CH3NH3PbI3 grain growth and interfacial properties in meso-structured perovskite solar cells fabricated by two-step deposition.

Although the two-step deposition (TSD) method is widely adopted for the high performance perovskite solar cells (PSCs), the CH3NH3PbI3 perovskite crystal growth mechanism during the TSD process and the photo-generated charge recombination dynamics in the mesoporous-TiO2 (mp-TiO2)/CH3NH3PbI3/hole transporting material (HTM) system remains unexploited. Herein, we modified the concentration of PbI2 (C(PbI2)) solution to control the perovskite crystal properties, and observed an abnormal CH3NH3PbI3 grain growth phenomenon atop mesoporous TiO2 film. To illustrate this abnormal grain growth mechanism, we propose that a grain ripening process is taking place during the transformation from PbI2 to CH3NH3PbI3, and discuss the PbI2 nuclei morphology, perovskite grain growing stage, as well as Pb:I atomic ratio difference among CH3NH3PbI3 grains with different morphology. These C(PbI2)-dependent perovskite morphologies resulted in varied charge carrier transfer properties throughout the mp-TiO2/CH3NH3PbI3/HTM hybrid, as illustrated by photoluminescence measurement. Furthermore, the effect of CH3NH3PbI3 morphology on light absorption and interfacial properties is investigated and correlated with the photovoltaic performance of PSCs.

Perovskite grain wrapping by converting interfaces and grain boundaries into robust and water-insoluble low-dimensional perovskites.

Stabilizing perovskite solar cells requires consideration of all defective sites in the devices. Substantial efforts have been devoted to interfaces, while stabilization of grain boundaries received less attention. Here, we report on a molecule tributyl(methyl)phosphonium iodide (TPI), which can convert perovskite into a wide bandgap one-dimensional (1D) perovskite that is mechanically robust and water insoluble. Mixing TPI with perovskite precursor results in a wrapping of perovskite grains with both grain surfaces and grain boundaries converted into several nanometer-thick 1D perovskites during the grain formation process as observed by direct mapping. The grain wrapping passivates the grain boundaries, enhances their resistance to moisture, and reduces the iodine released during light soaking. The perovskite films with wrapped grains are more stable under heat and light. The best device with wrapped grains maintained 92.2% of its highest efficiency after light soaking under 1-sun illumination for 1900 hours at 55°C open-circuit condition.

Blading of Conformal Electron-Transport Layers in p-i-n Perovskite Solar Cells.

Perovskite solar cells (PSCs) are promising to reduce the cost of photovoltaic system due to their low-cost raw materials and high-throughput solution process; however, fabrication of all the active layers in perovskite modules using a scalable solution process has not yet been demonstrated. Herein, the fabrication of highly efficient PSCs and modules in ambient conditions is reported, with all layers bladed except the metal electrode, by blading a 36 ± 9 nm-thick electron-transport layer (ETL) on perovskite films with a roughness of ≈80 nm. A combination of additives in phenyl-C61 -butyric acid methyl ester (PCBM) allows the PCBM to conformally cover the perovskites and still have a good electrical conductivity. Amine-functionalized molecules are added to enhance both the dispersity of PCBM and the affinity to perovskites. A PCBM dopant of 4-(2,3-dihydro-1,3-dimethyl-1H-benzimidazol-2-yl)-N,N-dimethylbenzenamine (N-DMBI) recovers the conductivity loss induced by the small amine molecules. PSCs (0.08 cm2 ) fabricated by the all-blading process reache an average efficiency of 22.4 ± 0.5% and a champion efficiency of 23.1% for perovskites with a bandgap of 1.51 eV, with much better stability compared to evaporated ETL PSCs. The all-bladed minimodule (25.03 cm2 ) shows an aperture efficiency of ≈19.3%, showing the good uniformity of the bladed ETLs.

Stabilizing perovskite-substrate interfaces for high-performance perovskite modules.

The interfaces of perovskite solar cells (PSCs) are important in determining their efficiency and stability, but the morphology and stability of imbedded perovskite-substrate interfaces have received less attention than have top interfaces. We found that dimethyl sulfoxide (DMSO), which is a liquid additive broadly applied to enhance perovskite film morphology, was trapped during film formation and led to voids at perovskite-substrate interfaces that accelerated the film degradation under illumination. Partial replacement of DMSO with solid-state carbohydrazide reduces interfacial voids. A maximum stabilized power conversion efficiency (PCE) of 23.6% was realized for blade-coated p-type/intrinsic/n-type (p-i-n) structure PSCs with no efficiency loss after 550-hour operational stability tests at 60°C. The perovskite mini-modules showed certified PCEs of 19.3 and 19.2%, with aperture areas of 18.1 and 50.0 square centimeters, respectively.

