Chemisorption-Induced Robust and Homogeneous Tungsten Disulfide Interlayer Enables Stable PEDOT-Free Organic Solar Cells with Over 19% Efficiency.

Construction of a high-quality charge transport layer (CTL) with intimate contact with the substrate via tailored interface engineering is crucial to increase the overall charge transfer kinetics and stability for a bulk-heterojunction (BHJ) organic solar cell (OSC). Here, we demonstrate a surface chemistry strategy to achieve a homogeneous composite hole transport layer (C-HTL) with robust substrate contact by self-assembling two-dimensional tungsten disulfide (WS2) nanosheets on a thin molybdenum oxide (MoO3) film-evaporated indium tin oxide (ITO) substrate. It is found that over such a well-defined C-HTL, WS2 is homogeneously tethered on the ITO/MoO3 substrate stemming from the strong electronic coupling interaction between the building blocks, which enables a favorable interfacial configuration in terms of uniformity. As a result, the D18:L8-BO-based OSC with C-HTL exhibits a power conversion efficiency (PCE) of 19.23%, an 11% improvement over the WS2-based control device, and the highest efficiency among single-junction PEDOT-free binary BHJ OSCs.

Beyond Conventional Enhancements: Self-Organization of a Buffer Material on Tin Oxide as a Game-Changer for Improving the Performance of Inverted Organic Solar Cells.

Inverted organic solar cells (OSCs) have garnered significant interest due to their remarkable stability. In this study, the efficiency and stability of inverted OSCs are enhanced via the in situ self-organization (SO) of an interfacial modification material Phen-NaDPO onto tin oxide (SnO2). During the device fabrication, Phen-NaDPO is spin-coated with the active materials all together on SnO2. Driven by the interactions with SnO2 and the thermodynamic forces due to its high surface energy and the convection flow, Phen-NaDPO spontaneously migrates to the SnO2 interface, resulting in the formation of an in situ modification layer on SnO2. This self-organization of Phen-NaDPO not only effectively reduces the work function of SnO2, but also enhances the ordered molecular stacking and manipulates the vertical morphology of the active layer, which suppress the surface trap-assisted recombination and minimize the charge extraction. As a result, the SO devices based on PM6:Y6 exhibit significantly improved photovoltaic performance with an enhanced power conversion efficiency of 17.62%. Moreover, the stability of the SO device is also improved. Furthermore, the SO ternary devices based on PM6:D18:L8-BO achieved an impressive PCE of 18.87%, standing as one of the highest values for single-junction inverted organic solar cells to date.

Origin of the Additive-Induced VOC Change in Non-Fullerene Organic Solar Cells.

Additives are often used to adjust the morphology of the active layer to improve the performance of organic solar cells (OSCs). Here, taking typical high-efficiency non-fullerene systems as examples, the effect of the additive on the device performance in non-fullerene OSCs is systematically investigated. Surprisingly, an unpresented VOC change is observed in the opposite direction of the two typical systems (PM6:Y6 and PTB7-Th: ITIC) appearing after the incorporation of the additive DIO, which can be affected by the morphological differences as indicated by the several morphological studies. The bewildering VOC change caused by the additive in different material systems is supposed to originate from the different energy level variations as verified by the energy level studies. Molecular dynamic (MD) and density functional theory (DFT) calculations are also included to get an insight into the dynamic of the additive-induced morphological differences that are supposed to contribute to the energy level changes. Combining a series of morphological and energic studies as well as the theoretical calculations, the origin of unforeseeable VOC changes caused by additives in non-fullerene OSCs is clarified, and provides in-depth insights into the effects of additives on device performance.

Wide Bandgap Conjugated Polymers Based on Difluorobenzoxadiazole for Efficient Non-Fullerene Organic Solar Cells.

