Composites comprising copper-doped zinc sulfide phosphor microparticles embedded in polydimethylsiloxane (ZnS:Cu-PDMS) have received significant attention over the past decade because of their bright and durable mechanoluminescence (ML); however, the underlying mechanism of this unique ML remains unclear. This study reports empirical and theoretical findings that confirm this ML is an electroluminescence (EL) of the ZnS:Cu phosphor induced by the triboelectricity generated at the ZnS:Cu microparticle-PDMS matrix interface. ZnS:Cu microparticles that exhibit bright ML are coated with alumina, an oxide with strong positive triboelectric properties; the contact separation between this oxide coating and PDMS, a polymer with strong negative triboelectric properties, produces sufficient interfacial triboelectricity to induce EL in ZnS:Cu microparticles. The ML of ZnS:Cu-PDMS composites varies on changing the coating material, exhibiting an intensity that is proportional to the amount of interfacial triboelectricity generated in the system. Finally, based on these findings, a mechanism that explains the ML of phosphor-polymer elastic composites (interfacial triboelectric field-driven alternating-current EL model) is proposed in this study. It is believed that understanding this mechanism will enable the development of new materials (beyond ZnS:Cu-PDMS systems) with bright and durable ML.
The neuroprotective effects of umbelliferone (UMB) were visualized in three-dimensional (3D) images on vesicle density changes of organotypic hippocampal slice tissues (OHSCs) induced by scopolamine by high voltage electron microscopy. Observations revealed that the number of vesicles decreased in OHSCs induced by scopolamine, and UMB was found to inhibit scopolamine-induced reduction in vesicles, resulting in an increase in vesicle count. These 3D models provide valuable insight for understanding the increase of synapse vesicles in hippocampal tissues treated with UMB.
Surface defects of metal halide perovskite nanocrystals (PNCs) substantially compromise the optoelectronic performances of the materials and devices via undesired charge recombination. However, those defects, mainly the vacancies, are structurally entangled with each other in the PNC lattice, necessitating a delicately designed strategy for effective passivation. Here, a synergistic metal ion doping and surface ligand exchange strategy is proposed to passivate the surface defects of CsPbBr3 PNCs with various divalent metal (e.g., Cd2+ , Zn2+, and Hg2+ ) acetate salts and didodecyldimethylammonium (DDA+ ) via one-step post-treatment. The addition of metal acetate salts to PNCs is demonstrated to suppress the defect formation energy effectively via the ab initio calculations. The developed PNCs not only have near-unity photoluminescence quantum yield and excellent stability but also show luminance of 1175 cd m-2 , current efficiency of 65.48 cd A-1 , external quantum efficiency of 20.79%, wavelength of 514 nm in optimized PNC light-emitting diodes with Cd2+ passivator and DDA ligand. The "organic-inorganic" hybrid engineering approach is completely general and can be straightforwardly applied to any combination of quaternary ammonium ligands and source of metal, which will be useful in PNC-based optoelectronic devices such as solar cells, photodetectors, and transistors.
The severely insufficient operational lifetime of perovskite light-emitting diodes (LEDs) is incompatible with the rapidly increasing external quantum efficiency, even as it approaches the theoretical limit, thereby significantly impeding the commercialization of perovskite LEDs. In addition, Joule heating induces ion migration and surface defects, degrades the photoluminescence quantum yield and other optoelectronic properties of perovskite films, and induces the crystallization of charge transport layers with low glass transition temperatures, resulting in LED degradation under continuous operation. Here, a novel thermally crosslinked hole transport material, poly(FCA60 -co-BFCA20 -co-VFCA20 ) (poly-FBV), with temperature-dependent hole mobility is designed, which is advantageous for balancing the charge injection of the LEDs and limiting the generation of Joule heating. The optimised CsPbI3 perovskite nanocrystal LEDs with poly-FBV realise approximately a 2-fold external quantum efficiency increase over the LED with commercial hole transport layer poly(4-butyl-phenyl-diphenyl-amine) (poly-TPD), owing to the balanced carrier injection and suppressed exciton quenching. Moreover, because of the Joule heating control provided by the novel crosslinked hole transport material, the LED utilising crosslinked poly-FBV has a 150-fold longer operating lifetime (490 min) than that utilizing poly-TPD (3.3 min). The study opens a new avenue for the use of PNC LEDs in commercial semiconductor optoelectronic devices.