Highly Efficient Pure-Blue Light-Emitting Diodes Based on Rubidium and Chlorine Alloyed Metal Halide Perovskite.

Perovskite light-emitting diodes (PeLEDs) are promising candidates for display and solid-state lighting, due to their tunable colors, high conversion efficiencies, and low cost. However, the performance of blue PeLEDs is far inferior to that of the near-infrared, red, and green counterparts. Here, the fabrication of pure-blue PeLEDs with an emission peak at 475 nm, a peak external quantum efficiency of 10.1%, and a maximum luminance of 14 000 cd m-2 is demonstrated by tailoring the compositions of perovskites. The pure-blue electroluminescence is achieved by simultaneous addition of rubidium and chlorine ions into CsPbBr3 and incorporation of phenylethylammonium chloride forms quasi-2D hybrid perovskites. The combination of these composition engineering results in blueshifted emissions without reducing the quantum yield. The judicious alloying is shown to be critical to result in the better morphology with suppressed current leakage and enhanced light outcoupling.

Metallic surface doping of metal halide perovskites.

Intentional doping is the core of semiconductor technologies to tune electrical and optical properties of semiconductors for electronic devices, however, it has shown to be a grand challenge for halide perovskites. Here, we show that some metal ions, such as silver, strontium, cerium ions, which exist in the precursors of halide perovskites as impurities, can n-dope the surface of perovskites from being intrinsic to metallic. The low solubility of these ions in halide perovskite crystals excludes the metal impurities to perovskite surfaces, leaving the interior of perovskite crystals intrinsic. Computation shows these metal ions introduce many electronic states close to the conduction band minimum of perovskites and induce n-doping, which is in striking contrast to passivating ions such as potassium and rubidium ion. The discovery of metallic surface doping of perovskites enables new device and material designs that combine the intrinsic interior and heavily doped surface of perovskites.

Benign ferroelastic twin boundaries in halide perovskites for charge carrier transport and recombination.

Grain boundaries have been established to impact charge transport, recombination and thus the power conversion efficiency of metal halide perovskite thin film solar cells. As a special category of grain boundaries, ferroelastic twin boundaries have been recently discovered to exist in both CH3NH3PbI3 thin films and single crystals. However, their impact on the carrier transport and recombination in perovskites remains unexplored. Here, using the scanning photocurrent microscopy, we find that twin boundaries have negligible influence on the carrier transport across them. Photoluminescence (PL) imaging and the spatial-resolved PL intensity and lifetime scanning confirm the electronically benign nature of the twin boundaries, in striking contrast to regular grain boundaries which block the carrier transport and behave as the non-radiative recombination centers. Finally, the twin-boundary areas are found still easier to degrade than grain interior.

Resolving spatial and energetic distributions of trap states in metal halide perovskite solar cells.

We report the profiling of spatial and energetic distributions of trap states in metal halide perovskite single-crystalline and polycrystalline solar cells. The trap densities in single crystals varied by five orders of magnitude, with a lowest value of 2 × 1011 per cubic centimeter and most of the deep traps located at crystal surfaces. The charge trap densities of all depths of the interfaces of the polycrystalline films were one to two orders of magnitude greater than that of the film interior, and the trap density at the film interior was still two to three orders of magnitude greater than that in high-quality single crystals. Suprisingly, after surface passivation, most deep traps were detected near the interface of perovskites and hole transport layers, where a large density of nanocrystals were embedded, limiting the efficiency of solar cells.

Tailoring solvent coordination for high-speed, room-temperature blading of perovskite photovoltaic films.

The efficiencies of small-pixel perovskite photovoltaics have increased to above 24%, while most reported fabrication methods cannot be transferred to scalable manufacturing process. Here, we report a method of fast blading large-area perovskite films at an unprecedented speed of 99 mm/s under ambient conditions by tailoring solvent coordination capability. Combing volatile noncoordinating solvents to Pb2+ and low-volatile, coordinating solvents achieves both fast drying and large perovskite grains at room temperature. The reproducible fabrication yields a certified module efficiency of 16.4%, with an aperture area of 63.7 cm2. This method can be applied for various perovskite compositions. The perovskite modules also show a small temperature coefficient of -0.13%/°C and nearly fully recoverable efficiency after 58 cycles of shading, much better than commercial silicon and thin-film solar modules.

