Air-Processed All-Inorganic Halide Perovskites Integrated Photorechargeable Supercapacitors.

Due to their easy integration for self-powered operation, integrated energy harvesting and storage could be the game changer in smart, flexible, and portable electronic devices. Three-electrode integration is the most promising approach among all possible configurations because it is less complex and compatible with most techniques. Although the photoconversion efficiency has increased above 20% due to the integration of high-performance perovskite solar cells, the electrochemical storage efficiency (efficacy of the integration) is much below 80% due to a significant potential drop and impedance mismatch. In this context, we introduced perovskite-based solid-state thin film supercapacitors integrated with stable, air-processed perovskite solar cells for an uninterrupted power supply. Our measurement shows that the best performance can be achieved by optimizing several parameters, including series-connected solar cells, light intensity, and photovoltaic active area. The critical challenge with these integrated systems is to maintain a uniform charging current of the supercapacitors throughout the charging cycle while minimizing self-discharging. We achieved an electrochemical storage efficiency of ∼87% at an overpotential of 0.8 V. The overpotential can be as low as 2 mV. We fabricated fully solution-processed series-connected solar cells to integrate with stacked supercapacitors to improve the operating voltage beyond 2.1 V. The photocharging and dark discharging of these integrated devices have been tested over 200 cycles, and a negligible drop in efficiency has been observed. Our detailed energy conversion and storage analysis in these systems unveils the mechanism and losses due to three-terminal integration.

Dual-edged sword of ion migration in perovskite materials for simultaneous energy harvesting and storage application.

Portable electronic devices and Internet of Things (IoT) require an uninterrupted power supply for their optimum performance and are key ingredients of the futuristic smart buildings - cities. The off-grid photovoltaic cells and photo-rechargeable energy storage devices meet the requirements for continuous data processing and transmission. In addition, these off-grid devices can solve the energy mismanagement problem famously called as "duck curve". The conventional approach is the external integration of a photovoltaic cell and an energy storage device through a complex multi-layered structure. However, this approach causes ohmic transport losses and requires additional complex device packaging leading to increased weight and high cost. Toward this narrative, in this viewpoint, we shed light on application of disruptive organic-inorganic hybrid halide perovskite bifunctional materials employed as smart photo-rechargeable energy devices. We also present hybrid halide lead-free perovskite materials for off-grid energy storage systems for indoor lighting applications.

Air stable highly luminescent 2D tin halide perovskite nanocrystals as photodetectors.

Hybrid and inorganic perovskite nanocrystals are a hot topic in materials chemistry due to their versatile optoelectronic properties. Herein, we report highly luminescent water stable lead-free orange emissive (OleylAm)2SnBr4 (OleylAm = oleylammonium cation) 2D tin halide perovskite nanocrystals in humid conditions in a solution-based process. The photoresponse study performed with the synthesized nanocrystals exhibits a responsivity of 4.9 mA W-1 at a 5 V operating voltage.

Intensity modulated photocurrent spectroscopy to investigate hidden kinetics at hybrid perovskite-electrolyte interface.

The numerous assorted accounts of the fundamental questions of ion migration in hybrid perovskites are making the picture further intricate. The review of photo-induced ion migration using small perturbation frequency domain techniques other than impedance spectroscopy is more crucial now. Herein, we probe into this by investigating perovskite-electrolyte (Pe-E) and polymer-aqueous electrolyte (Po-aqE) interface using intensity modulated photocurrent spectroscopy (IMPS) in addition to photoelectrochemical impedance spectroscopy (PEIS). We reported that the electronic-ionic interaction in hybrid perovskites including the low-frequency ion/charge transfer and recombination kinetics at the interface leads to the spiral feature in IMPS Nyquist plot of perovskite-based devices. This spiral trajectory for the perovskite-electrolyte interface depicts three distinct ion kinetics going on at the different time scales which can be more easily unveiled by IMPS rather than PEIS. Hence, IMPS is a promising alternative to PEIS. We used Peter's method of interpretation of IMPS plot in photoelectrochemistry to estimate charge transfer efficiency [Formula: see text] from the Rate Constant Model. The [Formula: see text] at low-frequency for Pe-E interface exceeds unity due to ion migration induced modified potential across the perovskite active layer. Hence, ion migration and mixed electronic-ionic conductivity of hybrid perovskites are responsible for the extraordinary properties of this material.

