Stabilizing Lead-Free All-Inorganic Tin Halide Perovskites by Ion Exchange

Jiang, Junke; Onwudinanti, Chidozie; Hatton, Ross A.; Bobbert, Peter A.; Tao, Shuxia

doi:10.1021/acs.jpcc.8b04013

Cited by 76 publications

(61 citation statements)

References 78 publications

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“…An extensive monitoring of oxidation of CsSnI 3 in the air by using additives SnCl 2 , SnBr 2 , and SnI 2 has been carried out to measure electronic, optical absorption spectrum with time and reported that it exhibits the highest stability by inhibiting the crystallization/decomposition . The addition of SnF 2 lowers the background charge carrier density by neutralizing traps . The mesostructured CsSnI 3 displayed a SPCE of 2.02% with the addition of 20% SnF 2 as an additive.…”

Section: Lead‐free Perovskitesmentioning

confidence: 99%

“…[213] The thin films of CsSnIBr 3 were fabricated with the addition of hypophosphorous acid (HPA) with thermal stability up to 473 K achieving a SPCE of 3% that last for over 77 d. [193] The results of a computational study on mixed cesium perovskite Rb y Cs 1−y Sn (Br x I 3−x ) 3 as a light absorber have revealed that the substitution of Rb + for Cs + enhanced the quality of perovskite film and its practical applicability in perovskite solar cells. [214] Another study on CsSnI 3 and CsSnI 3−x Br x as light absorbers in n-i-p devices structure reported an efficiency of 2%. CsSnI 3 has a small bandgap of 1.27 eV to a near-infrared absorption onset to 950 nm and exhibited a high charge carrier density up to27.67 mA cm −2 .…”

Section: Tin-based Perovskitesmentioning

confidence: 99%

“…[163,192] The addition of SnF 2 lowers the background charge carrier density by neutralizing traps. [214,216] The mesostructured CsSnI 3 displayed a SPCE of 2.02% with the addition of 20% SnF 2 as an additive. Also a spectral response of 950 nm is demonstrated with SnF 2 addition.…”

Section: Tin-based Perovskitesmentioning

confidence: 99%

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Potential Substitutes for Replacement of Lead in Perovskite Solar Cells: A Review

Kour¹,

et al. 2019

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Lead halide perovskites have displayed the highest solar power conversion efficiencies of 23% but the toxicity issues of these materials need to be addressed. Lead‐free perovskites have emerged as viable candidates for potential use as light harvesters to ensure clean and green photovoltaic technology. The substitution of lead by Sn, Ge, Bi, Sb, Cu and other potential candidates have reported efficiencies of up to 9%, but there is still a dire need to enhance their efficiencies and stability within the air. A comprehensive review is given on potential substitutes for lead‐free perovskites and their characteristic features like energy bandgaps and optical absorption as well as photovoltaic parameters like open‐circuit voltage (VOC), fill factor, short‐circuit current density (J SC), and the device architecture for their efficient use. Lead‐free perovskites do possess a suitable bandgap but have low efficiency. The use of additives has a significant effect on their efficiency and stability. The incorporation of cations like diethylammonium, phenylethyl ammonium, phenylethyl ammonium iodide, etc., or mixed cations at different compositions at the A‐site is reported with engineered bandgaps having significant efficiency and stability. Recent work on the advancement of lead‐free perovskites is also reviewed.

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Section: Lead‐free Perovskitesmentioning

confidence: 99%

Section: Tin-based Perovskitesmentioning

confidence: 99%

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Potential Substitutes for Replacement of Lead in Perovskite Solar Cells: A Review

Kour¹,

et al. 2019

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“…This substitution can not only result in long‐term stability in air but also maintain the high‐symmetry cubic structure with a different halogen X (X = Cl, Br, I). Furthermore, it is expected that the absorption range of A 2 SnX 6 can be simply altered by changing the halogen composition, which is beneficial to high‐performance solar cells and wavelength‐tuneable photodetectors …”

Section: Introductionmentioning

confidence: 99%

Lead‐Free Perovskite Derivative Cs₂SnCl₆₋_xBr_x Single Crystals for Narrowband Photodetectors