Synergistic Effect of Elevated Device Temperature and Excess Charge Carriers on the Rapid Light-Induced Degradation of Perovskite Solar Cells.

With power conversion efficiencies now reaching 24.2%, the major factor limiting efficient electricity generation using perovskite solar cells (PSCs) is their long-term stability. In particular, PSCs have demonstrated rapid degradation under illumination, the driving mechanism of which is yet to be understood. It is shown that elevated device temperature coupled with excess charge carriers due to constant illumination is the dominant force in the rapid degradation of encapsulated perovskite solar cells under illumination. Cooling the device to 20 °C and operating at the maximum power point improves the stability of CH3 NH3 PbI3 solar cells over 100× compared to operation under open circuit conditions at 60 °C. Light-induced strain originating from photothermal-induced expansion is also observed in CH3 NH3 PbI3 , which excludes other light-induced-strain mechanisms. However, strain and electric field do not appear to play any role in the initial rapid degradation of CH3 NH3 PbI3 solar cells under illumination. It is revealed that the formation of additional recombination centers in PSCs facilitated by elevated temperature and excess charge carriers ultimately results in rapid light-induced degradation. Guidance on the best methods for measuring the stability of PSCs is also given.

Bilateral alkylamine for suppressing charge recombination and improving stability in blade-coated perovskite solar cells.

The power conversion efficiencies (PCEs) of perovskite solar cells (PSCs) are already higher than that of other thin film technologies, but laboratory cell-fabrication methods are not scalable. Here, we report an additive strategy to enhance the efficiency and stability of PSCs made by scalable blading. Blade-coated PSCs incorporating bilateral alkylamine (BAA) additives achieve PCEs of 21.5 (aperture, 0.08 cm2) and 20.0% (aperture, 1.1 cm2), with a record-small open-circuit voltage deficit of 0.35 V under AM1.5G illumination. The stabilized PCE reaches 22.6% under 0.3 sun. Anchoring monolayer bilateral amino groups passivates the defects at the perovskite surface and enhances perovskite stability by exposing the linking hydrophobic alkyl chain. Grain boundaries are reinforced by BAA and are more resistant to mechanical bending and electron beam damage. BAA improves the device shelf lifetime to >1000 hours and operation stability to >500 hours under light, with 90% of the initial efficiency retained.

High Efficiency Inverted Planar Perovskite Solar Cells with Solution-Processed NiOx Hole Contact.

NiOx is a promising hole-transporting material for perovskite solar cells due to its high hole mobility, good stability, and easy processability. In this work, we employed a simple solution-processed NiOx film as the hole-transporting layer in perovskite solar cells. When the thickness of the perovskite layer increased from 270 to 380 nm, the light absorption and photogenerated carrier density were enhanced and the transporting distance of electron and hole would also increase at the same time, resulting in a large charge transfer resistance and a long hole-extracted process in the device, characterized by the UV-vis, photoluminescence, and electrochemical impedance spectroscopy spectra. Combining both of these factors, an optimal thickness of 334.2 nm was prepared with the perovskite precursor concentration of 1.35 M. Moreover, the optimal device fabrication conditions were further achieved by optimizing the thickness of NiOx hole-transporting layer and PCBM electron selective layer. As a result, the best power conversion efficiency of 15.71% was obtained with a Jsc of 20.51 mA·cm-2, a Voc of 988 mV, and a FF of 77.51% with almost no hysteresis. A stable efficiency of 15.10% was caught at the maximum power point. This work provides a promising route to achieve higher efficiency perovskite solar cells based on NiO or other inorganic hole-transporting materials.

Working from Both Sides: Composite Metallic Semitransparent Top Electrode for High Performance Perovskite Solar Cells.

We report herein perovskite solar cells using solution-processed silver nanowires (AgNWs) as transparent top electrode with markedly enhanced device performance, as well as stability by evaporating an ultrathin transparent Au (UTA) layer beneath the spin-coated AgNWs forming a composite transparent metallic electrode. The interlayer serves as a physical separation sandwiched in between the perovskite/hole transporting material (HTM) active layer and the halide-reactive AgNWs top-electrode to prevent undesired electrode degradation and simultaneously functions to significantly promote ohmic contact. The as-fabricated semitransparent PSCs feature a Voc of 0.96 V, a Jsc of 20.47 mA cm(-2), with an overall PCE of over 11% when measured with front illumination and a Voc of 0.92 V, a Jsc of 14.29 mA cm(-2), and an overall PCE of 7.53% with back illumination, corresponding to approximately 70% of the value under normal illumination conditions. The devices also demonstrate exceptional fabrication repeatability and air stability.