Photorechargeable Hybrid Halide Perovskite Supercapacitors.

Current approaches for off-grid power separate the processes for energy conversion from energy storage. With the right balance between the electronic and ionic conductivity and a semiconductor that can absorb light in the solar spectrum, we can combine energy harvesting with storage into a single photoelectrochemical energy storage device. We report here such a device, a halide perovskite-based photorechargeable supercapacitor. This device can be charged with an energy density of 30.71 W h kg-1 and a power density of 1875 W kg-1. By taking advantage of the semiconducting and ionic properties of halide perovskites, we report a method for fabricating efficient photorechargeable supercapacitors having a photocharging conversion efficiency (η) of ∼0.02% and a photoenergy density of ∼160 mW h kg-1 under a 20 mW cm-2 intensity white light source. Halide perovskites have a high absorption coefficient, large carrier diffusion length, and high ionic conductivity, while the electronic conductivity is improved significantly by mixing carbon black in porous perovskite electrodes to achieve efficient photorechargeable supercapacitors. We also report a detailed analysis of the photoelectrode to understand the working principles, stability, limitations, and prospects of halide perovskite-based photorechargeable supercapacitors.

Visualization of 3D to quasi 2D conversion of perovskite thin films via in situ photoluminescence measurement: a facile route to design a graded energy landscape.

2D-perovskites are generally more stable than 3D perovskites while charge transport in 2D-perovskites becomes inefficient. On the other hand, the instability of 3D perovskite films under heat, light and environmental conditions makes them inapplicable for practical purposes. Therefore, quasi-2D perovskites could be the optimum solution for stable yet highly efficient devices. Using the post-fabrication treatment method, we have converted methylammonium lead tribromide (MAPbBr3) 3D perovskite films into a quasi 2D-perovskite interfacial layer. In situ photoluminescence measurement during spin coating indicates a rapid conversion of 3D-perovskite into 2D-perovskites. The kinetics of oxygen and moisture diffusion, ion diffusion and electronic charge transport can be estimated from the time dependent PL measurements in the 3D and 2D/3D perovskite samples. 2D terminated perovskite samples show enhanced photoluminescence and improved stability in moisture and UV-irradiation. We also propose that a relatively wide bandgap of 2D-perovskite can give rise to a graded energy landscape at the interface for favorable charge separation. Simulation results reveal that the power conversion efficiency can be improved from 2.83% to 4.02% due to an increase in open-circuit voltage and fill factor in 2D/3D based MAPbBr3 solar cells without using any electron transport layer.

Advanced Strategies to Tailor the Nucleation and Crystal Growth in Hybrid Halide Perovskite Thin Films.

Remarkable improvement in the perovskite solar cell efficiency from 3.8% in 2009 to 25.5% today has not been a cakewalk. The credit goes to various device fabrication and designing techniques employed by the researchers worldwide. Even after tremendous research in the field, phenomena such as ion migration, phase segregation, and spectral instability are not clearly understood to date. One of the widely used techniques for the mitigation of ion migration is to reduce the defect density by fabricating the high-quality perovskite thin films. Therefore, understanding and controlling the perovskite crystallization and growth have become inevitably crucial. Some of the latest methods attracting attention are controlling perovskite film morphology by modulating the coating substrate temperature, antisolvent treatment, and solvent engineering. Here, the latest techniques of morphology optimization are discussed, focusing on the process of nucleation and growth. It can be noted that during the process of nucleation, the supersaturation stage can be induced faster by modifying the chemical potential of the system. The tailoring of Gibbs free energy and, hence, the chemical potential using the highly utilized techniques is summarized in this minireview. The thermodynamics of the crystal growth, design, and orientation by changing several parameters is highlighted.

Tunable ionic conductivity and photoluminescence in quasi-2D CH3NH3PbBr3 thin films incorporating sulphur doped graphene quantum dots.

