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.

Constructing Additives Synergy Strategy to Doctor-Blade Efficient CH3 NH3 PbI3 Perovskite Solar Cells under a Wide Range of Humidity from 45% to 82.

Perovskite solar cells (PSCs) have emerged as one of the most promising and competitive photovoltaic technologies, and doctor-blading is a facile and robust deposition technique to efficiently fabricate PSCs in large scale, especially matching with roll-to-roll process. Herein, it demonstrates the encouraging results of one-step, antisolvent-free doctor-bladed methylammonium lead iodide (CH3 NH3 PbI3, MAPbI3 ) PSCs under a wide range of humidity from 45% to 82%. A synergy strategy of ionic-liquid methylammonium acetate (MAAc) and molecular phenylurea additives is developed to modulate the morphology and crystallization process of MAPbI3 perovskite film, leading to high-quality MAPbI3 perovskite film with large-size crystal, low defect density, and ultrasmooth surface. Impressive power conversion efficiency (PCE) of 20.34% is achieved for doctor-bladed PSCs under the humidity over 80% with a device structure of ITO/SnO2 /MAPbI3 /Spiro-OMeTAD/Ag. It is the highest PCEs for one-step solution-processed MAPbI3 PSCs without antisolvent assistance. The research provides a facile and robust large-scale deposition technique to fabricate highly efficient and stable PSCs under a wide range of humidity, even with the humidity over 80%.

Tuning Hole Transport Properties via Pyrrole Derivation for High-Performance Perovskite Solar Cells.

Hole transport materials (HTMs) with high hole mobility, good band alignment and ease of fabrication are highly desirable for perovskite solar cells (PSCs). Here, we designed and synthesized novel organic HTMs, named T3, which can be synthesized in high yields with commercially available materials, featuring a substituted pyrrole core and triphenylamine peripheral arms. The capability of functionalization in the final synthetic step provides an efficient way to obtain a variety of T3-based HTMs with tunable energy levels and other properties. Among them, fluorine-substituted T3 (T3-F) exhibits the best band alignment and hole extraction properties, leading to PSCs with outstanding PCEs of 24.85 % and 24.03 % (certified 23.46 %) for aperture areas of 0.1 and 1 cm2 , respectively. The simple structure and tunable performance of T3 can inspire further optimization for efficient PSCs.

A 4-Arm Small Molecule Acceptor with High Photovoltaic Performance.

Manipulating the backbone of small molecule acceptors (SMAs) is of particular importance in developing efficient organic solar cells (OSCs). The common design is constructing 2-arm SMAs with linear or curved backbones. Herein, we report an acceptor 4A-DFIC with a 4-arm backbone unexpectedly generated in the reaction of an electron-rich aromatic diamine and hexaketocyclohexane. Single-crystal X-ray diffraction analysis indicates the rigid and twisted molecular plane and the effective molecular stacking of 4A-DFIC in solid state. 4A-DFIC shows a low band gap of 1.40 eV and excellent light-harvesting capability from visible to near-infrared region. Binary and ternary OSCs based on 4A-DFIC gave power conversion efficiencies (PCEs) of 15.76 % and 18.60 % (certified 18.1 %), respectively, which are the highest PCEs for multi-arm SMA-based OSCs to date.

Molecular Engineering of Potent Sensitizers for Very Efficient Light Harvesting in Thin-Film Solid-State Dye-Sensitized Solar Cells.

Dye-sensitized solar cells (DSSCs) have shown significant potential for indoor and building-integrated photovoltaic applications. Herein we present three new D-A-π-A organic sensitizers, XY1, XY2, and XY3, that exhibit high molar extinction coefficients and a broad absorption range. Molecular modifications of these dyes, featuring a benzothiadiazole (BTZ) auxiliary acceptor, were achieved by introducing a thiophene heterocycle as well as by shifting the position of BTZ on the conjugated bridge. The ensuing high molar absorption coefficients enabled the fabrication of highly efficient thin-film solid-state DSSCs with only 1.3 µm mesoporous TiO2 layer. XY2 with a molar extinction coefficient of 6.66 × 10(4) M(-1) cm(-1) at 578 nm led to the best photovoltaic performance of 7.51%.

