Abstract:We present solution-based fabrication and characterization of the lead-free perovskite-related methylammonium antimony iodide (CH 3 NH 3 ) 3 Sb 2 I 9 compound. By photothermal deflection spectroscopy (PDS), we determined a peak absorption coefficient α ≈ 10 5 cm −1 and an optical band gap of 2.14 eV for amorphous films of (CH 3 NH 3 ) 3 Sb 2 I 9 . Compared to the related Bi compound, the Sb-perovskite shows no exciton peak in its absorption spectrum. The photoluminescence emission (PL) is observed at 1.58 eV, … Show more
“…d) J−V curves of the Cs 3 Bi 2 I 9 -based solar cells, using a 0.1 V s −1 scanning rate. [142][143][144][145] For example, Karuppuswamy et al prepared large-grain MA 3 Sb 2 I 9 crystals, by a combination of additive incorporation, antisolvent treatment, and insertion of a hydrophobic interlayer. [141] Copyright 2018, Elsevier B.V. Figure 10.…”
serious challenges due to the inclusion of toxic Pb and instability against moisture, heat, and irradiation. In recent years, significant efforts have been paid to develop Pb-free halide perovskite and perovskite derivative absorber materials. However, so far, solar cells based on these materials show significantly inferior performances as compared to their Pb halide perovskite counterparts. Herein, we provide reviews on the fundamental understandings of the photovoltaic properties from Pb halide perovskites to Pb-free metal halide perovskites and perovskite derivatives as well as the experimental results reported in the literature. The results suggest that replacing Pb by nontoxic elements may degrade the superior photovoltaic properties seen in Pb halide perovskites, explaining the fact that all reported solar cells based on Pb-free perovskites or perovskite derivatives show performances significantly lower than Pb halide perovskite solar cells.
Overview: Approaches and Consequences of Pb ReplacementWe first provide an overview of the approaches and consequences of Pb replacement reported in the literature, as shown in Figure 1. In general, there are two categories for Pb replacement: using either homovalent elements such as Sn and Ge or heterovalent elements such as Bi and Sb. The heterovalent replacement category can be divided into two subcategories based on the ways to maintain the charge neutrality: ion-splitting and ordered vacancy. The ion-splitting subcategory can be further divided into mixed anion compounds with the formula of AB(Ch,X) 3 , where Ch represents a chalcogen element, and X represents a halogen element, and mixed cation compounds with a formula of A 2 B(I)B(III)X 6 , which are commonly called double perovskites. The ordered vacancy subcategory can also be divided into the B(III) compounds with a formula of A 3 ◻B(III)X 9 and the B(IV) compounds with a formula of A 2 ◻ B(IV)X 6 (the sign of ◻ indicates vacancy). Figure 1 also summarizes the photovoltaic properties and the stabilities of each group of materials, which provides a clear overview of the consequences of Pb replacement. While the homovalent replacement by Sn or Ge leads to instability, the heterovalent Pb replacement leads to degraded electronic properties mainly due to the reduction on electronic dimensionality. As a result, all the reported Pb-free perovskite and perovskite derivative solar Despite the exciting progress on power conversion efficiencies, the commercialization of the emerging lead (Pb) halide perovskite solar cell technology still faces significant challenges, one of which is the inclusion of toxic Pb. Searching for Pb-free perovskite solar cell absorbers is currently an attractive research direction. The approaches used for and the consequences of Pb replacement are reviewed herein. Reviews on the theoretical understanding of the electronic, optical, and defect properties of Pb and Pb-free halide perovskites and perovskite derivatives are provided, as well as the experimental results available in the literature....
“…d) J−V curves of the Cs 3 Bi 2 I 9 -based solar cells, using a 0.1 V s −1 scanning rate. [142][143][144][145] For example, Karuppuswamy et al prepared large-grain MA 3 Sb 2 I 9 crystals, by a combination of additive incorporation, antisolvent treatment, and insertion of a hydrophobic interlayer. [141] Copyright 2018, Elsevier B.V. Figure 10.…”
serious challenges due to the inclusion of toxic Pb and instability against moisture, heat, and irradiation. In recent years, significant efforts have been paid to develop Pb-free halide perovskite and perovskite derivative absorber materials. However, so far, solar cells based on these materials show significantly inferior performances as compared to their Pb halide perovskite counterparts. Herein, we provide reviews on the fundamental understandings of the photovoltaic properties from Pb halide perovskites to Pb-free metal halide perovskites and perovskite derivatives as well as the experimental results reported in the literature. The results suggest that replacing Pb by nontoxic elements may degrade the superior photovoltaic properties seen in Pb halide perovskites, explaining the fact that all reported solar cells based on Pb-free perovskites or perovskite derivatives show performances significantly lower than Pb halide perovskite solar cells.
