JIANG ZHI XUAN

A multifunctional conjugated benzene ammonium halide is introduced to enhance phase purity, reduce trap‐state density, and suppress nonradiative charge recombination. Blade‐coated solar cells based on stabilized formamidinium‐dominant perovskite compositions deliver an impressive efficiency of 22.0% and an improved operational stability.

Abstract

Currently, blade‐coated perovskite solar cells (PSCs) with high power conversion efficiencies (PCEs), that is, greater than 20%, normally employ methylammonium lead tri‐iodide with a sub‐optimal bandgap. Alloyed perovskites with formamidinium (FA) cation have narrower bandgap and thus enhance device photocurrent. However, FA‐alloyed perovskites show low phase stability and high moisture sensitivity. Here, it is reported that incorporating 0.83 molar percent organic halide salts (OHs) into perovskite inks enables phase‐pure, highly crystalline FA‐alloyed perovskites with extraordinary optoelectronic properties. The OH molecules modulate the crystal growth, enhance the phase stability, passivate ionic defects at the surface and/or grain boundaries, and enhance the moisture stability of the perovskite film. A high efficiency of 22.0% under 1 sun illumination for blade‐coated PSCs is demonstrated with an open‐circuit voltage of 1.18 V, corresponding to a very small voltage deficit of 0.33 V, and significantly improved operational stability with 96% of the initial efficiency retained under one sun illumination for 500 h.

An environmentally stable acetamidinium (Aa⁺)‐incorporated MAPbI₃ film is successfully fabricated via hot casting in air. The large Aa⁺ immobilizes ions and improves crystal structure of MAPbI₃ through strong coordination bonds. The corresponding Aa–MAPbI₃ device shows 20.68% power conversion efficiency. Its 80% is maintained after 1300 h testing at 85 °C and 85 relative humidity (RH)%.

Ion migration in organometal halide perovskite solar cell (OHPSC) and crystal structure evolution of organometal halide perovskites (OHPVSKs) in air are considered as one of the critical factors for unstable performance and of the urgent issues for the reliability of OHPSCs. Herein, a novel cation of acetamidinium (Aa⁺) with stronger coordinated bond with I⁻ than methylammonium is induced into OHPVSK to stabilize its crystal structure. By incorporating Aa⁺ ions into OHPVSKs, the power conversion efficiency (PCE) of OHPSC without an encapsulation can maintain higher than 75% of its initial PCE after a 200 h humidity (60–80% relative humidity (RH) in air) or a 24 h thermal stress test (85 °C in dry N₂). The Aa–MAPbI₃ device exhibits an outstanding efficiency of 20.68%, and over 80% of initial PCE is maintained after a 1300 h damp heat as encapsulated. This novel cation can be easily incorporated into OHPVSK via a hot casting process in air with a high environmental tolerance as compared with that from the conventional coating process, which suffers from sophisticated crystallization steps and a strict processing atmosphere. It extends processing windows for OHPVSK fabrication and provides a promising path toward mass production and further commercialization.

An effective intramolecular locking strategy is designed by introducing the central electron‐deficient quinoid to unfused ring A₁–D–A₂–D–A₁‐type nonfullerene small molecule acceptors (NF‐SMAs). The polymer solar cells (PSCs) based on BT2FIDT‐4Cl with difluorobenzothiadiazole central unit show a power conversion efficiency (PCE) of 12.5% with V _oc of near 1 V. This is the best result for nonfused ring NF‐SMAs with electron‐deficient A₂ unit in binary PSCs.

Abstract

Here, a pair of A₁–D–A₂–D–A₁ unfused ring core‐based nonfullerene small molecule acceptors (NF‐SMAs), BO2FIDT‐4Cl and BT2FIDT‐4Cl is synthesized, which possess the same terminals (A₁) and indacenodithiophene unit (D), coupling with different fluorinated electron‐deficient central unit (difluorobenzoxadiazole or difluorobenzothiadiazole) (A₂). BT2FIDT‐4Cl exhibits a slightly smaller optical bandgap of 1.56 eV, upshifted highest occupied molecular orbital energy levels, much higher electron mobility, and slightly enhanced molecular packing order in neat thin films than that of BO2FIDT‐4Cl . The polymer solar cells (PSCs) based on BT2FIDT‐4Cl:PM7 yield the best power conversion efficiency (PCE) of 12.5% with a V _oc of 0.97 V, which is higher than that of BO2FIDT‐4Cl ‐based devices (PCE of 10.4%). The results demonstrate that the subtle modification of A₂ unit would result in lower trap‐assisted recombination, more favorable morphology features, and more balanced electron and hole mobility in the PM7:BT2FIDT‐4Cl blend films. It is worth mentioning that the PCE of 12.5% is the highest value in nonfused ring NF‐SMA‐based binary PSCs with high V _oc over 0.90 V. These results suggest that appropriate modulation of the quinoid electron‐deficient central unit is an effective approach to construct highly efficient unfused ring NF‐SMAs to boost PCE and V _oc simultaneously.

