Recent Advances in Phosphorene: Structure, Synthesis, and Properties.

Phosphorene is a 2D phosphorus atomic layer arranged in a honeycomb lattice like graphene but with a buckled structure. Since its exfoliation from black phosphorus in 2014, phosphorene has attracted tremendous research interest both in terms of synthesis and fundamental research, as well as in potential applications. Recently, significant attention in phosphorene is motivated not only by research on its fundamental physical properties as a novel 2D semiconductor material, such as tunable bandgap, strong in-plane anisotropy, and high carrier mobility, but also by the study of its wide range of potential applications, such as electronic, optoelectronic, and spintronic devices, energy conversion and storage devices. However, a lot of avenues remain to be explored including the fundamental properties of phosphorene and its device applications. This review recalls the current state of the art of phosphorene and its derivatives, touching upon topics on structure, synthesis, characterization, properties, stability, and applications. The current needs and future opportunities for phosphorene are also discussed.

Local Built-In Field at the Sub-nanometric Heterointerface Mediates Cascade Electrochemical Conversion of Lithium-sulfur Batteries.

Heterogeneous catalytic mediators have been proposed to play a vital role in enhancing the multiorder reaction and nucleation kinetics in multielectron sulfur electrochemistry. However, the predictive design of heterogeneous catalysts is still challenging, owing to the lack of in-depth understanding of interfacial electronic states and electron transfer on cascade reaction in Li-S batteries. Here, a heterogeneous catalytic mediator based on monodispersed titanium carbide sub-nanoclusters embedded in titanium dioxide nanobelts is reported. The tunable catalytic and anchoring effects of the resulting catalyst are achieved by the redistribution of localized electrons caused by the abundant built-in fields in heterointerfaces. Subsequently, the resulting sulfur cathodes deliver an areal capacity of 5.6 mAh cm-2 and excellent stability at 1 C under sulfur loading of 8.0 mg cm-2 . The catalytic mechanism especially on enhancing the multiorder reaction kinetic of polysulfides is further demonstrated via operando time-resolved Raman spectroscopy during the reduction process in conjunction with theoretical analysis.

High-Efficiency CsPbI2Br Perovskite Solar Cells with over 83% Fill Factor by Synergistic Effects of a Multifunctional Additive.

All-inorganic CsPbI2Br with outstanding thermal stability and excellent photoelectric properties is considered as a promising candidate for photovoltaic applications. However, the efficiency of CsPbI2Br perovskite solar cells (PSCs) is still much lower than that of their organic-inorganic hybrid counterparts or CsPbI3-based devices. Herein, we obtained an optimized CsPbI2Br PSC (0.09 cm2) with a champion efficiency of 17.38% and a record fill factor of 83.6% by introducing potassium anthraquinone-1,8-disulfonate (DAD) in the precursor solution. The synergistic effect between the electronegative functional groups and K+ ions in the DAD structure can not only effectively regulate the crystallization growth process to improve the crystalline quality and stability of photo-active CsPbI2Br but also optimize the energy level alignment and passivate the defects to improve the carrier transport properties. The efficiency of the corresponding large-area device (5 cm × 5 cm with an active area of 19.25 cm2) reached 13.20%. Moreover, the optimized CsPbI2Br PSC exhibited negligible hysteresis and enhanced long-term storage stability as well as thermal stability. Our method produces more stable photo-active CsPbI2Br with excellent photoelectric properties for industrial applications or perovskite/silicon tandem cells.

Atomic Level Insights into Metal Halide Perovskite Materials by Scanning Tunneling Microscopy and Spectroscopy.

Metal halide perovskite materials (MHPMs) have attracted significant attention because of their superior optoelectronic properties and versatile applications. The power conversion efficiency of MHPM solar cells (PSCs) has skyrocketed to 25.5 %. Although the performance of PSCs is already competitive, several important challenges still need to be solved to realize commercial applications. A thorough understanding of surface atomic structures and structure-property relationships is at the heart of these remaining issues. Scanning tunneling microscopy (STM) and spectroscopy (STS) can be used to characterize the surface properties of MHPMs, which can offer crucial insights into MHPMs at the atomic scale. This Review summarizes recent progress in STM and STS studies on MHPMs, with a focus on the surface properties. We provide understanding from the comparative perspective of several different MHPMs. We also highlight a series of novel phenomena observed by STM and STS. Finally, we outline a few research topics of primary importance for future studies.

