Highly Macroporous Polyimide with Chemical Versatility Prepared from Poly(amic acid) Salt-Stabilized High Internal Phase Emulsion Template.

Macroporous polymers have gained significant attention due to their unique mass transport and size-selective properties. In this study, we focused on Polyimide (PI), a high-performance polymer, as an ideal candidate for macroporous structures. Despite various attempts to create macroporous PI (Macro PI) using emulsion templates, challenges remained, including limited chemical diversity and poor control over pore size and porosity. To address these issues, we systematically investigated the role of poly(amic acid) salt (PAAS) polymers as macrosurfactants and matrices. By designing 12 different PAAS polymers with diverse chemical structures, we achieved stable high internal phase emulsions (HIPEs) with >80 vol % internal volume. The resulting Macro PIs exhibited exceptional porosity (>99 vol %) after thermal imidization. We explored the structure-property relationships of these Macro PIs, emphasizing the importance of controlling pore size distribution. Furthermore, our study demonstrated the utility of these Macro PIs as separators in Li-metal batteries, providing stable charging-discharging cycles. Our findings not only enhance the understanding of emulsion-based macroporous polymers but also pave the way for their applications in advanced energy storage systems and beyond.

Properties and Applications of Self-Healing Polymeric Materials: A Review.

Self-healing polymeric materials, engineered to autonomously self-restore damages from external stimuli, are at the forefront of sustainable materials research. Their ability to maintain product quality and functionality and prolong product life plays a crucial role in mitigating the environmental burden of plastic waste. Historically, initial research on the development of self-healing materials has focused on extrinsic self-healing systems characterized by the integration of embedded healing agents. These studies have primarily focused on optimizing the release of healing agents and ensuring rapid self-healing capabilities. In contrast, recent advancements have shifted the focus towards intrinsic self-healing systems that utilize their inherent reactivity and interactions within the matrix. These systems offer the advantage of repeated self-healing over the same damaged zone, which is attributed to reversible chemical reactions and supramolecular interactions. This review offers a comprehensive perspective on extrinsic and intrinsic self-healing approaches and elucidates their unique properties and characteristics. Furthermore, various self-healing mechanisms are surveyed, and insights from cutting-edge studies are integrated.

Monitoring of 137Cs, 239+240Pu, and 90Sr in the marine environment of South Korea and their impact on marine biota: 10 years after the Fukushima accident.

This study conducted an analysis of the behavior of radionuclides and assessment their radioactive risk based on seawater and seabed sediment samples gathered from the East, South, and Yellow Seas of South Korea over the period from 2011 to 2020. The distribution for each radionuclides in seawater obtained from the East, South, and Yellow Seas were similar. However, the concentrations of 137Cs and 239+240Pu in sediments from the East Sea were observed to be higher compared to those from the South and Yellow Seas. This variation can be attributed to differences in the ocean inflow, water column properties, and seabed characteristics among the seas around South Korea. There were no statistically significant differences between the radioactive concentrations of seawater and seabed samples collected before and after the Fukushima accident, and no areas with unusually high radiation levels were detected. Using the distribution coefficient (Kds) and the concentration ratio (CR) calculated from the 2011-to-2020 data, we evaluated the radiological impact on fish. The ERICA tool was utilized to assess these data, and indicated a negligible radiological risk from radioactivity in the seawater, seabed sediments, and marine biota in the South Korean Ocean.

Recent progress of eco-friendly manufacturing process of efficient perovskite solar cells.

Perovskite solar cells (PSCs) have the potential to produce solar energy at a low cost, with flexibility, and high power conversion efficiency (PCE). However, there are still challenges to be addressed before mass production of PSCs, such as prevention from degradation under external stresses and the uniform, large-area formation of all layers. Among them, the most challenging aspect of mass production of PSCs is creating a high-quality perovskite layer using environmentally sustainable processes that are compatible with industry standards. In this review, we briefly introduce the recent progresses upon eco-friendly perovskite solutions/antisolvents and film formation processes. The eco-friendly production methods are categorized into two: (1) employing environmentally friendly solvents for perovskite precursor ink/solution, and (2) replacing harmful, volatile antisolvents or even limiting their use during the perovskite film formation process. General considerations and criteria for each category are provided, and detailed examples are presented, specifically focused on the works have done since 2021. In addition, the importance of controlling the crystallization behavior of the perovskite layer is highlighted to develop antisolvent-free perovskite formation methods.