Quantum-confined ZnO nanoshell photoanodes for mesoscopic solar cells.

We present a photoanode for dye-sensitized solar cell (DSC) based on ZnO nanoshell deposited by atomic layer deposition at 150 °C on a mesoporous insulating template. An ultrathin layer of ZnO between 3 and 6 nm, which exhibits quantum confinement effect, is found to be sufficient to transport the photogenerated electrons to the external contacts and exhibits near-unity collection efficiency. A 6 nm ZnO nanoshell on a 2.5 µm mesoporous nanoparticle Al2O3 template yields photovoltaic power conversion efficiency (PCE) of 4.2% in liquid DSC. Perovskite absorber (CH3NH3PbI3) based solid state solar cells made with similar ZnO nanostructures lead to a high PCE of 7%.

A hybrid electron donor comprising cyclopentadithiophene and dithiafulvenyl for dye-sensitized solar cells.

Two new photosensitizers featured with a cyanoacrylic acid electron acceptor (A) and a hybrid electron donor (D) of cyclopentadithiophene and dithiafulvenyl, either directly linked or separated by a phenyl ring, were synthesized and characterized. Both of them undergo two reversible oxidations and strongly absorb in the visible spectral region due to a photo-induced intramolecular charge-transfer (ICT) transition. To a great extent, the electronic interaction between the D and A units is affected by the presence of a phenyl spacer. Without a phenyl ring, the D unit appears more difficult to oxidize due to a strong electron-withdrawing effect of the A moiety. In sharp contrast, the insertion of the phenyl ring between the D and A units leads to a broken π-conjugation and therefore, the oxidation potentials remain almost unchanged compared to those of an analogue without the A group, suggesting that the electronic coupling between D and A units is relatively weak. As a consequence, the lowest-energy absorption band shows a slight hypsochromic shift upon the addition of the phenyl spacer, indicative of an increased HOMO-LUMO gap. In turn, the direct linkage of D and A units leads to an effective π-conjugation, thus substantially lowering the HOMO-LUMO gap. Moreover, the application in dye-sensitized solar cells was investigated, showing that the power conversion efficiency increases by the insertion of the phenyl unit.

Regulating a benzodifuran single molecule redox switch via electrochemical gating and optimization of molecule/electrode coupling.

We report a novel strategy for the regulation of charge transport through single molecule junctions via the combination of external stimuli of electrode potential, internal modulation of molecular structures, and optimization of anchoring groups. We have designed redox-active benzodifuran (BDF) compounds as functional electronic units to fabricate metal-molecule-metal (m-M-m) junction devices by scanning tunneling microscopy (STM) and mechanically controllable break junctions (MCBJ). The conductance of thiol-terminated BDF can be tuned by changing the electrode potentials showing clearly an off/on/off single molecule redox switching effect. To optimize the response, a BDF molecule tailored with carbodithioate (-CS2(-)) anchoring groups was synthesized. Our studies show that replacement of thiol by carbodithioate not only enhances the junction conductance but also substantially improves the switching effect by enhancing the on/off ratio from 2.5 to 8.

Influence of the donor size in D-π-A organic dyes for dye-sensitized solar cells.