Zhou

Luo

Rong

et al. 2019

Advanced Optical Materials

145

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Recently, lead-based perovskite materials with the formula APbX 3 (A = Cs, methylammonium; X = Cl, Br, I) have received broad attention for their excellent optical and electronic properties in the fields of photovoltaic solar cells, [1] light-emitting diodes (LEDs), [2] sensitive photodetectors, [3] etc. However, the presence of toxic lead and unsatisfactory stability against heat and humidity restrict their further application. [4] An effective method to solve these issues is to replace divalent Pb with tetravalent Sn, forming a molecular salt structure with the formula A 2 SnX 6 (X = Cl, Br, I), which is a 50% Sn defect perovskite derivative featuring isolated [SnX 6 ] 2− octahedra. [5] This substitution can not only result in long-term stability in air but also maintain the high-symmetry cubic structure with a different halogen X Lead-free and stable Sn halide perovskites demonstrate tremendous potential in the field of optoelectronic devices. Here, the structure and optical properties of the "defect" perovskites Cs 2 SnCl 6−x Br x are reported, as well as their use as photodetector materials. Millimeter-sized Cs 2 SnCl 6−x Br x single crystals are grown by the hydrothermal method, with the body color continuously changing from transparent to yellow and finally to dark red. Narrowband single-crystal photodetectors using Cs 2 SnCl 6−x Br x crystals are presented, which show a high detectivity of ≈2.71 × 10 10 Jones, with narrowband photodetection (full-width at half-maximum ≈45 nm) and high ion diffusion barriers. Moreover, the response spectra are continuously tuned from near violet to orange depending on the variation of the bandgap of the single crystals by changing the halide compositions. The strong surface charge recombination of the excess carriers near the crystal surfaces produced by short wavelength light elucidates the narrowband photodetection behavior. This work provides a new paradigm in the design of lead-free, stable, and high-performance perovskite derivatives for optoelectronics applications.

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“…It is also worth mentioning that, although the reaction enthalpies of reaction 2 are slightly positive (Figure 4f), such reactions are typically driven by entropy of mixing. [36] The addition of GA + cations accelerates the conversion of δ-CsPbI 3 to the perovskite (Figure 3i). We estimate the mixing enthalpy (ΔH mix ) for the ternary mixing of Cs + , GA + , and FA + in the perovskite phase relative to the binary compounds by…”

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confidence: 99%

Precise Control of Perovskite Crystallization Kinetics via Sequential A‐Site Doping

et al. 2020

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film deposition process to achieve desired morphology and microstructure. [2-6] Most of the high-efficiency PSCs were produced by either one-step or two-step fabrication methods. The very first MAPbI 3-based PSC was fabricated via a one-step spincoating process developed by Kojima et al. in 2009. [7] However, the one-step fabricated perovskite film typically exhibited a dendritic morphology with poor coverage. To address the morphology issue, a two-step spin-coating process was developed by Xiao et al. [8] and Im et al. [9] in 2014, which consisted of sequential depositions of an inorganic PbI 2 layer and an organic salt MAI. This two-step method gave rise to compact and pinhole-free MAPbI 3 perovskite films, significantly increasing the efficiency of MA-based PSCs to ≈17%. [9] In 2015, the record PCE received another boost through the development of a simpler antisolvent-assisted one-step method, which could form a very uniform perovskite thin film by promoting the crystallization process. [4,10] Meanwhile, MA cations were replaced by CH(NH 2) 2 + (FA) cations to improve the light Two-step-fabricated FAPbI 3-based perovskites have attracted increasing attention because of their excellent film quality and reproducibility. However, the underlying film formation mechanism remains mysterious. Here, the crystallization kinetics of a benchmark FAPbI 3-based perovskite film with sequential A-site doping of Cs + and GA + is revealed by in situ X-ray scattering and first-principles calculations. Incorporating Cs + in the first step induces an alternative pathway from δ-CsPbI 3 to perovskite α-phase, which is energetically more favorable than the conventional pathways from PbI 2. However, pinholes are formed due to the nonuniform nucleation with sparse δ-CsPbI 3 crystals. Fortunately, incorporating GA + in the second step can not only promote the phase transition from δ-CsPbI 3 to the perovskite α-phase, but also eliminate pinholes via Ostwald ripening and enhanced grain boundary migration, thus boosting efficiencies of perovskite solar cells over 23%. This work demonstrates the unprecedented advantage of the two-step process over the one-step process, allowing a precise control of the perovskite crystallization kinetics by decoupling the crystal nucleation and growth process.

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Stabilizing Lead-Free All-Inorganic Tin Halide Perovskites by Ion Exchange

Cited by 76 publications

References 78 publications

Potential Substitutes for Replacement of Lead in Perovskite Solar Cells: A Review

Potential Substitutes for Replacement of Lead in Perovskite Solar Cells: A Review

Lead‐Free Perovskite Derivative Cs₂SnCl₆₋_xBr_x Single Crystals for Narrowband Photodetectors

Precise Control of Perovskite Crystallization Kinetics via Sequential A‐Site Doping

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Stabilizing Lead-Free All-Inorganic Tin Halide Perovskites by Ion Exchange

Cited by 76 publications

References 78 publications

Potential Substitutes for Replacement of Lead in Perovskite Solar Cells: A Review

Potential Substitutes for Replacement of Lead in Perovskite Solar Cells: A Review

Lead‐Free Perovskite Derivative Cs2SnCl6−xBrx Single Crystals for Narrowband Photodetectors

Precise Control of Perovskite Crystallization Kinetics via Sequential A‐Site Doping

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Lead‐Free Perovskite Derivative Cs₂SnCl₆₋_xBr_x Single Crystals for Narrowband Photodetectors