Wide-Band-Gap (2.0 eV) Perovskite Solar Cells with a VOC of 1.325 V Fabricated by a Green-Solvent Strategy.

Perovskite-based tandem solar cells are promising candidates for next-generation photovoltaic devices. However, the defects caused by ion migration cause a large deficit of open-circuit voltage (VOC) in conventional wide-band-gap perovskite films. Here, we present a new strategy that employs nontoxic acetic acid and isopropanol as solvents to deposit a perovskite film with a 2.0 eV band gap in an ambient atmosphere. The in situ formed acetate anions strongly stabilize the intrinsic defects in perovskite films. These features effectively improve the phase stability of 2.0 eV Cs0.2FA0.8PbI0.9Br2.1 perovskite, allowing the VOC to reach 1.325 V and the corresponding power conversion efficiency to reach 10.62%, which is close to the state-of-art performance of perovskite solar cells employing perovskite around a 2.0 eV band gap.

Perovskite single-crystal thin films: preparation, surface engineering, and application.

Perovskite single-crystal thin films (SCTFs) have emerged as a significant research hotspot in the field of optoelectronic devices owing to their low defect state density, long carrier diffusion length, and high environmental stability. However, the large-area and high-throughput preparation of perovskite SCTFs is limited by significant challenges in terms of reducing surface defects and manufacturing high-performance devices. This review focuses on the advances in the development of perovskite SCTFs with a large area, controlled thickness, and high quality. First, we provide an in-depth analysis of the mechanism and key factors that affect the nucleation and crystallization process and then classify the methods of preparing perovskite SCTFs. Second, the research progress on surface engineering for perovskite SCTFs is introduced. Third, we summarize the applications of perovskite SCTFs in photovoltaics, photodetectors, light-emitting devices, artificial synapse and field-effect transistor. Finally, the development opportunities and challenges in commercializing perovskite SCTFs are discussed.

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.

Green and Facile Synthesis of Hybrid Composites with Ultralow Dielectric Properties from Water-Soluble Polyimide and Dual-Porous Silica Nanoparticles.

Here, we proposed an eco-friendly synthetic method for synthesizing hybrid composites with ultralow dielectric properties at high frequencies up to 28 GHz for true 5G communication from aqueous aromatic polyimide (PI) polymers and dual-porous silica nanoparticles (DPS). The "one-step" water-based emulsion template method was used to synthesize the macroporous silica nanoparticles (MPS). A substantially negative ζ potential was produced along the surface of MPS by the poly(vinylpyrrolidone)-based chemical functionalization, enabling excellent aqueous dispersion stability. The water-soluble poly(amic acid) (PAA), as a precursor to PI, was also "one-step" polymerized in an aqueous solution. The MPS were dispersed in a water-soluble PAA matrix to create the hybrid composite films using an entirely water-based approach. The compatibility between the PAA matrix and MPS was elucidated by investigating relatively diverse end-terminated PAAs (with either amine or carboxyl group). It was also discovered that, during a thermally activated imidization reaction, the MPS are in situ converted into the DPS with macro- and microporous structures (with a surface area of 1522.4 m2/g). The thermal, dielectric, mechanical, and morphological characteristics of each composite film were examined, while the amount of DPS in the PI matrix varied from 1 to 20 wt %. With the addition of 5 wt % DPS as an optimum condition, it showed ultralow dielectric properties, with the Dk and Df being 1.615 and 0.003 at a frequency of 28 GHz, respectively, and compatible mechanical properties, with the tensile strength and elastic modulus being 78.2 MPa and 0.32 GPa, respectively. These results can comprehensively satisfy various physical properties required as a substrate material for 5G communication devices.

Highly Self-Healable Polymeric Coating Materials Based on Charge Transfer Complex Interactions with Outstanding Weatherability.

In this study, we prepare highly self-healable polymeric coating materials using charge transfer complex (CTC) interactions. The resulting coating materials demonstrate outstanding thermal stability (1 wt% loss thermal decomposition temperature at 420 °C), rapid self-healing kinetics (in 5 min), and high self-healing efficiency (over 99%), which is facilitated by CTC-induced multiple interactions between the polymeric chains. In addition, these materials exhibit excellent optical properties, including transmittance over 91% and yellow index (YI) below 2, and show enhanced weatherability with a ΔYI value below 0.5 after exposure to UV light for 72 h. Furthermore, the self-healable coating materials developed in this study show outstanding mechanical properties by overcoming the limitations of conventional self-healing materials.

