Critical Intermediate Structure That Directs the Crystalline Texture and Surface Morphology of Organo-Lead Trihalide Perovskite

Hao Chung Chia, Hwo Shuenn Sheu, Yu Yun Hsiao, Shao Sian Li, Yi Kang Lan, Chung Yao Lin, Je Wei Chang, Yen Chien Kuo, Chia Hao Chen, Shih Chang Weng, Chun Jen Su, An Chung Su, Chun Wei Chen, U. Ser Jeng

Research output: Contribution to journalArticle

7 Citations (Scopus)

Abstract

We have identified an often observed yet unresolved intermediate structure in a popular processing with dimethylformamide solutions of lead chloride and methylammonium iodide for perovskite solar cells. With subsecond time-resolved grazing-incidence X-ray scattering and X-ray photoemission spectroscopy, supplemental with ab initio calculation, the resolved intermediate structure (CH3NH3)2PbI2Cl2·CH3NH3I features two-dimensional (2D) perovskite bilayers of zigzagged lead-halide octahedra and sandwiched CH3NH3I layers. Such intermediate structure reveals a hidden correlation between the intermediate phase and the composition of the processing solution. Most importantly, the 2D perovskite lattice of the intermediate phase is largely crystallographically aligned with the [110] planes of the three-dimensional perovskite cubic phase; consequently, with sublimation of Cl ions from the organo-lead octahedral terminal corners in prolonged annealing, the zigzagged octahedral layers of the intermediate phase can merge with the intercalated methylammonium iodide layers for templated growth of perovskite crystals. Regulated by annealing temperature and the activation energies of the intermediate and perovskite, deduced from analysis of temperature-dependent structural kinetics, the intermediate phase is found to selectively mature first and then melt along the layering direction for epitaxial conversion into perovskite crystals. The unveiled epitaxial conversion under growth kinetics controls might be general for solution-processed and intermediate-templated perovskite formation.

Original languageEnglish
Pages (from-to)36897-36906
Number of pages10
JournalACS Applied Materials and Interfaces
Volume9
Issue number42
DOIs
Publication statusPublished - Oct 25 2017
Externally publishedYes

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Perovskite
Surface morphology
Textures
Lead
Crystalline materials
Iodides
Annealing
Dimethylformamide
Crystals
Growth kinetics
Sublimation
Photoelectron spectroscopy
Processing
X ray spectroscopy
perovskite
X ray scattering
Activation energy
Ions
Temperature
Chemical analysis

Keywords

  • crystal growth kinetics
  • grazing-incidence X-ray scattering
  • intermediate-templated conversion
  • Organo-lead trihalide perovskite
  • X-ray photoemission spectroscopy

ASJC Scopus subject areas

  • Materials Science(all)

Cite this

Critical Intermediate Structure That Directs the Crystalline Texture and Surface Morphology of Organo-Lead Trihalide Perovskite. / Chia, Hao Chung; Sheu, Hwo Shuenn; Hsiao, Yu Yun; Li, Shao Sian; Lan, Yi Kang; Lin, Chung Yao; Chang, Je Wei; Kuo, Yen Chien; Chen, Chia Hao; Weng, Shih Chang; Su, Chun Jen; Su, An Chung; Chen, Chun Wei; Jeng, U. Ser.

In: ACS Applied Materials and Interfaces, Vol. 9, No. 42, 25.10.2017, p. 36897-36906.

Research output: Contribution to journalArticle

Chia, HC, Sheu, HS, Hsiao, YY, Li, SS, Lan, YK, Lin, CY, Chang, JW, Kuo, YC, Chen, CH, Weng, SC, Su, CJ, Su, AC, Chen, CW & Jeng, US 2017, 'Critical Intermediate Structure That Directs the Crystalline Texture and Surface Morphology of Organo-Lead Trihalide Perovskite', ACS Applied Materials and Interfaces, vol. 9, no. 42, pp. 36897-36906. https://doi.org/10.1021/acsami.7b12378
Chia, Hao Chung ; Sheu, Hwo Shuenn ; Hsiao, Yu Yun ; Li, Shao Sian ; Lan, Yi Kang ; Lin, Chung Yao ; Chang, Je Wei ; Kuo, Yen Chien ; Chen, Chia Hao ; Weng, Shih Chang ; Su, Chun Jen ; Su, An Chung ; Chen, Chun Wei ; Jeng, U. Ser. / Critical Intermediate Structure That Directs the Crystalline Texture and Surface Morphology of Organo-Lead Trihalide Perovskite. In: ACS Applied Materials and Interfaces. 2017 ; Vol. 9, No. 42. pp. 36897-36906.
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T1 - Critical Intermediate Structure That Directs the Crystalline Texture and Surface Morphology of Organo-Lead Trihalide Perovskite

