Self-powered perovskite photon-counting detectors.

Metal-halide perovskites (MHPs) have been successfully exploited for converting photons to charges or vice versa in applications of solar cells, light-emitting diodes and solar fuels1-3, for which all these applications involve strong light. Here we show that self-powered polycrystalline perovskite photodetectors can rival the commercial silicon photomultipliers (SiPMs) for photon counting. The photon-counting capability of perovskite photon-counting detectors (PCDs) is mainly determined by shallow traps, despite that deep traps also limit charge-collection efficiency. Two shallow traps with energy depth of 5.8 ± 0.8 millielectronvolts (meV) and 57.2 ± 0.1 meV are identified in polycrystalline methylammonium lead triiodide, which mainly stay at grain boundaries and the surface, respectively. We show that these shallow traps can be reduced by grain-size enhancement and surface passivation using diphenyl sulfide, respectively. It greatly suppresses dark count rate (DCR) from >20,000 counts per second per square millimetre (cps mm-2) to 2 cps mm-2 at room temperature, enabling much better response to weak light than SiPMs. The perovskite PCDs can collect γ-ray spectra with better energy resolution than SiPMs and maintain performance at high temperatures up to 85 °C. The zero-bias operation of perovskite detectors enables no drift of noise and detection property. This study opens a new application of photon counting for perovskites that uses their unique defect properties.

Strong-bonding hole-transport layers reduce ultraviolet degradation of perovskite solar cells.

The light-emitting diodes (LEDs) used in indoor testing of perovskite solar cells do not expose them to the levels of ultraviolet (UV) radiation that they would receive in actual outdoor use. We report degradation mechanisms of p-i-n-structured perovskite solar cells under unfiltered sunlight and with LEDs. Weak chemical bonding between perovskites and polymer hole-transporting materials (HTMs) and transparent conducting oxides (TCOs) dominate the accelerated A-site cation migration, rather than direct degradation of HTMs. An aromatic phosphonic acid, [2-(9-ethyl-9H-carbazol-3-yl)ethyl]phosphonic acid (EtCz3EPA), enhanced bonding at the perovskite/HTM/TCO region with a phosphonic acid group bonded to TCOs and a nitrogen group interacting with lead in perovskites. A hybrid HTM of EtCz3EPA with strong hole-extraction polymers retained high efficiency and improved the UV stability of perovskite devices, and a champion perovskite minimodule-independently measured by the Perovskite PV Accelerator for Commercializing Technologies (PACT) center-retained operational efficiency of >16% after 29 weeks of outdoor testing.

Manipulating Nucleation and Crystal Growth of Inorganic Perovskite Solar Cells.

Inorganic metal halide perovskite materials as sunlight absorbers for solar cells exhibit better thermal stability than organic-inorganic hybrid counterparts. Pure cesium lead triiodide (CsPbI3), with the most suitable band gap, suffers phase instability under an ambient environment. Nucleation and crystal growth are two crucial steps in fabricating a solution-processed perovskite film. A high-quality perovskite film with good morphology makes a significant impact on the efficiency and stability of perovskite solar cells. Dimethylformamide (DMF) is a commonly used aprotic solvent. However, it is difficult to obtain a high-quality inorganic perovskite film using DMF as a single solvent due to its slow evaporation and strong coordination with Pb2+. Here, we investigate dimethylacetamide (DMAc)/DMF as a cosolvent to prompt nucleation during the spin-coating process, leading to higher nucleation density and better surface coverage. In addition, we introduce CsBr in dimethylammonium lead triiodide (DMAPbI3)/CsI precursors to slow down the crystal growth process. CsBr does not increase the film band gap but leads to a pinhole-free film with better crystallinity. Through nucleation and crystal growth engineering, the power conversion efficiency of inorganic perovskite devices is improved to 17.67%, and ambient environment stability is significantly enhanced.

Lead-chelating hole-transport layers for efficient and stable perovskite minimodules.

The defective bottom interfaces of perovskites and hole-transport layers (HTLs) limit the performance of p-i-n structure perovskite solar cells. We report that the addition of lead chelation molecules into HTLs can strongly interact with lead(II) ion (Pb2+), resulting in a reduced amorphous region in perovskites near HTLs and a passivated perovskite bottom surface. The minimodule with an aperture area of 26.9 square centimeters has a power conversion efficiency (PCE) of 21.8% (stabilized at 21.1%) that is certified by the National Renewable Energy Laboratory (NREL), which corresponds to a minimal small-cell efficiency of 24.6% (stabilized 24.1%) throughout the module area. Small-area cells and large-area minimodules with lead chelation molecules in HTLs had a light soaking stability of 3010 and 2130 hours, respectively, at an efficiency loss of 10% from the initial value under 1-sun illumination and open-circuit voltage conditions.