We report two new molecularly engineered push-pull dyes, i.e., YA421 and YA422, based on substituted quinoxaline as a π-conjugating linker and bulky-indoline moiety as donor and compared with reported IQ4 dye. Benefitting from increased steric hindrance with the introduction of bis(2,4-dihexyloxy)benzene substitution on the quinoxaline, the electron recombination between redox electrolyte and the TiO2 surface is reduced, especially in redox electrolyte employing Co(II/III) complexes as redox shuttles. It was found that the open circuit photovoltages of IQ4, YA421, and YA422 devices with cobalt-based electrolyte are higher than those with iodide/triiodide electrolyte by 34, 62, and 135 mV, respectively. Moreover, the cells employing graphene nanoplatelets on top of gold spattered film as a counter electrode (CE) show lower charge-transfer resistance compared to platinum as a CE. Consequently, YA422 devices deliver the best power conversion efficiency due to higher fill factor, reaching 10.65% at AM 1.5 simulated sunlight. Electrochemical impedance spectroscopy and transient absorption spectroscopy analysis were performed to understand the electrolyte influence on the device performances with different counter electrode materials and donor structures of donor-π-acceptor dyes. Laser flash photolysis experiments indicate that even though the dye regeneration of YA422 is slower than that of the other two dyes, the slower back electron transfer of YA422 contributes to the higher device performance.

High-Efficiency Perovskite Solar Cells with Improved Interfacial Charge Extraction by Bridging Molecules.

The interface between the perovskite layer and electron transporting layer is a critical determinate for the performance and stability of perovskite solar cells (PSCs). The heterogeneity of the interface critically affects the carrier dynamics at the buried interface. To address this, a bridging molecule, (2-aminoethyl)phosphonic acid (AEP), is introduced for the modification of SnO2/perovskite buried interface in n-i-p structure PSCs. The phosphonic acid group strongly bonds to the SnO2 surface, effectively suppressing the surface carrier traps and leakage current, and uniforming the surface potential. Meanwhile, the amino group influences the growth of perovskite film, resulting in higher crystallinity, phase purity, and fewer defects. Furthermore, the bridging molecules facilitate the charge extraction at the interface, as indicated by the femtosecond transient reflection (fs-TR) spectroscopy, leading to champion power conversion efficiency (PCE) of 26.40% (certified 25.98%) for PSCs. Additionally, the strengthened interface enables improved operational durability of ≈1400 h for the unencapsulated PSCs under ISOS-L-1I protocol.

Realizing Stable Perovskite Solar Cells with Efficiency Exceeding 25.6% Through Crystallization Kinetics and Spatial Orientation Regulation.

Organic-inorganic hybrid perovskites have emerged as highly promising candidates for photovoltaic applications, owing to the exceptional optoelectronic properties and low cost. Nonetheless, the performance and stability of solar cells suffer from the defect states of perovskite films aroused by non-optically active phases and non-centralized crystal orientation. Herein, a versatile organic molecule, Hydantoin, to modulate the crystallization of perovskite, is developed. Benefiting from the diverse functional groups, more spatially oriented perovskite films with high crystallinity are formed. This enhancement is accompanied by a conspicuous reduction in defect density, yielding efficiency of 25.66% (certified 25.15%), with superb environmental stability. Notably, under the standard measurement conditions (ISOS-L-1I), the maximum power point (MPP) output maintains 96.8% of the initial efficiency for 1600 h and exhibits excellent ion migration suppression. The synergistic regulation of crystallization and spatial orientation offers novel avenues for propelling perovskite solar cell (PSC) development.

Probing charge transfer in benzodifuran-C60 dumbbell-type electron donor-acceptor conjugates: ground- and excited-state assays.

Rigid electron donor-acceptor conjugates (1-3) that combine π-extended benzodifurans as electron donors and C60 molecules as electron acceptors with different linkers have been synthesized and investigated with respect to intramolecular charge-transfer events. Electrochemistry, fluorescence, and transient absorption measurements revealed tunable and structure-dependent charge-transfer processes in the ground and excited states. Our experimental findings are underpinned by density-functional theory calculations.

Subnanometer Ga2O3 tunnelling layer by atomic layer deposition to achieve 1.1 V open-circuit potential in dye-sensitized solar cells.