In this work, two novel A‐DA₁D‐A‐type asymmetric SMAs are developed, namely C‐shaped BDTP‐4F and S‐shaped BTDTP‐4F . As a result, C‐shape BDTP‐4F‐based device yields a higher PCE (15.24%) than that of S‐shape BTDTP‐4F‐based device (13.12%), while for traditional A‐D‐A type SMAs, IDTP‐4F with S‐shape conformation is better than that of C‐shape IDTTP‐4F.

Abstract

Understanding the conformation effect on molecular packing, miscibility, and photovoltaic performance is important to open a new avenue for small‐molecule acceptor (SMA) design. Herein, two novel acceptor–(donor‐acceptor1‐donor)–acceptor (A‐DA1D‐A)‐type asymmetric SMAs are developed, namely C‐shaped BDTP‐4F and S‐shaped BTDTP‐4F . The BDTP‐4F ‐based polymer solar cells (PSCs) with PM6 as donor, yields a power conversion efficiency (PCE) of 15.24%, significantly higher than that of the BTDTP‐4F ‐based device (13.12%). The better PCE for BDTP‐4F ‐based device is mainly attributed to more balanced charge transport, weaker bimolecular recombination, and more favorable morphology. Additionally, two traditional A‐D‐A‐type SMAs (IDTP‐4F and IDTTP‐4F ) are also synthesized to investigate the conformation effect on morphology and device performance. Different from the device result above, here, IDTP‐4F with S‐shape conformation outperforms than IDTTP‐4F with C‐shape conformation. Importantly, it is found that for these two different types of SMA, the better performing binary blend has similar morphological characteristics. Specifically, both PM6:BDTP‐4F and PM6:IDTP‐4F blend exhibit perfect nanofibril network structure with proper domain size, obvious face‐on orientation and enhance donor‐acceptor interactions, thereby better device performance. This work indicates tuning molecular conformation plays pivotal role in morphology and device effciciency, shining a light on the molecular design of the SMAs.

Operationally stable and high‐efficiency all‐inorganic CsPbI_2.5Br_0.5 mixed‐halide perovskite solar cells are achieved for the first time, by introducing the different amount of PbI₂ in the all‐inorganic perovskite precursor. The 1.02‐PbI₂ devices maintain 76% of their initial efficiency (17.1%) after continuous power output at the maximum power point for 420 h under continuous full‐sun, AM 1.5G illumination (100 mW cm⁻²).

Abstract

Cesium‐based inorganic perovskites have recently attracted great research focus due to their excellent optoelectronic properties and thermal stability. However, the operational instability of all‐inorganic perovskites is still a main hindrance for the commercialization. Herein, a facile approach is reported to simultaneously enhance both the efficiency and long‐term stability for all‐inorganic CsPbI_2.5Br_0.5 perovskite solar cells via inducing excess lead iodide (PbI₂) into the precursors. Comprehensive film and device characterizations are conducted to study the influences of excess PbI₂ on the crystal quality, passivation effect, charge dynamics, and photovoltaic performance. It is found that excess PbI₂ improves the crystallization process, producing high‐quality CsPbI_2.5Br_0.5 films with enlarged grain sizes, enhanced crystal orientation, and unchanged phase composition. The residual PbI₂ at the grain boundaries also provides a passivation effect, which improves the optoelectronic properties and charge collection property in optimized devices, leading to a power conversion efficiency up to 17.1% with a high open‐circuit voltage of 1.25 V. More importantly, a remarkable long‐term operational stability is also achieved for the optimized CsPbI_2.5Br_0.5 solar cells, with less than 24% degradation drop at the maximum power point under continuous illumination for 420 h.

An autonomously longitudinal scaffold constructed by the interspersion of in situ polymerized methyl methacrylate in PbI₂ is introduced to effectively eliminate the dependence of sequential deposition on mesoporous TiO₂, and is applied in planar perovskite solar cells, with excellent performance. Moreover, this scaffold's cross‐linking grains are capable of releasing mechanical stress, impeding ion migration, and water/oxygen permeation.

