Combining wide-bandgap and narrow-bandgap perovskites to construct monolithic all-perovskite tandem solar cells offers avenues for continued increases in photovoltaic (PV) power conversion efficiencies (PCEs). However, actual efficiencies today are diminished by the subpar performance of narrow-bandgap subcells. Here we report a strategy to reduce Sn vacancies in mixed Pb–Sn narrow-bandgap perovskites that use metallic tin to reduce the Sn4+ (an oxidation product of Sn2+) to Sn2+ via a comproportionation reaction. We increase, thereby, the charge-carrier diffusion length in narrow-bandgap perovskites to 3 μm for the best materials. We obtain a PCE of 21.1% for 1.22-eV narrow-bandgap solar cells. We fabricate monolithic all-perovskite tandem cells with certified PCEs of 24.8% for small-area devices (0.049 cm2) and of 22.1% for large-area devices (1.05 cm2). The tandem cells retain 90% of their performance following 463 h of operation at the maximum power point under full 1-sun illumination. Improvements in the efficiency and stability of low-bandgap perovskite solar cells are key to enabling all-perovskite solar cells. Here, Lin et al. use metallic tin to prevent oxidation in such low-gap perovskite and demonstrate 24.8%-efficient tandems that are stable for over 400 h under operating conditions.

Monolithic all-perovskite tandem solar cells with 24.8% efficiency exploiting comproportionation to suppress Sn( ii ) oxidation in precursor ink

Recent Progresses on Defect Passivation toward Efficient Perovskite Solar Cells

Monolithic all-perovskite tandem solar cells offer an avenue to increase power conversion efficiency beyond the limits of single-junction cells. It is an important priority to unite efficiency, uniformity and stability, yet this has proven challenging because of high trap density and ready oxidation in narrow-bandgap mixed lead–tin perovskite subcells. Here we report simultaneous enhancements in the efficiency, uniformity and stability of narrow-bandgap subcells using strongly reductive surface-anchoring zwitterionic molecules. The zwitterionic antioxidant inhibits Sn2+ oxidation and passivates defects at the grain surfaces in mixed lead–tin perovskite films, enabling an efficiency of 21.7% (certified 20.7%) for single-junction solar cells. We further obtain a certified efficiency of 24.2% in 1-cm2-area all-perovskite tandem cells and in-lab power conversion efficiencies of 25.6% and 21.4% for 0.049 cm2 and 12 cm2 devices, respectively. The encapsulated tandem devices retain 88% of their initial performance following 500 hours of operation at a device temperature of 54–60 °C under one-sun illumination in ambient conditions. Ensuring both stability and efficiency in mixed lead–tin perovskite solar cells is crucial to the development of all-perovskite tandems. Xiao et al. use an antioxidant zwitterionic molecule to suppress tin oxidation thus enabling large-area tandem cells with 24.2% efficiency and operational stability over 500 hours.

All-perovskite tandem solar cells with 24.2% certified efficiency and area over 1 cm2 using surface-anchoring zwitterionic antioxidant

Tin perovskite is rising as a promising candidate to address the toxicity and theoretical efficiency limitation of lead perovskite. However, the voltage and efficiency of tin perovskite solar cells are much lower than lead counterparts. Herein, indene-C60 bisadduct with higher energy level is utilized as an electron transporting material for tin perovskite solar cells. It suppresses carrier concentration increase caused by remote doping, which significantly reduces interface carriers recombination. Moreover, indene-C60 bisadduct increases the maximum attainable photovoltage of the device. As a result, the use of indene-C60 bisadduct brings unprecedentedly high voltage of 0.94 V, which is over 50% higher than that of 0.6 V for device based on [6,6]-phenyl-C61-butyric acid methyl ester. The device shows a record power conversion efficiency of 12.4% reproduced in an accredited independent photovoltaic testing lab.

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Ultra-high open-circuit voltage of tin perovskite solar cells via an electron transporting layer design.