Ion migration in hybrid halide perovskites is ubiquitous in all conditions. However, the ionic conductivity can be manipulated by changing the material composition, operating temperature, light illumination, and applied bias as well as the nature of the interfaces of the devices. There have been various reports on electron ion coupling in hybrid perovskite semiconductors which gives rise to anomalous charge transport behavior in these devices under an applied bias. In this investigation, we have synthesized a mixture of 2D/3D perovskites by incorporating sulphur-doped graphene quantum dots (SGQDs) and demonstrated that the optical and electrical properties of the hybrid system can be tuned by controlling the ion conductivity through the active layer. It has been observed that the recombination resistance in undoped CH3NH3PbBr3 perovskites follows an anomalous behavior while the doped CH3NH3PbBr3 perovskite shows a monotonic increase with increasing applied bias due to reduced ionic conductivity. SGQDs at the grain boundaries of 2D/3D perovskites prohibit ion migration through the active layer, and therefore the electronic-ionic coupling is reduced. This results in increased recombination resistance with increasing applied bias.

The curious case of ion migration in solid-state and liquid electrolyte-based perovskite devices: unveiling the role of charge accumulation and extraction at the interfaces.

Electrochemical impedance spectroscopy (EIS) has been extensively used for the detailed investigation and understanding of the plethora of physical properties of variegated electrochemical and solid-state systems. Over the past few years, EIS has revealed many significant findings in hybrid halide perovskite (HHP)-based optoelectronic devices too. Photoinduced ion-migration, negative capacitance, anomalous mid-frequency capacitance, hysteresis, and instability to heat, light and moisture in HHP-based devices are among the few issues addressed by the IS technique. However, performing EIS in perovskite devices presents new challenges related to multilayer solid-state device geometry and complicated material properties. The ions in the perovskite behave in a specified manner, which is dictated by the energy-levels of the transport layer. Electronic-ionic coupling is one of the major challenges to understand ion transport kinetics in solid-state devices. In this work, we have performed impedance measurements in both solid-state (S-S) and liquid-electrolyte (L-E) device geometry to unfold the effect of charge transport layers on the ac ionic conductivity in perovskite materials. We have modelled the impedance spectra using the electrical equivalent circuit (EEC) and compared the behaviour of ions in different controlling environments. It was concluded that the AC as well as dc ionic conductivity and the accumulation of ions in the perovskite material are highly influenced by the nature of the interface in different device geometry. Charge accumulation in the S-S device gives rise to large polarisation, thereby negative capacitance or any inductive loop can be observed in the Nyquist plot while in the L-E device the presence of an electric double layer at the perovskite/electrolyte interface reduces the surface polarisation effect. Ionic conductivity is hopping limited in the low field regime and diffusion limited in the high field regime in the S-S device. Moreover, the perovskite/electrolyte based devices are promising candidates for electrolyte gated field-effect transistors, perovskite-based supercapacitors and electrochemical cells for water splitting or CO2 reduction.

Unraveling the antisolvent dripping delay effect on the Stranski-Krastanov growth of CH3NH3PbBr3 thin films: a facile route for preparing a textured morphology with improved optoelectronic properties.

Inorganic-organic hybrid perovskite materials have been a topic of interest for the last few years due to their superior optoelectronic properties. However, the optical properties of perovskite materials are strongly dependent on the film morphology. A textured film morphology is expected to have higher light absorption as well as light out-coupling efficiency compared to a smooth film. There have been numerous methods for controlling and optimizing the film morphology to achieve high efficiency in solar cells and light emitting diodes. Here we have demonstrated that controlled anti-solvent treatment at low temperature can lead to Stranski-Krastanov growth in CH3NH3PbBr3 thin films with superior optical and electronic properties for light emitting diode applications. We have studied their photoluminescence properties at the micro- to nano-scale via fluorescence microscopy, hyper-spectral imaging and scanning near-field optical microscopy. We have demonstrated that the nanostructured micro-islands are highly emissive because of large quasi-Fermi level splitting (QFLS) due to the localization of free charges in the smaller crystals. We have shown that the photoluminescence as well as electroluminescence can be improved by at least seven-fold due to the presence of micro-islands on a smooth background film enhancing light out-coupling. Photo-induced photoluminescence enhancement is also observed in smooth films while micro-islands show photo-degradation.

Unveiling the Morphology Effect on the Negative Capacitance and Large Ideality Factor in Perovskite Light-Emitting Diodes.

