Unraveling the Chemical Nature of the 3D "hollow" Hybrid Halide Perovskites

Ioannis Spanopoulos, Weijun Ke, Constantinos C. Stoumpos, Emily C. Schueller, Oleg Y. Kontsevoi, Ram Seshadri, Mercouri G Kanatzidis

Research output: Contribution to journalArticle

15 Citations (Scopus)

Abstract

The newly introduced class of 3D halide perovskites, termed "hollow" perovskites, has been recently demonstrated as light absorbing semiconductor materials for fabricating lead-free perovskite solar cells with enhanced efficiency and superior stability. Hollow perovskites derive from three-dimensional (3D) AMX3 perovskites (A = methylammonium (MA), formamidinium (FA); M = Sn, Pb; X = Cl, Br, I), where small molecules such as ethylenediammonium cations (en) can be incorporated as the dication without altering the structure dimensionality. We present in this work the inherent structural properties of the hollow perovskites and expand this class of materials to the Pb-based analogues. Through a combination of physical and spectroscopic methods (XRD, gas pycnometry, 1H NMR, TGA, SEM/EDX), we have assigned the general formula (A)1-x(en)x(M)1-0.7x(X)3-0.4x to the hollow perovskites. The incorporation of en in the 3D perovskite structure leads to massive M and X vacancies in the 3D [MX3] framework, thus the term hollow. The resulting materials are semiconductors with significantly blue-shifted direct band gaps from 1.25 to 1.51 eV for Sn-based perovskites and from 1.53 to 2.1 eV for the Pb-based analogues. The increased structural disorder and hollow nature were validated by single crystal X-ray diffraction analysis as well as pair distribution function (PDF) analysis. Density functional theory (DFT) calculations support the experimental trends and suggest that the observed widening of the band gap is attributed to the massive M and X vacancies, which create a less connected 3D hollow structure. The resulting materials have superior air stability, where in the case of Sn-based hollow perovskites it exceeds two orders of temporal magnitude compared to the conventional full perovskites of MASnI3 and FASnI3. The hollow perovskite compounds pose as a new platform of promising light absorbers that can be utilized in single junction or tandem solar cells.

Original languageEnglish
Pages (from-to)5728-5742
Number of pages15
JournalJournal of the American Chemical Society
Volume140
Issue number17
DOIs
Publication statusPublished - May 2 2018

Fingerprint

Perovskite
Vacancies
Semiconductors
Energy gap
Semiconductor materials
X ray diffraction analysis
Distribution functions
Density functional theory
Cations
Light
Structural properties
Energy dispersive spectroscopy
Solar cells
Lead
Gases
Positive ions
Nuclear magnetic resonance
Single crystals
X-Ray Diffraction
Scanning electron microscopy

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Spanopoulos, I., Ke, W., Stoumpos, C. C., Schueller, E. C., Kontsevoi, O. Y., Seshadri, R., & Kanatzidis, M. G. (2018). Unraveling the Chemical Nature of the 3D "hollow" Hybrid Halide Perovskites. Journal of the American Chemical Society, 140(17), 5728-5742. https://doi.org/10.1021/jacs.8b01034

Unraveling the Chemical Nature of the 3D "hollow" Hybrid Halide Perovskites. / Spanopoulos, Ioannis; Ke, Weijun; Stoumpos, Constantinos C.; Schueller, Emily C.; Kontsevoi, Oleg Y.; Seshadri, Ram; Kanatzidis, Mercouri G.

In: Journal of the American Chemical Society, Vol. 140, No. 17, 02.05.2018, p. 5728-5742.

