Counter-Doping Effect by Trivalent Cations in Tin-Based Perovskite Solar Cells.

Tin (Sn) -based perovskite solar cells (PSCs) normally show low open circuit voltage due to serious carrier recombination in the devices, which can be attributed to the oxidation and the resultant high p-type doping of the perovskite active layers. Considering the grand challenge to completely prohibit the oxidation of Sn-based perovskites, a feasible way to improve the device performance is to counter-dope the oxidized Sn-based perovskites by replacing Sn2+ with trivalent cations in the crystal lattice, which however is rarely reported. Here, the introduction of Sb3+, which can effectively counter-dope the oxidized perovskite layer and improve the carrier lifetime, is presented. Meanwhile, Sb3+ can passivate deep-level defects and improve carrier mobility of the perovskite layer, which are all favorable for the photovoltaic performance of the devices. Consequently, the target devices yield a relative enhancement of the power conversion efficiency (PCE) of 31.4% as well as excellent shelf-storage stability. This work provides a novel strategy to improve the performance of Sn-based PSCs, which can be developed as a universal way to compensate for the oxidation of Sn-based perovskites in optoelectronic devices.

Co-Self-Assembled Monolayers Modified NiOx for Stable Inverted Perovskite Solar Cells.

[4-(3,6-dimethyl-9H-carbazol-9yl)butyl]phosphonic acid (Me-4PACz) self-assembled molecules (SAM) are an effective method to solve the problem of the buried interface of NiOx in inverted perovskite solar cells (PSCs). However, the Me-4PACz end group (carbazole core) cannot forcefully passivate defects at the bottom of the perovskite film. Here, a Co-SAM strategy is employed to modify the buried interface of PSCs. Me-4PACz is doped with phosphorylcholine chloride (PC) to form a Co-SAM to improve the monolayer coverage and reduce leakage current. The phosphate group and chloride ions (Cl-) in PC can inhibit NiOx surface defects. Meantime, the quaternary ammonium ions and Cl- in PC can fill organic cations and halogen vacancies in the perovskite film to enable defects passivation. Moreover, Co-SAM can promote the growth of perovskite crystals, collaboratively solve the problem of buried defects, suppress nonradiative recombination, accelerate carrier transmission, and relieve the residual stress of the perovskite film. Consequently, the Co-SAM modified devices show power conversion efficiencies as high as 25.09% as well as excellent device stability with 93% initial efficiency after 1000 h of operation under one-sun illumination. This work demonstrates the novel approach for enhancing the performance and stability of PSCs by modifying Co-SAM on NiOx.

Highly Sensitive Broadband Phototransistors Based on Gradient Tin/Lead Mixed Perovskites.

Highly sensitive broadband photodetectors are critical to numerous cutting-edge technologies such as biomedical imaging, environment monitoring, and night vision. Here, phototransistors based on mixed Sn/Pb perovskites are reported, which demonstrate ultrahigh responsivity, gain and specific detectivity in a broadband from ultraviolet to near-infrared region. The interface properties of the perovskite phototransistors are optimized by a special three-step cleaning-healing-cleaning treatment, leading to a high hole mobility in the channel. The highly sensitive performance of the mixed Sn/Pb perovskite phototransistors can be attributed to the vertical compositional heterojunction automatically formed during the film deposition, which is helpful for the separation of photocarriers thereby enhancing a photogating effect in the perovskite channel. This work demonstrates a convenient approach to achieving high-performance phototransistors through tuning compositional gradient in mixed-metal perovskite channels.

High Open Circuit Voltage Over 1 V Achieved in Tin-Based Perovskite Solar Cells with a 2D/3D Vertical Heterojunction.

2D-3D mixed tin halide perovskites are outstanding candidate materials for lead-free perovskite solar cells (PSCs) due to their improved stability and decreased trap density in comparison with their pure 3D counterparts. However, the mixture of multiple phases may lead to poor charge transfer across the films and limit the device efficiency. Here, a stacked quasi-2D (down)-3D (top) double-layered structure in perovskite films prepared via vacuum treatment is demonstrated, which can result in a planar bilayer heterojunction. In addition, it is found that the introduction of guanidinium thiocyanate (GuaSCN) additive can improve the crystallinity and carrier mobility in the 2D perovskite layer and passivate defects in the whole film, leading to a long carrier lifetime (>140 ns) in photoluminescence measurements. As a result, the PSCs show a high open circuit voltage (VOC ) up to 1.01 V with a voltage loss of only 0.39 V, which represents the record values ever reported for tin-based PSCs. The champion device exhibits a power conversion efficiency (PCE) of 13.79% with decent stability, retaining 90% of the initial PCE for 1200 h storage in N2 -filled glovebox.

High-Performance Tin-Lead Mixed-Perovskite Solar Cells with Vertical Compositional Gradient.

Sn-Pb mixed perovskites with bandgaps in the range of 1.1-1.4 eV are ideal candidates for single-junction solar cells to approach the Shockley-Queisser limit. However, the efficiency and stability of Sn-Pb mixed-perovskite solar cells (PSCs) still lag far behind those of Pb-based counterparts due to the easy oxidation of Sn2+ . Here, a reducing agent 4-hydrazinobenzoic acid is introduced as an additive along with SnF2 to suppress the oxidation of Sn2+ . Meanwhile, a vertical Pb/Sn compositional gradient is formed spontaneously after an antisolvent treatment due to different solubility and crystallization kinetics of Sn- and Pb-based perovskites and it can be finely tuned by controlling the antisolvent temperature. Because the band structure of a perovskite is dependent on its composition, graded vertical heterojunctions are constructed in the perovskite films with a compositional gradient, which can enhance photocarrier separation and suppress carrier recombination in the resultant PSCs. Under optimal fabrication conditions, the Sn-Pb mixed PSCs show power conversion efficiency up to 22% along with excellent stability during light soaking.

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

Sn-Based Perovskite for Highly Sensitive Photodetectors.

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.