Wide bandgap polymers with a donor-acceptor alternating structure play a key role in constructing high-efficiency organic solar cells (OSCs). However, only a handful of high-performance polymers are available owing to the limited choices of acceptor units. 5,6-Difluorobenzo[c][1,2,5]oxadiazole (ffBX) is a promising acceptor unit with high ionization potential, and can afford high charge carrier mobility and strong aggregation for the resulting polymers. Historically, ffBX is successfully used in constructing high-performance polymer donors for fullerene-based OSCs. However, this unit is far less been explored in non-fullerene OSCs. In this work, three ffBX-based wide bandgap polymers (Oc00, Oc25, and Oc50) with varied solubilizing side chain content for application in non-fullerene OSCs are reported. The polymers show matched energy levels and complementary optical absorption with the state-of-the-art non-fullerene acceptor Y6. Moreover, the polymer solubility, solid state packing, and bulk-heterojunction morphology are finely tuned via side chain engineering. Encouragingly, a decent efficiency of 14.25% is realized by the polymer Oc25 when blended with Y6 due to the efficient charge transport and favorable active layer morphology. These results suggest the promising prospect of ffBX in constructing high-performance polymer donors for non-fullerene OSCs.

Mechanism of the Alcohol-Soluble Ionic Organic Interlayer in Organic Solar Cells.

In this article combining density functional theory (DFT) calculations and corresponding experimental measurements, the adsorption behaviors and working mechanism of the alcohol-soluble ionic organic interlayer on different electrode substrates were studied. The results suggest that, when the ionic organic bipyridine salt interlayer (FPyBr) is adsorbed on the Ag surface, Br- will break away from molecule chains and form new chemical bonds with the Ag substrate, as confirmed by both the X-ray photoelectron spectroscopy (XPS) study and DFT study for the first time. Charges are further found to transfer to the Ag substrate from the new interlayer molecular structure without Br-, resulting in adsorption dipoles directed from Ag to the interlayer. Moreover, the direction of the intrinsic dipole of the molecule itself on the Ag substrate is also verified, which is the same as that of the adsorption dipole. Subsequently, the superposition of the two dipoles results in a large reduction of the Ag substrate work function. In addition, the dipole formation mechanism of the interlayer on the ITO surface was also studied. The change in the work function of the ITO substrate by this interlayer is found to be smaller than that of Ag as confirmed by both a DFT study and scanning Kelvin probe microscopy (SKPM) results, which is mainly due to the reversed direction of the molecular intrinsic dipole with respect to the interfacial dipole. The worst device performance of organic solar cells based on the ITO-FPyBr substrate is considered to be one of the consequences of the feature. The findings here are of great importance for the study of the mechanism of the ionic organic interlayer in organic electronic devices, providing insightful understandings on how to further improve the material and device performance.

Molecular Engineering Enhances the Charge Carriers Transport in Wide Band-Gap Polymer Donors Based Polymer Solar Cells.

The novel and appropriate molecular design for polymer donors are playing an important role in realizing high-efficiency and high stable polymer solar cells (PSCs). In this work, four conjugated polymers (PIDT-O, PIDTT-O, PIDT-S and PIDTT-S) with indacenodithiophene (IDT) and indacenodithieno [3,2-b]thiophene (IDTT) as the donor units, and alkoxy-substituted benzoxadiazole and benzothiadiazole derivatives as the acceptor units have been designed and synthesized. Taking advantages of the molecular engineering on polymer backbones, these four polymers showed differently photophysical and photovoltaic properties. They exhibited wide optical bandgaps of 1.88, 1.87, 1.89 and 1.91 eV and quite impressive hole mobilities of 6.01 × 10-4, 7.72 × 10-4, 1.83 × 10-3, and 1.29 × 10-3 cm2 V-1 s-1 for PIDT-O, PIDTT-O, PIDT-S and PIDTT-S, respectively. Through the photovoltaic test via using PIDT-O, PIDTT-O, PIDT-S and PIDTT-S as donor materials and [6,6]-phenyl-C-71-butyric acid methyl ester (PC71BM) as acceptor materials, all the PSCs presented the high open circuit voltages (Vocs) over 0.85 V, whereas the PIDT-S and PIDTT-S based devices showed higher power conversion efficiencies (PCEs) of 5.09% and 4.43%, respectively. Interestingly, the solvent vapor annealing (SVA) treatment on active layers could improve the fill factors (FFs) extensively for these four polymers. For PIDT-S and PIDTT-S, the SVA process improved the FFs exceeding 71%, and ultimately the PCEs were increased to 6.05%, and 6.12%, respectively. Therefore, this kind of wide band-gap polymers are potentially candidates as efficient electron-donating materials for constructing high-performance PSCs.