Herein, we present the first use of a gallium oxide tunnelling layer to significantly reduce electron recombination in dye-sensitized solar cells (DSC). The subnanometer coating is achieved using atomic layer deposition (ALD) and leading to a new DSC record open-circuit potential of 1.1 V with state-of-the-art organic D-π-A sensitizer and cobalt redox mediator. After ALD of only a few angstroms of Ga(2)O(3), the electron back reaction is reduced by more than an order of magnitude, while charge collection efficiency and fill factor are increased by 30% and 15%, respectively. The photogenerated exciton separation processes of electron injection into the TiO(2) conduction band and the hole injection into the electrolyte are characterized in detail.

Crystallization and Orientation Modulation Enable Highly Efficient Doctor-Bladed Perovskite Solar Cells.

With the rapid rise in perovskite solar cells (PSCs) performance, it is imperative to develop scalable fabrication techniques to accelerate potential commercialization. However, the power conversion efficiencies (PCEs) of PSCs fabricated via scalable two-step sequential deposition lag far behind the state-of-the-art spin-coated ones. Herein, the additive methylammonium chloride (MACl) is introduced to modulate the crystallization and orientation of a two-step sequential doctor-bladed perovskite film in ambient conditions. MACl can significantly improve perovskite film quality and increase grain size and crystallinity, thus decreasing trap density and suppressing nonradiative recombination. Meanwhile, MACl also promotes the preferred face-up orientation of the (100) plane of perovskite film, which is more conducive to the transport and collection of carriers, thereby significantly improving the fill factor. As a result, a champion PCE of 23.14% and excellent long-term stability are achieved for PSCs based on the structure of ITO/SnO2/FA1-xMAxPb(I1-yBry)3/Spiro-OMeTAD/Ag. The superior PCEs of 21.20% and 17.54% are achieved for 1.03 cm2 PSC and 10.93 cm2 mini-module, respectively. These results represent substantial progress in large-scale two-step sequential deposition of high-performance PSCs for practical applications.

Combined Vacuum Evaporation and Solution Process for High-Efficiency Large-Area Perovskite Solar Cells with Exceptional Reproducibility.

Organic-inorganic hybrid perovskites exhibit outstanding performances in perovskite solar cells (PSCs). However, the complex solution chemistry of perovskites precursors renders it difficult to prepare large-area devices in a reproducible way, which is a prerequisite for the technology to make an impact beyond lab scale. Vacuum processing, instead, is an established technology for large-scale coating of thin films. However, with respect to the hybrid perovskites it is highly challenging due to the high vapor pressure of the organic ammonium halide. In this work, vacuum evaporation of lead iodide and solution processing of organic ammonium halide is combined to produce large-area homogeneous perovskite films with large grains in a highly reproducible way. The resulting PSCs achieve a power conversion efficiency (PCE) of 24.3% (certified 23.9%) on small area (0.10 cm2 ), 24.0% (certified 23.7%) on large area (1 cm2 ) and 20.0% for minimodule (16 cm2 ), and maintain 90% of its initial efficiency after 1000 h 1-sun operation. The vacuum evaporation prevents advert environmental effects on lead halide formation and guarantees a reproducible fabrication of high-quality large-area perovskite films, which opens a promising way for large-scale fabrication of perovskite optoelectronics.

A spectroscopic and computational study of a photoinduced cross-dehydrogenative coupling reaction of a stable semiquinone radical.

Norrish-type-II reaction on a semiquinone radical: stable semiquinone radicals serve as novel molecular platforms on which a Norrish-type-II photoreaction can be initiated. A detailed reaction scheme involving a 1,5-hydrogen transfer followed by a cyclization step that finally leads to a new C-C bond formation could be verified. Transient absorption spectroscopy and DFT calculations trace convincingly the intermediates and transition states along the reaction path.

Avoiding diffusion limitations in cobalt(III/II)-tris(2,2'-bipyridine)-based dye-sensitized solar cells by tuning the mesoporous TiO2 film properties.