Microwave-assisted ultrafast in-situ growth of N-doped carbon quantum dots on multiwalled carbon nanotubes as an efficient electrocatalyst for photovoltaics.

Multiwalled carbon nanotubes (MWCNTs) are at the forefront of metal-free electrocatalysts, however, the performance is still limited due to lack of functionality and dispersion. Coupling of MWCNTs with nitrogen doped carbon quantum dots (NCQDs) can impart the required active sites and dispersion. For the purpose, NCQDs are generally attached to MWCNTs by multistep processing, such as NCQDs synthesis, followed by their complex purification, surface activation, and crosslinking with MWCNT. The scalability of such a multistep process is limited, which is addressed by direct microwave-assisted growth of NCQDs on MWCNT. The concentration of reactants of NCQDs synthesis was optimized (with respect to MWCNTs), to achieve controlled direct growth of NCQDs on MWCNTs. The proposed strategy significantly reduced time and energy consumption, along with providing an overlapped interface for the fast charge transfer. Moreover, NCQDs' growth effectively modulated the surface reactivity and internal band structure of the MWCNTs. In response, dye-sensitized solar cells employing NCQDs modified MWCNT as a counter electrode showed 50% higher photovoltaic performance as compared to bare MWCNTs.

Crystal Size Effect on Carrier Transport of Microscale Perovskite Junctions via Soft Contact.

To reduce the size of optoelectronic devices, it is essential to understand the crystal size effect on the carrier transport through microscale materials. Here, we show a soft contact method to probe the properties of irregularly shaped microscale perovskite crystals by employing a movable liquid metal electrode to form a self-adaptative deformable electrode-perovskite-electrode junction. Accordingly, we demonstrate that (1) the photocurrents of perovskite quantum dot films and microplatelets show profound differences regarding both the on/off ratio and the response time upon light illumination; and (2) small-size perovskite (<50 µm) junctions may show negative differential resistance (NDR) behavior, whereas the NDR phenomenon is absent in large-size perovskite junctions within the same bias regime. Our studies provide a method for studying arbitrary-shaped crystals without mechanical damage, assisting the understanding of the photogenerated carriers transport through microscale crystals.

A Heterocyclic Polyurethane with Enhanced Self-Healing Efficiency and Outstanding Recovery of Mechanical Properties.

A functional polyurethane based on the heterocyclic group was synthesized and its self-healing and mechanical properties were examined. To synthesize a heterocyclic polyurethane, a polyol and a heterocyclic compound with di-hydroxyl groups at both ends were blended and the blended solution was reacted with a crosslinker containing multiple isocyanate groups. The heterocyclic polyurethane demonstrates better self-healing efficiency than the conventional polyurethane with no heterocyclic groups. Furthermore, unlike the conventional self-healing materials, the heterocyclic polyurethane examined in this study shows an outstanding recovery of the mechanical properties after the self-healing process. These results are attributed to the unique supramolecular network resulting from the strong hydrogen bonding interaction between the urethane group and the heterocyclic group in the heterocyclic polyurethane matrix.

Layer-by-Layer Self-Assembly of Hollow Nitrogen-Doped Carbon Quantum Dots on Cationized Textured Crystalline Silicon Solar Cells for an Efficient Energy Down-Shift.

Enhancing the efficiency of the crystalline silicon solar cell (c-Si SC) by coating the energy shifting layer with quantum dots (QDs) is a recent approach to efficiently utilize the high-energy spectrum of light. Carbon QDs are an attractive candidate for such applications; however, a small Stokes shift and nonuniform coating due to high aggregation are the bottlenecks to fully utilize their potential. For this purpose, here, we propose a layer-by-layer self-assembled uniform coating of eco-friendly red-emissive hollow nitrogen-doped carbon QDs (NR-CQDs) as an efficient energy-down-shifting layer. A unique hollow and conjugated structure of NR-CQDs was designed to achieve a large Stokes shift (UV-excited red emission) with a quantum yield (QY) comparable to Cd/Pb QDs. A highly uniform coating of intrinsically negatively charged NR-CQDs on c-Si SCs was achieved by cationizing the c-Si SC by bovine serum albumin (BSA) under mildly acidic conditions. By an opposite-charge-assisted, self-assembled overlayer, the short-circuit current density (Jsc) and power-conversion efficiency were increased by 5.8%, which is attributed to the large Stokes shift (255 nm) and high QY. Blue-emissive undoped carbon QDs were synthesized for comparison with the proposed NR-CQDs to elucidate the significance of the novel proposed structure.