High Sensitivity Polymer Visible-Near Infrared Photodetectors via an Inverted Device Structure and Manipulation of Injection Barrier Height.

Visible-near infrared photodetectors are reported with excellent overall device parameters from conjugated polymers with different optical bandgaps by optimal design in device structure and optimizing the thickness of the photoactive layer in nanoscale. The best visible-near infrared photodetectors show high detectivity (D*) of 1.7 × 10(13) Jones at a wavelength of 710 nm, which is among one of the best results of polymer photodetectors reported to date.

Recent Advances in Organic Photovoltaics: Device Structure and Optical Engineering Optimization on the Nanoscale.

Organic photovoltaic (OPV) devices, which can directly convert absorbed sunlight to electricity, are stacked thin films of tens to hundreds of nanometers. They have emerged as a promising candidate for affordable, clean, and renewable energy. In the past few years, a rapid increase has been seen in the power conversion efficiency of OPV devices toward 10% and above, through comprehensive optimizations via novel photoactive donor and acceptor materials, control of thin-film morphology on the nanoscale, device structure developments, and interfacial and optical engineering. The intrinsic problems of short exciton diffusion length and low carrier mobility in organic semiconductors creates a challenge for OPV designs for achieving optically thick and electrically thin device structures to achieve sufficient light absorption and efficient electron/hole extraction. Recent advances in the field of OPV devices are reviewed, with a focus on the progress in device architecture and optical engineering approaches that lead to improved electrical and optical characteristics in OPV devices. Successful strategies are highlighted for light wave distribution, modulation, and absorption promotion inside the active layer of OPV devices by incorporating periodic nanopatterns/nanostructures or incorporating metallic nanomaterials and nanostructures.

Revealing the AcOH-Induced Dissolution Mechanism of Alcohol-Soluble Interlayers.

Water/alcohol-soluble cathode interlayers are widely utilized in organic electronic devices. However, the mechanism by which acetic acid (AcOH) facilitates the solubility of neutral cathode interlayers in water/alcohol remains unclear. This paper focuses on the AcOH-induced dissolution mechanism of neutral cathode interlayer materials and establishes quantitative relationships for chemical reactions. It was found that AcOH could react acid-base with the amino groups of PFN or PDIN, resulting in the formation of trace amounts of quaternary ammonium salts, which ultimately enhance the solubility of PFN and PDIN in methanol. Additionally, this study clarifies the debate about the role of neutral cathode interlayers in organic electronic devices: It is primarily the unprotonated groups of water/alcohol-soluble cathode interlayers that play a critical role in interfacial modification rather than the protonated groups produced by postacid reaction, which lays an important theoretical foundation for the development of high-performance interfacial materials.

Processing the Interlayer and Optimizing the Active Layer by One-Step Dissolution Compensation in Organic Solar Cells.

Optimized morphology of the active layer and electrode interface is critical for obtaining high-performance organic solar cells. However, achieving this typically involves a multifaceted, sequential process that renders outcomes unpredictable. Here, by exploiting the dissolution compensation, we propose a one-step method that integrates interlayer fabrication and a controllable morphology optimization. Taking an "out of the box" approach, we incorporate the good solvent of the active layer into the interlayer solution to act as dissolution compensation, breaking the orthogonal solvent principles to allow the morphology of the active layer to evolve to an optimized state while the interface layer is being processed. Using two commercially available material systems, D18:Y6 and D18:L8-BO, as examples, it was found that the JSC and fill factor (FF) device can be improved by using an appropriate ratio of the compensation solvent chloroform in the interlayer solution. As a result, the power conversion efficiency of the device based on the two state-of-the-art systems can be increased by about 7.5% (D18:Y6, from 17.04 to 18.31%; D18:L8-BO, from 17.97 to 19.31%). This one-step strategy has been shown to be universally applicable to other diverse systems and provides a simple yet reliable method for accurately depositing high-quality interlayers with an optimized active layer morphology in high-performance organic solar cells and other solution-processable organic electronics.

Environmental remediation approaches by nanoscale zero valent iron (nZVI) based on its reductivity: a review.