To investigate the effect of miscibility between conjugated polymers (CPs) and Y6 on bulk-heterojunction (BHJ) type morphology, we propose three different CPs with similar chemical structures but different miscibility with Y6. After selectively removing Y6 from the CP/Y6 blend films, their interface morphology and interlocked dimensions are quantitatively compared using a square-wave model. As CP-Y6 miscibility increases, a higher intermixed interface is formed, providing an enlarged CP-Y6 interface area. Conversely, as the miscibility between CP and Y6 decreases, the height and width of the interlocked dimensions formed by phase separation gradually decrease and increase, respectively. Additionally, when the CP-Y6 interface morphology and electrical properties of the corresponding organic photovoltaic (OPV) device are correlated, as the highly intermixed CP-Y6 interface develops, the exciton dissociation efficiency increases owing to the reduced exciton diffusion length to be dissociated, but the bimolecular recombination tends to deteriorate simultaneously. Furthermore, if the miscibility between CP and Y6 is excessive, the formation of a charge transport pathway through phase separation is interrupted, deteriorating the charge transport capability in BHJ-type OPVs. However, it was confirmed that introducing F atoms into the conjugated backbone of CP can reduce the bimolecular recombination, providing ameliorated light-harvesting efficiency.
Cdx Hg1- x Se/HgS/Cdy Zn1- y S core/multi-shell quantum dots (QDs) exhibiting bright tissue-penetrating shortwave infrared (SWIR; 1000-1700 nm) photoluminescence (PL) are engineered. The new structure consists of a quasi-type-II Cdx Hg1- x Se/HgS core/inner shell domain creating luminescent bandgap tunable across SWIR window and a wide-bandgap Cdy Zn1- y S outer shell boosting the PL quantum yield (QY). This compositional sequence also facilitates uniform and coherent shell growth by minimizing interfacial lattice mismatches, resulting in high QYs in both organic (40-80%) and aqueous (20-70%) solvents with maximum QYs of 87 and 73%, respectively, which are comparable to those of brightest visible-to-near infrared QDs. Moreover, they maintain bright PL in a photocurable resin (QY 40%, peak wavelength ≈ 1300 nm), enabling the fabrication of SWIR-luminescent composites of diverse morphology and concentration. These composites are used to localize controlled amounts of SWIR QDs inside artificial (Intralipid) and porcine tissues and quantitatively evaluate the applicability as luminescent probes for deep-tissue imaging.
A string of monocyanated quinoxaline (Qx)-based D-A-type polymers systematically decorated with electron-attracting chlorine (Cl) atoms was created for use in non-fullerene polymer solar cells (PSCs). First, coupling of the benzodithiophene (BDT) donor and Qx acceptor with the strong electron-attracting cyano (CN) unit at its 5-position yielded the monocyanated reference polymer PB-CNQ. Subsequently, the additional Cl atoms were separately or simultaneously incorporated into the thiophene side groups of the BDT donor and Qx acceptor to create other objective polymers, PBCl-CNQ, PB-CNQCl, and PBCl-CNQCl. The Cl substituents on the BDT donor and Qx acceptor are represented by the names of the polymers. Owing to the favorable contributions of Cl substituents, the inverted-type non-fullerene PSCs based on partially chlorinated PBCl-CNQ (12.80%) and PB-CNQCl (13.93%) exhibited better power conversion efficiencies (PCEs) than the device based on unchlorinated reference PB-CNQ (11.19%). However, a significantly reduced PCE of 9.84% was observed for the device based on PBCl-CNQCl, in which Cl atoms were loaded on both the BDT donor and Qx acceptor at the same time. Hence, these results reveal that optimization of the number and position of Cl substituents in monocyanated Qx-based polymers is essential for enhancing their photovoltaic nature through the synergistic effects between two strong electron-attracting CN and Cl substituents.
