Guanidinium-Formamidinium Lead Iodide: A Layered Perovskite-Related Compound with Red Luminescence at Room Temperature

Nazarenko, Olga; Kotyrba, Martin; Yakunin, Sergii; Aebli, Marcel; Rainò, Gabriele; Benin, Bogdan M.; Wörle, Michael; Kovalenko, Maksym V.

doi:10.1021/jacs.8b00194

Cited by 124 publications

(127 citation statements)

References 39 publications

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“…It is notable that the ammonium groups (‐NH 2 ) of G cations form strong NH···I hydrogen bonds with the neighboring iodine ions of corner‐sharing PbI 6 octahedra (Figure b; Table S4, Supporting Information). Emphatically, compared with the previous studies on Cs + /G + , MA + /G + or FA + /G + systems in which G + acts as the “spacer”, the G + cation in (PA) 2 (G)Pb 2 I 7 is for the first time confined in the cavity instead of interlayer space. Figure c depicts that G cation resides in the barycenter of the polyhedral voids between the corner‐sharing PbI 6 octahedra.…”

Section: Resultsmentioning

confidence: 94%

Highly Sensitive and Ultrafast Responding Array Photodetector Based on a Newly Tailored 2D Lead Iodide Perovskite Crystal

Liu

et al. 2019

Advanced Optical Materials

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flexibility and allow for a molecule-level assembling of inorganic and organic components. [10][11][12][13][14] Structurally, inorganic perovskite layers (wells) and the organic spacers (barriers) are organized alternatively, resembling that of the quantumconfined motifs, which render a vast modulation of electronic and optical properties. [15][16][17][18] For instance, the conductive attributes for a series of tin(II)-based 2D hybrid perovskites have been finely tuned from semiconducting to metallic states by increasing the number of inorganic perovskite layers. [19,20] Particularly, their inherent 2D quantum-confined structures facilitate rapid dissociation of the photogenerated electron-hole pairs: the electrons transfer to inorganic conduction band and high electron mobility reduces recombination rate, thus creating the large photoconductivity gains. [21] Therefore, such unique characteristics make 2D hybrid perovskites promising candidates for assembling newly conceptual optoelectronic devices, particularly for the high-performance photodetectors.As an intriguing subclass, 2D Ruddlesden-Popper multilayered perovskites with a generic formula of (A 1 ) 2 (A 2 ) n−1 PbI 3n+1 (A 1 is bulky "spacer" sandwiched by perovskite layers and A 2 is small "perovskiter" cation in the cavity enclosed by PbI 6 octahedra), [22][23][24][25] have recently stimulated intensive research in the field of photodetection. [26][27][28] For example, photodetectors fabricated on single crystals of (C 4 H 9 NH 3 ) 2 (MA) 2 Pb 3 I 10 exhibit a detectivity up to ≈3.6 × 10 10 Jones. [27] Despite great efforts devoted to 2D hybrid perovskites, for practical application, the photosensitivity and responding rate of such photodetectors still need improved. [29][30][31] In this context, to design new 2D candidates are indispensable for the advance of highperformance photodetectors. In the known lead iodide ABX 3 system, the "perovskiter" is strictly limited by a very narrow selection of small-size organic cations, such as CH 3 NH 3 + (r = 217 pm) and NH 2 CHNH 2 + (r = 253 pm). [32] Owing to the strict restriction of tolerance-factor concept, it is almost impossible to accommodate organic cations with even large ionic radii into the perovskite cavity. [33] However, we propose that 2D organic-inorganic hybrid perovskites are emerging as the promising alternatives in photodetection, due to their unique merits stemming from intrinsic quantum-confined structures. Despite great ongoing effects, highly sensitive and ultrafast responding photodetectors of 2D hybrid perovskites remain a huge blank. Here, the first nanosecond-responsive array photodetector based on 2D perovskite crystals of (PA) 2 (G)Pb 2 I 7 (where PA = n-pentylaminium and G = guanidinium) is fabricated, which features a newly tailored bilayer motif with large-size G cation as "perovskiter" inside the distorted PbI 3 perovskite framework. This motif creates a new branch of the intriguing 2D hybrid perovskite family. Strikingly, both high photodetectivities (6.3 × 10 12 Jones) and respo...

