Reducing Surface Halide Deficiency for Efficient and Stable Iodide-Based Perovskite Solar Cells.

State-of-the-art, high-performance perovskite solar cells (PSCs) contain a large amount of iodine to realize smaller bandgaps. However, the presence of numerous iodine vacancies at the surface of the film formed by their evaporation during the thermal annealing process has been broadly shown to induce deep-level defects, incur nonradiative charge recombination, and induce photocurrent hysteresis, all of which limit the efficiency and stability of PSCs. In this work, modifying the defective surface of perovskite films with cadmium iodide (CdI2) effectively reduces the degree of surface iodine deficiency and stabilizes iodine ions via the formation of strong Cd-I ionic bonds. This largely reduces the interfacial charge recombination loss, yielding a high efficiency of 21.9% for blade-coated PSCs with an open-circuit voltage of 1.20 V, corresponding to a record small voltage deficit of 0.31 V. The CdI2 surface treatment also improves the operational stability of the PSCs, retaining 92% efficiency after constant illumination at 1 sun intensity for 1000 h. This work provides a promising strategy to optimize the surface/interface optoelectronic properties of perovskites for more efficient and stable solar cells and other optoelectronic devices.

Imperfections and their passivation in halide perovskite solar cells.

All highly-efficient organic-inorganic halide perovskite (OIHP) solar cells to date are made of polycrystalline perovskite films which contain a high density of defects, including point and extended imperfections. The imperfections in OIHP materials play an important role in the process of charge recombination and ion migration in perovskite solar cells (PSC), which heavily influences the resulting device energy conversion efficiency and stability. Here we review the recent advances in passivation of imperfections and suppressing ion migration to achieve improved efficiency and highly stable perovskite solar cells. Due to the ionic nature of OIHP materials, the defects in the photoactive films are inevitably electrically charged. The deep level traps induced by particular charged defects in OIHP films are major non-radiative recombination centers; passivation by coordinate bonding, ionic bonding, or chemical conversion have proven effective in mitigating the negative impacts of these deep traps. Shallow level charge traps themselves may contribute little to non-radiative recombination, but the migration of charged shallow level traps in OIHP films results in unfavorable band bending, interfacial reactions, and phase segregation, influencing the carrier extraction efficiency. Finally, the impact of defects and ion migration on the stability of perovskite solar cells is described.

Characterizing Density and Spatial Distribution of Trap States in Ta3N5 Thin Films for Rational Defect Passivation.

Tantalum nitride (Ta3N5) has gained significant attention as a potential photoanode material, yet it has been challenged by material quality issues. Defect-induced trap states are detrimental to the performance of any semiconductor material. Beyond influencing the performance of Ta3N5 films, defects can also accelerate the degradation in water during desired electrochemical applications. Defect passivation has provided an enormous boost to the development of many semiconductor materials but is currently in its infancy for Ta3N5. This is in part due to a lack of experimental understanding regarding the spatial and energetic distribution of trap states throughout Ta3N5 thin films. Here, we employ drive-level capacitance profiling (DLCP) to experimentally resolve the spatial and energetic distribution of trap states throughout Ta3N5 thin films. The density of deeper energetic traps is found to reach ∼2.5 to 6 × 1022 cm-3 at the interfaces of neat Ta3N5 thin films, over an order of magnitude greater than the bulk. In addition to the spatial profile of deep trap states, we report neat Ta3N5 thin films to be highly n-type in nature, owning a free carrier density of ∼9.74 × 1017 cm-3. This information, coupled with the present understanding of native oxide layers on Ta3N5, has facilitated the rational design of a targeted passivation strategy that simultaneously provides a means for catalyst immobilization. Loading catalyst via silatrane moieties suppresses the density of defects at the surface of Ta3N5 thin films by two orders of magnitude, while also reducing the free carrier density of films by over one order of magnitude, effectively dedoping the films to ∼2.40 × 1016 cm-3. The surface passivation of Ta3N5 films translates to suppressed defect-induced trapping and recombination of photoexcited carriers, as determined through absorption, photoluminescence, and transient photovoltage. This illustrates how developing a deeper understanding of the distribution and influence of defects in Ta3N5 thin films has the potential to guide future works and ultimately accelerate the integration and development of high-performance Ta3N5 thin film devices.

Blading Phase-Pure Formamidinium-Alloyed Perovskites for High-Efficiency Solar Cells with Low Photovoltage Deficit and Improved Stability.