Inorganic material passivation of defects toward efficient perovskite solar cells.

Surface passivation with organic materials is one of the most effective and popular strategies to improve the stability and efficiency of perovskite solar cells (PSCs). However, the secondary bonding formed between organic molecules and perovskite layers is still not strong enough to protect the perovskite absorber from degradation initialized by oxygen and water attacking at defects. Recently, passivation with inorganic materials has gradually been favored by researchers due to the effectiveness of chemical and mechanical passivation. Lead-containing substances, alkali metal halides, transition elements, oxides, hydrophobic substances, etc. have already been applied to the surface and interfacial passivation of PSCs. These inorganic substances mainly manipulate the nucleation and crystallization process of perovskite absorbers by chemically passivating defects along grain boundaries and surface or forming a mechanically protective layer simultaneously to prevent the penetration of moisture and oxygen, thereby improving the stability and efficiency of the PSCs. Herein, we mainly summarize inorganic passivating materials and their individual passivation principles and methods. Finally, this review offers a personal perspective for future research trends in the development of passivation strategies through inorganic materials.

3D Printer-Based Encapsulated Origami Electronics for Extreme System Stretchability and High Areal Coverage.

Stretchability and areal coverage of active devices are critical design considerations of stretchable or wearable photovoltaics and photodetections where high areal coverages are required. However, simultaneously maximizing both properties in conventional island-bridge structures through traditional two-dimensional manufacturing processes is difficult due to their inherent trade-offs. Here, a 3D printer-based strategy to achieve extreme system stretchability and high areal coverage through combining fused deposition modeling (FDM) and flexible conductive nanocomposites is reported. Distinguished from typical approaches of using conductive filaments for FDM which have a flexibility dilemma and conductivity trade-offs, the proposed axiomatic approach to embed a two-dimensional silver nanowire percolation network into the surfaces of flexible 3D printed structures offers sufficient conductivity and deformability as well as additional benefits of electrical junction enhancement and encapsulation of silver nanowires. Kirigami/origami-pattern-guided three-dimensional arrangements of encapsulated interconnections provide efficient control over stretchability and areal coverage. The suggested process enables a perovskite solar module with an initial areal coverage of ∼97% to be electrically and mechanically reversible with 400% system stretchability and 25 000% interconnect stretchability under the 1000 cycle test, by folding down or hiding the origami-applied interconnects under the islands. This 3D printing strategy of potentially low cost, large size capabilities, and high speed is promising for highly flexible future energy conversion applications.

Highly porous self-assembly of nitrogen-doped graphene quantum dots over reduced graphene sheets for photo-electrocatalytic electrode.

Nitrogen-doped graphene quantum dots (NGQDs) are a diverse organic catalyst, competitive with other metallic catalysts due to their low cost, high stability, biocompatibility, and eco-friendliness. Highly functional multi-edge surfaces of NGQDs play a key role in imparting superb photocatalytic and electrocatalytic activity. However, when coating NGQDs by conventional techniques, such surfaces are not exposed for catalysis, due to the unwanted overlap of NGQDs sheets. To avoid this issue, here we propose a facile technique to orient NGQDs in a three-dimensional (3D) self-assembled foam-like structure, over reduced graphene oxide coated woven carbon fabric. This 3D assembled structure provides highly exposed active surfaces, which are readily available for catalytic reactions: however, in the conventional uniformly coated NGQDs layer, catalytic activity was limited by complex diffusion. The superb catalytic activity of the assembled NGQDs was utilized for the degradation of organic pollutant (methylene blue dye) from water. Additionally, the proposed electrode revealed much higher electrocatalytic activity than the rare Pt catalyst, owing to the easy diffusion of electrolyte and fast quenching of charges through the porous structure. The assembled NGQDs showed 50% higher photocatalytic degradation compared to uniformly coated NGQDs, which was further accelerated (50%) by application of the biased potential of 2 V; i.e. photo-electrocatalysis. The novel photo-electrocatalytic electrode offers high conductivity, stability, and flexibility, which make this complete carbon electrode highly attractive for other catalytic applications such as fuel cells, supercapacitors, and water splitting.

Controlling the Morphology of Organic-Inorganic Hybrid Perovskites through Dual Additive-Mediated Crystallization for Solar Cell Applications.