Semiconducting lead halide perovskite nanocrystals (PNCs) are regarded as promising candidates for next-generation optoelectronic devices due to their solution processability and outstanding optoelectronic properties. While the field of light-emitting diodes (LEDs) and photovoltaics (PVs), two prime examples of optoelectronic devices, has recently seen a multitude of efforts toward high-performance PNC-based devices, realizing both devices with high efficiencies and stabilities through a single PNC processing strategy has remained a challenge. In this work, diphenylpropylammonium (DPAI) surface ligands, found through a judicious ab-initio-based ligand search, are shown to provide a solution to this problem. The universal PNC ink with DPAI ligands presented here, prepared through a solution-phase ligand-exchange process, simultaneously allows single-step processed LED and PV devices with peak electroluminescence external quantum efficiency of 17.00% and power conversion efficiency of 14.92% (stabilized output 14.00%), respectively. It is revealed that a careful design of the aromatic rings such as in DPAI is the decisive factor in bestowing such high performances, ease of solution processing, and improved phase stability up to 120 days. This work illustrates the power of ligand design in producing PNC ink formulations for high-throughput production of optoelectronic devices; it also paves a path for "dual-mode" devices with both PV and LED functionalities.
The choice of the chlorine (Cl) atom as an electron-withdrawing substituent in conjugated polymers leads to a higher potential in the commercialization of polymer solar cells than its fluorine counterpart because of the versatility and cost-effectiveness of the chlorination process. In addition, the population and location of Cl substituents can significantly influence the photovoltaic characteristics of polymers. In this study, three chlorinated quinoxaline-based polymers were invented to examine the numerical and positioning effects of the Cl atom on their photovoltaic characteristics. The number of Cl substituents in the reference polymer, PBCl-Qx, was adjusted to three: two Cl atoms in the benzodithiophene-type D unit and one Cl atom in the quinoxaline-type A unit. Subsequently, two more Cl atoms were selectively introduced at the 4- and 5-positions of the alkylated thiophene moieties at the 2,3-positions of the quinoxaline moiety in PBCl-Qx to obtain the additional polymers PBCl-Qx4Cl and PBCl-Qx5Cl, respectively. The conventional PBCl-Qx4Cl device exhibited a better power conversion efficiency (PCE) of 12.95% as compared to those of PBCl-Qx (12.44%) and PBCl-Qx5Cl (11.82%) devices. The highest PCE of the device with PBCl-Qx4Cl was ascribed to an enhancement in the open-circuit voltage and fill factor induced by the deeper energy level of the highest occupied molecular orbital and the favorable morphological features in its blended film with Y6.
Among the solution-processed devices, perovskite solar cells (PSCs) exhibit the highest power conversion efficiency (PCE) of over 25%; tremendous efforts are being undertaken to improve their stability. Recently, all-inorganic CsPbI2Br-based PSCs were reported to exhibit a significantly improved device stability, with a promising PCE of up to 16.79%. In this study, we report stable all-inorganic PSCs by incorporating novel dopant-free hole-transporting materials (HTMs). The synthesis strategy of the newly synthesized polymeric HTMs was similar to that of 2,2',7,7'-tetrakis(N,N-di-p-methoxyphenylamine)-9,9'-spirobifluorene (spiro-OMeTAD), with the exception that they were designed to exhibit dopant-free characteristics. In particular, their polymeric backbone structure was significantly simpler than that of spiro-OMeTADs, and they were easily synthesized in two steps from commercially available chemicals, with an overall yield of â¼50%. The cost of synthesis at the laboratory scale was calculated to be at least 2.4 times cheaper than that of spiro-OMeTADs. The PCE of dopant-free HTM-based PSCs was 11.01%, which is 1.5 times higher than that of the dopant-free spiro-OMeTAD-based devices (7.52%) and comparable to that of the doped spiro-OMeTAD-based devices (12.22%). Notably, the stability of the device based on our dopant-free HTM to atmospheric oxygen and moisture as well as heat and light irradiation was superior to that of devices based on doped and dopant-free spiro-OMeTAD HTMs. On consideration of the synthesis cost, device efficiency, and device stability, our dopant-free HTM is highly promising for all-inorganic PSCs.
