Mixed Organic Cations Promote Ambient Light-Induced Formation of Metallic Lead in Lead Halide Perovskite Crystals.

One major concern toward the performance and stability of halide perovskite-based optoelectronic devices is the formation of metallic lead that promotes nonradiative recombination of charge carriers. The origin of metallic lead formation is being disputed whether it occurs during the perovskite synthesis or only after light, electron, or X-ray beam irradiation or thermal annealing. Here, we show that the quantity of metallic lead detected in perovskite crystals depends on the concentration and composition of the precursor solution. Through a controlled crystallization process, we grew black-colored mixed dimethylammonium (DMA)/methylammonium (MA) lead tribromide crystals. The black color is suggested to be due to the presence of small lead clusters. Despite the unexpected black coloring, the crystals show higher crystallinity and less defect density with respect to the standard yellow-colored DMA/MAPbBr3 crystals, as indicated by X-ray rocking curve and dark current measurements, respectively. While the formation of metallic lead could still be induced by external factors, the precursor solution composition and concentration can facilitate the formation of metallic lead during the crystallization process. Our results indicate that additional research is required to fully understand the perovskite precursor solution chemistry.

Spin-Polarized Photocatalytic CO2 Reduction of Mn-Doped Perovskite Nanoplates.

"Spin" has been recently reported as an important degree of electronic freedom to improve the performance of electrocatalysts and photocatalysts. This work demonstrates the manipulations of spin-polarized electrons in CsPbBr3 halide perovskite nanoplates (NPLs) to boost the photocatalytic CO2 reduction reaction (CO2RR) efficiencies by doping manganese cations (Mn2+) and applying an external magnetic field. Mn-doped CsPbBr3 (Mn-CsPbBr3) NPLs exhibit an outstanding photocatalytic CO2RR compared to pristine CsPbBr3 NPLs due to creating spin-polarized electrons after Mn doping. Notably, the photocatalytic CO2RR of Mn-CsPbBr3 NPLs is significantly enhanced by applying an external magnetic field. Mn-CsPbBr3 NPLs exhibit 5.7 times improved performance of photocatalytic CO2RR under a magnetic field of 300 mT with a permanent magnet compared to pristine CsPbBr3 NPLs. The corresponding mechanism is systematically investigated by magnetic circular dichroism spectroscopy, ultrafast transient absorption spectroscopy, and density functional theory simulation. The origin of enhanced photocatalytic CO2RR efficiencies of Mn-CsPbBr3 NPLs is due to the increased number of spin-polarized photoexcited carriers by synergistic doping of the magnetic elements and applying a magnetic field, resulting in prolonged carrier lifetime and suppressed charge recombination. Our result shows that manipulating spin-polarized electrons in photocatalytic semiconductors provides an effective strategy to boost photocatalytic CO2RR efficiencies.

Mixed Dimethylammonium/Methylammonium Lead Halide Perovskite Crystals for Improved Structural Stability and Enhanced Photodetection.

The solvent acidolysis crystallization technique is utilized to grow mixed dimethylammonium/methylammonium lead tribromide (DMA/MAPbBr3 ) crystals reaching the highest dimethylammonium incorporation of 44% while maintaining the 3D cubic perovskite phase. These mixed perovskite crystals show suppression of the orthorhombic phase and a lower tetragonal-to-cubic phase-transition temperature compared to MAPbBr3 . A distinct behavior is observed in the temperature-dependent photoluminescence properties of MAPbBr3 and mixed DMA/MAPbBr3 crystals due to the different organic cation dynamics governing the phase transition(s). Furthermore, lateral photodetectors based on these crystals show that, at room temperature, the mixed crystals possess higher detectivity compared to MAPbBr3 crystals caused by structural compression and reduced surface trap density. Remarkably, the mixed-crystal devices exhibit large enhancement in their detectivity below the phase-transition temperature (at 200 K), while for the MAPbBr3 devices only insignificant changes are observed. The high detectivity of the mixed crystals makes them attractive for visible-light communication and for space applications. The results highlight the importance of the synthetic technique for compositional engineering of halide perovskites that governs their structural and optoelectronic properties.

Layered perovskite materials: key solutions for highly efficient and stable perovskite solar cells.

Metal halide perovskites having three-dimensional crystal structures are being applied successfully in various optoelectronic applications. To address their most challenging issues-instability and toxicity-without losing efficiency, lower-dimensional perovskites appear to be promising alternatives. Recently, two-dimensional (2D) perovskite solar cells have been developed exhibiting excellent photostability and moisture-stability, together with moderate device efficiency. This review summarizes the photophysical properties and operating mechanisms of 2D perovskites as well as recent advances in their applications in solar cell devices. Also presented is an agenda for the next-stage development of stable perovskite materials for solar cell applications, highlighting the issues of stability and toxicity that require further study to ensure commercialization.