Overview: Approaches and Consequences of Pb ReplacementWe first provide an overview of the approaches and consequences of Pb replacement reported in the literature, as shown in Figure 1. In general, there are two categories for Pb replacement: using either homovalent elements such as Sn and Ge or heterovalent elements such as Bi and Sb. The heterovalent replacement category can be divided into two subcategories based on the ways to maintain the charge neutrality: ion-splitting and ordered vacancy. The ion-splitting subcategory can be further divided into mixed anion compounds with the formula of AB(Ch,X) 3 , where Ch represents a chalcogen element, and X represents a halogen element, and mixed cation compounds with a formula of A 2 B(I)B(III)X 6 , which are commonly called double perovskites. The ordered vacancy subcategory can also be divided into the B(III) compounds with a formula of A 3 ◻B(III)X 9 and the B(IV) compounds with a formula of A 2 ◻ B(IV)X 6 (the sign of ◻ indicates vacancy). Figure 1 also summarizes the photovoltaic properties and the stabilities of each group of materials, which provides a clear overview of the consequences of Pb replacement. While the homovalent replacement by Sn or Ge leads to instability, the heterovalent Pb replacement leads to degraded electronic properties mainly due to the reduction on electronic dimensionality. As a result, all the reported Pb-free perovskite and perovskite derivative solar Despite the exciting progress on power conversion efficiencies, the commercialization of the emerging lead (Pb) halide perovskite solar cell technology still faces significant challenges, one of which is the inclusion of toxic Pb. Searching for Pb-free perovskite solar cell absorbers is currently an attractive research direction. The approaches used for and the consequences of Pb replacement are reviewed herein. Reviews on the theoretical understanding of the electronic, optical, and defect properties of Pb and Pb-free halide perovskites and perovskite derivatives are provided, as well as the experimental results available in the literature....
“…The optoelectronic properties of (CH 3 NH 3 ) 3 Sb 2 I 9 have been investigated by Hebig et al recently [55]. The compound has a zero-dimensional dimer structure comprising discrete bi-octahedral metal halide units Sb 2 I 9
3− of face-sharing BI 6 octahedra surrounded by CH 3 NH 3
+ cations to balance the charge neutrality.…”
Section: Heterovalent Substitution With Mono- Tri- and Tetravalent Cmentioning
confidence: 99%
“…10). In addition, a maximum external quantum efficiency (EQE) of about 12%, and only little hysteresis in planar perovskite solar cells are reported [55]. The authors attributed this low photocurrent density to an inefficient charge extraction, which might be improved using mesoporous scaffolds.Fig.…”
Section: Heterovalent Substitution With Mono- Tri- and Tetravalent Cmentioning
confidence: 99%
“…0.5[55, 163][NH 2 (CH 3 ) 2 ] 3 Sb 2 Cl 9
Exp.Monoclinic ( Pc ) at 200 K–––[159]Monoclinic ( P 2 1 / c ) at 298 K2D––[159, 168][NH 2 (CH 3 ) 2 ] 3 Sb 2 Br 9
Exp.Monoclinic ( P 2 1 / c )–––[167][NH(CH 3 ) 3 ] 3 Sb 2 Cl 9
Exp.Monoclinic ( Pc )2D––[160][N(CH 3 ) 4 ] 3 Sb 2 Cl 9
Exp.Hexagonal ( P 6 3 / mmc )0D––[158][N(CH 3 ) 4 ] 3 Sb 2 Br 9
Exp.Hexagonal ( P 6 3 / mmc )0D––[170](C 5 H 5 NH) 3 Sb 2 Cl 9
Exp.Monoclinic ( C 2/ c )1D––[170]Rb 3 Sb 2 Br 9
Exp.Trigonal ( P
m 1)–2.48–[162]Rb 3 Sb 2 I 9
Sim./exp.Monoclinic ( Pc )2D2.10.66[35]Monoclinic ( Pc )–1.94–[162]…”
Section: Heterovalent Substitution With Mono- Tri- and Tetravalent Cmentioning
Metal halide perovskites have revolutionized the field of solution-processable photovoltaics. Within just a few years, the power conversion efficiencies of perovskite-based solar cells have been improved significantly to over 20%, which makes them now already comparably efficient to silicon-based photovoltaics. This breakthrough in solution-based photovoltaics, however, has the drawback that these high efficiencies can only be obtained with lead-based perovskites and this will arguably be a substantial hurdle for various applications of perovskite-based photovoltaics and their acceptance in society, even though the amounts of lead in the solar cells are low. This fact opened up a new research field on lead-free metal halide perovskites, which is currently remarkably vivid. We took this as incentive to review this emerging research field and discuss possible alternative elements to replace lead in metal halide perovskites and the properties of the corresponding perovskite materials based on recent theoretical and experimental studies. Up to now, tin-based perovskites turned out to be most promising in terms of power conversion efficiency; however, also the toxicity of these tin-based perovskites is argued. In the focus of the research community are other elements as well including germanium, copper, antimony, or bismuth, and the corresponding perovskite compounds are already showing promising properties.Graphical abstract
“…The crystal structure,p hotovoltaic performance,c harge carrier lifetime,a nd device stability were studied. [21,22] Though the crystal structure of (NH 4 ) 3 Sb 2 I 9 has been reported, [23] its properties,such as light absorption, charge carrier mobilities,a nd photovoltaic performance,have not been investigated. [20] Antimony-containing perovskites,( CH 3 NH 3 ) 3 Sb 2 I 9 and Cs 3 Sb 2 I 9 ,w ere also developed and the optoelectronic properties were studied.…”
Af amily of perovskitel ight absorbers (NH 4 ) 3 Sb 2 I x Br 9Àx (0 x 9) was prepared. These materials show good solubility in ethanol, al ow-cost, hypotoxic, and environmentally friendly solvent. The light absorption of (NH 4 ) 3 Sb 2 I x Br 9Àx films can be tuned by adjusting Ia nd Br content. The absorption onset for (NH 4 ) 3 Sb 2 I x Br 9Àx films changes from 558 nm to 453 nm as xc hanges from 9t o0 . (NH 4 ) 3 Sb 2 I 9 single crystals were prepared, exhibiting ah ole mobility of 4.8 cm 2 V À1 s À1 and an electron mobility of 12.3 cm 2 V À1 s À1 .( NH 4 ) 3 Sb 2 I 9 solar cells gave an open-circuit voltage of 1.03 Vand apower conversion efficiency of 0.51 %.
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