Two bilayer organic-inorganic hybrid perovskite compounds exhibiting reversible phase transition and dielectric anomalies

Jiang, Zhentao; Hao, Yanling; Wang, Hui; Zhang, Xiuxiu; Yao, Jiaojiao; Li, Mingli; Wei, Zhenhong

doi:10.1016/j.jssc.2019.121104

Cited by 9 publications

(14 citation statements)

References 35 publications

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“…1−4,28−31,44−49 Apart from BA and PEA, a number of other spacers have demonstrated the capacity to form FAPbI 3 -based 2D perovskites while improving their optoelectronic properties and utility in photovoltaics. 26−28 This, for instance, involves 5-ammonium valeric acid (AVA), 29,42 2-(perfluorophenyl)ethylammonium (FEA), 12 benzylammonium (BN), 23 guanidinium (GUA), 30 n-pentylammonium (PA), 47 2-thiophenemethylammonium (TMA), 48 iso-butylammonium (IBA), 49 1-adamantylmethanammonium (ADAM), 1,4,50 and 1,4-phenylenedimethanammonium (PDMA). 2,3 T h in fi lms of RP and DJ phases based o n (ADAM) 2 FA n−1 Pb n I 3n+1 and (PDMA)FA n−1 Pb n I 3n+1 compositions, respectively (Figure 2a,b), have recently shown promising photovoltaic performances.…”

Section: Structural Propertiesmentioning

confidence: 99%

“…3 While neither ADAM-nor PDMA-based 2D perovskites have been isolated and characterized as single crystals to date, one of the few representative systems obtained based on (PA) 2 FAPb 2 I 7 and (TMA) 2 FAPb 2 I 7 phases demonstrated the formation of the corresponding layered 2D phases with comparable behaviors (Figure 4f). 47,48 In both of these systems, n-pentylammonium (PA) and 2-thiophenemethylammonium (TMA) spacers were found to template the layered FAPbI 3 -based perovskite scaffold, approaching an ideal cubic structure with increasing temperature. 47,48 Consequently, such templating effects contribute to stabilizing the α-FAPbI 3 phase and offer an important strategy for controlling the optoelectronic properties.…”

Section: Templating Effectsmentioning

confidence: 99%

“…47,48 In both of these systems, n-pentylammonium (PA) and 2-thiophenemethylammonium (TMA) spacers were found to template the layered FAPbI 3 -based perovskite scaffold, approaching an ideal cubic structure with increasing temperature. 47,48 Consequently, such templating effects contribute to stabilizing the α-FAPbI 3 phase and offer an important strategy for controlling the optoelectronic properties. 2,33−37,76,77…”

Section: Templating Effectsmentioning

confidence: 99%

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Layered Hybrid Formamidinium Lead Iodide Perovskites: Challenges and Opportunities

2021

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Metrics & MoreArticle Recommendations CONSPECTUS: Hybrid halide perovskite materials have become one of the leading candidates for various optoelectronic applications. They are based on organic−inorganic structures defined by the AMX 3 composition, were A is the central cation that can be either organic (e.g., methylammonium, formamidinium (FA)) or inorganic (e.g., Cs + ), M is a divalent metal ion (e.g., Pb 2+ or Sn 2+ ), and X is a halide anion (I − , Br − , or Cl − ). In particular, FAPbI 3 perovskites have shown remarkable optoelectronic properties and thermal stabilities. However, the photoactive α-FAPbI 3 (black) perovskite phase is not thermodynamically stable at ambient temperature and forms the δ-FAPbI 3 (yellow) phase that is not suitable for optoelectronic applications. This has stimulated intense research efforts to stabilize and realize the potential of the α-FAPbI 3 perovskite phase. In addition, hybrid perovskites were proven to be unstable against the external environmental conditions (air and moisture) and under device operating conditions (voltage and light), which is related to various degradation mechanisms. One of the strategies to overcome these instabilities has been based on low-dimensional hybrid perovskite materials, in particular layered two-dimensional (2D) perovskite phases composed of organic layers separating hybrid perovskite slabs, which were found to be more stable toward ambient conditions and ion migration. These materials are mostly based on S x A n−1 Pb n X 3n+1 composition with various mono-(x = 1) or bifunctional (x = 2) organic spacer cations that template hybrid perovskite slabs and commonly form either Ruddlesden−Popper (RP) or Dion−Jacobson (DJ) phases. These materials behave as natural quantum wells since charge carriers are confined to the inorganic slabs, featuring a gradual decrease in the band gap as the number of inorganic layers (n) increases from n = 1 (2D) to n = ∞ (3D). While various layered 2D perovskites have been developed, their FA-based analogues remain under-represented to date. Over the past few years, several research advances enabled the realization of FA-based layered perovskites, which have also demonstrated a unique templating effect in stabilizing the α-FAPbI 3 phase. This, for instance, involved the archetypical n-butylammonium and 2-phenylethylammonium organic spacers as well as guanidinium, 5-ammonium valeric acid, iso-butylammonium, benzylammonium, n-pentylammonium, 2-thiophenemethylammonium, 2-(perfluorophenyl)ethylammonium, 1-adamantylmethanammonium, and 1,4-phenylenedimethanammonium. FAPbBr 3 -based layered perovskites have also demonstrated potential in various optoelectronic applications, yet the opportunities associated with FAPbI 3 -based perovskites have attracted particular attention in photovoltaics, stimulating further developments. This Account provides an overview of some of these recent developments, with a particular focus on FAPbI 3 -based layered perovskites and their utility in photovoltaics, while outlining challenges and op...