Thiocyanate-Treated Perovskite-Nanocrystal-Based Light-Emitting Diodes with Insight in Efficiency Roll-Off.

Light emitting diodes (LED) based on halide perovskite nanocrystals (NC) have received widespread attention in recent years. In particular, LEDs based on CsPbBr3 NCs were the object of special interest. Here, we report for the first time green LED based on CsPbBr3 NCs treated with ammonium thiocyanate solution before purification with polar solvent. The champion device fabricated based on the treated CsPbBr3 NCs showed high efficiency and high stability during operation as well as during storage. A study on morphology and current distribution of NC films under applied voltages was carried out by conductive atomic force microscopy, giving a hint on efficiency roll-off. The current work provides a facile way to treat sensitive perovskite NCs and to fabricate perovskite NC-based LED with high stability. Moreover, the results shed new light on the relation between film morphology and device performance and on the possible mechanism of efficiency roll-off in NC LED.

Lead-Free Antimony-Based Light-Emitting Diodes through the Vapor-Anion-Exchange Method.

Hybrid lead halide perovskites continue to attract interest for use in optoelectronic devices such as solar cells and light-emitting diodes. Although challenging, the replacement of toxic lead in these systems is an active field of research. Recently, the use of trivalent metal cations (Bi3+ and Sb3+) that form defect perovskites A3B2X9 has received great attention for the development of solar cells, but their light-emissive properties have not previously been studied. Herein, an all-inorganic antimony-based two-dimensional perovskite, Cs3Sb2I9, was synthesized using the solution process. Vapor-anion-exchange method was employed to change the structural composition from Cs3Sb2I9 to Cs3Sb2Br9 or Cs3Sb2Cl9 by treating CsI/SbI3 spin-coated films with SbBr3 or SbCl3, respectively. This novel method facilitates the fabrication of Cs3Sb2Br9 or Cs3Sb2Cl9 through solution processing without the need of using poorly soluble precursors (e.g., CsCl and CsBr). We go on to demonstrate electroluminescence from a device employing Cs3Sb2I9 emitter sandwiched between ITO/PEDOT:PSS and TPBi/LiF/Al as the hole and electron injection electrodes, respectively. A visible-infrared radiance of 0.012 W·Sr-1·m-2 was measured at 6 V when Cs3Sb2I9 was the active emitter layer. These proof-of-principle devices suggest a viable path toward low-dimensional, lead-free A3B2X9 perovskite optoelectronics.

A lithium passivated MoO3 nanobelt decorated polypropylene separator for fast-charging long-life Li-S batteries.

Dissolution of lithium polysulfide (LiPS) into the electrolyte during discharging, causing shuttling of LiPS from the cathode to the lithium (Li) metal, is mainly responsible for the capacity decay and short battery life of lithium-sulfur batteries (LSBs). Herein, we designed a separator comprising polypropylene (PP) coated with MoO3 nanobelts (MNBs), prepared through facile grinding of commercial MoO3 powder. The formation of Li2Sn-MoO3 during discharging inhibited the polysulfide shuttling; during charging, Li passivated LixMoO3 facilitated ionic transfer during the redox reaction by decreasing the charge transfer resistance. This dual-interaction mechanism of LiPS-with both Mo and the formation of LixMoO3-resulted in a substantially high initial discharge capacity at a very high current density of 5C, with 29.4% of the capacity retained after 5000 cycles. The simple fabrication approach and extraordinary cycle life observed when using this MNB-coated separator suggest a scalable solution for future commercialization of LSBs.

Mitigating Metal Dendrite Formation in Lithium-Sulfur Batteries via Morphology-Tunable Graphene Oxide Interfaces.

Despite issues related to dendrite formation, research on Li metal anodes has resurged because of their high energy density. In this study, graphene oxide (GO) layers are decorated onto Li metal anodes through a simple process of drop-casting and spray-coating. The self-assembly of GO is exploited to synthesize coatings having compact, mesoporous, and macroporous morphologies. The abilities of the GO coatings to suppress dendrite formation are compared through Li|Li symmetrical cell charging at a current density of 5 mA cm-2 for 2000 cycles-a particularly abusive test. The macroporous structure possesses the lowest impedance, whereas the compact structure excels in terms of stability. Moreover, GO exhibits a low nucleation overpotential and is transformed into reduced GO with enhanced conductivity during the operation of the cells; both factors synergistically mitigate the issue of dendrite formation. Li-S batteries incorporating the GO-decorated Li anodes exhibit an initial capacity of 850 mA h g-1 and maintain their stability for 800 cycles at a C-rate of 1 C (1675 mA h g-1), suggesting the applicability of GO in future rechargeable batteries.