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Section: Resultsmentioning

confidence: 94%

Highly Sensitive and Ultrafast Responding Array Photodetector Based on a Newly Tailored 2D Lead Iodide Perovskite Crystal

Liu

et al. 2019

Advanced Optical Materials

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“…The majority of current research in this area is based on three‐dimensional (3D) perovskite structures, which have a general formula of ABX 3 , where A is monovalent cation, B is divalent metal cation, and X is halide . Slicing of 3D perovskite lattice along (100), (110), (111) crystallographic planes with the elimination of the octahedra lying in the slicing plane lead to common two‐dimensional (2D) perovskites with single‐octahedra or thicker slabs . Lowering the dimensionality to 2D with corner‐sharing octahedral layers and bulky organic cations separating perovskite layers gives rise to increased structural diversity and new functionalities .…”

Section: Figurementioning

confidence: 99%

“…[7] Slicing of 3D perovskite lattice along (100), (110), (111) crystallographic planes with the elimination of the octahedra lying in the slicing plane lead to common twodimensional (2D) perovskites with single-octahedra or thicker slabs. [8] Lowering the dimensionality to 2D with corner-sharing octahedral layers and bulky organic cations separating perovskite layers gives rise to increased structural diversity and new functionalities. [9][10][11] Besides,2 Dh ybrid perovskites have attracted much attention as alternative photovoltaic materials because of an improved stability arising from hydrophobic interactions,w hich block moisture diffusion in the material.…”

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confidence: 99%

Reversible Thermochromism and Strong Ferromagnetism in Two‐Dimensional Hybrid Perovskites

Sun

Liu

et al. 2019

Angewandte Chemie

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Two‐dimensional (2D) hybrid perovskites have shown many attractive properties associated with their soft lattices and multiple quantum well structure. Herein, we report the synthesis and characterization of two new multifunctional 2D hybrid perovskites, (PED)CuCl4 and (BED)2CuCl6, which show reversible thermochromic behavior, dramatic temperature‐dependent conductivity change, and strong ferromagnetism. Upon temperature change, the (PED)CuCl4 and (BED)2CuCl6 crystals exhibit a reversible color change between yellow and red‐brown. The associated structural changes were monitored by in situ temperature‐dependent powder X‐ray diffraction (PXRD). The (BED)2CuCl6 exhibits superior thermal stability, with a thermochromic working temperature up to 443 K. The conductivity of (BED)2CuCl6 changes over six orders of magnitude upon temperature change. The 2D perovskites exhibit ferromagnetic properties with Curie temperatures around 13 K.

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“…Thus, structural distortion can be considered a strategy to tune the optical properties, particularly for white‐light emitting materials, as their emission is associated with the presence of self‐trapped excitons that are localized in the inorganic layers . Along with chemical modifications, lattice deformations can be achieved by varying the physical parameters, among which temperature has been exploited the most in order to induce phase transitions . As the structure evolves from one phase to another, so does its electronic structure, as it is strongly dependent on the leadhalide bond length and the leadhalidelead dihedral angle.…”

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confidence: 99%

Revealing Photoluminescence Modulation from Layered Halide Perovskite Microcrystals upon Cyclic Compression

et al. 2018

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Halide perovskites show promise for high‐efficiency solar energy conversion and light‐emitting diode devices owing to their bandgap, which falls within the visible optical range. However, due to their rigidity, GPa pressures are necessary to control the complex interplay between their electronic and crystallographic structure. Layered perovskites are likely to be controlled using much lower pressures by exploiting the optical anisotropy of the embedded organic molecules in the structure. This work introduces layered perovskite microplatelets and demonstrates the extreme sensitivity of their emission to cyclic mechanical loading in the range of tens of MPa. A drastic change in their emission is observed in situ, from near‐white to an enhanced blue color. This process is reversible, as is evident from a hysteresis loop in the photoluminescence (PL) intensity of the microplatelets. A combination of experimental analysis and computational modelling shows that such behavior cannot be attributed to changes in the crystallographic structure of the flakes. Instead, it suggests that, thanks to their structural anisotropy, microplate alignment and reorientation are responsible for the observed PL modulation. The possibility to tune the optical emission of layered perovskite crystals via low pressures makes them highly interesting as active materials in applications where stress sensing or light modulation is desired.

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Guanidinium-Formamidinium Lead Iodide: A Layered Perovskite-Related Compound with Red Luminescence at Room Temperature

Cited by 124 publications

References 39 publications

Highly Sensitive and Ultrafast Responding Array Photodetector Based on a Newly Tailored 2D Lead Iodide Perovskite Crystal

Highly Sensitive and Ultrafast Responding Array Photodetector Based on a Newly Tailored 2D Lead Iodide Perovskite Crystal

Reversible Thermochromism and Strong Ferromagnetism in Two‐Dimensional Hybrid Perovskites

Revealing Photoluminescence Modulation from Layered Halide Perovskite Microcrystals upon Cyclic Compression

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