Research output: Contribution to journalArticle

Spanopoulos, I, Ke, W, Stoumpos, CC, Schueller, EC, Kontsevoi, OY, Seshadri, R & Kanatzidis, MG 2018, 'Unraveling the Chemical Nature of the 3D "hollow" Hybrid Halide Perovskites', Journal of the American Chemical Society, vol. 140, no. 17, pp. 5728-5742. https://doi.org/10.1021/jacs.8b01034
Spanopoulos I, Ke W, Stoumpos CC, Schueller EC, Kontsevoi OY, Seshadri R et al. Unraveling the Chemical Nature of the 3D "hollow" Hybrid Halide Perovskites. Journal of the American Chemical Society. 2018 May 2;140(17):5728-5742. https://doi.org/10.1021/jacs.8b01034
Spanopoulos, Ioannis ; Ke, Weijun ; Stoumpos, Constantinos C. ; Schueller, Emily C. ; Kontsevoi, Oleg Y. ; Seshadri, Ram ; Kanatzidis, Mercouri G. / Unraveling the Chemical Nature of the 3D "hollow" Hybrid Halide Perovskites. In: Journal of the American Chemical Society. 2018 ; Vol. 140, No. 17. pp. 5728-5742.
@article{062481225a38419db493ad53eed9cf77,
title = "Unraveling the Chemical Nature of the 3D {"}hollow{"} Hybrid Halide Perovskites",
abstract = "The newly introduced class of 3D halide perovskites, termed {"}hollow{"} perovskites, has been recently demonstrated as light absorbing semiconductor materials for fabricating lead-free perovskite solar cells with enhanced efficiency and superior stability. Hollow perovskites derive from three-dimensional (3D) AMX3 perovskites (A = methylammonium (MA), formamidinium (FA); M = Sn, Pb; X = Cl, Br, I), where small molecules such as ethylenediammonium cations (en) can be incorporated as the dication without altering the structure dimensionality. We present in this work the inherent structural properties of the hollow perovskites and expand this class of materials to the Pb-based analogues. Through a combination of physical and spectroscopic methods (XRD, gas pycnometry, 1H NMR, TGA, SEM/EDX), we have assigned the general formula (A)1-x(en)x(M)1-0.7x(X)3-0.4x to the hollow perovskites. The incorporation of en in the 3D perovskite structure leads to massive M and X vacancies in the 3D [MX3] framework, thus the term hollow. The resulting materials are semiconductors with significantly blue-shifted direct band gaps from 1.25 to 1.51 eV for Sn-based perovskites and from 1.53 to 2.1 eV for the Pb-based analogues. The increased structural disorder and hollow nature were validated by single crystal X-ray diffraction analysis as well as pair distribution function (PDF) analysis. Density functional theory (DFT) calculations support the experimental trends and suggest that the observed widening of the band gap is attributed to the massive M and X vacancies, which create a less connected 3D hollow structure. The resulting materials have superior air stability, where in the case of Sn-based hollow perovskites it exceeds two orders of temporal magnitude compared to the conventional full perovskites of MASnI3 and FASnI3. The hollow perovskite compounds pose as a new platform of promising light absorbers that can be utilized in single junction or tandem solar cells.",
author = "Ioannis Spanopoulos and Weijun Ke and Stoumpos, {Constantinos C.} and Schueller, {Emily C.} and Kontsevoi, {Oleg Y.} and Ram Seshadri and Kanatzidis, {Mercouri G}",
year = "2018",
month = "5",
day = "2",
doi = "10.1021/jacs.8b01034",
language = "English",
volume = "140",
pages = "5728--5742",
journal = "Journal of the American Chemical Society",
issn = "0002-7863",
publisher = "American Chemical Society",
number = "17",

}

TY - JOUR

T1 - Unraveling the Chemical Nature of the 3D "hollow" Hybrid Halide Perovskites

AU - Spanopoulos, Ioannis

AU - Ke, Weijun

AU - Stoumpos, Constantinos C.

AU - Schueller, Emily C.

AU - Kontsevoi, Oleg Y.

