical interaction strength between modifiers and perovskite as well as SnO2 gradually increases with the increase in the number of S=O and F. The defect passivation effect is positively correlated with the chemical interaction strength. The crystallization kinetics is regulated through the compromise between chemical interaction strength and wettability of substrates. Compared with Cl-, all non-halogen anions perform better in crystallization optimization, energy band regulation and defect passivation. The device with potassium bis (fluorosulfonyl) imide achieves a tempting efficiency of 24.17%.

Spontaneous Interface Healing by a Dynamic Liquid-Crystal Transition for High-Performance Perovskite Solar Cells.

Low-temperature solution processing of thin-film semiconductors is more cost-effective than traditional vacuum processing; however, it leads to more defects during fast bulk crystallization and residual tensile stress. Herein, a new strategy of dynamic liquid-crystal transition (DLCT) is developed to solve these problems in one step. The design principle is used to suggest that the DLCT molecule should firstly interact with the perovskite grains in the bulk and meanwhile go through a dynamic transition to spontaneously heal the interface. A thermotropic LC molecule (CBO6SS6OCB) is then designed to demonstrate the strategy. The LC interacting with perovskite colloid forms an intermediate adduct to retard the crystallization. The annealing processes stimulate the concentrated LC solid, causing it to flow to the electron transport layer to release the residual stress to attain improved electron extraction. Consequently, the device efficiency is increased to 24.38%, where its VOC of 1.184 V is among the best for the formamidine-based perovskite solar cells. Furthermore, the ambient stability (93.0% of initial efficiency after 2000 h of aging) and light stability (96.3% of initial efficiency after 500 h of aging) are much improved. This work conceives a new engineering of additive phase transition for high-performance perovskite solar cells.