Enhancing charge-emitting shallow traps in metal halide perovskites by >100 times by surface strain
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Engineering topics
Publications and source records attributed to Fei, Chengbin.
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Stability of perovskite solar cells (PSCs) under light, heat, humidity and their combinations have been notably improved recently. However, PSCs have poor reverse-bias stability that limits their real-world application. Here we report a systematic study on the degradation mechanisms of p-i-n structure PSCs under reverse bias. The oxidation of iodide by injected holes at the cathode side initialize the reverse-bias-induced degradation, then the generated neutral iodine oxidizes metal electrode such as copper, followed by drift of Cu+ into perovskites and its reduction by injected electrons, resulting in localized metallic filaments and thus device breakdown. A reinforced barrier with combined lithium fluoride, tin oxide and indium tin oxide at the cathode side reduces device dark current and avoids the corrosion of Cu0. It dramatically increases breakdown voltage to above -20 V and improved the T90 lifetime of PSCs to ~1,000 h under -1.6 V. The modified minimodule also maintained over 90% of its initial performance after 720 h of shadow tests.
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.
Flexible perovskite solar cells (F-PSCs), prized for their nature of soft and high power-weight compatibility, have attracted intensive attention. However, inferior buried perovskite-substrate interfaces due to low interfacial adhesion between perovskites and substrates and large deformation of flexible substrates have greatly limited the performance of F-PSCs. Here, we add organic molecule Entinostat (ET) into hole extraction material Poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] (PTAA) to enhance the adhesion at the perovskite/substrate interface using the interactions of ET with perovskites, PTAA and indium tin oxide (ITO) through its multiple function groups. Meanwhile, ET added into perovskites reduces the voids at the bottom perovskite film, due to its capability to tune the crystallization of perovskites by forming adduct with lead. Consequently, the inverted small area F-PSCs achieved an efficiency of 23.4%. The flexible perovskite minimodule with an area of 9 cm 2 achieved an aperture efficiency of ~19.0% certified by National Renewable Energy Laboratory. Furthermore, the optimized unencapsulated flexible minimodule retained 84% of the initial efficiency after 5000 bending cycles and retained 90% of the initial PCE (T90) after light soaking for >750 hours.
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Phenethylammonium (PEA + ) and butylammonium (BA + ) are widely used in three-dimensional (3D) perovskites to form two-dimensional (2D) perovskites at film surfaces and grain boundaries (GBs) for defect passivation and performance enhancement. Here, we show that these cations are unstable with 3D formamidinium (FA + )-containing perovskites under high-temperature light soaking. PEA + and BA + are found to deprotonate to amines, which then react with FA + to produce (phenethylamino)methaniminium (PEAMA + ) and (butylamino)methaniminium (BAMA + ), respectively, severely limiting device high-temperature photostability. Furthermore, removing these cations greatly improves the photostability but compromises device efficiency by leaving non-fully passivated surfaces and GBs. Ammonium cations with a high acid dissociation constant (pK a ), including PEAMA + (pK a =12.0) and BAMA + (pK a =12.0), can replace PEA + or BA + for passivation and are stable with FA-based perovskites due to their resistance to further deprotonation. P-i-n structure solar cells with PEAMA + additive maintained over 90% of their initial efficiency after light soaking at open circuit and 90 °C for 1500 hours.
Metal halide perovskite photovoltaic modules deployed outdoors and held at their maximum power point show daily, reversible, relative changes of up to 30% in efficiency between morning and afternoon. Predicting energy yield and quantifying reliability will require properly handling such daily performance changes.
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 (Pb 2+ ), resulting in a reduced amorphous region in perovskites near HTLs and a passivated perovskite bottom surface. Here, 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.
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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 fuels 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. Finally, this study opens a new application of photon counting for perovskites that uses their unique defect properties.
Perovskite-silicon tandem cells have shown much higher efficiencies than the single junction cells, which promises further reduction of energy cost from photovoltaics. Due to the protection by perovskites, silicon subcells in perovskite-silicon tandem cells may last much longer than they are designed for single junction devices. Here we report recycling silicon bottom cells from end-of-life perovskite-silicon tandem solar cells which further reduce their cost and enhance the sustainability. We demonstrate that silicon bottom cells can be recycled from end-oflife tandem cells by thermal delamination and chemical cleaning processes. The optoelectronic properties of silicon bottom cells were shown largely unchanged at the end-of-life tandem cells. The tandem cells refurbished from recycled silicon bottom cells show comparable efficiencies with those fabricated from fresh ones.
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.
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.
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 (S GB ) 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 S GB 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 S GB by four times, with the lowest SGB of 410 cm/s, which is comparable to surface recombination velocities after passivation.