AU - Seshadri, Ram

AU - Kanatzidis, Mercouri G

PY - 2018/5/2

Y1 - 2018/5/2

N2 - The newly introduced class of 3D halide perovskites, termed "hollow" perovskites, has been recently demonstrated as light absorbing semiconductor materials for fabricating lead-free perovskite solar cells with enhanced efficiency and superior stability. Hollow perovskites derive from three-dimensional (3D) AMX3 perovskites (A = methylammonium (MA), formamidinium (FA); M = Sn, Pb; X = Cl, Br, I), where small molecules such as ethylenediammonium cations (en) can be incorporated as the dication without altering the structure dimensionality. We present in this work the inherent structural properties of the hollow perovskites and expand this class of materials to the Pb-based analogues. Through a combination of physical and spectroscopic methods (XRD, gas pycnometry, 1H NMR, TGA, SEM/EDX), we have assigned the general formula (A)1-x(en)x(M)1-0.7x(X)3-0.4x to the hollow perovskites. The incorporation of en in the 3D perovskite structure leads to massive M and X vacancies in the 3D [MX3] framework, thus the term hollow. The resulting materials are semiconductors with significantly blue-shifted direct band gaps from 1.25 to 1.51 eV for Sn-based perovskites and from 1.53 to 2.1 eV for the Pb-based analogues. The increased structural disorder and hollow nature were validated by single crystal X-ray diffraction analysis as well as pair distribution function (PDF) analysis. Density functional theory (DFT) calculations support the experimental trends and suggest that the observed widening of the band gap is attributed to the massive M and X vacancies, which create a less connected 3D hollow structure. The resulting materials have superior air stability, where in the case of Sn-based hollow perovskites it exceeds two orders of temporal magnitude compared to the conventional full perovskites of MASnI3 and FASnI3. The hollow perovskite compounds pose as a new platform of promising light absorbers that can be utilized in single junction or tandem solar cells.

AB - The newly introduced class of 3D halide perovskites, termed "hollow" perovskites, has been recently demonstrated as light absorbing semiconductor materials for fabricating lead-free perovskite solar cells with enhanced efficiency and superior stability. Hollow perovskites derive from three-dimensional (3D) AMX3 perovskites (A = methylammonium (MA), formamidinium (FA); M = Sn, Pb; X = Cl, Br, I), where small molecules such as ethylenediammonium cations (en) can be incorporated as the dication without altering the structure dimensionality. We present in this work the inherent structural properties of the hollow perovskites and expand this class of materials to the Pb-based analogues. Through a combination of physical and spectroscopic methods (XRD, gas pycnometry, 1H NMR, TGA, SEM/EDX), we have assigned the general formula (A)1-x(en)x(M)1-0.7x(X)3-0.4x to the hollow perovskites. The incorporation of en in the 3D perovskite structure leads to massive M and X vacancies in the 3D [MX3] framework, thus the term hollow. The resulting materials are semiconductors with significantly blue-shifted direct band gaps from 1.25 to 1.51 eV for Sn-based perovskites and from 1.53 to 2.1 eV for the Pb-based analogues. The increased structural disorder and hollow nature were validated by single crystal X-ray diffraction analysis as well as pair distribution function (PDF) analysis. Density functional theory (DFT) calculations support the experimental trends and suggest that the observed widening of the band gap is attributed to the massive M and X vacancies, which create a less connected 3D hollow structure. The resulting materials have superior air stability, where in the case of Sn-based hollow perovskites it exceeds two orders of temporal magnitude compared to the conventional full perovskites of MASnI3 and FASnI3. The hollow perovskite compounds pose as a new platform of promising light absorbers that can be utilized in single junction or tandem solar cells.

UR - http://www.scopus.com/inward/record.url?scp=85046363099&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85046363099&partnerID=8YFLogxK

U2 - 10.1021/jacs.8b01034

DO - 10.1021/jacs.8b01034

M3 - Article

VL - 140

SP - 5728

EP - 5742

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

SN - 0002-7863

IS - 17

ER -