Dye-sensitized solar cells based on electrolytes containing cobalt complexes as redox shuttles typically suffer a major limitation in terms of slow diffusion of those couples through the mesoporous TiO(2) film. This results in a drop of the photocurrent density, particularly at high incident light intensities, reducing the overall cell performance. This work illustrates how tuning the four characteristic parameters of the mesoporous TiO(2) layer, namely film thickness, particle size, pore size and porosity, by simply optimizing the TiCl(4) post-treatment, completely eliminates diffusion problems of cobalt(III/II) tris(2,2'-bipyridine) and at the same time maximizes the short-circuit photocurrent density. As a result, a power conversion efficiency of 10.0% at AM 1.5 G 100 mW cm(-2) was reached in conjunction with an organic sensitizer.

A new generation of platinum and iodine free efficient dye-sensitized solar cells.

We report a series of cobalt complexes with various polypyridyl ligands, where the oxidation potential is tuned from 0.17 to 0.34 V vs. ferrocene. The highest occupied molecular orbitals (HOMO) of the cobalt complexes were stabilized by adding electron acceptor groups on pyridyl or replacing pyridyl by pyrazole. These complexes are then used as one-electron redox mediators in dye sensitized solar cells (DSSCs) together with polymer based cathode resulting in an excellent performance. The performance of DSSCs using the molecularly engineered cobalt redox shuttle and poly(3,4-alkylthiophenes) based cathode is better than the triiodide/iodide redox shuttle with platinized cathode. The use of high surface area poly(3,4-propylenedioxythiophene) based nanoporous layers allows higher catalytic activity thus minimizing the electrode-electrolyte interface issues.

Multifunctional succinate additive for flexible perovskite solar cells with more than 23% power-conversion efficiency.

Flexible perovskite solar cells (FPSCs) have emerged as power sources in versatile applications owing to their high-efficiency characteristics, excellent flexibility, and relatively low cost. Nevertheless, undesired strain in perovskite films greatly impacts the power-conversion efficiency (PCE) and stability of PSCs, particularly in FPSCs. Herein, a novel multifunctional organic salt, methylammonium succinate, which can alleviate strain and reinforce grain boundaries, was incorporated into the perovskite film, leading to relaxed microstrain and a lower defect concentration. As a result, a PCE of 25.4% for rigid PSCs and a record PCE of 23.6% (certified 22.5%) for FPSCs have been achieved. In addition, the corresponding FPSCs exhibited excellent bending durability, maintaining ∼85% of their initial efficiency after bending at a 6 mm radius for 10 000 cycles.

Collaborative Assembly of a Fluorine-Enriched Heterostructured Solid Electrolyte Interphase for Ultralong-Life Lithium Metal Batteries.

Lithium metal batteries have become potential high-energy storage devices because lithium metal has excellent theoretical capacity and low reduction potential. Unfortunately, the reckless growth of lithium dendrites leads to the decrease in Coulombic efficiency and the attenuation of cycle performance. Herein, we propose a collaborative assembly approach for a fluorine-enriched heterostructured solid electrolyte interphase (SEI) on lithium metal to enable stable and ultralong-life lithium metal batteries. The fluorine-enriched heterostructured SEI consists of an artificial precursor substrate K2ZrF6 and an epigenetically assembled LiF layer, and the composite structure cooperatively realizes the rapid conduction of Li+ ions and inhibits the formation of lithium dendrites. Benefiting from the heterostructured SEI, the symmetric cell exhibits an ultralong-time stable cycle of more than 7000 h at a high current and capacity density (4 mA cm-2 and 4 mA h cm-2, respectively), much longer than that of the lithium cell. Besides, the LiFePO4 full battery (LFP||Li-Zr) enables substantially enhanced cyclability over 800 cycles at 1 C. This work paves the way for dendrite-free and long-life lithium metal batteries with well-balanced heterostructured SEI engineering.