Understanding the interplay of stability and efficiency in A-site engineered lead halide perovskites

Four types of organic cation-mixed single crystals were successfully synthesized by partially substituting A site cations to investigate the effect of organic cations on structure, optical features, thermal stability, and electrical transport properties.

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Synthetic Variation and Structural Trends in Layered Two-Dimensional Alkylammonium Lead Halide Perovskites

10.26434/chemrxiv.7942628 ◽

2019 ◽

Author(s):

Watcharaphol Paritmongkol ◽

Nabeel Dahod ◽

Nannan Mao ◽

Shao-Liang Zheng ◽

William Tisdale

Keyword(s):

Crystal Structures ◽

Periodic Variation ◽

Two Dimensional ◽

Halide Anion ◽

Structural Distortions ◽

Spacer Layer ◽

Halide Perovskites ◽

Spacer Chain Length ◽

A Site ◽

Lead Halide

We report the cooling-induced crystallization of layered two-dimensional lead halide perovskites with controllable inorganic quantum-well thickness (n = 1, 2, 3, 4), organic spacer chain length (butyl-, pentyl-, hexylammonium), A-site cation (methylammonium, formamidinium), and halide anion (iodide, bromide). We report crystal structures for the iodide family as a function of these compositional parameters, and across their temperature dependent phase transitions. In general, lower symmetry crystal structures, increasing extents of organic-spacer interdigitation, and increasing organic-spacer corrugation tilts are observed at low temperature. In addition, greater structural distortions are seen in lead halide octahedra closest to the organic spacer layer, and larger-n structures exhibit periodic variation in Pb-I bond lengths. We also provide detailed guidance regarding the combination of synthetic parameters needed to achieve phase-pure crystals of each composition, and discuss difficulties encountered when trying to synthesize particular members of the 2D perovskite family containing formamidinium or cesium as the A-site cation. These results provide a foundation for understanding structural trends in 2D lead halide perovskites and the effect these trends have on their thermal, electrical, and optical properties.

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Role of lattice distortion and A site cation in the phase transitions of methylammonium lead halide perovskites

Physical Review Materials ◽

10.1103/physrevmaterials.2.065404 ◽

2018 ◽

Vol 2 (6) ◽

Cited By ~ 13

Author(s):

Jonathon R. Harwell ◽

Julia L. Payne ◽

Muhammad T. Sajjad ◽

Frank J. L. Heutz ◽

Daniel M. Dawson ◽

...

Keyword(s):

Phase Transitions ◽

Lattice Distortion ◽

Halide Perovskites ◽

A Site ◽

Lead Halide

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Size Isn’t Everything - Compositional Variation in Hybrid Organic-Inorganic Lead Halide Perovskites: Kinetically- versus Thermodynamically-controlled Synthesis

10.26434/chemrxiv.13729063 ◽

2021 ◽

Author(s):

Jiyu Tian ◽

Eli Zysman-Colman ◽

Finlay Morrison

Keyword(s):

Solid Solution ◽

Solid Solutions ◽

Compositional Variation ◽

X Ray Diffraction ◽

Solid Solution Formation ◽

X Ray ◽

H Nmr ◽

Halide Perovskites ◽

A Site ◽

Lead Halide

The formation and study of a partial solid solution <a></a><a>Az1-xFAxPbBr3</a>, using ‘similar’ sized cations azetidinium (Az+) and formamidinium (FA+), was explored via mechanosynthesis and precipitation synthesis. The composition and lattice parameters of samples from both syntheses were analysed by 1H NMR and Rietveld refinement of the powder X-ray diffraction. A clear mismatch in the composition of the perovskite was found between the precipitated samples and the corresponding solutions. Such a mismatch was not observed for samples obtained via mechanosynthesis. The discrepancy suggests products are kinetically-controlled during precipitation, compared to thermodynamically-controlled mechanosynthesis. Furthermore, the cell volume as a function of composition in both 6H (Az-rich) and 3C (FA-rich) solid solutions suggests that FA+ is actually smaller than Az+, contradicting the literature. In the 3C (Az-poor) solid solutions, the extent of Az1-xFAxPbBr3 is unexpectedly smaller than Az1-xMAxPbBr3, again in contradiction to the expectation based on the reported cation sizes. These results indicate that other factors, as yet unidentified, must also contribute to the solid solution formation of organic-inorganic hybrid perovskites, not simply the relative sizes of the A-site cations.

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A-site engineered lead halide perovskites lead to balanced stability and efficiency

Scilight ◽

10.1063/10.0001608 ◽

2020 ◽

Vol 2020 (28) ◽

pp. 281102

Author(s):

Savannah Mandel

Keyword(s):

Halide Perovskites ◽

A Site ◽

Lead Halide

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Synthetic Variation and Structural Trends in Layered Two-Dimensional Alkylammonium Lead Halide Perovskites

10.26434/chemrxiv.7942628.v1 ◽

2019 ◽

Cited By ~ 1

Author(s):

Watcharaphol Paritmongkol ◽

Nabeel Dahod ◽

Nannan Mao ◽

Shao-Liang Zheng ◽

William Tisdale

Keyword(s):