Spectral Stable Blue-Light-Emitting Diodes via Asymmetric Organic Diamine Based Dion-Jacobson Perovskites.

The spectral instability issue is a challenge in blue perovskite light-emitting diodes (PeLEDs). Dion-Jacobson (DJ) phase perovskites are promising alternatives to achieve high-quality blue PeLEDs. However, the current exploration of DJ phase perovskites is focused on symmetric divalent cations, and the corresponding efficiency of blue PeLEDs is still inferior to that of green and red ones. In this work, we report a new type of DJ phase CsPb(Br/Cl)3 perovskite via introduction of an asymmetric molecular configuration as the organic spacer cation in perovskites. The primary and tertiary ammonium groups on the asymmetric cations bridge with the lead halide octahedra forming the DJ phase structures. Stable photoluminescence spectra were demonstrated in perovskite films owing to the suppressed halide segregation. Meanwhile, the radiative recombination efficiency of charges is improved significantly as a result of the confinement effects and passivation of charge traps. Finally, we achieved an external quantum efficiency of 2.65% in blue PeLEDs with stable spectra emission under applied bias voltages. To our best knowledge, this is the first report of asymmetric cations used in PeLEDs, which provides a facile solution to the halide segregation issue in PeLEDs.

Unclonable Micro-Texture with Clonable Micro-Shape towards Rapid, Convenient, and Low-Cost Fluorescent Anti-Counterfeiting Labels.

An ideal anti-counterfeiting label not only needs to be unclonable and accurate but also must consider cost and efficiency. But the traditional physical unclonable function (PUF) recognition technology must match all the images in a database one by one. The matching time increases with the number of samples. Here, a new kind of PUF anti-counterfeiting label is introduced with high modifiability, low reagent cost (2.1 × 10-4 USD), simple and fast authentication (overall time 12.17 s), high encoding capacity (2.1 × 10623 ), and its identification software. All inorganic perovskite nanocrystalline films with clonable micro-profile and unclonable micro-texture are prepared by laser engraving for lyophilic patterning, liquid strip sliding for high throughput droplet generation, and evaporative self-assembling for thin film deposition. A variety of crystal film profile shapes can be used as "specificator" for image recognition, and the verification time of recognition technology based on this divide-and-conquer strategy can be decreased by more than 20 times.

Reducing Detrimental Defects for High-Performance Metal Halide Perovskite Solar Cells.

In several photovoltaic (PV) technologies, the presence of electronic defects within the semiconductor band gap limit the efficiency, reproducibility, as well as lifetime. Metal halide perovskites (MHPs) have drawn great attention because of their excellent photovoltaic properties that can be achieved even without a very strict film-growth control processing. Much has been done theoretically in describing the different point defects in MHPs. Herein, we discuss the experimental challenges in thoroughly characterizing the defects in MHPs such as, experimental assignment of the type of defects, defects densities, and the energy positions within the band gap induced by these defects. The second topic of this Review is passivation strategies. Based on a literature survey, the different types of defects that are important to consider and need to be minimized are examined. A complete fundamental understanding of defect nature in MHPs is needed to further improve their optoelectronic functionalities.

Unraveling the Impact of Halide Mixing on Perovskite Stability.

Increasing the stability of perovskites is essential for their integration in commercial photovoltaic devices. Halide mixing is suggested as a powerful strategy toward stable perovskite materials. However, the stabilizing effect of the halides critically depends on their distribution in the mixed compound, a topic that is currently under intense debate. Here we successfully determine the exact location of the I and Cl anions in the  CH3NH3PbBr3- yI y and CH3NH3PbBr3- zCl z mixed halide perovskite lattices and correlate it with the enhanced stability we find for the latter. By combining scanning tunneling microscopy and density functional theory, we predict that, for low ratios, iodine and chlorine incorporation have different effects on the electronic properties and stability of the CH3NH3PbBr3 perovskite material. In addition, we determine the optimal Cl incorporation ratio for stability increase without detrimental band gap modification, providing an important direction for the fabrication of stable perovskite devices. The increased material stability induced by chlorine incorporation is verified by performing photoelectron spectroscopy on a half-cell device architecture. Our findings provide an answer to the current debate on halide incorporation and demonstrate their direct influence on device stability.