The fast rise of organic and metallic pollution has brought significant risks to human health and the ecological environment. Consequently, the remediation of wastewater is in extremely urgent demand and has received increasing attention. Nanoscale zero valent iron (nZVI) possesses a high specific surface area and distinctive reactive interfaces, which offer plentiful active sites for the reduction, oxidation, and adsorption of contaminants. Given these abundant functionalities of nZVI, it has undergone significant and extensive studies on environmental remediation, linking to various mechanisms, such as reduction, oxidation, surface complexation, and coprecipitation, which have shown great promise for application in wastewater treatment. Among these functionalities of nZVI, reductivity is particularly important and widely adopted in dehalogenation, and reduction of nitrate, nitro compounds, and metal ions. The following review comprises a short survey of the most recent reports on the applications of nZVI based on its reductivity. It contains five sections, an introduction to the theme, chemical reduction applications, electrolysis-assisted reduction applications, bacterium-assisted reduction applications, and conclusions about the reported research with perspectives for future developments. Review and elaboration of the recent reductivity-dependent applications of nZVI may not only facilitate the development of more effective and sustainable nZVI materials and the protocols for comprehensive utilization of nZVI, but may also promote the exploration of innovative remediation approaches based on its reductivity.

An A-D-A'-D-A-Type Narrow Bandgap Electron Acceptor Based on Selenophene-Flanked Diketopyrrolopyrrole for Sensitive Near-Infrared Photodetection.

Near-infrared organic photodetectors possess great application potential in night vision, optical communication, and image sensing, but their development is limited by the lack of narrow bandgap organic semiconductors. A-D-A'-D-A-type molecules, featuring multiple intramolecular charge transfer effects, offer a robust framework for achieving near-infrared light absorption. Herein, we report a novel A-D-A'-D-A-type narrow bandgap electron acceptor named DPPSe-4Cl, which incorporates a selenophene-flanked diketopyrrolopyrrole (Se-DPP) unit as its central A' component. This molecule demonstrates exceptional near-infrared absorption properties with an absorption onset reaching 1120 nm and a low optical bandgap of 1.11 eV, owing to the strong electron-withdrawing ability and quinoidal resonance effect induced by the Se-DPP unit. By implementing a doping compensation strategy assisted by Y6 to reduce the trap density in the photoactive layer, the optimized organic photodetector based on DPPSe-4Cl exhibited efficient spectral response and remarkable sensitivity in the range of 300-1100 nm. Particularly, a specific detectivity surpassing 1012 Jones in the wavelength range of 410-1030 nm is achieved. This work offers a promising approach for developing highly sensitive visible to near-infrared broadband photodetection technology using organic semiconductors.

Ni-CoSe2 heterojunction coated by N-doped carbon for modified separators of high-performance Li-sulfur batteries.

Functional separators modified by transition metal compounds have been proven to be effective in suppressing the shuttle effect of polysulfides and accelerating sluggish electrode dynamics in lithium-sulfur batteries (LSBs). However, the behaviors of heterojunctions composed of transition metals and their compounds in LSBs are still rarely studied. Herein, we report a novel Ni-CoSe2 heterostructure coated with nitrogen-doped carbon. Compared to homogeneous cobalt diselenide, it exhibits much stronger adsorption and catalytic conversion abilities towards polysulfides. With the modified separators, the lithium-sulfur batteries exhibit significantly improved capacity retention and reduced polarization during cycling.

Graphene oxide as a multi-functional additive for compatilizer, enhancer, and barrier in ethylene vinyl alcohol copolymer/aramid pulp composites.

To improve the thermal, mechanical, and barrier properties of ethylene vinyl alcohol copolymer (EVOH)/aramid pulp (AP), graphene oxide (GO) was used as a compatilizer, enhancer, and barrier to fabricate EVOH-based composites. The results showed that graphene oxide serves as an ideal compatilizer to reinforce the interfacial action between the EVOH matrix and aramid pulp. The EVOH/AP/GO composite presented the best combination of thermal stability, tensile strength, oxygen barrier, and heat deformation temperature by adding only 1 wt% graphene oxide, compared to those of pure EVOH. Moreover, both scanning electron microscopy (SEM) and polarized optical microscopy (POM) photographs demonstrated that the aramid pulp dispersed homogeneously into the EVOH resin with the addition of 1 wt% graphene oxide. Our work provides a novel and facile way for producing a prominent EVOH-based composite, which can be potentially used in packaging fields in the future.