Crystal Structures ◽

Periodic Variation ◽

Two Dimensional ◽

Halide Anion ◽

Structural Distortions ◽

Spacer Layer ◽

Halide Perovskites ◽

Spacer Chain Length ◽

A Site ◽

Lead Halide

We report the cooling-induced crystallization of layered two-dimensional lead halide perovskites with controllable inorganic quantum-well thickness (n = 1, 2, 3, 4), organic spacer chain length (butyl-, pentyl-, hexylammonium), A-site cation (methylammonium, formamidinium), and halide anion (iodide, bromide). We report crystal structures for the iodide family as a function of these compositional parameters, and across their temperature dependent phase transitions. In general, lower symmetry crystal structures, increasing extents of organic-spacer interdigitation, and increasing organic-spacer corrugation tilts are observed at low temperature. In addition, greater structural distortions are seen in lead halide octahedra closest to the organic spacer layer, and larger-n structures exhibit periodic variation in Pb-I bond lengths. We also provide detailed guidance regarding the combination of synthetic parameters needed to achieve phase-pure crystals of each composition, and discuss difficulties encountered when trying to synthesize particular members of the 2D perovskite family containing formamidinium or cesium as the A-site cation. These results provide a foundation for understanding structural trends in 2D lead halide perovskites and the effect these trends have on their thermal, electrical, and optical properties.

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Exploring Multidimensional Lead Halide Perovskites Using Ultra−wideline 35/37Cl NMR Spectroscopy

10.26434/chemrxiv-2021-v0d1j ◽

2021 ◽

Author(s):

Diganta Sarkar ◽

Riley Hooper ◽

Abhoy Karmakar ◽

Victor Terskikh ◽

Vladimir Michaelis

Keyword(s):

Solid State ◽

Nmr Spectroscopy ◽

Inorganic Hybrid ◽

Nmr Parameters ◽

Ultrahigh Magnetic Fields ◽

Halide Perovskites ◽

Low Dimensional ◽

A Site ◽

Distinct Features ◽

Lead Halide

We report a rapid solid−state 35/37Cl NMR strategy for 3D organic−inorganic hybrid and low−dimensional (2D and 0D) all−inorganic lead−based perovskites embracing ultra-wideline acquisition approaches and moderate to ultrahigh magnetic fields. The observed quadrupolar NMR parameters (CQ and η), supported by GIPAW−DFT computations, revealed distinct features for unique local Cl environments with the variation of the A−site and dimensionality. 35Cl CQ values display the potential for becoming an informative probe of distinct Cl chemical environments.

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The effect of structural dimensionality on carrier mobility in lead-halide perovskites

Journal of Materials Chemistry A ◽

10.1039/c9ta05241k ◽

2019 ◽

Vol 7 (41) ◽

pp. 23949-23957 ◽

Cited By ~ 11

Author(s):

Noor Titan Putri Hartono ◽

Shijing Sun ◽

María C. Gélvez-Rueda ◽

Polly J. Pierone ◽

Matthew P. Erodici ◽

...

Keyword(s):

Solar Cell ◽

Charge Carrier ◽

Carrier Mobility ◽

Charge Carrier Mobility ◽

Cell Performance ◽

Solar Cell Performance ◽

Structural Dimensionality ◽

Halide Perovskites ◽

A Site ◽

Lead Halide

Changes in perovskite structural dimensionality brought by mixing A-site cations play an important role in determining the measured charge carrier mobility, and in the solar cell performance.

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Size Isn’t Everything - Compositional Variation in Hybrid Organic-Inorganic Lead Halide Perovskites: Kinetically- versus Thermodynamically-controlled Synthesis

10.26434/chemrxiv.13729063.v1 ◽

2021 ◽

Author(s):

Jiyu Tian ◽

Eli Zysman-Colman ◽

Finlay Morrison

Keyword(s):

Solid Solution ◽

Solid Solutions ◽

Compositional Variation ◽

X Ray Diffraction ◽

Solid Solution Formation ◽

X Ray ◽

H Nmr ◽

Halide Perovskites ◽

A Site ◽

Lead Halide

The formation and study of a partial solid solution <a></a><a>Az1-xFAxPbBr3</a>, using ‘similar’ sized cations azetidinium (Az+) and formamidinium (FA+), was explored via mechanosynthesis and precipitation synthesis. The composition and lattice parameters of samples from both syntheses were analysed by 1H NMR and Rietveld refinement of the powder X-ray diffraction. A clear mismatch in the composition of the perovskite was found between the precipitated samples and the corresponding solutions. Such a mismatch was not observed for samples obtained via mechanosynthesis. The discrepancy suggests products are kinetically-controlled during precipitation, compared to thermodynamically-controlled mechanosynthesis. Furthermore, the cell volume as a function of composition in both 6H (Az-rich) and 3C (FA-rich) solid solutions suggests that FA+ is actually smaller than Az+, contradicting the literature. In the 3C (Az-poor) solid solutions, the extent of Az1-xFAxPbBr3 is unexpectedly smaller than Az1-xMAxPbBr3, again in contradiction to the expectation based on the reported cation sizes. These results indicate that other factors, as yet unidentified, must also contribute to the solid solution formation of organic-inorganic hybrid perovskites, not simply the relative sizes of the A-site cations.

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THERMAL TRANSPORT BEHAVIORS IN LEAD HALIDE PEROVSKITES

10.1615/ihtc16.nmt.023055 ◽

2018 ◽

Author(s):

Wee-Liat Ong ◽

Giselle Elbaz ◽

Evan A. Doud ◽

Philip Kim ◽

Daniel Paley ◽

...

Keyword(s):

Thermal Transport ◽

Halide Perovskites ◽

Lead Halide

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