Complete surface passivation of colloidal quantum dots (CQDs) and their strong electronic coupling are key factors toward high-performance CQD-based photovoltaics (CQDPVs). Also, the CQD matrices must be protected from oxidative environments, such as ambient air and moisture, to guarantee air-stable operation of the CQDPVs. Herein, we devise a complementary and effective approach to reconstruct the oxidized CQD surface using guanidinium and pseudohalide. Unlike conventional halides, thiocyanate anions provide better surface passivation with effective replacement of surface oxygen species and additional filling of defective sites, whereas guanidinium cations promote the construction of epitaxial perovskite bridges within the CQD matrix and augment electronic coupling. Additionally, we replace a defective 1,2-ethanedithiol-treated CQD hole transport layer (HTL) with robust polymeric HTLs, based on a judicious consideration of the energy level alignment established at the CQD/HTL interface. These efforts collectively result in high-performance and stable CQDPVs with photocurrents over 30 mA cm-2, â¼80% quantum efficiency at excitonic peaks and stable operation under humid and ambient conditions. Elucidation of carrier dynamics further reveals that interfacial recombination associated with band alignment governs both the CQDPV performance and stability.
In this study, strong electron-withdrawing fluorine (F) and cyano (CN) substituents are selectively incorporated into the quinoxaline unit of two-dimensional (2D) D-A-type polymers to investigate their effects on the photovoltaic properties of the polymers. To construct the 2D polymeric structure, electron-donating benzodithiophene and methoxy-substituted triphenylamine are directly linked to the horizontal and vertical directions of the quinoxaline acceptor, respectively. After analyzing the structural, optical, and electrochemical properties of the resultant F- and CN-substituted polymers, labeled as PBCl-MTQF and PBCl-MTQCN, respectively, inverted-type polymer solar cells with a non-fullerene Y6 acceptor are fabricated to investigate the photovoltaic performances of the polymers. It is discovered that the maximum power conversion efficiency of PBCl-MTQF is 7.48%, whereas that of PBCl-MTQCN is limited to 3.52%. This significantly reduced PCE of the device based on PBCl-MTQCN is ascribed to the formation of irregular, large aggregates in the active layer, which can readily aggravate the charge recombination and charge transport kinetics of the device. Therefore, the photovoltaic performance of 2D quinoxaline-based D-A-type polymers is significantly affected by the type of electron-withdrawing substituent.
Development of colloidal quantum dot (CQD) inks enables single-step spin-coating of compact CQD films of appropriate thickness, enabling the promising performance of CQD photovoltaics (CQDPVs). Today's highest-performing CQD inks rely on volatile n-butylamine (BTA), but it is incompatible with scalable deposition methods since a rapid solvent evaporation results in irregular film thickness with an uneven surface. Here, we present a hybrid solvent system, consisting of BTA and N,N-dimethylformamide, which has a favorable acidity for colloidal stability as well as an appropriate vapor pressure, enabling a stable CQD ink that can be used to fabricate homogeneous, large-area CQD films via spray-coating. CQDPVs fabricated with the CQD ink exhibit suppressed charge recombination as well as fast charge extraction compared with conventional CQD ink-based PVs, achieving an improved power conversion efficiency (PCE) of 12.22% in spin-coated devices and the highest ever reported PCE of 8.84% among spray-coated CQDPVs.