An Anisotropic Hydrogel by Programmable Ionic Crosslinking for Sequential Two-Stage Actuation under Single Stimulus.

As one of the most important anisotropic intelligent materials, bi-layer stimuli-responsive actuating hydrogels have proven their wide potential in soft robots, artificial muscles, biosensors, and drug delivery. However, they can commonly provide a simple one-actuating process under one external stimulus, which severely limits their further application. Herein, we have developed a new anisotropic hydrogel actuator by local ionic crosslinking on the poly(acrylic acid) (PAA) hydrogel layer of the bi-layer hydrogel for sequential two-stage bending under a single stimulus. Under pH = 13, ionic-crosslinked PAA networks undergo shrinking (-COO-/Fe3+ complexation) and swelling (water absorption) processes. As a combination of Fe3+ crosslinked PAA hydrogel (PAA@Fe3+) with non-swelling poly(3-(1-(4-vinylbenzyl)-1H-imidazol-3-ium-3-yl)propane-1-sulfonate) (PZ) hydrogel, the as-prepared PZ-PAA@Fe3+ bi-layer hydrogel exhibits distinct fast and large-amplitude bidirectional bending behavior. Such sequential two-stage actuation, including bending orientation, angle, and velocity, can be controlled by pH, temperature, hydrogel thickness, and Fe3+ concentration. Furthermore, hand-patterning Fe3+ to crosslink with PAA enables us to achieve various complex 2D and 3D shape transformations. Our work provides a new bi-layer hydrogel system that performs sequential two-stage bending without switching external stimuli, which will inspire the design of programmable and versatile hydrogel-based actuators.

Efficient Cathode Buffer Material Based on Dibenzothiophene-S,S-dioxide for Both Conventional and Inverted Organic Solar Cells.

A novel conjugated molecule (PBSON) based on a main chain composed of bis(dibenzothiophene-S,S-dioxide) fused cyclopentadiene and side chains containing amino groups is presented as an efficient cathode buffer material (CBM) for organic solar cells (OSCs). PBSON showed a deep highest occupied molecular orbital (HOMO) energy level of -6.01 eV, which was beneficial for building hole-blocking layers at the cathodes of OSCs. The energy bandgap of PBSON reached 3.17 eV, implying high transmittance to visible and near-infrared light, which meant PBSON should be suitable for the applications to most inverted OSCs. The scanning Kelvin probe microscopy measurement and theoretical calculation on the PBSON/cathode interfacial interaction proved the excellent work function-regulating abilities of PBSON for various cathodes, suggesting that PBSON could promote the formation of Ohmic contacts at the cathodes and thus improve the transport and collection of electron carriers for OSCs. The characterization of electron-only devices demonstrated the good electron-transporting performance of PBSON at the cathodes. In the conventional OSCs, it was hinted that PBSON might restrain the infiltrations of evaporated cathode atoms into the active films, consequently reducing the reverse leakage currents. As a result, PBSON was able to boost the power conversion efficiencies (PCEs) by 58.2 and 56.4% for both conventional and inverted OSCs of the typical PTB7:PC71BM system, respectively, as compared to the unadorned devices. In terms of the classical PTB7-Th:PC71BM system, substantial increases in PCEs could also be found with PBSON interlayers, which were 54.7 and 59.8% for the conventional device and inverted device, respectively. Therefore, PBSON is a kind of promising CBM for realizing both conventional and inverted OSCs of high performance.

Recent Advances in Halide Perovskite Resistive Switching Memory Devices: A Transformation from Lead-Based to Lead-Free Perovskites.

