Understanding of the Intrinsic Difference between n- and p-Doping Propagation in Polymer Light-Emitting Electrochemical Cells: A Numerical Modeling Approach.

Distinct doping propagation characteristics between p-doping and n-doping in light-emitting electrochemical cells (LECs) have been highlighted by intensive reports. Typically, there are significant differences in the doping speeds between p-doping and n-doping, with the former exhibiting a sawtooth frontier and the latter displaying a more uniform frontier profile. In addition, experimental observations demonstrate a uniform motion instead of the theoretically suggested accelerated electrochemical doping frontier propagation. Therefore, there is an urgent need to establish a quantitative model that delves into the underlying mechanisms responsible for doping propagation in LECs. In this study, four variables were selected to investigate the detailed mechanism of electrochemical doping propagation: temperature, voltage, and concentrations of salt and solid electrolyte. Fluorescence imaging revealed that the n-doping and p-doping propagations behaved contrarily with increasing temperature and voltage. By numerically fitting the doping propagation frontier, equations were derived to describe the relationship between the speed of electrochemical doping propagation and temperature/voltage. The underlying mechanisms were elucidated, indicating that anions undergo motion through the cooperative effects of electric field drift and concentration diffusion, while cation transport strongly relies on poly(ethylene oxide) (PEO) segmental motions. In other words, the movement of anions within the electrolyte is characterized by a greater degree of freedom, whereas the motion of cations is significantly dependent on the segmental motions of PEO. The resulting equations were well-fitted with experimental data, providing a solid foundation for further theoretical investigations into electrochemical doping in various devices.

Microfluidics-Assisted Fabrication of Dual Stopband Photonic Microcapsules and Their Applications for Anticounterfeiting.

The assembly of two different kinds of colloidal particle-based photonic structures into an individual micro-object can achieve multifunctionality. In this study, core-shell photonic microcapsules with dual structural colors and photonic stop bands were prepared through a standard microfluidic technique. Photocurable resin suspension of silica nanoparticles and an aqueous suspension of nanogels were used as shell and core parts of microcapsules, respectively. The structural colors of shells and cores can be tuned by adjusting the concentrations of silica nanoparticles and soft nanogels in their corresponding suspensions. The individual microcapsules possess two distinct stop bands when the two suspensions are combined appropriately. Remarkably, the color information of the core part cannot be directly viewed at a macroscopic level (such as visual inspection) but can be detected at a microscopic scale (such as optical microscopy observation). The color information hidden enables the capability for information encryption and has potentially critical applications in anti-counterfeiting, display, and other fields.

Metal oxide nanoparticle-modified ITO electrode for high-performance solution-processed perovskite photodetectors.

Low dark current density plays a key role in determining the overall performance of perovskite photodetectors (PPDs). To achieve this goal, a hole transport layer (HTL) on the ITO side and a hole blocking layer (HBL) on the metal electrode side are commonly introduced in PPDs. Unlike traditional approaches, we realized a high-performance solution-processed broadband PPD using metal oxide (MO) nanoparticles (NPs) as the HBL on the ITO electrode and PC61BM as another HBL on the metal electrode side to reduce the device dark current. The PPDs based on TiO2 and SnO2 NP-modified layers show similar device performances at -0.5 V: a greater than 105 on/off ratio; over 100 dB linear dynamic range (LDR) under different visible light illumination; around 0.2 A W-1 responsivity (R); greater than 1012 jones detectivity (D*); and ∼20 µs rise time of the device. The MO NP interfacial layer can significantly suppress charge injection in the dark, while the accumulated photogenerated charges at the interface between the MO layer and the perovskite layer introduce band bending, leading to dramatically increased current under illumination. Therefore, the dark current density of the devices is significantly reduced and the optical gain is drastically enhanced. However, after UV illumination, the dark current of the TiO2 device dramatically increases while the dark current of the SnO2 device can stay the same as before since the UV illumination-induced conductivity and barrier height changes in the TiO2 layer cannot recover after removing the UV irradiation. These results indicate that the TiO2 NP layer is suitable for making a vis-NIR photodetector, while the SnO2 NP layer is a good candidate for UV-vis-NIR photodetectors. The facile solution-processed high-performance perovskite photodetector using MO NP-modified ITO is highly compatible with low cost, flexible, and large-area electronics.

Grain Growth of MAPbI3 via Diethylammonium Bromide Induced Grain Mergence.