Lead halide perovskites are promising semiconductors for light-emitting applications because they exhibit bright, bandgap-tunable luminescence with high colour purity1,2. Photoluminescence quantum yields close to unity have been achieved for perovskite nanocrystals across a broad range of emission colours, and light-emitting diodes with external quantum efficiencies exceeding 20 per cent-approaching those of commercial organic light-emitting diodes-have been demonstrated in both the infrared and the green emission channels1,3,4. However, owing to the formation of lower-bandgap iodide-rich domains, efficient and colour-stable red electroluminescence from mixed-halide perovskites has not yet been realized5,6. Here we report the treatment of mixed-halide perovskite nanocrystals with multidentate ligands to suppress halide segregation under electroluminescent operation. We demonstrate colour-stable, red emission centred at 620 nanometres, with an electroluminescence external quantum efficiency of 20.3 per cent. We show that a key function of the ligand treatment is to 'clean' the nanocrystal surface through the removal of lead atoms. Density functional theory calculations reveal that the binding between the ligands and the nanocrystal surface suppresses the formation of iodine Frenkel defects, which in turn inhibits halide segregation. Our work exemplifies how the functionality of metal halide perovskites is extremely sensitive to the nature of the (nano)crystalline surface and presents a route through which to control the formation and migration of surface defects. This is critical to achieve bandgap stability for light emission and could also have a broader impact on other optoelectronic applications-such as photovoltaics-for which bandgap stability is required.
Solution-processed near-infrared (NIR)-absorbing organic solar cells (OSCs) have been explored worldwide because of their potential as donor:acceptor bulk heterojunction (BHJ) blends. In addition, NIR-absorbing OSCs have attracted attention as high specialty equipment in next-generation optoelectronic devices, such as semitransparent solar cells and NIR photodetectors, owing to their feasibility for real-time commercial application in industry. With the introduction of NIR-absorbing non-fullerene acceptors (NFAs), the value of OSCs has been increasing while organic donor materials capable of absorbing light in the NIR region have not been actively studied yet compared to NIR-absorbing acceptor materials. Therefore, we present an overall understanding of NIR donors.
Efficient charge collection in photovoltaics is a key issue toward their high performance. Despite the promising performance of colloidal quantum dot (CQD)-based photovoltaics (CQDPVs), they suffer significant dissipation of photocurrent due to imperfect surface passivation of the CQD hole transport layer (HTL) by a single 1,2-ethaneditihol (EDT) ligand. To address the critical drawback of existing CQDPVs, we offer a hybrid passivation strategy, including both EDT and thiocyanate (SCN). The hybrid passivation leads to seamless surface passivation of CQDs, remarkably suppressing charge recombination. This strategy also augments the p-doping density of the CQD, resulting in a pronounced energy level bending at the active layer/HTL interface and facilitating efficient charge separation. Moreover, enhanced electronic coupling across the CQDs (originating from reduced inter-dot spacing) promotes rapid charge extraction. Consequently, the flawless charge collection by a hybrid-passivated HTL successfully retrieves the photocurrent, achieving an enhanced CQDPV power conversion efficiency of 12.70% compared with 11.49% for the control device.
A robust synthesis approach to develop CuO/ZnO nanocomposites using microwave-epoxide-assisted hydrothermal synthesis and their proficiency toward H2S gas-sensing application are reported. The low-cost metal salts (Cu and Zn) as precursors in aqueous media and epoxide (propylene oxide) as a proton scavenger/gelation agent are used for the formation of mixed metal hydroxides. The obtained sol was treated using the microwave hydrothermal process to yield the high-surface area (34.71 m2/g) CuO/ZnO nanocomposite. The developed nanocomposites (1.25-10 mol % Cu doping) showcase hexagonal ZnO and monoclinic CuO structures, with an average crystallite size in the range of 18-29 nm wrt Cu doping in the ZnO matrix. The optimized nanocomposite (2.5 mol % Cu doping) showed a lowest crystallite size of 21.64 nm, which reduced further to 18.06 nm upon graphene oxide addition. Morphological analyses (scanning electron microscopy and transmission electron microscopy) exhibited rounded grains along with copious channels typical for sol-gel-based materials . Elemental mapping displayed the good dispersion of Cu in the ZnO matrix. When these materials are employed as a gas sensor, they demonstrated high sensitivity and selectivity toward H2S gas in comparison with the reducing gases and volatile organic compounds under investigation. The systematic doping of Cu in the ZnO matrix exhibited an improved response from 76.66 to 94.28%, with reduction in operating temperature from 300 to 250 °C. The 2.5 mol % doped Cu in ZnO was found to impart a response of 23 s for 25 ppm of H2S. Gas-sensing properties are described using an interplay of epoxide-assisted sol-gel chemistry and structural and morphological properties of the developed material.