Due to their remarkable electrical and light absorption characteristics, hybrid organic-inorganic perovskites have recently gained popularity in several applications such as optoelectronics, lasers, and light-emitting diodes. Through this, there has recently been an increase in the use of halide perovskites (HPs) in resistive switching (RS) devices. However, lead-based (Pb-based) perovskites are notorious for being unstable and harmful to the environment. As a result, lead-free (Pb-free) perovskite alternatives are being investigated in achieving the long-term and sustainable use of RS devices. This work describes the characteristics of Pb-based and Pb-free perovskite RS devices. It also presents the recent advancements of HP RS devices, including the selection strategies of perovskite structures. In terms of resistive qualities, the directions of both HPs appear to be identical. Following that, the possible impact of switching from Pb-based to Pb-free HPs is examined to determine the requirement in RS devices. Finally, this work discusses the opportunities and challenges of HP RS devices in creating a stable, efficient, and sustainable memory storage technology.

High-quality WS2 film as a hole transport layer in high-efficiency non-fullerene organic solar cells.

Liquid-exfoliated 2D transition metal disulfides (TMDs) are potential substitutes for poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) as hole transport layers (HTLs) in Organic Solar Cells (OSCs). Herein, high-yield and high-quality WS2 flake layers are prepared by comprehensively controlling the initial concentration, sonication processing time and centrifugal speed. The WS2 layers deposited on in situ transparent indium tin oxide (ITO) without plasma treatment show higher uniformity and conductivity than that formed on ITO after plasma treatment. With a significant increase in the short-circuit current density (JSC), the power conversion efficiency (PCE) of PM6:Y6-based non-fullerene OSCs using optimized WS2 as the HTL is higher than that using PEDOT:PSS as the HTL(15.75% vs. 15.31%). Combining the morphology characteristics with carrier recombination characteristics, the higher quality of the ITO/WS2 composite substrate leads to better charge transport and a lower bimolecular recombination rate in OSCs, thereby improving the device performance.

Accelerating charge transfer via nonconjugated polyelectrolyte interlayers toward efficient versatile photoredox catalysis.

One of the challenges for high-efficiency single-component-based photoredox catalysts is the low charge transfer and extraction due to the high recombination rate. Here, we demonstrate a strategy to precisely control the charge separation and transport efficiency of the catalytic host by introducing electron or hole extraction interlayers to improve the catalytic efficiency. We use simple and easily available non-conjugated polyelectrolytes (NCPs) (i.e., polyethyleneimine, PEI; poly(allylamine hydrochloride), PAH) to form interlayers, wherein such NCPs consist of the nonconjugated backbone with charge transporting functional groups. Taking CdS as examples, it is shown that although PEI and PAH are insulators and therefore do not have the ability to conduct electricity, they can form good electron or hole transport extraction layers due to the higher charge-transfer kinetics of pendant groups along the backbones, thereby greatly improving the charge transfer capability of CdS. Consequently, the resultant PEI-/PAH-functionalized nanocomposites exhibit significantly enhanced and versatile photoredox catalysis.

An Alternating Copolymer Derived from Indolo[3,2-b]carbazole and 4,7-Di(thieno[3,2-b]thien-2-yl)-2,1,3-benzothiadiazole for Photovoltaic Cells.

An alternating narrow bandgap conjugated copolymer (PICZ-DTBT, E(g) = 1.83 eV) derived from 5,11-di(9-heptadecanyl)indolo[3,2-b]carbazole and 4,7-di(thieno[3,2-b]thien-2-yl)-2,1,3-benzothiadiazole (DTBT), was prepared by the palladium-catalyzed Suzuki coupling reaction. The resultant polymer absorbs light from 350-690 nm, exhibits two absorbance peaks at around 420 and 570 nm and has good solution processibility and thermal stability. The highest occupied molecular orbital (HOMO) energy level and lowest unoccupied molecular orbital (LUMO) level of the copolymer determined by cyclic voltammetry were about -5.18 and -3.35 eV, respectively. Prototype bulk heterojunction photovoltaic cells from solid-state composite films based on PICZ-DTBT and [6,6]-phenyl-C(71) butyric acid methyl ester (PC(71) BM), show power conversion efficiencies up to 2.4% under 80 mW · cm(-2) illumination (AM1.5) with an open-circuit voltage of V(oc) = 0.75 V, a short current density of J(sc) = 6.02 mA · cm(-2) , and a fill factor of 42%. This indicates that the copolymer PICZ-DTBT is a viable electron donor material for polymeric solar cells.