Influence of voids on the thermal and light stability of perovskite solar cells.

The formation of voids in perovskite films close to the buried interface has been reported during film deposition. These voids are thought to limits the efficiency and stability of perovskite solar cells (PSCs). Here, we studied the voids formed during operation in perovskite films that were optimized during the solution deposition process to avoid voids. New voids formed during operation are found to assemble along grain boundaries at the bottom interface, caused by the loss of residual solvent and conversion of amorphous phase to crystalline phase. Unexpectedly, the formation of these voids did not negatively affect the stability of PSCs. Decreasing the amorphous region in perovskites by thermal annealing decreased the positive iodide interstitial density, and improved the light stability of PSCs. The annealed devices maintained 90% of their initial efficiency and light soaking for 1900 hours at open circuit condition under 1-sun illumination at 50°C.

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.

High grain boundary recombination velocity in polycrystalline metal halide perovskites.

Understanding carrier recombination processes in metal halide perovskites is fundamentally important to further improving the efficiency of perovskite solar cells, yet the accurate recombination velocity at grain boundaries (GBs) has not been determined. Here, we report the determination of carrier recombination velocities at GBs (SGB) of polycrystalline perovskites by mapping the transient photoluminescence pattern change induced by the nonradiative recombination of carriers at GBs. Charge recombination at GBs is revealed to be even stronger than at surfaces of unpassivated films, with average SGB reaching 2200 to 3300 cm/s. Regular surface treatments do not passivate GBs because of the absence of contact at GBs. We find a surface treatment using tributyl(methyl)phosphonium dimethyl phosphate that can penetrate into GBs by partially dissolving GBs and converting it into one-dimensional perovskites. It reduces the average SGB by four times, with the lowest SGB of 410 cm/s, which is comparable to surface recombination velocities after passivation.

Recycling lead and transparent conductors from perovskite solar modules.

Perovskite photovoltaics are gaining increasing common ground to partner with or compete with silicon photovoltaics to reduce cost of solar energy. However, a cost-effective waste management for toxic lead (Pb), which might determine the fate of this technology, has not been developed yet. Here, we report an end-of-life material management for perovskite solar modules to recycle toxic lead and valuable transparent conductors to protect the environment and create dramatic economic benefits from recycled materials. Lead is separated from decommissioned modules by weakly acidic cation exchange resin, which could be released as soluble Pb(NO3)2 followed by precipitation as PbI2 for reuse, with a recycling efficiency of 99.2%. Thermal delamination disassembles the encapsulated modules with intact transparent conductors and cover glasses. The refabricated devices based on recycled lead iodide and recycled transparent conductors show comparable performance as devices based on fresh raw materials. Cost analysis shows this recycling technology is economically attractive.

Lead-adsorbing ionogel-based encapsulation for impact-resistant, stable, and lead-safe perovskite modules.

Despite the high-efficiency and low-cost prospect for perovskite solar cells, great concerns of lead toxicity and instability remain for this technology. Here, we report an encapsulation strategy for perovskite modules based on lead-adsorbing ionogel, which prevents lead leakage and withstand long-term stability tests. The ionogel layers integrated on both sides of modules enhance impact resistance. The self-healable ionogel can prevent water permeation into the perovskite layer and adsorb lead that might leak. The encapsulated devices pass the damp heat and thermal cycling accelerated stability tests according to International Electrotechnical Commission 61215 standard. The ionogel encapsulation reduces lead leakage to undetectable level after the hail-damaged module is soaked in water for 24 hours. Even being rolled over by a car followed by water soaking for 45 days, the ionogel encapsulation reduces lead leakage by three orders of magnitude. This work provides a strategy to simultaneously address lead leakage and stability for perovskite modules.

Effect of Composition on the Spin Relaxation of Lead Halide Perovskites.

Lead halide perovskites have been promising candidates in spintronics applications; however, the mechanism of spin relaxation is still unclear. Here, we compare the temperature-dependent spin dynamics of four perovskite films (XPbY3) with different compositions (X = CH3NH3, Cs; Y = I, Br). The room-temperature net spin lifetime is found to increase as the molar mass decreases, indicating the dominant role of spin orbital coupling in their spin relaxation. As the temperature is reduced from room temperature to 77 K, the spin relaxations in CH3NH3PbI3 and CsPbI3 are significantly slowed down while those of CH3NH3PbBr3 and CsPbBr3 are only slightly changed. Based on the analysis of phonon scattering of perovskites, it is suggested that two different mechanisms, Elliot-Yafet in which spin flips upon momentum scattering and D'yakonov-Perel in which spin relaxes between momentum scattering, are responsible for the spin relaxation in XPbI3 and XPbBr3 (X = CH3NH3, Cs), respectively.