To realize a high-efficiency perovskite solar cell (PSC), it is critical to optimize the morphology of the perovskite film for a uniform and smooth finish with large grain size during film formation. Using a chemical compound as an additive to the precursor solution has recently been established as a promising method to control the morphology of the perovskite film. In this study, we propose a new method to achieve an improved morphology of the methylammonium lead iodide perovskite film by simultaneous addition of dimethyl sulfoxide (DMSO) and methoxyammonium salt (MeO) (dual additives). We demonstrated that an appropriate amount of the MeO additive helps the precursors form a stable intermediated PbI2-DMSO adduct during film formation and enlarges the perovskite grains by retarding the kinetics of conversion of the adduct to the perovskite. Furthermore, we experimentally observed that the optical band gaps and crystal structures of perovskite films are reasonably unaffected by the MeO additive because MeO is almost eliminated during annealing. By optimizing the amount of MeO, we achieved improved device performances of the PSCs with a high power conversion efficiency of 19.71% that is ∼15% higher than that obtained for the control device (17.15%).

Highly Efficient Bifacial Dye-Sensitized Solar Cells Employing Polymeric Counter Electrodes.

Dye-sensitized solar cells (DSCs) are promising solar energy conversion devices with aesthetically favorable properties such as being colorful and having transparent features. They are also well-known for high and reliable performance even under ambient lighting, and these advantages distinguish DSCs for applications in window-type building-integrated photovoltaics (BIPVs) that utilize photons from both lamplight and sunlight. Therefore, investigations on bifacial DSCs have been done intensively, but further enhancement in performance under back-illumination is essential for practical window-BIPV applications. In this research, highly efficient bifacial DSCs were prepared by a combination of electropolymerized poly(3,4-ethylenedioxythiphene) (PEDOT) counter electrodes (CEs) and cobalt bipyridine redox ([Co(bpy)3]3+/2+) electrolyte, both of which manifested superior transparency when compared with conventional Pt and iodide counterparts, respectively. Keen electrochemical analyses of PEDOT films verified that superior electrical properties were achievable when the thickness of the film was reduced, while their high electrocatalytic activities were unchanged. The combination of the PEDOT thin film and [Co(bpy)3]3+/2+ electrolyte led to an unprecedented power conversion efficiency among bifacial DSCs under back-illumination, which was also over 85% of that obtained under front-illumination. Furthermore, the advantage of the electropolymerization process, which does not require an elevation of temperature, was demonstrated by flexible bifacial DSC applications.

Solution-Processed Ultrathin TiO2 Compact Layer Hybridized with Mesoporous TiO2 for High-Performance Perovskite Solar Cells.

The electron transport layer (ETL) is a key component of perovskite solar cells (PSCs) and must provide efficient electron extraction and collection while minimizing the charge recombination at interfaces in order to ensure high performance. Conventional bilayered TiO2 ETLs fabricated by depositing compact TiO2 (c-TiO2) and mesoporous TiO2 (mp-TiO2) in sequence exhibit resistive losses due to the contact resistance at the c-TiO2/mp-TiO2 interface and the series resistance arising from the intrinsically low conductivity of TiO2. Herein, to minimize such resistive losses, we developed a novel ETL consisting of an ultrathin c-TiO2 layer hybridized with mp-TiO2, which is fabricated by performing one-step spin-coating of a mp-TiO2 solution containing a small amount of titanium diisopropoxide bis(acetylacetonate) (TAA). By using electron microscopies and elemental mapping analysis, we establish that the optimal concentration of TAA produces an ultrathin blocking layer with a thickness of ∼3 nm and ensures that the mp-TiO2 layer has a suitable porosity for efficient perovskite infiltration. We compare PSCs based on mesoscopic ETLs with and without compact layers to determine the role of the hole-blocking layer in their performances. The hybrid ETLs exhibit enhanced electron extraction and reduced charge recombination, resulting in better photovoltaic performances and reduced hysteresis of PSCs compared to those with conventional bilayered ETLs.

Simple synthesis of multiple length-scale structured Nb2O5 with functional macrodomain-integrated mesoporous frameworks.

We report the simple synthesis of macro- and mesostructured Nb2O5 that have functional submicrometer-sized particles (macrodomain) embedded in mesoporous frameworks (nanodomain). Resol can macrophase-separate by self-polymerization and co-assemble with niobia sol into mesostructured frameworks. The resultant materials increase the power conversion efficiency due to light-scattering capability of submicrometer-sized particles.