The power conversion efficiency of organic–inorganic hybrid perovskite solar cells (PSCs) has been boosted to be comparable with that of commercial silicon solar cells. Although the fabrication cost of solution-processing PSCs can be lower than that of silicon solar cells, PSCs are still facing the big challenge of instability in air due to the presence of organic components in the perovskites. To obtain stable PSCs, fully replacing the A-site organic cations with pure inorganic cations is one of the promising methods. To date, many researchers have studied the inorganic PSCs with astonishing breakthroughs, and the PCE of inorganic lead-based PSCs has exceeded 17%. In this review, the recent progress of inorganic PSCs is summarized and discussed for different perovskite compositions. The challenges of inorganic PSCs are revealed, followed by the outlook of this field.

Recent progress of inorganic perovskite solar cells

Tin-based perovskites with excellent optoelectronic properties and suitable band gaps are promising candidates for the preparation of efficient lead-free perovskite solar cells (PSCs). However, it is challenging to prepare highly stable and efficient tin-based PSCs because Sn2+ in perovskites can be easily oxidized to Sn4+ upon air exposure. Here we report the fabrication of air-stable FASnI3 solar cells by introducing hydroxybenzene sulfonic acid or its salt as an antioxidant additive into the perovskite precursor solution along with excess SnCl2 . The interaction between the sulfonate group and the Sn2+ ion enables the in situ encapsulation of the perovskite grains with a SnCl2 -additive complex layer, which results in greatly enhanced oxidation stability of the perovskite film. The corresponding PSCs are able to maintain 80 % of the efficiency over 500 h upon air exposure without encapsulation, which is over ten times longer than the best result reported previously. Our results suggest a possible strategy for the future design of efficient and stable tin-based PSCs.

Antioxidant Grain Passivation for Air-Stable Tin-Based Perovskite Solar Cells

Perovskite‐Based Phototransistors and Hybrid Photodetectors

Maintaining the stability of tin halide perovskites is a major challenge in developing lead-free perovskite solar cells (PSCs). Adding extra SnX2 (X = F, Cl, or Br) in the precursor solution to inh...

Highly Air-Stable Tin-Based Perovskite Solar Cells through Grain-Surface Protection by Gallic Acid

Organic-inorganic hybrid perovskites have emerged as promising functional materials for high-performance photodetectors. However, the toxicity of Pb and the lack of internal gain mechanism in typical perovskites significantly hinder their practical applications. Herein, a low-voltage and high-performance photodetector based on a single layer of lead-free Sn-based perovskite film is reported. The device shows broadband response from ultraviolet to near-infrared light with a responsivity up to 105 A W-1 and a high gain at a low operating voltage. The outstanding performance is attributed to the high hole mobility, p-doping nature, and excellent optoelectronic properties of the Sn-based perovskite. Moreover, the device is assembled on a flexible substrate and demonstrates both high sensitivity and good bending stability. This work demonstrates a route for realizing nontoxic, low-cost, and high-performance perovskite photodetectors with a simple device structure.

https://onlinelibrary.wiley.com/doi/pdf/10.1002/advs.201900751

Sn-Based Perovskite for Highly Sensitive Photodetectors.

2D Ruddlesden-Popper perovskites have attracted wide attention recently because of tunable optoelectronic properties and have been used as alternatives to their 3D counterparts in various optoelectronic devices. Here, a series of (PEA)2(MA) n -1Pb n I3 n +1 perovskite thin films is designed and fabricated by a convenient hot-casting method to obtain gradient n in the films, which leads to the formation of vertical heterojunctions that can enhance charge separation in the films under light illumination. Based on a single gradient perovskite film, a highly sensitive and stable photodetector with a responsivity up to 149 AW-1 and a specific detectivity of 2 × 1012 Jones is obtained. This work paves a way to realizing high-performance optoelectronic devices with enhanced charge separation by introducing compositional gradient in a perovskite film.

https://onlinelibrary.wiley.com/doi/pdf/10.1002/advs.202000776

Chun Ki Liu

Papers

Antioxidant Grain Passivation for Air-Stable Tin-Based Perovskite Solar Cells

Perovskite‐Based Phototransistors and Hybrid Photodetectors

Highly Air-Stable Tin-Based Perovskite Solar Cells through Grain-Surface Protection by Gallic Acid

Sn-Based Perovskite for Highly Sensitive Photodetectors.

Gradient 2D/3D Perovskite Films Prepared by Hot-Casting for Sensitive Photodetectors.