Various additives are used to improve the film morphology, crystal quality, and grain size for the sake of enhancing the performance of three-dimensional perovskite solar cells. Although significant enhancement in the performance of devices has been made due to the introduction of additives, an in-depth understanding of the additive-related crystallization kinetics and the growth mechanism is still lacking. Here, the grain growth mechanism of diethylammonium bromide (DABr)-doped MAPbI3 is investigated using in situ dynamic microscopy techniques. The results reveal that the alkyl chains of DABr restrain the growth of grains of MAPbI3 during spin-coating, and DABr-induced grain mergence during the annealing process, achieving large grains on the micrometer scale. Meanwhile, the crystallization of MAPbI3 with DABr is significantly improved and the number of defects is reduced. The solar cell with optimized DABr doping MAPbI3 as the active layer presents a higher power conversion efficiency (PCE) of 19.58% with a fill factor of 79.81%.

Improving ternary blend morphology by adding a conjugated molecule into non-fullerene polymer solar cells.

The use of ternary polymer solar cells (PSCs) is a promising strategy to enhance photovoltaic performance while improving the fill factor (FF) of a device, but is still a challenge due to the complicated morphology. Herein, ternary PSCs are fabricated via adding the conjugated small molecule p-DTS(FBTTh2)2 into a well-known blended film, PTB7-Th:IEICO-4F. The ternary blend morphology and device characterization reveal that the addition of p-DTS(FBTTh2)2 can improve crystallinity and optimize morphology, leading to the FF of the optimized device increasing to 73.69%. In combination with the advantages of an ultra-narrow bandgap material, IEICO-4F, with a broad optical absorption spectrum, the optimized ternary solar cell exhibits a high short-circuit current-density (J SC) of 25.22 mA cm-2. The best power conversion efficiency (PCE) is 12.84% for this optimized ternary device with 10 wt% p-DTS(FBTTh2)2 in the donors. This work indicates that incorporating a small molecule with high crystallinity into host binary non-fullerene PSCs would give an active layer with high crystallinity, thus greatly enhancing the FFs and PCEs of PSCs.

Efficient Quasi-Two-Dimensional Perovskite Light-Emitting Diodes with Improved Multiple Quantum Well Structure.

Quasi-two-dimensional (quasi-2D) perovskites with a multiple quantum well structure can enhance the exciton binding energy and controllable quantum confine effect, which are attractive materials for efficient perovskite light-emitting diodes (PeLEDs). However, the multiphase mixtures contained in these materials would cause nonradiative recombination at the perovskite film surface. Here, a facile solution surface treatment is adopted to improve the multiple quantum well structure of the quasi-2D perovskite emitting layer, which can reduce the influence of defectinduced nonradiative recombination and the electric-field-induced dissociation of excitons for the PeLEDs. The improved multiple quantum well structure is verified by UV absorption spectra and temperature-dependent photoluminescence spectra measurements. The photoluminescence quantum yield of the quasi-2D perovskite film with surface treatment has been approximately increased by 200%. Meanwhile, the electroluminescence device achieves a current efficiency of 45.9 cd/A.

In vivo molecular imaging for immunotherapy using ultra-bright near-infrared-IIb rare-earth nanoparticles.

The near-infrared-IIb (NIR-IIb) (1,500-1,700 nm) window is ideal for deep-tissue optical imaging in mammals, but lacks bright and biocompatible probes. Here, we developed biocompatible cubic-phase (α-phase) erbium-based rare-earth nanoparticles (ErNPs) exhibiting bright downconversion luminescence at ~1,600 nm for dynamic imaging of cancer immunotherapy in mice. We used ErNPs functionalized with cross-linked hydrophilic polymer layers attached to anti-PD-L1 (programmed cell death-1 ligand-1) antibody for molecular imaging of PD-L1 in a mouse model of colon cancer and achieved tumor-to-normal tissue signal ratios of ~40. The long luminescence lifetime of ErNPs (~4.6 ms) enabled simultaneous imaging of ErNPs and lead sulfide quantum dots emitting in the same ~1,600 nm window. In vivo NIR-IIb molecular imaging of PD-L1 and CD8 revealed cytotoxic T lymphocytes in the tumor microenvironment in response to immunotherapy, and altered CD8 signals in tumor and spleen due to immune activation. The cross-linked functionalization layer facilitated 90% ErNP excretion within 2 weeks without detectable toxicity in mice.

Two-dimensional additive diethylammonium iodide promoting crystal growth for efficient and stable perovskite solar cells.

