Route to Stable Lead-Free Double Perovskites with the Electronic Structure of CH3NH3PbI3: A Case for Mixed-Cation [Cs/CH3NH3/CH(NH2)2]2InBiBr6

Volonakis, George; Haghighirad, Amir A.; Snaith, Henry J.; Giustino, Feliciano

doi:10.1021/acs.jpclett.7b01584

Cited by 89 publications

(93 citation statements)

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“…[203] Particularly, they found that the B(I)-on-B(III) and B(III)-on-B(I) cation antisites create deep states in the bandgap (Figure 17e), which may cause significant recombination, detrimentally affecting the carrier lifetime and V OC , as is the case of Cu 2 ZnSn(Se,S) 4 . [202] Copyright 2017, American Chemical Society. Overall, it seems quite challenging to support highefficiency solar cells with Pb-free halide double perovskites.…”

Section: D a 2 B(i)b(ii)x 6 Halide Double Perovskitesmentioning

confidence: 99%

From Lead Halide Perovskites to Lead‐Free Metal Halide Perovskites and Perovskite Derivatives

2019

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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....

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Section: D a 2 B(i)b(ii)x 6 Halide Double Perovskitesmentioning

confidence: 99%

From Lead Halide Perovskites to Lead‐Free Metal Halide Perovskites and Perovskite Derivatives

2019

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“…[184] For instance, a mixed A-cation double perovskite, (Cs/MA/ FA) 2 InBiBr 6 , was predicted to have comparable stability with MAPbI 3 . [184] For instance, a mixed A-cation double perovskite, (Cs/MA/ FA) 2 InBiBr 6 , was predicted to have comparable stability with MAPbI 3 .…”

Section: Wwwadvancedsciencenewscommentioning

confidence: 99%

“…The organic cation based double perovskites have better thermal stability than their MAPbX 3 counterparts. [184] Copyright 2017, American Chemical Society. [154] The thermal analysis (Figure 15c,d) shows that (MA) 2 AgBiBr 6 can be stable up to ≈550 K with a heating rate of 10 K min −1 .…”

Section: Wwwadvancedsciencenewscommentioning

confidence: 99%

Progress of Lead‐Free Halide Double Perovskites

Igbari

Wang

Liao

2019

Advanced Energy Materials

379

314

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Although impressive performance has been obtained, PSCs are still far from commercial or real-life availability due to serious issues such as toxicity [15,16] and poor stability to heat, [17] oxygen, [18] moisture, [19,20] electric field, [21] and light. [18,22] The toxic nature of hybrid organic-inorganic lead halide perovskites has been traced to the presence of Pb in its chemical composition. [15,16,[23][24][25] Pb 2+ readily dissolves in water (e.g., rain water) to form a toxic solution capable of causing serious environmental pollution, harmful to human beings and the ecosystem. Besides their sensitivity to moisture, oxygen, light, electric field, or thermal stress, an existing self-degradation pathway [26,27] is also a big issue in hybrid organic-inorganic lead halide perovskites. Mixed-halide and mixed-cation perovskites have been investigated to address these issues. [28][29][30][31][32] The group IV elements, tin (Sn) [23,[33][34][35] and germanium (Ge), [34,36] have been employed as the replacements for Pb. However, the device performance through this approach has fallen short of the Pb-based ones. For example, the PCEs reported for Sn-based perovskite solar cells are usually less than 10%. [23,[33][34][35][37][38][39][40] In addition, the easy oxidation of Sn and Ge from the +2 state to the +4 state due to their high energy 5s and 4s orbitals makes them less promising for application in stable and long-term PSCs. [41] High throughput calculations also demonstrate that these substitutions are likely to compromise the ideal optoelectronic properties of MAPbI 3 . [42,43] Furthermore, low dimensional (e.g., 2D, 1D, and 0D) perovskites have also been used to address the stability issues in PSCs. [44][45][46][47][48] Recently, a stabilized PCE of 21.7% resulting from a 2D/3D bilayer PSC was reported. [49] However, the highest certified PCE in a 2D-only planar PSC is 15.3%, [50] which is far below that of their 3D perovskite-based counterparts. It thus stimulates the interest to develop new classes of materials which can solve the issues of toxicity and stability while still maintaining the fascinating properties of lead-based perovskite materials.Recent theoretical calculations demonstrate that a halide double perovskite structure, A 2 B′B″X 6 , which could be formed through a replacement of two toxic Pb 2+ in the crystal lattice with a pair of nontoxic heterovalent (i.e., monovalent and trivalent) metal cations, is a promising alternative to realize high-performance, lead-free, and stable PSCs. [51,52] Although, spectroscopic limited maximum efficiency (SLME) calculations revealed an efficiency limit less than 8% for the most prominent member www.advancedsciencenews.com double perovskites with a vacancy ordered structure. [88] In particular, the unit cell axis of Cs 2 AgBiBr 6 is given to be ≈11.25 Å, [25] which is two times larger than that of MAPbBr 3 (≈5.92 Å). [89] Both Ag + and Bi 3+ occupy the B-site of the crystal lattice with slightly varied metal-halide bond lengths. The dissimilar bond lengths st...

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“…However, Xiao et al205 used a combination of theoretical and experimental study to show that Cs 2 InBiCl 6 and Cs 2 InSbCl 6 were unstable due to spontaneous oxidation of In + into In 3+ . Lately, Volonakis et al206 proposed the rule of designing a useful double perovskite material: mimicking the electronic structure of MAPbI 3 . To stabilize the double perovskite structure of A 2 In + Bi 3+ X 6 , they suggested the use of mixed‐A‐site‐cation double perovskite (Cs/MA/FA) 2 InBiBr 6 rather than all‐inorganic double perovskites.…”

Section: Lead‐free Halide Hybrid Perovskite and Related Absorbersmentioning

confidence: 99%

Lead‐Free Hybrid Perovskite Absorbers for Viable Application: Can We Eat the Cake and Have It too?

2017

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Many years since the booming of research on perovskite solar cells (PSCs), the hybrid perovskite materials developed for photovoltaic application form three main categories since 2009: (i) high‐performance unstable lead‐containing perovskites, (ii) low‐performance lead‐free perovskites, and (iii) moderate performance and stable lead‐containing perovskites. The search for alternative materials to replace lead leads to the second group of perovskite materials. To date, a number of these compounds have been synthesized and applied in photovoltaic devices. Here, lead‐free hybrid light absorbers used in PV devices are focused and their recent developments in related solar cell applications are reviewed comprehensively. In the first part, group 14 metals (Sn and Ge)‐based perovskites are introduced with more emphasis on the optimization of Sn‐based PSCs. Then concerns on halide hybrids of group 15 metals (Bi and Sb) are raised, which are mainly perovskite derivatives. At the same time, transition metal Cu‐based perovskites are also referred. In the end, an outlook is given on the design strategy of lead‐free halide hybrid absorbers for photovoltaic applications. It is believed that this timely review can represent our unique view of the field and shed some light on the direction of development of such promising materials.

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Route to Stable Lead-Free Double Perovskites with the Electronic Structure of CH₃NH₃PbI₃: A Case for Mixed-Cation [Cs/CH₃NH₃/CH(NH₂)₂]₂InBiBr₆

Cited by 89 publications

References 67 publications

From Lead Halide Perovskites to Lead‐Free Metal Halide Perovskites and Perovskite Derivatives

From Lead Halide Perovskites to Lead‐Free Metal Halide Perovskites and Perovskite Derivatives

Progress of Lead‐Free Halide Double Perovskites

Lead‐Free Hybrid Perovskite Absorbers for Viable Application: Can We Eat the Cake and Have It too?

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