Single-crystal perovskite thin films were prepared by a scalable, one-step, geometrically confined lateral crystal growth (GC-LCG) method on a patterned rolling mold and used for a photovoltaic study. A record solar cell efficiency of 9.50 % under 0.1â sun with an electrode spacing of 1.5â µm is attained in lateral single-crystal perovskite materials. Moreover, successful integration for high-source-power-generation interdigitated electrode units patterned in series (1×4), parallel (4×1), and combination (4 series×4 parallel) configurations is devised and affords maximum efficiencies of 7.99, 8.19, and 7.96 %, respectively. Additionally, the cell performances under various illumination intensities (0.1, 0.2, 0.4, 0.6, 0.8, 1.0â sun) to mimic daily sunshine angles and an indoor environment at 1000â lux are elucidated for which short-circuit current (JSC ) values (19.60â mA cm-2 and η=7.43 %) under 1.0â sun and a significant efficiency of 8.13 % under indoor conditions are obtained. This work represents a significant step towards next-generation, efficient, lateral photovoltaics for possible module integration.
Solution processed transparent conductive electrodes (TCEs) were fabricated via layer-by-layer (LBL) deposition of silver nanowires (AgNWs). First, the AgNWs were coated on (3-Mercaptopropyl)trimethoxysilane modified glass substrates. Then, multilayer AgNW films were obtained by using 1,3-propanedithiol as a linker via LBL deposition, which made it possible to control the optical transmittance and sheet resistance of multilayer thin films. Next, thermal annealing of AgNW films was performed in order to agent their electrical conductivity. AgNW monolayer films were characterized by UV-Vis spectrometer, field emission scanning electron microscopy, optical microscopy, atomic force microscopy and sheet resistance measurement by four-point probe method. The high performances were achieved with multilayer films, which provided sheet resistances of 9 Ω/sq, 11 Ω/sq with optical transmittances of 71%, 70% at 550 nm, which are comparable to commercial indium tin oxide (ITO) electrodes. Finally, an organic photovoltaic device was fabricated on the AgNW multilayer electrodes for demonstration purpose, which exhibited power conversion efficiency of 1.1%.
Lead-free, water-resistant photovoltaic absorbers are of significant interest for use in environment-friendly and water-stable thin film solar cells. However, there are no reports on the water-resistance characteristics of such photoactive materials. Here, we demonstrate that silver bismuth sulfide (AgBiS2) nanocrystal solids exhibit inherent water resistance and can be employed as effective photovoltaic absorbers in all-solid-state thin film solar cells that show outstanding air and moisture stabilities under ambient conditions. The results of X-ray photon spectroscopy (XPS) and X-ray diffraction (XRD) analyses show that there is no change in the chemical composition and crystal structure of the AgBiS2 nanocrystal solids after a water treatment. Based on these results, AgBiS2 nanocrystal solar cells are fabricated. These devices also do not show any drop in performance after a water treatment, confirming that the AgBiS2 nanocrystal solids are indeed highly water-resistant. In contrast, lead sulfide (PbS) colloidal quantum dot (CQD) solar cells show significant decrease in performance after a similar water treatment. Using XPS analysis and density functional theory (DFT) calculations, we confirm that the iodine removal and the surface hydroxylation of the water-treated PbS CQD solids are the primary reasons for the observed decrease in the device performance of the CQD solar cells.