Perovskite light-emitting diodes have almost reached the threshold for potential commercialization within a few years of research. However, there are still some unsolved puzzles such as large ideality factor and the presence of large negative capacitance especially at the low-frequency regime yet to be addressed. Here, we have fabricated a methylammonium lead tri-bromide perovskite n-i-p structure for light-emitting diodes from a smooth and textured emissive layer and demonstrated for the first time that these two factors are strongly dependent on the perovskite film morphology. Bias-dependent capacitance measurement also reveals the transition between negative to positive capacitance in textured films at the low-frequency regime. We have observed an anomalous capacitive behavior at the mid-frequency regime in smooth perovskite films but not in textured films. The relatively large ideality factor and anomalous capacitive behavior observed in perovskite light-emitting diodes are due to the presence of strong coupling between ions and electrons near the electrode interface. Therefore, the ideality factor and anomalous capacitance at the mid-frequency regime can be decreased by minimizing electronic-ionic coupling in textured perovskite films, while light outcoupling can be improved significantly.

Elucidating tuneable ambipolar charge transport and field induced bleaching at the CH3NH3PbI3/electrolyte interface.

Charge transport through lead trihalide based perovskites is more complex than through any other semiconducting materials due to their mixed electronic-ionic conductivity as well as ambipolarity. Here we have investigated charge transport through a perovskite/electrolyte interface using electrochemical impedance spectroscopy (EIS) under illumination and applied bias conditions. Similar trends in EIS were observed with positively biased as well as negatively biased working electrodes, indicating ambipolar charge transport through the perovskite layer. Ionic conductivity upon photo-illumination plays a significant role in modulating charge transport at the interface by creating an additional built-in field which flips its polarity at a moderate applied bias voltage. Therefore, anomalous charge transport resistance is observed under illumination at around 400 to 600 mV applied bias. Electric field induced UV-Vis absorption spectroscopy shows a decrease in absorption when both positive and negative bias voltages are applied to a perovskite coated ITO working electrode, indicating the occurrence of excited state charge transfer at the electrolyte interface. Two distinct electric field induced bleaching bands have been observed at around 480 nm and 750 nm, similar to the two photobleaching bands due to the dual nature of the excited states in lead halide perovskites.

Origin of Low Open-Circuit Voltage in Surfactant-Stabilized Organic-Nanoparticle-Based Solar Cells.

Organic-nanoparticle-based solar cells have drawn great attention due to their eco-friendly and environmentally friendly fabrication procedure. However, these surfactant-stabilized nanoparticles suffer open-circuit voltage loss due to charge trapping and poor extraction rate at the polymer cathode interface. Here, we have investigated the origin of voltage loss and charge trapping in surfactant-stabilized nanoparticle-based devices. Efficient organic photovoltaic (OPV) devices have been fabricated from an aqueous dispersion of poly(3-hexylthiophene-2,5-diyl) (P3HT) and [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) nanoparticles stabilized by anionic surfactants. AC impedance spectroscopy has been used to understand the charge transport properties in the dark and in operando conditions. We have demonstrated the similarities in the charge transport properties, as well as photocarrier dynamics of the nanoparticle-based OPVs and the bulk heterojunction OPVs despite fundamental differences in their nanostructure morphology. This study emphasizes the possibility of fabricating highly efficient OPVs from organic nanoparticles by reducing surface defects and excess doping of the polymers.

Tunable Percolation in Semiconducting Binary Polymer Nanoparticle Glasses.

Binary polymer nanoparticle glasses provide opportunities to realize the facile assembly of disparate components, with control over nanoscale and mesoscale domains, for the development of functional materials. This work demonstrates that tunable electrical percolation can be achieved through semiconducting/insulating polymer nanoparticle glasses by varying the relative percentages of equal-sized nanoparticle constituents of the binary assembly. Using time-of-flight charge carrier mobility measurements and conducting atomic force microscopy, we show that these systems exhibit power law scaling percolation behavior with percolation thresholds of ∼24-30%. We develop a simple resistor network model, which can reproduce the experimental data, and can be used to predict percolation trends in binary polymer nanoparticle glasses. Finally, we analyze the cluster statistics of simulated binary nanoparticle glasses, and characterize them according to their predominant local motifs as (p(i), p(1-i))-connected networks that can be used as a supramolecular toolbox for rational material design based on polymer nanoparticles.

High Efficiency Tandem Thin-Perovskite/Polymer Solar Cells with a Graded Recombination Layer.