Top Illuminated Hysteresis-Free Perovskite Solar Cells Incorporating Microcavity Structures on Metal Electrodes: A Combined Experimental and Theoretical Approach.

Further technological development of perovskite solar cells (PSCs) will require improvements in power conversion efficiency and stability, while maintaining low material costs and simple fabrication. In this Research Article, we describe top-illuminated ITO-free, stable PSCs featuring microcavity structures, wherein metal layers on both sides on the active layers exerted light interference effects in the active layer, potentially increasing the light path length inside the active layer. The optical constants (refractive index and extinction coefficient) of each layer in the PSC devices were measured, while the optical field intensity distribution was simulated using the transfer matrix method. The photocurrent densities of perovskite layers of various thicknesses were also simulated; these results mimic our experimental values exceptionally well. To modify the cavity electrode surface, we deposited a few nanometers of ultrathin MoO3 (2, 4, and 6 nm) in between the Ag and poly(3,4-ethylenedioxythiophene):polystyrenesulfonate (PEDOT:PSS) layers provide hydrophobicity to the Ag surface and elevate the work function of Ag to match that of the hole transport layer. We achieved a power conversion efficiency (PCE) of 13.54% without hysteresis in the device containing a 4 nm-thick layer of MoO3. In addition, we fabricated these devices on various cavity electrodes (Al, Ag, Au, Cu); those prepared using Cu and Au anodes displayed improved device stability of up to 72 days. Furthermore, we prepared flexible PSCs having a PCE of 12.81% after incorporating the microcavity structures onto poly(ethylene terephthalate) as the substrate. These flexible solar cells displayed excellent stability against bending deformation, maintaining greater than 94% stability after 1000 bending cycles and greater than 85% after 2500 bending cycles performed with a bending radius of 5 mm.

Photovoltaic Performance of Vapor-Assisted Solution-Processed Layer Polymorph of Cs3Sb2I9.

The presence of toxic lead (Pb) remains a major obstruction to the commercial application of perovskite solar cells. Although antimony (Sb)-based perovskite-like structures A3M2X9 can display potentially useful photovoltaic behavior, solution-processed Sb-based perovskite-like structures usually favor the dimer phase, which has poor photovoltaic properties. In this study, we prepared a layered polymorph of Cs3Sb2I9 through solution-processing and studied its photovoltaic properties. The exciton binding energy and exciton lifetime of the layer-form Cs3Sb2I9 were approximately 100 meV and 6 ns, respectively. The photovoltaic properties of the layered polymorph were superior to those of the dimer polymorph. A solar cell incorporating the layer-form Cs3Sb2I9 exhibited an open-circuit voltage of 0.72 V and a power conversion efficiency of 1.5%-the highest reported for an all-inorganic Sb-based perovskite.

Modified Separator Performing Dual Physical/Chemical Roles to Inhibit Polysulfide Shuttle Resulting in Ultrastable Li-S Batteries.

In this paper we describe a modified (AEG/CH) coated separator for Li-S batteries in which the shuttling phenomenon of the lithium polysulfides is restrained through two types of interactions: activated expanded graphite (AEG) flakes interacted physically with the lithium polysulfides, while chitosan (CH), used to bind the AEG flakes on the separator, interacted chemically through its abundance of amino and hydroxyl functional groups. Moreover, the AEG flakes facilitated ionic and electronic transfer during the redox reaction. Live H-cell discharging experiments revealed that the modified separator was effective at curbing polysulfide shuttling; moreover, X-ray photoelectron spectroscopy analysis of the cycled separator confirmed the presence of lithium polysulfides in the AEG/CH matrix. Using this dual functional interaction approach, the lifetime of the pure sulfur-based cathode was extended to 3000 cycles at 1C-rate (1C = 1670 mA/g), decreasing the decay rate to 0.021% per cycle, a value that is among the best reported to date. A flexible battery based on this modified separator exhibited stable performance and could turn on multiple light-emitting diodes. Such modified membranes with good mechanical strength, high electronic conductivity, and anti-self-discharging shield appear to be a scalable solution for future high-energy battery systems.

Bifacial Perovskite Solar Cells Featuring Semitransparent Electrodes.