Abstract

Sequential deposition is certified as an effective technology to obtain high‐performance perovskite solar cells (PVSCs), which can be derivatized into large‐scale industrial production. However, dense lead iodide (PbI₂) causes incomplete reaction and unsatisfactory solution utilization of perovskite in planar PVSCs without mesoporous titanium dioxide as a support. Here, a novel autonomously longitudinal scaffold constructed by the interspersion of in situ self‐polymerized methyl methacrylate (sMMA) in PbI₂ is introduced to fabricate efficient PVSCs with excellent flexural endurance and environmental adaptability. By this strategy perovskite solution can be confined within an organic scaffold with vertical crystal growth promoted, effectively inhibiting exciton accumulation and recombination at grain boundaries. Additionally, sMMA cross‐linked perovskite network can release mechanical stress and occupy the main channels for ion migration and water/oxygen permeation to significantly improve operational stability, which opens up a new strategy for the commercial development of large‐area PVSCs in flexible electronics.

A synthetic polyhalide ligand (2‐picolyl)amine triiodide as a molecular glue is used to passivate halide vacancies at grain boundaries directionally and throughout grain bulk of perovskites. The inverted perovskite solar cells after passivation are allowed to be more efficient, and are profoundly stabilized in both ambient air and light‐soaking circumstances.

The fundamental instability of hybrid perovskite solar cells originates from the considerable halide vacancies. Furthermore, the local roles of halide vacancies between grain boundaries and grain bulk generally conflict, thus inhibiting complete passivation. To overcome this obstacle, a rational polyhalide ligand, di‐(2‐picolyl)amine triiodide, is designed as a molecular “glue” to achieve comprehensive passivation. Unlike a monohalide ligand, this ligand has multiple iodide ions and a quasiplanar tridentate chelation capability, contributing to directional passivation along the grain boundaries and overall passivation throughout the grain bulk. Using this molecular glue passivation, the best inverted solar cell yields an efficiency of 20.02%. Moreover, the relative stability of this cell in ambient air (≈40% humidity, 800 h aging) and under light‐soaking conditions (500 h aging) is profoundly enhanced by 33.33% and 22.26%, respectively. Herein, important insights into the design of passivating molecules to achieve low‐defect perovskites toward the development of multifunctional devices are provided.

Ambipolar black phosphorene (BP) nanosheets with tailored thicknesses concurrently enhance carrier extraction at both the electron‐transport layer/perovskite and hole‐transport layer/perovskite interfaces for high‐efficiency perovskite solar cells, demonstrating the appealing implementation of BP as a dual‐functional carrier‐transport material for a diversity of optoelectronic devices, including solar cells, photodetectors, sensors, light‐emitting diodes, etc.

Abstract

2D black phosphorene (BP) carries a stellar set of physical properties such as conveniently tunable bandgap and extremely high ambipolar carrier mobility for optoelectronic devices. Herein, the judicious design and positioning of BP with tailored thickness as dual‐functional nanomaterials to concurrently enhance carrier extraction at both electron transport layer/perovskite and perovskite/hole transport layer interfaces for high‐efficiency and stable perovskite solar cells is reported. The synergy of favorable band energy alignment and concerted cascade interfacial carrier extraction, rendered by concurrent positioning of BP, delivered a progressively enhanced power conversion efficiency of 19.83% from 16.95% (BP‐free). Investigation into interfacial engineering further reveals enhanced light absorption and reduced trap density for improved photovoltaic performance with BP incorporation. This work demonstrates the appealing characteristic of rational implementation of BP as dual‐functional transport material for a diversity of optoelectronic devices, including photodetectors, sensors, light‐emitting diodes, etc.

A secondary bond‐constructed isotropic electron transfer 3D‐network is fabricated based on biomass‐derived demethylated kraft lignin (D_MeKL). Secondary bonds successfully modify the contact of the perylene diiminde/active layer and conjugate‐blocked linkages in D_MeKL, to overcome anisotropy‐aroused electron transfer barriers at the cathode interface. The enhancement of cross/vertical‐sectional electron transfer performance and well‐matched energy levels yields the highest power conversion efficiency reported among biomaterial‐based organic solar cells.