Perovskite-containing tandem solar cells are attracting attention for their potential to achieve high efficiencies. We demonstrate a series connection of a ∼ 90 nm thick perovskite front subcell and a ∼ 100 nm thick polymer:fullerene blend back subcell that benefits from an efficient graded recombination layer containing a zwitterionic fullerene, silver (Ag), and molybdenum trioxide (MoO3). This methodology eliminates the adverse effects of thermal annealing or chemical treatment that occurs during perovskite fabrication on polymer-based front subcells. The record tandem perovskite/polymer solar cell efficiency of 16.0%, with low hysteresis, is 75% greater than that of the corresponding ∼ 90 nm thick perovskite single-junction device and 65% greater than that of the polymer single-junction device. The high efficiency of this hybrid tandem device, achieved using only a ∼ 90 nm thick perovskite layer, provides an opportunity to substantially reduce the lead content in the device, while maintaining the high performance derived from perovskites.

Kinetics of Ion Transport in Perovskite Active Layers and Its Implications for Active Layer Stability.

Solar cells fabricated using alkyl ammonium metal halides as light absorbers have the right combination of high power conversion efficiency and ease of fabrication to realize inexpensive but efficient thin film solar cells. However, they degrade under prolonged exposure to sunlight. Herein, we show that this degradation is quasi-reversible, and that it can be greatly lessened by simple modifications of the solar cell operating conditions. We studied perovskite devices using electrochemical impedance spectroscopy (EIS) with methylammonium (MA)-, formamidinium (FA)-, and MA(x)FA(1-x) lead triiodide as active layers. From variable temperature EIS studies, we found that the diffusion coefficient using MA ions was greater than when using FA ions. Structural studies using powder X-ray diffraction (PXRD) show that for MAPbI3 a structural change and lattice expansion occurs at device operating temperatures. On the basis of EIS and PXRD studies, we postulate that in MAPbI3 the predominant mechanism of accelerated device degradation under sunlight involves thermally activated fast ion transport coupled with a lattice-expanding phase transition, both of which are facilitated by absorption of the infrared component of the solar spectrum. Using these findings, we show that the devices show greatly improved operation lifetimes and stability under white-light emitting diodes, or under a solar simulator with an infrared cutoff filter or with cooling.

Multiscale active layer morphologies for organic photovoltaics through self-assembly of nanospheres.

We address here the need for a general strategy to control molecular assembly over multiple length scales. Efficient organic photovoltaics require an active layer comprised of a mesoscale interconnected networks of nanoscale aggregates of semiconductors. We demonstrate a method, using principles of molecular self-assembly and geometric packing, for controlled assembly of semiconductors at the nanoscale and mesoscale. Nanoparticles of poly(3-hexylthiophene) (P3HT) or [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) were fabricated with targeted sizes. Nanoparticles containing a blend of both P3HT and PCBM were also fabricated. The active layer morphology was tuned by the changing particle composition, particle radii, and the ratios of P3HT:PCBM particles. Photovoltaic devices were fabricated from these aqueous nanoparticle dispersions with comparable device performance to typical bulk-heterojunction devices. Our strategy opens a revolutionary pathway to study and tune the active layer morphology systematically while exercising control of the component assembly at multiple length scales.

Efficient charge transport in assemblies of surfactant-stabilized semiconducting nanoparticles.

Charge transport through a semiconducting nanoparticle assembly is demonstrated. The hole mobility of low and high molecular weight and regioreglular poly(3-hexylthiophene) (P3HT) nanoparticles is on the order of 2 × 10(-4) to 5 × 10(-4) cm(2) V(-1) s(-1) , which is comparable to drop-cast thin films of pristine P3HT. Various methods are employed to understand the nature and importance of the nanoparticle packing.

Single-pixel, single-layer polymer device as a tricolor sensor with signals mimicking natural photoreceptors.

Color sensing procedures typically involve multiple active detectors or a photodetector coupled to a filter array. We demonstrate the possibility of using a single polymer layer based device structure for multicolor sensing. The device structure does not require any color filters or any subpixelation, and it distinguishes colors without any external bias. The color sensing relies on an appropriate thickness of the active polymer layer that results in a characteristic polarity and temporal profile of the photocurrent signal in response to various incident colors. The device characteristics reveal interesting similarities to the features observed in natural photosensitive systems including retinal cone cells.