Inorganic-organic hybrid perovskite solar cells (PSCs) are promising devices for providing future clean energy because of their low cost, ease of fabrication, and high efficiencies, similar to those of silicon solar cells. These materials have been investigated for their potential use in bifacial PSCs, which can absorb light from both sides of the electrodes. Here, we fabricated bifacial PSCs featuring transparent BCP/Ag/MoO3 rear electrodes, which we formed through low-temperature processing using thermal evaporation methods. We employed a comprehensive optical distribution program to calculate the distributions of the optical field intensities with constant thicknesses of the absorbing layer in the top electrode configuration. The best PSC having a transparent BCP/Ag/MoO3 electrode achieved PCEs of 13.49% and 9.61% when illuminated from the sides of the indium tin oxide and BCP/Ag/MoO3 electrodes, respectively. We observed significant power enhancement when operating this PSC using mirror reflectors and bifacial light illumination from both sides of the electrodes.

Enhance the light-harvesting capability of the ITO-free inverted small molecule solar cell by ZnO nanorods.

The ITO-free inverted SMPV1:PC71BM solar cells with an Al doped ZnO (AZO) transparent electrodes are fabricated. The AZO thin film prepared by pulsed laser deposition (PLD) technique exhibits high transmission (>85%) and low sheet resistance (~30 Ω/sq) and the power conversion efficiency (PCE) of devices based on AZO electrode can reach around 4%. To further enhance the light harvesting of the absorption layer of solar cells, ZnO nanorods interlayer is grown on the AZO layer before the deposition the active layer. The absorption spectrums of devices under various conditions are also simulated by RCWA method to identify the optical saturation length of the ZnO nanorods. The PCE of ITO-free inverted small molecule solar cell improved with ZnO nanorods can reach 6.6%.

High photosensitivity and broad spectral response of multi-layered germanium sulfide transistors.

In this paper, we report the optoelectronic properties of multi-layered GeS nanosheet (∼28 nm thick)-based field-effect transistors (called GeS-FETs). The multi-layered GeS-FETs exhibit remarkably high photoresponsivity of Rλ ∼ 206 A W(-1) under 1.5 µW cm(-2) illumination at λ = 633 nm, Vg = 0 V, and Vds = 10 V. The obtained Rλ ∼ 206 A W(-1) is excellent as compared with a GeS nanoribbon-based and the other family members of group IV-VI-based photodetectors in the layered-materials realm, such as GeSe and SnS2. The gate-dependent photoresponsivity of GeS-FETs was further measured to be able to reach Rλ ∼ 655 A W(-1) operated at Vg = -80 V. Moreover, the multi-layered GeS photodetector holds high external quantum efficiency (EQE ∼ 4.0 × 10(4)%) and specific detectivity (D* ∼ 2.35 × 10(13) Jones). The measured D* is comparable to those of the advanced commercial Si- and InGaAs-based photodiodes. The GeS photodetector also shows an excellent long-term photoswitching stability over a long period of operation (>1 h). These extraordinary properties of high photocurrent generation, broad spectral range, and long-term stability make the GeS-FET photodetector a highly qualified candidate for future optoelectronic applications.

Planar Heterojunction Perovskite Solar Cells Incorporating Metal-Organic Framework Nanocrystals.

Zr-based porphyrin metal-organic framework (MOF-525) nanocrystals with a crystal size of about 140 nm are synthesized and incorporated into perovskite solar cells. The morphology and crystallinity of the perovskite thin film are enhanced since the micropores of MOF-525 allow the crystallization of perovskite to occur inside; this observation results in a higher cell efficiency of the obtained MOF/perovskite solar cell.

Using an airbrush pen for layer-by-layer growth of continuous perovskite thin films for hybrid solar cells.

In this manuscript we describe hybrid heterojunction solar cells, having the device architecture glass/indium tin oxide/poly(3,4-ethylenedioxythiopene)/poly(styrenesulfonic acid)/perovskite/[6,6]-phenyl-C61-butyric acid methyl ester/C60/2,9-dimethyl- 4,7-diphenyl-1,10-phenanthroline/Al, fabricated using lead halide perovskite obtained through spray-coating at a low precursor concentration. To study the relationship between the morphology and device performance, we recorded scanning electron microscopy images of perovskite films prepared at various precursor ratios, spray volumes, substrate temperatures, and postspray annealing temperatures. Optimization of the spray conditions ensured uniform film growth and high surface area coverage at low substrate temperatures. Lead halide perovskite solar cells prepared under the optimal conditions displayed an average power conversion efficiency (PCE) of approximately 9.2%, with 85% of such devices having efficiencies of greater than 8.3%. The best-performing device exhibited a short-circuit current density of 17.3 mA cm(-2), a fill factor of 0.63, and an open-circuit voltage of 0.93 V, resulting in a PCE of 10.2%. Because spray-coating technology allows large-area deposition, we also fabricated devices having areas of 60 and 342 mm(2), achieving PCEs with these devices of 6.88 and 4.66%, respectively.