Methylammonium lead iodide perovskite photovoltaics have attracted remarkable attention due to their exceptional power conversion efficiencies (PCEs). The film morphology of organometallic halide perovskite plays a very important role in the performance of planar perovskite solar cells (PVSCs). Previous methods have been explored to control the crystal growth for getting a compact and smooth perovskite film. Here, we report an effective and reproducible approach for enhancing the stability and the efficiency of PVSCs by incorporating a small quantity of two-dimensional (2D) material diethylammonium iodide (DAI) in three-dimensional (3D) MAPbI3, which can facilitate the perovskite crystallization processes and improve the resulting film crystal quality. The fabricated (DA2PbI4)0.05MAPbI3 perovskite hybrid films exhibit good morphology with larger grains and uniform morphology. Simultaneously, reduced defects and enhanced carrier lifetime within a full device indicate enhanced crystallization effects as a result of the DAI inclusion. The photovoltaic device attains a high photocurrent of 22.95 mA cm-2 and a high fill factor of 79.04%, resulting in an overall PCE of 19.05%. Moreover, the stability of the 10% DAI doped perovskite solar cell is also improved. These results offer a promising stable and efficient light-absorbing material for solid-state photovoltaics and other applications.

Investigation on the Overshoot of Transient Open-Circuit Voltage in Methylammonium Lead Iodide Perovskite Solar Cells.

Although the performance of hybrid organic-inorganic perovskite solar cells (PSCs) is encouraging, the detailed working principles and mechanisms of PSCs remain to be further studied. In this work, an overshoot phenomenon of open-circuit voltage (Voc) was observed when the illumination light pulse was switched off. The evolution of the Voc overshoot was systematically investigated along with the intensity and the width of the light pulse, the background illumination, and pretreatment by different bias. Based on the experimental results, we could conclude that the Voc overshoot originated from carrier motion against carrier collection direction, which happened at the ionic-accumulation-induced band bending areas near the interfaces between the perovskite active layer and the two carrier transport layers. The investigation on the Voc overshoot can help us to better understand ionic migration, carrier accumulation, and recombination of PSCs under open-circuit conditions.

Recent Advances in Designing High-Capacity Anode Nanomaterials for Li-Ion Batteries and Their Atomic-Scale Storage Mechanism Studies.

Lithium-ion batteries (LIBs) have been widely applied in portable electronics (laptops, mobile phones, etc.) as one of the most popular energy storage devices. Currently, much effort has been devoted to exploring alternative high-capacity anode materials and thus potentially constructing high-performance LIBs with higher energy/power density. Here, high-capacity anode nanomaterials based on the diverse types of mechanisms, intercalation/deintercalation mechanism, alloying/dealloying reactions, conversion reaction, and Li metal reaction, are reviewed. Moreover, recent studies in atomic-scale storage mechanism by utilizing advanced microscopic techniques, such as in situ high-resolution transmission electron microscopy and other techniques (e.g., spherical aberration-corrected scanning transmission electron microscopy, cryoelectron microscopy, and 3D imaging techniques), are highlighted. With the in-depth understanding on the atomic-scale ion storage/release mechanisms, more guidance is given to researchers for further design and optimization of anode nanomaterials. Finally, some possible challenges and promising future directions for enhancing LIBs' capacity are provided along with the authors personal viewpoints in this research field.

Narrow Band Gap Conjugated Polyelectrolytes.