AU - Chia, Hao Chung

AU - Sheu, Hwo Shuenn

AU - Hsiao, Yu Yun

AU - Li, Shao Sian

AU - Lan, Yi Kang

AU - Lin, Chung Yao

AU - Chang, Je Wei

AU - Kuo, Yen Chien

AU - Chen, Chia Hao

AU - Weng, Shih Chang

AU - Su, Chun Jen

AU - Su, An Chung

AU - Chen, Chun Wei

AU - Jeng, U. Ser

PY - 2017/10/25

Y1 - 2017/10/25

N2 - We have identified an often observed yet unresolved intermediate structure in a popular processing with dimethylformamide solutions of lead chloride and methylammonium iodide for perovskite solar cells. With subsecond time-resolved grazing-incidence X-ray scattering and X-ray photoemission spectroscopy, supplemental with ab initio calculation, the resolved intermediate structure (CH3NH3)2PbI2Cl2·CH3NH3I features two-dimensional (2D) perovskite bilayers of zigzagged lead-halide octahedra and sandwiched CH3NH3I layers. Such intermediate structure reveals a hidden correlation between the intermediate phase and the composition of the processing solution. Most importantly, the 2D perovskite lattice of the intermediate phase is largely crystallographically aligned with the [110] planes of the three-dimensional perovskite cubic phase; consequently, with sublimation of Cl ions from the organo-lead octahedral terminal corners in prolonged annealing, the zigzagged octahedral layers of the intermediate phase can merge with the intercalated methylammonium iodide layers for templated growth of perovskite crystals. Regulated by annealing temperature and the activation energies of the intermediate and perovskite, deduced from analysis of temperature-dependent structural kinetics, the intermediate phase is found to selectively mature first and then melt along the layering direction for epitaxial conversion into perovskite crystals. The unveiled epitaxial conversion under growth kinetics controls might be general for solution-processed and intermediate-templated perovskite formation.

AB - We have identified an often observed yet unresolved intermediate structure in a popular processing with dimethylformamide solutions of lead chloride and methylammonium iodide for perovskite solar cells. With subsecond time-resolved grazing-incidence X-ray scattering and X-ray photoemission spectroscopy, supplemental with ab initio calculation, the resolved intermediate structure (CH3NH3)2PbI2Cl2·CH3NH3I features two-dimensional (2D) perovskite bilayers of zigzagged lead-halide octahedra and sandwiched CH3NH3I layers. Such intermediate structure reveals a hidden correlation between the intermediate phase and the composition of the processing solution. Most importantly, the 2D perovskite lattice of the intermediate phase is largely crystallographically aligned with the [110] planes of the three-dimensional perovskite cubic phase; consequently, with sublimation of Cl ions from the organo-lead octahedral terminal corners in prolonged annealing, the zigzagged octahedral layers of the intermediate phase can merge with the intercalated methylammonium iodide layers for templated growth of perovskite crystals. Regulated by annealing temperature and the activation energies of the intermediate and perovskite, deduced from analysis of temperature-dependent structural kinetics, the intermediate phase is found to selectively mature first and then melt along the layering direction for epitaxial conversion into perovskite crystals. The unveiled epitaxial conversion under growth kinetics controls might be general for solution-processed and intermediate-templated perovskite formation.

KW - crystal growth kinetics

KW - grazing-incidence X-ray scattering

KW - intermediate-templated conversion

KW - Organo-lead trihalide perovskite

KW - X-ray photoemission spectroscopy

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EP - 36906

JO - ACS applied materials & interfaces

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