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Section: Structural Propertiesmentioning

confidence: 99%

Section: Templating Effectsmentioning

confidence: 99%

Section: Templating Effectsmentioning

confidence: 99%

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Layered Hybrid Formamidinium Lead Iodide Perovskites: Challenges and Opportunities

2021

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“…[122] It was also found that the 2D perovskite with ThMA as the spacer has close to an ideal cubic structure, which is expected to act as a template to induce and form a stable α-FAPbI 3 . [123] By using a series of thiophene alkylammonium cations (Figure 8f) as 2D perovskite spaces, Sutanto et al revealed a dynamical structural mutation of the 2D/3D interface. They found that 2-thiophenemethylammonium iodide (2-TMAI) and 3-thiophenemethylammonium iodide (3-TMAI) based 2D structures can incorporate ions at the surface of 3D perovskites and dynamically self-transform into a quasi-2D structure.…”

Section: Thiophenaminesmentioning

confidence: 99%

From Structural Design to Functional Construction: Amine Molecules in High‐Performance Formamidinium‐Based Perovskite Solar Cells

Tang

et al. 2022

Angewandte Chemie

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Formamidinium (FA) based perovskites are considered as one of the most promising light‐absorbing perovskite materials owing to their narrower band gap and better thermal stability compared to conventional methylammonium‐based perovskites. Constant improvement by using various additives stimulates the potential application of these perovskites. Amine molecules with different structures have been widely used as typical additives in FA‐based perovskite solar cells, and decent performances have been achieved. Thus, a systematic review focusing on structural regulation and functional construction of amines in FA‐based perovskites is of significance. Herein, we analyze the construction mechanism of different structural amines on the functional perovskite crystals. The influence of amine molecules on specific perovskite properties including defect conditions, charge transfer, and moisture resistance are evaluated. Finally, we summarize the design rules of amine molecules for the application in high‐performance FA‐based perovskites and propose directions for the future development of additive molecules.

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“…As many other copper perovskites, (CEA) 2 CuCl 4 shows reversible thermochromism. [ 20–22 ] However, to date, there are no reports of irreversible thermochromic transitions in copper halide perovskites. To the best of our knowledge, the only other reports of halide perovskites that present irreversible thermochromism are those reported by Sourisseau [ 23 ] in 2007, and more recently, by our research group.…”

Section: Introductionmentioning

confidence: 99%

Reversible and Irreversible Thermochromism in Copper‐Based Halide Perovskites

Pareja-Rivera

Solis‐Ibarra

2021

Advanced Optical Materials

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Copper‐based layered perovskites have shown abundant phase transitions and thermochromic behaviors. However, there are very few cases of perovskites with irreversible transitions. Here, the thermochromic behavior of two perovskites (CEA)2CuCl4 and (BEA)2CuCl4 is discussed, where CEA = 2‐chloroethylammonium and BEA = 2‐bromoethylammonium, the latter of which is reported for the first time. These materials exhibit a reversible and irreversible thermochromic behavior determined by the nature of the organic cation. Using nuclear magnetic resonance, X‐ray diffraction, and optical absorption, it was possible to investigate the mechanism for this transition: a topochemical exchange reaction between the organic and inorganic halides in (BEA)2CuCl4 to yield the mixed‐halide perovskite (BEA)1.1(CEA)0.9CuCl3.1Br0.9. These materials and the fundamental principles shown herein have potential use as low‐cost irreversible thermochromic sensors and their design.

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Two bilayer organic-inorganic hybrid perovskite compounds exhibiting reversible phase transition and dielectric anomalies

Cited by 9 publications

References 35 publications

Layered Hybrid Formamidinium Lead Iodide Perovskites: Challenges and Opportunities

Layered Hybrid Formamidinium Lead Iodide Perovskites: Challenges and Opportunities

From Structural Design to Functional Construction: Amine Molecules in High‐Performance Formamidinium‐Based Perovskite Solar Cells

Reversible and Irreversible Thermochromism in Copper‐Based Halide Perovskites

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