Real-Space Imaging of the Atomic Structure of Organic-Inorganic Perovskite.

Organic-inorganic perovskite is a promising class of materials for photovoltaic applications and light emitting diodes. However, so far commercialization is still impeded by several drawbacks. Atomic-scale effects have been suggested to be possible causes, but an unequivocal experimental view at the atomic level is missing. Here, we present a low-temperature scanning tunneling microscopy study of single crystal methylammonium lead bromide CH3NH3PbBr3. Topographic images of the in situ cleaved perovskite surface reveal the real-space atomic structure. Compared to the bulk we observe modified arrangements of atoms and molecules on the surface. With the support of density functional theory we explain these by surface reconstruction and a substantial interplay of the orientation of the polar organic cations (CH3NH3)(+) with the position of the hosting anions. This leads to structurally and electronically distinct domains with ferroelectric and antiferroelectric character. We further demonstrate local probing of defects, which may also impact device performance.

Large changes of graphene conductance as a function of lattice orientation between stacked layers.

Using the conductive tip of an atomic force microscope as an electrode, we found that the electrical conductance of graphite terraces separated by steps can vary by large factors of up to 100, depending on the relative lattice orientation of the surface and subsurface layers. This effect can be attributed to interlayer interactions that, when stacked commensurately in a Bernal sequence (ABAB...), cause the band gap to open. Misaligned layers, on the other hand, behave like graphene. Angular misorientations of a few degrees were found to cause large increases in the conductance of the top layer, with the maximum occurring around 30°. These results suggest new applications for graphene multilayers by stacking layers at various angles to control the resistance of the connected graphene ribbons in devices.

Boosting the Performances of Semitransparent Organic Photovoltaics via Synergetic Near-Infrared Light Management.

Semitransparent organic photovoltaics (ST-OPVs) offer promising prospects for application in building-integrated photovoltaic systems and greenhouses, but further improvement of their performance faces a delicate trade-off between the two competing indexes of power conversion efficiency (PCE) and average visible transmittance (AVT). Herein, the authors take advantage of coupling plasmonics with the optical design of ST-OPVs to enhance near-infrared absorption and hence simultaneously improve efficiency and visible transparency to the maximum extent. By integrating core-bishell PdCu@Au@SiO2 nanotripods that act as optically isotropic Lambertian sources with near-infrared-customized localized surface plasmon resonance in an optimal ternary PM6:BTP-eC9:L8-BO-based ST-OPV, it is shown that their interplay with a multilayer optical coupling layer, consisting of ZnS(130 nm)/Na3AlF6(60 nm)/WO3(100 nm)/LaF3(50 nm) identified from high-throughput optical screening, leads to a record-high PCE of 16.14% (certified as 15.90%) along with an excellent AVT of 33.02%. The strong enhancement of the light utilization efficiency by ≈50% as compared to the counterpart device without optical engineering provides an encouraging and universal pathway for promoting breakthroughs in ST-OPVs from meticulous optical design.

Sensitivity to molecular order of the electrical conductivity in oligothiophene monolayer films.

Using conducting probe atomic force microscopy (CAFM), we show that electrical conductivity in oligothiophene molecular films deposited on SiO(2)/Si wafers is extremely sensitive to degree of crystalline order in the film. By locally distorting the molecular order in the films through the controlled application of pressure with the AFM tip, the lateral charge transport was reduced by factors varying from 2 to 10, even when no changes in the height of the film could be observed.

Pathways of Water-Induced Lead-Halide Perovskite Surface Degradation: Insights from In Situ Atomic-Scale Analysis.