Two essential structural elements define a class of materials called conjugated polyelectrolytes (CPEs). The first is a polymer framework with an electronically delocalized, π-conjugated structure. This component allows one to adjust desirable optical and electronic properties, for example the range of wavelengths absorbed, emission quantum yields, electron affinity, and ionization potential. The second defining feature is the presence of ionic functionalities, which are usually linked via tethers that can modulate the distance of the charged groups relative to the backbone. These ionic groups render CPEs distinct relative to their neutral conjugated polymer counterparts. Solubility in polar solvents, including aqueous media, is an immediately obvious difference. This feature has enabled the development of optically amplified biosensor protocols and the fabrication of multilayer organic semiconductor devices through deposition techniques using solvents with orthogonal properties. Important but less obvious potential advantages must also be considered. For example, CPE layers have been used to introduce interfacial dipoles and thus modify the effective work function of adjacent electrodes. One can thereby modulate the barriers for charge injection into semiconductor layers and improve the device efficiencies of organic light-emitting diodes and solar cells. With a hydrophobic backbone and hydrophilic ionic sites, CPEs can also be used as dispersants for insoluble materials. Narrow band gap CPEs (NBGCPEs) have been studied only recently. They contain backbones that comprise electron-rich and electron-poor fragments, a combination that leads to intramolecular charge transfer excited states and enables facile oxidation and reduction. One particularly interesting combination is NBGCPEs with anionic sulfonate side groups, for which spontaneous self-doping in aqueous media is observed. That no such doping is observed with cationic NBGCPEs indicates that the interplay between electrostatic forces and the redox chemistry of the organic semiconducting chain is essential for stabilizing the polaronic states and increasing the conductivity of the bulk. Capitalizing upon the properties of NBGCPEs has resulted in a range of new applications. When doped, they can be introduced as interlayers in organic and perovskite solar cells. Single-walled carbon nanotubes can be n- or p-doped with NBGCPEs, depending on whether the same backbone contains attached cationic or anionic side groups, respectively. The resulting dispersions can be used to fabricate flexible thermoelectric devices in which the n- and p-semiconductor legs are nearly identical in terms of chemical composition. Electrostatic interactions with negatively charged cell walls, in combination with the long-wavelength absorption and high photothermal efficiencies, have been used to create effective agents for photothermal killing of bacteria. Additionally, recent results have shown that cationic NBGCPEs can effectively n-dope graphene and that this doping is temperature-dependent. The preferential charge carriers can therefore be chosen to be electrons or holes depending on the applied temperature.

Topological Transformation of π-Conjugated Molecules Reduces Resistance to Crystallization.

Two electronically delocalized molecules were designed as models to understand how molecular shape impacts the tradeoff between solubility and crystallization tendencies in molecular semiconductors. The more soluble compound TT contains a non-planar bithiophene central fragment, whereas CT has a planar cyclopentadithiophene unit. Calorimetry studies show that CT can crystallize more easily than TT. However, absorption spectroscopy shows that the initially amorphous TT film can eventually form crystals in which the molecular shape is significantly more planar. Two thermally reversible polymorphs for TT were observed by XRD and grazing-incidence wide-angle X-ray scattering (GIWAXS) measurements. These findings are relevant within the context of designing soft semiconductors that exhibit high solubility and a tendency to provide stable organized structures with desirable electronic properties.

Improved Li+ Storage through Homogeneous N-Doping within Highly Branched Tubular Graphitic Foam.

A novel carbon structure, highly branched homogeneous-N-doped graphitic (BNG) tubular foam, is designed via a novel N, N-dimethylformamide (DMF)-mediated chemical vapor deposition method. More structural defects are found at the branched portions as compared with the flat tube domains providing abundant active sites and spacious reservoirs for Li+ storage. An individual BNG branch nanobattery is constructed and tested using in situ transmission electron microscopy and the lithiation process is directly visualized in real time.

Contribution of heavy metals to toxicity of coal combustion related fine particulate matter (PM2.5) in Caenorhabditis elegans with wild-type or susceptible genetic background.

Contribution of chemical components in coal combustion related fine particulate matter (PM2.5) to its toxicity is largely unclear. We focused on heavy metals in PM2.5 to investigate their contribution to toxicity formation in Caenorhabditis elegans. Among 8 heavy metals examined (Fe, Zn, Pb, As, Cd, Cr, Cu, and Ni), Pb, Cr, and Cu potentially contributed to PM2.5 toxicity in wild-type nematodes. Combinational exposure to any two of these three heavy metals caused higher toxicity than exposure to Pb, Cr, or Cu alone. Toxicity from the combinational exposure to Pb, Cr, and Cu at the examined concentrations was higher than exposure to PM2.5 (100 mg/L). Moreover, mutation of sod-2 or sod-3 gene encoding Mn-SOD increased susceptibility in nematodes exposed to Fe, Zn, or Ni, although Fe, Zn, or Ni at the examined concentration did not lead to toxicity in wild-type nematodes. Our results highlight the potential contribution of heavy metals to PM2.5 toxicity in environmental organisms.

Zn stress-induced inhibition of bean PvSR2-GUS fusion gene splicing is gene-specific in transgenic tobacco.

The stress-related gene no. 2 of Phaseolus vulgaris (PvSR2) is metal inducible and contains a single intron. Here, we report that Zn stress inhibited the splicing of the PvSR2-beta-glucuronidase (GUS) fusion gene in a concentration- and time-dependent manner in tobacco seedlings. The inhibition appears to be specific for the PvSR2-GUS transgene: splicing of four endogenous tobacco genes was unaffected by Zn stress. Our results provide in vivo evidence that Zn stress-dependent intron retention is transgene specific in plants.