Currently, blade-coated perovskite solar cells (PSCs) with high power conversion efficiencies (PCEs), that is, greater than 20%, normally employ methylammonium lead tri-iodide with a sub-optimal bandgap. Alloyed perovskites with formamidinium (FA) cation have narrower bandgap and thus enhance device photocurrent. However, FA-alloyed perovskites show low phase stability and high moisture sensitivity. Here, it is reported that incorporating 0.83 molar percent organic halide salts (OHs) into perovskite inks enables phase-pure, highly crystalline FA-alloyed perovskites with extraordinary optoelectronic properties. The OH molecules modulate the crystal growth, enhance the phase stability, passivate ionic defects at the surface and/or grain boundaries, and enhance the moisture stability of the perovskite film. A high efficiency of 22.0% under 1 sun illumination for blade-coated PSCs is demonstrated with an open-circuit voltage of 1.18 V, corresponding to a very small voltage deficit of 0.33 V, and significantly improved operational stability with 96% of the initial efficiency retained under one sun illumination for 500 h.

Interfacial Molecular Doping of Metal Halide Perovskites for Highly Efficient Solar Cells.

Tailoring the doping of semiconductors in heterojunction solar cells shows tremendous success in enhancing the performance of many types of inorganic solar cells, while it is found challenging in perovskite solar cells because of the difficulty in doping perovskites in a controllable way. Here, a small molecule of 4,4',4″,4″'-(pyrazine-2,3,5,6-tetrayl) tetrakis (N,N-bis(4-methoxyphenyl) aniline) (PT-TPA) which can effectively p-dope the surface of FAx MA1- x PbI3 (FA: HC(NH2 )2 ; MA: CH3 NH3 ) perovskite films is reported. The intermolecular charge transfer property of PT-TPA forms a stabilized resonance structure to accept electrons from perovskites. The doping effect increases perovskite dark conductivity and carrier concentration by up to 4737 times. Computation shows that electrons in the first two layers of octahedral cages in perovskites are transferred to PT-TPA. After applying PT-TPA into perovskite solar cells, the doping-induced band bending in perovskite effectively facilitates hole extraction to hole transport layer and expels electrons toward cathode side, which reduces the charge recombination there. The optimized devices demonstrate an increased photovoltage from 1.12 to 1.17 V and an efficiency of 23.4% from photocurrent scanning with a stabilized efficiency of 22.9%. The findings demonstrate that molecular doping is an effective route to control the interfacial charge recombination in perovskite solar cells which is in complimentary to broadly applied defect passivation techniques.

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.

Enhancing electron diffusion length in narrow-bandgap perovskites for efficient monolithic perovskite tandem solar cells.

Developing multijunction perovskite solar cells (PSCs) is an attractive route to boost PSC efficiencies to above the single-junction Shockley-Queisser limit. However, commonly used tin-based narrow-bandgap perovskites have shorter carrier diffusion lengths and lower absorption coefficient than lead-based perovskites, limiting the efficiency of perovskite-perovskite tandem solar cells. In this work, we discover that the charge collection efficiency in tin-based PSCs is limited by a short diffusion length of electrons. Adding 0.03 molar percent of cadmium ions into tin-perovskite precursors reduce the background free hole concentration and electron trap density, yielding a long electron diffusion length of 2.72 ± 0.15 µm. It increases the optimized thickness of narrow-bandgap perovskite films to 1000 nm, yielding exceptional stabilized efficiencies of 20.2 and 22.7% for single junction narrow-bandgap PSCs and monolithic perovskite-perovskite tandem cells, respectively. This work provides a promising method to enhance the optoelectronic properties of narrow-bandgap perovskites and unleash the potential of perovskite-perovskite tandem solar cells.

Excess charge-carrier induced instability of hybrid perovskites.

Identifying the origin of intrinsic instability for organic-inorganic halide perovskites (OIHPs) is crucial for their application in electronic devices, including solar cells, photodetectors, radiation detectors, and light-emitting diodes, as their efficiencies or sensitivities have already been demonstrated to be competitive with commercial available devices. Here we show that free charges in OIHPs, whether generated by incident light or by current-injection from electrodes, can reduce their stability, while efficient charge extraction effectively stabilizes the perovskite materials. The excess of both holes and electrons reduce the activation energy for ion migration within OIHPs, accelerating the degradation of OIHPs, while the excess holes and electrons facilitate the migration of cations or anions, respectively. OIHP solar cells capable of efficient charge-carrier extraction show improved light stability under regular operation conditions compared to an open-circuit condition where the photo-generated charges are confined in the perovskite layers.