While organic-inorganic hybrid perovskites are emerging as promising materials for next-generation photovoltaic applications, the origins and pathways of perovskite instability remain speculative. In particular, the degradation of perovskite surfaces by ambient water is a crucial subject for determining the long-term viability of perovskite-based solar cells. Here, we conducted surface characterization and atomic-scale analysis of the reaction mechanisms for methylammonium lead bromide (MA(CH3NH3)PbBr3) single crystals using ambient-pressure atomic force microscopy (AP-AFM) and near-ambient-pressure X-ray photoelectron spectroscopy (NAP-XPS) in environments ranging from ultrahigh vacuum to 0.01 mbar of water vapor. MAPbBr3 single crystals, grown by a solution process, were mechanically cleaved under UHV conditions to obtain an atomically clean surface. Consecutive topography and friction force measurements in low-pressure water (pwater ≈ 10-5 mbar) revealed the formation of degraded patches, one atomic layer deep, gradually increasing their coverage until the surface was entirely covered at a water exposure of 4.7 × 104 langmuir (L). At the perimeters of these degraded patches, a higher friction coefficient was observed, along with an interstitial step height, which we attribute to a structure equivalent to that of the MA-Br terminated surface. Combined with NAP-XPS analysis, our results demonstrate that water vapor induces the dissociation of surface methylammonium ligands, eventually resulting in the depletion of the surface MA and the full coverage of hydrocarbon species after exposure to 0.01 mbar of water vapor.

Modulation of perovskite degradation with multiple-barrier for light-heat stable perovskite solar cells.

The long-term stability of perovskite solar cells remains one of the most important challenges for the commercialization of this emerging photovoltaic technology. Here, we adopt a non-noble metal/metal oxide/polymer multiple-barrier to suppress the halide consumption and gaseous perovskite decomposition products release with the chemically inert bismuth electrode and Al2O3/parylene thin-film encapsulation, as well as the tightly closed system created by the multiple-barrier to jointly suppress the degradation of perovskite solar cells, allowing the corresponding decomposition reactions to reach benign equilibria. The resulting encapsulated formamidinium cesium-based perovskite solar cells with multiple-barrier maintain 90% of their initial efficiencies after continuous operation at 45 °C for 5200 h and 93% of their initial efficiency after continuous operation at 75 °C for 1000 h under 1 sun equivalent white-light LED illumination.

Graphene-Like Conjugated Molecule as Hole-Selective Contact for Operationally Stable Inverted Perovskite Solar Cells and Modules.

Further enhancing the operational lifetime of inverted-structure perovskite solar cells (PSCs) is crucial for their commercialization, and the design of hole-selective contacts at the illumination side plays a key role in operational stability. In this work, the self-anchoring benzo[rst]pentaphene (SA-BPP) is developed as a new type of hole-selective contact toward long-term operationally stable inverted PSCs. The SA-BPP molecule with a graphene-like conjugated structure shows a higher photostability and mobility than that of the frequently-used triphenylamine and carbazole-based hole-selective molecules. Besides, the anchoring groups of SA-BPP promote the formation of a large-scale uniform hole contact on ITO substrate and efficiently passivate the perovskite absorbers. Benefiting from these merits, the champion efficiencies of 22.03% for the small-sized cells and 17.08% for 5 × 5 cm2 solar modules on an aperture area of 22.4 cm2 are achieved based on this SA-BPP contact. Also, the SA-BPP-based device exhibits promising operational stability, with an efficiency retention of 87.4% after 2000 h continuous operation at the maximum power point under simulated 1-sun illumination, which indicates an estimated T80 lifetime of 3175 h. This novel design concept of hole-selective contacts provides a promising strategy for further improving the PSC stability.

Electrical transport properties of oligothiophene-based molecular films studied by current sensing atomic force microscopy.

Using conducting probe atomic force microscopy (CAFM) we have investigated the electrical conduction properties of monolayer films of a pentathiophene derivative on a SiO(2)/Si-p+ substrate. By a combination of current-voltage spectroscopy and current imaging we show that lateral charge transport takes place in the plane of the monolayer via hole injection into the highest occupied molecular orbitals of the pentathiophene unit. Our CAFM data suggest that the conductivity is anisotropic relative to the crystalline directions of the molecular lattice.