Abstract

Fabricating high‐efficient electron transporting interfacial layers (ETLs) with isotropic features is highly desired for all‐directional electron transfer/collection from an anisotropic active layer, achieving excellent power conversion efficiency (PCEs) on nonfullerene acceptor (NFA) organic solar cells (OSCs). The complicated synthesis and cost‐consumption in exploring versatile materials arouse great interest in the development of binary‐doping interlayers without phase separation and flexible manipulation. Herein, for the first time, a novel cathode interfacial layer based on biomass‐derived demethylated kraft lignin (D_MeKL) is proposed. Features of multiple phenolic‐hydroxyl (PhOH) and uniform‐distributed render D_MeKL to exhibit an excellent bonding capacity with amino terminal substituted perylene diiminde (PDIN), and successfully form a high‐efficient isotropic electron transfer 3D network. Synchronously, secondary bonds completely modify conjugate‐blocked linkages of D_MeKL, significantly enhance the electron transporting performance on cross‐section and vertical‐sections, and repair the contact of PDIN with active layer. The D_MeKL/PDIN‐based 3D‐network exhibits well‐matched work function (WF) (–4.34 eV) with cathode (–4.30 eV) and energy level of electron acceptor (–4.11 eV). D_MeKL/PDIN‐based NFAs‐OSC shows excellent short‐circuit current density (26.61 mA cm^–2) and PCE (16.02%) beyond the classic PDIN‐based NFA‐OSC (25.64 mA cm^–2, 15.41%), which is the highest PCEs among biomaterials interlayers. The results supply a novel method to achieve high‐efficient cathode interlayer for NFAs‐OSCs.

Herein, covalent functionalization of group 14 layered materials and insights into their potential in electrochemical applications are reported. Specifically, 2D siloxene, germanane, and methylgermanane, with their fast heterogeneous electron transfer rates, portray promising properties for dopamine sensing as well as oxygen reduction and hydrogen evolution catalysis.

Abstract

2D monoelemental group 14 materials beyond graphene, such as silicene and germanene, have recently gained a lot of attention. Covalent functionalization of group 14 layered materials can lead to significant tuning of their properties. While optical and electronic properties of germanene, silicene, and their derivatives have been studied in detail previously, there is no information on their electrochemistry and toxicity. Herein, electrochemical applications of 2D siloxene, germanane, and methylgermanane, specifically for detection of an important biomarker, dopamine, as well as catalyzation of oxygen reduction and hydrogen evolution reactions, which are important in energy applications, are explored. Among the three materials, germanane portrays most superior properties for the electrochemical applications mentioned. All three materials possess fast heterogeneous electron transfer rates, relative to bare glassy carbon electrodes. In addition, toxicity studies of these materials are conducted to gain insights on their possible harmful effects toward human health. The results of this study show siloxene nontoxic while germanane and methylgermanane impose dose‐dependent toxicity. Interestingly, methylation successfully reduce the toxicity of methylgermanane at lower concentrations. These studies provide fundamental insights into electrochemical and toxic properties of functionalized group 14 layered materials for future electrochemical applications.

The undercoordinated ionic defects at heterojunction interfaces remain challenges that limit the performances and stability of perovskite photoelectric devices. A self‐phase separated doping strategy is developed to link multilayer heterojunction interfaces including both the energy level and trap states, paving a novel route for nonequilibrium distributed dopants to solve the key challenge of interface defects.

Abstract

In perovskite solar cells (PSCs), the interfaces of the halide perovskite/electron transport layer (ETL) and ETL/metal oxide electrode (MOE) always attract and trap free carriers via the surface electrostatic force, altering quasi‐Fermi level (E _Fq) splitting of contact interfaces, and significantly limit the charge extraction efficiency and intrinsic stability of devices. Herein, a graded “bridge” is first reported to link the MOE and perovskite interfaces by self vertical phase separation doping (PSD), diminishing the side effect of notorious ionic defects via both reinforced interface E _bi and the vacancies filling. Experimental and theoretical results prove that the inhomogeneous distribution of CsF in the bulk or surface of PC₆₁BM would not only form metal–oxygen (M–O) dipole on MOE, reinforcing the interface E _bi, but also create a graded energy bridge to alleviate the disadvantage of band offset raised by the enhanced interface E _bi, which significantly avoid the carrier accumulation and recombination at defective interfaces. Employing PSD, the power conversion efficiency of the devices approaches 21% with a high open‐circuit voltage (1.148 V) and delivers a high stability of 89% after aging 60 days in atmosphere without encapsulation, which is the highest efficiency of organic electron transport layers for n–i–p PSCs.