Ultrafast Carrier Dynamics of Dual Emissions from the Orthorhombic Phase in Methylammonium Lead Iodide Perovskites Revealed by Two-Dimensional Coherent Spectroscopy.

The fundamental understanding of photoexcitation landscape and dynamics in hybrid organic-inorganic perovskites is essential for improving their performance in solar cells and other applications. The dual emission features from the orthorhombic phase in perovskites have been the focus of numerous recent studies, and yet their underlying molecular origin remains elusive. We use optical two-dimensional coherent spectroscopy to study the carrier dynamics and coupling of the dual emissions in a methylammonium lead iodide film at 115 K. The two-dimensional spectra reveal an ultrafast redistribution of the photoexcited carriers into the two emission resonances within 250 fs. The high-energy resonance is a short-lived transient state, and the low-energy emission state interacts with coherent phonons. The observed carrier dynamics provide important experimental evidence that can be compared with potential theoretical models and contribute to the understanding of the dual emissions as well as the overall energy level structure in hybrid organic-inorganic perovskites.

Continuous Size Tuning of Monodispersed ZnO Nanoparticles and Its Size Effect on the Performance of Perovskite Solar Cells.

ZnO has been demonstrated to be a promising candidate to fabricate high efficiency perovskite solar cells (PSCs) in terms of its better electron extraction and transport properties. However, the inability of synthesis of ZnO nanoparticles (NPs) with minimal surface defects and agglomeration remains a great challenge hindering the fabrication of highly efficient PSCs. In this work, highly crystalline and agglomeration-free ZnO NPs with controlled size were synthesized through a facile solvothermal method. Such ZnO NPs were applied in the fabrication of meso-structured PSCs. The solar cells with ∼40 nm ZnO NPs exhibit the highest power conversion efficiency (PCE) of 15.92%. Steady-state and time-resolved photoluminescence measurements revealed the faster injection and lower charge recombination at the interface of ∼40 nm ZnO NPs and perovskite, resulting in significantly enhanced JSC and VOC.

Enhanced Performance of PbS-quantum-dot-sensitized Solar Cells via Optimizing Precursor Solution and Electrolytes.

This work reports a PbS-quantum-dot-sensitized solar cell (QDSC) with power conversion efficiency (PCE) of 4%. PbS quantum dots (QDs) were grown on mesoporous TiO2 film using a successive ion layer absorption and reaction (SILAR) method. The growth of QDs was found to be profoundly affected by the concentration of the precursor solution. At low concentrations, the rate-limiting factor of the crystal growth was the adsorption of the precursor ions, and the surface growth of the crystal became the limiting factor in the high concentration solution. The optimal concentration of precursor solution with respect to the quantity and size of synthesized QDs was 0.06 M. To further increase the performance of QDSCs, the 30% deionized water of polysulfide electrolyte was replaced with methanol to improve the wettability and permeability of electrolytes in the TiO2 film, which accelerated the redox couple diffusion in the electrolyte solution and improved charge transfer at the interfaces between photoanodes and electrolytes. The stability of PbS QDs in the electrolyte was also improved by methanol to reduce the charge recombination and prolong the electron lifetime. As a result, the PCE of QDSC was increased to 4.01%.

Dynamic Growth of Pinhole-Free Conformal CH3NH3PbI3 Film for Perovskite Solar Cells.

Two-step dipping is one of the popular low temperature solution methods to prepare organic-inorganic halide perovskite (CH3NH3PbI3) films for solar cells. However, pinholes in perovskite films fabricated by the static growth method (SGM) result in low power conversion efficiency (PCE) in the resulting solar cells. In this work, the static dipping process is changed into a dynamic dipping process by controlled stirring PbI2 substrates in CH3NH3I isopropanol solution. The dynamic growth method (DGM) produces more nuclei and decreases the pinholes during the nucleation and growth of perovskite crystals. The compact perovskite films with free pinholes are obtained by DGM, which present that the big perovskite particles with a size of 350 nm are surrounded by small perovskite particles with a size of 50 nm. The surface coverage of the perovskite film is up to nearly 100%. Such high quality perovskite film not only eliminated pinholes, resulting in reduced charge recombination of the solar cells, but also improves the light harvesting efficiency. As a result, the PCE of the perovskite solar cells is increased from 11% for SGM to 13% for DGM.