Regulated synthesis of Zr-metal-organic frameworks with variable hole size and its influence on the performance of novel MOF-based heterogeneous amino acid-thiourea catalysts.

We present an efficient and easy synthesis method for incorporating organocatalytic moieties into Zr-metal organic frameworks (Zr-MOFs). The catalytic activity and selectivity of the new chiral catalysts were improved by adjusting the aperture of the MOF cavities. The hole size of the Zr-MOF was modulated by adding acid and replacing bridge ligands during synthesis. The difunctional chiral units of amino acid-thiourea are anchored onto the Zr-MOF by a mild synthesis method from an isothiocyanate intermediate which could effectively avoid the racemization of chiral moieties in the synthesis process. By means of specific surface area measurement (BET), scanning electron microscopy (SEM) and powder X-ray Diffraction (PXRD), it was confirmed that Zr-MOFs with different pore sizes were synthesized without breaking the basic octahedral structure of the MOF. Finally, good yields (up to 83%) and ee values (up to 73%) were achieved with the new heterogeneous catalysts in 48 hours for the aldol reaction of 4-nitrobenzaldehyde with acetone. By contrast, using the catalyst support without modulating the synthesis, the yield (30%) and the ee-value (26%) were both low. Experiments have confirmed the important influence on the reaction selectivity of providing a suitable reaction environment by controlling the aperture of MOF cavities.

Heterogeneous FASnI3 Absorber with Enhanced Electric Field for High-Performance Lead-Free Perovskite Solar Cells.

Lead-free tin perovskite solar cells (PSCs) have undergone rapid development in recent years and are regarded as a promising eco-friendly photovoltaic technology. However, a strategy to suppress charge recombination via a built-in electric field inside a tin perovskite crystal is still lacking. In the present study, a formamidinium tin iodide (FASnI3) perovskite absorber with a vertical Sn2+ gradient was fabricated using a Lewis base-assisted recrystallization method to enhance the built-in electric field and minimize the bulk recombination loss inside the tin perovskites. Depth-dependent X-ray photoelectron spectroscopy revealed that the Fermi level upshifts with an increase in Sn2+ content from the bottom to the top in this heterogeneous FASnI3 film, which generates an additional electric field to prevent the trapping of photo-induced electrons and holes. Consequently, the Sn2+-gradient FASnI3 absorber exhibits a promising efficiency of 13.82% for inverted tin PSCs with an open-circuit voltage increase of 130 mV, and the optimized cell maintains over 13% efficiency after continuous operation under 1-sun illumination for 1,000 h.

Hexaazatriphenylene (HAT) versus tri-HAT: the bigger the better?

A new hexaazatriphenylene (HAT) derivative formed by the fusion of three HAT units has been prepared and its electronic and molecular structures have been fully characterized by optical and vibrational Raman spectroscopy, electrochemistry, solid-state UV and inverse photoemission spectroscopy (UPS and IPES), and by quantum-chemical calculations. A comparative HAT versus tri-HAT study was performed. The fusion of three HAT molecules causes modifications in the optical and electrochemical properties consistent with enhanced π-electron delocalization attained in a bigger planar core. Such combined experimental and theoretical studies are useful to balance chemical design with supramolecular engineering directed to find enhanced characteristics for new organic semiconductor applications.

Defect Passivation for Perovskite Solar Cells: from Molecule Design to Device Performance.

Perovskite solar cells (PSCs) are a promising third-generation photovoltaic (PV) technology developed rapidly in recent years. Further improvement of their power conversion efficiency is focusing on reducing the non-radiative charge recombination induced by the defects in metal halide perovskites. So far, defect passivation by the organic small molecule has been considered as a promising approach for boosting the PSC performance owing to their large structure flexibility adapting to passivating variable kinds of defect states and perovskite compositions. Here, the recent progress of defect passivation toward efficient and stable PSCs was reviewed from the viewpoint of molecular structure design and device performance. To comprehensively reveal the structure-performance correlation of passivation molecules, it was separately discussed how the functional groups, organic frameworks, and side chains affect the corresponding PV parameters of PSCs. Finally, a guideline was provided for researchers to select more suitable passivation agents, and a perspective was given on future trends in development of passivation strategies.